CN104843729B - Process and its application of zeolite are prepared under a kind of normal temperature and pressure - Google Patents
Process and its application of zeolite are prepared under a kind of normal temperature and pressure Download PDFInfo
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- CN104843729B CN104843729B CN201510222588.XA CN201510222588A CN104843729B CN 104843729 B CN104843729 B CN 104843729B CN 201510222588 A CN201510222588 A CN 201510222588A CN 104843729 B CN104843729 B CN 104843729B
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Abstract
The invention discloses process and its application that zeolite is prepared under a kind of normal temperature and pressure, including：Flyash is mixed with alkali lye, is put in planetary ball mill, and the multiple abrading-balls not waited using diameter perform grinding at normal temperatures and pressures, and the stable crystal structure structure such as the mullite destroyed using localized hyperthermia in flyash, it is dry after be to obtain crystallization of zeolites sample.By means of the invention it is possible to prepare zeolite in the way of saving, be easy to manipulation, and result in combination property more preferably product.
Description
Technical field
Field is utilized the invention belongs to solid waste resource, more particularly, to preparing zeolite under a kind of normal temperature and pressure
Process and its application.
Background technology
In China, thermal power plant produces 10-20% flyash every year, and yield increases year by year, and the processing of flyash is not
Land resource, Expenses Cost are only taken up, and is possible to pollute the environment for a long time.Two methods are typically used in the processing of flyash：
One kind is thermal power plant's expropriation of land storage flyash, and flyash is discharged into storage ashpit precipitation by wet technique coal ash discharging stores, or by dry
Flyash is transported to ash disposal area and stored by method ash discharge；Another is that flyash is comprehensively utilized, and is generally used for building materials life
Production, architectural engineering etc..According to statistics, utilization rate U.S. of flyash has reached 39%, and Europe has reached 47%, and the reality of China
Border utilization rate is but less than 30%.And with the growth of China's economic, the utilization to coal will continue to increase, therefore, flyash
Using in urgent need to be improved.
Because flyash main oxides composition is SiO2And Al2O3, have close chemical composition and two kinds of compositions with zeolite
Content is higher, therefore the higher zeolite of economic value can be synthesized using it.Zeolite often should such as be adsorbed waste water in the absorption of pollutant
In Cr (VI).And common zeolite only has the effect of physical absorption to Cr (VI), the zeolite of flyash synthesis is due in flyash
The presence of low price ferro element, and with electronation, for handling during the Cr in waste water (VI) due to its chemisorption
And it is more efficient.
Have much using the research of synthetic zeolite from flyash, the more commonly used there are two methods：One is hydro-thermal method, be
Pass through water-bath synthetic zeolite in autoclave；Two be two-step method, i.e., first in tube furnace alkali fusion, then again by hydro-thermal method come
Synthetic zeolite.Comparatively speaking, water-bath synthetic zeolite needs more than 100 DEG C of temperature；And two-step method synthetic zeolite, in alkali fusion
Part, it is necessary to temperature be more up to more than 500 DEG C, compare the consumption energy.And two methods are to more stable in flyash
Crystal structure --- mullite execution is poor.
And mechanical lapping can not only cause grinding-material solid to refine by the mechanical impact of abrading-ball；And with machine
The progress of tool process of lapping, the chemical energy that mechanical energy is converted into reactive material is stored in inside material, so as to increase reactive material
Activation energy.According to above feature, by the method for mechanical lapping, flyash can carry out synthetic zeolite as raw material.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides prepare zeolite under a kind of normal temperature and pressure
Process, wherein by its reaction partner and its key ingredient than and other reaction conditions design, can be in normal temperature
Normal pressure, be easy to manipulation under conditions of i.e. acquisition needed for zeolite product；Especially since can be in flyash table in ball-milling technology
Face produces localized hyperthermia, destroys the stable crystal structure of mullite in flyash, has accordingly dramatically speeded up the Si in flyash
Oxide and Al oxides and the Na in solution+Or K+Ions binding, so as to further promote the formation of zeolite product.
According to one aspect of the present invention there is provided the process that zeolite is prepared under a kind of normal temperature and pressure, its feature exists
In comprising the following steps：
OH is configured to NaOH solution or KOH solution-Ion concentration is 1mol/L~4mol/L aqueous slkali, by fine coal
Ash is positioned in ball grinder jointly with this aqueous slkali, and between the two with 10g~25g:100ml solid-to-liquid ratio mixes to be formed
Suspension；Then, add the abrading-ball of multiple diameter specification into the suspension, the diameters of these abrading-balls be limited at 2mm~
In the range of 15mm；
Above-mentioned ball grinder is positioned in planetary ball mill, and milled processed is performed under conditions of normal temperature and pressure, wherein
The rotating speed of the milled processed is set to 350rpm~500rpm, and milling time is set to 6h~24h；Then, ball milling is taken out
Tank, the inside solution is poured out and filtered together with solid, lower under conditions of then 60 DEG C~90 DEG C to dry 4h~24h；This grinds
During mill, fine coal gray surface can form local high temperature, and under the mating reaction of strong alkali solution, the Si oxygen in flyash
Compound and Al oxides dissolving, while so that in flyash mullite stable crystal structure be destroyed, and then cause be present in
Na in alkali lye+Or K+Si with coming from powdered coal ash4+And Al3+It is combined, ultimately forms required zeolite product.
As it is further preferred that the solid-to-liquid ratio of the flyash and the aqueous slkali is further configured to 12g~17g:
100ml。
As it is further preferred that the abrading-ball of the sizes specification be designed it is as follows：Diameter 2mm small size abrading-ball
5~9, a diameter of 5mm middle size abrading-ball 6~11 and a diameter of 15mm large scale abrading-ball 5~9.
It is another aspect of this invention to provide that additionally providing by the zeolite prepared by the process of the present invention, Cr (VI)
Absorption on application.
In general, by the contemplated above technical scheme of the present invention compared with prior art, with advantages below：
1st, by using flyash and aqueous slkali as reaction partner, and the ball-milling technology of appropriate process conditions is selected
Processing is performed, accordingly may be such that whole course of reaction can be operated at normal temperatures and pressures, without complex reactions such as HTHPs
The participation of condition, and non-exhaust emission, energy-conserving and environment-protective；
2nd, it is designed by concrete processing procedure and its key condition to ball-milling technology, test fine coal gray surface can
Local high temperature is formed, so that mullite structure is destroyed in flyash, Si oxides and the dissolving of Al oxides, and and alkali lye
In Na+Or K+With reference to and form zeolite, and this method combines drying process and crystallization process, is improving technique
Simplification of flowsheet is gone back while effect；
3rd, the zeolite of this method synthesis does not only have physical absorption to the Cr (VI) in liquid, and has chemisorbed, with business
Industry zeolite is compared more preferable to Cr (VI) treatment effect.
Brief description of the drawings
Fig. 1 is present invention process flow chart.
Fig. 2 a are the SEM figures of the powdered coal ash of the embodiment of the present invention 1, and Fig. 2 b are the SEM of the zeolite product of embodiment 1
Figure.
Fig. 3 is the powdered coal ash of the embodiment of the present invention 1 and the XRD spectrum of zeolite product；Wherein curve RFA represents fine coal
Ash, curve ZFA represents zeolite；Peak Q represents quartz, and peak C represents calcium oxide, and peak L represents calcium carbonate, and peak Ma represents magnetic iron ore, peak M
Mullite is represented, peak X represents X-type zeolite.
Fig. 4 is the commercial zeolite sample of the powdered coal ash, zeolite product and purchase of the embodiment of the present invention 1 to Cr (VI)
Equilibrium adsorption spirogram.
Fig. 5 be the zeolite product of the embodiment of the present invention 1 during Cr (VI) solution is adsorbed, Cr (VI) valence state turns
Change.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Not constituting conflict each other can just be mutually combined.
Embodiment 1
The preparation method of Na-X type zeolites, comprises the following steps：
80g NaOH reagents are taken, are dissolved in 1L deionized waters, the NaOH solution that concentration is 2mol/L is made；
Quality is configured into aqueous slkali 160ml with step 1 by 20g flyash and is positioned over the ball grinder that volume is 250ml
It is middle to be mixed, and add diameter 2mm small size abrading-ball 5, a diameter of 5mm middle size abrading-ball 8 and a diameter of
15mm large scale abrading-ball 7；
Ball grinder is put in planetary ball mill, in normal temperature and pressure, rotating speed is the 6h that under the conditions of 350rpm, works；
Ball grinder is taken out, the inside solution is poured out together with solid, is filtered, 24h is then dried at 60 DEG C, that is, is obtained
Required zeolite product.
Embodiment 2
The preparation method of zeolite, comprises the following steps：
224g KOH reagents are taken, are dissolved in 1L deionized waters, the KOH solution that concentration is 4mol/L is made；
Quality is configured into aqueous slkali 200ml with step 1 by 20g flyash and is positioned over the ball grinder that volume is 300ml
It is middle to be mixed, and add diameter 2mm small size abrading-ball 9, a diameter of 5mm middle size abrading-ball 6 and a diameter of
15mm large scale abrading-ball 9；
Ball grinder is put in planetary ball mill, in normal temperature and pressure, rotating speed is the 24h that under the conditions of 500rpm, works；
Ball grinder is taken out, the inside solution is poured out together with solid, is filtered, 4h is then dried at 90 DEG C, that is, is obtained
Required zeolite product.
Embodiment 3
The preparation method of zeolite, comprises the following steps：
40g NaOH reagents are taken, are dissolved in 1L deionized waters, the NaOH solution that concentration is 2mol/L is made；
Quality is configured into aqueous slkali 100ml with step 1 by 25g flyash and is positioned over the ball grinder that volume is 150ml
It is middle to be mixed, and add diameter 2mm small size abrading-ball 7, a diameter of 5mm middle size abrading-ball 11 and a diameter of
15mm large scale abrading-ball 5；
Ball grinder is put in planetary ball mill, in normal temperature and pressure, rotating speed is the 4h that under the conditions of 450rpm, works；
Ball grinder is taken out, the inside solution is poured out together with solid, is filtered, 12h is then dried at 80 DEG C, that is, is obtained
Required zeolite product.
Embodiment 4
The preparation method of zeolite, comprises the following steps：
The flyash of 250ml deionized waters, 50g KOH reagents and 40g is positioned in the ball grinder that volume is 500ml
It is sufficiently mixed, suspension of the flyash in alkali lye is made, and add diameter 3mm small size abrading-ball 7 wherein, directly
Footpath is 5mm middle size abrading-ball 8, a diameter of 7mm middle size abrading-ball 9 and a diameter of 15mm large scale abrading-ball 9；
Ball grinder is put in planetary ball mill, in normal temperature and pressure, rotating speed is the 4h that under the conditions of 450rpm, works；
Ball grinder is taken out, the inside solution is poured out together with solid, is filtered, 12h is then dried at 80 DEG C, that is, is obtained
Required zeolite product.
Embodiment 5
Embodiment 2 is repeated by described same steps, but the quality of flyash is 24g in step 2, step 1 is configured
Aqueous slkali volume is 200ml, and the abrading-ball size scale of addition is respectively, diameter 2mm abrading-ball 5, diameter 3mm abrading-ball 6,
Diameter 5mm abrading-ball 4, diameter 7mm abrading-ball 3, diameter 14mm abrading-ball 7.
Embodiment 6
Embodiment 3 is repeated by described same steps, but the quality of flyash is 17g in step 2, step 1 is configured
Aqueous slkali volume is 100ml, and the abrading-ball size scale of addition is respectively, diameter 3mm abrading-ball 5, diameter 14mm abrading-ball 8
It is individual.
Embodiment 7
Embodiment 4 is repeated by described same steps, but 300ml deionized waters, 40g NaOH reagents are used in step 1
And 40g flyash.
Performance test
Fig. 2 a and Fig. 2 b are that powdered coal ash and zeolite product are swept in QUANTA200 environment in the embodiment of the present invention 1 respectively
Retouch the SEM figures in Electronic Speculum.As can be seen that the particle smoother in flyash sample, and pass through preparation technology of the present invention and obtain
The zeolite product arrived, surface becomes coarse, specific surface area increase.
Using full-automatic specific surface area and pore analysis instrument (Micromeritics, model：ASAP 2020) to the present invention
Powdered coal ash and zeolite product carry out the analysis of specific surface area size in embodiment 1.It the results are shown in Table 1.
The specific surface area size of the flyash of table 1 and the zeolite of synthesis
As can be seen from Table 1, the zeolite product synthesized in embodiment 1 compared with powdered coal ash, its specific surface area it is big
It is small to add 20 times.Therefore the zeolite synthesized in embodiment 1 is compared with powdered coal ash, physisorption enhancing.
Fig. 3 is that powdered coal ash and zeolite product are detected through X ' Pert Pro X-ray diffractometers in the embodiment of the present invention 1
The XRD spectrum of gained.Its test parameter is：2 θ angular ranges are 10 ° to 65 °, and measurement step-length is 0.013 °.As can be seen that real
The zeolite product synthesized in example 1 is applied compared with powdered coal ash, the peak of X-type zeolite occurs, and broadening with mullite peak
With reduction.This phenomenon shows destructurized, the X-type zeolite generation in product of mullite in powdered coal ash.
Each 1g of the commercial zeolite of zeolite product and purchase synthesized in embodiment 1 in powdered coal ash, embodiment 1, point
It is not added to Cr (VI) concentration for 40mg/L, volume is in 50ml solution, carries out the adsorption experiment that the time is 120min, as a result
As shown in Figure 4.As can be seen that the zeolite product synthesized in embodiment 1 is higher than flyash and purchase to Cr (VI) equilibrium adsorption capacity
The commercial zeolite bought, there is preferable adsorption effect.
Fig. 5 be the zeolite product synthesized in embodiment 1 during Cr (VI) solution is adsorbed, Cr (VI) valence state turns
Change.As can be seen from Figure, in solution and solid the Cr of other valence states appearance.This phenomenon shows, is chemisorbed on and adsorbed
Presence in journey.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not used to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include
Within protection scope of the present invention.
Claims (4)
1. the process of zeolite is prepared under a kind of normal temperature and pressure, it is characterised in that comprise the following steps：
(1) it is configured to OH with NaOH solution or KOH solution-Ion concentration is 1mol/L~4mol/L aqueous slkali, by flyash
It is positioned over jointly in ball grinder with this aqueous slkali, and between the two with 10g~25g:100ml solid-to-liquid ratio mixing is outstanding to be formed
Turbid liquid；Then, the abrading-ball of multiple diameter specification is added into the suspension, the diameter of these abrading-balls is limited at 2mm~15mm
In the range of；
(2) above-mentioned ball grinder is positioned in planetary ball mill, and milled processed is performed under conditions of normal temperature and pressure, wherein should
The rotating speed of milled processed is set to 350rpm~500rpm, and milling time is set to 6h~24h；Then, ball grinder is taken out,
The inside solution is poured out and filtered together with solid, 4h~24h is dried under conditions of then 60 DEG C~90 DEG C；This process of lapping
In, fine coal gray surface can form local high temperature, and under the mating reaction of strong alkali solution, Si oxides in flyash and
Al oxides dissolve, while so that in flyash mullite stable crystal structure be destroyed, and then cause be present in alkali lye
Na+Or K+Si with coming from powdered coal ash4+And Al3+It is combined, ultimately forms required zeolite product.
2. the process of zeolite is prepared under a kind of normal temperature and pressure as claimed in claim 1, it is characterised in that the flyash
12g~17g is further configured to the solid-to-liquid ratio of the aqueous slkali:100ml.
3. the process of zeolite is prepared under a kind of normal temperature and pressure as claimed in claim 1, it is characterised in that a variety of chis
The abrading-ball of very little specification is designed as follows：Diameter 2mm small size abrading-ball 5~9, a diameter of 5mm middle size abrading-ball 6~
The large scale abrading-ball of 11 and a diameter of 15mm 5~9.
4. the zeolite according to prepared by any processes of claim 1-3, the application in the absorption of Cr (VI).
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| CN106268627A (en) * | 2016-07-29 | 2017-01-04 | 国电新能源技术研究院 | A kind of flyash low-temperature alkaline processes synthetic adsorbent technique and the method processing heavy metal garbage thereof |
| CN112573533B (en) * | 2020-12-25 | 2022-08-02 | 华中科技大学 | Method for preparing zeolite by directionally regulating and controlling biomass ash and application thereof |
| CN116462206A (en) * | 2023-05-11 | 2023-07-21 | 浙江大学 | Method for preparing zeolite from fly ash |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1180044A (en) * | 1996-10-15 | 1998-04-29 | 李泽民 | Method for producing molecular sieve material by using flyash |
| CN101503202A (en) * | 2009-02-11 | 2009-08-12 | 陕西理工学院 | Technique for hydro-thermal synthesis of high purity zeolite and fly ash zeolite adsorbing agent from fly ash |
| CN103204518A (en) * | 2013-04-16 | 2013-07-17 | 四川建筑职业技术学院 | Method for synthesizing zeolite by circulating fluidized-bed coal ash and bottom ash |
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2015
- 2015-05-04 CN CN201510222588.XA patent/CN104843729B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1180044A (en) * | 1996-10-15 | 1998-04-29 | 李泽民 | Method for producing molecular sieve material by using flyash |
| CN101503202A (en) * | 2009-02-11 | 2009-08-12 | 陕西理工学院 | Technique for hydro-thermal synthesis of high purity zeolite and fly ash zeolite adsorbing agent from fly ash |
| CN103204518A (en) * | 2013-04-16 | 2013-07-17 | 四川建筑职业技术学院 | Method for synthesizing zeolite by circulating fluidized-bed coal ash and bottom ash |
Non-Patent Citations (1)
| Title |
|---|
| 利用粉煤灰合成A型沸石分子筛的实验研究;李智专等;《中国资源综合利用》;20110131;第29卷(第1期);第43-45页 * |
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