CN104843729A - Zeolite preparation process at normal temperature and pressure and application thereof - Google Patents
Zeolite preparation process at normal temperature and pressure and application thereof Download PDFInfo
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- CN104843729A CN104843729A CN201510222588.XA CN201510222588A CN104843729A CN 104843729 A CN104843729 A CN 104843729A CN 201510222588 A CN201510222588 A CN 201510222588A CN 104843729 A CN104843729 A CN 104843729A
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Abstract
The invention discloses a zeolite preparation process at normal temperature and pressure and application thereof. The process includes mixing fly ash and alkali liquor, placing into a planetary ball mill, grinding through multiple grinding balls with different diameters at normal temperature and pressure, destabilizing mullite and other stable crystal structures of fly ash through partial high temperature, and obtaining zeolite crystallized samples after drying. By means of the process, the zeolite can be prepared in energy-saving and operation-facilitated manners, and the products with better comprehensive performances can be obtained.
Description
Technical field
The invention belongs to solid waste resource and utilize field, more specifically, under relating to a kind of normal temperature and pressure, prepare processing method and the application thereof of zeolite.
Background technology
In China, thermal power plant produces the flyash of 10-20% every year, and output increases year by year, the process not only land occupation resource of flyash, Expenses Cost, and likely pollutes the environment for a long time.Two kinds of methods are generally used in the process of flyash: one is thermal power plant's expropriation of land storage flyash, by wet technique coal ash discharging, flyash is entered storage ashpit precipitation and store, or by dry method ash discharge, flyash being transported to ash disposal area stores; Another fully utilizes flyash, is generally used for production of construction materials, construction work etc.According to statistics, the utilization ratio U.S. of flyash reaches 39%, and Europe reaches 47%, and the practical efficiency of China is less than 30%.And along with the growth of China's economic, continuation increased the utilization of coal, therefore, utilizing of flyash is in urgent need to be improved.
Because flyash main oxides consists of SiO
2and Al
2o
3, have close chemical constitution with zeolite and two kinds of component contents are higher, therefore the zeolite that its synthesis economic worth is higher can be utilized.Zeolite often by should in the absorption of pollutent, as the Cr (VI) in absorption waste water.And common zeolite only has the effect of physical adsorption to Cr (VI), the zeolite that flyash synthesizes is due to the existence of flyash middle or low price ferro element, and there is chemical reduction, for the treatment of during Cr (VI) in waste water, due to its chemisorption, efficiency is higher.
Utilize the research of synthetic zeolite from flyash to have a lot, relatively more conventional has two kinds of methods: one is hydrothermal method, is namely by water-bath synthetic zeolite in autoclave; Two is two-step approachs, i.e. elder generation's alkali fusion in tube furnace, and then carrys out synthetic zeolite by hydrothermal method.Comparatively speaking, water-bath synthetic zeolite needs the temperature of more than 100 DEG C; And two step synthesis zeolite, in the part of alkali fusion, the temperature of needs, more up to more than 500 DEG C, compares the consumption energy.And two kinds of methods are to crystalline structure more stable in flyash---mullite execution is poor.
And mechanical mill is by the mechanical impact of abrading-ball, the refinement of abrasive substance solid can not only be made; And along with the carrying out of mechanical grinding process, changes mechanical energy is that the chemical energy of reactive material is stored in material inside, thus increase the activation energy of reactive material.According to above feature, by the method for mechanical mill, flyash can carry out synthetic zeolite as starting material.
Summary of the invention
For above defect or the Improvement requirement of prior art, the processing method of zeolite is prepared under the invention provides a kind of normal temperature and pressure, wherein by the design to its reaction partner and key ingredient ratio and other reaction conditionss, can normal temperature and pressure, be convenient to the condition that manipulates under namely obtain required zeolite product; Especially, due to localized hyperthermia can be produced on flyash surface in ball-milling technology, destroy the stable crystal structure of mullite in flyash, the corresponding Na significantly accelerated in Si oxide compound in flyash and Al oxide compound and solution
+or K
+ionic bond, thus the formation promoting zeolite product further.
According to one aspect of the present invention, prepare the processing method of zeolite under providing a kind of normal temperature and pressure, it is characterized in that, comprise the following steps:
OH is configured to by NaOH solution or KOH solution
-ionic concn is the alkaline solution of 1mol/L ~ 4mol/L, by flyash therewith alkaline solution be jointly positioned in ball grinder, and between the two with the solid-to-liquid ratio of 10g ~ 25g:100ml mixing form suspension liquid; Then, add the abrading-ball of multiple diameter specification in this suspension liquid, the diameter of these abrading-balls is limited within the scope of 2mm ~ 15mm;
Be positioned in planetary ball mill by above-mentioned ball grinder, and perform milled processed under the condition of normal temperature and pressure, wherein the rotating speed of this milled processed is set to 350rpm ~ 500rpm, and milling time is set to 6h ~ 24h; Then, take out ball grinder, the inside solution is poured out together with solid and filters, the lower dry 4h ~ 24h of condition of then 60 DEG C ~ 90 DEG C; In this process of lapping, flyash surface can form the high temperature of local, and under the mating reaction of strong alkali solution, the Si oxide compound in flyash and Al oxide dissolution, make the stable crystal structure of mullite in flyash be destroyed simultaneously, and then make the Na that is present in alkali lye
+or K
+with the Si coming from powdered coal ash
4+and Al
3+in conjunction with, the zeolite product needed for final formation.
As further preferably, the solid-to-liquid ratio of described flyash and described alkaline solution is set as 12g ~ 17g:100ml further.
As further preferably, the abrading-ball of described sizes specification is designed as follows: the small size abrading-ball of diameter 2mm 5 ~ 9, the large size abrading-ball 5 ~ 9 of diameter to be the middle size abrading-ball 6 ~ 11 of 5mm and diameter be 15mm.
According to another aspect of the present invention, additionally provide the zeolite prepared by processing method of the present invention, the application in the absorption of Cr (VI).
In general, the above technical scheme conceived by the present invention compared with prior art, is had the following advantages:
1, by adopting flyash and alkaline solution as reaction partner, and select the ball-milling technology of suitable processing condition to perform process, corresponding whole reaction process can be operated at normal temperatures and pressures, and without the need to the participation of the complex reaction conditions such as High Temperature High Pressure, and non-exhaust emission, energy-conserving and environment-protective;
2, by designing the concrete treating processes of ball-milling technology and key condition thereof, test flyash surface can form the high temperature of local, thus in flyash, mullite structure is destroyed, Si oxide compound and Al oxide dissolution, and with the Na in alkali lye
+or K
+in conjunction with and form zeolite, and drying process and crystallisation process combine by the method, while improving technological effect, go back simplification of flowsheet;
3, the zeolite of the method synthesis not only has physical adsorption to the Cr (VI) in liquid, and has chemisorption, and the treatment effect comparing Cr (VI) with commercial zeolite is better.
Accompanying drawing explanation
Fig. 1 is present invention process schema.
Fig. 2 a is the SEM figure of the powdered coal ash of the embodiment of the present invention 1, Fig. 2 b is that the SEM of the zeolite product of embodiment 1 schemes.
Fig. 3 is the powdered coal ash of the embodiment of the present invention 1 and the XRD figure spectrum of zeolite product; Wherein curve RFA represents flyash, and curve ZFA represents zeolite; Peak Q represents quartz, and peak C represents calcium oxide, and peak L represents calcium carbonate, and peak Ma represents magnetite, and peak M represents mullite, and peak X represents X-type zeolite.
Fig. 4 be the powdered coal ash of the embodiment of the present invention 1, zeolite product and purchase commercial zeolite sample to the equilibrium adsorption spirogram of Cr (VI).
Fig. 5 be the zeolite product of the embodiment of the present invention 1 in the process of absorption Cr (VI) solution, the valence state of Cr (VI) transforms.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.In addition, if below in described each embodiment of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
Embodiment 1
The preparation method of Na-X type zeolite, comprises the following steps:
Get 80g NaOH reagent, be dissolved in 1L deionized water, obtained concentration is the NaOH solution of 2mol/L;
The flyash being 20g by quality and step 1 configuration alkaline solution 160ml to be positioned over volume be mix in the ball grinder of 250ml, and add the small size abrading-ball 5 of diameter 2mm, the large size abrading-ball 7 of diameter to be the middle size abrading-ball 8 of 5mm and diameter be 15mm;
Be put in by ball grinder in planetary ball mill, at normal temperature and pressure, rotating speed is under 350rpm condition, work 6h;
Take out ball grinder, poured out by the inside solution together with solid, filter, then dry 24h at 60 DEG C, namely obtains required zeolite product.
Embodiment 2
The preparation method of zeolite, comprises the following steps:
Get 224g KOH reagent, be dissolved in 1L deionized water, obtained concentration is the KOH solution of 4mol/L;
The flyash being 20g by quality and step 1 configuration alkaline solution 200ml to be positioned over volume be mix in the ball grinder of 300ml, and add the small size abrading-ball 9 of diameter 2mm, the large size abrading-ball 9 of diameter to be the middle size abrading-ball 6 of 5mm and diameter be 15mm;
Be put in by ball grinder in planetary ball mill, at normal temperature and pressure, rotating speed is under 500rpm condition, work 24h;
Take out ball grinder, poured out by the inside solution together with solid, filter, then dry 4h at 90 DEG C, namely obtains required zeolite product.
Embodiment 3
The preparation method of zeolite, comprises the following steps:
Get 40g NaOH reagent, be dissolved in 1L deionized water, obtained concentration is the NaOH solution of 2mol/L;
The flyash being 25g by quality and step 1 configuration alkaline solution 100ml to be positioned over volume be mix in the ball grinder of 150ml, and add the small size abrading-ball 7 of diameter 2mm, the large size abrading-ball 5 of diameter to be the middle size abrading-ball 11 of 5mm and diameter be 15mm;
Be put in by ball grinder in planetary ball mill, at normal temperature and pressure, rotating speed is under 450rpm condition, work 4h;
Take out ball grinder, poured out by the inside solution together with solid, filter, then dry 12h at 80 DEG C, namely obtains required zeolite product.
Embodiment 4
The preparation method of zeolite, comprises the following steps:
The flyash of 250ml deionized water, 50g KOH reagent and 40g being positioned over volume is fully mix in the ball grinder of 500ml, the obtained suspension liquid of flyash in alkali lye, and add the small size abrading-ball 7 of diameter 3mm wherein, diameter is the middle size abrading-ball 8 of 5mm, the large size abrading-ball 9 of diameter to be the middle size abrading-ball 9 of 7mm and diameter be 15mm;
Be put in by ball grinder in planetary ball mill, at normal temperature and pressure, rotating speed is under 450rpm condition, work 4h;
Take out ball grinder, poured out by the inside solution together with solid, filter, then dry 12h at 80 DEG C, namely obtains 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 to configure alkaline solution volume be 200ml, the abrading-ball size scale added is respectively, the abrading-ball of diameter 2mm 5, the abrading-ball of diameter 3mm 6, the abrading-ball of diameter 5mm 4, the abrading-ball of diameter 7mm 3, the abrading-ball of diameter 14mm 7.
Embodiment 6
Repeat embodiment 3 by described same steps, but in step 2, the quality of flyash is 17g, step 1 to configure alkaline solution volume be 100ml, the abrading-ball size scale added is respectively, the abrading-ball of diameter 3mm 5, the abrading-ball of diameter 14mm 8.
Embodiment 7
Repeat embodiment 4 by described same steps, but in step 1, adopt the flyash of 300ml deionized water, 40g NaOH reagent and 40g.
Performance test
Fig. 2 a and Fig. 2 b is powdered coal ash and the zeolite product SEM figure in QUANTA200 environmental scanning electronic microscope in the embodiment of the present invention 1 respectively.Can find out, the particle smoother in flyash sample, and the zeolite product obtained through preparation technology of the present invention, surface becomes coarse, and specific surface area increases.
Full-automatic specific surface area and pore analysis instrument (Micromeritics, model: ASAP 2020) is adopted powdered coal ash in the embodiment of the present invention 1 and zeolite product to be carried out to the analysis of specific surface area size.The results are shown in Table 1.
The specific surface area size of the zeolite of table 1 flyash and synthesis
As can be seen from Table 1, in embodiment 1, the zeolite product of synthesis is compared with powdered coal ash, and the size of its specific surface area adds 20 times.Therefore the zeolite of synthesis is compared with powdered coal ash in embodiment 1, physisorption strengthens.
Fig. 3 is that in the embodiment of the present invention 1, powdered coal ash and zeolite product detect the XRD figure spectrum of gained through X ' Pert Pro X-ray diffractometer.Its test parameter is: 2 θ angular ranges are 10 ° to 65 °, and measuring step-length is 0.013 °.Can find out, in embodiment 1, the zeolite product of synthesis is compared with powdered coal ash, and the peak of X-type zeolite occurs, and is attended by broadening and minimizing of mullite peak.This phenomenon shows the destructurized of mullite in powdered coal ash, and in product, X-type zeolite generates.
The zeolite product synthesized in powdered coal ash, embodiment 1 in embodiment 1 and each 1g of commercial zeolite of purchase, adding Cr (VI) concentration respectively to is 40mg/L, volume is in the solution of 50ml, and the time of carrying out is the adsorption experiment of 120min, and result as shown in Figure 4.Can find out, the zeolite product of synthesis in embodiment 1, to the commercial zeolite of the equilibrium adsorption capacity of Cr (VI) higher than flyash and purchase, has good adsorption effect.
Fig. 5 be the zeolite product of synthesis in embodiment 1 in the process of absorption Cr (VI) solution, the valence state of Cr (VI) transforms.As can be seen from Figure, the appearance of the Cr of other valence states in solution and solid.This phenomenon shows, is chemisorbed on the existence in adsorption process.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. prepare a processing method for zeolite under normal temperature and pressure, it is characterized in that, comprise the following steps:
(1) OH is configured to by NaOH solution or KOH solution
-ionic concn is the alkaline solution of 1mol/L ~ 4mol/L, by flyash therewith alkaline solution be jointly positioned in ball grinder, and between the two with the solid-to-liquid ratio of 10g ~ 25g:100ml mixing form suspension liquid; Then, add the abrading-ball of multiple diameter specification in this suspension liquid, the diameter of these abrading-balls is limited within the scope of 2mm ~ 15mm;
(2) be positioned in planetary ball mill by above-mentioned ball grinder, and perform milled processed under the condition of normal temperature and pressure, wherein the rotating speed of this milled processed is set to 350rpm ~ 500rpm, and milling time is set to 6h ~ 24h; Then, take out ball grinder, the inside solution is poured out together with solid and filters, the lower dry 4h ~ 24h of condition of then 60 DEG C ~ 90 DEG C; In this process of lapping, flyash surface can form the high temperature of local, and under the mating reaction of strong alkali solution, the Si oxide compound in flyash and Al oxide dissolution, make the stable crystal structure of mullite in flyash be destroyed simultaneously, and then make the Na that is present in alkali lye
+or K
+with the Si coming from powdered coal ash
4+and Al
3+in conjunction with, the zeolite product needed for final formation.
2. prepare the processing method of zeolite under a kind of normal temperature and pressure as claimed in claim 1, it is characterized in that, the solid-to-liquid ratio of described flyash and described alkaline solution is set as 12g ~ 17g:100ml further.
3. under a kind of normal temperature and pressure as claimed in claim 1, prepare the processing method of zeolite, it is characterized in that, the abrading-ball of described sizes specification is designed as follows: the small size abrading-ball of diameter 2mm 5 ~ 9, the large size abrading-ball 5 ~ 9 of diameter to be the middle size abrading-ball 6 ~ 11 of 5mm and diameter be 15mm.
4. the zeolite prepared by the processing method of claim 1-3, the application in the absorption of Cr (VI).
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Cited By (3)
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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 |
| CN112573533A (en) * | 2020-12-25 | 2021-03-30 | 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 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112573533A (en) * | 2020-12-25 | 2021-03-30 | 华中科技大学 | Method for preparing zeolite by directionally regulating and controlling biomass ash and application 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 |
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