CN101486471A - Method for preparing zeolite molecular sieves having different Si/Al ratios from fly ash - Google Patents
Method for preparing zeolite molecular sieves having different Si/Al ratios from fly ash Download PDFInfo
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- CN101486471A CN101486471A CNA2009100213257A CN200910021325A CN101486471A CN 101486471 A CN101486471 A CN 101486471A CN A2009100213257 A CNA2009100213257 A CN A2009100213257A CN 200910021325 A CN200910021325 A CN 200910021325A CN 101486471 A CN101486471 A CN 101486471A
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- flyash
- zeolite molecular
- molecular sieve
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Abstract
The invention discloses a method for preparing a zeolite molecular sieve with different Si/Al ratios by using fly ash. The method adopts the fly ash as a raw material, solid sodium hydroxide is added into the fly ash, sodium silicate and alumina are used for adjusting the Si/Al ratio in the mixture, and then the mixture is melted at high temperature. A liquid melt reacts with a small amount of water vapor in a reaction kettle, and the zeolite molecular sieve is generated 12 hours later. The method has simple equipment and simple and convenient operation, clinkers do not need to be ground and stirred, and only a small amount of water vapor (nonsolvent water) is required in the reaction to participate in the reaction; therefore, no pollution to environment is generated during the production process, the reaction temperature range is comparatively wide, the reaction time is short and energy is saved. The method is a quite simple and convenient and feasible method for preparing the zeolite molecular sieve of various (especially high-silica) microcellular structures, and is more applicable to mass industrialized production. The method of the invention provides a good application way for the comprehensive utilization of the fly ash.
Description
Technical field
The present invention relates to the method for a kind of flyash utilization of waste material (processing), particularly a kind of method (or claiming to regulate silica alumina ratio-alkali fusion-steaming process) of utilizing the different Si/Al of fly-ash Preparation than zeolite molecular sieve.
Background technology
Zeolite is a kind of crystalline aluminosilicate, and silicon wherein, aluminium atom all form silicon-oxy tetrahedron or aluminum-oxygen tetrahedron with Sauerstoffatom, the three-dimensional framework that connects into complexity, opens by shared Sauerstoffatom between the tetrahedron, the duct and the cavity of the rule that distributing in the structure.These ducts and cavity can be in conjunction with the molecules of specific size, and positively charged ion wherein has interchangeability.Therefore, zeolite have very big specific surface area with good absorption, separate, performance such as ion-exchange, catalysis, have purposes widely in fields such as petrochemical complex, environment protection.Multi-field have a good prospects for application, become the new focus in investigation of materials field, hole.Industrial synthesis zeolite is to adopt industrial chemicals such as water glass (water glass), white carbon black, sodium aluminate, aluminum oxide, sodium metaaluminate, cost height and complex process.
China's flyash quantity discharged reaches 1.6 hundred million tons, and still increases with annual 1000 ten thousand tons speed, and its utilization ratio also belongs to low-level in China, China to the utilization of coal ash rate only between 30%~40%.At present, the technique means of Comprehensive Utilization Power Plant waste flyash improves constantly, the goods and materials product that utilizes flyash production to help national economy has become the main flow of using flyash, it is mainly used in building brickmaking, cement raw material, roadbed material, soil improvement agent, loading material of rubber etc., and usage quantity far is unable to catch up with the speed that increases newly of annual flyash, flyash still need significantly be developed and go deep into to utilize, especially utilize main chemical compositions wherein, with the high value added product is that the Application and Development that leads is a direction of flyash future development, it also is the hot issue that present insider extremely pays close attention to, for example, utilize flyash to produce cement, the aluminum oxide road that moved towards the industrialization, and utilize flyash to produce white carbon black, technology such as molecular sieve also are in the stage of fumbling of industry.
The composition of the mineral substance of flyash is mainly quartz, mullite, vitreum and a spot of carbon, magnetite etc., and main chemical composition is SiO
2, Al
2O
3, both content are more than 70%.In view of the composition of flyash and the volcanic ash that forms natural zeolite have similarity, 1985, Holler
[1]Deng the research that utilizes the flyash synthesis zeolite that takes the lead in having carried out, this research has been pointed out a feasible approach for total utilization of PCA and searching synthesis of molecular sieve new raw material, and its achievement in research has just caused extensive concern once announcing.Thereafter, the various countries researchist utilize the different places of production flyash, prepared dissimilar zeolite molecular sieves by different synthetic process.According to the domestic and foreign literature report as can be known, the method for synthetic zeolite mainly contains original position water (solvent) thermal synthesis method
[2] [8], alkali melts-the hot method of water (solvent)
[3] [4], microwave assisting method
[5] [6], add crystal seed method
[7]With two step synthesis methods
[8] [9]Etc. technology.And the different Si/Al of inhomogeneity are by add crystal seed method under hydrothermal condition than prepare zeolite
[7]The perhaps Si/Al mol ratio in the regulator solution
[10] [10](document sees reference) realizes.These methods are not only grasped and are done that operation is loaded down with trivial details, energy consumption is high, water consumption is big, and production process can cause very big pollution to environment, and it is not high to generate the transformation efficiency of zeolite yet.Given this, the flyash synthetic zeolite is difficult to realize industrialization, and majority state also is in the experimental study stage at present.
Reference:
【1】Holler?H,Wirsching?U.Zeolites?formation?from?fly?ash[J].Mineral,1985,63(1):21-43。
【2】Querol?X,Plana?F,Alastuey?A,et?al.Synthesis?of?Na-zeolites?from?flyash[J].Fuel,1997,76(8):793-799。
【3】Ye?Yaping,Zeng?Xiaoqiang,Qian?Weilan?and?Wang?Mingwen.Synthesis?of?pure?zeolites?from?supersaturated?silicon?and?aluminum?alkaliextracts?from?fused?coal?fly?ash[J].Fuel,2008,87(10-11):1880-1886。
【4】F.Fotovat,H.Kazemian,M.Kazemeini.Synthesis?of?Na-A?andfaujasitic?zeolites?from?high?silicon?fly?ash.Materials?Research?Bulletin[J].2009(44):913—917。
【5】Querol?X,Alastuey?A,Lopez-SolerA.A?fastmethod?for?recycling?flyash:microwave-assisted?zeolite?synthesis[J].Environ?Sci?Techno,1997,31(9):2527-2533。
【6】Miki?I,Hidenobu?T,Yukari?E,et?al.Microwave-assisted?zeolitesynthesis?from?coal?fly?ash?in?hydrothermal?process[J].Fuel,2005,84:1482-1486。
【7】La?Rosa?J?L,Kwan?S,Grutzeck?MW.Zeolite?formation?in?class?FflyAsh?blended?cement?pastes[J].J?Am?Ceram?Soc,1992,75(6):1574-1578。
【8】Chun-Feng?Wang,Jian-Sheng?Li,Lian-Jun?Wang,Xiu-Yun?Sun.Influence?of?NaOH?concentrations?on?synthesis?of?pure-form?zeolite?A?from?flyash?using?two-stage?method[J].Journal?of?Hazardous?Materials.2008(155):58-64。
【9】Hidekazu?Tanaka,Hajime?Eguchi,Satoshi?Fujimoto,RyoziHino.Two-step?process?for?synthesis?of?a?single?phase?Na-A?zeolite?from?coal?flyash?by?dialysis.Fuel?2006(85)1329-1334。
【10】La?Rosa?J?L,Kwan?S,Grutzeck?MW.Zeolite?formation?in?class?F?flyAsh?blended?cement?pastes[J].J?Am?Ceram?Soc,1992,75(6):1574-1578。
Summary of the invention
The object of the invention is, a kind of method of utilizing the different Si/Al of fly-ash Preparation than zeolite molecular sieve is provided, and this method is suitable for industrialization flyash is produced zeolite product, also will open up a kind of new approach for the recycling of flyash.
In order to realize above-mentioned task, the present invention takes following technical solution:
A kind of method of utilizing the different Si/Al of fly-ash Preparation than zeolite molecular sieve is characterized in that, specifically comprises the steps:
Step 1, get flyash 10g with etc. quality levigated NaOH solid mix, obtain mixture;
Step 2 is used Na
2SiO
39H
2O and Al
2O
3Regulate the Si/Al mol ratio in the mixture, get the mixture of different Si/Al mol ratios;
Step 3 with mixture fusion 2 hours~3 hours under 850 ℃ of temperature in retort furnace, generates the flyash grog;
Step 4, get the flyash grog and be placed in the reactor, and in tap water: the ratio of flyash grog 〉=1:2 (mass/volume) is got tap water and is joined in the reactor, in reactor inside, tap water and flyash grog are separated from each other, and wherein tap water is used to produce steam;
Step 5, it is in 100 ℃ the baking oven 12 hours that reactor is placed on temperature range, can generate zeolite molecular sieve.
The present invention adopts adjusting silica alumina ratio-alkali fusion-steaming process at 100 ℃, and 12h can generate zeolite product (this for example is reflected at other temperature, and room temperature can take place to high temperature, and temperature rising speed of response is accelerated, and variation of temperature does not influence the kind of zeolite product).Compare with the present both at home and abroad method of synthetic zeolite, processing unit simple (can with the better various containers of sealing property), the time spent is short, energy consumption is little, be convenient to operation and transformation efficiency is very high and the pollution of having avoided water (solvent) thermal synthesis to cause a large amount of waters that environment is brought.
Description of drawings
Fig. 1 is a method flow diagram of the present invention;
Fig. 2 is the reactor figure that steaming process uses;
Fig. 3 is the SEM figure (amplifying 20000 times) of synthetic zeolite molecular sieve.
The present invention is described in further detail below in conjunction with accompanying drawing.
Embodiment
Referring to Fig. 1,, specifically comprise the steps: according to the method for utilizing the different Si/Al of fly-ash Preparation than zeolite molecular sieve of the present invention
1, get flyash and with XRD and XRF analysis means flyash is analyzed, the chemical ingredients in the flyash mainly is: SiO
2Account for 54.20%, Al
2O
3Account for 26.40%, all the other are other impurity; Its main thing is mullite and quartz mutually;
2, get 10g flyash and homogenous quantities levigated NaOH powder mixes (deviation 20% also can), different Si/Al molar mixture;
3, use Na
2SiO
39H
2O and Al
2O
3Regulate the Si/Al mol ratio in the mixture: Si/Al mol ratio control method is as follows:
According to the XRF experimental data of powdered coal ash, the silica alumina ratio in the flyash is 1.75:1, uses Al
2O
3And Na
2SiO
39H
2O regulates the Si/Al mol ratio (working method: if will regulate the Si/Al mol ratio less than 1.75:1, then need to add Al in the fine coal
2O
3Increase the content of aluminium, adding Al
2O
3Also need add simultaneously and Al
2O
3NaOH solid identical in quality is to regulate the alkali number of mixture.For example, the grog that the Si/Al mol ratio equals 1:1 be obtained, the Al of 2g need be in said mixture, added
2O
3After, add the NaOH solid of 2g again, obtain the mixture that the Si/Al mol ratio is 1:1; If will regulate Si/Al mol ratio in the grog greater than 1.75:1, the Starso that then need add respective quality gets final product with the content that increases silicon, and for example: the Si/Al mol ratio that regulate flyash is 2, adds 3.74gNa at needs in said mixture
2SiO
39H
2O gets final product;
4, mixture is placed in the retort furnace, under 850 ℃ of temperature fusion 2-3 hour, generate the flyash grog;
5, take by weighing the 2g grog and put into reactor (Fig. 2), this reactor internal structure is a levels, the upper strata is used to place the flyash grog, lower floor is used to place tap water, press tap water: (unit: the tap water that ratio mL/g) is got more than or equal to 1mL adds lower floor in the reactor to material 〉=1:2 for mass/volume, v/m, by water generates steam from the beginning, so just guaranteed that tap water separates with the flyash grog.
6, this reactor is placed in the baking oven of 100 ℃ of temperature and placed 12 hours, places and take out reaction product after 12 hours, through washing, separate, dry post precipitation and be designated as product N;
With thing phase composite and the pattern of XRD and SEM assaying reaction product N, reaction product N is zeolite molecular sieve (Fig. 3) as can be known.
Certainly, also reactor can be placed under room temperature to 200 ℃ even the higher condition, place 12 hours, can generate zeolite molecular sieve.The temperature rising speed of response that experiment showed, through the contriver will be accelerated, and temperature variation does not influence the kind of product.
Claims (3)
1, a kind of method of utilizing the different Si/Al of fly-ash Preparation than zeolite molecular sieve is characterized in that, specifically comprises the steps:
Step 1, get flyash 10g with etc. quality levigated NaOH solid mix, obtain mixture;
Step 2 is used Na
2SiO
39H
2O and Al
2O
3Regulate the Si/Al mol ratio in the mixture, get the mixture of different Si/Al mol ratios;
Step 3 with mixture fusion 2~3 hours under 850 ℃ of temperature in retort furnace, generates the flyash grog;
Step 4, get the flyash grog and be placed in the reactor, and in tap water: the ratio of flyash grog 〉=1:2 (mass/volume) is got tap water and is joined in the reactor, in reactor inside, tap water and flyash grog are separated from each other, and wherein tap water is used to produce steam;
Step 5 is under room temperature to 200 ℃ even the higher condition with reactor in temperature range, places 12 hours, can generate zeolite molecular sieve.
According to claim 1 to method, it is characterized in that 2, the temperature of described reactor is 100 ℃.
According to claim 1 to method, it is characterized in that 3, the Si/Al mol ratio in the described adjusting mixture is the XRF experimental data according to powdered coal ash, add Al
2O
3Increase the content of aluminium, adding Al
2O
3Also add simultaneously and Al
2O
3NaOH solid identical in quality is to regulate the alkali number of mixture.
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Cited By (6)
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 |
CN102557283A (en) * | 2012-01-16 | 2012-07-11 | 北京道顺国际技术开发有限责任公司 | Aerating filter with molecular sieve prepared by adopting coal ash in power plant |
CN102963903A (en) * | 2012-11-30 | 2013-03-13 | 北京交通大学 | Method for preparing P1-type zeolite |
CN103073089A (en) * | 2013-02-05 | 2013-05-01 | 中国环境科学研究院 | Method for removing ammonia nitrogen from landfill leachate by using P1 type fly ash molecular sieve |
CN103787354A (en) * | 2014-01-28 | 2014-05-14 | 淮南师范学院 | Method for preparing MCM-41 molecular sieve by utilizing fly ash and application of MCM-41 molecular sieve |
CN103818920A (en) * | 2013-12-24 | 2014-05-28 | 淮南师范学院 | Method for preparing Si-Al ordered mesoporous molecular sieve |
-
2009
- 2009-02-27 CN CNA2009100213257A patent/CN101486471A/en active Pending
Cited By (8)
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 |
CN102173433B (en) * | 2011-03-09 | 2013-06-05 | 南京理工大学 | Process for synthesizing single-phase sodalite from fly ash |
CN102557283A (en) * | 2012-01-16 | 2012-07-11 | 北京道顺国际技术开发有限责任公司 | Aerating filter with molecular sieve prepared by adopting coal ash in power plant |
CN102963903A (en) * | 2012-11-30 | 2013-03-13 | 北京交通大学 | Method for preparing P1-type zeolite |
CN103073089A (en) * | 2013-02-05 | 2013-05-01 | 中国环境科学研究院 | Method for removing ammonia nitrogen from landfill leachate by using P1 type fly ash molecular sieve |
CN103818920A (en) * | 2013-12-24 | 2014-05-28 | 淮南师范学院 | Method for preparing Si-Al ordered mesoporous molecular sieve |
CN103787354A (en) * | 2014-01-28 | 2014-05-14 | 淮南师范学院 | Method for preparing MCM-41 molecular sieve by utilizing fly ash and application of MCM-41 molecular sieve |
CN103787354B (en) * | 2014-01-28 | 2016-06-08 | 淮南师范学院 | One utilizes coal ash for manufacturing for the application of Cr (VI) ion in MCM-41 molecular sieve adsorption solution |
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Open date: 20090722 |