CN101475189B - Method for preparing zeolite molecular sieve from fly ash by using alkali fusion-trace amount water - Google Patents
Method for preparing zeolite molecular sieve from fly ash by using alkali fusion-trace amount water Download PDFInfo
- Publication number
- CN101475189B CN101475189B CN2009100209980A CN200910020998A CN101475189B CN 101475189 B CN101475189 B CN 101475189B CN 2009100209980 A CN2009100209980 A CN 2009100209980A CN 200910020998 A CN200910020998 A CN 200910020998A CN 101475189 B CN101475189 B CN 101475189B
- Authority
- CN
- China
- Prior art keywords
- flyash
- molecular sieve
- zeolite molecular
- water
- fly ash
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention discloses a method for preparing a zeolite molecular sieve by adopting alkali fusion-trace water to fly ash, which comprises the following steps that: the fly ash is taken as a raw material and is fused with solid sodium hydroxide at high temperature, and a liquid melt reacts with a small amount of water in a reaction kettle for 24 hours to generate the zeolite molecular sieve. The method has simple equipment as well as simple and convenient operation, cannot cause pollution to the environment during the production, is a simple, convenient and feasible method for preparing zeolite molecular sieves with micropore structures, and is more suitable for industrialized batch production. The method provides a good application approach for 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 flyash adopts alkali fusion-trace water (non-solvent water) to prepare the method for 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 water glass, sodium aluminate, Al (OH)
39H
2Industrial chemicals such as O, 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], the hot method of alkali fusion-water (solvent)
[3] [4], microwave assisting method
[5] [6], add crystal seed method
[7]Etc. technology (document sees reference).These methods not only energy consumption big, environment is polluted greatly, and the transformation efficiency of generation zeolite is not high 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?fromfly?ash[J].Fuel，1997，76(8)：793-799。
【3】Shigemoto?N，Shirakami?S，Hirano?S，et?al.Preparation?andcharacterization?of?zeolites?from?coal?fly?ash[J].Chem?Soc?Jpn，1992，5：484-492。
【4】SingerA，Berkgaut?V.Cation?exchange?p?roperties?of?hydrothermallytreated?coal?fly?ash[J].Environ?Sci?Technol，1995，29(9)：1748-1753。
【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?zeolite?synthesis?from?coal?fly?ash?in?hydrothermal?p?rocess[J].Fuel，2005，84：1482-1486。
【7】La?Rosa?J?L，Kwan?S，Grutzeck?MW.Zeolite?formation?in?class?FflyAsh?blended?cementpastes[J].JAm?Ceram?Soc，1992，75(6)：1574-1578。
Summary of the invention
The object of the invention is, provides flyash to adopt alkali fusion-trace water (non-solvent water) to prepare the method for zeolite molecular sieve, 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:
Flyash adopts alkali fusion-trace water to prepare the method for zeolite molecular sieve, it is characterized in that, specifically comprises the steps:
Step 1 is got the flyash ball milling, crosses 300 mesh sieves;
Step 2 is got a certain amount of NaOH solid, grind the back with etc. the flyash behind mistake 300 mesh sieves of quality mix, obtain mixture;
Step 3 is loaded on mixture in the crucible and places in the retort furnace, and fusion is 2 hours～3 hours under 850 ℃ of temperature, generates the flyash grog;
Step 4, get the flyash grog, press the flyash grog in the flyash grog: the weight ratio of water (mass/volume)=2: 1 (g/ml of unit) adds tap water, and put into the tetrafluoroethylene reactor, with reactor in room temperature to 200 ℃, even the temperature condition that is higher than 200 ℃ was placed 24 hours the generation zeolite molecular sieve down.
The preferred temperature of reactor is 100 ℃.
The present invention adopts alkali fusion-trace water law in room temperature to 200 ℃, even the temperature condition that is higher than 200 ℃ is placed down, can generate 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 method to cause a large amount of waters that environment is brought.
Description of drawings
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 is that zeolite amplifies 20000 times of SEM figure;
The present invention is described in further detail below in conjunction with accompanying drawing.
Embodiment
Referring to Fig. 1, adopt alkali fusion-trace water to prepare the method for zeolite molecular sieve according to flyash of the present invention, specifically comprise the steps:
1, gets the flyash ball milling, cross 300 mesh sieves, obtain superfined flyash; With XRD and XRF analysis means superfined flyash is analyzed then, the chemical ingredients in the superfined 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 a certain amount of NaOH solid, grind the back with etc. the flyash behind mistake 300 mesh sieves of quality mix, obtain mixture;
3, mixture is placed in the retort furnace, under 850 ℃ of temperature fusion 2-3 hour, generate the flyash grog;
4, this flyash grog is the alkali fusion thing, and outward appearance is the green particles shape, and its is remembered as material M;
5, take by weighing 2g material M, put into the tetrafluoroethylene reactor, and adding 1mL left and right sides tap water (deviation is not more than 1mL), reactor was placed under 100 ℃ of conditions in 24 hours, perhaps in room temperature to 200 ℃, even the temperature condition that is higher than 200 ℃ places down in 24 hours, takes out reaction product, and this reaction product is designated as N;
Thing phase composite with XRD determining reaction product N, detect XRD analysis and SEM figure pattern mutually according to thing and observe as can be known, the zeolite that is generated is identical with the zeolite thing that the fusion-room temperature long placing method is generated, the about 1 μ m size of crystal grain, SEM figure sees Fig. 2, and visible reaction product N is zeolite molecular sieve.
Claims (2)
1. flyash adopts alkali fusion-trace water to prepare the method for zeolite molecular sieve, it is characterized in that, specifically comprises the steps:
Step 1 is got the flyash ball milling, crosses 300 mesh sieves;
Step 2 is got a certain amount of NaOH solid, grind the back with etc. the flyash behind mistake 300 mesh sieves of quality mix, obtain mixture;
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, in the flyash grog, press mass ratio and add tap water, its ratio is the flyash grog: water=2: 1, and the deviation that adds water is in 1ml/g, and put into the tetrafluoroethylene reactor, reactor in room temperature to 200 ℃, even is higher than 200 ℃ temperature condition and places down in 24 hours, generate zeolite molecular sieve.
2. the method for claim 1 is characterized in that, the temperature of described reactor is 100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100209980A CN101475189B (en) | 2009-01-21 | 2009-01-21 | Method for preparing zeolite molecular sieve from fly ash by using alkali fusion-trace amount water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100209980A CN101475189B (en) | 2009-01-21 | 2009-01-21 | Method for preparing zeolite molecular sieve from fly ash by using alkali fusion-trace amount water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101475189A CN101475189A (en) | 2009-07-08 |
| CN101475189B true CN101475189B (en) | 2011-05-04 |
Family
ID=40835980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100209980A Expired - Fee Related CN101475189B (en) | 2009-01-21 | 2009-01-21 | Method for preparing zeolite molecular sieve from fly ash by using alkali fusion-trace amount water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101475189B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798124B (en) * | 2010-04-10 | 2011-08-31 | 太原理工大学 | Method for treating ammonia and nitrogen in coking wastewater |
| CN103408032B (en) * | 2013-07-21 | 2015-05-06 | 太原理工大学 | Method for supercritical hydrothermal synthesis of flyash zeolite |
| CN103435064B (en) * | 2013-08-20 | 2015-05-13 | 东北石油大学 | Method for preparing nano-scale ZSM-5 molecular sieve by using coal ash |
| CN103586010A (en) * | 2013-10-30 | 2014-02-19 | 中国科学院过程工程研究所 | Method for preparing molecular sieve by using fly ash and mercury removal use of prepared molecular sieve |
| CN103756470A (en) * | 2013-12-13 | 2014-04-30 | 张家港市双林制墨涂装有限公司 | Preparation method of fly ash microbead heat insulation material |
| CN103787363B (en) * | 2013-12-17 | 2015-08-19 | 西安建筑科技大学 | A kind of method utilizing flyash filter cake Dry synthesis Na-X and hydroxysodalite |
| CN107697927A (en) * | 2017-11-14 | 2018-02-16 | 江苏理工学院 | A kind of preparation method using flyash as the NaA molecular sieve of raw material |
| CN113277527A (en) * | 2021-05-08 | 2021-08-20 | 宁夏大学 | Method for rapidly preparing Na-X and Na-A molecular sieves by taking fly ash as raw material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389399A (en) * | 2002-07-08 | 2003-01-08 | 中国地质大学（武汉） | Synthesis of zeolite with flyash |
-
2009
- 2009-01-21 CN CN2009100209980A patent/CN101475189B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389399A (en) * | 2002-07-08 | 2003-01-08 | 中国地质大学（武汉） | Synthesis of zeolite with flyash |
Non-Patent Citations (1)
| Title |
|---|
| Michihiro Miyake et al.Preparation of activated carbon–zeolite composite materials from coal fly ash.Microporous and Mesoporous Materials.2007,112170–177. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101475189A (en) | 2009-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101475189B (en) | Method for preparing zeolite molecular sieve from fly ash by using alkali fusion-trace amount water | |
| Yaping et al. | Synthesis of pure zeolites from supersaturated silicon and aluminum alkali extracts from fused coal fly ash | |
| Temuujin et al. | Effect of fly ash preliminary calcination on the properties of geopolymer | |
| Chen et al. | Early solidification/stabilization mechanism of heavy metals (Pb, Cr and Zn) in Shell coal gasification fly ash based geopolymer | |
| Jiao et al. | Thermal stability of a silica-rich vanadium tailing based geopolymer | |
| Xu et al. | Low-reactive circulating fluidized bed combustion (CFBC) fly ashes as source material for geopolymer synthesis | |
| CN101318788B (en) | Inorganic polymer material for sealing heavy metal castoff | |
| CN107188442B (en) | A kind of trade waste base geological polymer and preparation method thereof | |
| CN107857496A (en) | A kind of method of comprehensive utilization of coal gasification fine slag | |
| Fan et al. | Recycling of municipal solid waste incineration fly ash in foam ceramic materials for exterior building walls | |
| CN104402017B (en) | A kind of method of synthetic zeolite from flyash | |
| CN102627305A (en) | Method using alkaline process to extract alumina in coal ash | |
| CN104492372A (en) | Preparation method and application of material for adsorbing heavy metals in wastewater | |
| CN101486471A (en) | Method for preparing zeolite molecular sieves having different Si/Al ratios from fly ash | |
| CN108059171A (en) | A kind of method of flyash synthesis HZSM-5 type zeolites | |
| CN101956441B (en) | Lightweight environment-friendly bricks prepared from waste incineration flyash and preparation method thereof | |
| Zou et al. | Study on preparation of glass-ceramics from multiple solid waste and coupling mechanism of heavy metals | |
| CN101481118B (en) | Method for preparing zeolite molecular sieve from fly ash by using alkali fusion-steaming process | |
| Santhosh et al. | Cold sintering of colloidal silica particles using different alkali solutions | |
| CN109437849A (en) | A kind of preparation method with the modified tapestry brick processed of domestic garbage incineration flyash | |
| CN101486470B (en) | Method for preparing zeolite molecular sieve from fly ash by using fly ash adjusted silica alumina ratio-alkali fusion-trace amount hydrothermal process | |
| CN101475191B (en) | Method for preparing zeolite molecular sieve from fly ash by using alkali fusion-room temperature long placing | |
| CN104743571A (en) | Method for preparing 13X type molecular sieve through coal ash | |
| Terzano et al. | Characterization of different coal fly ashes for their application in the synthesis of zeolite X as cation exchanger for soil remediation | |
| Sverguzova et al. | Application of sorbent waste material for porous ceramics production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110504 Termination date: 20120121 |