CN101486470B - Method for preparing zeolite molecular sieve from fly ash by using fly ash adjusted silica alumina ratio-alkali fusion-trace amount hydrothermal process - Google Patents
Method for preparing zeolite molecular sieve from fly ash by using fly ash adjusted silica alumina ratio-alkali fusion-trace amount hydrothermal process Download PDFInfo
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- CN101486470B CN101486470B CN2009100213238A CN200910021323A CN101486470B CN 101486470 B CN101486470 B CN 101486470B CN 2009100213238 A CN2009100213238 A CN 2009100213238A CN 200910021323 A CN200910021323 A CN 200910021323A CN 101486470 B CN101486470 B CN 101486470B
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Abstract
The invention discloses a method for preparing a zeolite molecular sieve by a hydro-thermal method that utilizes fly ash to adjust Si/Al ratio-alkaline fusion-trace amount, which 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 (nonsolvent water) 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 only a small amount of water (nonsolvent water) is required in the reaction to participate in the reaction; therefore, no pollution to environment is generated during the production process, reaction temperature range is comparatively wide, 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 flyash that utilizes is regulated silica alumina ratio-alkali fusion-trace Hydrothermal Preparation 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 adopts 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 the original position hydrothermal synthesis method
[2], alkali fusion-hydrothermal method
[3] [4], microwave assisting method
[5] [6]And the preparation of dissimilar molecular sieves is by add crystal seed method under hydrothermal condition
[7]The perhaps Si/Al mol ratio in the regulator solution
[8](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?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?zeolitesynthesis?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?cement?pastes[J].J?Am?Ceram?Soc，1992，75(6)：1574-1578。
【8】R.Terzano，M.Spagnuolo，L.Medici，F.Tateo，P.Ruggiero.Zeolitesynthesis?from?pre-treated?coal?fly?ash?in?presence?of?soil?as?a?tool?for?soilremediation[J].Applied?Clay?Science，2005(29)99-110。
Summary of the invention
The object of the invention is, a kind of method of utilizing flyash to regulate silica alumina ratio-alkali fusion-trace Hydrothermal Preparation zeolite molecular sieve is provided, 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 flyash to regulate silica alumina ratio-alkali fusion-trace Hydrothermal Preparation zeolite molecular sieve is characterized in that, specifically comprises the steps:
Step 1, get flyash with etc. the NaOH solid of quality mix, obtain mixture,
Step 2 with the Si/Al mol ratio in water glass and the aluminum oxide adjusting mixture, gets 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 is got the flyash grog, and in the flyash grog: water=2: 1 (mass/volume) ratio adds water and stirs evenly, and puts into the tetrafluoroethylene reactor;
Step 5 is placed reactor 12 hours under room temperature to 200 ℃ condition, generates zeolite molecular sieve.
The present invention adopt the hot method of adjusting silica alumina ratio-alkali fusion-non-(aqueous solvent) temperature for example room temperature-high temperature this reaction can take place, the high more speed of response of temperature is accelerated, temperature variation does not influence the kind of product, 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 method flow diagram of the present invention;
Fig. 2 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, by regulating the method for silica alumina ratio-alkali fusion-trace Hydrothermal Preparation zeolite molecular sieve, specifically comprise the steps: according to the flyash that utilizes 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 a certain amount of NaOH solid, with etc. quality (deviation 20% also can) flyash mix, obtain mixture;
3, use Na
2SiO
39H
2O and Al
2O
3Regulate the Si/Al mol ratio in the mixture, get different Si/Al molar mixture; Si/Al mol ratio control method is as follows:
According to the XRF experimental data of powdered coal ash, the Si/Al mol 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 Si/Al mol ratio and be 1: 1 mixture; 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, this flyash grog is the alkali fusion thing, and outward appearance is the green particles shape, and its is remembered as grog M;
6, get flyash grog 2g, and according to grog: water=2: 1 (mass/volume, the g/ml of unit) gets the 1ml tap water and the coal ash grog mixes, and together joins in the tetrafluoroethylene reactor.This reactor is put into 100 ℃ of temperature baking ovens, place after 12 hours, can generate zeolite molecular sieve N.
With thing phase composite and the pattern of XRD and SEM assaying reaction product N, reaction product N is zeolite molecular sieve (Fig. 2) 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 high more speed of response of temperature that experiment showed, through the contriver will be accelerated, and temperature variation does not influence the kind of product.
Claims (3)
1. a method of utilizing flyash to regulate silica alumina ratio-alkali fusion-trace Hydrothermal Preparation zeolite molecular sieve is characterized in that, specifically comprises the steps:
Step 1, get flyash with etc. the NaOH solid of quality mix, obtain mixture, regulate Si/Al mol ratio in the mixture with water glass and aluminum oxide, the mixture of different Si/Al mol ratios;
Step 2 with mixture fusion 2 hours～3 hours under 850 ℃ of temperature in retort furnace, generates the flyash grog;
Step 3 is got the flyash grog, and in the flyash grog: water=2: 1m/v g/mL ratio adds water and stirs evenly, and puts into the tetrafluoroethylene reactor;
Step 4 is placed reactor 12 hours under room temperature to 200 ℃ condition, generates zeolite molecular sieve.
2. method according to claim 1 is characterized in that the temperature of described reactor is 100 ℃.
3. method according to claim 1 is characterized in that the Si/Al mol ratio in the described adjusting mixture is the XRF experimental data according to powdered coal ash, adds 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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| CN112919490A (en) * | 2021-03-17 | 2021-06-08 | 浙江大学 | Method for preparing molecular sieve based on red mud-biomass ash-fly ash doping tempering |
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| CN101164884A (en) * | 2007-10-12 | 2008-04-23 | 山东轻工业学院 | Multistage synthesis method for coal ash zeolite |
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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,第112卷170-177. * |
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