CN1394806A - Preparation of zeolite/mullite composite hollow microsphere by using fly-ash hollow microbead - Google Patents
Preparation of zeolite/mullite composite hollow microsphere by using fly-ash hollow microbead Download PDFInfo
- Publication number
- CN1394806A CN1394806A CN 02112272 CN02112272A CN1394806A CN 1394806 A CN1394806 A CN 1394806A CN 02112272 CN02112272 CN 02112272 CN 02112272 A CN02112272 A CN 02112272A CN 1394806 A CN1394806 A CN 1394806A
- Authority
- CN
- China
- Prior art keywords
- zeolite
- mullite
- fly ash
- hollow
- fau
- 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.)
- Granted
Links
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to a method for preparing zeolite FAU/mullite and LTA/mullite composite zeolite hollow microspheres by using flyash hollow microbeads as raw material and utilizing crystal seed induction in-situ hydrothermal crystallization process. The flyash is a solid waste, and contains lots of glass body with hollow structure, called flyash hollow microbeads. Said invention uses two different small granular zeolites of FAU and LTA as crystal seed, and makes them implement hydrothermal crystallization in NaOH alkali solution containing aluminium or containing no aluminium, and makes the active silicon aluminium components in the flyash hollow microbead crystallize into zeolite, and the inert mullite can not be converted, the original hollow structure can be retained so as to can obtain the composite hollow microspheres supported by outer-layer compact zeolite membrane.
Description
Technical field
The present invention is to be that the crystal seed of raw material induces the original position hydrothermal crystallizing to prepare the method for zeolite FAU/ mullite and LTA/ mullite composite hollow microsphere with coal fly ash hollow micro bead.The hollow zeolite microballoon is a kind of have low density, high-ratio surface, better thermostability, infiltrative type material of surface of good, bound zeolite inherent character can be used to some extent at aspects such as catalysis, absorption, ion-exchange and carrier, slow releasing capsule.
Background technology
Flyash is by fine dusts that buring solid fuel gave out such as coal-burning power plants, and quantity is very big, deals with improperly to increase flue dust, atmosphere pollution; The solid waste of discharging can cause the river to silt up as if entering in the water system, objectionable impurities wherein also can work the mischief to human body and biology.China's coal-burning power plant's year discharging lime-ash quantity is very big, add accumulation for many years deposit ash, serious environment pollution not only, but also want land occupation causes very big threat to the environment for human survival and the ecosystem.If properly handled, and flyash is again the potential resources that serves many purposes, and carries out the comprehensive utilization of flyash, and " turn harm into good, turn waste into wealth ", the protection environment is secular techno-economic policy of China.Content at China's total utilization of PCA comprises: flyash is used to produce building materials, construction work is built the road, backfill, improve the soil, produce compound manure, an ash earth backing is made ground, an ash plantation, and flyash is made stopping composition, reclaims useful matter from flyash, but these have disposed a spot of flyash, still have a large amount of flyash to need to handle.Utilizing the main component silico-aluminate in the flyash is overseas utilization and handle one of important channel of flyash in recent years as the feedstock production zeolite molecular sieve.Directly as alkali fusion indirect utilization flyash synthetic zeolite report is arranged early to water of coal ash thermal treatment or in conjunction with other, but the zeolite of these methods or preparation is not really practical, perhaps method is economical inadequately simple, needs higher temperature as alkali fusion, wastes a large amount of energy.FAU and LTA are the zeolites (FAU and LTA are three word codes that International Zeolite Association is classified to zeolite according to the crystalline texture of zeolite) that important use is arranged industrial, as in fields such as catalysis, absorption, ion-exchanges.In addition, the hollow structure to coal fly ash hollow micro bead also seldom causes concern in the preparation of zeolitic material.
Summary of the invention
The objective of the invention is to study a kind of method of utilizing coal fly ash hollow micro bead to prepare zeolite/mullite composite hollow microsphere.This method is simple to operation, with low cost, environmental friendliness.
Involved in the present invention induces the original position hydrothermal crystallizing to prepare the method for zeolite FAU/ mullite and LTA/ mullite composite hollow microsphere with the coal fly ash hollow micro bead crystal seed, can make that active silica-alumina composition crystallization is zeolite FAU or LTA in the coal fly ash hollow micro bead, and the inert mullite can not transform, original hollow structure keeps, thereby makes the compound hollow microballoon that is supported by fine and close zeolite membrane of skin and internal layer mullite macropore.
The method of technology of the present invention is as follows:
1. coal fly ash hollow micro bead adsorbs zeolite seed crystal: coal fly ash hollow micro bead is at first used anionic polymer (as PSS) or cationic polymers (as PDDA) to modify and is with corresponding electric charge, in the zeolite glue of certain pH, adsorb zeolite seed crystal then, then after filtration, drying.
2. hydrothermal crystallizing: coal fly ash hollow micro bead hydrothermal crystallizing in containing aluminium or not aluminiferous NaOH alkaline solution of absorption zeolite seed crystal, by the coal fly ash hollow micro bead of certain volume mass than mixed alkali liquor and absorption zeolite seed crystal, aging certain hour, hydrothermal treatment consists then, crystallization temperature is 60-120 ℃, and crystallization time is 6-72 hour.
3. product washing and dry: wash zeolite product with water near neutral, be drying to obtain powdery product at a certain temperature.
Actual conditions is as follows:
The used zeolite seed crystal granular size of preparation composite hollow ball 50-300nm can be the dispersive monomer in 1, also can be little coacervate; For by the flyash synthetic zeolite, the size of crystal seed without limits.
The concentration of NaOH is 1-4M in 2, aluminiferous alkali lye Na
+Concentration be 1-4M, and NaOH/NaAlO
2Mol ratio be 4-10, the volume mass of alkali lye and coal fly ash hollow micro bead is than being 5-30, digestion time 0-24 hour.
The washing zeolite product is to nearly neutrality, drying at a certain temperature in 3.
Obtain zeolite FAU/ mullite or LTA/ mullite composite hollow microsphere behind coal fly ash hollow micro bead electrostatic adhesion FAU or the LTA zeolite seed crystal after hydrothermal crystallizing, washing, the drying respectively.
The zeolite seed crystal granular size is in the 50-300nm better effects if.
The inventive method can be applicable to flyash synthetic zeolite FAU or LTA.
The invention provides by the crystal seed that with flyash or its cenosphere is raw material induces the original position hydrothermal crystallizing to prepare the method for zeolite FAU/ mullite or LTA/ mullite composite hollow microsphere and FAU or LTA zeolite.The inventive method can make that active silica-alumina composition crystallization is zeolite FAU or LTA in the coal fly ash hollow micro bead, and the inert mullite can not transform, original hollow structure keeps, thereby makes the compound hollow microballoon that is supported by fine and close zeolite membrane of skin and internal layer mullite macropore.This preparation method is easy and simple to handle, cheap, the utilization ratio height of raw material resources, environmental friendliness, and flyash or its cenosphere transformation efficiency are higher, and the zeolite FAU/ mullite of gained and LTA/ mullite composite hollow microsphere micro-sphere structure remain intact.
Description of drawings
Fig. 1 is the XRD figure spectrum of coal fly ash hollow micro bead (a), example 1 (b), example 2 (c) and example 3 (d) product, the XRD figure spectrum of contrast raw material, the diffraction peak that other crystalline phases among the product figure beyond no tangible FAU and the LTA generate, mullite crystalline phase peak in the raw material does not have to change substantially, and quartzy peak weakens greatly even disappears, and shows that coal fly ash hollow micro bead can effectively be converted into zeolite under crystal seed is induced.Wherein the zeolite of example 2 (c) generation is the mixing crystalline phase of LTA and FAU, and that example 2 (b) and example 2 (d) generation is respectively single zeolite FAU and LTA.
Fig. 2 is the SEM figure of raw material coal fly ash hollow micro bead, shows it is the microsphere with hollow structure.
Fig. 3, Fig. 4, Fig. 5 are respectively the SEM figure of example 1, example 2, example 3, show the most of zeolite membrane for one deck densification of tiny balloon surface of product, and raw material residue spherical shell then becomes the mullite frame supported of macropore.
Embodiment
Below example be to be that the crystal seed of raw material induces the original position hydrothermal crystallizing to prepare further specifying that zeolite FAU/ mullite and LTA/ mullite composite hollow microsphere done to coal fly ash hollow micro bead provided by the present invention.
Example 1
The coal fly ash hollow micro bead that provides with flyash research centre, Henan (contains SiO
256.21%, Al
2O
329.45%, main crystalline phase is mullite and quartz, choosing diameter is example less than the cenosphere of 100 μ m), the FAU crystal seed that at first adsorbs size about one deck 100nm, the coal fly ash hollow micro bead that 0.08g is adsorbed the FAU crystal seed mixes the teflon-lined reactor of putting into 15ml with the 2M NaOH solution of 1ml, seal back 100 ℃ of following crystallization 48 hours, obtain sample through washing drying, characterize detection through XRD (Rigaku D/max-IIA x ray powder diffraction instrument) and SEM (Philips XL 30 scanning electronic microscope), XRD spectrum and SEM figure see accompanying drawing.
Example 2
The LTA crystal seed of size replaces the FAU kind about 200nm, and other experimental procedure is the same, and XRD spectrum and SEM figure see accompanying drawing.
Example 3
Contain aluminum solutions (NaOH: NaAlO with 1ml
2: H
2O=9: 1: 250 mol ratio) replace NaOH solution, other experimental procedure is with example 2, and XRD spectrum and SEM figure see accompanying drawing.
Example 4-7
Press example 1 described method and handle the fly ash hollow microballoon, the hydrothermal crystallizing temperature is respectively 70 ℃, 80 ℃, 90 ℃, 110 ℃, and crystallization time is 12,20,40,50 hours, and other conditions are constant, and products obtained therefrom is a zeolite FAU/ mullite composite hollow ball.
Example 8-10
Press example 1 described method and handle the fly ash hollow microballoon, concentration of lye is respectively 1.5M, 2.5M, 4M, and other conditions are constant, and products obtained therefrom is a zeolite FAU/ mullite composite hollow ball.
Example 11-13
Press example 2 described methods and handle the fly ash hollow microballoon, the hydrothermal crystallizing temperature is respectively 70 ℃, 80 ℃, 90 ℃, 110 ℃, crystallization time is 12,20,40,50 hours, and other conditions are constant, and products obtained therefrom is a zeolite L TA/FAU/ mullite composite hollow ball.
Example 14-16
Press example 2 described methods and handle the fly ash hollow microballoon, concentration of lye is respectively 1.5M, 2.5M, 4M, and other conditions are constant, and products obtained therefrom is a zeolite L TA/FAU/ mullite composite hollow ball.
Example 17-20
Press example 3 described methods and handle the fly ash hollow microballoon, the hydrothermal crystallizing temperature is respectively 70 ℃, 80 ℃, 90 ℃, 110 ℃, and crystallization time is 12,20,40,50 hours, and other conditions are constant, and products obtained therefrom is a zeolite L TA/ mullite composite hollow ball.
Example 14-16
Press example 3 described methods and handle the fly ash hollow microballoon, contain the NaOH of aluminum solutions: NaAlO
2: H
2The O mol ratio was respectively 8: 2: 250,7.5: 2.5: 250 and 7: 3: 250, and products obtained therefrom is a zeolite L TA/ mullite composite hollow ball.
Claims (3)
1. one kind is the method for feedstock production zeolite/mullite composite hollow microsphere with the coal fly ash hollow micro bead, the technology that it is characterized in that preparing zeolite FAU/ mullite and LTA/ mullite composite hollow microsphere is the zeolite seed crystal electrostatic adhesion, then at the hydrothermal crystallizing in aluminium or the not aluminiferous NaOH alkaline solution that contains of certain volume, actual conditions is: (1) electrostatic adhesion method is with anionic polymer or the corresponding electric charge of cationic polymer modified coal fly ash hollow micro bead band, in the zeolite glue, adsorb zeolite seed crystal then, the pH=10-14 of zeolite glue; (2) the hydrothermal crystallizing temperature is 60-120 ℃, and crystallization time is 6-72 hour; (3) concentration of NaOH is 1-4M, aluminiferous alkali lye Na
+Concentration be 1-4M, and NaOH/NaAlO
2Mol ratio be 4-10; (4) volume mass of alkali lye and coal fly ash hollow micro bead is than being 5-30.
2. the method for preparing zeolite/mullite composite hollow microsphere by the described coal fly ash hollow micro bead of claim 1 is characterized in that the zeolite seed crystal size is 50-300nm.
3. by the method for the described coal fly ash hollow micro bead zeolite/mullite composite hollow microsphere of claim 1, it is characterized in that this method also can be used for ordinary fly ash is changeed brilliant be zeolite FAU or LTA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02112272 CN1202996C (en) | 2002-06-27 | 2002-06-27 | Preparation of zeolite/mullite composite hollow microsphere by using fly-ash hollow microbead |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02112272 CN1202996C (en) | 2002-06-27 | 2002-06-27 | Preparation of zeolite/mullite composite hollow microsphere by using fly-ash hollow microbead |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1394806A true CN1394806A (en) | 2003-02-05 |
| CN1202996C CN1202996C (en) | 2005-05-25 |
Family
ID=4741976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02112272 Expired - Fee Related CN1202996C (en) | 2002-06-27 | 2002-06-27 | Preparation of zeolite/mullite composite hollow microsphere by using fly-ash hollow microbead |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1202996C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313207C (en) * | 2004-02-13 | 2007-05-02 | 中国石油天然气集团公司 | Method for preparing uniform nanometer molecular sieve material with high catalytic activity |
| CN107870108A (en) * | 2017-11-21 | 2018-04-03 | 淄博职业学院 | Toughening type ceramic fibre mullite prepares the well cementation test block performance test of oil well water-impervious |
| CN114272892A (en) * | 2022-03-04 | 2022-04-05 | 中国华电科工集团有限公司 | CO (carbon monoxide)2Trapping adsorbent and preparation method and application thereof |
-
2002
- 2002-06-27 CN CN 02112272 patent/CN1202996C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313207C (en) * | 2004-02-13 | 2007-05-02 | 中国石油天然气集团公司 | Method for preparing uniform nanometer molecular sieve material with high catalytic activity |
| CN107870108A (en) * | 2017-11-21 | 2018-04-03 | 淄博职业学院 | Toughening type ceramic fibre mullite prepares the well cementation test block performance test of oil well water-impervious |
| CN114272892A (en) * | 2022-03-04 | 2022-04-05 | 中国华电科工集团有限公司 | CO (carbon monoxide)2Trapping adsorbent and preparation method and application thereof |
| CN114272892B (en) * | 2022-03-04 | 2022-05-17 | 中国华电科工集团有限公司 | CO (carbon monoxide)2Trapping adsorbent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1202996C (en) | 2005-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Querol et al. | Synthesis of Na-zeolites from fly ash | |
| Miyake et al. | Preparation of activated carbon–zeolite composite materials from coal fly ash | |
| CN113428873B (en) | Method for preparing fly ash-based HS-type molecular sieve by microwave alkali fusion | |
| Belardi et al. | Crystallization of K–L and K–W zeolites from fly-ash | |
| CN1161275C (en) | Preparation of cancrinite zeolite hollow microsphere by using fly-ash hollow microbead | |
| CN1202996C (en) | Preparation of zeolite/mullite composite hollow microsphere by using fly-ash hollow microbead | |
| CN101993089B (en) | Method for preparing nano flyash zeolite | |
| CN105439169A (en) | Method for synthesizing sodium type zeolite from fly ash and active carbon | |
| CN1116106C (en) | Preparation of activated carbon-zeolite composition with coal gangue | |
| CN113479902B (en) | Method for synthesizing analcite from illite clay by hydrothermal-alkaline process and analcite | |
| Sangita et al. | Synthesis of zeolite from waste fly ash by using different methods | |
| CN108341416B (en) | Needle-shaped nano zeolite material prepared from metakaolin as well as method and application thereof | |
| Mun et al. | Chemical conversion of paper sludge incineration ash into synthetic zeolite | |
| Gitari et al. | Hydrothermal conversion of south african coal fly ash into pure phase zeolite Na‐P1 | |
| CN115385356B (en) | Method for preparing 13X molecular sieve by utilizing fly ash solid phase | |
| CN110790281A (en) | Process for synthesizing analcite by using engineering waste soil through hydrothermal alkaline method | |
| CN113582194B (en) | Method for preparing zeolite microspheres based on fly ash and zeolite microspheres | |
| Wang et al. | Preparation and characterization of granular zeolite material from construction and demolition waste for lead removal | |
| Alfiyan et al. | Utilization of fly ash as ceramic support mixture for the synthesis of zeolite pervaporation membrane | |
| CN1724479A (en) | Method of comprehensive utilization of phophogypsum | |
| CN118341410A (en) | Substrate sludge active covering material and preparation method and application thereof | |
| CN115318242A (en) | Method for synthesizing different carbon dioxide adsorbents by building clay bricks | |
| Li et al. | Electrolytic manganese residue and red mud co-treatment: Synthesizing zeolite X and adsorbing leaching solution from electrolytic manganese residue | |
| CN116532086A (en) | Preparation method and application of coal gangue-plastic activated carbon molecular sieve with controllable structure | |
| JPH07113075A (en) | Soil conditioner and production thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| 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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |