CN105692632B - A method of preparing tobermorite with gained white residue after acid treatment aluminum-extracted pulverized fuel ash - Google Patents
A method of preparing tobermorite with gained white residue after acid treatment aluminum-extracted pulverized fuel ash Download PDFInfo
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- CN105692632B CN105692632B CN201410707019.XA CN201410707019A CN105692632B CN 105692632 B CN105692632 B CN 105692632B CN 201410707019 A CN201410707019 A CN 201410707019A CN 105692632 B CN105692632 B CN 105692632B
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Abstract
A method of preparing tobermorite with gained white residue after acid treatment aluminum-extracted pulverized fuel ash.The present invention provide it is a kind of putting forward the method that the white residue generated after aluminium prepares tobermorite using aluminous fly-ash acid system, include the following steps：Acid sludge and calcium hydroxide or calcium oxide or the mainly calcareous raw material containing calcium oxide are mixed in a certain ratio and are dissolved in 0.1~100g/L sig waters, reacts 1-15h at 100-230 DEG C, through being filtered, washed, drying, obtains tobermorite.The tobermorite prepared using this method, can be made self-thermal insulation material, can also be used as additive for industry such as rubber, papermaking, plastics.The preparation method of the present invention is simple, and low energy consumption.
Description
Technical field
The invention belongs to solid waste recycling fields, in particular it relates to which a kind of using acid treatment high-alumina fly
Coal ash puies forward the method that white residue prepares tobermorite obtained by aluminium.
Background technology
Flyash is to recycle the fine ash got off in the flue gas formed after coal dust firing, is the primary solids that coal-burning power plant generates
Waste.According to open source information, the 1t coals that often burn can generate 250~300kg flyash.Since the establishment of the nation, discharge over the years does not add
Using and there is the flyash total amount of grey field at 2,500,000,000 tons or more, and with the increase of coal in China consumption figure, China's powder in heap
The annual emissions of coal ash can also increase therewith, and according to statistics, the discharge capacity of China's flyash has reached 4.8 hundred million tons for 2010, and 2015
Year will rise to 5.8 hundred million tons.In the flyash of northern China accumulation, the content of aluminium oxide is very high in some flyash,
Its mass percentage is 35%~50%, is equivalent to the content of aluminium oxide in China's middle-low bauxite, great extraction valence
Value.According to investigations, Inner Mongol coal aluminium symbiotic mineral total amount is more than 50,000,000,000 t, can generate 15,000,000,000 t aluminous fly-ash.If by wherein oxygen
Change average 40% meter of aluminium content, alumina content is about 6,000,000,000 t in this part flyash, and bauxite resource is seriously deficient in China
Instantly, can this partial oxidation bauxite resource efficiently use extremely important to the strategic security of China's aluminum i ndustry.
In the technology for extracting aluminium oxide using aluminous fly-ash as raw material, acid system is wherein typical a kind of.But use acid system
Processing aluminous fly-ash is will produce largely when carrying aluminium with the useless white residue of silica solid as main component, abbreviation white residue.Such as
The useless white residue in this part of fruit cannot efficiently use, and can cause secondary pollution to environment, be detrimental to health.Therefore, the utilization of white residue
Problems demand solve, and the high value added utilization of white residue be even more there is an urgent need to.
Calcium silicates type is more, and wherein tobermorite is a kind of hydrated calcium silicate, its small, thermal coefficient with unit weight
Low, the features such as high temperature resistant and intensity are big, it is chiefly used in preparing thermal insulation material, is widely used in the row such as metallurgy, building materials, electric power, chemical industry
In industry kiln, equipment and pipe insulation engineering.Currently, the preparation of tobermorite material be with silica flour, diatomite, zeolite,
The high silicon matter such as bentonite is as siliceous raw material, using quick lime, white lime, gypsum and carbide slag etc. as calcareous raw material, through one
Serial reaction, molding etc. form, while to increase its intensity, also tending to that the materials such as reinforcing fiber are added in blending process.Example
If a kind of CN103172333A processes preparing ultralight tobermorite calcium-silicate thermal insulation material announced are exactly to use silicon
Diatomaceous earth and lime are respectively siliceous raw material and calcareous raw material, are prepared by the processes such as dispensing, gel reaction, compacting, steam-cured, drying
Tobermorite material；CN102731120A announce it is a kind of using zirconium white residue produce thermal insulation material tobermorite method be
Do siliceous raw material and calcareous raw material respectively using zirconium white residue and lime, by washing, dispensing, reaction, be added fiber, moulding at
The processes such as type, drying prepare tobermorite material.A kind of manufacture high temperature resistant calcium-silicate thermal insulation material that CN1043220C is announced
Method be using quartz and white lime make siliceous raw material and calcareous raw material respectively, pass through dispensing, steam pressure reaction, blowing, press filtration
The processes such as molding, drying prepare calcium-silicate thermal insulation material.Although the siliceous raw material type of tobermorite made above is more,
Limited source, and mostly Resources.And the white residue after carrying aluminium using secondary resource aluminous fly-ash acid system is as siliceous raw material system
Standby tobermorite is simultaneously used as the method for preparing self-thermal insulation material, and there is not been reported so far.
Invention content
It is that siliceous raw material uses Dynamic Water heat seal to carry aluminium gained white residue using aluminous fly-ash acid system the present invention provides one kind
At the method that method prepares tobermorite, the tobermorite that this method obtains can be used for preparing self-thermal insulation material.Therefore, originally
Invention not only provides excellent tobermorite preparation method, and additionally provides tobermorite conduct prepared by the present invention
The application of self-thermal insulation material.The present invention can effectively alleviate aluminous fly-ash acid system carry aluminium generation white residue bulk deposition cause
Problem of environmental pollution.
The method that white residue prepares tobermorite obtained by after acid treatment aluminum-extracted pulverized fuel ash of the present invention, including following step
Suddenly：
1) it pre-processes：By described with gained white residue washing process after acid treatment aluminum-extracted pulverized fuel ash, treated white residue
PH value is 6~7；
2) dispensing：White residue and calcareous raw material press CaO and SiO after pre-processing2Molar ratio is 0.6~1.2 mixing, is mixed
Material is closed, then mixture is pressed 1:5~1:40 ratio is dissolved in sig water, obtains mixed slurry；
3) it reacts：The mixed slurry that step 2) is obtained carries out synthetic reaction in closed container, and reaction temperature is 100~
230 DEG C, the reaction time is 1~15h, is filtered after reaction, obtains tobermorite wet slag.
Above-mentioned white residue and calcareous raw material preferably press CaO and SiO2Molar ratio is 0.8~1.0 mixing.
Above-mentioned calcareous raw material is calcium hydroxide or calcium oxide, or the waste residue containing calcium oxide, the waste residue containing calcium oxide be
Refer to the waste residue based on calcium hydroxide or calcium oxide, such as carbide slag or ardealite.
Lye Na used in the present invention2A concentration of 0.1~100g/L of O.The lye can be NaOH solution or Na2CO3
The mixed liquor of solution or the two can also be the mixed liquor of NaOH and other sodium salts, that is, meet Na in solution2O a concentration of 0.1
The present invention may be implemented in the lye of~100g/L.
The method according to the present invention for preparing tobermorite type calcium silicates, the preferred reaction temperature of step 3) is 180~
220℃；The preferred reaction time is 7~9h.
Of the present invention referred to gained white residue after acid treatment aluminum-extracted pulverized fuel ash uses existing arbitrary acid treatment powder
Coal ash carries the white residue obtained after aluminium.Especially aluminous fly-ash acid system puies forward solid waste produced by aluminium, and main component is
SiO2And Al2O3。
The method according to the present invention for preparing tobermorite will constantly be stirred slurry in step 3) reaction process
It mixes, by slurry filtration after the completion of reaction, obtains the tobermorite wet slag of different-shape.
Any closed appearance that may be synthesized reaction that closed container can be known in the art needed for present invention reaction
Device, such as reaction kettle etc..
The present invention also provides by the tobermorite of gained white residue preparation after the above-mentioned aluminum-extracted pulverized fuel ash with acid treatment
Using especially as the application of self-thermal insulation material.
Based on above application, it is preferable that provide a kind of method preparing self-thermal insulation material, include the following steps：
1) fiber is added：Tobermorite wet slag produced by the present invention is added to 2~10% cotton fiber or paper fiber,
And it is uniformly mixed；
2) compression moulding：By the wet slag for the being added to fiber mold compression moulding obtained by step 1), obtains Tuo Beimo and come
Stone self-heat conserving product；
3) steam-cured：The tobermorite self-heat conserving product of compression moulding in step 2) is steam-cured at 150~180 DEG C, make
The crystal form of tobermorite is more complete.
4) dry：Tobermorite self-heat conserving product after will be steam-cured in step 3) dries 2~15h at 50~150 DEG C,
Tobermorite self-heat conserving finished product is prepared and is completed.
The method that white residue provided by the invention prepares tobermorite type calcium silicates has following apparent superiority：
(1) present invention carries solid slag caused by aluminium using aluminous fly-ash acid system and does siliceous raw material, not only solves
Aluminous fly-ash acid system carries the problem of solid slag accumulation pollution environment caused by aluminium, and also achieves the high-valued profit of white residue
With；
(2) tobermorite that the present invention synthesizes is deposited with the spherical state that nanometer tobermorite whisker is mutually entwined
, therefore the product unit weight of compression moulding is relatively low, superior performance；
(3) present invention using dynamic autoclaved technology method with aluminous fly-ash acid system carry aluminium generation white residue and containing calcium oxide
Calcareous raw material synthesizes tobermorite, and mainly support shellfish is synthesized by steam curing process with conventional method siliceous raw material and calcareous raw material
Mullite flow is compared, reaction process mass transfer effect more preferably, to energy consumption it is lower.
(4) present invention is not necessarily to any special installation, and simple for process, low energy consumption, easy to implement to promote, economic benefit and society
Benefit is apparent, and a new way is opened for white residue recycling obtained by acid treatment flyash.
Description of the drawings
Fig. 1 be the present invention with aluminous fly-ash acid system carry aluminium generation white residue be that raw material prepares tobermorite (Tuo Bei
Mullite-type calcium silicates) process route chart.
Fig. 2 is tobermorite scanning electron microscope (SEM) photo that the embodiment of the present invention 4 synthesizes.
Fig. 3 is tobermorite scanning electron microscope (SEM) photo that the embodiment of the present invention 5 synthesizes.
Specific implementation mode
Embodiment 1
The raw material of the present embodiment is the white residue that aluminous fly-ash acid system proposes aluminium generation, wherein containing 27.34% Al2O3With
55.66% SiO2.By above-mentioned white residue and calcium hydroxide with CaO/SiO2Molar ratio is 0.6 dispensing, is dissolved in Na2O is a concentration of
In the lye of 0.1g/L, control solid-to-liquid ratio is 1:5, its slurry is subjected to synthetic reaction, reaction temperature 200 in a kettle
DEG C, reaction time 15h, slurry is filtered by vacuum after reaction, obtains tobermorite wet slag, and gained wet slag is added after suction filtration
Selected mold compression moulding is used after entering 2% cotton fiber；By moulded products in 180 DEG C of steam-cured 1.5h, will be steam-cured after product
The dry 5h at 130 DEG C.Moulding material unit weight is 393kg/m3, compression strength 1.65MPa, linear shrinkage ratio 0.42%.
Embodiment 2
The raw material of the present embodiment is the white residue that aluminous fly-ash acid system proposes aluminium generation, wherein containing 13.08% Al2O3With
74.15% SiO2.By above-mentioned white residue and calcium oxide with CaO/SiO2Molar ratio is 1.0 dispensings, is dissolved in Na2A concentration of 10g/L of O
Lye in, control solid-to-liquid ratio be 1:30, its slurry is subjected to synthetic reaction in a kettle, reaction temperature is 210 DEG C, reaction
Time is 6h, and slurry is filtered by vacuum after reaction, obtains tobermorite wet slag；5% cotton is added in gained slag phase after suction filtration
With selected mold compression moulding after fiber；By moulded products in 165 DEG C of steam-cured 2h, will be steam-cured after product it is dry at 50 DEG C
15h.Moulding material unit weight is 215kg/m3, compression strength 0.98MPa, thermal coefficient 0.058W/ (mk), linear shrinkage ratio
0.60%.
Embodiment 3
The raw material of the present embodiment is the white residue that aluminous fly-ash acid system proposes aluminium generation, wherein containing 9.80% Al2O3With
55.04% SiO2.By above-mentioned white residue and carbide slag with CaO/SiO2Molar ratio is 1.0 dispensings, is dissolved in Na2A concentration of 20g/L of O
Lye in, control solid-to-liquid ratio be 1:5, its slurry is subjected to synthetic reaction in a kettle, reaction temperature is 180 DEG C, reaction
Time is 12h, and slurry is filtered by vacuum after reaction, obtains tobermorite wet slag；3% paper is added in gained slag phase after suction filtration
With selected mold compression moulding after fiber；By moulded products in 180 DEG C of steam-cured 2.5h, will be steam-cured after product at 105 DEG C
Dry 8h.Moulding material unit weight is 268kg/m3, compression strength 1.31MPa.
Embodiment 4
The raw material of the present embodiment is the white residue that aluminous fly-ash acid system proposes aluminium generation, wherein containing 13.08% Al2O3With
74.15% SiO2.By above-mentioned white residue and calcium hydroxide with CaO/SiO2Molar ratio is 0.83 dispensing, is dissolved in Na2A concentration of 5g/ of O
In the lye of L, control solid-to-liquid ratio is 1:40, its slurry is subjected to synthetic reaction in a kettle, reaction temperature is 230 DEG C, instead
It is 1h between seasonable, slurry is filtered by vacuum after reaction, obtains tobermorite wet slag, and gained slag phase is added 2.5% after suction filtration
Paper fiber after with selected mold compression moulding；By moulded products in 150 DEG C of steam-cured 1h, will be steam-cured after product at 100 DEG C
Lower dry 5h.Moulding material unit weight is 220kg/m3, compression strength 1.34MPa, flexural strength 0.41MPa.
Embodiment 5
The raw material of the present embodiment is the white residue that aluminous fly-ash acid system proposes aluminium generation, wherein containing 25.11% Al2O3With
40.92% SiO2.By above-mentioned white residue and ardealite with CaO/SiO2Molar ratio is 1.2 dispensings, is dissolved in Na2A concentration of 100g/L of O
Lye in, control solid-to-liquid ratio be 1:35, its slurry is subjected to synthetic reaction in a kettle, reaction temperature is 220 DEG C, reaction
Time is 9h, and slurry is filtered by vacuum after reaction, obtains tobermorite wet slag, and pattern is as shown in Figure 3；Gained after suction filtration
Slag phase uses selected mold compression moulding after 5% paper fiber is added；By moulded products in 180 DEG C of steam-cured 1h, after steam-cured
Product dry 8h at 120 DEG C.Moulding material unit weight is 312kg/m3, compression strength 2.20MPa.
Fig. 2~Fig. 3 is representational scanning electron microscope (SEM) photo (embodiment 4, the implementation of tobermorite of the present invention
Example 5).Tobermorite of the present invention can prepare the product of different-shape, such as crystal whisker-shaped, sheet according to its preparation condition difference
Etc..
Certainly, the present invention can also there are many embodiments, without deviating from the spirit and substance of the present invention, are familiar with
Those skilled in the art can disclosure according to the present invention make various corresponding changes and modification, but these it is corresponding change and
Deformation should all belong to the protection domain of appended claims of the invention.
Claims (4)
1. a kind of method that gained white residue prepares tobermorite after aluminum-extracted pulverized fuel ash with acid treatment, includes the following steps：
1) it pre-processes：To be 6~7 with gained white residue washing process after acid treatment aluminum-extracted pulverized fuel ash, white residue pH value that treated；
2) dispensing：By after washing white residue and calcareous raw material press CaO and SiO2Molar ratio is 0.6~1.2 mixing, obtains mixture,
Mixture is pressed into liquid-solid ratio 5 again:1~40:1mL/g is dissolved in lye, obtains mixed slurry；Wherein, Na in the lye2O is dense
Degree is 0.1~20g/L, and the calcareous raw material is calcium hydroxide or calcium oxide, or the waste residue containing calcium oxide；
3) it reacts：The mixed slurry that step 2) is obtained carries out synthetic reaction in closed container, and reaction temperature is 180~230
DEG C, the reaction time is 1~15h, is filtered, washed after reaction, up to tobermorite wet slag after drying.
2. the method according to claim 1 for preparing tobermorite, which is characterized in that the waste residue containing calcium oxide is
Carbide slag or ardealite.
3. the method according to claim 1 for preparing tobermorite, which is characterized in that the step 3) reaction temperature is
180~220 DEG C.
4. the method according to claim 1 or 3 for preparing tobermorite, which is characterized in that when the step 3) reaction
Between be 3~8h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106315605B (en) * | 2016-08-31 | 2018-04-10 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Method for preparing 1.1nm tobermorite from low-grade attapulgite clay |
| CN106495173B (en) * | 2016-10-27 | 2019-05-07 | 辽宁工程技术大学 | A method of tobermorite is produced with siliceous waste and carbide slag microwave heating |
| CN106966402B (en) * | 2017-03-24 | 2020-03-10 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | Method for preparing tobermorite by using calcium silicate slag |
| CN108910902B (en) * | 2018-08-24 | 2022-07-12 | 内蒙古中建亚太建材科技有限公司 | Method for synthesizing tobermorite composite heat-insulating material from high-alumina fly ash |
| CN116396087B (en) * | 2023-04-04 | 2024-03-15 | 广东简一(集团)陶瓷有限公司 | Low-temperature high-strength diatomite ceramic tile prepared from modified tobermorite fiber and preparation method thereof |
| CN117510174A (en) * | 2023-11-07 | 2024-02-06 | 上海荣势环保科技有限公司 | Novel calcium silicate board for passive fireproof system |
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| CN101913613A (en) * | 2010-08-16 | 2010-12-15 | 昊青薪材（北京）技术有限公司 | Process for synthesizing aciform wollastonite powder by desiliconizing alkaline liquor |
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| 高铝粉煤灰处理过程中的结构演变;张永康;《中国优秀硕士学位论文全文数据库工程科技I辑》;20130215(第2期);52-56页 * |
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