CN102826815A - High-calcium fly ash solid sealing material and preparation method thereof - Google Patents
High-calcium fly ash solid sealing material and preparation method thereof Download PDFInfo
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- CN102826815A CN102826815A CN2012103196293A CN201210319629A CN102826815A CN 102826815 A CN102826815 A CN 102826815A CN 2012103196293 A CN2012103196293 A CN 2012103196293A CN 201210319629 A CN201210319629 A CN 201210319629A CN 102826815 A CN102826815 A CN 102826815A
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- calcium fly
- desulfurated plaster
- sealing material
- composite chemical
- chemical admixture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention discloses a high-calcium fly ash solid sealing material and a preparation method thereof. The high-calcium fly ash solid sealing material takes high-calcium fly ash as a main raw material and a solution prepared from sodium hydroxide and liquid sodium silicate as a composite chemical additive; heat treatment desulfurization gypsum or thermal activated sludge can be also added; and in a certain curing environment, the system is enabled to have better performances, the curing effect respectively meets the requirement of a toxicity characteristic leaching procedure (TCLP) specified by United States Environmental Protection Agency on a leaching concentration limit; and the high-calcium fly ash solid sealing material can be applied to actual engineering instead of ordinary portland cement within a certain range. According to the high-calcium fly ash solid sealing material disclosed by the invention, industrial wastes such as the high-calcium fly ash, desulfurization gypsum or sludge are utilized, so that the burden of the environment is relieved, the cost is reduced, the resource consumption is reduced and favorable economic and social benefits are obtained.
Description
The application is that application number is dividing an application of 201010163512.1 application.
The applying date of original application is on 04 28th, 2010; Application number is 201010163512.1; Invention and created name is: high-calcium flyash fixed sealing material and preparation method thereof.
Technical field
The invention belongs to field of materials, relate to and utilize the trade waste high-calcium fly ass, and excite environment-friendly type fixed closure material of prepared a kind of low-carbon emission and preparation method thereof with the composite chemical admixture.
Background technology
Cement is a kind of traditional gelling material, can be as the safe disposal material of nuclear pollution and heavy metal danger wastes, i.e. fixed sealing material.Cement be human economic development and social progress when making huge contribution because its high resource, high energy gamma source consumption, high carbon emission and other serious environmental pollutions of causing more and more do not meet the requirement of the current strategy of sustainable development.Various countries launch respectively the development of relative measures restriction Cement industry scale, competitively give cement technology with higher scientific and technological content, and making it is that the mankind are unlikely to cause serious burden to environment when benefiting.Simultaneously, various countries also develop novel green gelling material in succession, to replace this traditional fixed sealing material.
Geopolymer is to be that raw material passes through a kind of less energy-consumption, long lifetime, the no CO that the reaction of mineral bunching generates with the silica-aluminum materials
2The high-performance inorganic polymkeric substance of discharging.Geopolymer has higher early strength and good endurance quality with respect to ordinary Portland cement, therefore, often is considered to a kind of fixed sealing material that can be used for the danger wastes safe disposal that is superior to cement.Along with the progress of the mankind to the reinforcement and the research work of environmental protection consciousness, the starting material of preparation geopolymer have also been widened from natural mineral raw and have been industrial solid castoff capable of using.
Flyash is that a kind of that the fuel-burning power plant emits is the industry byproduct of staple with the sial; Ordinary fly ash is the very low low calcium fly ash of calcium oxide content that bituminous coal emits as power fuel; High-calcium fly ass then brown coal, subbituminous coal or sub-bituminous coal emits as power fuel, its (SiO
2+ Al
2O
3+ Fe
2O
3) quality percentage composition>=50%, quality percentage composition>=10% of CaO.Along with the develop rapidly of power industry, flyash especially high-calcium fly ass is piled up the new source of pollution of formation, needs badly and disposes utilization.In addition, for realizing the clean burning of the energy, each firepower electrical plant of various countries all will be installed the flue gas desulfurization purification process, and desulfurated plaster is the by product of this technology, and its chemical ingredients mainly is a terra alba.And mud is a kind of chief city waste, the strictness day by day of the reinforcement of Along with people's Environmental awareness and quality index, and the mud that water and sewage treatment process produced has become the inevitable special waste of water pollution control technology.The annual sludge discharged amount in China municipal sewage plant is huge, and especially in China big city, the mud problem of outlet is very outstanding.These mud can only take up an area of landfill or independent burning disposal at present, still do not have rational treating method.
Summary of the invention
The present invention is main raw material(s) with the high-calcium fly ass; With sodium silicate and the prepared solution of sodium hydroxide is the composite chemical admixture; Also can add thermal treatment desulfurated plaster or thermal activation mud, prepare novel fixed sealing material, can partly replace or be superior to cement within the specific limits.
High-calcium fly ass can be used for developing high-calcium fly ash geopolymer because of it contains higher sal composition.And desulfurated plaster its dehydration after low temperature calcination becoming anhydrite; At desulfurated plaster and high-calcium fly ass is to condense except that self in the main system to produce the intensity; Also play the effect of sulphate activation agent, certain stimulation effect is arranged, desulfurated plaster contains a small amount of unreacted CaCO
3With the part soluble salt, like potassium, sodium salt, the existence of these impurity can be quickened aquation, stimulating activity.Its main thing phase composite after thermal activation treatment of air-dry mud is CaO, MgO and SiO
2, when thermal activation mud is incorporated in the high-calcium fly ass, the salic minerals composition that it contains can be used its silicon and aluminum source pioneer phase as the geopolymer material, and a large amount of calcareous composition and alkaline matter K
2O and Na
2O; Can be used as the alkali-activator of ground polyreaction; For the ground polyreaction provides higher alkaline environment; Increase the basicity of thermal activation mud-high-calcium fly ash geopolymer reaction system, help the stripping and the diffusion of sial title complex of depolymerization and the depolymerization of high-calcium fly ass sial phase, the formation of polymer gel post.
What this invention utilized is trade waste, approach is provided at first for the utilization of waste, has also reduced cost, has reduced resource consumption, and it has unburned and characteristics no grog, has practiced thrift energy consumption, meets the requirement of energy-saving and emission-reduction; This novel fixed sealing material has only the discharging of a spot of greenhouse gases simultaneously, is a kind of gelling material of environment-friendly type of low-carbon emission; In addition, it can replace cement to a certain extent, can reduce Cement Production, has just reduced high resource, the energy consumption in the cement production process, and high carbon emission has also reduced its immense pressure that environment is caused.In addition, the present invention is a kind of fixed sealing material, can the treatment of wastes with processes of wastes against one another, and the requirement that tallies with the national condition meets the current social Development Trend, has good economic benefit and social benefit.
Technical scheme of the present invention is following:
The invention provides a kind of high-calcium flyash fixed sealing material, the raw material of this fixed sealing material comprises high-calcium fly ass and composite chemical admixture, and wherein: the composite chemical admixture is formulated by sodium hydroxide and sodium silicate, modulus M (SiO
2)/n (Na
2O) be 1.5 ~ 2.0; Quantity relative ratio relationship between these two kinds of raw materials is: by the Na of composite chemical admixture introducing
2The quality of O is 10% ~ 15% of a high-calcium fly ass quality.
The preparation method of above-mentioned fixed sealing material carries out according to the following steps:
A, sodium hydroxide and liquid sodium silicate are mixed, control its modulus M (SiO
2)/n (Na
2O) be 1.5 ~ 2.0, it is subsequent use to process the composite chemical admixture.
B, in high-calcium fly ass, add the composite chemical admixture, the Na that introduces by the composite chemical admixture
2The quality of O is 10% ~ 15% of a high-calcium fly ass quality, promptly gets sample.
C, the sample hydro-thermal maintenance 8h under 75 ° of C that makes, maintenance 28d under the dislocation room temperature promptly gets high-calcium flyash fixed sealing material of the present invention then.
Further, subsequent use behind the gained composite chemical admixture ageing 24h among the step a, can further improve the activity of composite chemical admixture.
Further, the wc of controlling the system that high-calcium fly ass, composite chemical admixture constitute among the step b is 0.4.
The invention provides another kind of high-calcium flyash fixed sealing material; The raw material of this fixed sealing material comprises high-calcium fly ass, thermal treatment desulfurated plaster and composite chemical admixture, and wherein: the thermal treatment desulfurated plaster is that desulfurated plaster gets at temperature lower calcination 0.5h ~ 1.5h of 600 ~ 800 ° of C; The composite chemical admixture is formulated by sodium hydroxide and liquid sodium silicate, modulus M (SiO
2)/n (Na
2O) be 1.5 ~ 2.0; Quantity relative ratio relationship between these three kinds of raw materials is: the mass ratio≤1:9 of thermal treatment desulfurated plaster and high-calcium fly ass; Na by the introducing of composite chemical admixture
2The quality of O is 10% ~ 15% of thermal treatment desulfurated plaster and a high-calcium fly ass quality sum.
The preparation method of above-mentioned fixed sealing material carries out according to the following steps:
A, sodium hydroxide and liquid sodium silicate solution are mixed, control its modulus M (SiO
2)/n (Na
2O) be 1.5 ~ 2.0, it is subsequent use to process the composite chemical admixture.
B, with the temperature lower calcination 0.5h ~ 1.5h of desulfurated plaster at 600 ~ 800 ° of C, make the thermal treatment desulfurated plaster, cooling back is subsequent use.
C, with the thermal treatment desulfurated plaster with after high-calcium fly ass mixes according to mass ratio≤1:9, add the composite chemical admixture, the Na that introduces by the composite chemical admixture
2The quality of O is 10% ~ 15% of thermal treatment desulfurated plaster and a high-calcium fly ass quality sum, promptly gets sample.
D, the sample hydro-thermal maintenance 8h under 75 ° of C that makes, maintenance 28d under the dislocation room temperature promptly gets high-calcium flyash fixed sealing material of the present invention then.
Step a among this preparation method, b be order in no particular order.
Further, subsequent use behind the gained composite chemical admixture ageing 24h among the step a, can further improve the activity of composite chemical admixture.
Further, the wc of controlling the system that high-calcium fly ass, thermal treatment desulfurated plaster, composite chemical admixture constitute among the step c is 0.4.
The present invention also provides a kind of high-calcium flyash fixed sealing material; The raw material of this fixed sealing material comprises high-calcium fly ass, thermal activation mud and composite chemical admixture, and wherein: thermal activation mud is that air-dry mud gets at temperature lower calcination 0.5h ~ 1.5h of 800 ~ 900 ° of C; The composite chemical admixture is formulated by sodium hydroxide and liquid sodium silicate, modulus M (SiO
2)/n (Na
2O) be 1.5 ~ 2.0; Quantity relative ratio relationship between these three kinds of raw materials is: the mass ratio≤1:9 of thermal activation mud and high-calcium fly ass; Na by the introducing of composite chemical admixture
2The quality of O is 10% ~ 15% of thermal activation mud and a high-calcium fly ass quality sum.
The preparation method of above-mentioned fixed sealing material carries out according to the following steps:
A, sodium hydroxide and liquid sodium silicate are mixed, control its modulus M (SiO
2)/n (Na
2O) be 1.5 ~ 2.0, it is subsequent use to process the composite chemical admixture.
B, with the temperature lower calcination 0.5h ~ 1.5h of air-dry mud at 800 ~ 900 ° of C, make thermal activation mud, cooling back is subsequent use.
C, with thermal activation mud with after high-calcium fly ass mixes according to mass ratio≤1:9, add the composite chemical admixture, the Na that introduces by the composite chemical admixture
2The quality of O is 10% ~ 15% of thermal activation mud and a high-calcium fly ass quality sum, promptly gets sample.
D, the sample hydro-thermal maintenance 8h under 75 ° of C that makes, maintenance 28d under the dislocation room temperature promptly gets high-calcium flyash fixed sealing material of the present invention then.
Step a among this preparation method, b be order in no particular order.
Further, subsequent use behind the gained composite chemical admixture ageing 24h among the step a, can further improve the activity of composite chemical admixture.
Further, the wc of controlling the system that high-calcium fly ass, thermal activation mud and composite chemical admixture constitute among the step c is 0.4.
Aforementioned three kinds of high-calcium flyash fixed sealing materials all satisfy the requirement of the leaching concentration limit of Environmental Protection Agency toxicity characteristic leaching procedure (TCLP) regulation to the solid envelope effect of heavy metal, can replace ordinary Portland cement within the specific limits and apply to actual engineering.
Embodiment
Main raw material(s) high-calcium fly ass and the desulfurated plaster of three embodiment below the present invention are taken from certain power plant, and air-dry mud is the open-air natural air drying mud of stacking in certain water treatment plant, and the staple of high-calcium fly ass, air-dry mud and desulfurated plaster is seen table 1.The composite chemical admixture is formulated by sodium hydroxide and sodium silicate, and used sodium hydroxide is the chemical reagent that contains 99.2%NaOH, and commercially available liquid sodium silicate solid content 38.3% contains 9.1%Na
2O, 29.2%SiO
2With 61.7% water.
The main chemical compositions of table 1 high-calcium fly ass, desulfurated plaster and air-dry mud and content (wt.%)
Embodiment is the preparation and the application of a kind of high-calcium flyash fixed sealing material of the present invention 1., carries out according to the following steps:
A, sodium hydroxide and liquid sodium silicate are mixed, control its modulus M (SiO
2)/n (Na
2O) be 1.5, process the composite chemical admixture, subsequent use behind the ageing 24h.
B, in high-calcium fly ass, add the composite chemical admixture, the Na that introduces by the composite chemical admixture
2The quality of O is 10% of a high-calcium fly ass quality, and hierarchy of control wc is 0.4, and in system, seals 0.025% plumbous Pb (II) admittedly, and 0.025% chromium Cr (VI) and 0.01% mercury Hg (II) promptly get the sample that seals application admittedly.
Sample hydro-thermal maintenance 8h under 75 ° of C that c, the solid envelope that makes are used, maintenance 28d under the dislocation room temperature promptly gets high-calcium flyash fixed sealing material of the present invention then, and can detect its application result.
Embodiment is the preparation and the application of the another kind of high-calcium flyash fixed sealing material of the present invention 2., carries out according to the following steps:
A, sodium hydroxide and liquid sodium silicate are mixed, control its modulus M (SiO
2)/n (Na
2O) be 1.5, process the composite chemical admixture, subsequent use behind the ageing 24h.
B, with the temperature lower calcination 1h of desulfurated plaster at 800 ° of C, make the thermal treatment desulfurated plaster, cooling back is subsequent use.
C, with the thermal treatment desulfurated plaster with after high-calcium fly ass mixes with mass ratio 1:9, add the composite chemical admixture, the Na that introduces by the composite chemical admixture
2The quality of O is 10% of thermal treatment desulfurated plaster and a high-calcium fly ass quality sum; Hierarchy of control wc is 0.4, and in system, seals 0.025% plumbous Pb (II) admittedly, 0.025% chromium Cr (VI); Mercury Hg (II) with 0.01% promptly gets the sample that seals application admittedly.
Sample hydro-thermal maintenance 8h under 75 ° of C that d, the solid envelope that makes are used, maintenance 28d under the dislocation room temperature promptly gets high-calcium flyash fixed sealing material of the present invention then, and can detect its application result.
Embodiment is the preparation and the application of another high-calcium flyash fixed sealing material of the present invention 3., carries out according to the following steps:
A, sodium hydroxide and liquid sodium silicate are mixed, control its modulus M (SiO
2)/n (Na
2O) be 1.5, process the composite chemical admixture, subsequent use behind the ageing 24h.
B, with the temperature lower calcination 1h of air-dry mud at 900 ° of C, make thermal activation mud, cooling back is subsequent use.
C, with thermal activation mud with after high-calcium fly ass mixes according to mass ratio 1:9, add the composite chemical admixture, the Na that introduces by the composite chemical admixture
2The quality of O is 10% of thermal activation mud and a high-calcium fly ass quality sum, and hierarchy of control wc is 0.4, and in system, seals 0.025% plumbous Pb (II) admittedly, and 0.025% chromium Cr (VI) and 0.01% mercury Hg (II) promptly get the sample that seals application admittedly.
Sample hydro-thermal maintenance 8h under 75 ° of C that d, the solid envelope that makes are used, maintenance 28d under the dislocation room temperature promptly gets high-calcium flyash fixed sealing material of the present invention then, and can detect its application result.
More than the high-calcium flyash fixed sealing material that makes among three embodiment the solid envelope effect of heavy metal is seen table 2
Table 2 fixed sealing material seals the leaching concentration of its heavy metal behind the heavy metal and envelope rate admittedly admittedly
Can know according to table 2; Three kinds of high-calcium flyash fixed sealing materials that above-mentioned three embodiment make all satisfy the requirement of the leaching concentration limit of Environmental Protection Agency toxicity characteristic leaching procedure (TCLP) regulation to the solid envelope effect of heavy metal; Admittedly the envelope rate is high; Admittedly seal effectively, can replace ordinary Portland cement within the specific limits and apply to actual engineering.
Above-mentioned description to embodiment is can understand and use the present invention for the ease of the those of ordinary skill of this technical field.The personnel of skilled obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (4)
1. high-calcium flyash fixed sealing material; It is characterized in that: the raw material of this fixed sealing material comprises high-calcium fly ass, thermal treatment desulfurated plaster and composite chemical admixture, and wherein: the thermal treatment desulfurated plaster is that desulfurated plaster gets at temperature lower calcination 0.5h ~ 1.5h of 600 ° of C ~ 800 ° C; The composite chemical admixture is formulated by sodium hydroxide and liquid sodium silicate, modulus M (SiO
2)/n (Na
2O) be 1.5 ~ 2.0; Quantity relative ratio relationship between these three kinds of raw materials is: thermal treatment desulfurated plaster and high-calcium fly ass mass ratio≤1:9; Na by the introducing of composite chemical admixture
2The quality of O is 10% ~ 15% of thermal treatment desulfurated plaster and a high-calcium fly ass quality sum.
2. the preparation method of the described fixed sealing material of claim 1, carry out according to the following steps:
A, sodium hydroxide and liquid sodium silicate are mixed, control its modulus M (SiO
2)/n (Na
2O) be 1.5 ~ 2.0, it is subsequent use to process the composite chemical admixture;
B, desulfurated plaster is warming up to temperature lower calcination 0.5h ~ 1.5h of 600 ° of C ~ 800 ° C, makes the thermal treatment desulfurated plaster, the cooling back is subsequent use;
C, with the thermal treatment desulfurated plaster with after high-calcium fly ass mixes according to mass ratio≤1:9, add the composite chemical admixture, the Na that introduces by the composite chemical admixture
2The quality of O is 10% ~ 15% of thermal treatment desulfurated plaster and a high-calcium fly ass quality sum, promptly gets sample;
D, the sample hydro-thermal maintenance 8h under 75 ° of C that makes, maintenance 28d under the dislocation room temperature promptly gets high-calcium flyash fixed sealing material of the present invention then;
Perhaps, carry out according to the following steps:
A, desulfurated plaster is warming up to temperature lower calcination 0.5h ~ 1.5h of 600 ° of C ~ 800 ° C, makes the thermal treatment desulfurated plaster, the cooling back is subsequent use;
B, sodium hydroxide and liquid sodium silicate are mixed, control its modulus M (SiO
2)/n (Na
2O) be 1.5 ~ 2.0, it is subsequent use to process the composite chemical admixture;
C, with the thermal treatment desulfurated plaster with after high-calcium fly ass mixes according to mass ratio≤1:9, add the composite chemical admixture, the Na that introduces by the composite chemical admixture
2The quality of O is 10% ~ 15% of thermal treatment desulfurated plaster and a high-calcium fly ass quality sum, promptly gets sample;
D, the sample hydro-thermal maintenance 8h under 75 ° of C that makes, maintenance 28d under the dislocation room temperature promptly gets high-calcium flyash fixed sealing material of the present invention then.
3. preparation method according to claim 2 is characterized in that: the wc of controlling the system of high-calcium fly ass, thermal treatment desulfurated plaster, composite chemical admixture formation among the step c is 0.4.
4. according to arbitrary described preparation method in claim 2 or 3, it is characterized in that: subsequent use behind the gained composite chemical admixture ageing 24h among the step a.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103196293A CN102826815A (en) | 2010-04-28 | 2010-04-28 | High-calcium fly ash solid sealing material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103196293A CN102826815A (en) | 2010-04-28 | 2010-04-28 | High-calcium fly ash solid sealing material and preparation method thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010163512A Division CN101857386A (en) | 2010-04-28 | 2010-04-28 | High-calcium flyash fixed sealing material and preparation method thereof |
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|---|---|
| CN102826815A true CN102826815A (en) | 2012-12-19 |
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ID=47330158
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| CN2012103196293A Pending CN102826815A (en) | 2010-04-28 | 2010-04-28 | High-calcium fly ash solid sealing material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103641346A (en) * | 2013-12-10 | 2014-03-19 | 北京科技大学 | Method for preparing geopolymer gelled material from heavy metal gypsum |
| CN104291745A (en) * | 2014-07-24 | 2015-01-21 | 北方民族大学 | Method for preparing geopolymer by utilizing waste acid sludge |
| CN110964531A (en) * | 2018-09-26 | 2020-04-07 | 广东清大同科环保技术有限公司 | Desulfurization gypsum granular soil and preparation method thereof |
| CN113773002A (en) * | 2021-08-26 | 2021-12-10 | 常州大学 | Sulfuric acid corrosion resistant geopolymer concrete and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641346A (en) * | 2013-12-10 | 2014-03-19 | 北京科技大学 | Method for preparing geopolymer gelled material from heavy metal gypsum |
| CN103641346B (en) * | 2013-12-10 | 2016-01-20 | 北京科技大学 | A kind of heavy metal gypsum prepares the method for geopolymer gelling material |
| CN104291745A (en) * | 2014-07-24 | 2015-01-21 | 北方民族大学 | Method for preparing geopolymer by utilizing waste acid sludge |
| CN110964531A (en) * | 2018-09-26 | 2020-04-07 | 广东清大同科环保技术有限公司 | Desulfurization gypsum granular soil and preparation method thereof |
| CN110964531B (en) * | 2018-09-26 | 2021-11-02 | 广东清大同科环保技术有限公司 | Desulfurization gypsum granular soil and preparation method thereof |
| CN113773002A (en) * | 2021-08-26 | 2021-12-10 | 常州大学 | Sulfuric acid corrosion resistant geopolymer concrete and preparation method thereof |
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Application publication date: 20121219 |