CN112679128A - Liquid-state melting sintering-cold quenching method for sulfur-added calcium, silicon and aluminum oxide material - Google Patents
Liquid-state melting sintering-cold quenching method for sulfur-added calcium, silicon and aluminum oxide material Download PDFInfo
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- CN112679128A CN112679128A CN202110075353.8A CN202110075353A CN112679128A CN 112679128 A CN112679128 A CN 112679128A CN 202110075353 A CN202110075353 A CN 202110075353A CN 112679128 A CN112679128 A CN 112679128A
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Abstract
The invention discloses a liquid-state melting sintering-cold quenching method for a sulfur-added calcium, silicon and aluminum oxide material, wherein the method comprises the following steps: (1) melting and sintering the sulfur-added calcium, silicon and aluminum oxide materials to obtain molten liquid materials; (2) performing cold quenching on the molten liquid material to obtain solid particles; (3) the solid particles are ground to obtain a sulphur-rich slag. The method adopts the melting sintering and cold quenching processes to treat the sulfur-added calcium, silicon and aluminum oxide materials, can convert the sulfur-added calcium, silicon and aluminum oxide materials into sulfur-rich slag, and the slag can be used for preparing building materials, thereby obviously improving the utilization value of the sulfur-added calcium, silicon and aluminum oxide materials.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a liquid-state fusion sintering-cold quenching method for a sulfur-added calcium, silicon and aluminum oxide material.
Background
Coal in southwest of China contains more ferric sulfide, generates a large amount of sulfur dioxide during combustion, is usually combusted by a fluidized bed, and limestone is added into a furnace for desulfurization, so that coal ash contains more ferric oxide, anhydrous calcium sulfate and calcium oxide. After the ferric oxide is subjected to reduction magnetic separation, the residual coal ash is difficult to utilize due to high sulfur and high calcium.
In the world, the alumina yield accounts for more than 50 percent in China, the alumina production generates a large amount of red mud, and the annual production in China is more than 1 hundred million tons at present. Because of special properties of each component and insufficient technical capability, only 4 percent of the components are utilized at a low value, and the rest components are only buried, thereby causing serious pollution. The high-value conversion and utilization of the waste have important practical significance. The red mud after recovery of alumina and alkali by reduction magnetic separation of ferric oxide and melting-cold quenching is high in calcium and silicon, low in activity and difficult to utilize.
Therefore, the technology for obtaining high utilization value of the existing red mud tailings with high sulfur and high calcium coal ash, high calcium and high silicon and low activity needs to be researched.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a liquid-state melting sintering-cold quenching method for a sulfur-enriched calcium, silicon, and aluminum oxide material, which uses a melting sintering and cold quenching process to treat the sulfur-enriched calcium, silicon, and aluminum oxide material, and can convert the waste sulfur-enriched calcium, silicon, and aluminum oxide material into sulfur-rich slag, and the slag can be used for preparing building materials, thereby significantly improving the utilization value of the sulfur-enriched calcium, silicon, and aluminum oxide.
In one aspect of the invention, the invention provides a liquid-state fusion sintering-cold quenching method for a sulfur-enriched calcium, silicon and aluminum oxide material. According to an embodiment of the invention, the method comprises:
(1) mixing the sulfur-added calcium, silicon and aluminum oxide materials with gypsum for melting and sintering so as to obtain a molten liquid material;
(2) performing cold quenching on the molten liquid material to obtain solid particles;
(3) the solid particles are ground to obtain a sulphur-rich slag.
According to the liquid-state melt sintering-cold quenching method for the sulfur-added calcium, silicon and aluminum oxide materials, the sulfur-added calcium, silicon and aluminum oxide materials mainly comprise calcium oxide, silicon dioxide, aluminum oxide and calcium sulfate, the calcium oxide, silicon oxide and aluminum oxide materials are melted into liquid state, the obtained molten liquid material is subjected to cold quenching, all components are not in time to crystallize, so that solid particles with high reaction activity can be obtained, and finally the obtained solid particles are ground to obtain the sulfur-rich slag. Specifically, in hydration, calcium oxide and silicon dioxide form a high-quality strength factor, and aluminum oxide and calcium sulfate generate ettringite which has the function of compensating shrinkage or micro-expansion. Compared with the existing calcium sulphoaluminate with similar functions and common application, the sulfur-rich slag obtained by the method has the characteristics of low equipment investment, low cost and ultralow pollution emission, and is completely prepared from solid wastes. Therefore, the method adopts the melting sintering and cold quenching processes to treat the sulfur-added calcium, silicon and aluminum oxide materials, can convert the waste sulfur-added calcium, silicon and aluminum oxide materials into sulfur-rich slag, and the slag can be used for preparing building materials, thereby obviously improving the utilization value of the sulfur-added calcium, silicon and aluminum oxide materials.
In addition, the liquid-state melting sintering-cold quenching method for the sulfur-added calcium, silicon and aluminum oxide material according to the embodiment of the invention can also have the following additional technical characteristics:
in some embodiments of the invention, in step (1), the sulfur content of the sulfidized calcium, silicon, aluminum oxide feed is not less than 3 mass%.
In some embodiments of the invention, in step (1), the sulfur-enriched calcium, silicon, aluminum oxide material is fluidized bed combustion desulfurized fly ash or gypsum-enriched fly ash or red mud tailings.
In some embodiments of the invention, in step (1), the calcium sulfate content of the sulfidized calcium, silicon, aluminum oxide material is no greater than 0.5 times the equivalent weight of aluminum oxide in the sulfidized calcium, silicon, aluminum oxide material. Thus, sulfur-rich slag of high utility value can be obtained.
In some embodiments of the present invention, in step (1), the melt sintering apparatus is a melt furnace. Thus, the investment and operation cost can be reduced.
In some embodiments of the present invention, in the step (1), the melting and sintering temperature is 1150 to 1400 ℃. Thus, sulfur-rich slag of high utility value can be obtained.
In some embodiments of the invention, in step (2), the cold quench rate is not less than 500 ℃/s. Thus, sulfur-rich slag of high utility value can be obtained.
In some embodiments of the invention, in step (2), the solid particles have a particle size of no greater than 5 mm. Thus, sulfur-rich slag of high utility value can be obtained.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a liquid state sinter-quench method for a sulfur-enhanced calcium, silicon, aluminum oxide material in accordance with one embodiment of the invention.
Detailed Description
The following detailed description of the embodiments of the present invention is intended to be illustrative, and not to be construed as limiting the invention.
In one aspect of the invention, the invention provides a method for liquid-state melt sintering-cold quenching of a sulfur-enriched calcium, silicon and aluminum oxide material. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: melting and sintering the sulfur-enriched calcium, silicon and aluminum oxide material
In this step, the sulfur-enriched calcium, silicon, and aluminum oxide material in the present application may be defined as "any material having a sulfur content of not less than 3% (mass%) and including calcium oxide, silicon dioxide, aluminum oxide, calcium sulfate, etc.," for example, the sulfur-enriched calcium, silicon, and aluminum oxide material is fluidized bed combustion desulfurized fly ash or gypsum-enriched fly ash or red mud tailings, wherein the fluidized bed combustion fly ash is the residual material after magnetizing and selecting iron from ash slag generated by burning high-sulfur coal in a fluidized bed boiler and adding limestone for desulfurization in the boiler; the fly ash or red mud tail powder added with gypsum is the tail powder left after the fly ash or red mud is subjected to recovery of ferric oxide, alkali and aluminum oxide, and calcium sulfate-containing materials such as desulfurization byproduct gypsum and the like are added, wherein the materials mainly contain oxides of aluminum, calcium and silicon and calcium sulfate.
Furthermore, the content of calcium sulfate in the material of the calcium, silicon and aluminum oxides with increased sulfur is not higher than 0.5 time of the equivalent weight of aluminum oxide in the material of the calcium, silicon and aluminum oxides with increased sulfur.
Further, the above-mentioned equipment for performing the melting and sintering reaction on the sulfur-enriched calcium, silicon, and aluminum oxide material includes, but is not limited to, a melting furnace, as long as the sulfur-enriched calcium, silicon, and aluminum oxide material is mixed with gypsum for melting and sintering, compared with the conventional technology in which a rotary kiln is used for sintering a material having a function of compensating shrinkage or micro expansion, it is impossible to avoid the occurrence of a liquid phase and try to control the liquefaction degree, so the reaction is slow, the equipment is correspondingly large, and part of calcium sulfate therein is decomposed to release sulfur dioxide, thereby causing pollution. And this application adopts the melting furnace to carry out liquid melting process rapidly, and the temperature is also even, can not appear calcium sulfate and decompose. Meanwhile, the melting and sintering temperature is 1150-1400 ℃, preferably 1200-1300 ℃, and the materials are in a good liquid state under the temperature condition, so that good chemical reaction performance is ensured.
S200: cold quenching the molten liquid material
In the step, the obtained molten liquid material is subjected to cold quenching, and all components are not in time to crystallize, so that solid particles with high reaction activity can be obtained. Specifically, in the hydration process, calcium oxide and silicon dioxide form high-quality strength factors, and aluminum oxide and calcium sulfate generate ettringite which has the function of compensating shrinkage or micro-expansion. Further, the cold quenching rate is not lower than 500 ℃/s, namely the molten liquid material obtained in the melting and sintering process is discharged from the melting and sintering equipment and then is rapidly cold quenched, so that the temperature of the molten liquid material is reduced from more than 1100 ℃ to less than 200 ℃ within 2 seconds, and solid particles with the particle size of not more than 5mm are obtained. It should be noted that the manner of quenching in this step is not particularly limited as long as rapid quenching of the molten liquid material can be achieved.
S300: grinding the solid particles to fine
In the step, the obtained solid particles are ground to obtain the sulfur-rich slag. It should be noted that, in the present application, there is no particular limitation on the particle size of the solid particles after being ground, as long as the functions of improving strength and compensating shrinkage or micro-expansion can be satisfied.
According to the liquid-state melting sintering-cold quenching method for the sulfur-added calcium, silicon and aluminum oxide materials, the sulfur-added calcium, silicon and aluminum oxide materials mainly comprise calcium oxide, silicon dioxide, aluminum oxide and calcium sulfate, once the sulfur-added calcium, silicon and aluminum oxide materials are melted into a liquid state, the obtained molten liquid material is subjected to cold quenching, all components are not crystallized, so that solid particles with high reaction activity can be obtained, and finally the obtained solid particles are ground to obtain the sulfur-rich slag. Specifically, in hydration, calcium oxide and silicon dioxide form a high-quality strength factor, and aluminum oxide and calcium sulfate generate ettringite which has the function of compensating shrinkage or micro-expansion. Compared with the existing calcium sulphoaluminate with similar functions and common application, the sulfur-rich slag obtained by the method has the characteristics of low equipment investment, low cost and ultralow pollution emission, and is completely prepared from solid wastes. Therefore, the method adopts the melting sintering and cold quenching processes to treat the sulfur-added calcium, silicon and aluminum oxide materials, can convert the waste sulfur-added calcium, silicon and aluminum oxide materials into sulfur-rich slag, and the slag can be used for preparing building materials, thereby obviously improving the utilization value of the sulfur-added calcium, silicon and aluminum oxide materials.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (8)
1. A method for liquid-state fusion sintering-cold quenching of a sulfur-enriched calcium, silicon and aluminum oxide material is characterized by comprising the following steps:
(1) melting and sintering the sulfur-added calcium, silicon and aluminum oxide materials to obtain molten liquid materials;
(2) performing cold quenching on the molten liquid material to obtain solid particles;
(3) the solid particles are ground to obtain a sulphur-rich slag.
2. The method of claim 1, wherein in step (1), the sulfur content of the sulfur-enriched calcium, silicon, aluminum oxide feed is not less than 3 mass%.
3. The method according to claim 1, wherein in step (1), the sulfur-enriched calcium, silicon and aluminum oxide material is fluidized bed combustion desulfurized coal ash or gypsum-enriched fly ash or red mud tailings.
4. The process of claim 1, wherein in step (1), the calcium sulfate content of the sulfidized calcium, silicon, aluminum oxide material is no greater than 0.5 times the aluminum oxide equivalent weight of the sulfidized calcium, silicon, aluminum oxide material.
5. The method of claim 1, wherein in step (1), the melt-sintering apparatus is a melt furnace.
6. The method according to claim 1, wherein in the step (1), the melt sintering temperature is 1150-1400 ℃.
7. The method of claim 1, wherein in step (2), the quenching rate is not less than 500 ℃/s.
8. The method according to claim 1, wherein in step (2), the solid particles have a particle size of not more than 5 mm.
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Application publication date: 20210420 |