CN216191117U - Reaction system for recycling aluminum oxide in aluminum-based hazardous waste - Google Patents
Reaction system for recycling aluminum oxide in aluminum-based hazardous waste Download PDFInfo
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- CN216191117U CN216191117U CN202122337348.8U CN202122337348U CN216191117U CN 216191117 U CN216191117 U CN 216191117U CN 202122337348 U CN202122337348 U CN 202122337348U CN 216191117 U CN216191117 U CN 216191117U
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Abstract
The utility model discloses a reaction system for recovering aluminum oxide in aluminum-based hazardous waste, which is characterized in that aluminum-based solid waste, an alkaline additive and a calcium additive in a certain ratio are uniformly mixed in a mixing and stirring bin, the mixing and stirring bin, a dry forming machine and a high-temperature reactor are sequentially communicated, the high-temperature reactor is communicated with a flue gas cooler and a digester, the digester is communicated with a solid-liquid separator, and the solid-liquid separator is respectively communicated with a sodium aluminate storage tank and a high-silicon high-calcium solid material storage bin. The reaction system adopts the principle of dry-method ternary roasting for treating secondary aluminum ash, combines the green efficient treatment of toxic components such as aluminum nitride, soluble fluoride salt and chloride salt in the secondary aluminum ash with the efficient extraction process of valuable aluminum elements in the secondary aluminum ash, adopts ternary dry-method forming roasting, and reacts all aluminum-containing components (aluminum oxide, aluminum nitride, metallic aluminum, magnesium aluminate spinel and the like) in the aluminum ash with alkaline additives to generate soluble sodium aluminate clinker. The recovery rate of the alumina and the sodium oxide is more than 95 percent, and the roasting energy consumption is reduced by more than 40 percent.
Description
Technical Field
The utility model relates to the technical field of harmless treatment and resource utilization of solid/hazardous waste, in particular to a reaction system for recycling aluminum oxide in aluminum-based hazardous waste.
Background
A large amount of aluminum-based dangerous solid wastes are generated in the processes of aluminum electrolysis production, casting, aluminum alloy production and processing and waste aluminum alloy regeneration, and the total amount of the aluminum-based dangerous solid wastes is up to more than 200 million tons every year in China. The organic fertilizer contains aluminum nitride, soluble fluorine chloride salt and other substances, can react with water at normal temperature to generate toxic gases such as ammonia gas and the like, and salt accumulated in soil can cause salinization, thereby causing serious threats to human health and ecological environment safety. Meanwhile, the aluminum-based dangerous solid waste contains abundant valuable aluminum resources, the aluminum element of the aluminum-based dangerous solid waste can reach 30-50%, and the aluminum-based dangerous solid waste has extremely high recovery value. But because of the lack of green and economic resource utilization technology, the aluminum-based dangerous solid waste is still mainly treated by adopting a stockpiling mode at present.
The patents with the grant publication numbers CN106747301A, CN109127654A and CN109052445A only focus on the extraction and recovery of aluminum element in aluminum ash, and do not consider the treatment and recycling of aluminum nitride, chloride and fluoride in aluminum ash, which is easy to cause secondary pollution in production.
Patent No. CN109928413A discloses mixing aluminum ash with sodium carbonate, sodium bicarbonate and sodium peroxide to form mixed sodium salt, and pressing into briquette; and drying the obtained agglomerates, sequentially placing the agglomerates in an air atmosphere at 300-500 ℃ for primary low-temperature roasting, placing the agglomerates in a strong oxidizing atmosphere at 700-875 ℃ for secondary high-temperature roasting, and leaching roasted products by using an alkaline solution to obtain a sodium aluminate solution. This method has the following drawbacks: (1) only by binary roasting of aluminum ash and sodium salt, impurity silicon element in the aluminum ash can be combined with aluminum element in the aluminum ash and sodium element in the sodium salt to generate water-insoluble sodium aluminosilicate which enters slag, so that the recovery rate of aluminum in the aluminum ash is only about 75%, the recovery rate of sodium in the sodium salt is only about 85%, and a great amount of valuable elements of aluminum and sodium are lost; (2) the treatment of a large amount of soluble fluoride salt and chloride salt in the aluminum ash is not considered, and the aluminum ash enters a sodium aluminate solution product after roasting and dissolving steps, so that the subsequent recycling of the sodium aluminate solution is influenced.
Patent No. CN105347361A discloses a comprehensive utilization and treatment method of aluminum ash, which comprises the steps of carrying out catalytic deamination on the aluminum ash, adding an additive, mixing and forming to obtain dispersed particles, then carrying out high-temperature drying and sintering, and finally dissolving out the particles in water to obtain a sodium aluminate solution and solid slag. The method has the defects that the aluminum ash needs to be treated by a wet denitrification step before sintering, a large amount of ammonia gas and fluoride-containing chloride wastewater are generated, the recovery of the ammonia gas has high requirement on the treatment quality of a factory, and the safe operation procedure is complex; the waste water evaporation crystallization and salt recovery are large in energy consumption and poor in economical efficiency.
Patent publication No. CN108640137A and CN208471557U disclose a method and a device for treating inert aluminum ash in an aluminum ash treatment process, wherein aluminum ash, alkali and lime milk are prepared into slurry and sprayed into a rotary kiln for sintering, and then the slurry is crushed by a mill and dissolved in a dissolution tank for dissolving clinker. Although the method can realize the recovery of the valuable aluminum element in the aluminum ash, the treatment that a large amount of toxic ammonia gas is released when aluminum nitride in the aluminum ash meets water is ignored, the serious threat to the environment and the health is caused, and meanwhile, the recovery of chloride in the aluminum ash is not considered, and the working condition is abnormal when the chloride enters a dissolution system.
SUMMERY OF THE UTILITY MODEL
The utility model provides a reaction system for recovering aluminum oxide in aluminum-based hazardous waste, and the existing system has the following problems that a pyrogenic process system only considers the utilization of the aluminum oxide in aluminum ash, other impurities are still left in a product, and the reaction system has high energy consumption and low product value; in the existing sintering method system, aluminum nitride in aluminum ash releases a large amount of toxic ammonia gas when meeting water in the process of preparing raw slurry, the energy consumption is high, and only the energy consumption required by evaporating water in the slurry accounts for 40 percent of the energy consumption in the whole sintering process; in a wet system, the recovery rate of aluminum is too low, and the recovery rates of aluminum under normal pressure and high pressure are only 34% and 55%, so that aluminum nitride in aluminum ash is hydrolyzed to generate a large amount of toxic ammonia gas and fluorine-containing chloride salt wastewater, and the recovery cost is increased.
To solve the above technical problem, an embodiment of the present invention provides the following solutions:
the embodiment of the utility model provides a reaction system for recovering aluminum oxide in aluminum-based hazardous waste, which comprises a mixing and stirring bin, wherein aluminum-based solid waste, an alkaline additive and a calcium additive in a certain ratio are uniformly mixed in the mixing and stirring bin, a dry-method forming machine and a high-temperature reactor are sequentially communicated, the uniformly mixed material enters the dry-method forming machine to form particles, the particles enter the high-temperature reactor to be roasted to generate flue gas and a roasted product, the high-temperature reactor is respectively communicated with a flue gas cooler and a digester, the flue gas enters the flue gas cooler to be condensed and recovered to obtain chloride crystals, the roasted product enters the digester to be leached out slurry, the digester is communicated with a solid-liquid separator, the slurry enters the solid-liquid separator to separate a sodium aluminate solution and filter residues, and the solid-liquid separator is respectively communicated with a sodium aluminate storage tank and a high-silicon high-calcium solid material storage bin, and the sodium aluminate solution enters the sodium aluminate storage tank for storage, and the filter residue enters the high-silicon high-calcium solid material storage bin.
Preferably, the aluminum-based solid waste, the alkaline additive and the calcium additive are accurately mixed according to the content of alumina, iron oxide, silicon oxide and soluble fluorine in the aluminum-based solid waste to obtain the aluminum-based solid waste, the alkaline additive and the calcium additive in a certain ratio.
Preferably, the reaction system further comprises an aluminum-based solid waste storage bin, an alkaline additive storage bin and a calcium additive storage bin which are communicated with the mixing and stirring bin, and the aluminum-based solid waste in the aluminum-based solid waste storage bin, the alkaline additive in the alkaline additive storage bin and the calcium additive in the calcium additive storage bin enter the mixing and stirring bin.
Preferably, the roasting reaction process of the particles in the high-temperature reactor comprises the following steps:
Al2O3+Na2O＝2NaAlO2；
2AlN+Na2O+1.5O2＝2NaAlO2+N2；
2Al+Na2O+1.5O2＝2NaAlO2；
Fe2O3+Na2O＝2NaFeO2；
MgAl2O4+Na2O＝MgO+2NaAlO2；
SiO2+2CaO＝Ca2SiO4；
2NaF+CaO＝CaF2+Na2O；
2KF+CaO＝CaF2+K2O。
preferably, the digestion process reaction of the roasted product in the digester comprises:
NaAlO2+2H2O＝NaAl(OH)4；
NaFeO2+2H2O＝NaOH+Fe(OH)3；
F-+Ca2+＝CaF2。
the scheme of the utility model at least comprises the following beneficial effects:
in the scheme, (1) the aluminum element in the aluminum ash mainly exists in a form of alpha-type alumina with stable property, is difficult to dissolve in acid and alkali, and is difficult to effectively extract by adopting a common wet method. The reaction system of the embodiment realizes the high-efficiency extraction of valuable elements in the secondary aluminum ash by the coupling high-temperature roasting of the alkaline additive and the calcareous additive with the secondary aluminum ash, the aluminum recovery rate of the roasted material is more than 95%, the sodium recovery rate is more than 96%, and compared with a wet process route (the recovery rate is 50% -70%), the recovery rate of the reaction system is obviously improved, the obtained sodium aluminate solution can be used for producing various aluminum oxides, and the high-value resource utilization of the secondary aluminum ash is realized;
(2) the reaction system of the embodiment directly utilizes dry-method molding, avoids the pretreatment steps of toxic ammonia gas release by hydrolysis of aluminum nitride in aluminum ash and washing for desalination, solves the problem of high energy consumption caused by feeding wet slurry into a furnace, does not bring water into the roasting process, reduces the energy consumption of the whole roasting process by more than 40 percent, and simultaneously reduces the bonding of dust and materials on a hearth; at high temperature, aluminum nitride is combined with an alkaline additive to be converted into sodium aluminate and nontoxic nitrogen, chloride is volatilized into a gas phase and is cooled and recovered, soluble fluoride and a calcareous additive are combined to generate water-insoluble calcium fluoride, so that high equipment and treatment cost of processes such as safe treatment of toxic gas ammonia gas and evaporation of salt-containing wastewater are saved, green and efficient treatment of harmful components in secondary aluminum ash is realized, the removal rate of aluminum nitride is more than 99%, the removal rate of soluble fluorine is more than 98%, and the removal rate of chloride is more than 96%;
(3) the silicon oxide in the aluminum ash reacts with the calcareous additive to generate high-activity dicalcium silicate, so that loss caused by combination of the silicon oxide with valuable elements such as aluminum and sodium is avoided, and meanwhile, the obtained high-silicon high-calcium solid material can be used as a calcareous raw material for producing cement; no three wastes are generated in the recovery process of the secondary aluminum ash, and the low-cost full-component green comprehensive resource recycling of the secondary aluminum ash is realized.
Drawings
FIG. 1 is a schematic diagram of a reaction system for recovering alumina in aluminum-based hazardous waste according to the present invention.
Reference numerals:
1. storing the aluminum-based solid waste in a bin; 2. storing the alkaline additive in a warehouse; 3. a calcareous additive storage bin; 4. a mixing and stirring bin; 5. a dry-method forming machine; 6. a high temperature reactor; 7. a flue gas cooler; 8. a digester; 9. a solid-liquid separator; 10. a sodium aluminate storage tank; 11. high-silicon high-calcium solid material storage bin.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
As shown in fig. 1, the present embodiment provides a reaction system for recovering aluminum oxide from aluminum-based hazardous waste, the reaction system adopts a principle of dry-method ternary roasting to treat secondary aluminum ash, so as to combine the green efficient treatment of toxic components such as aluminum nitride, soluble fluoride salt and chloride salt in the secondary aluminum ash with the efficient extraction process of valuable aluminum elements in the secondary aluminum ash, and adopts ternary dry-method forming roasting to react all aluminum-containing components (aluminum oxide, aluminum nitride, metallic aluminum, magnesium aluminate spinel, etc.) in the aluminum ash with alkaline additives to generate soluble sodium aluminate clinker. The reaction system comprises a mixing and stirring bin 4, aluminum-based solid waste, an alkaline additive and a calcium additive in a certain ratio are uniformly mixed in the mixing and stirring bin 4, a dry forming machine 5 and a high-temperature reactor 6 are sequentially communicated, the uniformly mixed material enters the dry forming machine 5 to form particles, the particles enter the high-temperature reactor 6 to be roasted to generate flue gas and roasted products, the high-temperature reactor 6 is respectively communicated with a flue gas cooler 7 and a digester 8, the flue gas enters the flue gas cooler 7 to be condensed and recovered to obtain chloride crystals, the roasted products enter the digester 8 and are leached out of slurry, the digester 8 is communicated with a solid-liquid separator 9, the slurry enters the solid-liquid separator 9 to separate sodium aluminate solution and filter residue, the solid-liquid separator 9 is respectively communicated with a sodium aluminate storage tank 10 and a high-silicon high-calcium solid material storage bin 11, the sodium aluminate solution enters the sodium aluminate storage tank 10 to be stored, the filter residue enters a high-silicon high-calcium solid material storage bin 11.
The reaction system of the implementation has the following beneficial effects:
(1) the aluminum element in the aluminum ash mainly exists in a form of alpha-type alumina with stable property, is difficult to dissolve in acid and alkali, and is difficult to effectively extract by adopting a common wet method. The reaction system of the embodiment realizes the high-efficiency extraction of valuable elements in the secondary aluminum ash by the coupling high-temperature roasting of the alkaline additive and the calcareous additive with the secondary aluminum ash, the aluminum recovery rate of the roasted material is more than 95%, the sodium recovery rate is more than 96%, and compared with a wet process route (the recovery rate is 50% -70%), the recovery rate of the reaction system is obviously improved, the obtained sodium aluminate solution can be used for producing various aluminum oxides, and the high-value resource utilization of the secondary aluminum ash is realized;
(2) the reaction system of the embodiment directly utilizes dry-method molding, avoids the pretreatment steps of toxic ammonia gas release by hydrolysis of aluminum nitride in aluminum ash and washing for desalination, solves the problem of high energy consumption caused by feeding wet slurry into a furnace, does not bring water into the roasting process, reduces the energy consumption of the whole roasting process by more than 40 percent, and simultaneously reduces the bonding of dust and materials on a hearth; at high temperature, aluminum nitride is combined with an alkaline additive to be converted into sodium aluminate and nontoxic nitrogen, chloride is volatilized into a gas phase and is cooled and recovered, soluble fluoride and a calcareous additive are combined to generate water-insoluble calcium fluoride, so that high equipment and treatment cost of processes such as safe treatment of toxic gas ammonia gas and evaporation of salt-containing wastewater are saved, green and efficient treatment of harmful components in secondary aluminum ash is realized, the removal rate of aluminum nitride is more than 99%, the removal rate of soluble fluorine is more than 98%, and the removal rate of chloride is more than 96%;
(3) the silicon oxide in the aluminum ash reacts with the calcareous additive to generate high-activity dicalcium silicate, so that loss caused by combination of the silicon oxide with valuable elements such as aluminum and sodium is avoided, and meanwhile, the obtained high-silicon high-calcium solid material can be used as a calcareous raw material for producing cement; no three wastes are generated in the recovery process of the secondary aluminum ash, and the low-cost full-component green comprehensive resource recycling of the secondary aluminum ash is realized.
The aluminum-based solid waste, the alkaline additive and the calcium additive are accurately mixed according to the content of alumina, iron oxide, silicon oxide and soluble fluorine in the aluminum-based solid waste to obtain the aluminum-based solid waste, the alkaline additive and the calcium additive in a certain ratio. According to the formula, the aluminum-based solid waste, the alkaline additive and the calcium additive are accurately mixed according to the content of specific components in the aluminum-based solid waste, so that the high-efficiency extraction of valuable aluminum and sodium resources and the green detoxification of harmful aluminum nitride, chloride and soluble fluoride components in the valuable aluminum and sodium resources are realized.
The reaction system of the embodiment further comprises an aluminum-based solid waste storage bin 1, an alkaline additive storage bin 2 and a calcium additive storage bin 3 which are communicated with the mixing and stirring bin 4, wherein the aluminum-based solid waste in the aluminum-based solid waste storage bin 1, the alkaline additive in the alkaline additive storage bin 2 and the calcium additive in the calcium additive storage bin 3 enter the mixing and stirring bin 4.
The roasting reaction process of the particles in the high-temperature reactor 6 comprises the following steps:
Al2O3+Na2O＝2NaAlO2；
2AlN+Na2O+1.5O2＝2NaAlO2+N2；
2Al+Na2O+1.5O2＝2NaAlO2；
Fe2O3+Na2O＝2NaFeO2；
MgAl2O4+Na2O＝MgO+2NaAlO2；
SiO2+2CaO＝Ca2SiO4；
2NaF+CaO＝CaF2+Na2O；
2KF+CaO＝CaF2+K2O。
the reaction of the roasted product in the digestion process in the digester 8 comprises the following steps:
NaAlO2+2H2O＝NaAl(OH)4；
NaFeO2+2H2O＝NaOH+Fe(OH)3；
F-+Ca2+＝CaF2。
the application process of the reaction system for recovering the alumina in the aluminum-based hazardous waste comprises the following steps:
the aluminum-based solid waste in the aluminum-based solid waste storage bin 1, the alkaline additive in the alkaline additive storage bin 2 and the calcium additive in the calcium additive storage bin 3 enter a mixing and stirring bin 4 according to a certain proportion to be mixed uniformly, the mixture is sent to a dry forming machine 5 to form particles, the particles enter a high-temperature reactor 6 to be roasted to generate flue gas and roasted products, the flue gas enters a cooler to be recycled to obtain chloride crystals, the chloride crystals can be used as a refining agent, the roasted products enter a digester 8 to dissolve out slurry, the slurry enters a solid-liquid separator 9 to be subjected to solid-liquid separation to obtain sodium aluminate solution and filter residues, the sodium aluminate solution enters a sodium aluminate storage tank 10 to be stored, the sodium aluminate solution is used for seed crystal decomposition to prepare various aluminum oxides, the filter residues enter a high-silicon high-calcium solid material storage bin 11 to be stored, and the filter residues are used as raw materials for preparing cement.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the utility model as defined in the appended claims.
Claims (2)
1. A reaction system for recovering aluminum oxide in aluminum-based hazardous waste is characterized by comprising a mixing and stirring bin, wherein the mixing and stirring bin, a dry forming machine and a high-temperature reactor are sequentially communicated, uniformly mixed materials enter the dry forming machine to form particles, the particles enter the high-temperature reactor to be roasted to generate flue gas and roasted products, the high-temperature reactor is respectively communicated with a flue gas cooler and a stripper, the flue gas enters the flue gas cooler to be condensed and recovered to obtain chloride crystals, the roasted products enter the stripper to strip slurry, the stripper is communicated with a solid-liquid separator, the slurry enters the solid-liquid separator to separate sodium aluminate solution and filter residue, the solid-liquid separator is respectively communicated with a storage bin for sodium aluminate and high-silicon high-calcium solid materials, and the sodium aluminate solution enters a sodium aluminate storage tank to be stored, and the filter residue enters the high-silicon high-calcium solid material storage bin.
2. The reaction system for recovering aluminum oxide in aluminum-based dangerous waste according to claim 1, further comprising an aluminum-based solid waste bin, an alkaline additive bin and a calcium additive bin which are communicated with the mixing and stirring bin, wherein the aluminum-based solid waste in the aluminum-based solid waste bin, the alkaline additive in the alkaline additive bin and the calcium additive in the calcium additive bin enter the mixing and stirring bin.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114888043A (en) * | 2022-05-17 | 2022-08-12 | 中铝山西新材料有限公司 | Method and device for treating secondary aluminum ash |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114888043A (en) * | 2022-05-17 | 2022-08-12 | 中铝山西新材料有限公司 | Method and device for treating secondary aluminum ash |
| CN114888043B (en) * | 2022-05-17 | 2024-02-06 | 中铝山西新材料有限公司 | Treatment method and device for secondary aluminum ash |
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