CN113802007B - Method and system for treating waste cathode of aluminum electrolysis cell - Google Patents

Method and system for treating waste cathode of aluminum electrolysis cell Download PDF

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CN113802007B
CN113802007B CN202111034638.3A CN202111034638A CN113802007B CN 113802007 B CN113802007 B CN 113802007B CN 202111034638 A CN202111034638 A CN 202111034638A CN 113802007 B CN113802007 B CN 113802007B
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flue gas
lead
dust
oxygen
zinc
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CN113802007A (en
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辛鹏飞
吴卫国
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China ENFI Engineering Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
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    • C22B13/00—Obtaining lead
    • C22B13/02—Obtaining lead by dry processes
    • C22B13/025—Recovery from waste materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/0028—Smelting or converting
    • C22B15/0052—Reduction smelting or converting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
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Abstract

The invention provides a treatment method and a treatment system for waste cathodes of an aluminum electrolysis cell. The waste cathode of the aluminum electrolysis cell comprises carbon and fluoride, and the treatment method comprises the following steps: sequentially melting and reducing smelting a mixture of a waste cathode of an aluminum electrolysis cell and a lead-zinc-containing material and oxygen to obtain lead metal, slag and dust-containing flue gas, wherein the dust-containing flue gas comprises smoke dust containing lead oxide and zinc oxide and fluorine-containing flue gas; removing fluorine elements in the dust-containing flue gas to obtain defluorinated flue gas; the weight ratio of the waste cathode of the aluminum electrolysis cell to the lead and zinc in the lead and zinc containing material is (8-35) (10-60), the temperature of the melting process and the reduction smelting process is 1100-1350 ℃, and the oxygen ventilation amount in the melting process is 80-100 Nm 3 The oxygen gas is introduced into the reduction smelting process at a rate of 12.5-30 Nm per ton of the mixture 3 Per ton of mixture. The method can realize the cooperative treatment of the waste cathode of the aluminum electrolysis cell and the industrial hazardous waste containing lead and zinc.

Description

Method and system for treating waste cathode of aluminum electrolysis cell
Technical Field
The invention relates to the field of recovery of waste cathodes of aluminum electrolysis cells, in particular to a treatment method and a treatment system of waste cathodes of aluminum electrolysis cells.
Background
A large number of waste cathodes are generated in the aluminum electrolysis process, and because the cathodes are permeated with electrolyte such as sodium fluoride in the use process, the waste cathodes contain a large number of fluoride, and meanwhile, the cathodes can generate substances such as NaCN in the use process. F in waste cathode leaching liquid - And CN - The content exceeds the requirements of national related emission standards of dangerous wastes. In this standard, aluminum electrolytic solid waste is classified into HW32 inorganic fluoride waste, HW07 heat-treated cyanide-containing waste, and HW33 inorganic cyanide waste.
The waste cathode comprises carbon and electrolyte, belongs to dangerous waste, and therefore, has to be subjected to harmless treatment. The current waste cathode treatment methods can be divided into four types: landfill stacking, physical separation, chemical leaching and high-temperature heat treatment. The physical separation method mainly comprises a floatation method; the chemical leaching method comprises an acid-base leaching method, an ultrasonic wave and pressure leaching method and the like. The high-temperature heat treatment method comprises a high-temperature hydrolysis method, a rotary kiln roasting treatment process and the like.
The flotation method is low in cost for separating the waste cathode, but the flow is long, and dust secondary pollution is generated in the material preparation process. The chemical leaching method has complex process flow, large investment and less industrial application at present.
The prior art provides a harmless treatment method of an aluminum electrolysis cell waste cell liner, which comprises the steps of crushing the cell liner comprising cathode carbon blocks and the like, adding a mixture of limestone and silicon dioxide into the crushed material, and roasting the mixture in a rotary kiln at the roasting temperature of 650-1000 ℃ to obtain solid slag meeting the common solid waste requirement. Although the waste cathode is calcined by the rotary kiln to realize harmless treatment, the produced slag is highly alkaline, which can improve the leachability of residual fluoride and cyanide. Meanwhile, the waste cathode is calcined by adopting a rotary kiln calcination method, and carbon in the waste cathode is only used as fuel, so that the strong reduction characteristic of the waste cathode cannot be fully exerted.
Based on the above problems, it is necessary to provide a new harmless treatment method for the waste cathode.
Disclosure of Invention
The invention mainly aims to provide a treatment method and a treatment system for waste cathodes of an aluminum electrolysis cell, which are used for solving the problems of lower recovery rate and complex process flow of the existing treatment method for waste cathodes of the aluminum electrolysis cell.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for treating an aluminum electrolysis cell waste cathode containing carbon and fluoride, the method comprising: sequentially melting and reducing smelting a mixture of a waste cathode of an aluminum electrolysis cell and a lead-zinc-containing material and oxygen to obtain lead metal, slag and dust-containing flue gas, wherein the dust-containing flue gas comprises smoke dust containing lead oxide and zinc oxide and fluorine-containing flue gas; removing fluorine elements in the dust-containing flue gas to obtain defluorinated flue gas; wherein the weight ratio of the waste cathode of the aluminum electrolysis cell to the lead and zinc in the lead and zinc containing material is (8 to the upper part)35 10-60%, the temperature of the melting process and the reduction smelting process is 1100-1350 ℃, and the oxygen inlet amount in the melting process is 80-100 Nm 3 The oxygen gas is introduced into the reduction smelting process at a rate of 12.5-30 Nm per ton of the mixture 3 Per ton of mixture.
Further, the process for removing fluorine in the dust-containing flue gas comprises the following steps: reacting fluorine-containing flue gas in the dust-containing flue gas with lead-zinc-containing flue gas at 150-200 ℃ to obtain primary defluorinated flue gas and flue gas containing lead fluoride and zinc fluoride; reacting the primary defluorinated flue gas with a defluorinating agent to obtain defluorinated flue gas; preferably, the fluorine scavenger is selected from one or more of the group consisting of alumina, calcia and silica.
Further, the weight ratio of the waste cathode of the aluminum electrolysis cell to lead and zinc in the lead-zinc-copper-containing material is (15-20): (50-60) and the temperature of the melting process and the reduction smelting process is 1150-1250 ℃.
Further, the treatment method of the waste cathode of the aluminum electrolysis cell further comprises the following steps: and adding a calcium-containing flux in the reduction smelting process, and enabling the calcium-containing flux to undergo a solidification reaction with residual fluoride which is not decomposed to obtain calcium fluoride.
Further, the calcium-containing flux is selected from one or more of the group consisting of limestone, calcium oxide and calcium carbonate,
preferably, the addition amount of the calcium-containing flux is 8-20wt% based on the total weight of the aluminum electrolysis cell waste cathode, the lead-zinc-containing material and the calcium-containing flux.
Further, molten liquid is generated through a melting process and a reduction smelting process, oxygen is blown into the molten liquid below the liquid level of the molten liquid by adopting at least one spray gun, and an included angle between each spray gun and the liquid level of the molten liquid is-15-90 degrees.
Further, before the melting process, the treatment method of the aluminum electrolysis cell waste cathode further comprises granulating the mixture, preferably, the granularity of the granules prepared in the granulating process is 5-30 mm, and in the granules, the granules with granularity of 8-20 mm account for more than 85% of the total weight of the granules, and the granules with granularity of 20-30 mm account for less than or equal to 15% of the total weight of the granules.
Further, the treatment method of the waste cathode of the aluminum electrolysis cell further comprises the following steps: and carrying out desulfurization treatment on the defluorinated flue gas to obtain purified flue gas.
Further, the lead-zinc-containing material further contains copper element, preferably, the weight percentage of the lead element in the lead-zinc-containing material is less than or equal to 20wt%, the weight percentage of the zinc element is less than or equal to 5wt%, and the weight percentage of the copper element is less than or equal to 5wt%, based on the weight of the lead-zinc-containing material.
In another aspect, the present application further provides a treatment system for a waste cathode of an aluminum electrolysis cell, where the treatment system for a waste cathode of an aluminum electrolysis cell includes: a molten pool smelting unit and a defluorination unit. A molten pool, an oxygen inlet, a dust-containing flue gas outlet, a metal outlet and a slag discharge port are arranged in the molten pool smelting unit, and the feed inlet is used for adding waste cathodes of the aluminum electrolysis cell and lead-zinc-containing materials; the defluorination unit is provided with a dust-containing flue gas inlet which is communicated with the dust-containing flue gas outlet through a dust-containing flue gas conveying pipeline, and is used for removing fluorine elements in the dust-containing flue gas.
Further, the bath smelting unit includes: a bath smelting device, at least one spray gun, an oxygen supply device and an oxygen flow control device. The molten pool smelting device is provided with a charging port, an oxygen inlet, a dust-containing flue gas outlet, a metal outlet and a slag discharging port; each spray gun is immersed below the liquid level of the molten pool, and oxygen is sprayed into the molten pool; oxygen supply means for supplying oxygen into each lance; the oxygen flow control device is used for controlling the flow of oxygen in each spray gun.
Further, the bath smelting unit includes: the device comprises a molten pool smelting device, at least one spray gun, an oxygen supply device, a nitrogen supply device and a gas composition regulating device, wherein the molten pool smelting device is provided with a feed inlet, an oxygen inlet, a dust-containing flue gas outlet, a metal outlet and a slag discharge port; each spray gun is immersed below the liquid level of the molten pool, and oxygen is sprayed into the molten pool; oxygen supply means for supplying oxygen into each lance; the nitrogen supply device is used for supplying nitrogen into each spray gun; the gas composition adjusting device is respectively and electrically connected with the oxygen supply device and the nitrogen supply device so as to control the oxygen content sprayed by each spray gun.
Further, the included angle between each spray gun and the liquid level in the molten pool is-15-90 degrees.
Further, each lance is disposed at a side or bottom of the bath smelting device.
Further, the treatment system of the waste cathode of the aluminum electrolysis cell further comprises a mixing granulation device, wherein the mixing granulation device is provided with a raw material inlet and a mixing granule outlet, and the mixing granule outlet is communicated with the charging port.
Further, the treatment system of the waste cathode of the aluminum electrolysis cell further comprises a waste heat recovery device which is communicated with the dust-containing flue gas conveying pipeline and is used for recovering heat in the dust-containing flue gas.
Further, the defluorination unit comprises a dry defluorination device, wherein the dry defluorination device is provided with a defluorination agent inlet, a dust-containing flue gas inlet, a first defluorination flue gas outlet and a first defluorination flue gas outlet, and the dust-containing flue gas inlet is communicated with the dust-containing flue gas outlet through a dust-containing flue gas conveying pipeline.
Further, the defluorination unit further comprises an electric dust removing device which is arranged on the dust-containing flue gas conveying pipeline between the waste heat recovery device and the dust-containing flue gas inlet, and the electric dust removing device is provided with a second defluorination flue gas outlet and a second defluorination flue gas outlet.
Further, the treatment system of the waste cathode of the aluminum electrolysis cell further comprises a flue gas purification device, wherein the flue gas purification device is provided with a desulfurizing agent inlet and a gas inlet to be purified, and the gas inlet to be purified is communicated with a first defluorinated flue gas outlet and is used for desulfurizing the first defluorinated flue gas.
By applying the technical scheme of the invention, the method provided by the application is used for treating the waste cathode of the aluminum electrolysis cell, so that the combustion heat release property and the reducibility of carbon in the waste cathode can be simultaneously utilized, and the cooperative treatment of the industrial hazardous waste containing lead and zinc is realized. The reaction generated by industrial hazardous waste in the treatment process can consume heat generated by the combustion of the waste cathode, so that the heat balance of a molten pool is stable when a large amount of waste cathodes are treated, overheating does not occur, and the treatment capacity of the waste cathodes is improved. In addition, the process flow is shortened, and the environmental protection of the treatment system is improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
fig. 1 shows a process flow chart of a treatment method of a waste cathode provided in embodiment 1 of the present invention; and
FIG. 2 shows a schematic diagram of a disposal system for spent cathodes according to an exemplary embodiment of the invention;
fig. 3 is a schematic structural view showing a disposal system for a spent cathode according to a preferred embodiment of the present invention.
Wherein the above figures include the following reference numerals:
10. a molten pool smelting unit; 11. a molten pool smelting device; 101. a feed inlet; 102. a dust-laden flue gas outlet; 12. a spray gun; 13. an oxygen supply device; 14. an oxygen flow control device; 15. nitrogen supply means; 16. a gas composition regulating device; 17. a water supply device; 18. a calcium-containing flux supply device;
20. a defluorination unit; 201. a dust-laden flue gas inlet; 21. a dry defluorination device; 22. an electric dust removing device;
30. a mixing granulation device; 301. a mixed pellet outlet; 40. a waste heat recovery device; 50. a flue gas purifying device.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As described in the background art, the existing aluminum electrolysis waste cathode treatment method has the defects of low recovery rate and complex process flow. In view of the foregoing technical problems, in an exemplary embodiment of the present application, a method for treating a waste cathode of an aluminum electrolysis cell is provided, as shown in fig. 1, where the waste cathode of the aluminum electrolysis cell contains carbon and fluoride, and the waste cathode of the aluminum electrolysis cellThe method for treating the old cathode comprises the following steps: sequentially melting and reducing smelting a mixture of a waste cathode of an aluminum electrolysis cell and a lead-zinc-containing material and oxygen to obtain lead metal, slag and dust-containing flue gas, wherein the dust-containing flue gas comprises smoke dust containing lead oxide and zinc oxide and fluorine-containing flue gas; removing fluorine elements in the dust-containing flue gas to obtain defluorinated flue gas; wherein the weight ratio of the waste cathode of the aluminum electrolysis cell to lead and zinc in the lead and zinc containing material is (8-35) (10-60), the temperature of the melting process and the reduction smelting process is 1100-1350 ℃, and the oxygen ventilation amount in the melting process is 80-100 Nm 3 The oxygen gas is introduced into the reduction smelting process at a rate of 12.5-30 Nm per ton of the mixture 3 Per ton of mixture.
In the smelting process of a molten pool, lead-zinc-containing materials (for example, lead-zinc-containing industrial hazardous wastes or lead-zinc-containing industrial hazardous wastes) are melted to form a melt, and carbon in a waste cathode of the aluminum electrolysis cell is completely combusted in the molten pool, so that more heat is provided for smelting; cyanide in the waste cathode is smelted and decomposed, so that harmless treatment is realized; and meanwhile, fluoride in the waste cathode is decomposed to form fluorine-containing flue gas which enters the flue gas. And then, reducing the oxygen inlet amount, and incompletely burning the carbon in the waste cathode in a molten pool to form a reducing atmosphere, wherein lead elements and zinc elements in the lead-zinc-copper-containing material are reduced into partial elemental lead and elemental zinc in the reducing atmosphere, and then, the partial elemental lead and elemental zinc enter smoke to undergo an oxidation reaction to obtain smoke dust containing lead oxide and zinc oxide. And meanwhile, removing fluorine elements in the dust-containing flue gas to obtain defluorinated flue gas. The weight ratio of the waste cathode of the aluminum electrolysis cell to lead and zinc in the lead and zinc containing material, the reduction temperature, the oxygen inlet amount in the melting process and the oxygen inlet amount in the reduction process are limited in the ranges, so that the treatment efficiency of the waste cathode is further improved.
In summary, the method provided by the application is used for treating the waste cathode of the aluminum electrolysis cell, so that the combustion heat release property and the reducibility of carbon in the waste cathode can be simultaneously utilized, and the cooperative treatment of the industrial hazardous waste containing lead and zinc is realized. The reaction generated by industrial hazardous waste in the treatment process can consume heat generated by the combustion of the waste cathode, so that the heat balance of a molten pool is stable when a large amount of waste cathodes are treated, overheating does not occur, and the treatment capacity of the waste cathodes is improved; in addition, the process flow is shortened, and the environmental protection of the treatment system is improved.
In a preferred embodiment, in the smelting process, when oxygen is directly introduced, the oxygen content can be used for controlling the smelting atmosphere by adjusting the introduced amount of the oxygen; when the mixed gas of oxygen and other inert atmospheres (such as nitrogen) is introduced, the smelting atmosphere can be controlled by adjusting the weight ratio of oxygen to nitrogen.
In the treatment method provided by the application, the fluorine element in the fluorine-containing flue gas can be removed by adopting a method commonly used in the field. In a preferred embodiment, the process for removing fluorine from the dusty flue gas comprises: reacting fluorine-containing flue gas in the dust-containing flue gas with lead-zinc-containing flue gas at 150-200 ℃ to obtain primary defluorinated flue gas and flue gas containing lead fluoride and zinc fluoride; and reacting the primary defluorinated flue gas with a defluorinating agent to obtain the defluorinated flue gas. In the removal method, the fluorine-containing flue gas and the lead-zinc-containing flue dust are reacted to realize preliminary defluorination, and then the preliminary defluorination flue gas obtained through the preliminary defluorination step is reacted with the defluorination agent, so that the defluorination process can be realized to a deeper degree. Therefore, the two-stage defluorination treatment can improve the removal rate of fluorine element and the environmental protection of the treatment method.
Preferably, the preliminary defluorination process is performed in an electric dust collector. After the fluorine-containing flue gas reacts with the lead-zinc-containing flue gas, the obtained flue gas containing lead fluoride and zinc fluoride can be subjected to dust removal treatment on primary defluorinated flue gas while removing fluorine elements in an electric dust removal device. The fluorine removing agent used in the second defluorination process may be of a kind commonly used in the art. Preferably, the fluorine scavenger includes, but is not limited to, one or more of the group consisting of alumina, calcia, and silica. The fluorine removing agents have low price and better combination property with fluorine, so that the fluorine removing agents are selected as the fluorine removing agents, thereby being beneficial to further improving the defluorination effect and reducing the process cost.
In the treatment process, the carbon in the waste cathode is required to be used as reductionThe agent reduces the metal elements in the lead-zinc-copper-containing material, so that in order to further improve the synergistic smelting effect of the waste cathode of the aluminum electrolysis cell and the lead-zinc-copper-containing material, preferably, the weight ratio of the waste cathode of the aluminum electrolysis cell to the lead-zinc in the lead-zinc-copper-containing material is (15-20): (50-60); the temperature of the melting process and the reduction smelting process is 1150-1250 ℃. Optionally, the weight ratio of the waste cathode of the aluminum electrolysis cell to lead and zinc in the lead-zinc-copper-containing material is 8:51, 8:58, 12:51, 15:50, 20:60 or 35:10; the temperature of the melting process and the reduction smelting process is 1100 ℃, 1150 ℃, 1250 ℃ or 1350 ℃; the oxygen inlet amount in the melting process was 80Nm 3 90Nm per ton of mixture 3 Per ton of mixture or 100Nm 3 Oxygen was introduced at a rate of 12.5Nm per ton of the mixture during the reduction smelting 3 Per ton of mixture, 20Nm 3 Per ton of mixture or 30Nm 3 Per ton of mixture.
In a preferred embodiment, the method for treating the waste cathode of the aluminum electrolysis cell further comprises the following steps: and adding a calcium-containing flux in the reduction smelting process, and enabling the calcium-containing flux to undergo a solidification reaction with residual fluoride which is not decomposed to obtain calcium fluoride. The addition of the calcium-containing flux can greatly reduce the smelting temperature, and the calcium-containing flux can form insoluble matters from undegraded residual fluoride or other impurities, so that the defluorination efficiency is reduced, and the purity of lead metal is improved. Optionally, the calcium-containing flux is added in an amount of 1, 5, 8, 10, 15, 20wt% based on the total weight of the aluminum electrolysis cell waste cathode, the lead-zinc-containing material and the calcium-containing flux. Preferably, the calcium-containing flux includes, but is not limited to, one or more of the group consisting of limestone, calcium oxide, and calcium carbonate; based on the total weight of the waste cathode of the aluminum electrolysis cell, the lead-zinc containing material and the calcium-containing flux, the addition amount of the calcium-containing flux is 8-20wt%.
In a preferred embodiment, the melt is produced by a melting process and a reduction smelting process, oxygen is blown into the melt below the surface of the melt by at least one lance, and the angle between each lance and the surface of the melt is-15 to 90 degrees. Blowing oxygen into the lance at a specific angle below the level of the melt can form strong agitation to the melt produced in the smelting process, which is advantageous for further improving the smelting effect and the slag discharge efficiency. The contact time of oxygen and the molten liquid can be adjusted by adjusting the included angle between the spray gun and the liquid level of the molten liquid, thereby being beneficial to improving the smelting effect. Alternatively, the angle between each lance and the level of the melt may be-15, 30 °, 45 °, 60 ° and 90 °.
In a preferred embodiment, the above-described process further comprises granulating the mixture prior to performing the melting process. Before smelting, the raw materials are granulated, so that dust pollution caused by raw material powder in the smelting process can be avoided, and the waste cathode of the aluminum electrolysis cell and the lead-zinc-containing material in the smelting process can be ensured to be cooperatively smelted according to a specific proportion. More preferably, the granules produced by the granulation process have a particle size of 5mm to 30mm, and in the granules, the granules having a particle size of 8 to 20mm account for > 85% of the total weight of the granules, and the granules having a particle size of 20 to 30mm account for less than or equal to 15% of the total weight of the granules. The adoption of the granulating process for treating the raw materials is beneficial to further improving the environmental protection of the process, and is beneficial to further improving the synergistic smelting effect of two materials and improving the smelting efficiency and the recovery rate of metal elements.
In order to further improve the environmental protection property of the defluorinated flue gas, preferably, the treatment method of the waste cathode of the aluminum electrolysis cell further comprises the following steps: and carrying out desulfurization treatment on the defluorinated flue gas to obtain purified flue gas.
In a preferred embodiment, the lead-zinc-containing material further comprises copper element, preferably, the lead element in the lead-zinc-containing material is less than or equal to 20wt%, the zinc element is less than or equal to 5wt% and the copper element is less than or equal to 5wt% based on the weight of the lead-zinc-containing material.
In another aspect, the present application further provides a treatment system for a waste cathode of an aluminum electrolysis cell, as shown in fig. 2 and 3, where the treatment system includes: a bath smelting unit 10 and a defluorination unit 20. A molten pool, an oxygen inlet, a dust-containing flue gas outlet 102, a metal outlet and a slag discharge port are arranged in the molten pool smelting unit 10, wherein the feed inlet 101 is communicated with a flue gas zone of the molten pool, and the feed inlet 101 is used for adding an aluminum electrolysis cell waste cathode and lead-zinc containing materials; the defluorination unit 20 is provided with a dust-containing flue gas inlet 201, the dust-containing flue gas inlet 201 is communicated with the dust-containing flue gas outlet 102 through a dust-containing flue gas conveying pipeline, and the defluorination unit 20 is used for removing fluorine elements in dust-containing flue gas.
In the bath smelting unit 10, lead-zinc-containing materials (for example, lead-zinc-containing industrial hazardous waste or lead-zinc-containing industrial hazardous waste) are melted to form a melt, and carbon in the waste cathode of the aluminum electrolysis cell is completely combusted in the bath, so that more heat is provided for smelting; cyanide in the waste cathode is smelted and decomposed, so that harmless treatment is realized; and meanwhile, fluoride in the waste cathode is decomposed to form fluorine-containing flue gas which enters the flue gas. And then, reducing the oxygen inlet amount, and incompletely burning the carbon in the waste cathode in a molten pool to form a reducing atmosphere, wherein lead elements and zinc elements in the lead-zinc-copper-containing material are reduced into partial simple substance lead steam and simple substance zinc steam under the reducing atmosphere, and then, the partial simple substance lead steam and the simple substance zinc steam enter smoke to undergo an oxidation reaction, so that smoke dust containing lead oxide and zinc oxide is obtained. Finally, removing fluorine elements in the dust-containing flue gas in a defluorination device to obtain defluorination flue gas, thereby improving the environmental protection of the whole treatment system of the waste cathode of the aluminum electrolysis cell.
In summary, the treatment device provided by the application is used for treating the waste cathode of the aluminum electrolysis cell, so that the combustion heat release property and the reducibility of carbon in the waste cathode can be simultaneously utilized, and the synergistic treatment of hazardous wastes in the lead-zinc-containing industry is realized. The reaction generated by industrial hazardous waste in the treatment process can consume heat generated by the combustion of the waste cathode, so that the heat balance of a molten pool is stable when a large amount of waste cathodes are treated, overheating does not occur, and the treatment capacity of the waste cathodes is improved; in addition, the process flow is shortened, and the environmental protection of the treatment system is improved.
In a preferred embodiment, as shown in fig. 2, the treatment system of the waste cathode of the aluminum electrolysis cell further comprises: a bath smelting device 11, at least one lance 12, an oxygen supply device 13 and an oxygen flow control device 14. The melting bath smelting device 11 is provided with the charging port 101, an oxygen inlet, a dust-containing flue gas outlet 102, a metal outlet and a slag discharging port; each lance 12 is submerged below the level of the bath and injects oxygen into the bath; oxygen supply means 13 for supplying oxygen into each lance 12; oxygen flow control device 14 is used to control the flow of oxygen in each lance 12. Blowing oxygen into lance 12 at a specific angle below the level of the melt can create a strong agitation of the melt produced by the smelting process, which is advantageous for further improving the smelting result and slag discharge efficiency. The oxygen flow control device 14 controls the oxygen flow, and thus the reaction atmosphere in the bath smelting device 11.
In another preferred embodiment, as shown in fig. 3, the treatment system of the waste cathode of the aluminum electrolysis cell further comprises: a bath smelting unit 11, at least one lance 12, an oxygen supply unit 13, a nitrogen supply unit 15 and a gas composition regulating unit 16. The melting bath smelting device 11 is provided with the charging port 101, an oxygen inlet, a dust-containing flue gas outlet 102, a metal outlet and a slag discharging port; each lance 12 is submerged below the level of the bath and injects oxygen into the bath; oxygen supply means 13 for supplying oxygen into each lance 12; nitrogen gas supply means 15 for supplying nitrogen gas into each of the lances 12; the gas composition adjusting device 16 is electrically connected with the oxygen supply device 13 and the nitrogen supply device 15 respectively to control the oxygen content sprayed by each spray gun 12. Blowing oxygen into lance 12 at a specific angle below the level of the melt can create a strong agitation of the melt produced by the smelting process, which is advantageous for further improving the smelting result and slag discharge efficiency. The nitrogen gas supply device 15 and the gas composition adjusting device 16 are arranged to control the oxygen gas inlet amount, thereby controlling the reaction atmosphere in the molten pool smelting device 11.
In a preferred embodiment, the angle between each lance 12 and the level of the bath is-15 to 90. Limiting the angle between each lance 12 and the level of liquid in the bath within the above-described range is advantageous in increasing the range and depth of agitation of the bath smelting device 11 by the lances 12, thereby further increasing smelting efficiency.
In a preferred embodiment, each lance 12 is positioned at the side or bottom of bath smelting device 11. Compared with the arrangement of the spray gun 12 at the top of the molten pool smelting device 11, the arrangement of the spray gun 12 at the side and the bottom of the molten pool smelting device 11 can enable the molten pool smelting device to perform a reduction smelting process to a deeper degree, thereby being beneficial to further improving the recovery rate of metal elements and the treatment efficiency of the waste cathode of the aluminum electrolysis cell.
In a preferred embodiment, as shown in fig. 2 and 3, the treatment system of the waste cathode of the aluminium electrolysis cell further comprises a mixing granulation device 30, the mixing granulation device 30 being provided with a raw material inlet and a mixing granule outlet 301, the mixing granule outlet 301 being in communication with the feed inlet 101. Before smelting, the reaction raw materials are granulated in the mixing granulating device 30, so that dust pollution caused by raw material powder in the smelting process can be avoided, and the waste cathode of the aluminum electrolysis cell and the lead-zinc-containing material in the smelting process can be ensured to be cooperatively smelted according to a specific proportion.
In order to further reduce the heat energy loss of the above treatment system, as shown in fig. 2 and 3, preferably, the treatment system for the waste cathode of the aluminum electrolysis cell further comprises a waste heat recovery device 40, and the waste heat recovery device 40 is communicated with the dust-containing flue gas conveying pipeline and is used for recovering heat in the dust-containing flue gas.
The defluorination unit 20 may be any device commonly used in the art that can perform the function of removing fluorine in flue gas, and its structure is not particularly limited. As shown in fig. 2 and 3, in a preferred embodiment, the defluorination unit 20 includes a dry defluorination device 21, and the dry defluorination device 21 is provided with a defluorination agent inlet, a dust-containing flue gas inlet 201, a first defluorination flue gas outlet and a first defluorination flue gas outlet, wherein the dust-containing flue gas inlet 201 is communicated with the dust-containing flue gas outlet 102 through a dust-containing flue gas conveying pipeline. In the dry defluorination device 21, the fluorine-containing flue gas and the lead-zinc-containing flue dust can react with the defluorination agent, and a deep defluorination process can be realized, so that the tail gas purification degree is further improved.
In order to further increase the defluorination efficiency, as shown in fig. 2 and 3, the dust content in the defluorinated flue gas is reduced. Preferably, the defluorination unit 20 further comprises an electric dust collector 22, the electric dust collector 22 is arranged on the dust-containing flue gas conveying pipeline between the waste heat recovery device 40 and the dust-containing flue gas inlet 201, and the electric dust collector 22 is provided with a second defluorination flue gas outlet and a second defluorination flue gas outlet.
In order to further improve the environmental protection property of the defluorinated flue gas, preferably, as shown in fig. 2 and 3, the treatment system of the waste cathode of the aluminum electrolysis cell further comprises a flue gas purifying device 50, wherein the flue gas purifying device 50 is provided with a desulfurizing agent inlet and a gas inlet to be purified, and the gas inlet to be purified is communicated with the first defluorinated flue gas outlet and is used for desulfurizing the first defluorinated flue gas.
In a preferred embodiment, as shown in figures 2 and 3, the above-mentioned treatment system for the spent cathodes of aluminium electrolysis cells also comprises a water supply means 17, which water supply means 17 is provided with a water supply port, which water supply port communicates with a feed port 101 for feeding water into the bath smelting means 11. The addition of a quantity of water to the bath smelting unit 11 enables it to form water gas, thereby facilitating further improvement of the efficiency of reduction smelting.
In a preferred embodiment, as shown in fig. 2 and 3, the above-mentioned treatment system for aluminum electrolysis cell waste cathodes further comprises a calcium-containing flux supply device 18, wherein the calcium-containing flux supply device 18 is provided with a calcium-containing flux supply port, which is in communication with the feed port 101 for feeding the calcium-containing flux into the bath smelting device 11. The addition of the calcium-containing flux can greatly reduce the smelting temperature, and the calcium-containing flux can form insoluble matters from undegraded residual fluoride or other impurities, so that the defluorination efficiency is improved, and the purity of lead metal is improved.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
The composition of the spent graphite cathode in the examples is shown in Table 1.
TABLE 1
Composition of the components C Na 2 O Al 2 O 3 CaO F
Content by weight percent 55 15 11 1.23 11
The composition of the lead zinc copper hazardous waste is shown in table 2.
TABLE 2
Composition of the components Pb Zn Cu Fe SiO 2
Content by weight percent 70 5 1 8 6
The process flow is shown in fig. 1.
The waste graphite cathode, flux (CaO) and lead, zinc and copper containing hazardous waste which are crushed preliminarily are mixed according to a ratio of 10:5:85 (wherein the weight ratio of the waste graphite cathode to lead and zinc in the lead-zinc-copper-containing hazardous waste is 8:51) to obtain a mixed material; and then granulating. The particle size requirements are shown in Table 3.
TABLE 3 Table 3
Particle size 5mm～30mm 8～20mm 20～30mm
Proportion, percent 100 ＞85 ≤15
Adding the mixed and granulated granules into a molten pool smelting device 11 (side-blown molten pool smelting furnace), wherein the feeding amount is 50t/h, supplementing oxygen into a molten pool through a submerged oxygen lance, and controlling the oxygen lance to have an angle of 90 degrees with the liquid level of the molten pool and the pressure of 0.3MPa, wherein the temperature of the molten pool is 1100 ℃; the carbon part in the waste cathode is used as fuel to provide heat for the molten pool reaction, and is also used as a reducing agent to provide a reducing atmosphere for the molten pool. The molten pool reaction is divided into a melting period, a reduction period and a discharge periodSlag three-stage operation, wherein the bubbling amount of oxygen in the three stages is 4500Nm respectively 3 /h，1500Nm 3 /h,1000Nm 3 And/h. And obtaining dust-containing flue gas, high-copper lead bullion metal alloy and slag.
The flue gas produced by the waste heat boiler enters an electric dust collection system, the outlet temperature of the electric dust collector is 180 ℃, znO, pbO and fluorine-containing flue gas in the flue gas react in electric dust collection, 10-15% of fluorine in the flue gas is removed, and primary defluorinated flue gas and defluorinating agent (Al) are obtained 2 O 3 Excessive) carrying out dry defluorination to obtain defluorinated flue gas; and finally, carrying out desulfurization treatment on the defluorinated flue gas to obtain purified tail gas.
In the metal phase, the content of lead element was 95.0%, and the recovery rate was 97.0%.
Example 2
The differences from example 1 are: the weight ratio of the waste cathode of the aluminum electrolysis cell to lead and zinc in the lead and zinc containing material is 12:51, the addition amount of the flux (CaO) is 5wt% based on the total weight of the waste cathode of the aluminum electrolysis cell, the lead and zinc containing material and the solvent, and the temperature in the reduction smelting process is 1250 ℃.
In the metal phase, the content of lead element was 96.0%, and the recovery rate was 98.5%.
Example 3
The differences from example 1 are: the weight ratio of the waste cathode of the aluminum electrolysis cell to the lead and zinc in the lead and zinc containing material is 35:10, and the addition amount of the flux (CaO) is 5wt% based on the total weight of the waste cathode of the aluminum electrolysis cell, the lead and zinc containing material and the solvent.
In the metal phase, the content of lead element was 94.1%, and the recovery rate was 96.3%.
Example 4
The differences from example 2 are: the weight ratio of the waste cathode of the aluminum electrolysis cell to lead and zinc in the lead and zinc containing material is 15:50, and the addition amount of the flux (CaO) is 5wt% based on the total weight of the waste cathode of the aluminum electrolysis cell, the lead and zinc containing material and the solvent.
In the metal phase, the content of lead element was 97.0%, and the recovery rate was 99.0%.
Example 5
The differences from example 2 are: the weight ratio of the waste cathode of the aluminum electrolysis cell to the lead and zinc in the lead and zinc containing material is 20:60, and the addition amount of the flux (CaO) is 5wt% based on the total weight of the waste cathode of the aluminum electrolysis cell, the lead and zinc containing material and the solvent.
In the metal phase, the content of lead element was 96.5%, and the recovery rate was 97.8%.
Example 6
The differences from example 1 are: the weight ratio of the waste cathode of the aluminum electrolysis cell to the lead and zinc in the lead and zinc containing material is 45:50, and the addition amount of the flux (CaO) is 15wt% based on the total weight of the waste cathode of the aluminum electrolysis cell, the lead and zinc containing material and the solvent.
In the metal phase, the content of lead element was 93.5%, and the recovery rate was 92.0%.
Example 7
The differences from example 1 are: oxygen flow during melting was 80Nm 3 Oxygen gas is introduced into the reduction smelting process at a rate of 12.5Nm 3 And/t, the melting and reduction smelting temperature is 1350 ℃.
In the metal phase, the content of lead element was 94.6%, and the recovery rate was 96.0%.
Example 8
The differences from example 1 are: the oxygen flow during the melting was 100Nm 3 Oxygen gas is introduced into the reduction smelting process at an amount of 20Nm 3 And/t, the melting and reduction smelting temperature is 1150 ℃.
In the metal phase, the content of lead element was 97.4%, and the recovery rate was 98.1%.
Example 9
The differences from example 1 are: the oxygen flow during the melting was 120Nm 3 Oxygen gas is introduced into the reduction smelting process at an amount of 10Nm 3 And/t, the melting and reduction smelting temperature is 1000 ℃.
In the metal phase, the content of lead element was 93.5%, and the recovery rate was 93.8%.
Example 10
The differences from example 1 are: the included angle between the spray gun and the liquid level of the melt is 60 degrees.
In the metal phase, the content of lead element was 97%, and the recovery rate was 98%.
Example 11
The differences from example 1 are: the included angle between the spray gun and the liquid level of the melt is 45 degrees.
In the metal phase, the content of lead element was 97.1%, and the recovery rate was 98.6%.
Example 12
The differences from example 1 are: the addition amount of the calcium-containing flux was 1wt%.
In the metal phase, the content of lead element was 90%, and the recovery rate was 92%.
Example 13
The differences from example 1 are: the addition amount of the calcium-containing flux was 8wt%.
In the metal phase, the content of lead element was 96%, and the recovery rate was 97.1%.
Example 14
The differences from example 1 are: the addition amount of the calcium-containing flux was 20wt%.
In the metal phase, the content of lead element was 96.5%, and the recovery rate was 97.5%.
Comparative example 1
The differences from example 1 are: the weight ratio of the waste cathode of the aluminum electrolysis cell to the lead and zinc in the lead and zinc containing material is 1:10, and the addition amount of the flux (CaO) is 5wt% based on the total weight of the waste cathode of the aluminum electrolysis cell, the lead and zinc containing material and the solvent.
In the metal phase, the content of lead element was 93%, and the recovery rate was 90%.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
as can be seen from comparative examples 1 to 6 and comparative example 1, the weight ratio of the waste cathode of the aluminum electrolysis cell to lead and zinc in the lead and zinc containing material is limited within the preferred range of the application, which is beneficial to improving the content and recovery rate of lead element in the metal phase.
Comparing examples 1, 2 and 7 to 9, it is understood that limiting the temperature and oxygen passage of the melting and reduction smelting process to the ranges preferred herein is advantageous for improving the content and recovery rate of lead element in the metal phase.
Comparing examples 1, 10 to 14, it is understood that limiting the angle of oxygen injection and the amount of addition of the calcium-containing flux to the preferred ranges of the present application is advantageous in improving the content and recovery rate of lead element in the metal phase.
It should be noted that the terms "first," "second," and the like in the description and in the claims of the present application are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described herein.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (12)

1. The method for treating the waste cathode of the aluminum electrolysis cell comprises carbon and fluoride and is characterized by comprising the following steps of:
granulating a mixture of the waste cathode of the aluminum electrolysis cell and a lead-zinc-containing material; the granularity of the granules prepared in the granulating process is 5-30 mm; sequentially melting and reducing the mixture after granulating and oxygen to obtain lead metal, slag and dust-containing flue gas, wherein the dust-containing flue gas comprises smoke dust containing lead oxide and zinc oxide and fluorine-containing flue gas;
reacting fluorine-containing flue gas in the dust-containing flue gas with lead-zinc-containing flue gas at 150-200 ℃ to obtain primary defluorinated flue gas and flue gas containing lead fluoride and zinc fluoride; then reacting the primary defluorinated flue gas with a defluorinating agent to obtain defluorinated flue gas; the fluorine removing agent is selected from one or more of the group consisting of aluminum oxide, calcium oxide and silicon dioxide;
desulfurizing the defluorinated flue gas to obtain purified flue gas;
wherein the method comprises the steps ofThe weight ratio of the waste cathode of the aluminum electrolysis cell to the lead and zinc in the lead and zinc containing material is (8-35): (10-60), the temperature of the melting process and the reduction smelting process is 1100-1350 ℃, and the oxygen ventilation amount in the melting process is 80-100 Nm 3 The oxygen gas is introduced into the reduction smelting process in an amount of 12.5 to 30 per ton of the mixture 30Nm 3 Per ton of the mixture;
the melting process and the reduction smelting process produce molten liquid, oxygen is blown into the molten liquid below the liquid level of the molten liquid by adopting at least one spray gun, and an included angle between each spray gun and the liquid level of the molten liquid is 30-90 degrees;
adding a calcium-containing flux in the reduction smelting process, and enabling the calcium-containing flux to undergo a solidification reaction with residual fluoride which is not decomposed to obtain calcium fluoride; the calcium-containing flux is selected from one or more of the group consisting of limestone, calcium oxide and calcium carbonate; based on the total weight of the waste cathode of the aluminum electrolysis cell, the lead-zinc containing material and the calcium-containing flux, the addition amount of the calcium-containing flux is 8-20 wt%.
2. The method for treating a waste cathode of an aluminum electrolysis cell according to claim 1, wherein the weight ratio of the waste cathode of the aluminum electrolysis cell to lead and zinc in the lead-zinc-containing material is (15-20): (50-60); the temperature of the melting process and the reduction smelting process is 1150-1250 ℃.
3. The method for treating waste cathodes of aluminum electrolysis cells according to claim 1, wherein the Pb-Zn-containing material further comprises Cu,
based on the weight of the lead-zinc containing material, the weight percentage of lead element in the lead-zinc containing material is less than or equal to 20wt percent, the weight percentage of zinc element is less than or equal to 5wt percent, and the weight percentage of copper element is less than or equal to 5wt percent.
4. The treatment system of the waste cathode of the aluminum electrolysis cell is characterized by comprising the following components:
the molten pool smelting unit (10), a molten pool, a charging port (101) communicated with a flue gas zone of the molten pool, an oxygen inlet, a dust-containing flue gas outlet (102), a metal outlet and a slag discharging port are arranged in the molten pool smelting unit (10), and the charging port (101) is used for adding waste cathodes of aluminum electrolysis cells and lead-zinc-containing materials;
the device comprises a defluorination unit (20), wherein the defluorination unit (20) is provided with a dust-containing flue gas inlet (201), the dust-containing flue gas inlet (201) is communicated with a dust-containing flue gas outlet (102) through a dust-containing flue gas conveying pipeline, and the defluorination unit (20) is used for removing fluorine elements in dust-containing flue gas;
the bath smelting unit (10) comprises:
a molten pool smelting device (11), wherein the molten pool smelting device (11) is provided with the charging port (101), the oxygen inlet, the dust-containing flue gas outlet (102), the metal outlet and the slag discharging port;
at least one lance (12), each lance (12) being submerged below the level of the bath and injecting oxygen into the bath;
an oxygen supply device (13), the oxygen supply device (13) being configured to supply oxygen into each of the lances (12);
and oxygen flow control means (14), said oxygen flow control means (14) being arranged to control the flow of oxygen in each of said lances (12).
5. The system for treating a spent cathode of an aluminium electrolysis cell according to claim 4, wherein the bath smelting unit (10) comprises:
a molten pool smelting device (11), wherein the molten pool smelting device (11) is provided with the charging port (101), the oxygen inlet, the dust-containing flue gas outlet (102), the metal outlet and the slag discharging port;
at least one lance (12), each lance (12) being submerged below the level of the bath and injecting oxygen into the bath;
an oxygen supply device (13), the oxygen supply device (13) being configured to supply oxygen into each of the lances (12);
-nitrogen supply means (15), said nitrogen supply means (15) being adapted to supply nitrogen into each of said lances (12);
and the gas composition regulating device (16), wherein the gas composition regulating device (16) is electrically connected with the oxygen supply device (13) and the nitrogen supply device (15) respectively so as to control the oxygen content sprayed by each spray gun (12).
6. A system for treating the spent cathodes of aluminium electrolysis cells according to claim 4 or 5, characterised in that the angle between each lance (12) and the level of liquid in the bath is 30-90 °.
7. The system for treating the waste cathodes of aluminium electrolysis cells according to claim 6, wherein each lance (12) is arranged at the side or bottom of the bath smelting device (11).
8. The treatment system of aluminum electrolysis cell waste cathodes according to claim 7, further comprising a mixing granulation device (30), the mixing granulation device (30) being provided with a raw material inlet and a mixing pellet outlet (301), the mixing pellet outlet (301) being in communication with the feed inlet (101).
9. The treatment system of aluminum electrolysis cell waste cathodes according to claim 7, further comprising a waste heat recovery device (40), the waste heat recovery device (40) being in communication with the dust-laden flue gas transfer line for recovering heat from the dust-laden flue gas.
10. The treatment system of an aluminum electrolysis cell waste cathode according to claim 9, wherein the defluorination unit (20) comprises a dry defluorination device (21), and the dry defluorination device (21) is provided with a defluorination agent inlet, the dust-containing flue gas inlet (201), a first defluorination flue gas outlet and a first defluorination flue gas outlet.
11. The treatment system of aluminum electrolysis cell waste cathodes according to claim 10, wherein the defluorination unit (20) further comprises an electric dust collector (22), the electric dust collector (22) is arranged on the dust-containing flue gas conveying pipeline between the waste heat recovery device (40) and the dust-containing flue gas inlet (201), and the electric dust collector (22) is provided with a second defluorination flue gas outlet and a second defluorination flue gas outlet.
12. The treatment system of aluminum electrolysis cell waste cathodes according to claim 11, further comprising a flue gas cleaning device (50), the flue gas cleaning device (50) being provided with a desulfurizing agent inlet and a gas inlet to be cleaned, the gas inlet to be cleaned being in communication with the first defluorinated flue gas outlet for desulfurizing the first defluorinated flue gas.
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