CN108728660B - Copper slag dilution method - Google Patents
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- CN108728660B CN108728660B CN201810639270.5A CN201810639270A CN108728660B CN 108728660 B CN108728660 B CN 108728660B CN 201810639270 A CN201810639270 A CN 201810639270A CN 108728660 B CN108728660 B CN 108728660B
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
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Abstract
The invention provides a method for diluting copper slag. The device adopted by the method comprises a copper slag dilution treatment furnace and a wire feeding device, wherein the copper slag dilution treatment furnace takes electric heat or plasma heat as a heat source and is provided with a copper slag inlet, a wire feeding hole and a matte discharging hole; the copper slag depletion method comprises the following steps: introducing the copper slag into a copper slag dilution treatment furnace through a copper slag inlet; feeding carbon powder wires into the copper slag dilution treatment furnace through wire feeding holes by using a wire feeding device; under the action of electric heat or plasma heat, the copper slag is subjected to reduction and dilution treatment by utilizing the carbon powder wire. The method for diluting the copper slag can effectively improve the reduction dilution efficiency of the copper slag, and has the advantages of short flow, low cost, capability of simultaneously recovering heavy metals such as lead and zinc in the slag and the like.
Description
Technical Field
The invention relates to the technical field of metal smelting, in particular to a copper slag dilution method.
Background
In the existing copper smelting process, 2-7 t of copper slag is generated every time 1t of copper is smelted, and the copper and other metal contents in the slag are high. The copper content in the slag produced by different smelting processes is different, the copper content in the copper slag is 0.8-12%, the copper slag also contains metals such as lead, zinc and the like, the lead content is about 0.5-10%, and the zinc content is about 1.0-8%.
At present, domestic copper slag is mainly depleted by adopting a mineral separation technology, and the method mainly comprises the steps of slag slow cooling, crushing, fine grinding and the like. Such as: the chinese patent application No. 2014106829920.6 proposes a method for directly recovering iron resources in slag, including pelletizing, drying, reducing and ore dressing after cooling copper slag. However, the method has the problems of large occupied area, high investment cost, serious heat waste and the like. In recent years, the annual emission of copper slag in the world reaches more than 6000 million tons, the annual emission of copper slag in China reaches 1500 million tons, if the slag is diluted and utilized by adopting a beneficiation method, the stockpiling of the beneficiation slag causes great harm to the surrounding environment, and lead and zinc in the slag cannot be recycled, so that great resource waste is caused.
In recent years, researchers at home and abroad carry out a plurality of researches on the pyrometallurgical treatment of copper slag, but no mature process exists, and the following defects mainly exist: (1) adding lump coal or pulverized coal for reduction and dilution, wherein the lump coal and the pulverized coal can float on the surface of slag, and a large amount of reducing agent is combusted in flue gas and cannot play a good reducing role; the molten pool is static, which is not beneficial to the aggregation and growth of copper matte (metal) in the slag, and the dynamic condition is poor; (2) the reducing agent blowing process has large investment and high production cost.
Disclosure of Invention
The invention mainly aims to provide a method for diluting copper slag, which aims to solve the problems that the prior art cannot give consideration to low cost, short flow, high efficiency and incapability of recovering heavy metals such as lead, zinc and the like when copper slag is recovered and treated.
The invention mainly aims to provide a copper slag dilution method, which adopts a device comprising a copper slag dilution treatment furnace and a wire feeding device, wherein the copper slag dilution treatment furnace takes electric heat or plasma heat as a heat source and is provided with a copper slag inlet, a wire feeding hole and a matte discharging port; the copper slag depletion method comprises the following steps: introducing the copper slag into a copper slag dilution treatment furnace through a copper slag inlet; feeding carbon powder wires into the copper slag dilution treatment furnace through wire feeding holes by using a wire feeding device; under the action of electric heat or plasma heat, the copper slag is subjected to reduction and dilution treatment by utilizing the carbon powder wire.
Further, the copper slag depletion treatment furnace is an ore-smelting electric furnace or a plasma furnace.
Further, in the step of reduction and dilution treatment, an additive is introduced into the copper slag dilution treatment furnace to participate in the reduction and dilution treatment; preferably, the additive is one or more of pyrite, sulphur and low matte.
Further, the copper content in the copper slag is 0.8-12 wt%, the lead content is 0.5-10%, and the zinc content is 1.0-8%; preferably, the addition amount of the additive is 1-20% of the weight of the copper slag; preferably, the weight of the carbon powder in the added carbon powder wire is taken as A, and the weight of the theoretical carbon blending required for reducing copper oxide, lead oxide and zinc oxide in the copper slag is taken as B, wherein A/B is 0.8-2.0; preferably, the copper slag is liquid copper slag generated in a copper smelting process.
Further, the diameter of the carbon powder wire is 10-30 mm, and the carbon content of the carbon powder in the carbon powder wire is 50-98%.
Further, the carbon powder wire comprises a carbon powder core layer and a metal sheath coated on the surface of the carbon powder core layer, the metal sheath is made of iron sheet or aluminum sheet, and the thickness of the metal sheath is preferably 0.1-0.5 mm.
Furthermore, in the step of feeding the carbon powder wire, the wire end of the carbon powder wire is placed in a molten layer in the copper slag depletion treatment furnace, the height from the inner bottom wall of the copper slag depletion treatment furnace to the molten slag layer is recorded as H, and the height from the inner bottom wall of the copper slag depletion treatment furnace to the wire end of the carbon powder wire is recorded as H, wherein H/H is 1/3-1/2.
Furthermore, the temperature of the reduction and dilution treatment is 1200-1400 ℃, and the time is 1-3 h.
Further, copper matte, slag and tail gas are obtained in the step of reduction and dilution treatment, and the method for diluting copper slag also comprises the step of water quenching treatment of the slag.
Further, the copper slag depletion method also comprises a step of post-treating the tail gas, and the post-treating step comprises the following steps: carrying out waste heat recovery treatment on the tail gas to obtain cold flue gas; and carrying out dust collection treatment on the cold flue gas.
By utilizing the copper slag depletion method provided by the invention, the carbon powder is fed into the copper slag depletion treatment furnace by adopting a wire feeding process, and then the copper slag is subjected to reduction depletion treatment by taking electric heat or plasma heat as a heat source. Compared with the traditional mineral processing technology, the method for processing the copper slag has the advantages that the process is simple, the heat carried by the copper slag from the front-stage process can be effectively utilized, the occupied area of the device is small, and the equipment cost is low. Meanwhile, the method can reduce the lead oxide and the zinc oxide in the copper slag together, recover copper and a small amount of lead and zinc, and avoid chemical agents added in the beneficiation process, so that the method not only brings great economic benefit to enterprises, but also greatly reduces potential safety hazards. Compared with the fire method dilution process, the method can directly feed the carbon powder into the melt layer at the middle lower part of the slag in the furnace body through the wire feeding device. Therefore, carbon powder in the carbon powder line can be more fully contacted with the melt at the middle lower part of the slag to play the function of a reducing agent, so that copper oxide in the copper slag is reduced into copper matte under the condition of higher dilution kinetics, and a small amount of lead oxide and zinc oxide can be reduced into corresponding metal simple substances to enter tail gas (lead and zinc can be gasified to enter the tail gas), so that the recovery is convenient.
Based on the reasons, the method for diluting the copper slag can effectively improve the reduction dilution efficiency of the copper slag, and has the advantages of short flow, low cost, capability of simultaneously recovering heavy metals such as lead and zinc in the slag and the like.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
figure 1 shows a schematic view of a copper slag depletion plant according to an embodiment of the invention.
Wherein the figures include the following reference numerals:
10. a copper slag dilution treatment furnace; 11. a furnace body; 12. heating the electrode; 20. a wire feeding device; 30. a waste heat recovery device; 40. a dust collecting device; 50. an additive storage bin;
a. copper slag; b. a carbon powder wire; c. copper matte; d. slag; e. and (4) tail gas.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
As described in the background art, the prior art cannot give consideration to low cost, short process, high efficiency and non-recovery of heavy metals such as lead, zinc and the like when recovering and treating copper slag.
In order to solve the problems, the invention provides a copper slag dilution method, as shown in fig. 1, the adopted device comprises a copper slag dilution treatment furnace 10 and a wire feeding device 20, the copper slag dilution treatment furnace 10 takes electric heat or plasma heat as a heat source, the copper slag dilution treatment furnace 10 is provided with a copper slag inlet, a wire feeding hole and a matte discharging port; the copper slag depletion method comprises the following steps: introducing the copper slag a into a copper slag dilution treatment furnace 10 through a copper slag inlet; feeding a carbon powder line b into the copper slag dilution treatment furnace 10 through a line feeding hole by using a line feeding device 20; and (3) carrying out reduction and depletion treatment on the copper slag a by using the carbon powder wire b under the action of electric heat or plasma heat.
By utilizing the copper slag depletion method provided by the invention, the wire feeding device 20 is adopted to feed carbon powder into the copper slag depletion treatment furnace 10, and then the copper slag is subjected to reduction depletion treatment by taking electric heat or plasma heat as a heat source. Compare in traditional ore dressing technology, utilize above-mentioned device to handle the copper sediment, the flow is simple, can effectively utilize the copper sediment itself to come out from anterior segment process and be the heat of carrying, and the device area is little, equipment cost is low. Meanwhile, the device can carry out reduction treatment on lead oxide and zinc oxide in the copper slag together, recover copper and a small amount of lead and zinc, and avoid chemical agents added in the mineral separation process, so that great economic benefits are brought to enterprises, and potential safety hazards are greatly reduced. Compared with the fire method dilution process, the invention can directly feed the carbon powder into the melt layer at the middle lower part of the slag in the furnace body through the wire feeding device 20. Therefore, carbon powder in the carbon powder line can be more fully contacted with the melt at the middle lower part of the slag to play the function of a reducing agent, so that copper oxide in the copper slag is reduced into copper matte under the condition of higher dilution kinetics, and a small amount of lead oxide and zinc oxide can also be reduced into corresponding metal simple substances to enter tail gas, thereby facilitating the recovery.
Based on the reasons, the copper slag dilution device provided by the invention can effectively improve the reduction dilution efficiency of the copper slag, and has the beneficial effects of short flow, low cost, capability of simultaneously recovering heavy metals such as lead and zinc in the slag and the like.
In a preferred embodiment, the copper slag-depleted treatment furnace 10 is an ore-smelting electric furnace or a plasma furnace. The ore-smelting electric furnace or the plasma furnace can provide stable heat for the dilution process of the copper slag, and the added carbon powder line can be basically and completely used as a reducing agent, so that the dilution kinetic condition can be further improved, and the production efficiency is improved.
In a preferred embodiment, in the step of reducing and impoverishing, an additive is simultaneously introduced into the copper slag impoverishing furnace 10 to participate in the reducing and impoverishing; preferably, the additive is one or more of pyrite, sulphur and low matte. The addition of the additives is beneficial to reducing the copper matte grade in the slag and further improving the recovery rate of copper.
The copper slag dilution treatment is carried out based on a special wire feeding process, so that the copper slag used in the process provided by the invention is wider in range, and in a preferred embodiment, the copper content in the copper slag is 0.8-12 wt%, the lead content is 0.5-10%, and the zinc content is 1.0-8%.
In order to further improve the dilution efficiency of the copper slag and the recovery rate of copper (a small amount of other metals such as lead, zinc and the like), the addition amount of the additive is 1-20% of the weight of the copper slag. More preferably, the weight of the carbon powder in the added carbon powder wire is represented as A, and the weight of the theoretical carbon blending required for reducing copper oxide, lead oxide and zinc oxide in the copper slag is represented as B, wherein A/B is 0.8-2.0. The "theoretical carbon-added weight required for reducing copper oxide, lead oxide and zinc oxide in the copper slag" refers to the theoretical amount of carbon required for reducing these oxides to elemental metals.
In order to more fully utilize the heat carried by the copper slag and save energy consumption, the copper slag is preferably liquid copper slag generated in the copper smelting process. The temperature of the liquid copper matte produced in the copper smelting process is 1180-1250 ℃. The liquid copper slag is directly transferred to the copper slag dilution treatment furnace 10 through a chute or a slag ladle, and the waste heat of the liquid copper slag is fully utilized.
The carbon powder line used in the dilution method of the present invention can be a carbon powder line which is commercially available at present, and in a preferred embodiment, the diameter of the carbon powder line is 10-30 mm, and the carbon content of the carbon powder in the carbon powder line is 50-98%. More preferably, the carbon powder wire comprises a carbon powder core layer and a metal sheath coated on the surface of the carbon powder core layer, the metal sheath is made of iron sheet or aluminum sheet, and the thickness of the metal sheath is preferably 0.1-0.5 mm. The metal sheath can be melted at high temperature after entering the melt of the furnace body 11, or can be dissolved in slag after reacting with other metal oxides and oxidizing.
In a preferred embodiment, in the step of feeding the carbon powder wire, the wire end of the carbon powder wire is placed in a molten layer in the copper slag-depleted treatment furnace 10, the height from the inner bottom wall of the copper slag-depleted treatment furnace 10 to the molten slag layer is represented as H, and the height from the inner bottom wall of the copper slag-depleted treatment furnace 10 to the wire end of the carbon powder wire is represented as H, wherein H/H is 1/3-1/2. Therefore, on one hand, the carbon powder line is more fully contacted with the melt, the dilution condition is better, and on the other hand, after the metal oxide in the middle of the molten pool completes the reduction reaction, the metal oxide can enter the bottom of the molten pool through the sedimentation effect to form a more stable copper matte layer, so that the copper matte can be conveniently discharged.
The copper slag depletion process based on the invention has better dynamic conditions and can effectively shorten the depletion period. In a preferred embodiment, the temperature of the reduction and dilution treatment is 1200-1400 ℃ and the time is 1-3 h.
In a preferred embodiment, the step of reduction and dilution treatment obtains copper matte c, slag d and tail gas c, and the copper slag dilution method further comprises the step of water quenching treatment of the slag d. And discharging the slag d from a slag discharge port, and performing water quenching treatment, wherein the slag d is not subjected to fine grinding and mineral separation, no medicament is added, and heavy metals such as lead, zinc and the like in the slag are recycled, so that the slag d does not belong to hazardous waste and has low influence on the surrounding environment.
In a preferred embodiment, the copper slag depletion process further comprises a step of post-treating the tail gas e, the post-treatment step comprising: carrying out waste heat recovery treatment on the tail gas e to obtain cold flue gas; and carrying out dust collection treatment on the cold flue gas. On the one hand, the waste heat in the tail gas can be recycled, on the other hand, the emission of particles can be reduced, the environmental protection performance of the device is improved, and lead simple substances and zinc simple substances which are carried in the tail gas and generated by reduction can be recycled.
When the method is used for treating the copper slag, the Cu content in the slag can be less than or equal to 0.5 percent, the Pb content can be less than or equal to 0.2 percent, and the Zn content can be less than or equal to 0.2 percent. The copper content in the copper matte can reach 40-80%, and the copper matte can enter a subsequent process (such as an air refining process) to produce an anode plate after being discharged.
It should be noted that during the actual stripping treatment, CO or CO is formed after the reductant participates in the stripping2And a part of combustible materials can be entrained in the tail gas, and the part of combustible materials above the molten slag can also be partially combusted to provide heat for the furnace body 11.
According to another aspect of the present invention, there is also provided a copper slag dilution device, as shown in fig. 1, which includes a copper slag dilution treatment furnace 10 and a wire feeding device 20, wherein the copper slag dilution treatment furnace 10 uses electric heat or plasma heat as a heat source, the copper slag dilution treatment furnace 10 is provided with a copper slag inlet, a wire feeding hole and a matte discharging hole, the copper slag inlet is used for introducing copper slag a, and the matte discharging hole is used for discharging copper matte c obtained by reduction dilution treatment; and the wire feeding device 20 is used for feeding the carbon powder wire b into the copper slag depletion treatment furnace 10 through a wire feeding hole so as to perform reduction depletion treatment on the copper slag.
By utilizing the copper slag dilution device provided by the invention, the wire feeding device 20 is adopted to feed carbon powder into the copper slag dilution treatment furnace 10, and then the electric heat or the plasma heat is used as a heat source to carry out reduction dilution treatment on the copper slag. Compare in traditional ore dressing technology, utilize above-mentioned device to handle the copper sediment, the flow is simple, can effectively utilize the copper sediment itself to come out from anterior segment process and be the heat of carrying, and the device area is little, equipment cost is low. Meanwhile, the device can carry out reduction treatment on lead oxide and zinc oxide in the copper slag together, recover copper and a small amount of lead and zinc, and avoid chemical agents added in the mineral separation process, so that great economic benefits are brought to enterprises, and potential safety hazards are greatly reduced. Compared with the fire method dilution process, the invention can directly feed the carbon powder into the melt layer at the middle lower part of the slag in the furnace body through the wire feeding device 20. Therefore, carbon powder in the carbon powder line can be more fully contacted with the melt at the middle lower part of the slag to play the function of a reducing agent, so that copper oxide in the copper slag is reduced into copper matte under the condition of higher dilution kinetics, and a small amount of lead oxide and zinc oxide can be reduced into corresponding metal simple substances to enter tail gas (lead and zinc can be gasified to enter the tail gas), so that the recovery is convenient.
Based on the reasons, the copper slag dilution device provided by the invention can effectively improve the reduction dilution efficiency of the copper slag, and has the beneficial effects of short flow, low cost, capability of simultaneously recovering heavy metals such as lead and zinc in the slag and the like.
In the actual dilution process, the wire feeding device 20 controls the entering speed of the carbon powder wire, and the carbon powder enters the melt and then reacts with copper (a small amount of lead and zinc) oxide to generate CO and CO2And the gas reduces the metal existing in the oxide state into the metal elementary substance state, and other metals such as copper settle and are discharged from the matte discharging port. And in the process that the gas escapes from the melt, the gas can also play a role in stirring the melt, so that the metal particles can be promoted to aggregate, grow and settle, and the reduction reaction is promoted to be carried out.
In a preferred embodiment, the copper slag-depleted treatment furnace 10 is an ore-smelting electric furnace or a plasma furnace. The ore-smelting electric furnace or the plasma furnace can provide stable heat for the dilution process of the copper slag, and the added carbon powder line can be basically and completely used as a reducing agent, so that the dilution kinetic condition can be further improved, and the production efficiency is improved.
In a preferred embodiment, as shown in FIG. 1, the copper slag dilution treatment furnace 10 comprises a furnace body 11 and a heating electrode 12, wherein a copper slag inlet and a wire feeding hole are arranged at the top of the furnace body 11, a matte discharging port is arranged below the side of the furnace body 11, and the furnace body 11 is also provided with an electrode hole; the heating electrode 12 extends through the electrode hole to the inside of the furnace body 11 to supply heat to the furnace body 11. In the actual operation process, the power is supplied to the heating electrode 12 through the power supply, and then the heating electrode 12 is used for supplying heat to the copper slag system in the furnace body 11. The number of the heating electrodes 12 may be adjusted according to the capacity of the furnace 11 and the amount of the copper slag to be processed, as will be understood by those skilled in the art.
In order to facilitate the feeding operation and control the height of the feeding wire, in a preferred embodiment, the feeding holes are multiple, and the multiple feeding holes are distributed on the top of the furnace body 11. The wire feeding holes are distributed at the top of the furnace body 11, and after the carbon powder wires are fed into the wire feeding holes through the wire feeding device 20, the carbon powder wires can enter the inside of the melt under the self gravity to be contacted with the melt, and the height of the wire end can be conveniently controlled in the process. In addition, a plurality of feeding holes are arranged, so that carbon powder wires can be fed at different positions, and the dilution reduction efficiency is further improved. Preferably, the number of the feeding holes is 3-8, and the aperture of each feeding hole is 30-100 mm.
In a preferred embodiment, a slag tap is further provided in the furnace body 11 at a lower portion of the furnace body on a side opposite to the matte tap for discharging slag d produced in the reduction and dilution treatment. In the actual production process, as shown in fig. 1, in the depletion system in the furnace 11, copper matte is located below and some slag floating on the surface of the melt is located above. Therefore, the slag can be discharged through the slag tap. Preferably, the copper slag depletion device further comprises a slag cooling device for cooling the slag d discharged from the slag tap hole. The specific cooling method can adopt a cooling form commonly used in the field, such as water quenching and the like.
In order to further improve the effect of copper slag depletion, in a preferred embodiment, the top of the furnace body 11 is further provided with an additive inlet for introducing an additive. The additive can be a vulcanizing agent, a trapping agent and the like, is favorable for reducing the copper matte grade in the slag, and further improves the recovery rate of copper.
In a preferred embodiment, the additive inlet is co-located with the copper slag inlet. Therefore, the additive and the copper slag can be added at the same position, and the operation convenience is improved. Preferably, the copper slag depletion apparatus further comprises an additive bin 50, the additive bin 50 being connected to the additive inlet for providing the additive.
In a preferred embodiment, the copper slag dilution treatment furnace 10 is further provided with a tail gas outlet, the copper slag dilution device further comprises a waste heat recovery device 30 and a dust collection device 40, the waste heat recovery device 30 is provided with a hot flue gas inlet and a cold flue gas outlet, and the hot flue gas inlet is connected with the tail gas outlet; the dust collecting device 40 is connected with the cold flue gas outlet. Like this on the one hand can retrieve the waste heat in the tail gas e and utilize, on the one hand can also reduce the particulate matter and discharge, improves the environmental protection nature of device, and can retrieve the lead simple substance and the zinc simple substance that are reduced out that carry in the tail gas.
The beneficial effects of the present invention are further illustrated by the following examples:
example 1
The copper slag dilution device shown in figure 1 is used for diluting copper slag, wherein the copper slag dilution device is shown in figure 1, three heating electrodes are arranged in the furnace body, the volume of the part of the electrode extending into the cavity accounts for 4 percent of the total volume of the cavity, and the power density of the electrode is 200kW/m2The process conditions are as follows:
adding copper slag into the furnace, and raising the temperature of slag in the furnace to 1400 ℃; feeding a carbon powder wire (5 feeding holes are formed above a furnace body), wherein the carbon powder wire comprises a carbon powder core layer and an iron sheet coated on the surface of the carbon powder core layer, the thickness of the iron sheet is 0.1mm, the diameter of the carbon powder wire is 10mm, and the carbon content in the carbon powder is 98%; and (3) recording the weight of the carbon powder in the added carbon powder wire as A, and recording the weight of theoretical carbon preparation required for reducing copper oxide, lead oxide and zinc oxide in the copper slag as B, wherein A/B is 0.8. In the wire feeding process, the wire end of the carbon powder wire is placed in a melt layer in a copper slag depletion treatment furnace, the height from the inner bottom wall of the copper slag depletion treatment furnace to the slag layer is recorded as H, the height from the inner bottom wall of the copper slag depletion treatment furnace to the wire end of the carbon powder wire is recorded as H, wherein H/H is 1/3; adding pyrite into the furnace body to further capture copper metal in the slag, wherein the adding amount is 3% of the total weight of the smelting slag; and returning the obtained copper matte to the smelting furnace.
And (3) processing results: 20 ten thousand tons of annual treated copper smelting slag contains 3.5 percent of copper, 0.95 percent of lead and 2.76 percent of zinc; after the copper slag is treated, the tailings contain 0.32% of copper, 0.06% of lead and 0.12% of zinc; the copper grade of the copper matte is 35.12%. The copper recovery rate of the whole system is about 90.54%, the lead recovery rate is about 98.5%, and the zinc recovery rate is 96%.
Example 2
The device and process used are the same as in example 1, except that: H/H1/2.
And (3) processing results: 20 ten thousand tons of annual treated copper smelting slag contains 3.5 percent of copper, 0.95 percent of lead and 2.76 percent of zinc; after the copper slag is treated, the slag contains 0.35 percent of copper, 0.09 percent of lead and 0.17 percent of zinc; the copper grade of the copper matte is 33.81%. The copper recovery rate of the whole system is about 88.8 percent, the lead recovery rate is about 95.6 percent, and the zinc recovery rate is 93 percent.
Example 3
The device and process used are the same as in example 1, except that: H/H2/3.
And (3) processing results: 20 ten thousand tons of annual treated copper smelting slag contains 3.5 percent of copper, 0.95 percent of lead and 2.76 percent of zinc; after the copper slag is treated, the slag contains 0.33 percent of copper, 0.08 percent of lead and 0.14 percent of zinc; the copper grade of the copper matte is 34.25%. The copper recovery rate of the whole system is about 89.6 percent, the lead recovery rate is about 97.0 percent, and the zinc recovery rate is 94.5 percent.
Example 4
The device and process used are the same as in example 1, except that: the adding amount of the pyrite is 20 percent of the total weight of the copper slag, and A/B is 2.0.
And (3) processing results: 20 ten thousand tons of annual treated copper smelting slag contains 3.5 percent of copper, 0.95 percent of lead and 2.76 percent of zinc; after the copper slag is treated, the tailings contain 0.30% of copper, 0.04% of lead and 0.10% of zinc; the copper grade of the copper matte is 36.5 percent. The copper recovery rate of the whole system is about 91.3 percent, the lead recovery rate is about 98.9 percent, and the zinc recovery rate is 98.2 percent.
Example 5
The device and process used are the same as in example 1, except that: the adding amount of the pyrite is 1 percent of the total weight of the copper slag, and A/B is 0.7.
And (3) processing results: 20 ten thousand tons of annual treated copper smelting slag contains 3.5 percent of copper, 0.95 percent of lead and 2.76 percent of zinc; after the copper slag is treated, the slag contains 0.40 percent of copper, 0.12 percent of lead and 0.21 percent of zinc; the copper grade of the copper matte is 30.54 percent. The copper recovery rate of the whole system is about 85.2 percent, the lead recovery rate is about 87.0 percent, and the zinc recovery rate is 91.3 percent.
Comparative example 1
The device and process used are the same as in example 1, except that: the wire feeding process is not adopted, and equal amount of carbon powder is directly added into the furnace body through the charging hole.
And (3) processing results: 20 ten thousand tons of annual treated copper smelting slag contains 3.5 percent of copper, 0.95 percent of lead and 2.76 percent of zinc; after the copper slag is treated, the slag contains 1.05 percent of copper, 0.56 percent of lead and 0.98 percent of zinc; the copper grade of the copper matte is 23.38%. The copper recovery rate of the whole system is about 73.1 percent, the lead recovery rate is about 63.8 percent, and the zinc recovery rate is 74.7 percent.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
by utilizing the copper slag dilution device provided by the invention, the carbon powder is fed into the copper slag dilution treatment furnace by adopting a wire feeding process, and then the copper slag is subjected to reduction dilution treatment by taking electric heat or plasma heat as a heat source. Compare in traditional ore dressing technology, utilize above-mentioned device to handle the copper sediment, the flow is simple, can effectively utilize the copper sediment itself to come out from anterior segment process and be the heat of carrying, and the device area is little, equipment cost is low. Meanwhile, the device can carry out reduction treatment on lead oxide and zinc oxide in the copper slag together, recover copper and a small amount of lead and zinc, and avoid chemical agents added in the mineral separation process, so that great economic benefits are brought to enterprises, and potential safety hazards are greatly reduced. Compared with the fire method dilution process, the method can directly feed the carbon powder into the melt layer at the middle lower part of the slag in the furnace body through the wire feeding device. Therefore, carbon powder in the carbon powder line can be more fully contacted with the melt at the middle lower part of the slag to play the function of a reducing agent, so that copper oxide in the copper slag is reduced into copper matte under the condition of higher dilution kinetics, and a small amount of lead oxide and zinc oxide can also be reduced into corresponding metal simple substances to enter tail gas, thereby facilitating the recovery.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. The copper slag dilution method is characterized in that the copper slag dilution method adopts a device comprising a copper slag dilution treatment furnace (10) and a wire feeding device (20), wherein the copper slag dilution treatment furnace (10) takes electric heat or plasma heat as a heat source, and the copper slag dilution treatment furnace (10) is provided with a copper slag inlet, a wire feeding hole and a matte discharging hole; the copper slag depletion method comprises the following steps:
introducing the copper slag into the copper slag dilution treatment furnace (10) through the copper slag inlet;
feeding carbon powder wires into the copper slag dilution treatment furnace (10) through the wire feeding holes by using the wire feeding device (20);
and carrying out reduction and dilution treatment on the copper slag by utilizing the carbon powder wire under the action of the electric heat or the plasma heat.
2. The copper slag depletion method according to claim 1, characterized in that the copper slag depletion treatment furnace (10) is an ore-smelting electric furnace or a plasma furnace.
3. The copper slag depletion method according to claim 1, characterized in that in the step of reducing depletion treatment, an additive is simultaneously introduced into the copper slag depletion treatment furnace (10) to participate in the reducing depletion treatment.
4. A copper slag depletion process according to claim 3, characterized in that the additive is one or more of pyrite, sulphur and low matte.
5. The method for depleting copper slag according to claim 3, wherein the copper slag contains 0.8 to 12 wt% of copper, 0.5 to 10 wt% of lead and 1.0 to 8 wt% of zinc.
6. The method for depleting copper slag according to claim 5, wherein the additive is added in an amount of 1-20% by weight of the copper slag.
7. The method for copper slag depletion according to claim 5, characterized in that the weight of carbon powder added to the carbon powder line is represented as A, and the weight of theoretical carbon added required for reduction of copper oxides, lead oxides and zinc oxides in the copper slag is represented as B, wherein A/B is 0.8-2.0.
8. The copper slag depletion method according to claim 5, characterized in that the copper slag is liquid copper slag produced in a copper smelting process.
9. The copper slag depletion method according to any one of claims 1 to 8, wherein the diameter of the carbon powder line is 10 to 30mm, and the carbon content of carbon powder in the carbon powder line is 50 to 98%.
10. The copper slag depletion method according to claim 9, wherein the carbon powder wire comprises a carbon powder core layer and a metal skin coated on the surface of the carbon powder core layer, and the metal skin is made of iron or aluminum.
11. The copper slag depletion method according to claim 10, wherein the thickness of the metal sheath is 0.1 to 0.5 mm.
12. The copper slag depletion method according to any one of claims 1 to 8, characterized in that in the step of feeding the carbon dust wire, the wire end of the carbon dust wire is placed in the melt layer in the copper slag depletion furnace (10), and the height of the inner bottom wall of the copper slag depletion furnace (10) from the melt layer is denoted as H, and the height of the inner bottom wall of the copper slag depletion furnace (10) from the wire end of the carbon dust wire is denoted as H, wherein H/H is 1/3-1/2.
13. The copper slag depletion method according to claim 12, wherein the temperature of the reductive depletion treatment is 1200 to 1400 ℃ and the time is 1 to 3 hours.
14. The copper slag impoverishment method according to any one of claims 1 to 8, characterized in that the step of reductive impoverishment results in copper matte, slag and tail gas, and the method further comprises the step of water quenching the slag.
15. The copper slag depletion method according to claim 14, further comprising the step of post-treating the tail gas, the post-treating step comprising:
carrying out waste heat recovery treatment on the tail gas to obtain cold flue gas; and
and carrying out dust collection treatment on the cold flue gas.
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| CN201810639270.5A CN108728660B (en) | 2018-06-20 | 2018-06-20 | Copper slag dilution method |
| EA202092301A EA202092301A1 (en) | 2018-06-20 | 2019-06-18 | DEVICE AND METHOD FOR DRAINING COPPER SLAG |
| PCT/CN2019/091716 WO2019242607A1 (en) | 2018-06-20 | 2019-06-18 | Copper slag depletion device and method |
| CL2020002999A CL2020002999A1 (en) | 2018-06-20 | 2020-11-18 | Copper slag depletion device and method |
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| CN108728660B (en) * | 2018-06-20 | 2020-07-17 | 中国恩菲工程技术有限公司 | Copper slag dilution method |
| CN109652660A (en) * | 2019-01-21 | 2019-04-19 | 中国恩菲工程技术有限公司 | Copper ashes processing system and method |
| CN111020207A (en) * | 2020-01-06 | 2020-04-17 | 中国恩菲工程技术有限公司 | Treatment device and treatment method for copper blowing slag |
| CN111139357A (en) * | 2020-01-07 | 2020-05-12 | 中国恩菲工程技术有限公司 | Method for diluting copper-containing sludge |
| CN112458299A (en) * | 2020-11-25 | 2021-03-09 | 中国恩菲工程技术有限公司 | Method and device for treating lead reducing slag |
| CN114164345B (en) * | 2021-11-01 | 2023-07-21 | 昆明理工大学 | Method for cooperatively treating lead-zinc smelting slag and copper-containing material |
| CN114686632B (en) * | 2022-04-08 | 2024-03-22 | 瀜矿环保科技(上海)有限公司 | Copper slag recycling and CO based on industrial solid waste 2 Mineralization coupling method and mineralization coupling system |
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| WO2007066350A1 (en) * | 2005-12-09 | 2007-06-14 | Council Of Scientific And Industrial Research | A process for recovery of iron from copper slag |
| CN101838739A (en) * | 2009-07-21 | 2010-09-22 | 中国恩菲工程技术有限公司 | Electrothermal impoverishment process for copper smelting slag |
| CN101914655A (en) * | 2010-08-03 | 2010-12-15 | 沈阳午飞炉料有限公司 | Method for manufacturing solid cored-wires made of high purity calcium metal |
| CN105063371A (en) * | 2015-09-02 | 2015-11-18 | 云南锡业股份有限公司铜业分公司 | Method for reducing copper slags in top-blowing converting furnace |
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| SE427047B (en) * | 1976-06-17 | 1983-02-28 | Gnii Tsvetny | PROCEDURE AND OVEN FOR THE TREATMENT OF NON-IRON METAL INDUSTRY RECOVERY COATS WITH CARBONAL REDUCING AGENT |
| CN107036443A (en) * | 2017-05-19 | 2017-08-11 | 中国恩菲工程技术有限公司 | Electric heating dilution stove |
| CN108728660B (en) * | 2018-06-20 | 2020-07-17 | 中国恩菲工程技术有限公司 | Copper slag dilution method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007066350A1 (en) * | 2005-12-09 | 2007-06-14 | Council Of Scientific And Industrial Research | A process for recovery of iron from copper slag |
| CN101838739A (en) * | 2009-07-21 | 2010-09-22 | 中国恩菲工程技术有限公司 | Electrothermal impoverishment process for copper smelting slag |
| CN101914655A (en) * | 2010-08-03 | 2010-12-15 | 沈阳午飞炉料有限公司 | Method for manufacturing solid cored-wires made of high purity calcium metal |
| CN105063371A (en) * | 2015-09-02 | 2015-11-18 | 云南锡业股份有限公司铜业分公司 | Method for reducing copper slags in top-blowing converting furnace |
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| CN108728660A (en) | 2018-11-02 |
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