WO2018228073A1 - Anode copper production method and device - Google Patents
Anode copper production method and device Download PDFInfo
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- WO2018228073A1 WO2018228073A1 PCT/CN2018/085309 CN2018085309W WO2018228073A1 WO 2018228073 A1 WO2018228073 A1 WO 2018228073A1 CN 2018085309 W CN2018085309 W CN 2018085309W WO 2018228073 A1 WO2018228073 A1 WO 2018228073A1
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- copper
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- 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
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- 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
-
- 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
- C22B5/16—Dry methods smelting of sulfides or formation of mattes with volatilisation or condensation of the metal being produced
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- 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
- 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
- C22B7/04—Working-up slag
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B1/00—Shaft or like vertical or substantially vertical furnaces
- F27B1/02—Shaft or like vertical or substantially vertical furnaces with two or more shafts or chambers, e.g. multi-storey
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B3/00—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces
- F27B3/04—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces of multiple-hearth type; of multiple-chamber type; Combinations of hearth-type furnaces
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/02—Rotary-drum furnaces, i.e. horizontal or slightly inclined of multiple-chamber or multiple-drum type
- F27B7/04—Rotary-drum furnaces, i.e. horizontal or slightly inclined of multiple-chamber or multiple-drum type with longitudinal divisions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present application relates to the field of copper smelting, and in particular to an anode copper production method and apparatus.
- the traditional fire method copper smelting process includes three steps of smelting, blowing and refining, wherein the smelting furnace smelts copper concentrate into 40-60% copper-copper (also called copper bismuth) containing copper; Copper is blown into blister copper; the refining furnace (anode furnace) refines the blister copper into anode copper, and then sends it to electrolysis to produce a cathode copper plate.
- the production process requires two steps of blowing and refining from copper crucible to anode copper. The production process is long, the efficiency is low, and the cost is relatively high.
- the main purpose of the present application is to provide a method and an apparatus for producing an anode copper, which solves the problems of the prior art that the copper beryllium to anode copper production process is too long, the efficiency is low, and the production cost is high.
- an anode copper production method comprising the steps of: transporting a copper crucible into a copper making furnace, and injecting oxygen-enriched air into the copper crucible in the copper making furnace The oxidation treatment is performed to cause the copper beryllium to carry out a copper-forming reaction to form an anode copper; wherein the volume percentage of oxygen in the oxygen-enriched air is 30 to 80%.
- the cold material is simultaneously added to the copper-making furnace, and/or the water mist is sprayed into the copper-making furnace, and/or the cooling element is disposed outside the furnace body of the copper-making furnace; It includes one or more of waste copper, electrolytic residual copper and solid copper.
- the metal copper and the copper-making slag are obtained, and when the oxygen in the metal copper in the copper-making furnace is less than 0.2% by weight, the copper slag is discharged.
- Copper furnace metal copper as anode copper; when the metal copper in the coppermaking furnace contains more than 0.2wt% oxygen, the copper slag is discharged into the coppermaking furnace, and then a reducing agent is introduced into the coppermaking furnace to the metal copper.
- the copper oxide impurities in the reduction reaction are carried out to obtain an anode copper.
- the flux is added from the top of the copper making furnace; at the same time, the oxygen-enriched air is sprayed into the copper making furnace by the bottom blowing method for oxidation treatment, or optionally sprayed
- the reducing agent is subjected to a reduction reaction.
- the flux is selected from quartz stone and/or limestone.
- the reducing agent is selected from one or more of natural gas, liquefied petroleum gas, and a solid carbon-based reducing agent.
- the solid carbon-based reducing agent is pulverized coal and/or lump coal.
- the copper content of the copper matte is 70% by weight or more.
- the copper content of the copper matte is 70 to 78% by weight.
- an anode copper production apparatus comprising a copper-making furnace provided with a copper crucible inlet and a copper-making slag outlet, and a copper-making furnace for copper-making reaction of the copper crucible To generate anode copper and copper slag; the anode copper production device further comprises a spray gun, which is arranged at the side or the bottom of the copper making furnace, and is used for injecting oxygen into the copper making furnace by 30-80% by volume. Air and optional reducing agent.
- the copper making furnace is also provided with a flux inlet for introducing a flux.
- the furnace body of the copper making furnace is a horizontal cylindrical furnace body.
- the copper making furnace is further provided with a cold material inlet for adding one or more of electrolytic copper residual, waste copper and solid copper to the copper making furnace.
- the anode copper production apparatus further includes a cooling device for cooling the copper making furnace.
- the cooling device is a negative pressure water jacket device or a water spray mist cooling device.
- the water spray device is used to spray water mist into the inside of the furnace body of the copper making furnace.
- the copper making furnace is further provided with an anode copper outlet;
- the anode copper production device is further provided with a casting device, and the casting device is connected with the anode copper outlet for casting the anode copper.
- the casting apparatus is a double disc casting machine.
- the copper crucible is transported into a copper making furnace, and oxygen-enriched air is sprayed into the copper-making furnace to oxidize the copper crucible, so that the copper crucible is subjected to a copper-making reaction to form an anode.
- Copper wherein the volume percentage of oxygen in the oxygen-enriched air is 30 to 80%.
- the invention oxidizes the copper ruthenium in a high oxygen-rich state to cause a copper-making reaction, and can be converted from copper ruthenium to anode copper in one step, which greatly simplifies the production process of the anode copper and improves the production efficiency of the anode copper. And save production costs.
- FIG. 1 is a schematic structural view of a copper making furnace provided according to an embodiment of the present application.
- FIG. 2 is a schematic structural view of an anode copper production apparatus according to an embodiment of the present application.
- FIG. 3 is a schematic structural view of a short-flow copper smelting system according to an embodiment of the present application.
- FIG. 4 is a schematic structural diagram of a short-flow copper smelting system according to an embodiment of the present application.
- FIG. 5 is a block diagram showing the structure of a short-flow copper smelting system according to an embodiment of the present application.
- FIG. 6 shows a schematic structural diagram of a short-flow copper smelting system according to an embodiment of the present application.
- the present invention provides an anode copper production method comprising the steps of: transporting a copper crucible into a copper making furnace, and injecting oxygen-enriched air into the copper making furnace to oxidize the copper crucible to The copper crucible is subjected to a copper-forming reaction to form an anode copper; wherein the volume percentage of oxygen in the oxygen-enriched air is 30 to 80%.
- the invention oxidizes the copper ruthenium in a high oxygen-rich state to cause a copper-making reaction, and can be converted from copper ruthenium to anode copper in one step, which greatly simplifies the production process of the anode copper and improves the production efficiency of the anode copper. And save production costs.
- the above copper-making reaction is used to directly produce anode copper.
- the cold material is simultaneously added to the copper-making furnace, and/or the water mist is sprayed into the copper-making furnace, and/or disposed outside the furnace body of the copper-making furnace.
- a cooling element wherein the cold material comprises one or more of waste copper, electrolytic residual copper, and solid copper.
- CN103382528 proposes a two-step copper smelting process, which first melts copper concentrate into 65-78% copper-copper in a smelting furnace, and then directly produces an anode by oxidation-reduction reaction in a converting furnace. copper.
- This method mainly has the problem of heat balance and the flue gas problem brought about by it: the redox reaction in the blowing furnace emits a large amount of heat, which must be carried away in some way to maintain the heat balance; the process regulates oxygen, air, The amount of nitrogen, the heat of reaction is carried away by the gas, so the total amount of gas injected must be more, and the relative oxygen concentration is necessarily lower, which makes the amount of flue gas large, and the sulfur dioxide content in the flue gas is very low. Therefore, the subsequent flue gas treatment system and the acid production system are large in scale, large in investment, and high in operating cost.
- the patent does not indicate how to achieve a copper-copper grade of 65 to 78% in the melting furnace.
- the present invention adopts the method of adding cold material to the copper making furnace, and/or spraying water mist into the copper making furnace, and/or cooling outside the furnace body of the copper making furnace.
- the thermal balance of the components are as follows:
- the added cold material may be one or more of waste copper, electrolytic residual copper, and solid copper.
- waste copper electrolytic residual copper
- solid copper waste copper, electrolytic residual copper, and solid copper.
- copper smelting plants use separate metallurgical furnaces to melt and refine secondary copper materials such as waste copper and electrolytic residual copper. This requires not only additional fuel to heat the cold material, but more importantly, the purchase of separate equipment. The construction of separate workshops and the configuration of individual workers has greatly increased the operating costs of the plant.
- a water jacket which is also for heat dissipation to achieve heat balance of the furnace body.
- the injection of water mist has the following advantages: 1) Control the furnace temperature more effectively. Since the gasification of water can absorb a large amount of heat, a small change in the amount of water injected can cause a large change in heat, so that the furnace temperature can be controlled more accurately and effectively; 2) the life of the spray gun is extended.
- the gas injected into the spray gun is less than the low oxygen enrichment concentration, the working strength of the spray gun is low, and the cooling effect of the water can also extend the life of the spray gun itself; 3) 40% rich
- the oxygen concentration can be nearly 1 times higher than the low oxygen rich concentration (21% to 25%).
- the high oxygen enrichment concentration (for example, 40%) can handle nearly twice as much material; 4) low energy consumption and low power consumption.
- the power of the water spray device is much smaller than the size of the device that is blasted into the air.
- the copper-making furnace of the present invention can be carried out under conditions of high oxygen-rich concentration blowing.
- the metal copper and the copper-making slag are obtained, and when the metal copper in the copper-making furnace contains less than 0.2% by weight of oxygen, The copper slag is discharged into the copper making furnace, and the metal copper is used as the anode copper; when the metal copper in the copper making furnace contains more than 0.2% by weight of oxygen, the copper slag is discharged into the copper making furnace and then introduced into the copper making furnace.
- the reducing agent reduces the copper oxide impurities in the metallic copper to obtain an anode copper.
- the purpose of the copper-making reaction is to remove sulfur and other impurities from the copper crucible to obtain a qualified anode copper.
- the impurity removal process mainly uses an oxidation reaction to oxidize impurities in copper to remove slag.
- the metal copper in the coppermaking furnace contains less than 0.2% by weight of oxygen, on the one hand, it is indicated that the impurities are more sufficiently oxidized and enter the copper slag, and on the other hand, the copper is substantially not subjected to peroxidation.
- the process of the copper-making reaction in the process of the copper-making reaction, the process of oxidizing only does not reduce, and the anode copper can be directly obtained.
- the oxygen contained in the metallic copper in the copper-making furnace is higher than 0.2% by weight, it is indicated that part of the copper is oxidized while removing impurities.
- a reducing agent may be further added to carry out a reduction reaction of these copper oxide impurities.
- the reduction reaction is carried out after the copper-making slag is discharged from the copper-making furnace, and it is also possible to prevent the impurities previously oxidized and slag from being dissolved back into the metallic copper, thereby further ensuring the grade of the anode copper.
- the flux is added from the top of the copper making furnace; meanwhile, the oxygen-enriched air is sprayed into the copper making furnace for oxidation treatment by bottom blowing.
- a reducing agent may be sprayed to carry out the reduction reaction.
- the flux is selected from the group consisting of quartz and/or limestone.
- the reducing agent is selected from one or more of natural gas, liquefied petroleum gas, and solid carbon-based reducing agent, and the solid carbon-based reducing agent is preferably pulverized coal and/or lump coal.
- the copper content of the copper matte is 70% by weight or more, which can avoid the problem that the copper slag amount is too large due to the copper content of the copper matte is too high, and the copper straightness caused by the copper crucible is prevented.
- the copper content of the copper ruthenium is 70 to 78% by weight, which can further avoid the problem that the copper content of the smelting slag is too high due to the excessive copper content of the first copper ruthenium, and the problem of low copper direct yield is prevented. .
- the copper bismuth contains copper at 70 to 78%, elements such as lead, zinc and bismuth enter the smelting slag in the form of an oxide, which facilitates subsequent recovery of these elements from the CR furnace. If the copper bismuth contains low copper, such as 40-50%, some of these elements will remain in the copper bismuth, which is not conducive to subsequent recovery from the CR furnace.
- an anode copper production apparatus as shown in FIG. 1, which comprises a copper making furnace 20 provided with a copper crucible inlet and a copper making slag outlet, and a copper making furnace 20 It is used for copper-making reaction of copper bismuth to generate anode copper and copper slag; the anode copper production device further comprises a spray gun which is arranged at the side or the bottom of the copper-making furnace 20 for injecting oxygen into the copper-making furnace 20.
- the volume percentage is 30 to 80% of oxygen-enriched air and an optional reducing agent.
- the production device provided by the invention can perform copper-making reaction on copper bismuth in a high oxygen-rich state, and can convert copper bismuth into anode copper in one step, which greatly simplifies the production process of anode copper, improves the production efficiency of anode copper, and saves Production costs.
- the metal copper in the coppermaking furnace contains less than 0.2% oxygen
- the impurities are more sufficiently oxidized and enter the copper slag
- the copper is substantially not subjected to peroxidation.
- the process of the copper-making reaction in the process of the copper-making reaction, the process of oxidizing only does not reduce, and the anode copper can be directly obtained.
- the oxygen content in the metallic copper in the copper-making furnace is higher than 0.2%, it indicates that some copper is oxidized while removing impurities.
- a reducing agent may be further added to carry out a reduction reaction of these copper oxide impurities.
- the reduction reaction is carried out after the copper-making slag is discharged from the copper-making furnace, and it is also possible to prevent the impurities previously oxidized and slag from being dissolved back into the metallic copper, thereby further ensuring the grade of the anode copper.
- the copper making furnace 20 is also provided with a flux inlet for introducing a flux.
- a flux inlet for introducing a flux.
- the introduction of a flux facilitates further improvement of the grade of the anode copper.
- the furnace body of the copper making furnace 20 is a horizontal cylindrical furnace body.
- the copper making furnace 20 is further provided with a cold material inlet for adding one or more of electrolytic copper residuals, scrap copper and solid copper crucibles to the copper making furnace 20.
- the anode copper production apparatus further includes a cooling device for cooling the copper making furnace 20. More preferably, the cooling device is a vacuum water jacket device or a water mist cooling device. Further preferably, the water spray device is used to spray water mist into the inside of the furnace body of the copper making furnace 20.
- CN103382528 proposes a two-step copper smelting process, which first melts copper concentrate into 65-78% copper-copper in a smelting furnace, and then directly produces an anode by oxidation-reduction reaction in a converting furnace. copper.
- This method mainly has the problem of heat balance and the flue gas problem brought about by it: the redox reaction in the blowing furnace emits a large amount of heat, which must be carried away in some way to maintain the heat balance; the process regulates oxygen, air, The amount of nitrogen, the heat of reaction is carried away by the gas, so the total amount of gas injected must be more, and the relative oxygen concentration is necessarily lower, which makes the amount of flue gas large, and the sulfur dioxide content in the flue gas is very low. Therefore, the subsequent flue gas treatment system and the acid production system are large in scale, large in investment, and high in operating cost.
- the patent does not indicate how to achieve a copper-copper grade of 65 to 78% in the melting furnace.
- the present invention adopts the method of adding cold material to the copper making furnace, and/or spraying water mist into the copper making furnace, and/or cooling outside the furnace body of the copper making furnace.
- the thermal balance of the components are as follows:
- the added cold material may be one or more of waste copper, electrolytic residual copper, and solid copper.
- waste copper electrolytic residual copper
- solid copper waste copper, electrolytic residual copper, and solid copper.
- copper smelting plants use separate metallurgical furnaces to melt and refine secondary copper materials such as waste copper and electrolytic residual copper. This requires not only additional fuel to heat the cold material, but more importantly, the purchase of separate equipment. The construction of separate workshops and the configuration of individual workers has greatly increased the operating costs of the plant.
- a water jacket which is also for heat dissipation to achieve heat balance of the furnace body.
- the injection of water mist has the following advantages: 1) Control the furnace temperature more effectively. Since the gasification of water can absorb a large amount of heat, a small change in the amount of water injected can cause a large change in heat, so that the furnace temperature can be controlled more accurately and effectively; 2) the life of the spray gun is extended.
- the gas injected into the spray gun is less than the low oxygen enrichment concentration, the working strength of the spray gun is low, and the cooling effect of the water can also extend the life of the spray gun itself; 3) 40% rich
- the oxygen concentration can be nearly 1 times higher than the low oxygen rich concentration (21% to 25%).
- the high oxygen enrichment concentration (for example, 40%) can handle nearly twice as much material; 4) low energy consumption and low power consumption.
- the power of the water spray device is much smaller than the size of the device that is blasted into the air.
- the copper-making furnace of the present invention can be carried out under conditions of high oxygen-rich concentration blowing.
- the obtained anode copper is a copper melt.
- the copper making furnace 20 is further provided with an anode copper outlet; the anode copper production device is further provided with a casting device 40, and the casting device 40 is in communication with the anode copper outlet for the anode Copper is cast.
- the copper melt can be further cast by forming the casting apparatus 40 to form a product such as an anode copper plate. More preferably, the casting apparatus 40 is a double disc casting machine.
- the present application proposes a short-process copper smelting method, which comprises a smelting furnace, a copper-making furnace, a CR furnace, a first flow tank and a second flow tank; the smelting furnace is provided with a copper sputum outlet And the smelting slag outlet; the copper making furnace is provided with a copper crucible inlet, the copper crucible inlet is connected to the copper crucible outlet through the first laundering tank; the CR furnace is provided with a molten slag inlet, and the molten slag inlet is connected to the melting slag outlet through the second laundering;
- the process copper smelting method comprises the steps of: smelting a copper concentrate in a smelting furnace to obtain a first copper slag and a smelting slag; and performing a copper-making reaction on the first copper bismuth in a copper-making furnace to generate an anode copper and a copper slag And
- noise slag means: slag that does not cause heavy metal contamination.
- the CR furnace is called a fully recycled furnace.
- the copper smelting method of the present invention adopts a copper-plating device with a pick-up type, and the copper bismuth end of the smelting furnace is directly connected to the copper-making furnace through the launder, and the smelting furnace is discharged.
- the slag end is directly connected to the CR furnace through the launder, which realizes short-process copper smelting.
- the step of smelting the copper concentrate in the smelting furnace comprises: mixing the copper concentrate with the first flux to obtain a mixture; and feeding the mixture into the smelting furnace at the first oxidizing agent Melting is carried out under the action to obtain a first copper crucible and a smelting slag.
- the bottom blowing smelting method or the side blowing smelting method is employed in the smelting process. The use of the bottom blowing smelting method or the side blowing smelting method can further improve the copper enamel grade.
- the first flux is selected from quartz stone and/or limestone; the first oxidant is selected from one or more of oxygen, compressed air, and oxygen-enriched air.
- oxygen-enriched air refers to a gas having a concentration of oxygen greater than the concentration of oxygen in the air, such as may be obtained by incorporating oxygen into the air.
- the first oxidizing agent in the step of smelting the copper concentrate in the smelting furnace, is injected in an amount corresponding to 120 Nm 3 or more of O 2 per ton of copper concentrate to make the copper of the first copper bismuth.
- the content is 70% by weight or more.
- the injection amount of the first oxidant is controlled to be 120 Nm 3 or more and O 2 per ton of copper concentrate, so that the copper content of the first copper ruthenium is 70% by weight or more, thereby avoiding the copper content of the first copper ruthenium being too low.
- the problem of the large amount of copper slag caused is to prevent the problem of low copper yield due to it.
- the first oxidizing agent is injected in an amount of 120 to 200 Nm 3 O 2 per ton of copper concentrate so that the copper content of the first copper cerium is 70 to 78% by weight, which can further avoid the copper content of the first copper ruthenium.
- the high smelting slag copper contains an excessively high problem, preventing the problem of low copper yield.
- elements such as lead, zinc and bismuth enter the smelting slag in the form of oxides, which facilitates subsequent recovery of these elements from the CR furnace. If the copper bismuth contains low copper, such as 40-50%, some of these elements will remain in the copper bismuth, which is not conducive to subsequent recovery from the CR furnace.
- the cooled copper-making slag is put into a melting furnace and smelted together with the copper concentrate.
- the melting temperature in the smelting process is 1150 to 1300 ° C
- the first flux is added in an amount of 1 to 20% by weight based on the total weight of the copper ore.
- the step of performing a copper-making reaction on the first copper crucible in the copper-making furnace further comprises: simultaneously adding cold material to the copper-making furnace, and/or spraying water mist into the copper-making furnace, And/or providing a cooling element outside the furnace body of the coppermaking furnace; wherein the cold material comprises one or more of waste copper, electrolytic residual copper and solid copper.
- CN103382528 proposes a two-step copper smelting process, which first melts copper concentrate into 65-78% copper-copper in a smelting furnace, and then directly produces an anode by oxidation-reduction reaction in a converting furnace. copper.
- This method mainly has the problem of heat balance and the flue gas problem brought about by it: the redox reaction in the blowing furnace emits a large amount of heat, which must be carried away in some way to maintain the heat balance; the process regulates oxygen, air, The amount of nitrogen, the heat of reaction is carried away by the gas, so the total amount of gas injected must be more, and the relative oxygen concentration is necessarily lower, which makes the amount of flue gas large, and the sulfur dioxide content in the flue gas is very low. Therefore, the subsequent flue gas treatment system and the acid production system are large in scale, large in investment, and high in operating cost.
- the patent does not indicate how to achieve a copper-copper grade of 65 to 78% in the melting furnace.
- the present invention adopts the method of adding cold material to the copper making furnace, and/or spraying water mist into the copper making furnace, and/or cooling outside the furnace body of the copper making furnace.
- the thermal balance of the components are as follows:
- the added cold material may be one or more of waste copper, electrolytic residual copper, and solid copper.
- waste copper electrolytic residual copper
- solid copper waste copper, electrolytic residual copper, and solid copper.
- copper smelting plants use separate metallurgical furnaces to melt and refine secondary copper materials such as waste copper and electrolytic residual copper. This requires not only additional fuel to heat the cold material, but more importantly, the purchase of separate equipment. The construction of separate workshops and the configuration of individual workers has greatly increased the operating costs of the plant.
- a water jacket which is also for heat dissipation to achieve heat balance of the furnace body.
- the injection of water mist has the following advantages: 1) Control the furnace temperature more effectively. Since the gasification of water can absorb a large amount of heat, a small change in the amount of water injected can cause a large change in heat, so that the furnace temperature can be controlled more accurately and effectively; 2) the life of the spray gun is extended.
- the gas injected into the spray gun is less than the low oxygen enrichment concentration, the working strength of the spray gun is low, and the cooling effect of the water can also extend the life of the spray gun itself; 3) 40% rich
- the oxygen concentration can be nearly 1 times higher than the low oxygen rich concentration (21% to 25%).
- the high oxygen enrichment concentration (for example, 40%) can handle nearly twice as much material; 4) low energy consumption and low power consumption.
- the power of the water spray device is much smaller than the size of the device that is blasted into the air.
- the copper-making furnace of the present invention can be carried out under conditions of high oxygen-rich concentration blowing.
- the first copper crucible is oxidized by injecting oxygen-enriched air into the copper-making furnace to perform a copper-making reaction, and the volume of oxygen in the oxygen-enriched air The percentage is 30 to 80%.
- the oxygen concentration of the blowing furnace is 9-60%, since it relies on the gas to carry away heat, the actual oxygen concentration can only be maintained below 25%, and the high oxygen-rich concentration cannot be truly achieved.
- the above-mentioned heat balance means can fully achieve an oxygen-enriched air concentration of 30 to 80%.
- the metal copper and the copper-making slag are obtained; when the metal copper in the copper-making furnace contains less than 0.2% by weight of oxygen, The copper slag is discharged from the coppermaking furnace to obtain anode copper.
- the oxygen in the metal copper in the coppermaking furnace is higher than 0.2 wt%, the copper slag is discharged into the coppermaking furnace, and the reducing agent is introduced into the coppermaking furnace.
- the copper oxide impurities in the metallic copper are subjected to a reduction reaction to obtain an anode copper.
- the purpose of the copper-making reaction is to remove the sulfur element and other impurities in the first copper crucible to obtain a qualified anode copper.
- the impurity removal process mainly uses an oxidation reaction to oxidize impurities in copper to remove slag.
- the metal copper in the coppermaking furnace contains less than 0.2% by weight of oxygen, on the one hand, it is indicated that the impurities are more sufficiently oxidized and enter the copper slag, and on the other hand, the copper is substantially not subjected to peroxidation.
- the process of the copper-making reaction in the process of the copper-making reaction, the process of oxidizing only does not reduce, and the anode copper can be directly obtained.
- the oxygen contained in the metallic copper in the copper-making furnace is higher than 0.2% by weight, it is indicated that part of the copper is oxidized while removing impurities.
- a reducing agent may be further added to carry out a reduction reaction of these copper oxide impurities.
- the reduction reaction is carried out after the copper-making slag is discharged from the copper-making furnace, and it is also possible to prevent the impurities previously oxidized and slag from being dissolved back into the metallic copper, thereby further ensuring the grade of the anode copper.
- the second flux is added from the top of the copper making furnace; meanwhile, the bottom blowing method is used in the copper making furnace.
- the oxygen-enriched air is sprayed for oxidation treatment, or alternatively, the first reducing agent is sprayed for reduction.
- the second flux is selected from the group consisting of quartz stone and/or limestone.
- the first reducing agent is selected from one or more of natural gas, liquefied petroleum gas, and solid carbon-based reducing agent.
- the solid carbon-based reducing agent is a pulverized coal and/or a solid carbonaceous reducing agent.
- the function of the above CR furnace is to recover valuable metals in the smelting slag by reducing fuming and sedimentation, and to make harmless slag.
- the CR furnace includes a cavity including a reducing reduction chamber and a settling chamber; and the step of recovering the valuable metal in the smelting slag includes: smelting the slag in the reducing smoulding chamber Performing reduction and smoulding treatment to obtain valuable metal flue gas and reducing slag, and sedimenting the reducing slag in the sedimentation chamber to obtain second copper ruthenium and harmless slag; or sedimenting the smelting slag in the sedimentation chamber, The second copper ruthenium and the sedimentation slag are obtained, and the sedimentation slag is subjected to reduction and smoulding treatment in the reduction smoulding cavity to obtain a valuable metal smog and a harmless slag.
- the above CR furnace is an integrated recovery furnace, which simultaneously includes a reduction smoulding chamber and a settling chamber.
- the smelting slag is successively subjected to reduction smoulding treatment and sedimentation treatment.
- the magnetic iron (ferric oxide) in the smelting slag can be reduced to ferrous oxide for slag formation, which can reduce the viscosity of the smelting slag, thereby improving the subsequent sedimentation separation effect and facilitating
- the second copper ruthenium is separated from the reducing slag.
- the valuable metal oxides such as zinc, lead and antimony are reduced to metal, they are separated into valuable metal fumes due to their volatility, thereby achieving the purpose of recovering valuable metals.
- the reduced slag flowing dynamics
- the reduced slag after the reduction smoulding treatment directly enters the sedimentation separation, on the one hand, the treatment efficiency can be greatly improved; on the other hand, since the reducing slag directly enters the sedimentation treatment, a more stable flow state can be maintained, and in the process There are only slight temperature changes or even no temperature changes. The two reasons make it have better sedimentation effect, which can further improve the recovery rate of the second copper matte.
- the sedimentation treatment is set before the step of reducing the fuming treatment.
- the copper ruthenium in the smelting slag can be separated first, and then subjected to reduction and smouldering treatment to further recover valuable metals such as zinc, lead, and antimony.
- the present invention more preferably adopts a method of first reducing the post-smoothing sedimentation treatment, compared to the manner of reducing the fuming treatment after the sedimentation.
- the advantage is that the higher the sedimentation separation temperature, the better the separation effect.
- the temperature required for the reduction of flue gas is very high (1200 to 1400 ° C). Therefore, the temperature of the material after the first reduction of flue gas is high, and separation can be achieved in the sedimentation stage without additional heating.
- this method of first reducing the post-smoothing sedimentation treatment can also replenish the sedimentation treatment.
- the specific heating method can be as follows: the electrode can be heated or insulated in the settling section (for example, 3 to 6 electrodes can be set), and/or the submerged combustion nozzle can be provided (the submerged combustion nozzle ejects fuel and oxygen, and the amount of oxygen Control is in the state of incomplete combustion of the fuel).
- the method of first reducing the post-smoothing sedimentation treatment has the following advantages: after the reducing slag stays in the settling chamber for a certain period of time, the sedimentation stratification of the dross can be more fully realized, the harmless slag is discharged from the upper part, and the second copper slag is discharged from the lower part. release.
- the smelting slag may be successively subjected to a plurality of reduction smouldering and sedimentation steps, or the smelting slag may be divided into a plurality of parts for performing a reductive smouldering and sedimentation step.
- a partition wall is further disposed in the cavity to divide the cavity into a reduction smoulding chamber and a sedimentation chamber, and the smog reduction and smog chamber and the sedimentation chamber are respectively located in the horizontal direction of the partition wall.
- Side, and the communication channel connecting the reducing chamber and the settling chamber is disposed near the bottom of the chamber.
- the step of reducing the fuming treatment comprises: adding a second reducing agent to the reducing nicotizing chamber for reductive fuming treatment; preferably, the second reducing agent is selected from the group consisting of natural gas, gas, liquefied petroleum gas, One or more of the iron powder and the solid carbon-based reducing agent, more preferably the solid carbon-based reducing agent is selected from the group consisting of lump coal and/or pulverized coal.
- the reagent is selected for reduction and fuming treatment, and the recovery of valuable metals is more thorough.
- the oxidant is injected into the reduction smoulding chamber to provide heat by combustion, and the oxidant may also react with the reducing agent to form a reducing gas such as carbon monoxide, and reduce the effect together with the added reducing agent.
- a reducing gas such as carbon monoxide
- a side blowing lance is disposed in the reducing smoulding chamber, and in the step of reducing the smoulding treatment, the second reducing agent is blasted into the reducing smoulding chamber by a side blasting gun.
- the reducing smoulding chamber is further provided with a venting port, and the step of reducing the smoulding treatment further comprises: introducing a secondary air at the upper portion of the reducing smoulding chamber or at the venting port. In this way, the valuable metal flue gas can be oxidized to a valuable metal oxide, and then the flue gas can be recovered.
- the reaction temperature is 1200 to 1400 °C. More preferably, when the reduction flue gasification treatment step is located before the sedimentation treatment step, a collector is added to the reduction flue gas chamber while the reduction flue gas treatment is performed; preferably, the trap agent is selected from the first vulcanizing agent and/or copper Concentrate, more preferably the first vulcanizing agent is selected from the group consisting of pyrite and/or pyrite.
- a second vulcanizing agent and/or copper concentrate is added to the sedimentation chamber while the sedimentation treatment is performed, and preferably the second vulcanizing agent is selected from the group consisting of pyrite, pyrite and One or more of lead slag copper scum.
- a vulcanizing agent and/or a copper concentrate facilitates the reduction of the copper bismuth grade in the smelting slag to be converted into a low-grade copper ruthenium (second copper ruthenium), which can reduce the copper content in the harmless slag and further increase the copper content. Recovery rate.
- a slag such as lead slag copper scum as a vulcanizing agent, wherein the lead is also It can be volatilized and recovered together with the lead in the sedimentation slag in the reduction fuming step, so that the refractory materials generated in some production processes can be fully utilized to realize comprehensive utilization of resources without adding additional equipment investment and process links.
- the step of the sedimentation treatment further comprises: injecting an inert gas and/or a sulfur dioxide gas into the settling chamber. This creates a weak agitation which facilitates the separation of copper and slag. More preferably, the sulfur dioxide gas is bubbled in, which acts as a partial vulcanizing agent in addition to the agitation action, and is more advantageous for producing a low-grade copper beryllium in the sedimentation stage.
- the copper smelting method further comprises the step of returning the second copper crucible to the melting furnace for melting. This can increase the utilization of copper.
- the copper smelting method further comprises the step of returning the second copper crucible to the copper making furnace for copper making.
- This can increase the utilization of copper. Since the second copper crucible is generally added in a cooled state (and a solid second copper crucible), it can also function as a heat balance.
- the obtained copper is a copper melt; after the step of the copper-making reaction, the copper smelting method further comprises casting the copper melt.
- the step of molding This allows the copper melt to be further cast into a product such as a copper anode plate.
- a copper smelting system comprising a smelting furnace 10, a copper making furnace 20, a CR furnace 30, a first launder and a second stream a tank; wherein the melting furnace 10 is used for smelting copper concentrate to produce a first copper crucible and smelting slag; the melting furnace 10 is provided with a first copper crucible outlet and a smelting slag outlet; and the copper making furnace 20 is provided with a copper crucible inlet, The copper crucible inlet and the first copper crucible outlet are communicated through the first launder, and the copper making furnace 20 is used for copper-making reaction of the first copper crucible to generate anode copper and copper-making slag; the CR furnace 30 is provided with a smelting slag inlet, which is The smelting slag outlet is connected through the second launder for reducting fuming and sedimentation of
- the copper ore can be smelted by the melting furnace 10 to obtain a first copper crucible and a smelting slag.
- the smelting slag can be reduced and smelted and settled by the CR furnace 30, and the valuable metals in the smelting slag such as metal zinc, lead, bismuth, and the like can be recovered.
- the valuable metals in the smelting slag such as metal zinc, lead, bismuth, and the like can be recovered.
- the beneficiation process not only greatly reduces the factory floor space, but also makes the process more simple. It also fundamentally eliminates the pollution caused by the beneficiation agent added in the slag beneficiation process.
- the CR furnace 30 communicates with the slag end of the melting furnace 10, and the copper making furnace 20 communicates with the copper rim end of the melting furnace 10.
- the first copper crucible is subjected to a copper-making reaction to form a higher-grade anode copper, and on the other hand, the molten slag produced in the smelting process is obtained.
- the recycling process that is, the use of a pick-up copper smelting device, greatly shortens the steps of copper smelting, and has a good industrialized large-scale application prospect.
- the CR furnaces 30 are a plurality of units arranged in parallel or in series.
- the plurality of CR furnaces 30 can produce the second copper crucible, the valuable metal, and the water-damaged harmless slag by continuous operation or alternate operation, thereby improving the processing efficiency.
- the copper making furnace 20 is a plurality of tubes arranged in parallel. This also improves the capabilities of the device.
- the copper making furnace 20 is two in parallel, and the CR furnace is one; or
- the copper making furnace 20 is one, and the CR furnace is two in parallel; or
- two copper-making furnaces 20 are arranged in parallel, and the CR furnaces are also two disposed in parallel.
- the CR furnace 30 includes a cavity including a reduced reduction smoulding chamber 31 and a settling chamber 32, and the reducing smoulding chamber 31 is in communication with the smelting slag outlet for reducing the smelting slag.
- the reducing smog chamber 31 is provided with a flue gas outlet
- the settling chamber 32 is connected with the reducing smoating chamber 31 for sedimentation treatment of the reducing slag after the reduction and the smoulding treatment
- the settling chamber 32 is provided with a first The second copper crucible outlet and the slag discharge port (shown in FIG.
- the CR furnace 30 includes a cavity including a reduced reduction smoulding chamber 31 and a settling chamber 32, and the settling chamber 32 communicates with the smelting slag outlet. It is used for sedimentation treatment of the smelting slag, and the sedimentation chamber 32 is provided with a second copper sputum outlet, and the reduction smoulding chamber 31 is connected with the sedimentation chamber 32 for reducing and smoulding the sedimentation slag after the settlement treatment, and reducing the smoke
- the chemistry chamber 31 is provided with a flue gas outlet and a slag discharge port.
- the CR furnace 30 provided by the present invention is an integrated device, which includes a reducing flue gas chamber 31 and a settling chamber 32, and a connection relationship between the reduction flue gas chamber 31 and the sedimentation chamber 32, which can be determined to reduce the flue gas. , post-settling; or settle first, then reduce the fuming.
- the smelting slag can be first subjected to reduction and smouldering treatment, and then subjected to sedimentation treatment.
- the magnetic iron (ferric oxide) in the smelting slag can be reduced to ferrous oxide for slag formation, which can reduce the viscosity of the smelting slag and thereby improve the subsequent sedimentation separation effect. It is convenient to separate the second copper crucible from the reducing slag.
- the valuable metal oxides such as zinc, lead and antimony are reduced to metal, they are separated into valuable metal fumes due to their volatility, thereby achieving the purpose of recovering valuable metals.
- the obtained reducing slag flowing dynamics
- the smelting slag after reduction and smoulding treatment directly enters the sedimentation separation, which can greatly improve the treatment efficiency; on the other hand, the reducing slag directly enters the sedimentation treatment, and can maintain a more stable flow state. In the process, there is only a slight temperature change or even no temperature change. The two reasons make it have better sedimentation effect, which can further improve the recovery rate of the second copper matte.
- the smelting slag can be first subjected to sedimentation treatment and then subjected to reduction smoulding treatment.
- the copper ruthenium in the smelting slag can be separated first, and then the reduction smoulding treatment stage can be further carried out to further recover valuable metals such as zinc, lead and bismuth therein.
- the present invention more preferably adopts a method of first reducing the post-smoothing sedimentation treatment, compared to the manner of reducing the fuming treatment after the sedimentation.
- the advantage is that the higher the sedimentation separation temperature, the better the separation effect.
- the temperature required for the reduction of flue gas is very high (1200 to 1400 ° C). Therefore, the temperature of the material after the first reduction of flue gas is high, and separation can be achieved in the sedimentation stage without additional heating.
- this method of first reducing the post-smoothing sedimentation treatment can also replenish the sedimentation treatment.
- the method of reducing the flue gas after sedimentation and separation is inevitably required to replenish heat during the sedimentation process.
- the specific heating method can be as follows: the electrode can be heated or insulated in the settling section (for example, 3 to 6 electrodes can be set), and/or the submerged combustion nozzle can be provided (the submerged combustion nozzle ejects fuel and oxygen, and the amount of oxygen Control is in the state of incomplete combustion of the fuel).
- the method of first reducing the post-smoothing sedimentation treatment has the following advantages: after the reducing slag stays in the settling chamber for a certain period of time, the sedimentation stratification of the dross can be more fully realized, the harmless slag is discharged from the upper part, and the second copper slag is discharged from the lower part. release.
- a partition wall 33 is further disposed in the cavity to divide the cavity into a reduction smoulding chamber 31 and a settling chamber 32, and a reduction smoulding chamber 31 and a settling chamber 32.
- the two sides of the partition wall 33 are respectively located in the horizontal direction, and the communication passages of the reduction tobacco chamber 31 and the sedimentation chamber 32 are disposed near the bottom of the chamber.
- a fluid melt which reacts in the reduction smoulding chamber 31 and a melt which is subjected to sedimentation treatment in the sedimentation chamber can achieve a smoother flow, and the partition wall can block the reduction smog chamber.
- the agitation and the floating material on the surface further enhance the effect of the sedimentation treatment.
- the partition wall 33 is a water-cooled partition wall.
- the reduction smoulding chamber 31 is further provided with a side lance, which is disposed at the side or bottom of the reduction smoulding chamber 31 for injecting a reducing agent into the reduction smoulding chamber 31.
- the reducing tobacco chamber is further provided with a smoke outlet for discharging valuable metal smoke.
- the reduction smoulding chamber is further provided with a feed port for adding a collector to the reduction smoulding chamber 31.
- the settling chamber 32 is also provided with a heating device for performing the settling chamber 32. Keep warm or warm. This can prevent the sedimentation chamber 32 from cooling down, further ensuring the sedimentation separation effect.
- the heating device is an immersion combustion nozzle or electrode.
- the copper making furnace 20 is further provided with a second spray gun and a flux inlet, and the second spray gun is disposed at the side or the bottom of the copper making furnace 20 for alternately adding oxidizing agent to the copper making furnace 20 or Reducing agent; the flux inlet is used to pass the flux.
- the furnace body of the copper making furnace 20 is a horizontal cylindrical furnace body.
- a plurality of copper-making furnaces 20 may be arranged in parallel to perform alternate operations or simultaneous operations.
- an appropriate amount of water mist can be sprayed into the second spray gun to absorb excess heat generated during the copper making process, reduce the amount of smoke, and prolong the life of the spray gun.
- the coppermaking furnace 20 is also provided with a copper melt outlet; the copper smelting system further includes a casting apparatus 40 in communication with the copper melt outlet for casting the copper melt.
- the obtained anode copper is a copper melt.
- the copper melt can be further cast by forming the casting apparatus 40 to form a product such as an anode copper plate. More preferably, the casting apparatus 40 is a double disc casting machine.
- the copper making furnace 20 is further provided with a copper slag outlet for discharging copper slag; the smelting furnace 10 is further provided with a copper slag inlet for introducing the cooled copper slag.
- the melting furnace 10 is further provided with a copper slag outlet for discharging copper slag; the smelting furnace 10 is further provided with a copper slag inlet for introducing the cooled copper slag.
- the melting furnace 10 is further provided with a second copper crucible inlet for introducing the cooled second copper sulfur into the melting furnace 10. This can further improve the utilization of copper.
- the copper making furnace 20 is further provided with a cold material inlet for adding one or more of electrolytic copper residual, waste copper and solid copper to the copper making furnace 20.
- a cold material inlet for adding one or more of electrolytic copper residual, waste copper and solid copper to the copper making furnace 20.
- the residual electrolytic copper residual in the later electrolysis process and the purchased waste copper and solid copper crucible can be passed into the copper making furnace as a cold material to better realize the heat balance in the copper making furnace. Injecting oxygen into the conditions creates conditions.
- the copper making system further includes a cooling device for cooling the copper making furnace 20.
- a cooling device for cooling the copper making furnace 20. This ensures that the copper-making furnace 20 maintains thermal equilibrium during the copper-making reaction stage, creating conditions for injecting oxygen into the copper-making furnace, and further extending the furnace life.
- Cooling equipment includes, but is not limited to, a negative pressure water jacket device or a spray cooling device
- the melting furnace 10 is a top-blowing smelting furnace, a flash smelting furnace, a bottom-blowing smelting furnace or a side-blown smelting furnace.
- the copper smelting apparatus shown in Fig. 3 is used for copper smelting, and the process conditions of each apparatus are as follows:
- Melting furnace melting temperature is 1300 ° C; flux is quartz stone, the amount of addition is 10% of the total weight of copper ore; oxidant is oxygen, the amount of addition is 150Nm 3 O 2 per ton of copper ore;
- the flux is quartz stone, which is added in an amount of 20% of the total weight of the first copper crucible; the oxidant is oxygen-enriched air having a volumetric oxygen content of 40%, and the addition amount is 200Nm 3 O per ton of the first copper crucible. 2 ; using a spray gun to spray oxidant into the coppermaking furnace, also spray water mist; at the same time add cold waste copper to the coppermaking furnace; the reducing agent is pulverized coal, before the reducing agent is sprayed, the copper slag is firstly sprayed After the discharge, the copper slag is cooled and returned to the smelting furnace.
- CR furnace first reduction of fuming, post-sedimentation; in the step of reducing fuming treatment, the reaction temperature is 1200 ° C; the reducing agent is pulverized coal, the amount of addition is 10% of the total weight of the smelting slag; a small amount of oxygen is supplied to provide combustion-supporting Heat; sulfur dioxide gas is introduced into the settling chamber, and the vulcanizing agent pyrite is added to make low-grade copper bismuth; the low-grade copper bismuth obtained is returned to the melting furnace.
- Treatment results 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; smelting output 250,000 tons of copper, 75% copper, 650,000 tons of smelting, 3% copper, smelting
- the slag contains 2.77% zinc; the copper-making furnace produces 235,000 tons of anode copper, 99.3% copper, and 0.05% sulfur; the smelting slag is treated with CR furnace (reduction ashing and sedimentation), the slag contains 0.3% copper, and the slag contains zinc. 0.28%.
- the copper recovery rate of the entire system is about 99%, and the zinc recovery rate is about 80%.
- the treatment method is the same as that of the first embodiment, except that the copper ore raw materials are different, as follows:
- the processing method is the same as that in Embodiment 1, except that:
- Melting furnace melting temperature is 1300 ° C; flux is quartz stone, the amount of addition is 20% of the total weight of copper ore; oxidant is oxygen, the amount of addition is 200Nm 3 O 2 per ton of copper ore;
- Treatment results 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; 260,000 tons of copper smelting, 78% copper, 620,000 tons of smelting slag, 4% copper, smelting
- the slag contains 2.05% zinc; the copper-making furnace produces 236,000 tons of anode copper, 99.5% copper, 0.03% sulfur; the smelting slag is treated with CR furnace (reduction ashing and sedimentation), the slag contains 0.2% copper, and the slag contains zinc. 0.26%.
- the copper recovery rate of the entire system is about 99%, and the zinc recovery rate is about 82%.
- the processing method is the same as that in Embodiment 1, except that:
- the melting temperature is 1150 ° C;
- the flux is quartz stone, the amount of addition is 1% of the total weight of the copper ore;
- the oxidant is oxygen, the amount of addition is 120Nm 3 O 2 per ton of copper ore;
- Treatment results 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; 260,000 tons of copper smelting, 70% copper, 700,000 tons of smelting, 2.5% copper, smelting
- the slag contains 3.25% zinc; the copper making furnace produces 231,000 tons of anode copper, containing 99.1% copper and 0.03% sulfur; the smelting slag is treated by CR furnace (reduction ashing and sedimentation), the slag contains 0.3% copper, and the slag contains zinc. 0.27%.
- the copper recovery rate of the entire system is about 99%, and the zinc recovery rate is about 80%.
- the processing method is the same as that in Embodiment 1, except that:
- the melting temperature is 1100 ° C;
- the flux is quartz stone, the amount of addition is 0.8% of the total weight of the copper ore;
- the oxidant is oxygen, the amount of addition is 90Nm 3 O 2 per ton of copper ore;
- Treatment results 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; smelting output 200,000 tons of copper, 65% copper, 780,000 tons of smelting, 5% copper, smelting
- the slag contains 4.71% zinc; the copper making furnace produces 228,000 tons of anode copper, 98.0% copper, and 0.1% sulfur; the smelting slag is treated with CR furnace (reduction ashing and sedimentation), the slag contains 0.6% copper, and the slag contains zinc. 0.49%.
- the overall system copper recovery rate is about 95%, and the zinc recovery rate is about 78%.
- the processing method is the same as that in Embodiment 1, except that:
- the flux is quartz stone, which is added in an amount of 20% of the total weight of the first copper crucible; the oxidant is oxygen-enriched air having an oxygen volume content of 80%, and the addition amount is 120Nm 3 O per ton of the first copper crucible. 2 ; using a spray gun to spray oxidant into the copper making furnace, also spray water mist; at the same time, add cold waste copper to the copper making furnace; the reducing agent is pulverized coal; before the reducing agent is sprayed, the copper slag is firstly sprayed Drain, cool and return to the melting furnace.
- Treatment results 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; smelting output 250,000 tons of copper, 75% copper, 650,000 tons of smelting, 3% copper, smelting
- the slag contains 2.77% zinc; the copper-making furnace produces 246,000 tons of anode copper, 99.5% copper, 0.03% sulfur; the smelting slag is treated with CR furnace (reduction ashing and sedimentation), the slag contains 0.4% copper, and the slag contains zinc. 0.32%.
- the copper recovery rate of the whole system is about 99.6%, and the zinc recovery rate is about 80%.
- the processing method is the same as that in Embodiment 1, except that:
- the flux is quartz stone, which is added in an amount of 20% of the total weight of the first copper crucible; the oxidant is oxygen-enriched air having an oxygen volume content of 30%, and the addition amount is 140Nm 3 O per ton of the first copper crucible. 2 ; using a spray gun to spray oxidant into the copper making furnace, also spray water mist, while adding cold waste copper to the copper making furnace; reducing agent is pulverized coal; before spraying the reducing agent, first make copper slag Drain, cool and return to the melting furnace.
- Treatment results 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; smelting output 250,000 tons of copper, 75% copper, 650,000 tons of smelting, 3% copper, smelting
- the slag contains 2.77% zinc; the copper-making furnace produces 220,000 tons of anode copper, 98.8% copper, 0.03% sulfur; the smelting slag is treated with CR furnace (reduction ashing and sedimentation), the slag contains 0.5% copper, and the slag contains zinc. 0.34%.
- the overall system copper recovery rate is about 98.7%, and the zinc recovery rate is about 75%.
- the processing method is the same as that in Embodiment 1, except that:
- the flux is quartz stone, which is added in an amount of 20% of the total weight of the first copper crucible;
- the oxidant is oxygen-enriched air having a volume content of 25% oxygen, and the addition amount is 140Nm 3 O per ton of the first copper crucible. 2 ;
- the reducing agent is pulverized coal; no water mist is sprayed, and no cold material is added;
- Treatment results 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; smelting output 250,000 tons of copper, 75% copper, 650,000 tons of smelting, 3% copper, smelting
- the slag contains 2.77% zinc; the copper-making furnace produces 182,000 tons of anode copper, 97.6% copper, and 0.12% sulfur.
- the slag contains 0.41% copper and the slag contains zinc 0.50. %.
- the copper recovery rate of the entire system is about 95%, and the zinc recovery rate is about 70%.
- the processing method is the same as that in Embodiment 1, except that:
- CR furnace first reduction of fuming, post-sedimentation; in the step of reducing fuming treatment, the reaction temperature is 1350 ° C; the reducing agent is pulverized coal, the amount of addition is 10% of the total weight of the smelting slag; a small amount of oxygen is supplied to provide heat;
- the low-grade copper bismuth is formed by adding a vulcanizing agent pyrite; sulfur dioxide gas is introduced into the sedimentation chamber, and the low-grade copper bismuth is returned to the melting furnace.
- Treatment results 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; smelting output 250,000 tons of copper, 75% copper, 650,000 tons of smelting, 3% copper, smelting
- the slag contains 2.77% zinc; the copper-making furnace produces 235,000 tons of anode copper, 99.3% copper, and 0.05% sulfur; the smelting slag is treated with CR furnace (reduction ashing and sedimentation), the slag contains 0.1% copper, and the slag contains zinc. 0.19%.
- the overall system copper recovery rate is about 99%, and the zinc recovery rate is about 85%.
- the processing method is the same as that in Embodiment 1, except that:
- CR furnace first settling, then reducing fuming; in the step of reducing fuming treatment, the reaction temperature is 1350 ° C; the reducing agent is pulverized coal, the amount of addition is 10% of the total weight of the smelting slag; a small amount of oxygen is supplied to provide heat; The settling chamber performs electrode heating.
- Treatment results 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; smelting output 250,000 tons of copper, 72% copper, 630,000 tons of smelting, 3.5% copper, smelting
- the slag contains 2.63% zinc; the copper making furnace produces 240,000 tons of anode copper, 99.3% copper, and 0.05% sulfur; the smelting slag is treated with CR furnace (reduction ashing and sedimentation), the slag contains 0.6% copper, and the slag contains zinc. 0.54%.
- the overall system copper recovery rate is about 98.5%, and the zinc recovery rate is about 68%.
- the annual processing amount is large, and the anode copper (refers to the copper product whose purity can reach the electrolytic anode copper) has large output, and the recovery rate of the valuable metal is high.
- the method of adding cold material and spraying water mist into the copper-making furnace greatly improves the oxygen content of the oxidant in the copper-making reaction, so that the reaction can complete the copper-making reaction under the condition of high oxygen-rich concentration without generating overheating.
- the phenomenon also effectively improves the copper-sulfur production efficiency and the copper content of the anode copper.
- the technical solution in the eighth embodiment of the present invention also uses the short-flow copper smelting process to effectively recover the valuable metal in the smelting slag, and directly produces the anode.
- the incorporation of copper into harmless slag is also within the scope of protection of the present invention.
- the present invention effectively recovers valuable metals in the smelting slag during the smelting process by reducing fuming and sedimentation, thereby realizing resource recovery and reducing environmental pollution.
- the invention takes the melting furnace as the core and simultaneously shortens the product end and the slag end, thereby greatly simplifying the copper smelting process. It is estimated that the average zinc content in the slag is calculated according to 3%, the recovery rate is calculated according to 80%, and the copper smelting enterprise with 200,000 t/a can recover 19,000 t/a of zinc, which greatly improves the economic benefits of the enterprise and greatly simplifies.
- the process of slag treatment has greatly reduced the footprint and solved the potential pollution risk of slag tailings.
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Abstract
An anode copper production method and device. The production method comprises the following steps: conveying copper matte to a copper production furnace (20), and injecting oxygen-enriched air into the copper production furnace (20) to perform oxidation treatment on the copper matte so that the copper matte undergoes a copper production reaction to generate anode copper, the volume percentage of oxygen in the oxygen-enriched air ranging from 30 to 80%.
Description
本申请涉及炼铜领域,具体而言,涉及一种阳极铜生产方法及装置。The present application relates to the field of copper smelting, and in particular to an anode copper production method and apparatus.
传统的火法炼铜工艺,包括熔炼、吹炼、精炼三个步骤,其中熔炼炉将铜精矿熔炼成含铜40~60%的冰铜(也叫铜锍);吹炼炉将该冰铜吹炼成粗铜;精炼炉(阳极炉)将粗铜精炼成阳极铜,后续送去电解生产阴极铜板。该生产流程从铜锍到阳极铜需经过吹炼和精炼两个步骤,生产流程长,效率低,成本相对过高。The traditional fire method copper smelting process includes three steps of smelting, blowing and refining, wherein the smelting furnace smelts copper concentrate into 40-60% copper-copper (also called copper bismuth) containing copper; Copper is blown into blister copper; the refining furnace (anode furnace) refines the blister copper into anode copper, and then sends it to electrolysis to produce a cathode copper plate. The production process requires two steps of blowing and refining from copper crucible to anode copper. The production process is long, the efficiency is low, and the cost is relatively high.
发明内容Summary of the invention
本申请的主要目的在于提供一种阳极铜生产方法及装置,以解决现有技术的将铜锍到阳极铜的生产流程过长、效率低、生产成本高的问题。The main purpose of the present application is to provide a method and an apparatus for producing an anode copper, which solves the problems of the prior art that the copper beryllium to anode copper production process is too long, the efficiency is low, and the production cost is high.
为了实现上述目的,根据本申请的一个方面,提供了一种阳极铜生产方法,其包括以下步骤:将铜锍输送至造铜炉中,并在造铜炉中喷入富氧空气对铜锍进行氧化处理,以使铜锍进行造铜反应,生成阳极铜;其中,富氧空气中氧气的体积百分比为30~80%。In order to achieve the above object, according to an aspect of the present application, there is provided an anode copper production method comprising the steps of: transporting a copper crucible into a copper making furnace, and injecting oxygen-enriched air into the copper crucible in the copper making furnace The oxidation treatment is performed to cause the copper beryllium to carry out a copper-forming reaction to form an anode copper; wherein the volume percentage of oxygen in the oxygen-enriched air is 30 to 80%.
进一步地,造铜反应的步骤中,同时向造铜炉中加入冷料,和/或向造铜炉中喷入水雾,和/或在造铜炉的炉体外部设置冷却元件;其中冷料包括废杂铜、电解残极铜和固态铜锍中的一种或多种。Further, in the step of the copper-making reaction, the cold material is simultaneously added to the copper-making furnace, and/or the water mist is sprayed into the copper-making furnace, and/or the cooling element is disposed outside the furnace body of the copper-making furnace; It includes one or more of waste copper, electrolytic residual copper and solid copper.
进一步地,造铜反应的步骤中,在进行氧化处理的步骤之后,得到金属铜和造铜渣,当造铜炉中的金属铜中含氧低于0.2wt%时,将造铜渣排出造铜炉,金属铜作为阳极铜;当造铜炉中的金属铜中含氧高于0.2wt%时,将造铜渣排出造铜炉后,向造铜炉中通入还原剂以对金属铜中的铜氧化物杂质进行还原反应,进而得到阳极铜。Further, in the step of the copper-making reaction, after the step of performing the oxidation treatment, the metal copper and the copper-making slag are obtained, and when the oxygen in the metal copper in the copper-making furnace is less than 0.2% by weight, the copper slag is discharged. Copper furnace, metal copper as anode copper; when the metal copper in the coppermaking furnace contains more than 0.2wt% oxygen, the copper slag is discharged into the coppermaking furnace, and then a reducing agent is introduced into the coppermaking furnace to the metal copper. The copper oxide impurities in the reduction reaction are carried out to obtain an anode copper.
进一步地,对铜锍进行氧化处理的步骤中,将熔剂从造铜炉的顶部加入;同时,采用底吹的方式向造铜炉中喷入富氧空气进行氧化处理,或可选地喷入还原剂进行还原反应。Further, in the step of oxidizing the copper crucible, the flux is added from the top of the copper making furnace; at the same time, the oxygen-enriched air is sprayed into the copper making furnace by the bottom blowing method for oxidation treatment, or optionally sprayed The reducing agent is subjected to a reduction reaction.
进一步地,熔剂选自石英石和/或石灰石。Further, the flux is selected from quartz stone and/or limestone.
进一步地,还原剂选自天然气、液化石油气及固体碳基还原剂中的一种或多种。Further, the reducing agent is selected from one or more of natural gas, liquefied petroleum gas, and a solid carbon-based reducing agent.
进一步地,固体碳基还原剂为粉煤和/或块煤。Further, the solid carbon-based reducing agent is pulverized coal and/or lump coal.
进一步地,铜锍的铜含量为大于等于70wt%。Further, the copper content of the copper matte is 70% by weight or more.
进一步地,铜锍的铜含量为70~78wt%。Further, the copper content of the copper matte is 70 to 78% by weight.
根据本发明的另一方面,还提供了一种阳极铜生产装置,其包括造铜炉,造铜炉设置有铜锍入口和造铜渣出口,造铜炉用于对铜锍进行造铜反应以生成阳极铜和造铜渣;阳极铜生产装置还包括喷枪,喷枪设置在造铜炉的侧部或底部,用于向造铜炉内喷入氧气的体积百分比为30~80%的富氧空气和可选的还原剂。According to another aspect of the present invention, there is also provided an anode copper production apparatus comprising a copper-making furnace provided with a copper crucible inlet and a copper-making slag outlet, and a copper-making furnace for copper-making reaction of the copper crucible To generate anode copper and copper slag; the anode copper production device further comprises a spray gun, which is arranged at the side or the bottom of the copper making furnace, and is used for injecting oxygen into the copper making furnace by 30-80% by volume. Air and optional reducing agent.
进一步地,造铜炉还设置有用于通入熔剂的熔剂入口。Further, the copper making furnace is also provided with a flux inlet for introducing a flux.
进一步地,造铜炉的炉体为卧式圆筒型炉体。Further, the furnace body of the copper making furnace is a horizontal cylindrical furnace body.
进一步地,造铜炉还设置有冷料入口,用于向造铜炉中加入电解铜残极、废杂铜及固态铜锍中的一种或多种。Further, the copper making furnace is further provided with a cold material inlet for adding one or more of electrolytic copper residual, waste copper and solid copper to the copper making furnace.
进一步地,阳极铜生产装置还包括冷却设备,冷却设备用于对造铜炉进行降温。Further, the anode copper production apparatus further includes a cooling device for cooling the copper making furnace.
进一步地,冷却设备为负压水套装置或喷水雾冷却装置。Further, the cooling device is a negative pressure water jacket device or a water spray mist cooling device.
进一步地,喷水雾装置用于向造铜炉的炉体内部进行喷水雾。Further, the water spray device is used to spray water mist into the inside of the furnace body of the copper making furnace.
进一步地,造铜炉还设置有阳极铜出口;阳极铜生产装置还设置有浇铸设备,浇铸设备与阳极铜出口连通,用于对阳极铜进行浇铸处理。Further, the copper making furnace is further provided with an anode copper outlet; the anode copper production device is further provided with a casting device, and the casting device is connected with the anode copper outlet for casting the anode copper.
进一步地,浇铸设备为双圆盘浇铸机。Further, the casting apparatus is a double disc casting machine.
本发明提供的上述阳极铜生产方法中,将铜锍输送至造铜炉中,并在造铜炉中喷入富氧空气对铜锍进行氧化处理,以使铜锍进行造铜反应,生成阳极铜;其中,所述富氧空气中氧气的体积百分比为30~80%。本发明在高富氧状态下对铜锍进行了氧化处理,使其发生造铜反应,一步即可从铜锍转变为阳极铜,大大简化了阳极铜的生产工艺,提高了阳极铜的生产效率,且节约了生产成本。In the above method for producing anode copper provided by the present invention, the copper crucible is transported into a copper making furnace, and oxygen-enriched air is sprayed into the copper-making furnace to oxidize the copper crucible, so that the copper crucible is subjected to a copper-making reaction to form an anode. Copper; wherein the volume percentage of oxygen in the oxygen-enriched air is 30 to 80%. The invention oxidizes the copper ruthenium in a high oxygen-rich state to cause a copper-making reaction, and can be converted from copper ruthenium to anode copper in one step, which greatly simplifies the production process of the anode copper and improves the production efficiency of the anode copper. And save production costs.
构成本申请的一部分的说明书附图用来提供对本申请的进一步理解,本申请的示意性实施例及其说明用于解释本申请,并不构成对本申请的不当限定。在附图中:The accompanying drawings, which are incorporated in the claims of the claims In the drawing:
图1示出了根据本申请的一种实施例提供的造铜炉的结构示意图;1 is a schematic structural view of a copper making furnace provided according to an embodiment of the present application;
图2示出了根据本申请的一种实施例提供的阳极铜生产装置的结构示意图;2 is a schematic structural view of an anode copper production apparatus according to an embodiment of the present application;
图3示出了根据本申请的一种实施例提供的短流程炼铜系统的结构示意图;3 is a schematic structural view of a short-flow copper smelting system according to an embodiment of the present application;
图4示出了根据本申请的一种实施例提供的短流程炼铜系统的结构示意图;4 is a schematic structural diagram of a short-flow copper smelting system according to an embodiment of the present application;
图5示出了根据本申请的一种实施例提供的短流程炼铜系统的结构示意图;以及FIG. 5 is a block diagram showing the structure of a short-flow copper smelting system according to an embodiment of the present application;
图6示出了根据本申请的一种实施例提供的短流程炼铜系统的结构示意图。FIG. 6 shows a schematic structural diagram of a short-flow copper smelting system according to an embodiment of the present application.
其中,上述附图包括以下附图标记:Wherein, the above figures include the following reference numerals:
10、熔炼炉;20、造铜炉;30、CR炉;31、还原烟化腔;32、沉降腔;33、隔墙;40、浇铸设备。10, melting furnace; 20, copper furnace; 30, CR furnace; 31, reducing the fuming chamber; 32, sedimentation chamber; 33, partition wall; 40, casting equipment.
应该指出,以下详细说明都是例示性的,旨在对本申请提供进一步的说明。除非另有指明,本文使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。It should be noted that the following detailed description is illustrative and is intended to provide a further description of the application. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise indicated.
需要注意的是,这里所使用的术语仅是为了描述具体实施方式,而非意图限制根据本申请的示例性实施方式。如在这里所使用的,除非上下文另外明确指出,否则单数形式也意图包括复数形式,此外,还应当理解的是,当在本说明书中使用术语“包含”和/或“包括”时,其指明存在特征、步骤、操作、器件、组件和/或它们的组合。It is to be noted that the terminology used herein is for the purpose of describing particular embodiments, and is not intended to limit the exemplary embodiments. As used herein, the singular " " " " " " There are features, steps, operations, devices, components, and/or combinations thereof.
正如背景技术所介绍的,现有技术的炼铜方法流程冗长,阳极铜的生产效率低、生产成本高。为了解决该问题,本发明提供了一种阳极铜生产方法,其包括以下步骤:将铜锍输送至造铜炉中,并在造铜炉中喷入富氧空气对铜锍进行氧化处理,以使铜锍进行造铜反应,生成阳极铜;其中,富氧空气中氧气的体积百分比为30~80%。本发明在高富氧状态下对铜锍进行了氧化处理,使其发生造铜反应,一步即可从铜锍转变为阳极铜,大大简化了阳极铜的生产工艺,提高了阳极铜的生产效率,且节约了生产成本。As described in the background art, the prior art copper smelting process has a long process, and the anode copper has low production efficiency and high production cost. In order to solve the problem, the present invention provides an anode copper production method comprising the steps of: transporting a copper crucible into a copper making furnace, and injecting oxygen-enriched air into the copper making furnace to oxidize the copper crucible to The copper crucible is subjected to a copper-forming reaction to form an anode copper; wherein the volume percentage of oxygen in the oxygen-enriched air is 30 to 80%. The invention oxidizes the copper ruthenium in a high oxygen-rich state to cause a copper-making reaction, and can be converted from copper ruthenium to anode copper in one step, which greatly simplifies the production process of the anode copper and improves the production efficiency of the anode copper. And save production costs.
上述造铜反应用以直接产出阳极铜。在一种优选的实施方式中,造铜反应的步骤中,同时向造铜炉中加入冷料,和/或向造铜炉中喷入水雾,和/或在造铜炉的炉体外部设置冷却元件;其中冷料包括废杂铜、电解残极铜和固态铜锍中的一种或多种。The above copper-making reaction is used to directly produce anode copper. In a preferred embodiment, in the step of the copper-making reaction, the cold material is simultaneously added to the copper-making furnace, and/or the water mist is sprayed into the copper-making furnace, and/or disposed outside the furnace body of the copper-making furnace. a cooling element; wherein the cold material comprises one or more of waste copper, electrolytic residual copper, and solid copper.
为缩短流程,CN103382528提出一种两步炼铜工艺,该工艺首先在熔炼炉中将铜精矿熔炼成含铜65~78%的冰铜,然后在吹炼炉中进行氧化还原反应直接生产阳极铜。该方法主要存在热平衡问题,以及由其带来的烟气问题:吹炼炉中的氧化还原反应放出大量热,这些热必须通过某种方式带走以维持热平衡;该工艺通过调节氧气、空气、氮气的量,通过气体带走反应热,因此喷入的气体总量必须更多,相对的氧气浓度必然较低,这就使得烟气量很大,而烟气中二氧化硫含量很低。因此,后续烟气处理系统和制酸系统规模大、投资大、运行成本高。同时,喷入的气量大,还会导致整个熔体搅动较剧烈,熔体冲刷炉衬的动能大,炉寿短。此外,该专利也没有指出如何使熔炼炉中的冰铜品位达到65~78%。In order to shorten the process, CN103382528 proposes a two-step copper smelting process, which first melts copper concentrate into 65-78% copper-copper in a smelting furnace, and then directly produces an anode by oxidation-reduction reaction in a converting furnace. copper. This method mainly has the problem of heat balance and the flue gas problem brought about by it: the redox reaction in the blowing furnace emits a large amount of heat, which must be carried away in some way to maintain the heat balance; the process regulates oxygen, air, The amount of nitrogen, the heat of reaction is carried away by the gas, so the total amount of gas injected must be more, and the relative oxygen concentration is necessarily lower, which makes the amount of flue gas large, and the sulfur dioxide content in the flue gas is very low. Therefore, the subsequent flue gas treatment system and the acid production system are large in scale, large in investment, and high in operating cost. At the same time, the amount of gas injected is large, which will lead to more intense agitation of the whole melt, and the kinetic energy of the melt scouring lining is large, and the furnace life is short. In addition, the patent does not indicate how to achieve a copper-copper grade of 65 to 78% in the melting furnace.
与上述专利中的热平衡方式不同的是,本发明中采用了向造铜炉中加入冷料,和/或向造铜炉中喷入水雾,和/或在造铜炉的炉体外部设置冷却元件的热平衡方式。各方式的优势如下:Different from the heat balance method in the above patent, the present invention adopts the method of adding cold material to the copper making furnace, and/or spraying water mist into the copper making furnace, and/or cooling outside the furnace body of the copper making furnace. The thermal balance of the components. The advantages of each method are as follows:
对于加入冷料的方式:由于造铜炉中发生的反应是放热反应,加入冷料有利于实现热平衡,同时利用反应放出的热量熔化冷料,充分利用热量。加入的冷料可以是废杂铜、电解残极铜和固态铜锍中的一种或多种。目前炼铜工厂中,都采用单独的冶金炉熔化、精炼废杂铜、电解残极铜等二次铜物料,这不但需要额外的燃料来加热冷料,更重要的是需要购置单独的设备、建设单独的车间、配置单独的工人,大大增加了工厂运行成本。而采用本发明上述实施 方式,在不额外增加设备、厂房、人员的情况下,不但处理了废杂铜、电解残极铜等物料,还节省了熔化物料需要的能源、资源,经济效益十分显著。总之,利用造铜炉的富裕热量熔化杂铜,降低了杂铜的处理成本。For the method of adding the cold material: since the reaction occurring in the copper making furnace is an exothermic reaction, the addition of the cold material is beneficial to achieve the heat balance, and at the same time, the heat released by the reaction is used to melt the cold material, and the heat is fully utilized. The added cold material may be one or more of waste copper, electrolytic residual copper, and solid copper. At present, copper smelting plants use separate metallurgical furnaces to melt and refine secondary copper materials such as waste copper and electrolytic residual copper. This requires not only additional fuel to heat the cold material, but more importantly, the purchase of separate equipment. The construction of separate workshops and the configuration of individual workers has greatly increased the operating costs of the plant. By adopting the above-mentioned embodiment of the present invention, not only the equipment, the factory building and the personnel are added, but also the waste copper, the electrolytic residual copper and the like are processed, and the energy and resources required for the molten material are saved, and the economic benefit is remarkable. . In short, the use of the rich heat of the copper-making furnace to melt the copper, reducing the processing cost of the copper.
对于设置炉体冷却元件的方式:优选采用水套,这也是为了散热,实现炉体热平衡。For the way of setting the cooling element of the furnace body: it is preferable to use a water jacket, which is also for heat dissipation to achieve heat balance of the furnace body.
对于喷入水雾的方式:由于水在气化时吸收大量热,因此可以在最终气量较小的情况下带走更多热量,使造铜反应可以在高富氧吹炼条件下进行,而高富氧浓度吹炼正好解决了CN103382528等专利中采用低富氧浓度吹炼导致的上述问题。此外,喷入水雾还有如下优点:1)更有效地控制炉温。由于水的气化能够吸收大量热,喷入水量的较小变化能够引起热量的较大变化,因此能够更加准确有效地控制炉温;2)延长喷枪寿命。由于高富氧吹炼的效率高,喷枪喷入的气量比低富氧浓度吹炼要少,喷枪的工作强度低,而且水的冷却作用也可以延长喷枪本身的寿命;3)以40%的富氧浓度为例,其熔炼强度可以比低富氧浓度(21%~25%)高近1倍。在烟气量相同的情况下,高富氧浓度(例如40%)能够处理的物料量要高近1倍;4)能耗低,动力消耗低。喷水雾装置的功率比鼓入空气的装置规模小很多。For the way of spraying water mist: Since water absorbs a large amount of heat during gasification, it can take more heat in the case of a smaller final gas volume, so that the copper-making reaction can be carried out under high oxygen-rich blowing conditions, and high oxygen enrichment The concentration blowing just solves the above problems caused by the low oxygen enrichment concentration blowing in the patents such as CN103382528. In addition, the injection of water mist has the following advantages: 1) Control the furnace temperature more effectively. Since the gasification of water can absorb a large amount of heat, a small change in the amount of water injected can cause a large change in heat, so that the furnace temperature can be controlled more accurately and effectively; 2) the life of the spray gun is extended. Due to the high efficiency of high oxygen enrichment, the gas injected into the spray gun is less than the low oxygen enrichment concentration, the working strength of the spray gun is low, and the cooling effect of the water can also extend the life of the spray gun itself; 3) 40% rich For example, the oxygen concentration can be nearly 1 times higher than the low oxygen rich concentration (21% to 25%). In the case of the same amount of flue gas, the high oxygen enrichment concentration (for example, 40%) can handle nearly twice as much material; 4) low energy consumption and low power consumption. The power of the water spray device is much smaller than the size of the device that is blasted into the air.
正因为本发明上述的热平衡方式,使得本发明中的造铜炉可以在高富氧浓度吹炼的条件下进行。Because of the above-described heat balance mode of the present invention, the copper-making furnace of the present invention can be carried out under conditions of high oxygen-rich concentration blowing.
在一种优选的实施方式中,造铜反应的步骤中,在进行氧化处理的步骤之后,得到金属铜和造铜渣,当造铜炉中的金属铜中含氧低于0.2wt%时,将造铜渣排出造铜炉,金属铜作为阳极铜;当造铜炉中的金属铜中含氧高于0.2wt%时,将造铜渣排出造铜炉后,向造铜炉中通入还原剂以对金属铜中的铜氧化物杂质进行还原反应,进而得到阳极铜。In a preferred embodiment, in the step of the copper-making reaction, after the step of performing the oxidation treatment, the metal copper and the copper-making slag are obtained, and when the metal copper in the copper-making furnace contains less than 0.2% by weight of oxygen, The copper slag is discharged into the copper making furnace, and the metal copper is used as the anode copper; when the metal copper in the copper making furnace contains more than 0.2% by weight of oxygen, the copper slag is discharged into the copper making furnace and then introduced into the copper making furnace. The reducing agent reduces the copper oxide impurities in the metallic copper to obtain an anode copper.
造铜反应的目的是将铜锍中的硫元素和其他杂质去除,得到合格的阳极铜。而除杂过程主要是利用氧化反应将铜中的杂质氧化造渣除去。当造铜炉中的金属铜中含氧低于0.2wt%时,一方面表明杂质被较充分氧化并进入到造铜渣中,另一方面表明铜基本没有被过氧化。此时,本发明中在造铜反应过程中采用只氧化不还原的工艺,即可直接得到阳极铜。当造铜炉中的金属铜中含氧高于0.2wt%时,表明在除杂的同时,有部分铜被氧化。此时可以进一步加入还原剂,将这些铜氧化物杂质进行还原反应。且本发明在将造铜渣排出造铜炉以后进行还原反应,还能够防止之前被氧化造渣的杂质返溶回金属铜中,从而能够进一步保证阳极铜的品位。The purpose of the copper-making reaction is to remove sulfur and other impurities from the copper crucible to obtain a qualified anode copper. The impurity removal process mainly uses an oxidation reaction to oxidize impurities in copper to remove slag. When the metal copper in the coppermaking furnace contains less than 0.2% by weight of oxygen, on the one hand, it is indicated that the impurities are more sufficiently oxidized and enter the copper slag, and on the other hand, the copper is substantially not subjected to peroxidation. At this time, in the present invention, in the process of the copper-making reaction, the process of oxidizing only does not reduce, and the anode copper can be directly obtained. When the oxygen contained in the metallic copper in the copper-making furnace is higher than 0.2% by weight, it is indicated that part of the copper is oxidized while removing impurities. At this time, a reducing agent may be further added to carry out a reduction reaction of these copper oxide impurities. Further, in the present invention, the reduction reaction is carried out after the copper-making slag is discharged from the copper-making furnace, and it is also possible to prevent the impurities previously oxidized and slag from being dissolved back into the metallic copper, thereby further ensuring the grade of the anode copper.
在一种优选的实施方式中,对铜锍进行氧化处理的步骤中,将熔剂从造铜炉的顶部加入;同时,采用底吹的方式向造铜炉中喷入富氧空气进行氧化处理,或可选地喷入还原剂进行还原反应。优选地,熔剂选自石英石和/或石灰石。优选地,还原剂选自天然气、液化石油气及固体碳基还原剂中的一种或多种,固体碳基还原剂优选为粉煤和/或块煤。以上工艺和试剂,能够进一步提高造铜反应的效果。In a preferred embodiment, in the step of oxidizing the copper crucible, the flux is added from the top of the copper making furnace; meanwhile, the oxygen-enriched air is sprayed into the copper making furnace for oxidation treatment by bottom blowing. Alternatively, a reducing agent may be sprayed to carry out the reduction reaction. Preferably, the flux is selected from the group consisting of quartz and/or limestone. Preferably, the reducing agent is selected from one or more of natural gas, liquefied petroleum gas, and solid carbon-based reducing agent, and the solid carbon-based reducing agent is preferably pulverized coal and/or lump coal. The above processes and reagents can further enhance the effect of the copper making reaction.
在一种优选的实施方式中,铜锍的铜含量为大于等于70wt%,这样可以避免因铜锍的铜含量过低造成的造铜炉渣量偏大的问题,防止因其带来的铜直收率低的问题。更优选铜锍的铜含量为70~78wt%,这可以进一步避免因第一铜锍的铜含量过高导致的熔炼渣铜含过高的问题,防止因此带来的铜直收率低的问题。此外,铜锍含铜在70~78%时,铅锌锑等元素以氧化 物形式进入熔炼渣,有利于后续从CR炉回收这些元素。若铜锍含铜低,如40~50%时,这些元素的一部分会留在铜锍中,不利于后续从CR炉回收。In a preferred embodiment, the copper content of the copper matte is 70% by weight or more, which can avoid the problem that the copper slag amount is too large due to the copper content of the copper matte is too high, and the copper straightness caused by the copper crucible is prevented. The problem of low yield. More preferably, the copper content of the copper ruthenium is 70 to 78% by weight, which can further avoid the problem that the copper content of the smelting slag is too high due to the excessive copper content of the first copper ruthenium, and the problem of low copper direct yield is prevented. . In addition, when the copper bismuth contains copper at 70 to 78%, elements such as lead, zinc and bismuth enter the smelting slag in the form of an oxide, which facilitates subsequent recovery of these elements from the CR furnace. If the copper bismuth contains low copper, such as 40-50%, some of these elements will remain in the copper bismuth, which is not conducive to subsequent recovery from the CR furnace.
根据本发明的另一方面,还提供了一种阳极铜生产装置,如图1所示,其包括造铜炉20,造铜炉20设置有铜锍入口和造铜渣出口,造铜炉20用于对铜锍进行造铜反应以生成阳极铜和造铜渣;阳极铜生产装置还包括喷枪,喷枪设置在造铜炉20的侧部或底部,用于向造铜炉20内喷入氧气的体积百分比为30~80%的富氧空气和可选的还原剂。本发明提供的生产装置能够在高富氧状态下对铜锍进行造铜反应,一步即可将铜锍转变为阳极铜,大大简化了阳极铜的生产工艺,提高了阳极铜的生产效率,且节约了生产成本。According to another aspect of the present invention, there is also provided an anode copper production apparatus, as shown in FIG. 1, which comprises a copper making furnace 20 provided with a copper crucible inlet and a copper making slag outlet, and a copper making furnace 20 It is used for copper-making reaction of copper bismuth to generate anode copper and copper slag; the anode copper production device further comprises a spray gun which is arranged at the side or the bottom of the copper-making furnace 20 for injecting oxygen into the copper-making furnace 20. The volume percentage is 30 to 80% of oxygen-enriched air and an optional reducing agent. The production device provided by the invention can perform copper-making reaction on copper bismuth in a high oxygen-rich state, and can convert copper bismuth into anode copper in one step, which greatly simplifies the production process of anode copper, improves the production efficiency of anode copper, and saves Production costs.
具体地,当造铜炉中的金属铜中含氧低于0.2%时,一方面表明杂质被较充分氧化并进入到造铜渣中,另一方面表明铜基本没有被过氧化。此时,本发明中在造铜反应过程中采用只氧化不还原的工艺,即可直接得到阳极铜。当造铜炉中的金属铜中含氧高于0.2%时,表明在除杂的同时,有部分铜被氧化。此时可以进一步加入还原剂,将这些铜氧化物杂质进行还原反应。且本发明在将造铜渣排出造铜炉以后进行还原反应,还能够防止之前被氧化造渣的杂质返溶回金属铜中,从而能够进一步保证阳极铜的品位。Specifically, when the metal copper in the coppermaking furnace contains less than 0.2% oxygen, on the one hand, it is indicated that the impurities are more sufficiently oxidized and enter the copper slag, and on the other hand, the copper is substantially not subjected to peroxidation. At this time, in the present invention, in the process of the copper-making reaction, the process of oxidizing only does not reduce, and the anode copper can be directly obtained. When the oxygen content in the metallic copper in the copper-making furnace is higher than 0.2%, it indicates that some copper is oxidized while removing impurities. At this time, a reducing agent may be further added to carry out a reduction reaction of these copper oxide impurities. Further, in the present invention, the reduction reaction is carried out after the copper-making slag is discharged from the copper-making furnace, and it is also possible to prevent the impurities previously oxidized and slag from being dissolved back into the metallic copper, thereby further ensuring the grade of the anode copper.
在一种优选的实施方式中,造铜炉20还设置有用于通入熔剂的熔剂入口。通入熔剂有利于进一步提高阳极铜的品位。优选地,造铜炉20的炉体为卧式圆筒型炉体。In a preferred embodiment, the copper making furnace 20 is also provided with a flux inlet for introducing a flux. The introduction of a flux facilitates further improvement of the grade of the anode copper. Preferably, the furnace body of the copper making furnace 20 is a horizontal cylindrical furnace body.
在一种优选的实施例中,造铜炉20还设置有冷料入口,用于向造铜炉20中加入电解铜残极、废杂铜及固态铜锍中的一种或多种。优选地,阳极铜生产装置还包括冷却设备,冷却设备用于对造铜炉20进行降温。更优选地,冷却设备为负压水套装置或喷水雾冷却装置。进一步优选地,喷水雾装置用于向造铜炉20的炉体内部进行喷水雾。In a preferred embodiment, the copper making furnace 20 is further provided with a cold material inlet for adding one or more of electrolytic copper residuals, scrap copper and solid copper crucibles to the copper making furnace 20. Preferably, the anode copper production apparatus further includes a cooling device for cooling the copper making furnace 20. More preferably, the cooling device is a vacuum water jacket device or a water mist cooling device. Further preferably, the water spray device is used to spray water mist into the inside of the furnace body of the copper making furnace 20.
为缩短流程,CN103382528提出一种两步炼铜工艺,该工艺首先在熔炼炉中将铜精矿熔炼成含铜65~78%的冰铜,然后在吹炼炉中进行氧化还原反应直接生产阳极铜。该方法主要存在热平衡问题,以及由其带来的烟气问题:吹炼炉中的氧化还原反应放出大量热,这些热必须通过某种方式带走以维持热平衡;该工艺通过调节氧气、空气、氮气的量,通过气体带走反应热,因此喷入的气体总量必须更多,相对的氧气浓度必然较低,这就使得烟气量很大,而烟气中二氧化硫含量很低。因此,后续烟气处理系统和制酸系统规模大、投资大、运行成本高。同时,喷入的气量大,还会导致整个熔体搅动较剧烈,熔体冲刷炉衬的动能大,炉寿短。此外,该专利也没有指出如何使熔炼炉中的冰铜品位达到65~78%。In order to shorten the process, CN103382528 proposes a two-step copper smelting process, which first melts copper concentrate into 65-78% copper-copper in a smelting furnace, and then directly produces an anode by oxidation-reduction reaction in a converting furnace. copper. This method mainly has the problem of heat balance and the flue gas problem brought about by it: the redox reaction in the blowing furnace emits a large amount of heat, which must be carried away in some way to maintain the heat balance; the process regulates oxygen, air, The amount of nitrogen, the heat of reaction is carried away by the gas, so the total amount of gas injected must be more, and the relative oxygen concentration is necessarily lower, which makes the amount of flue gas large, and the sulfur dioxide content in the flue gas is very low. Therefore, the subsequent flue gas treatment system and the acid production system are large in scale, large in investment, and high in operating cost. At the same time, the amount of gas injected is large, which will lead to more intense agitation of the whole melt, and the kinetic energy of the melt scouring lining is large, and the furnace life is short. In addition, the patent does not indicate how to achieve a copper-copper grade of 65 to 78% in the melting furnace.
与上述专利中的热平衡方式不同的是,本发明中采用了向造铜炉中加入冷料,和/或向造铜炉中喷入水雾,和/或在造铜炉的炉体外部设置冷却元件的热平衡方式。各方式的优势如下:Different from the heat balance method in the above patent, the present invention adopts the method of adding cold material to the copper making furnace, and/or spraying water mist into the copper making furnace, and/or cooling outside the furnace body of the copper making furnace. The thermal balance of the components. The advantages of each method are as follows:
对于加入冷料的方式:由于造铜炉中发生的反应是放热反应,加入冷料有利于实现热平衡,同时利用反应放出的热量熔化冷料,充分利用热量。加入的冷料可以是废杂铜、电解残极铜和固态铜锍中的一种或多种。目前炼铜工厂中,都采用单独的冶金炉熔化、精炼废杂铜、电解残极铜等二次铜物料,这不但需要额外的燃料来加热冷料,更重要的是需要购置单 独的设备、建设单独的车间、配置单独的工人,大大增加了工厂运行成本。而采用本发明上述实施方式,在不额外增加设备、厂房、人员的情况下,不但处理了废杂铜、电解残极铜等物料,还节省了熔化物料需要的能源、资源,经济效益十分显著。总之,利用造铜炉的富裕热量熔化杂铜,降低了杂铜的处理成本。For the method of adding the cold material: since the reaction occurring in the copper making furnace is an exothermic reaction, the addition of the cold material is beneficial to achieve the heat balance, and at the same time, the heat released by the reaction is used to melt the cold material, and the heat is fully utilized. The added cold material may be one or more of waste copper, electrolytic residual copper, and solid copper. At present, copper smelting plants use separate metallurgical furnaces to melt and refine secondary copper materials such as waste copper and electrolytic residual copper. This requires not only additional fuel to heat the cold material, but more importantly, the purchase of separate equipment. The construction of separate workshops and the configuration of individual workers has greatly increased the operating costs of the plant. By adopting the above-mentioned embodiment of the present invention, not only the equipment, the factory building and the personnel are added, but also the waste copper, the electrolytic residual copper and the like are processed, and the energy and resources required for the molten material are saved, and the economic benefit is remarkable. . In short, the use of the rich heat of the copper-making furnace to melt the copper, reducing the processing cost of the copper.
对于设置炉体冷却元件的方式:优选采用水套,这也是为了散热,实现炉体热平衡。For the way of setting the cooling element of the furnace body: it is preferable to use a water jacket, which is also for heat dissipation to achieve heat balance of the furnace body.
对于喷入水雾的方式:由于水在气化时吸收大量热,因此可以在最终气量较小的情况下带走更多热量,使造铜反应可以在高富氧吹炼条件下进行,而高富氧浓度吹炼正好解决了CN103382528等专利中采用低富氧浓度吹炼导致的上述问题。此外,喷入水雾还有如下优点:1)更有效地控制炉温。由于水的气化能够吸收大量热,喷入水量的较小变化能够引起热量的较大变化,因此能够更加准确有效地控制炉温;2)延长喷枪寿命。由于高富氧吹炼的效率高,喷枪喷入的气量比低富氧浓度吹炼要少,喷枪的工作强度低,而且水的冷却作用也可以延长喷枪本身的寿命;3)以40%的富氧浓度为例,其熔炼强度可以比低富氧浓度(21%~25%)高近1倍。在烟气量相同的情况下,高富氧浓度(例如40%)能够处理的物料量要高近1倍;4)能耗低,动力消耗低。喷水雾装置的功率比鼓入空气的装置规模小很多。For the way of spraying water mist: Since water absorbs a large amount of heat during gasification, it can take more heat in the case of a smaller final gas volume, so that the copper-making reaction can be carried out under high oxygen-rich blowing conditions, and high oxygen enrichment The concentration blowing just solves the above problems caused by the low oxygen enrichment concentration blowing in the patents such as CN103382528. In addition, the injection of water mist has the following advantages: 1) Control the furnace temperature more effectively. Since the gasification of water can absorb a large amount of heat, a small change in the amount of water injected can cause a large change in heat, so that the furnace temperature can be controlled more accurately and effectively; 2) the life of the spray gun is extended. Due to the high efficiency of high oxygen enrichment, the gas injected into the spray gun is less than the low oxygen enrichment concentration, the working strength of the spray gun is low, and the cooling effect of the water can also extend the life of the spray gun itself; 3) 40% rich For example, the oxygen concentration can be nearly 1 times higher than the low oxygen rich concentration (21% to 25%). In the case of the same amount of flue gas, the high oxygen enrichment concentration (for example, 40%) can handle nearly twice as much material; 4) low energy consumption and low power consumption. The power of the water spray device is much smaller than the size of the device that is blasted into the air.
正因为本发明上述的热平衡方式,使得本发明中的造铜炉可以在高富氧浓度吹炼的条件下进行。对铜锍进行造铜反应的步骤中,得到的阳极铜为铜熔体。Because of the above-described heat balance mode of the present invention, the copper-making furnace of the present invention can be carried out under conditions of high oxygen-rich concentration blowing. In the step of copper-making reaction of copper matte, the obtained anode copper is a copper melt.
在一种优选的实施方式中,如图2所示,造铜炉20还设置有阳极铜出口;阳极铜生产装置还设置有浇铸设备40,浇铸设备40与阳极铜出口连通,用于对阳极铜进行浇铸处理。通过设置浇铸设备40可以进一步将铜熔体浇铸形成阳极铜板等产品。更优选地,浇铸设备40为双圆盘浇铸机。In a preferred embodiment, as shown in FIG. 2, the copper making furnace 20 is further provided with an anode copper outlet; the anode copper production device is further provided with a casting device 40, and the casting device 40 is in communication with the anode copper outlet for the anode Copper is cast. The copper melt can be further cast by forming the casting apparatus 40 to form a product such as an anode copper plate. More preferably, the casting apparatus 40 is a double disc casting machine.
除了以上阳极铜的生产流程长、效率低等问题,现有技术中对熔炼渣的处理需要大面积渣缓冷场和复杂的渣选矿环节,增加了建设成本和技术复杂度,且存在有价金属流失浪费、污染环境的问题。为了解决如上问题,本申请提出了一种短流程炼铜方法,其采用的炼铜装置包括熔炼炉、造铜炉、CR炉、第一流槽及第二流槽;熔炼炉设置有铜锍出口和熔炼渣出口;造铜炉设置有铜锍入口,铜锍入口通过第一流槽与铜锍出口连通;CR炉设置有熔炼渣入口,熔炼渣入口通过第二流槽与熔炼渣出口连通;短流程炼铜方法包括以下步骤:将铜精矿在熔炼炉中进行熔炼,得到第一铜锍和熔炼渣;在造铜炉中对第一铜锍进行造铜反应,生成阳极铜和造铜渣;以及在CR炉中对熔炼渣进行还原烟化和沉降以综合回收熔炼渣中的有价金属,并造无害渣;有价金属包括铅、锌及锑中的一种或多种;短流程炼铜方法同时完成了产出阳极铜、熔炼渣中有价金属综合回收以及CR炉直接产出无害渣。上述方法相比现有技术,总流程大大缩短,有利于缩减建设成本,降低技术复杂度,且实现了资源综合回收并消除了环保隐患。In addition to the above problems of long production process and low efficiency of anode copper, the treatment of smelting slag in the prior art requires a large area of slag slow cooling field and complicated slag beneficiation, which increases construction cost and technical complexity, and has valuable metals. Loss of waste and environmental pollution. In order to solve the above problems, the present application proposes a short-process copper smelting method, which comprises a smelting furnace, a copper-making furnace, a CR furnace, a first flow tank and a second flow tank; the smelting furnace is provided with a copper sputum outlet And the smelting slag outlet; the copper making furnace is provided with a copper crucible inlet, the copper crucible inlet is connected to the copper crucible outlet through the first laundering tank; the CR furnace is provided with a molten slag inlet, and the molten slag inlet is connected to the melting slag outlet through the second laundering; The process copper smelting method comprises the steps of: smelting a copper concentrate in a smelting furnace to obtain a first copper slag and a smelting slag; and performing a copper-making reaction on the first copper bismuth in a copper-making furnace to generate an anode copper and a copper slag And reducing smelting and sedimentation of the smelting slag in the CR furnace to comprehensively recover valuable metals in the smelting slag and to make harmless slag; the valuable metals include one or more of lead, zinc and bismuth; The process copper smelting method simultaneously completes the production of anode copper, the comprehensive recovery of valuable metals in the smelting slag, and the direct production of harmless slag by the CR furnace. Compared with the prior art, the above method greatly shortens the total process, is conducive to reducing construction costs, reducing technical complexity, and achieving comprehensive resource recovery and eliminating environmental hazards.
此处所述“无害渣”是指:不会造成重金属污染的渣。As used herein, "harmless slag" means: slag that does not cause heavy metal contamination.
CR炉全称为全面回收(completely recycle)炉。The CR furnace is called a fully recycled furnace.
上述方法中,在得到熔炼渣后,通过对熔炼渣进行还原烟化和沉降能够回收熔炼渣中的有价金属,比如金属锌、铅、锑等。这就有效解决了现有的炼铜工艺中有价金属流失浪费的问题,并避免了这些流失金属对环境的污染问题;另一方面,对熔炼渣进行还原烟化和沉降取代了原来的渣选矿流程,不但大大缩减了工厂占地面积,使工艺流程更加简单,还从根本上消除了渣选矿流程中加入的选矿药剂造成的污染。与此同时,需要说明的是,本发明的上述炼铜方法,采用了一担挑式的炼铜装置,将熔炼炉的铜锍端直接通过流槽与造铜炉连通,将熔炼炉的出渣端直接通过流槽与CR炉连通,实现了短流程炼铜,同时完成了产出阳极铜、熔炼渣中有价金属综合回收以及CR炉直接产出无害渣,具有很好的工业化大规模应用前景。In the above method, after the smelting slag is obtained, valuable metals such as metal zinc, lead, antimony, etc., in the smelting slag can be recovered by reducing smelting and sedimentation of the smelting slag. This effectively solves the problem of waste of valuable metals in the existing copper smelting process, and avoids the pollution of these metals to the environment; on the other hand, the reduction smelting and sedimentation of the smelting slag replaces the original slag. The beneficiation process not only greatly reduces the factory floor space, but also makes the process more simple. It also fundamentally eliminates the pollution caused by the beneficiation agent added in the slag beneficiation process. At the same time, it should be noted that the copper smelting method of the present invention adopts a copper-plating device with a pick-up type, and the copper bismuth end of the smelting furnace is directly connected to the copper-making furnace through the launder, and the smelting furnace is discharged. The slag end is directly connected to the CR furnace through the launder, which realizes short-process copper smelting. At the same time, it completes the production of anode copper, the comprehensive recovery of valuable metals in the smelting slag and the direct production of harmless slag by the CR furnace, which has a good industrialization. Scale application prospects.
在一种优选的实施方式中,将铜精矿在熔炼炉中进行熔炼的步骤包括:将铜精矿与第一熔剂混合,得到混合料;将混合料投入熔炼炉中,在第一氧化剂的作用下进行熔炼,得到第一铜锍和熔炼渣。优选地,熔炼过程中采用底吹熔炼法或侧吹熔炼法。利用底吹熔炼法或侧吹熔炼法,能够进一步提高铜锍品位。更优选地,第一熔剂选自石英石和/或石灰石;第一氧化剂选自氧气、压缩空气及富氧空气中的一种或多种。In a preferred embodiment, the step of smelting the copper concentrate in the smelting furnace comprises: mixing the copper concentrate with the first flux to obtain a mixture; and feeding the mixture into the smelting furnace at the first oxidizing agent Melting is carried out under the action to obtain a first copper crucible and a smelting slag. Preferably, the bottom blowing smelting method or the side blowing smelting method is employed in the smelting process. The use of the bottom blowing smelting method or the side blowing smelting method can further improve the copper enamel grade. More preferably, the first flux is selected from quartz stone and/or limestone; the first oxidant is selected from one or more of oxygen, compressed air, and oxygen-enriched air.
此处所述“富氧空气”是指氧气浓度大于空气中氧气浓度的气体,比如可以通过在空气中掺入氧气获得。As used herein, "oxygen-enriched air" refers to a gas having a concentration of oxygen greater than the concentration of oxygen in the air, such as may be obtained by incorporating oxygen into the air.
在一种优选的实施方式中,将铜精矿在熔炼炉中进行熔炼的步骤中,第一氧化剂的喷入量为每吨铜精矿对应120Nm
3以上O
2以使第一铜锍的铜含量为大于等于70wt%。将第一氧化剂的喷入量控制为每吨铜精矿对应120Nm
3以上O
2,可以使第一铜锍的铜含量为大于等于70wt%,这样可以避免因第一铜锍的铜含量过低造成的造铜炉渣量偏大的问题,防止因其带来的铜直收率低的问题。更优选第一氧化剂的喷入量为每吨铜精矿对应120~200Nm
3O
2以使第一铜锍的铜含量为70~78wt%,这可以进一步避免因第一铜锍的铜含量过高导致的熔炼渣铜含过高的问题,防止因此带来的铜直收率低的问题。此外,铜锍含铜在70~78%时,铅锌锑等元素以氧化物形式进入熔炼渣,有利于后续从CR炉回收这些元素。若铜锍含铜低,如40~50%时,这些元素的一部分会留在铜锍中,不利于后续从CR炉回收。
In a preferred embodiment, in the step of smelting the copper concentrate in the smelting furnace, the first oxidizing agent is injected in an amount corresponding to 120 Nm 3 or more of O 2 per ton of copper concentrate to make the copper of the first copper bismuth. The content is 70% by weight or more. The injection amount of the first oxidant is controlled to be 120 Nm 3 or more and O 2 per ton of copper concentrate, so that the copper content of the first copper ruthenium is 70% by weight or more, thereby avoiding the copper content of the first copper ruthenium being too low. The problem of the large amount of copper slag caused is to prevent the problem of low copper yield due to it. More preferably, the first oxidizing agent is injected in an amount of 120 to 200 Nm 3 O 2 per ton of copper concentrate so that the copper content of the first copper cerium is 70 to 78% by weight, which can further avoid the copper content of the first copper ruthenium. The high smelting slag copper contains an excessively high problem, preventing the problem of low copper yield. In addition, when the copper bismuth contains copper at 70 to 78%, elements such as lead, zinc and bismuth enter the smelting slag in the form of oxides, which facilitates subsequent recovery of these elements from the CR furnace. If the copper bismuth contains low copper, such as 40-50%, some of these elements will remain in the copper bismuth, which is not conducive to subsequent recovery from the CR furnace.
在一种优选的实施方式中,将铜精矿在熔炼炉中进行熔炼的步骤中,将冷却后的造铜渣投入熔炼炉中与铜精矿一起进行熔炼处理。通过加入冷却后的造铜渣,可以缓解熔炼过程中的过热问题,可以使熔炼过程更容易在较高的富氧浓度下进行,并因此减少产生的烟气量。In a preferred embodiment, in the step of melting the copper concentrate in the melting furnace, the cooled copper-making slag is put into a melting furnace and smelted together with the copper concentrate. By adding the cooled copper slag, the problem of overheating during the smelting process can be alleviated, and the smelting process can be more easily carried out at a higher oxygen-rich concentration, and thus the amount of flue gas generated can be reduced.
除此以外,优选熔炼过程中的熔炼温度为1150~1300℃,第一熔剂的加入量为所述铜矿总重量的1~20%。In addition to this, it is preferred that the melting temperature in the smelting process is 1150 to 1300 ° C, and the first flux is added in an amount of 1 to 20% by weight based on the total weight of the copper ore.
上述造铜反应用以直接产出阳极铜。在一种优选的实施方式中,在造铜炉中对第一铜锍进行造铜反应的步骤还包括:同时向造铜炉中加入冷料,和/或向造铜炉中喷入水雾,和/或在造铜炉的炉体外部设置冷却元件;其中冷料包括废杂铜、电解残极铜和固态铜锍中的一种或多种。The above copper-making reaction is used to directly produce anode copper. In a preferred embodiment, the step of performing a copper-making reaction on the first copper crucible in the copper-making furnace further comprises: simultaneously adding cold material to the copper-making furnace, and/or spraying water mist into the copper-making furnace, And/or providing a cooling element outside the furnace body of the coppermaking furnace; wherein the cold material comprises one or more of waste copper, electrolytic residual copper and solid copper.
为缩短流程,CN103382528提出一种两步炼铜工艺,该工艺首先在熔炼炉中将铜精矿熔炼成含铜65~78%的冰铜,然后在吹炼炉中进行氧化还原反应直接生产阳极铜。该方法主要存 在热平衡问题,以及由其带来的烟气问题:吹炼炉中的氧化还原反应放出大量热,这些热必须通过某种方式带走以维持热平衡;该工艺通过调节氧气、空气、氮气的量,通过气体带走反应热,因此喷入的气体总量必须更多,相对的氧气浓度必然较低,这就使得烟气量很大,而烟气中二氧化硫含量很低。因此,后续烟气处理系统和制酸系统规模大、投资大、运行成本高。同时,喷入的气量大,还会导致整个熔体搅动较剧烈,熔体冲刷炉衬的动能大,炉寿短。此外,该专利也没有指出如何使熔炼炉中的冰铜品位达到65~78%。In order to shorten the process, CN103382528 proposes a two-step copper smelting process, which first melts copper concentrate into 65-78% copper-copper in a smelting furnace, and then directly produces an anode by oxidation-reduction reaction in a converting furnace. copper. This method mainly has the problem of heat balance and the flue gas problem brought about by it: the redox reaction in the blowing furnace emits a large amount of heat, which must be carried away in some way to maintain the heat balance; the process regulates oxygen, air, The amount of nitrogen, the heat of reaction is carried away by the gas, so the total amount of gas injected must be more, and the relative oxygen concentration is necessarily lower, which makes the amount of flue gas large, and the sulfur dioxide content in the flue gas is very low. Therefore, the subsequent flue gas treatment system and the acid production system are large in scale, large in investment, and high in operating cost. At the same time, the amount of gas injected is large, which will lead to more intense agitation of the whole melt, and the kinetic energy of the melt scouring lining is large, and the furnace life is short. In addition, the patent does not indicate how to achieve a copper-copper grade of 65 to 78% in the melting furnace.
与上述专利中的热平衡方式不同的是,本发明中采用了向造铜炉中加入冷料,和/或向造铜炉中喷入水雾,和/或在造铜炉的炉体外部设置冷却元件的热平衡方式。各方式的优势如下:Different from the heat balance method in the above patent, the present invention adopts the method of adding cold material to the copper making furnace, and/or spraying water mist into the copper making furnace, and/or cooling outside the furnace body of the copper making furnace. The thermal balance of the components. The advantages of each method are as follows:
对于加入冷料的方式:由于造铜炉中发生的反应是放热反应,加入冷料有利于实现热平衡,同时利用反应放出的热量熔化冷料,充分利用热量。加入的冷料可以是废杂铜、电解残极铜和固态铜锍中的一种或多种。目前炼铜工厂中,都采用单独的冶金炉熔化、精炼废杂铜、电解残极铜等二次铜物料,这不但需要额外的燃料来加热冷料,更重要的是需要购置单独的设备、建设单独的车间、配置单独的工人,大大增加了工厂运行成本。而采用本发明上述实施方式,在不额外增加设备、厂房、人员的情况下,不但处理了废杂铜、电解残极铜等物料,还节省了熔化物料需要的能源、资源,经济效益十分显著。总之,利用造铜炉的富裕热量熔化杂铜,降低了杂铜的处理成本。For the method of adding the cold material: since the reaction occurring in the copper making furnace is an exothermic reaction, the addition of the cold material is beneficial to achieve the heat balance, and at the same time, the heat released by the reaction is used to melt the cold material, and the heat is fully utilized. The added cold material may be one or more of waste copper, electrolytic residual copper, and solid copper. At present, copper smelting plants use separate metallurgical furnaces to melt and refine secondary copper materials such as waste copper and electrolytic residual copper. This requires not only additional fuel to heat the cold material, but more importantly, the purchase of separate equipment. The construction of separate workshops and the configuration of individual workers has greatly increased the operating costs of the plant. By adopting the above-mentioned embodiment of the present invention, not only the equipment, the factory building and the personnel are added, but also the waste copper, the electrolytic residual copper and the like are processed, and the energy and resources required for the molten material are saved, and the economic benefit is remarkable. . In short, the use of the rich heat of the copper-making furnace to melt the copper, reducing the processing cost of the copper.
对于设置炉体冷却元件的方式:优选采用水套,这也是为了散热,实现炉体热平衡。For the way of setting the cooling element of the furnace body: it is preferable to use a water jacket, which is also for heat dissipation to achieve heat balance of the furnace body.
对于喷入水雾的方式:由于水在气化时吸收大量热,因此可以在最终气量较小的情况下带走更多热量,使造铜反应可以在高富氧吹炼条件下进行,而高富氧浓度吹炼正好解决了CN103382528等专利中采用低富氧浓度吹炼导致的上述问题。此外,喷入水雾还有如下优点:1)更有效地控制炉温。由于水的气化能够吸收大量热,喷入水量的较小变化能够引起热量的较大变化,因此能够更加准确有效地控制炉温;2)延长喷枪寿命。由于高富氧吹炼的效率高,喷枪喷入的气量比低富氧浓度吹炼要少,喷枪的工作强度低,而且水的冷却作用也可以延长喷枪本身的寿命;3)以40%的富氧浓度为例,其熔炼强度可以比低富氧浓度(21%~25%)高近1倍。在烟气量相同的情况下,高富氧浓度(例如40%)能够处理的物料量要高近1倍;4)能耗低,动力消耗低。喷水雾装置的功率比鼓入空气的装置规模小很多。For the way of spraying water mist: Since water absorbs a large amount of heat during gasification, it can take more heat in the case of a smaller final gas volume, so that the copper-making reaction can be carried out under high oxygen-rich blowing conditions, and high oxygen enrichment The concentration blowing just solves the above problems caused by the low oxygen enrichment concentration blowing in the patents such as CN103382528. In addition, the injection of water mist has the following advantages: 1) Control the furnace temperature more effectively. Since the gasification of water can absorb a large amount of heat, a small change in the amount of water injected can cause a large change in heat, so that the furnace temperature can be controlled more accurately and effectively; 2) the life of the spray gun is extended. Due to the high efficiency of high oxygen enrichment, the gas injected into the spray gun is less than the low oxygen enrichment concentration, the working strength of the spray gun is low, and the cooling effect of the water can also extend the life of the spray gun itself; 3) 40% rich For example, the oxygen concentration can be nearly 1 times higher than the low oxygen rich concentration (21% to 25%). In the case of the same amount of flue gas, the high oxygen enrichment concentration (for example, 40%) can handle nearly twice as much material; 4) low energy consumption and low power consumption. The power of the water spray device is much smaller than the size of the device that is blasted into the air.
正因为本发明上述的热平衡方式,使得本发明中的造铜炉可以在高富氧浓度吹炼的条件下进行。在一种优选的实施方式中,进行造铜反应的步骤中,在造铜炉中喷入富氧空气对第一铜锍进行氧化处理,以进行造铜反应,且富氧空气中氧气的体积百分比为30~80%。尽管CN103382528提到吹炼炉氧浓度9~60%,但由于其是依靠气体带走热量,实际氧浓度只能维持在25%以下,无法真正实现高富氧浓度。而本发明中依靠上述热平衡手段,完全能够达到30~80%的富氧空气浓度。Because of the above-described heat balance mode of the present invention, the copper-making furnace of the present invention can be carried out under conditions of high oxygen-rich concentration blowing. In a preferred embodiment, in the step of performing a copper-making reaction, the first copper crucible is oxidized by injecting oxygen-enriched air into the copper-making furnace to perform a copper-making reaction, and the volume of oxygen in the oxygen-enriched air The percentage is 30 to 80%. Although CN103382528 mentions that the oxygen concentration of the blowing furnace is 9-60%, since it relies on the gas to carry away heat, the actual oxygen concentration can only be maintained below 25%, and the high oxygen-rich concentration cannot be truly achieved. In the present invention, the above-mentioned heat balance means can fully achieve an oxygen-enriched air concentration of 30 to 80%.
在一种优选的实施方式中,造铜反应的步骤中,在进行氧化处理的步骤之后,得到金属铜和造铜渣;当造铜炉中的金属铜中含氧低于0.2wt%时,将造铜渣排出造铜炉,得到阳极铜; 当造铜炉中的金属铜中含氧高于0.2wt%时,将造铜渣排出造铜炉后,向造铜炉中通入还原剂以对金属铜中的铜氧化物杂质进行还原反应,进而得到阳极铜。In a preferred embodiment, in the step of the copper-making reaction, after the step of performing the oxidation treatment, the metal copper and the copper-making slag are obtained; when the metal copper in the copper-making furnace contains less than 0.2% by weight of oxygen, The copper slag is discharged from the coppermaking furnace to obtain anode copper. When the oxygen in the metal copper in the coppermaking furnace is higher than 0.2 wt%, the copper slag is discharged into the coppermaking furnace, and the reducing agent is introduced into the coppermaking furnace. The copper oxide impurities in the metallic copper are subjected to a reduction reaction to obtain an anode copper.
造铜反应的目的是将第一铜锍中的硫元素和其他杂质去除,得到合格的阳极铜。而除杂过程主要是利用氧化反应将铜中的杂质氧化造渣除去。当造铜炉中的金属铜中含氧低于0.2wt%时,一方面表明杂质被较充分氧化并进入到造铜渣中,另一方面表明铜基本没有被过氧化。此时,本发明中在造铜反应过程中采用只氧化不还原的工艺,即可直接得到阳极铜。当造铜炉中的金属铜中含氧高于0.2wt%时,表明在除杂的同时,有部分铜被氧化。此时可以进一步加入还原剂,将这些铜氧化物杂质进行还原反应。且本发明在将造铜渣排出造铜炉以后进行还原反应,还能够防止之前被氧化造渣的杂质返溶回金属铜中,从而能够进一步保证阳极铜的品位。The purpose of the copper-making reaction is to remove the sulfur element and other impurities in the first copper crucible to obtain a qualified anode copper. The impurity removal process mainly uses an oxidation reaction to oxidize impurities in copper to remove slag. When the metal copper in the coppermaking furnace contains less than 0.2% by weight of oxygen, on the one hand, it is indicated that the impurities are more sufficiently oxidized and enter the copper slag, and on the other hand, the copper is substantially not subjected to peroxidation. At this time, in the present invention, in the process of the copper-making reaction, the process of oxidizing only does not reduce, and the anode copper can be directly obtained. When the oxygen contained in the metallic copper in the copper-making furnace is higher than 0.2% by weight, it is indicated that part of the copper is oxidized while removing impurities. At this time, a reducing agent may be further added to carry out a reduction reaction of these copper oxide impurities. Further, in the present invention, the reduction reaction is carried out after the copper-making slag is discharged from the copper-making furnace, and it is also possible to prevent the impurities previously oxidized and slag from being dissolved back into the metallic copper, thereby further ensuring the grade of the anode copper.
在一种优选的实施方式中,在造铜炉中对第一铜锍进行氧化处理的步骤中,将第二熔剂从造铜炉的顶部加入;同时,采用底吹的方式向造铜炉中喷入富氧空气进行氧化处理,或可选地喷入第一还原剂进行还原反应。优选地,第二熔剂选自石英石和/或石灰石。优选地,第一还原剂选自天然气、液化石油气及固体碳基还原剂中的一种或多种,优选固体碳基还原剂为粉煤和/或固体含碳还原剂。以上工艺和试剂,能够进一步提高造铜反应的效果。In a preferred embodiment, in the step of oxidizing the first copper crucible in the copper making furnace, the second flux is added from the top of the copper making furnace; meanwhile, the bottom blowing method is used in the copper making furnace. The oxygen-enriched air is sprayed for oxidation treatment, or alternatively, the first reducing agent is sprayed for reduction. Preferably, the second flux is selected from the group consisting of quartz stone and/or limestone. Preferably, the first reducing agent is selected from one or more of natural gas, liquefied petroleum gas, and solid carbon-based reducing agent. Preferably, the solid carbon-based reducing agent is a pulverized coal and/or a solid carbonaceous reducing agent. The above processes and reagents can further enhance the effect of the copper making reaction.
上述CR炉的作用是通过还原烟化和沉降回收熔炼渣中的有价金属,并造无害渣。在一种优选的实施方式中,CR炉包括腔体,腔体包括相连通的还原烟化腔和沉降腔;回收熔炼渣中的有价金属的步骤包括:将熔炼渣在还原烟化腔中进行还原烟化处理,得到有价金属烟气和还原渣,以及将还原渣在沉降腔中进行沉降处理,得到第二铜锍和无害渣;或者将熔炼渣在沉降腔中进行沉降处理,得到第二铜锍和沉降渣,以及将沉降渣在还原烟化腔中进行还原烟化处理,得到有价金属烟气和无害渣。The function of the above CR furnace is to recover valuable metals in the smelting slag by reducing fuming and sedimentation, and to make harmless slag. In a preferred embodiment, the CR furnace includes a cavity including a reducing reduction chamber and a settling chamber; and the step of recovering the valuable metal in the smelting slag includes: smelting the slag in the reducing smoulding chamber Performing reduction and smoulding treatment to obtain valuable metal flue gas and reducing slag, and sedimenting the reducing slag in the sedimentation chamber to obtain second copper ruthenium and harmless slag; or sedimenting the smelting slag in the sedimentation chamber, The second copper ruthenium and the sedimentation slag are obtained, and the sedimentation slag is subjected to reduction and smoulding treatment in the reduction smoulding cavity to obtain a valuable metal smog and a harmless slag.
上述CR炉为一体化回收炉,其同时包括还原烟化腔和沉降腔。在第一种处理方式中,对熔炼渣先后进行了还原烟化处理、沉降处理。将熔炼渣进行还原烟化处理时,能够将熔炼渣中的磁性铁(四氧化三铁)还原为氧化亚铁进行造渣,这样能够减少熔炼渣的粘度,从而提高后续的沉降分离效果,便于第二铜锍从还原渣中分离。同时,锌、铅、锑等有价金属氧化物被还原为金属后,因其具有易挥发性而转化为有价金属烟气被分离出来,从而达到了回收有价金属的目的。还原烟化处理后,得到还原渣(呈流动态)进入沉降腔中进行沉降分离,得到第二铜锍与无害渣。更重要地,经还原烟化处理后的还原渣直接进入沉降分离,一方面能够极大地改善处理效率;另一方面由于还原渣直接进入沉降处理,能够保持更稳定地流态,且在此过程中仅有微小的温度变化甚至没有温度变化,两方面的原因使其具有更好的沉降效果,能够进一步提高第二铜锍的回收率。The above CR furnace is an integrated recovery furnace, which simultaneously includes a reduction smoulding chamber and a settling chamber. In the first treatment method, the smelting slag is successively subjected to reduction smoulding treatment and sedimentation treatment. When the smelting slag is subjected to reduction and fuming treatment, the magnetic iron (ferric oxide) in the smelting slag can be reduced to ferrous oxide for slag formation, which can reduce the viscosity of the smelting slag, thereby improving the subsequent sedimentation separation effect and facilitating The second copper ruthenium is separated from the reducing slag. At the same time, after the valuable metal oxides such as zinc, lead and antimony are reduced to metal, they are separated into valuable metal fumes due to their volatility, thereby achieving the purpose of recovering valuable metals. After the reduction smoulding treatment, the reduced slag (flowing dynamics) is obtained and enters into the sedimentation chamber for sedimentation separation to obtain the second copper ruthenium and the harmless slag. More importantly, the reduced slag after the reduction smoulding treatment directly enters the sedimentation separation, on the one hand, the treatment efficiency can be greatly improved; on the other hand, since the reducing slag directly enters the sedimentation treatment, a more stable flow state can be maintained, and in the process There are only slight temperature changes or even no temperature changes. The two reasons make it have better sedimentation effect, which can further improve the recovery rate of the second copper matte.
对于第二种处理方式,是将沉降处理设置在了还原烟化处理的步骤之前。这样,可以先将熔炼渣中的铜锍分离出来后,再进行还原及烟化处理,进一步回收其中的锌、铅、锑等有价金属。For the second treatment, the sedimentation treatment is set before the step of reducing the fuming treatment. In this way, the copper ruthenium in the smelting slag can be separated first, and then subjected to reduction and smouldering treatment to further recover valuable metals such as zinc, lead, and antimony.
需要说明的是,相比于先沉降后还原烟化处理的方式,本发明更优选采用先还原烟化后沉降处理的方式。对于先还原烟化后沉降处理的方式,其优点在于:沉降分离的温度越高,分离效果越好。而还原烟化需要的温度很高(1200~1400℃),因此,先还原烟化后的物料本身温度很高,不需额外加热就可在沉降阶段实现分离。当然,这种先还原烟化后沉降处理的方式,也可以对沉降处理进行补热。然而,先沉降分离后还原烟化的方式,则必然要在沉降处理的过程中进行补热。具体的补热方式可以如下:可以在沉降段用电极(比如可以设置3~6根电极)加热或保温,和/或设浸没式燃烧喷嘴(浸没式燃烧喷嘴喷出燃料和氧气,氧气的量控制在使燃料不完全燃烧状态)。此外,先还原烟化后沉降处理的方式还具有如下优点:还原渣在沉降腔停留一定时间后,可以更充分实现渣锍的沉降分层,无害渣从上部放出,第二铜锍从下部放出。It should be noted that the present invention more preferably adopts a method of first reducing the post-smoothing sedimentation treatment, compared to the manner of reducing the fuming treatment after the sedimentation. For the method of first reducing the post-smoothing sedimentation treatment, the advantage is that the higher the sedimentation separation temperature, the better the separation effect. The temperature required for the reduction of flue gas is very high (1200 to 1400 ° C). Therefore, the temperature of the material after the first reduction of flue gas is high, and separation can be achieved in the sedimentation stage without additional heating. Of course, this method of first reducing the post-smoothing sedimentation treatment can also replenish the sedimentation treatment. However, the method of reducing the flue gas after sedimentation and separation is inevitably required to replenish heat during the sedimentation process. The specific heating method can be as follows: the electrode can be heated or insulated in the settling section (for example, 3 to 6 electrodes can be set), and/or the submerged combustion nozzle can be provided (the submerged combustion nozzle ejects fuel and oxygen, and the amount of oxygen Control is in the state of incomplete combustion of the fuel). In addition, the method of first reducing the post-smoothing sedimentation treatment has the following advantages: after the reducing slag stays in the settling chamber for a certain period of time, the sedimentation stratification of the dross can be more fully realized, the harmless slag is discharged from the upper part, and the second copper slag is discharged from the lower part. release.
在具体的操作中,可以先后对熔炼渣进行多次还原烟化及沉降步骤,也可以将熔炼渣分为多部分分别进行还原烟化及沉降步骤。这是本领域技术人员根据本发明的教导能够想到的,在此不再赘述。In a specific operation, the smelting slag may be successively subjected to a plurality of reduction smouldering and sedimentation steps, or the smelting slag may be divided into a plurality of parts for performing a reductive smouldering and sedimentation step. This is conceivable by those skilled in the art in accordance with the teachings of the present invention and will not be described herein.
在一种优选的实施方式中,腔体中还设置有隔墙,以将腔体分为还原烟化腔和沉降腔,烟化还原烟化腔和沉降腔沿水平方向分别位于隔墙的两侧,且还原烟化腔和沉降腔的连通通道靠近腔体底部设置。这样设置,在还原烟化腔中进行反应的具有流动性的熔体和沉降腔中进行沉降处理的熔体之间,能够实现更平稳的流动,且隔墙能够阻断还原烟化腔中的搅动和表面的浮料,从而进一步提高沉降处理的效果。In a preferred embodiment, a partition wall is further disposed in the cavity to divide the cavity into a reduction smoulding chamber and a sedimentation chamber, and the smog reduction and smog chamber and the sedimentation chamber are respectively located in the horizontal direction of the partition wall. Side, and the communication channel connecting the reducing chamber and the settling chamber is disposed near the bottom of the chamber. In this way, a smoother flow can be achieved between the fluid melt which reacts in the reduction smoulding chamber and the melt which settles in the settling chamber, and the partition wall can block the reduction in the smoulding chamber. The agitating and floating material on the surface further enhances the effect of the sedimentation treatment.
在一种优选的实施方式中,还原烟化处理的步骤包括:向还原烟化腔中加入第二还原剂以进行还原烟化处理;优选第二还原剂选自天然气、煤气、液化石油气、铁粉及固体碳基还原剂中的一种或多种,更优选固体碳基还原剂选自为块煤和/或粉煤。选用该试剂进行还原烟化处理,对于有价金属的回收更为彻底。在实际操作过程中,同时向还原烟化腔中喷入氧化剂,以通过燃烧提供热量,同时氧化剂还可能与还原剂反应生成一氧化碳等还原气体,与加入的还原剂一并起还原作用。In a preferred embodiment, the step of reducing the fuming treatment comprises: adding a second reducing agent to the reducing nicotizing chamber for reductive fuming treatment; preferably, the second reducing agent is selected from the group consisting of natural gas, gas, liquefied petroleum gas, One or more of the iron powder and the solid carbon-based reducing agent, more preferably the solid carbon-based reducing agent is selected from the group consisting of lump coal and/or pulverized coal. The reagent is selected for reduction and fuming treatment, and the recovery of valuable metals is more thorough. In the actual operation, the oxidant is injected into the reduction smoulding chamber to provide heat by combustion, and the oxidant may also react with the reducing agent to form a reducing gas such as carbon monoxide, and reduce the effect together with the added reducing agent.
在一种优选的实施方式中,还原烟化腔中设置有侧吹喷枪,还原烟化处理的步骤中,利用侧吹喷枪将第二还原剂鼓入还原烟化腔中。更优选地,还原烟化腔中还设置有出烟口,还原烟化处理的步骤还包括:在还原烟化腔的上部或者出烟口处引入二次风。这样可以将有价金属烟气氧化为有价金属氧化物,后进行烟气回收。In a preferred embodiment, a side blowing lance is disposed in the reducing smoulding chamber, and in the step of reducing the smoulding treatment, the second reducing agent is blasted into the reducing smoulding chamber by a side blasting gun. More preferably, the reducing smoulding chamber is further provided with a venting port, and the step of reducing the smoulding treatment further comprises: introducing a secondary air at the upper portion of the reducing smoulding chamber or at the venting port. In this way, the valuable metal flue gas can be oxidized to a valuable metal oxide, and then the flue gas can be recovered.
在一种优选的实施方式中,还原烟化处理的步骤中,反应温度为1200~1400℃。更优选地,当还原烟化处理步骤位于沉降处理步骤之前时,在还原烟化处理的同时,向还原烟化腔中加入捕集剂;优选捕集剂选自第一硫化剂和/或铜精矿,更优选第一硫化剂选自硫铁矿和/或黄铁矿。当还原烟化处理步骤位于沉降处理步骤之后时,在沉降处理的同时,向沉降腔中加入第二硫化剂和/或铜精矿,优选第二硫化剂选自硫铁矿、黄铁矿及炼铅铜浮渣中的一种或多种。In a preferred embodiment, in the step of reducing the fuming treatment, the reaction temperature is 1200 to 1400 °C. More preferably, when the reduction flue gasification treatment step is located before the sedimentation treatment step, a collector is added to the reduction flue gas chamber while the reduction flue gas treatment is performed; preferably, the trap agent is selected from the first vulcanizing agent and/or copper Concentrate, more preferably the first vulcanizing agent is selected from the group consisting of pyrite and/or pyrite. When the reduction flue gasification treatment step is located after the sedimentation treatment step, a second vulcanizing agent and/or copper concentrate is added to the sedimentation chamber while the sedimentation treatment is performed, and preferably the second vulcanizing agent is selected from the group consisting of pyrite, pyrite and One or more of lead slag copper scum.
加入硫化剂和/或铜精矿,有利于降低熔炼渣中的铜锍品位,使其转变为低品位铜锍(第二铜锍),这样可以降低无害渣中的铜含量,进一步提高铜的回收率。而在还原烟化处理步骤 位于沉降处理步骤之后的方式中,因为沉降渣还会进行后续的还原烟化步骤进行回收,因而可以采用炼铅铜浮渣这样的废渣作为硫化剂,其中的铅还可以在还原烟化步骤中与沉降渣中的铅一并挥发并回收,这样可以充分利用一些生产过程中产生的难处理杂料,实现资源综合利用,且不增添额外的设备投资和工艺环节。The addition of a vulcanizing agent and/or a copper concentrate facilitates the reduction of the copper bismuth grade in the smelting slag to be converted into a low-grade copper ruthenium (second copper ruthenium), which can reduce the copper content in the harmless slag and further increase the copper content. Recovery rate. In the manner after the reduction smouldering step is located after the sedimentation treatment step, since the sediment slag is further subjected to a subsequent reduction smoulding step for recovery, it is possible to use a slag such as lead slag copper scum as a vulcanizing agent, wherein the lead is also It can be volatilized and recovered together with the lead in the sedimentation slag in the reduction fuming step, so that the refractory materials generated in some production processes can be fully utilized to realize comprehensive utilization of resources without adding additional equipment investment and process links.
更优选地,沉降处理的步骤还包括:向沉降腔中鼓入惰性气体和/或二氧化硫气体。这样可以形成微弱的搅动,这有利于铜和渣的分离。更优选鼓入二氧化硫气体,其除了搅动作用外,还充当了部分硫化剂的作用,更有利于在沉降阶段造低品位铜锍。More preferably, the step of the sedimentation treatment further comprises: injecting an inert gas and/or a sulfur dioxide gas into the settling chamber. This creates a weak agitation which facilitates the separation of copper and slag. More preferably, the sulfur dioxide gas is bubbled in, which acts as a partial vulcanizing agent in addition to the agitation action, and is more advantageous for producing a low-grade copper beryllium in the sedimentation stage.
在一种优选的实施方式中,在得到第二铜锍的步骤之后,炼铜方法还包括将第二铜锍返回熔炼炉进行熔炼的步骤。这样能够提高铜的利用率。In a preferred embodiment, after the step of obtaining the second copper crucible, the copper smelting method further comprises the step of returning the second copper crucible to the melting furnace for melting. This can increase the utilization of copper.
在一种优选的实施方式中,在得到第二铜锍的步骤之后,炼铜方法还包括将第二铜锍返回造铜炉进行造铜的步骤。这样能够提高铜的利用率。由于第二铜锍一般是以冷却状态(及固态第二铜锍)加入,因此还能起到热平衡的作用。In a preferred embodiment, after the step of obtaining the second copper crucible, the copper smelting method further comprises the step of returning the second copper crucible to the copper making furnace for copper making. This can increase the utilization of copper. Since the second copper crucible is generally added in a cooled state (and a solid second copper crucible), it can also function as a heat balance.
在一种优选的实施方式中,对第一铜锍进行造铜反应的步骤中,得到的铜为铜熔体;在造铜反应的步骤之后,上述炼铜方法还包括对铜熔体进行浇铸成型的步骤。这样可以进一步将铜熔体浇铸形成铜阳极板等产品。In a preferred embodiment, in the step of performing a copper-making reaction on the first copper ruthenium, the obtained copper is a copper melt; after the step of the copper-making reaction, the copper smelting method further comprises casting the copper melt. The step of molding. This allows the copper melt to be further cast into a product such as a copper anode plate.
根据本发明的另一方面,还提供了一种炼铜系统,如图3至6所示,该炼铜系统包括熔炼炉10,造铜炉20,CR炉30、第一流槽及第二流槽;其中熔炼炉10用于对铜精矿进行熔炼以产出第一铜锍与熔炼渣;熔炼炉10设置有第一铜锍出口和熔炼渣出口;造铜炉20设置有铜锍入口,铜锍入口与第一铜锍出口通过第一流槽连通,造铜炉20用于对第一铜锍进行造铜反应,生成阳极铜和造铜渣;CR炉30设置有熔炼渣入口,其与熔炼渣出口通过第二流槽连通,用于对熔炼渣进行还原烟化和沉降以回收熔炼渣中的有价金属。According to another aspect of the present invention, there is also provided a copper smelting system, as shown in Figures 3 to 6, the smelting system comprising a smelting furnace 10, a copper making furnace 20, a CR furnace 30, a first launder and a second stream a tank; wherein the melting furnace 10 is used for smelting copper concentrate to produce a first copper crucible and smelting slag; the melting furnace 10 is provided with a first copper crucible outlet and a smelting slag outlet; and the copper making furnace 20 is provided with a copper crucible inlet, The copper crucible inlet and the first copper crucible outlet are communicated through the first launder, and the copper making furnace 20 is used for copper-making reaction of the first copper crucible to generate anode copper and copper-making slag; the CR furnace 30 is provided with a smelting slag inlet, which is The smelting slag outlet is connected through the second launder for reducting fuming and sedimentation of the smelting slag to recover valuable metals in the smelting slag.
上述装置中,利用熔炼炉10能够对铜矿进行熔炼,得到第一铜锍和熔炼渣。在得到熔炼渣后,利用CR炉30能够对熔炼渣进行还原烟化和沉降,进而能够回收熔炼渣中的有价金属,比如金属锌、铅、锑等。这就有效解决了现有的炼铜工艺中有价金属流失浪费的问题,并避免了这些流失金属对环境的污染问题;另一方面,对熔炼渣进行还原烟化和沉降取代了原来的渣选矿流程,不但大大缩减了工厂占地面积,使工艺流程更加简单,还从根本上消除了渣选矿流程中加入的选矿药剂造成的污染。与此同时,需要说明的是,本发明的上述炼铜装置,CR炉30与熔炼炉10的出渣端连通,造铜炉20与熔炼炉10的铜锍端连通。这样在将铜矿进行熔炼得到第一铜锍和熔炼渣后,一方面将第一铜锍进行造铜反应处理生成了品位较高的阳极铜,一方面又将熔炼过程中产出的熔炼渣进行了回收处理,即采用的一担挑式的炼铜装置,极大地缩短了铜冶炼的步骤,具有很好的工业化大规模应用前景。In the above apparatus, the copper ore can be smelted by the melting furnace 10 to obtain a first copper crucible and a smelting slag. After the smelting slag is obtained, the smelting slag can be reduced and smelted and settled by the CR furnace 30, and the valuable metals in the smelting slag such as metal zinc, lead, bismuth, and the like can be recovered. This effectively solves the problem of waste of valuable metals in the existing copper smelting process, and avoids the pollution of these metals to the environment; on the other hand, the reduction smelting and sedimentation of the smelting slag replaces the original slag. The beneficiation process not only greatly reduces the factory floor space, but also makes the process more simple. It also fundamentally eliminates the pollution caused by the beneficiation agent added in the slag beneficiation process. At the same time, it should be noted that in the copper smelting apparatus of the present invention, the CR furnace 30 communicates with the slag end of the melting furnace 10, and the copper making furnace 20 communicates with the copper rim end of the melting furnace 10. After the copper ore is smelted to obtain the first copper crucible and the smelting slag, the first copper crucible is subjected to a copper-making reaction to form a higher-grade anode copper, and on the other hand, the molten slag produced in the smelting process is obtained. The recycling process, that is, the use of a pick-up copper smelting device, greatly shortens the steps of copper smelting, and has a good industrialized large-scale application prospect.
在一种优选的实施方式中,CR炉30为并联或串联设置的多个。这样,多个CR炉30采用连续作业或交替作业方式产出第二铜锍、有价金属和水碎无害渣,能够提高处理效率。当然,也可以利用多个CR炉30串联式处理熔炼渣,以进一步提高处理效果。在此不再赘述。In a preferred embodiment, the CR furnaces 30 are a plurality of units arranged in parallel or in series. Thus, the plurality of CR furnaces 30 can produce the second copper crucible, the valuable metal, and the water-damaged harmless slag by continuous operation or alternate operation, thereby improving the processing efficiency. Of course, it is also possible to use a plurality of CR furnaces 30 to treat the smelting slag in series to further improve the treatment effect. I will not repeat them here.
在本发明一种优选的实施例中,造铜炉20为并联设置的多个。这样同样可以提高设备的能力。In a preferred embodiment of the invention, the copper making furnace 20 is a plurality of tubes arranged in parallel. This also improves the capabilities of the device.
在本发明一种典型的实施例中,如图4所示,造铜炉20为并联设置的两个,CR炉为一个;或者,In an exemplary embodiment of the present invention, as shown in FIG. 4, the copper making furnace 20 is two in parallel, and the CR furnace is one; or
在本发明另一种典型的实施例中,如图5所示,造铜炉20为一个,CR炉为并联设置的两个;或者,In another exemplary embodiment of the present invention, as shown in FIG. 5, the copper making furnace 20 is one, and the CR furnace is two in parallel; or
在本发明又一种典型的实施例中,如图6所示,造铜炉20并联设置的两个,CR炉也为并联设置的两个。In still another exemplary embodiment of the present invention, as shown in Fig. 6, two copper-making furnaces 20 are arranged in parallel, and the CR furnaces are also two disposed in parallel.
在一种优选的实施方式中,CR炉30包括腔体,腔体包括相连通的还原烟化腔31和沉降腔32,还原烟化腔31与熔炼渣出口连通,用于对熔炼渣进行还原烟化处理,还原烟化腔31上设置有烟气出口,沉降腔32与还原烟化腔31连通,用于对还原及烟化处理后的还原渣进行沉降处理,且沉降腔32设置有第二铜锍出口和排渣口(如图3所示);或者,CR炉30包括腔体,腔体包括相连通的还原烟化腔31和沉降腔32,沉降腔32与熔炼渣出口连通,用于对熔炼渣进行沉降处理,且沉降腔32设置有第二铜锍出口,还原烟化腔31与沉降腔32连通,用于对沉降处理后的沉降渣进行还原及烟化处理,还原烟化腔31上设置有烟气出口及排渣口。In a preferred embodiment, the CR furnace 30 includes a cavity including a reduced reduction smoulding chamber 31 and a settling chamber 32, and the reducing smoulding chamber 31 is in communication with the smelting slag outlet for reducing the smelting slag. In the smoulding treatment, the reducing smog chamber 31 is provided with a flue gas outlet, and the settling chamber 32 is connected with the reducing smoating chamber 31 for sedimentation treatment of the reducing slag after the reduction and the smoulding treatment, and the settling chamber 32 is provided with a first The second copper crucible outlet and the slag discharge port (shown in FIG. 3); or, the CR furnace 30 includes a cavity including a reduced reduction smoulding chamber 31 and a settling chamber 32, and the settling chamber 32 communicates with the smelting slag outlet. It is used for sedimentation treatment of the smelting slag, and the sedimentation chamber 32 is provided with a second copper sputum outlet, and the reduction smoulding chamber 31 is connected with the sedimentation chamber 32 for reducing and smoulding the sedimentation slag after the settlement treatment, and reducing the smoke The chemistry chamber 31 is provided with a flue gas outlet and a slag discharge port.
这样,本发明提供的CR炉30为一体化设备,其同时包括相连通的还原烟化腔31和沉降腔32,选择还原烟化腔31和沉降腔32的连接关系,可以决定先还原烟化,后沉降;或者先沉降,后还原烟化。Thus, the CR furnace 30 provided by the present invention is an integrated device, which includes a reducing flue gas chamber 31 and a settling chamber 32, and a connection relationship between the reduction flue gas chamber 31 and the sedimentation chamber 32, which can be determined to reduce the flue gas. , post-settling; or settle first, then reduce the fuming.
当还原烟化腔31与熔炼渣出口连通,沉降腔32与还原烟化腔31连通时,能够对熔炼渣先进行还原烟化处理,后进行沉降处理。将熔炼渣进行还原及烟化处理时,能够将熔炼渣中的磁性铁(四氧化三铁)还原为氧化亚铁进行造渣,这样能够减少熔炼渣的粘度,从而提高后续的沉降分离效果,便于第二铜锍从还原渣中分离。同时,锌、铅、锑等有价金属氧化物被还原为金属后,因其具有易挥发性而转化为有价金属烟气被分离出来,从而达到了回收有价金属的目的。还原烟化处理后,得到的还原渣(呈流动态)进入沉降腔中进行沉降分离,进一步得到第二铜锍与无害渣。更重要地,采用一体化设备,经还原烟化处理后的熔炼渣直接进入沉降分离,一方面能够极大地改善处理效率;另一方面由于还原渣直接进入沉降处理,能够保持更稳定地流态,且在此过程中仅有微小的温度变化甚至没有温度变化,两方面的原因使其具有更好的沉降效果,能够进一步提高第二铜锍的回收率。When the reduction smoulding chamber 31 is in communication with the smelting slag outlet and the settling chamber 32 is in communication with the reducing smoulding chamber 31, the smelting slag can be first subjected to reduction and smouldering treatment, and then subjected to sedimentation treatment. When the smelting slag is subjected to reduction and smelting treatment, the magnetic iron (ferric oxide) in the smelting slag can be reduced to ferrous oxide for slag formation, which can reduce the viscosity of the smelting slag and thereby improve the subsequent sedimentation separation effect. It is convenient to separate the second copper crucible from the reducing slag. At the same time, after the valuable metal oxides such as zinc, lead and antimony are reduced to metal, they are separated into valuable metal fumes due to their volatility, thereby achieving the purpose of recovering valuable metals. After the reduction smoulding treatment, the obtained reducing slag (flowing dynamics) enters the sedimentation chamber for sedimentation separation, and further obtains the second copper ruthenium and the harmless slag. More importantly, with integrated equipment, the smelting slag after reduction and smoulding treatment directly enters the sedimentation separation, which can greatly improve the treatment efficiency; on the other hand, the reducing slag directly enters the sedimentation treatment, and can maintain a more stable flow state. In the process, there is only a slight temperature change or even no temperature change. The two reasons make it have better sedimentation effect, which can further improve the recovery rate of the second copper matte.
当还原烟化腔31与熔炼渣出口连通,沉降腔32与还原烟化腔31连通时,能够对熔炼渣先进行沉降处理,后进行还原烟化处理。这样,可以先将熔炼渣中的铜锍分离出来后,再进行还原烟化处理阶段,进一步回收其中的锌、铅、锑等有价金属。需要说明的是,相比于先沉降后还原烟化处理的方式,本发明更优选采用先还原烟化后沉降处理的方式。对于先还原烟化后沉降处理的方式,其优点在于:沉降分离的温度越高,分离效果越好。而还原烟化需要的温度很高(1200~1400℃),因此,先还原烟化后的物料本身温度很高,不需额外加热就可在沉降阶段实现分离。当然,这种先还原烟化后沉降处理的方式,也可以对沉降处理进行 补热。然而,先沉降分离后还原烟化的方式,则必然要在沉降处理的过程中进行补热。具体的补热方式可以如下:可以在沉降段用电极(比如可以设置3~6根电极)加热或保温,和/或设浸没式燃烧喷嘴(浸没式燃烧喷嘴喷出燃料和氧气,氧气的量控制在使燃料不完全燃烧状态)。此外,先还原烟化后沉降处理的方式还具有如下优点:还原渣在沉降腔停留一定时间后,可以更充分实现渣锍的沉降分层,无害渣从上部放出,第二铜锍从下部放出。When the reduction smoulding chamber 31 is in communication with the smelting slag outlet and the settling chamber 32 is in communication with the reducing smoulding chamber 31, the smelting slag can be first subjected to sedimentation treatment and then subjected to reduction smoulding treatment. In this way, the copper ruthenium in the smelting slag can be separated first, and then the reduction smoulding treatment stage can be further carried out to further recover valuable metals such as zinc, lead and bismuth therein. It should be noted that the present invention more preferably adopts a method of first reducing the post-smoothing sedimentation treatment, compared to the manner of reducing the fuming treatment after the sedimentation. For the method of first reducing the post-smoothing sedimentation treatment, the advantage is that the higher the sedimentation separation temperature, the better the separation effect. The temperature required for the reduction of flue gas is very high (1200 to 1400 ° C). Therefore, the temperature of the material after the first reduction of flue gas is high, and separation can be achieved in the sedimentation stage without additional heating. Of course, this method of first reducing the post-smoothing sedimentation treatment can also replenish the sedimentation treatment. However, the method of reducing the flue gas after sedimentation and separation is inevitably required to replenish heat during the sedimentation process. The specific heating method can be as follows: the electrode can be heated or insulated in the settling section (for example, 3 to 6 electrodes can be set), and/or the submerged combustion nozzle can be provided (the submerged combustion nozzle ejects fuel and oxygen, and the amount of oxygen Control is in the state of incomplete combustion of the fuel). In addition, the method of first reducing the post-smoothing sedimentation treatment has the following advantages: after the reducing slag stays in the settling chamber for a certain period of time, the sedimentation stratification of the dross can be more fully realized, the harmless slag is discharged from the upper part, and the second copper slag is discharged from the lower part. release.
在一种优选的实施方式中,如图3所示,腔体中还设置有隔墙33,以将腔体分为还原烟化腔31和沉降腔32,还原烟化腔31和沉降腔32沿水平方向分别位于隔墙33的两侧,且还原烟化腔31和沉降腔32的连通通道靠近腔体底部设置。这样设置,在还原烟化腔31中进行反应的具有流动性的熔体和沉降腔中进行沉降处理的熔体之间,能够实现更平稳的流动,且隔墙能够阻断还原烟化腔中的搅动和表面的浮料,从而进一步提高沉降处理的效果。优选地,上述隔墙33为水冷隔墙。In a preferred embodiment, as shown in FIG. 3, a partition wall 33 is further disposed in the cavity to divide the cavity into a reduction smoulding chamber 31 and a settling chamber 32, and a reduction smoulding chamber 31 and a settling chamber 32. The two sides of the partition wall 33 are respectively located in the horizontal direction, and the communication passages of the reduction tobacco chamber 31 and the sedimentation chamber 32 are disposed near the bottom of the chamber. With this arrangement, a fluid melt which reacts in the reduction smoulding chamber 31 and a melt which is subjected to sedimentation treatment in the sedimentation chamber can achieve a smoother flow, and the partition wall can block the reduction smog chamber. The agitation and the floating material on the surface further enhance the effect of the sedimentation treatment. Preferably, the partition wall 33 is a water-cooled partition wall.
在一种优选的实施方式中,还原烟化腔31还设置有侧吹喷枪,第一喷枪设置在还原烟化腔31的侧部或底部,用于向还原烟化腔31中喷入还原剂。更优选地,还原烟化腔中还设置有出烟口,用以排出有价金属烟气。进一步优选地,还原烟化腔中还设置有加料口,用于向还原烟化腔31中加入捕集剂。In a preferred embodiment, the reduction smoulding chamber 31 is further provided with a side lance, which is disposed at the side or bottom of the reduction smoulding chamber 31 for injecting a reducing agent into the reduction smoulding chamber 31. . More preferably, the reducing tobacco chamber is further provided with a smoke outlet for discharging valuable metal smoke. Further preferably, the reduction smoulding chamber is further provided with a feed port for adding a collector to the reduction smoulding chamber 31.
在一种优选的实施方式中,当还原烟化腔31与熔炼渣出口连通,沉降腔32与还原烟化腔31连通时,沉降腔32还设置有供热装置,用于对沉降腔32进行保温或升温。这样能够防止沉降腔32降温,进一步保证沉降分离效果。优选地,供热装置为浸没式燃烧喷嘴或电极。In a preferred embodiment, when the reduction smoulding chamber 31 is in communication with the smelting slag outlet and the settling chamber 32 is in communication with the reducing smoulding chamber 31, the settling chamber 32 is also provided with a heating device for performing the settling chamber 32. Keep warm or warm. This can prevent the sedimentation chamber 32 from cooling down, further ensuring the sedimentation separation effect. Preferably, the heating device is an immersion combustion nozzle or electrode.
在一种优选的实施方式中,造铜炉20还设置有第二喷枪和熔剂入口,第二喷枪设置在造铜炉20的侧部或底部,用于向造铜炉20内交替加入氧化剂或还原剂;熔剂入口用于通入熔剂。这样,能够在造铜炉一个设备中完成对铜锍的精炼,将其品位提高到电解阳极铜的品位。优选地,造铜炉20的炉体为卧式圆筒型炉体。在实际操作中,可以并联设置多台造铜炉20,进行交替作业或者同时作业的方式。优选地,第二喷枪中可喷入适量水雾以吸收造铜过程中产生的过剩热量,减少烟气量,延长喷枪寿命。In a preferred embodiment, the copper making furnace 20 is further provided with a second spray gun and a flux inlet, and the second spray gun is disposed at the side or the bottom of the copper making furnace 20 for alternately adding oxidizing agent to the copper making furnace 20 or Reducing agent; the flux inlet is used to pass the flux. In this way, the refining of the copper crucible can be completed in one equipment of the copper making furnace, and the grade is improved to the grade of the electrolytic anode copper. Preferably, the furnace body of the copper making furnace 20 is a horizontal cylindrical furnace body. In actual operation, a plurality of copper-making furnaces 20 may be arranged in parallel to perform alternate operations or simultaneous operations. Preferably, an appropriate amount of water mist can be sprayed into the second spray gun to absorb excess heat generated during the copper making process, reduce the amount of smoke, and prolong the life of the spray gun.
在一种优选的实施方式中,造铜炉20还设置有铜熔体出口;炼铜系统还包括浇铸设备40,浇铸设备40与铜熔体出口连通,用于对铜熔体进行浇铸处理。对第一铜锍进行造铜反应的步骤中,得到的阳极铜为铜熔体。通过设置浇铸设备40可以进一步将铜熔体浇铸形成阳极铜板等产品。更优选地,浇铸设备40为双圆盘浇铸机。In a preferred embodiment, the coppermaking furnace 20 is also provided with a copper melt outlet; the copper smelting system further includes a casting apparatus 40 in communication with the copper melt outlet for casting the copper melt. In the step of subjecting the first copper crucible to a copper-making reaction, the obtained anode copper is a copper melt. The copper melt can be further cast by forming the casting apparatus 40 to form a product such as an anode copper plate. More preferably, the casting apparatus 40 is a double disc casting machine.
在一种优选的实施方式中,造铜炉20还设置有造铜渣出口,用以排出造铜渣;熔炼炉10还设置有造铜渣入口,用以将冷却后的造铜渣通入熔炼炉10中。In a preferred embodiment, the copper making furnace 20 is further provided with a copper slag outlet for discharging copper slag; the smelting furnace 10 is further provided with a copper slag inlet for introducing the cooled copper slag. In the melting furnace 10.
在一种优选的实施方式中,熔炼炉10还设置有第二铜锍入口,用以将冷却后的第二铜硫通入至熔炼炉10中。这样能够进一步提高铜的利用率。In a preferred embodiment, the melting furnace 10 is further provided with a second copper crucible inlet for introducing the cooled second copper sulfur into the melting furnace 10. This can further improve the utilization of copper.
在一种优选的实施方式中,造铜炉20还设置有冷料入口,用以向造铜炉20中加入电解铜残极、废杂铜及固态铜锍中的一种或多种。这样可以将后期电解过程中残余的电解铜残极和 外购的废杂铜、固态铜锍作为冷料通入造铜炉中,更好地实现造铜炉中的热平衡,为向造铜炉中喷入富氧创造条件。In a preferred embodiment, the copper making furnace 20 is further provided with a cold material inlet for adding one or more of electrolytic copper residual, waste copper and solid copper to the copper making furnace 20. In this way, the residual electrolytic copper residual in the later electrolysis process and the purchased waste copper and solid copper crucible can be passed into the copper making furnace as a cold material to better realize the heat balance in the copper making furnace. Injecting oxygen into the conditions creates conditions.
在一种优选的实施方式中,造铜系统还包括冷却设备,冷却设备用于对造铜炉20进行降温。这样能够保证造铜炉20在造铜反应阶段维持热平衡,为向造铜炉中喷入富氧创造条件,此外还能延长炉寿。冷却设备包括但不限于负压水套装置或喷雾冷却装置In a preferred embodiment, the copper making system further includes a cooling device for cooling the copper making furnace 20. This ensures that the copper-making furnace 20 maintains thermal equilibrium during the copper-making reaction stage, creating conditions for injecting oxygen into the copper-making furnace, and further extending the furnace life. Cooling equipment includes, but is not limited to, a negative pressure water jacket device or a spray cooling device
在一种优选的实施方式中,熔炼炉10为顶吹熔炼炉、闪速熔炼炉、底吹熔炼炉或侧吹熔炼炉。In a preferred embodiment, the melting furnace 10 is a top-blowing smelting furnace, a flash smelting furnace, a bottom-blowing smelting furnace or a side-blown smelting furnace.
以下通过实施例进一步说明本发明的有益效果:The beneficial effects of the present invention are further illustrated by the following examples:
实施例1Example 1
利用图3所示炼铜装置进行炼铜,各装置工艺条件如下:The copper smelting apparatus shown in Fig. 3 is used for copper smelting, and the process conditions of each apparatus are as follows:
熔炼炉:熔炼温度为1300℃;熔剂为石英石,其加入量为铜矿总重量的10%;氧化剂为氧气,其加入量为每吨铜矿加入150Nm
3O
2;
Melting furnace: melting temperature is 1300 ° C; flux is quartz stone, the amount of addition is 10% of the total weight of copper ore; oxidant is oxygen, the amount of addition is 150Nm 3 O 2 per ton of copper ore;
造铜炉:熔剂为石英石,其加入量为第一铜锍总重量的20%;氧化剂为氧气体积含量40%的富氧空气,其加入量为每吨第一铜锍中加入200Nm
3O
2;使用喷枪向造铜炉中喷入氧化剂的同时,还喷入水雾;同时向造铜炉中加入冷料废杂铜;还原剂为粉煤,喷入还原剂之前,先将造铜渣排出,造铜渣冷却后返回熔炼炉。
Copper-making furnace: the flux is quartz stone, which is added in an amount of 20% of the total weight of the first copper crucible; the oxidant is oxygen-enriched air having a volumetric oxygen content of 40%, and the addition amount is 200Nm 3 O per ton of the first copper crucible. 2 ; using a spray gun to spray oxidant into the coppermaking furnace, also spray water mist; at the same time add cold waste copper to the coppermaking furnace; the reducing agent is pulverized coal, before the reducing agent is sprayed, the copper slag is firstly sprayed After the discharge, the copper slag is cooled and returned to the smelting furnace.
CR炉:先还原烟化,后沉降;还原烟化处理的步骤中,反应温度为1200℃;还原剂为粉煤,其加入量为熔炼渣总重量的10%;少量通入氧气提供助燃补热;沉降腔中通入二氧化硫气体,并加入硫化剂黄铁矿造低品位铜锍;所得低品位铜锍返回熔炼炉。CR furnace: first reduction of fuming, post-sedimentation; in the step of reducing fuming treatment, the reaction temperature is 1200 ° C; the reducing agent is pulverized coal, the amount of addition is 10% of the total weight of the smelting slag; a small amount of oxygen is supplied to provide combustion-supporting Heat; sulfur dioxide gas is introduced into the settling chamber, and the vulcanizing agent pyrite is added to make low-grade copper bismuth; the low-grade copper bismuth obtained is returned to the melting furnace.
处理结果:年处理100万吨铜精矿,精矿含铜20%,含锌2%;熔炼产出铜锍25万吨,含铜75%,熔炼渣65万吨,含铜3%,熔炼渣含锌2.77%;造铜炉产出阳极铜23.5万吨,含铜99.3%,含硫0.05%;熔炼渣经CR炉处理(还原烟化及沉降)后渣含铜0.3%,渣含锌0.28%。整个系统铜回收率约99%,锌回收率约为80%。Treatment results: 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; smelting output 250,000 tons of copper, 75% copper, 650,000 tons of smelting, 3% copper, smelting The slag contains 2.77% zinc; the copper-making furnace produces 235,000 tons of anode copper, 99.3% copper, and 0.05% sulfur; the smelting slag is treated with CR furnace (reduction ashing and sedimentation), the slag contains 0.3% copper, and the slag contains zinc. 0.28%. The copper recovery rate of the entire system is about 99%, and the zinc recovery rate is about 80%.
实施例2Example 2
处理方法同实施例1相同,不同之处在于铜矿原料不同,具体如下:The treatment method is the same as that of the first embodiment, except that the copper ore raw materials are different, as follows:
年处理150万吨铜精矿,精矿含铜25%,含锌1.5%,含锑0.5%;熔炼产出铜锍40万吨,含铜75%,熔炼渣100万吨,含铜2%,熔炼渣含锌2.03%;造铜炉产出阳极铜45万吨,含铜99.2%,含硫0.03%;熔炼渣经CR炉处理后渣含铜0.3%,渣含锌0.20%。整个系统铜回收率约99%,锌回收率约为80%。Annual processing of 1.5 million tons of copper concentrate, concentrate containing 25% copper, 1.5% zinc, containing 0.5% smelting; smelting output of 400,000 tons of copper, 75% copper, 1 million tons of smelting, 2% copper The smelting slag contains 2.03% of zinc; the copper making furnace produces 450,000 tons of anode copper, containing 99.2% of copper and 0.03% of sulfur; the slag contains 0.3% of copper after slag treatment by the CR furnace, and the slag contains 0.20% of zinc. The copper recovery rate of the entire system is about 99%, and the zinc recovery rate is about 80%.
实施例3Example 3
处理方法同实施例1,不同之处在于:The processing method is the same as that in Embodiment 1, except that:
熔炼炉:熔炼温度为1300℃;熔剂为石英石,其加入量为铜矿总重量的20%;氧化剂为氧气,其加入量为每吨铜矿加入200Nm
3O
2;
Melting furnace: melting temperature is 1300 ° C; flux is quartz stone, the amount of addition is 20% of the total weight of copper ore; oxidant is oxygen, the amount of addition is 200Nm 3 O 2 per ton of copper ore;
处理结果:年处理100万吨铜精矿,精矿含铜20%,含锌2%;熔炼产出铜锍26万吨,含铜78%,熔炼渣62万吨,含铜4%,熔炼渣含锌2.05%;造铜炉产出阳极铜23.6万吨,含铜99.5%,含硫0.03%;熔炼渣经CR炉处理(还原烟化及沉降)后渣含铜0.2%,渣含锌0.26%。整个系统铜回收率约99%,锌回收率约为82%。Treatment results: 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; 260,000 tons of copper smelting, 78% copper, 620,000 tons of smelting slag, 4% copper, smelting The slag contains 2.05% zinc; the copper-making furnace produces 236,000 tons of anode copper, 99.5% copper, 0.03% sulfur; the smelting slag is treated with CR furnace (reduction ashing and sedimentation), the slag contains 0.2% copper, and the slag contains zinc. 0.26%. The copper recovery rate of the entire system is about 99%, and the zinc recovery rate is about 82%.
实施例4Example 4
处理方法同实施例1,不同之处在于:The processing method is the same as that in Embodiment 1, except that:
熔炼炉:熔炼温度为1150℃;熔剂为石英石,其加入量为铜矿总重量的1%;氧化剂为氧气,其加入量为每吨铜矿加入120Nm
3O
2;
Melting furnace: the melting temperature is 1150 ° C; the flux is quartz stone, the amount of addition is 1% of the total weight of the copper ore; the oxidant is oxygen, the amount of addition is 120Nm 3 O 2 per ton of copper ore;
处理结果:年处理100万吨铜精矿,精矿含铜20%,含锌2%;熔炼产出铜锍26万吨,含铜70%,熔炼渣70万吨,含铜2.5%,熔炼渣含锌3.25%;造铜炉产出阳极铜23.1万吨,含铜99.1%,含硫0.03%;熔炼渣经CR炉处理(还原烟化及沉降)后渣含铜0.3%,渣含锌0.27%。整个系统铜回收率约99%,锌回收率约为80%。Treatment results: 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; 260,000 tons of copper smelting, 70% copper, 700,000 tons of smelting, 2.5% copper, smelting The slag contains 3.25% zinc; the copper making furnace produces 231,000 tons of anode copper, containing 99.1% copper and 0.03% sulfur; the smelting slag is treated by CR furnace (reduction ashing and sedimentation), the slag contains 0.3% copper, and the slag contains zinc. 0.27%. The copper recovery rate of the entire system is about 99%, and the zinc recovery rate is about 80%.
实施例5Example 5
处理方法同实施例1,不同之处在于:The processing method is the same as that in Embodiment 1, except that:
熔炼炉:熔炼温度为1100℃;熔剂为石英石,其加入量为铜矿总重量的0.8%;氧化剂为氧气,其加入量为每吨铜矿加入90Nm
3O
2;
Melting furnace: the melting temperature is 1100 ° C; the flux is quartz stone, the amount of addition is 0.8% of the total weight of the copper ore; the oxidant is oxygen, the amount of addition is 90Nm 3 O 2 per ton of copper ore;
处理结果:年处理100万吨铜精矿,精矿含铜20%,含锌2%;熔炼产出铜锍20万吨,含铜65%,熔炼渣78万吨,含铜5%,熔炼渣含锌4.71%;造铜炉产出阳极铜22.8万吨,含铜98.0%,含硫0.1%;熔炼渣经CR炉处理(还原烟化及沉降)后渣含铜0.6%,渣含锌0.49%。整个系统铜回收率约95%,锌回收率约为78%。Treatment results: 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; smelting output 200,000 tons of copper, 65% copper, 780,000 tons of smelting, 5% copper, smelting The slag contains 4.71% zinc; the copper making furnace produces 228,000 tons of anode copper, 98.0% copper, and 0.1% sulfur; the smelting slag is treated with CR furnace (reduction ashing and sedimentation), the slag contains 0.6% copper, and the slag contains zinc. 0.49%. The overall system copper recovery rate is about 95%, and the zinc recovery rate is about 78%.
实施例6Example 6
处理方法同实施例1,不同之处在于:The processing method is the same as that in Embodiment 1, except that:
造铜炉:熔剂为石英石,其加入量为第一铜锍总重量的20%;氧化剂为氧气体积含量80%的富氧空气,其加入量为每吨第一铜锍中加入120Nm
3O
2;使用喷枪向造铜炉中喷入氧化剂的同时,还喷入水雾;同时向造铜炉中加入冷料废杂铜;还原剂为粉煤;喷入还原剂之前,先将造铜渣排出,冷却后返回熔炼炉。
Copper-making furnace: the flux is quartz stone, which is added in an amount of 20% of the total weight of the first copper crucible; the oxidant is oxygen-enriched air having an oxygen volume content of 80%, and the addition amount is 120Nm 3 O per ton of the first copper crucible. 2 ; using a spray gun to spray oxidant into the copper making furnace, also spray water mist; at the same time, add cold waste copper to the copper making furnace; the reducing agent is pulverized coal; before the reducing agent is sprayed, the copper slag is firstly sprayed Drain, cool and return to the melting furnace.
处理结果:年处理100万吨铜精矿,精矿含铜20%,含锌2%;熔炼产出铜锍25万吨,含铜75%,熔炼渣65万吨,含铜3%,熔炼渣含锌2.77%;造铜炉产出阳极铜24.6万吨,含铜99.5%,含硫0.03%;熔炼渣经CR炉处理(还原烟化及沉降)后渣含铜0.4%,渣含锌0.32%。整个系统铜回收率约99.6%,锌回收率约为80%。Treatment results: 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; smelting output 250,000 tons of copper, 75% copper, 650,000 tons of smelting, 3% copper, smelting The slag contains 2.77% zinc; the copper-making furnace produces 246,000 tons of anode copper, 99.5% copper, 0.03% sulfur; the smelting slag is treated with CR furnace (reduction ashing and sedimentation), the slag contains 0.4% copper, and the slag contains zinc. 0.32%. The copper recovery rate of the whole system is about 99.6%, and the zinc recovery rate is about 80%.
实施例7Example 7
处理方法同实施例1,不同之处在于:The processing method is the same as that in Embodiment 1, except that:
造铜炉:熔剂为石英石,其加入量为第一铜锍总重量的20%;氧化剂为氧气体积含量30%的富氧空气,其加入量为每吨第一铜锍中加入140Nm
3O
2;使用喷枪向造铜炉中喷入氧化剂的同时,还喷入水雾,同时向造铜炉中加入冷料废杂铜;还原剂为粉煤;喷入还原剂之前,先将造铜渣排出,冷却后返回熔炼炉。
Copper-making furnace: the flux is quartz stone, which is added in an amount of 20% of the total weight of the first copper crucible; the oxidant is oxygen-enriched air having an oxygen volume content of 30%, and the addition amount is 140Nm 3 O per ton of the first copper crucible. 2 ; using a spray gun to spray oxidant into the copper making furnace, also spray water mist, while adding cold waste copper to the copper making furnace; reducing agent is pulverized coal; before spraying the reducing agent, first make copper slag Drain, cool and return to the melting furnace.
处理结果:年处理100万吨铜精矿,精矿含铜20%,含锌2%;熔炼产出铜锍25万吨,含铜75%,熔炼渣65万吨,含铜3%,熔炼渣含锌2.77%;造铜炉产出阳极铜22.0万吨,含铜98.8%,含硫0.03%;熔炼渣经CR炉处理(还原烟化及沉降)后渣含铜0.5%,渣含锌0.34%。整个系统铜回收率约98.7%,锌回收率约为75%。Treatment results: 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; smelting output 250,000 tons of copper, 75% copper, 650,000 tons of smelting, 3% copper, smelting The slag contains 2.77% zinc; the copper-making furnace produces 220,000 tons of anode copper, 98.8% copper, 0.03% sulfur; the smelting slag is treated with CR furnace (reduction ashing and sedimentation), the slag contains 0.5% copper, and the slag contains zinc. 0.34%. The overall system copper recovery rate is about 98.7%, and the zinc recovery rate is about 75%.
实施例8Example 8
处理方法同实施例1,不同之处在于:The processing method is the same as that in Embodiment 1, except that:
造铜炉:熔剂为石英石,其加入量为第一铜锍总重量的20%;氧化剂为氧气体积含量25%的富氧空气,其加入量为每吨第一铜锍中加入140Nm
3O
2;还原剂为粉煤;不喷入水雾,不加入冷料;
Copper-making furnace: the flux is quartz stone, which is added in an amount of 20% of the total weight of the first copper crucible; the oxidant is oxygen-enriched air having a volume content of 25% oxygen, and the addition amount is 140Nm 3 O per ton of the first copper crucible. 2 ; the reducing agent is pulverized coal; no water mist is sprayed, and no cold material is added;
处理结果:年处理100万吨铜精矿,精矿含铜20%,含锌2%;熔炼产出铜锍25万吨,含铜75%,熔炼渣65万吨,含铜3%,熔炼渣含锌2.77%;造铜炉产出阳极铜18.2万吨,含铜97.6%,含硫0.12%;熔炼渣还原贫化(还原烟化及沉降)后渣含铜0.41%,渣含锌0.50%。整个系统铜回收率约95%,锌回收率约为70%。Treatment results: 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; smelting output 250,000 tons of copper, 75% copper, 650,000 tons of smelting, 3% copper, smelting The slag contains 2.77% zinc; the copper-making furnace produces 182,000 tons of anode copper, 97.6% copper, and 0.12% sulfur. After reduction and reduction of smelting slag (reduction ashing and sedimentation), the slag contains 0.41% copper and the slag contains zinc 0.50. %. The copper recovery rate of the entire system is about 95%, and the zinc recovery rate is about 70%.
实施例9Example 9
处理方法同实施例1,不同之处在于:The processing method is the same as that in Embodiment 1, except that:
CR炉:先还原烟化,后沉降;还原烟化处理的步骤中,反应温度为1350℃;还原剂为粉煤,其加入量为熔炼渣总重量的10%;少量通入氧气提供热量;加入硫化剂黄铁矿造低品位铜锍;沉降腔中通入二氧化硫气体,所得低品位铜锍返回熔炼炉。CR furnace: first reduction of fuming, post-sedimentation; in the step of reducing fuming treatment, the reaction temperature is 1350 ° C; the reducing agent is pulverized coal, the amount of addition is 10% of the total weight of the smelting slag; a small amount of oxygen is supplied to provide heat; The low-grade copper bismuth is formed by adding a vulcanizing agent pyrite; sulfur dioxide gas is introduced into the sedimentation chamber, and the low-grade copper bismuth is returned to the melting furnace.
处理结果:年处理100万吨铜精矿,精矿含铜20%,含锌2%;熔炼产出铜锍25万吨,含铜75%,熔炼渣65万吨,含铜3%,熔炼渣含锌2.77%;造铜炉产出阳极铜23.5万吨,含铜99.3%,含硫0.05%;熔炼渣经CR炉处理(还原烟化及沉降)后渣含铜0.1%,渣含锌0.19%。整个系统铜回收率约99%,锌回收率约为85%。Treatment results: 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; smelting output 250,000 tons of copper, 75% copper, 650,000 tons of smelting, 3% copper, smelting The slag contains 2.77% zinc; the copper-making furnace produces 235,000 tons of anode copper, 99.3% copper, and 0.05% sulfur; the smelting slag is treated with CR furnace (reduction ashing and sedimentation), the slag contains 0.1% copper, and the slag contains zinc. 0.19%. The overall system copper recovery rate is about 99%, and the zinc recovery rate is about 85%.
实施例10Example 10
处理方法同实施例1,不同之处在于:The processing method is the same as that in Embodiment 1, except that:
CR炉:先沉降,后还原烟化;还原烟化处理的步骤中,反应温度为1350℃;还原剂为粉煤,其加入量为熔炼渣总重量的10%;少量通入氧气提供热量;沉降腔进行电极补热。CR furnace: first settling, then reducing fuming; in the step of reducing fuming treatment, the reaction temperature is 1350 ° C; the reducing agent is pulverized coal, the amount of addition is 10% of the total weight of the smelting slag; a small amount of oxygen is supplied to provide heat; The settling chamber performs electrode heating.
处理结果:年处理100万吨铜精矿,精矿含铜20%,含锌2%;熔炼产出铜锍25万吨,含铜72%,熔炼渣63万吨,含铜3.5%,熔炼渣含锌2.63%;造铜炉产出阳极铜24万吨,含铜99.3%,含硫0.05%;熔炼渣经CR炉处理(还原烟化及沉降)后渣含铜0.6%,渣含锌0.54%。整个系统铜回收率约98.5%,锌回收率约为68%。Treatment results: 1 million tons of copper concentrate per year, 20% copper in concentrate, 2% zinc; smelting output 250,000 tons of copper, 72% copper, 630,000 tons of smelting, 3.5% copper, smelting The slag contains 2.63% zinc; the copper making furnace produces 240,000 tons of anode copper, 99.3% copper, and 0.05% sulfur; the smelting slag is treated with CR furnace (reduction ashing and sedimentation), the slag contains 0.6% copper, and the slag contains zinc. 0.54%. The overall system copper recovery rate is about 98.5%, and the zinc recovery rate is about 68%.
从以上的描述中,可以看出,本申请上述的实施例实现了如下技术效果:From the above description, it can be seen that the above-mentioned embodiments of the present application achieve the following technical effects:
采用本发明提供的炼铜工艺,年处理量大,阳极铜(指纯度能够达到电解阳极铜的铜产品)产量大,有价金属回收率较高。特别地,由实施例1、实施例5至8中的数据可知,相较于实施例8中未在造铜炉中加入冷料或喷入水雾的技术方案而言,实施例1、5至7中采用在造铜炉中加入冷料和喷入水雾的方式,极大地提高了造铜反应中氧化剂的含氧量,使反应能够在高富氧浓度的条件下完成造铜反应而不产生过热现象,也有效提高了铜硫产出效率和阳极铜的含铜率。当然,尽管未在造铜炉中加入冷料和喷入水雾,本发明实施例8中的技术方案同样采用短流程炼铜工艺有效回收了熔炼渣中的有价金属,同时直接产出了阳极铜并造无害渣,也属于本发明的保护范围。By adopting the copper smelting process provided by the invention, the annual processing amount is large, and the anode copper (refers to the copper product whose purity can reach the electrolytic anode copper) has large output, and the recovery rate of the valuable metal is high. In particular, from the data in Example 1, Examples 5 to 8, it can be seen that Examples 1, 5 to the technical solution in which no cold material or water mist is added to the coppermaking furnace in Embodiment 8 In the 7th method, the method of adding cold material and spraying water mist into the copper-making furnace greatly improves the oxygen content of the oxidant in the copper-making reaction, so that the reaction can complete the copper-making reaction under the condition of high oxygen-rich concentration without generating overheating. The phenomenon also effectively improves the copper-sulfur production efficiency and the copper content of the anode copper. Of course, although the cold material is not added to the coppermaking furnace and the water mist is sprayed, the technical solution in the eighth embodiment of the present invention also uses the short-flow copper smelting process to effectively recover the valuable metal in the smelting slag, and directly produces the anode. The incorporation of copper into harmless slag is also within the scope of protection of the present invention.
总之,本发明通过还原烟化及沉降有效回收了熔炼过程中熔炼渣里的有价金属,实现了资源回收,减轻了环境污染。另,本发明以熔炼炉为核心,从产品端和渣端同时缩短,大大简化了炼铜工艺。初步估算,渣中平均含锌按照3%计算,回收率按照80%计算,20万t/a的铜冶炼企业可回收锌1.9万t/a,对企业的经济效益有大幅提高,同时大大简化了渣处理的工艺流程,占地面积大大减少,也解决了渣尾矿的潜在污染风险。In summary, the present invention effectively recovers valuable metals in the smelting slag during the smelting process by reducing fuming and sedimentation, thereby realizing resource recovery and reducing environmental pollution. In addition, the invention takes the melting furnace as the core and simultaneously shortens the product end and the slag end, thereby greatly simplifying the copper smelting process. It is estimated that the average zinc content in the slag is calculated according to 3%, the recovery rate is calculated according to 80%, and the copper smelting enterprise with 200,000 t/a can recover 19,000 t/a of zinc, which greatly improves the economic benefits of the enterprise and greatly simplifies. The process of slag treatment has greatly reduced the footprint and solved the potential pollution risk of slag tailings.
以上所述仅为本申请的优选实施例而已,并不用于限制本申请,对于本领域的技术人员来说,本申请可以有各种更改和变化。凡在本申请的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本申请的保护范围之内。The above description is only the preferred embodiment of the present application, and is not intended to limit the present application, and various changes and modifications may be made to the present application. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of this application are intended to be included within the scope of the present application.
Claims (18)
- 一种阳极铜生产方法,其特征在于,所述生产方法包括以下步骤:将铜锍输送至造铜炉中,并在所述造铜炉中喷入富氧空气对所述铜锍进行氧化处理,以使所述铜锍进行造铜反应,生成所述阳极铜;其中,所述富氧空气中氧气的体积百分比为30~80%。An anode copper production method, characterized in that the production method comprises the steps of: transporting a copper crucible into a coppermaking furnace, and injecting oxygen-enriched air into the coppermaking furnace to oxidize the copper crucible The copper beryllium is subjected to a copper-forming reaction to form the anode copper; wherein the volume percentage of oxygen in the oxygen-enriched air is 30 to 80%.
- 根据权利要求1所述的阳极铜生产方法,其特征在于,所述造铜反应的步骤中,同时向所述造铜炉中加入冷料,和/或向所述造铜炉中喷入水雾,和/或在所述造铜炉的炉体外部设置冷却元件;其中所述冷料包括废杂铜、电解残极铜和固态铜锍中的一种或多种。The anode copper production method according to claim 1, wherein in the step of forming a copper, cold material is simultaneously added to the copper making furnace, and/or water mist is sprayed into the copper making furnace. And/or providing a cooling element outside the furnace body of the coppermaking furnace; wherein the cold material comprises one or more of scrap copper, electrolytic residual copper, and solid copper crucible.
- 根据权利要求2所述的阳极铜生产方法,其特征在于,所述造铜反应的步骤中,在进行所述氧化处理的步骤之后,得到金属铜和所述造铜渣,The anode copper production method according to claim 2, wherein in the step of forming a copper, after the step of performing the oxidation treatment, metallic copper and the copper-making slag are obtained.当所述造铜炉中的金属铜中含氧低于0.2wt%时,将所述造铜渣排出所述造铜炉,所述金属铜作为所述阳极铜;When the metal copper in the copper-making furnace contains less than 0.2% by weight of oxygen, the copper-making slag is discharged to the copper-making furnace, and the metal copper is used as the anode copper;当所述造铜炉中的金属铜中含氧高于0.2wt%时,将所述造铜渣排出所述造铜炉后,向所述造铜炉中通入还原剂以对所述金属铜中的铜氧化物杂质进行还原反应,进而得到所述阳极铜。When the oxygen in the metal copper in the coppermaking furnace is higher than 0.2% by weight, after the copper-making slag is discharged from the copper-making furnace, a reducing agent is introduced into the copper-making furnace to the metal The copper oxide impurities in the copper are subjected to a reduction reaction to further obtain the anode copper.
- 根据权利要求1至3中任一项所述的阳极铜生产方法,其特征在于,对所述铜锍进行氧化处理的步骤中,将熔剂从所述造铜炉的顶部加入;同时,采用底吹的方式向所述造铜炉中喷入所述富氧空气进行所述氧化处理,或可选地喷入还原剂进行所述还原反应。The method for producing an anode copper according to any one of claims 1 to 3, wherein in the step of oxidizing the copper matte, the flux is added from the top of the copper making furnace; The oxygen-enriched air is sprayed into the copper-making furnace for the oxidation treatment, or alternatively, a reducing agent is sprayed to carry out the reduction reaction.
- 根据权利要求4所述的阳极铜生产方法,其特征在于,所述熔剂选自石英石和/或石灰石。The method of producing an anode copper according to claim 4, wherein the flux is selected from the group consisting of quartz stone and/or limestone.
- 根据权利要求4所述的阳极铜生产方法,其特征在于,所述还原剂选自天然气、液化石油气及固体碳基还原剂中的一种或多种。The anode copper production method according to claim 4, wherein the reducing agent is one or more selected from the group consisting of natural gas, liquefied petroleum gas, and solid carbon-based reducing agent.
- 根据权利要求6所述的阳极铜生产方法,其特征在于,所述固体碳基还原剂为粉煤和/或块煤。The anode copper production method according to claim 6, wherein the solid carbon-based reducing agent is pulverized coal and/or lump coal.
- 根据权利要求1至7中任一项所述的阳极铜生产方法,其特征在于,所述铜锍的铜含量为大于等于70wt%。The method for producing an anode copper according to any one of claims 1 to 7, wherein the copper matte has a copper content of 70% by weight or more.
- 根据权利要求8所述的阳极铜生产方法,其特征在于,所述铜锍的铜含量为70~78wt%。The anode copper production method according to claim 8, wherein the copper matte has a copper content of 70 to 78% by weight.
- 一种阳极铜生产装置,其特征在于,包括造铜炉(20),所述造铜炉(20)设置有铜锍入口和造铜渣出口,所述造铜炉(20)用于对铜锍进行造铜反应以生成阳极铜和造铜渣;所述阳极铜生产装置还包括喷枪,所述喷枪设置在所述造铜炉(20)的侧部或底部,用于向所述造铜炉(20)内喷入氧气的体积百分比为30~80%的富氧空气和可选的还原剂。An anode copper production apparatus, comprising: a copper making furnace (20) provided with a copper crucible inlet and a copper making slag outlet, the copper making furnace (20) being used for copper Performing a copper-making reaction to form anode copper and copper-making slag; the anode copper production apparatus further includes a spray gun disposed at a side or a bottom of the copper-making furnace (20) for making the copper The furnace (20) is sprayed with oxygen in an amount of 30 to 80% by volume of oxygen-enriched air and optionally a reducing agent.
- 根据权利要求10所述的阳极铜生产装置,其特征在于,所述造铜炉(20)还设置有用于通入熔剂的熔剂入口。The anode copper production apparatus according to claim 10, characterized in that the copper making furnace (20) is further provided with a flux inlet for introducing a flux.
- 根据权利要求11所述的阳极铜生产装置,其特征在于,所述造铜炉(20)的炉体为卧式圆筒型炉体。The anode copper production apparatus according to claim 11, wherein the furnace body of the copper making furnace (20) is a horizontal cylindrical furnace body.
- 根据权利要求10至12中任一项所述的阳极铜生产装置,其特征在于,所述造铜炉(20)还设置有冷料入口,用于向所述造铜炉(20)中加入电解铜残极、废杂铜及固态铜锍中的一种或多种。The anode copper production apparatus according to any one of claims 10 to 12, characterized in that the copper making furnace (20) is further provided with a cold material inlet for adding to the copper making furnace (20) One or more of electrolytic copper residual, waste copper and solid copper.
- 根据权利要求13所述的阳极铜生产装置,其特征在于,所述阳极铜生产装置还包括冷却设备,所述冷却设备用于对所述造铜炉(20)进行降温。The anode copper production apparatus according to claim 13, wherein said anode copper production apparatus further comprises a cooling device for cooling said copper making furnace (20).
- 根据权利要求14所述的阳极铜生产装置,其特征在于,所述冷却设备为负压水套装置或喷水雾冷却装置。The anode copper production apparatus according to claim 14, wherein the cooling device is a negative pressure water jacket device or a water spray mist cooling device.
- 根据权利要求15所述的阳极铜生产装置,其特征在于,所述喷水雾装置用于向所述造铜炉(20)的炉体内部进行喷水雾。The anode copper production apparatus according to claim 15, wherein the water spray device is configured to spray water mist into the inside of the furnace body of the copper making furnace (20).
- 根据权利要求10所述的阳极铜生产装置,其特征在于,所述造铜炉(20)还设置有阳极铜出口;所述阳极铜生产装置还设置有浇铸设备(40),所述浇铸设备(40)与所述阳极铜出口连通,用于对阳极铜进行浇铸处理。The anode copper production apparatus according to claim 10, wherein the copper making furnace (20) is further provided with an anode copper outlet; the anode copper production apparatus is further provided with a casting device (40), the casting equipment (40) communicating with the anode copper outlet for casting the anode copper.
- 根据权利要求17所述的阳极铜生产装置,其特征在于,所述浇铸设备(40)为双圆盘浇铸机。The anode copper production apparatus according to claim 17, wherein said casting apparatus (40) is a double disc casting machine.
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CN201710449049.9A CN107326195A (en) | 2017-06-14 | 2017-06-14 | Short route copper smelting method |
CN201710449064.3A CN107227410A (en) | 2017-06-14 | 2017-06-14 | Short route copper metallurgy system |
CN201710449064.3 | 2017-06-14 | ||
CN201710449049.9 | 2017-06-14 |
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PCT/CN2018/085309 WO2018228073A1 (en) | 2017-06-14 | 2018-05-02 | Anode copper production method and device |
PCT/CN2018/085310 WO2018228074A1 (en) | 2017-06-14 | 2018-05-02 | Copper smelting slag comprehensive recovery method and device |
PCT/CN2018/085311 WO2018228075A1 (en) | 2017-06-14 | 2018-05-02 | Method and system for short-process copper smelting |
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PCT/CN2018/085311 WO2018228075A1 (en) | 2017-06-14 | 2018-05-02 | Method and system for short-process copper smelting |
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CN113718114B (en) * | 2021-08-20 | 2023-03-03 | 白银有色集团股份有限公司 | Method for regulating flue gas temperature and hearth negative pressure in reduction stage of anode furnace |
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RU2741038C1 (en) | 2021-01-22 |
WO2018228075A1 (en) | 2018-12-20 |
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WO2018228074A1 (en) | 2018-12-20 |
PE20200197A1 (en) | 2020-01-28 |
CL2019003631A1 (en) | 2020-04-13 |
ZA202000147B (en) | 2022-07-27 |
ZA202000143B (en) | 2021-10-27 |
CL2019003629A1 (en) | 2020-04-17 |
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