Lead, zinc and copper refining equipment and its application

Abstract

The present invention provides a lead-zinc-copper refining device, comprising: a bed layer part, comprising a material cup, a furnace body and a furnace belly arranged in sequence from top to bottom, the material cup is fixedly installed at one end of the furnace body away from the molten pool part, the furnace body is connected with the furnace belly, the furnace body is fixedly installed with a smoke exhaust port, and the furnace belly is fixedly installed with a first air supply port; a molten pool part is connected with one end of the furnace belly away from the furnace body, the molten pool part includes a reduction zone and a clarification zone along the length extension direction, the reduction zone is located at one end of the molten pool part close to the bed layer part, the clarification zone is fixedly installed with a slag discharge port and a siphon port in sequence from top to bottom, and the reduction zone is fixedly installed with a spray gun. The present invention can coordinately process solid and liquid lead-zinc-copper oxide materials in an integrated and efficient manner, with remarkable effects, and is worthy of promotion.

Description

Technical Field

[0001] The invention belongs to the technical field of comprehensive utilization of resources such as resources environment, metallurgy and urban minerals, and specifically relates to a lead, zinc and copper refining device and application thereof. Background Art

[0002] As my country's requirements for solid waste management and recycling are further improved, the disposal and resource recovery of metal-based solid wastes are receiving more and more attention. Among them, pyrometallurgical smelting processes have significant advantages in terms of scale, reduction, harmlessness, and comprehensive resource recovery, especially bath smelting. The bath smelting process improves production efficiency and economic benefits by strengthening the chemical reaction of furnace gas-charge-melt in the bath, and has been widely used in low-energy and high-efficiency smelting of metals such as copper, nickel, and lead. However, there are few reports on bath smelting technology in the treatment of high-zinc melts (Zn% ≥ 20%) and the simultaneous reduction and recovery of lead, zinc, and copper. The main reason is the lack of bath smelting equipment and processes for zinc.

[0003] Since ZnO has a high melting point, usually around 1975°C, it is difficult for high-zinc materials to melt and flow at conventional smelting temperatures (1150°C ~ 1300°C). The zinc oxide in high-zinc materials is easily combined with iron oxides and silicon dioxide to form stable zinc ferrite and zinc silicate, resulting in a small content of free zinc oxide, low activity, and difficulty in reduction, which has long restricted the development of direct zinc smelting technology in the molten pool.

[0004] For example, the "oxygen bottom blowing smelting-bottom blowing molten reduction-oxygen-enriched fuming three-furnace process" developed by China ENFI treats lead-zinc and polymetallic solid waste. An oxygen bottom blowing furnace is used to melt, desulfurize and slag the lead-zinc and polymetallic solid waste, a bottom blowing reduction furnace is used for reduction, and oxygen-enriched fuming is used to recover other valuable metals. However, zinc is recovered in the form of zinc oxide ash, and metallic zinc cannot be obtained directly.

[0005] In addition, lead and copper smelting also has the problems outlined in the above-mentioned prior art, such as low direct recovery rate of lead, zinc and copper, and complicated subsequent recovery process. Summary of the invention

[0006] In order to solve the technical problems of low direct recovery rate of lead, zinc and copper and complicated subsequent recovery process in the above-mentioned prior art, the present invention provides a lead, zinc and copper refining device, comprising:

[0007] The bed layer part includes a charging cup, a furnace body and a furnace belly which are sequentially arranged from top to bottom, the charging cup is fixedly installed at one end of the furnace body away from the molten pool part, the furnace body is communicated with the furnace belly, the furnace body is fixedly installed with a smoke exhaust port, and the furnace belly is fixedly installed with a first air supply port;

[0008] The molten pool portion is connected to one end of the furnace belly away from the furnace body. The molten pool portion includes a reduction zone and a clarification zone along the length extension direction. The reduction zone is located at one end of the molten pool portion close to the bed portion. The clarification zone is fixedly installed with a slag discharge port and a siphon port from top to bottom, and the reduction zone is fixedly installed with a spray gun.

[0009] Furthermore, the direction from the reduction zone to the clarification zone is a first direction, the spray gun is fixedly installed on the pool wall extending along the first direction and arranged opposite to the reduction zone, the spray gun is arranged toward the first direction, and the angle between the spray gun and the pool wall increases successively along the first direction.

[0010] Furthermore, a first water jacket structure is fixedly installed on the outer surface of the furnace belly, a second water jacket structure is fixedly installed on the outer surface of the molten pool part, and the inner lining of the bed layer part is built with refractory bricks.

[0011] Furthermore, the first air supply port is tubular, and is arranged around a side of the furnace belly away from the furnace body, and the first air supply port is fixedly installed on the outer wall of the furnace belly and is connected to the inside of the furnace belly;

[0012] The number of the first air supply openings is 8 to 24, the angle between the first air supply openings and the cross section of the furnace belly is -15° to 30°, and the cross-sectional area of ​​the first air supply openings is 3 to 120 cm 2 .

[0013] Furthermore, an external melt inlet is provided at one end of the reduction zone away from the clarification zone.

[0014] The present invention also provides an application of the lead, zinc and copper refining device as described in any one of the above items in recovering valuable metals.

[0015] Further, the steps include:

[0016] S1. The oxide material is put into the bed portion by the material cup, a bed material is formed in the bed portion, and a first reducing agent with an oxygen-rich gas as a carrier is blown into the furnace from the first air inlet, and the bed material is reduced to obtain a reduction residue and a first zinc-containing gas after reduction;

[0017] S2. The reduction residue drips from the bed portion to the smelting portion to form a melt to be reduced;

[0018] S3. The spray gun blows a second reducing agent with an oxygen-rich gas as a carrier into the molten pool, and the melt to be reduced is stirred by the second reducing agent to obtain an alloy and slag, and the alloy and slag are allowed to stand and then separated;

[0019] Among them, the alloy is discharged from the siphon port and the slag is discharged from the slag discharge port.

[0020] The present invention also provides an application of the lead-zinc-copper refining device described above in the recovery of lead-zinc-copper, wherein the mass fraction of the copper element in the oxide material is greater than 5%, the reduction temperature in step S1 is 1050-1350°C, and the reduction time in step S1 is 60-150 min; the reduction temperature in step S3 is 1100-1350°C, and the reduction time in step S3 is 30-120 min.

[0021] Furthermore, the amount of the first reducing agent added is 5-15% of the mass of the oxide material, and the amount of the second reducing agent blown in is 0.6-1.8 of the mass of the second reducing agent required to reduce all the metal oxides in the melt to be reduced into metal elements.

[0022] Furthermore, the sum of the mass fractions of lead and zinc elements in the oxide material is greater than 30%, the reduction temperature in step S1 is 1200-1400° C., and the reduction time in step S1 is 60-150 min; the reduction temperature in step S3 is 1200-1350° C., and the reduction time in step S3 is 30-150 min.

[0023] Compared with the prior art, the present invention has at least the following advantages:

[0024] The lead, zinc and copper refining device of the present invention utilizes a vertical coupling arrangement of a bed layer and a molten pool, which can synergistically process solid materials and liquid materials. In addition, the solid materials do not require high-energy consumption and high-pollution pre-treatment such as sintering, and have a high adaptability and high-capacity material processing capability.

[0025] On the other hand, the present invention takes into account the smelting advantages of high reduction ability of the column blast furnace and the molten pool smelting furnace in the common technology, so that it can achieve the application effect of 1+1>2. At the same time, it also overcomes the limitations of the following common technologies: the single molten pool smelting often has technical defects such as large furnace gas dust and zinc vapor in the form of oxidation state during the smelting process; and the column blast reduction still has technical defects such as low thermal utilization rate, high energy consumption and carbon consumption, and poor material compatibility. The present invention uses the bed layer to filter and purify the dust in the furnace and the zinc vapor reduced by the molten pool and the bed layer by ingenious coupling, greatly reducing the dust rate in the furnace, while enabling zinc to be efficiently recovered in the form of pure steam. At the same time, the thermal insulation performance of the bed layer (including the bed layer part and its internal bed layer material) can effectively inhibit the occurrence of the low-temperature oxidation side reaction of Zn(g)+CO2(g)=ZnO+CO(g), and the closed bed layer ensures that Zn(g) is not oxidized by external oxygen. Through the linkage between the bed layer and the molten pool, lead, zinc and copper can be efficiently reduced in one go. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying creative work.

[0027] Figure 1 It is a schematic structural diagram of a lead, zinc and copper refining device in one embodiment of the present invention.

[0028] Description of the drawings: 1. Bed layer; 2. Molten pool; 3. Furnace body; 4. Furnace belly; 5. Reduction zone; 6. Clarification zone; 7. Charging cup; 8. Smoke exhaust port; 9. First air supply port; 10. External melt inlet; 11. Spray gun; 12. Slag discharge port; 13. Siphon port. DETAILED DESCRIPTION

[0029] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] Furthermore, the technical solutions between the various embodiments of the present invention may be combined with each other, but this must be based on the fact that they can be implemented by ordinary technicians in the field. When the combination of technical solutions is mutually contradictory or cannot be implemented, it should be deemed that such combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0031] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise specified in the present invention, both endpoints of each numerical range and any value between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention are familiar to those skilled in the art and the description of the present invention, and any methods, equipment and materials of the prior art similar or equivalent to the methods, equipment and materials described in the embodiments of the present invention can also be used to implement the present invention.

[0032] The present invention provides a lead, zinc and copper refining device, comprising a bed portion 1 and a molten pool portion 2.

[0033] The bed portion 1 includes a charge cup 7, a furnace body 3 and a furnace belly 4 which are arranged in sequence from top to bottom. The charge cup 7 is fixedly installed at one end of the furnace body 3 away from the molten pool portion 2. The furnace body 3 is connected to the furnace belly 4. The furnace body 3 is fixedly installed with a smoke exhaust port 8, and the furnace belly 4 is fixedly installed with a first air supply port 9.

[0034] The charging cup 7 is an openable and closable charging device for charging the lead, zinc and copper refining device and observing the furnace condition.

[0035] The furnace body 3 and the furnace belly 4 can be a three-dimensional space that is wide at the top and narrow at the bottom. For example, the furnace body 3 can be columnar, and the furnace belly 4 can be closed from top to bottom, and the diameter of the lower cross section of the furnace belly 4 is smaller than the diameter of the upper cross section of the furnace belly 4. The two can be an internal cavity furnace body surrounded by a furnace shell and prefabricated as a whole. Among them, the total length of the furnace body 3 and the furnace belly 4 can be 2 to 10 meters, and the diameter of the cross section of the furnace body 3 can be 2 to 8 meters.

[0036] In some embodiments, the temperature of the tuyere area of ​​the first air supply port 9 can be 1100-1400°C, and a first water jacket structure can be fixedly installed on the outer surface of the furnace belly 4 to cool down and alleviate the heat load of the furnace body of the lead, zinc and copper refining device.

[0037] The first water jacket structure can be a steel plate spray type water jacket or a copper water jacket. The water jacket structure can be surrounded by multiple water jackets, divided into upper and lower layers, and each water jacket has a separate inlet and outlet water pipe.

[0038] In other embodiments, a secondary air port may be provided in the furnace body 3 to supplement the oxygen required for combustion in the furnace (i.e., in the lead, zinc, and copper refining device, the same below) and strengthen the mixing of the oxide materials in the furnace. In addition, the combustion and heat transfer in the furnace may be controlled by adjusting the primary and secondary air ratio during operation.

[0039] The first air inlet 9 is usually a hollow tubular structure connected to the external spray gun 11, which can be fixedly installed on the furnace belly 4 and arranged around the outer wall of the furnace belly 4. The number of the first air inlet 9 can be 8 to 24. The first air inlet 9 can be used to inject oxygen-rich gas and reducing agent to regulate the temperature, oxygen concentration, and oxygen flow rate in the furnace.

[0040] In some embodiments, the distance between the first air inlet 9 and the top of the bed material can be 1 to 8 meters, and the cross-sectional area of ​​the first air inlet 9 can be 3 to 120 cm 2 The angle between the central axis of the first air supply port 9 and the horizontal plane can be -15°≤α≤30°.

[0041] The smoke outlet 8 may be a hollow tubular structure fixedly mounted on the outer wall of the furnace body 3. One end of the smoke outlet 8 away from the lead-zinc-copper refining device may be fixedly connected to a lead rain / zinc rain condensing device to capture and recover metallic zinc in the first zinc-containing gas and the second zinc-containing gas.

[0042] In specific applications, when the oxide material is thrown from the material cup 7 onto the material column to form a bed material, the bed material is supported and rubbed by the furnace wall of the furnace belly 4 and the blowing force of the first air supply port 9, forming an arch-shaped bed material with a certain pressure resistance in the bed portion 1. The reducing agent and the hot air in the furnace react chemically to generate CO and CO2, and CO reduces the metal oxides in the bed material (i.e., the material column) to generate metal. Among them, the lead-removing compounds about 1000mm below the material surface of the material column are basically reduced to metallic lead, and the liquid phase is maintained at a high temperature in the furnace, and crude lead is formed together with the copper, silver, antimony and other metals produced by the reduction, and the gangue slag is melted and descends to the molten pool portion 2 together with the crude lead (the crude lead and gangue are the reduction residues).

[0043] The molten pool portion 2 is connected to one end of the furnace belly 4 away from the furnace body 3. The molten pool portion 2 includes a reduction zone 5 and a clarification zone 6 along the length extension direction. The reduction zone 5 is located at one end of the molten pool portion 2 close to the bed portion 1. The clarification zone 6 is fixedly installed with a slag discharge port 12 and a siphon port 13 from top to bottom, and the reduction zone 5 is fixedly installed with a spray gun 11.

[0044] The molten pool portion 2 may be a three-dimensional space with a rectangular cross section, and may be 1-8 meters in height, 2-8 meters in width, and 4-10 meters in length.

[0045] The reduction zone 5 is directly opposite to the bottom of the bed layer 1 to carry the reduction residues dripping after the bed layer materials are reduced. A spray gun 11 is fixedly connected to the reduction part.

[0046] The cross-sectional area of ​​the spray gun 11 can be 5 to 120 cm 2 The height of the spray gun 11 from the bottom of the molten pool 2 can be 60 cm to 2 meters; the spray gun 11 can be a horizontally inclined spray gun 11, and the spray gun 11 can generally face the side of the clarification zone 6 to provide power for the flow of the melt to be reduced; the angle between the spray gun 11 and the furnace wall of the molten pool 2 can vary between 35° and 90° depending on the position, with the angle being 90° on the side close to the clarification zone 6 and decreasing gradually away from the clarification zone 6.

[0047] In some embodiments, an external melt inlet 10 can be fixedly installed in the reduction zone 5 to collect the external oxidative desulfurization melt, and the oxidative desulfurization melt can be combined with the reduction residue to form a melt to be reduced. The lead, zinc and copper refining device can be used to treat lead, zinc and copper hazardous waste and urban minerals in large quantities, effectively solving the problems of insufficient primary resources and low recycling rate of solid waste resources, and promoting the green and sustainable development of the circular economy and metallurgical industry.

[0048] In other embodiments, the temperature of the melt to be reduced in the molten pool 2 may be 1100-1350° C. A second water jacket structure may be provided on the outer wall of the molten pool 2 to cool the furnace wall and protect the furnace shell.

[0049] In a specific application, the reduction zone 5 gathers the oxidation desulfurization melt introduced from the outside and the reduction residues dripping from the bed material reduction melt to form a melt to be reduced. The melt to be reduced is rapidly reduced under the spraying and stirring of the spray gun 11 as the reducing agent is continuously blown in. After the reduction and slag making is completed, the alloy settles and is separated from the slag. The alloy can be discharged from the siphon port 13 for further refining and recovery, and the slag can be discharged from the slag discharge port 12 and then enter the fume furnace for recovery and treatment.

[0050] The lead, zinc and copper refining device of the present invention is arranged by vertically coupling the bed layer with the molten pool. On the one hand, it can collaboratively process solid materials and liquid materials, and has high compatibility and high-capacity material processing capabilities; on the other hand, the present invention takes into account the smelting advantages of the high reduction ability of the material column blast furnace and the molten pool smelting furnace in the common technology, so that it can achieve the application effect of 1+1>2. At the same time, it also overcomes the limitations existing in the following common technologies: the single molten pool smelting often has technical defects such as large furnace gas dust and zinc vapor in the form of oxidation state during the smelting process; and the material column blast reduction still has technical defects such as low thermal utilization rate, high energy consumption and carbon consumption, and poor material compatibility. The present invention ingeniously couples the bed layer with the molten pool, and uses the bed layer to filter and purify the dust in the furnace and the zinc vapor reduced by the molten pool and the bed layer at the same time, which greatly reduces the dust rate in the furnace and enables zinc to be efficiently recovered in the form of pure vapor. At the same time, the thermal insulation performance of the bed (including the bed portion 1 and its internal bed materials) can effectively inhibit the occurrence of the low-temperature oxidation side reaction of Zn(g)+CO2(g)=ZnO+CO(g), and the closed bed ensures that Zn(g) is not oxidized by external oxygen. Through the linkage of the bed and the molten pool, lead, zinc and copper can be efficiently reduced in one go.

[0051] In some embodiments, the direction from the reduction zone 5 to the clarification zone 6 may be a first direction. The spray gun 11 is fixedly mounted on a pool wall of the reduction zone 5 extending along the first direction and arranged opposite to the pool wall. The spray gun 11 is arranged toward the first direction, and the angle between the spray gun 11 and the pool wall increases successively along the first direction.

[0052] The spray guns 11 arranged opposite to each other on both sides of the molten pool support the injection of gas, powdered reducing agent, flux, etc. into the molten pool, strongly stir the molten material to be reduced, strengthen the mass and heat transfer in the molten pool part 2, and accelerate the chemical reaction in the molten material to be reduced.

[0053] In some embodiments, a first water jacket structure may be fixedly installed on the outer surface of the furnace bosh 4, a second water jacket structure may be fixedly installed on the outer surface of the molten pool portion 2, and the inner lining of the bed portion 1 may be built with refractory bricks.

[0054] Refractory bricks can include alumina-magnesia bricks to play the role of heat insulation and protection of the furnace body. The thermal insulation performance of the closed bed material can effectively inhibit the low-temperature oxidation side reaction of Zn(g)+CO2(g)=ZnO+CO(g) of Zn(g), ensuring that Zn(g) is not oxidized by external oxygen.

[0055] In some embodiments, the first air supply port 9 is tubular and is arranged around a side of the furnace belly 4 away from the furnace body 3. The first air supply port 9 is fixedly installed on the outer wall of the furnace belly 4 and is connected to the inside of the furnace belly 4.

[0056] The number of the first air supply ports 9 is 8 to 24, the angle between the first air supply ports 9 and the cross section of the furnace belly 4 is -15 to 30°, and the cross-sectional area of ​​the first air supply ports 9 is 3 to 120 cm 2 .

[0057] In some embodiments, a melt inlet may be provided at one end of the reduction zone 5 away from the clarification zone 6 .

[0058] The present invention also provides an application of the lead, zinc and copper refining device as described in any one of the above items in recovering valuable metals.

[0059] In some embodiments, the above application includes the steps of:

[0060] S1. The oxide material is put into the bed portion 1 from the material cup 7 to form a bed material in the bed portion 1. A first reducing agent with an oxygen-rich gas as a carrier is blown into the furnace belly 4 from the first air supply port 9. After the bed material is reduced, a reduction residue and a first zinc-containing gas are obtained.

[0061] The oxide materials may include lead-zinc oxide materials and secondary material agglomerates such as urban minerals, sintered blocks of lead-zinc-copper sulfide ores, roasted sands of lead-zinc-copper sulfide ores, waste zinc-manganese batteries, waste circuit boards, etc.

[0062] S2. The reduction residue drips from the bed portion 1 to the smelting portion to form a melt to be reduced.

[0063] The reduction residues include crude lead and gangue.

[0064] S3. The spray gun 11 is blown into the molten pool portion 2 with an oxygen-rich gas as a carrier of the second reducing agent, and the melt to be reduced is reduced under the stirring of the second reducing agent to obtain an alloy and slag, and the alloy and the slag are allowed to stand and then separated;

[0065] The alloy is discharged from the siphon port 13 , and the slag is discharged from the slag discharge port 12 .

[0066] The lead, zinc and copper refining device of the present invention can be applied to the reduction and recovery of copper-rich oxide materials (the mass fraction of copper in the copper-rich oxide materials is greater than 5%), and the copper-rich oxide materials mainly include copper ore dust, recycled copper dust and copper-containing sludge produced in the process of primary and recycled copper smelting (matte smelting, copper matte blowing, crude copper refining, electric furnace copper smelting). Most of these dusts and sludges contain valuable metals such as copper, lead, zinc, tin, bismuth, antimony, tin, arsenic and precious metals, and are important secondary resources.

[0067] In the prior art, there is no existing process for targeted and efficient reduction of copper-rich oxide materials. The above copper-rich oxide materials are usually directly returned to the original copper smelting and re-smelted with ingredients. Direct re-smelting with ingredients not only increases the circulation of smoke in the smelting process, but also reduces the concentrate processing capacity of the smelting system; long-term operation will affect the normal operation of the acid-making system, resulting in the inability of impurity elements to open the circuit, and a vicious cycle of enrichment in the system, thereby affecting the quality of crude copper and further causing the cathode copper impurities to exceed the standard.

[0068] If the copper-rich oxide materials produced during the copper smelting process are treated in a targeted manner, such as using a rotary kiln, electric furnace, etc. to reduce and recover the copper-containing oxide materials, a high investment cost is required and the economic efficiency is poor.

[0069] The present invention utilizes the lead-zinc-copper refining device to specifically treat copper-rich oxide materials, efficiently collects and treats secondary resources such as copper ore dust, recycled copper dust and copper-containing sludge produced during the copper smelting process, and cleverly designs the lead-zinc-copper refining device, which can simultaneously reduce and recover metals from solid / liquid copper-rich oxide materials. The copper-rich oxide materials can also be mixed with oxide materials such as lead and zinc, and the lead, zinc and copper can be synergistically reduced and recovered during the lead-zinc smelting process.

[0070] In some embodiments, when the lead-zinc-copper refining device of the present invention is applied to the above-mentioned copper-rich lead-zinc oxide material (the mass fraction of the copper element in the oxide material is greater than 5%), the reduction temperature in step S1 is 1050-1350°C, and the reduction time in step S1 is 60-150 min; the reduction temperature in step S3 is 1100-1350°C, and the reduction time in step S3 is 30-150 min.

[0071] In other embodiments, when the lead, zinc and copper refining device of the present invention is applied to the above-mentioned copper-rich material (the mass fraction of copper in the oxide material is greater than 5%), the amount of the first reducing agent added can be 5-15% of the mass of the oxide material, and the amount of the second reducing agent blown in can be 0.6-1.8 of the mass of the second reducing agent required to reduce all the metal oxides in the melt to be reduced into metal elements.

[0072] The lead, zinc and copper refining device of the present invention can be applied to the reduction and recovery of high-lead and high-zinc materials (the sum of the mass fractions of lead and zinc in the oxide material is greater than 30%).

[0073] Due to the high melting point of ZnO (1975℃), high-zinc materials are difficult to melt and flow at conventional smelting temperatures (1150℃~1300℃), which has long restricted the development of molten pool direct zinc smelting technology.

[0074] In the existing zinc smelting wet smelting, the leaching process produces a large amount of iron- and zinc-containing waste slag, which needs to be disposed of and recycled using pyrometallurgical technology.

[0075] The existing zinc smelting pyrometallurgy mainly includes the "sintering-closed blast reduction-fuming" process, the Kifset lead-zinc joint smelting process and the "oxygen bottom blowing smelting-bottom blowing molten reduction-oxygen-enriched fuming blowing three-furnace" process. 1) The sintered block is directly recovered by blast reduction. The sintering process has high energy consumption and heavy low-concentration SO2 pollution, which restricts the promotion and popularization of this technology. 2) The Kifset lead-zinc joint smelting process can only process desulfurized melts with a zinc content of less than 18% in industry. When the zinc content is higher than 18%, the melt is difficult to flow, and it is easy to have furnace stagnation and dead furnace problems. 3) The "oxygen bottom blowing smelting-bottom blowing molten reduction-oxygen-enriched fuming blowing three-furnace process" treats lead-zinc multi-metal solid waste, uses an oxygen bottom blowing furnace to melt, desulfurize and slag the lead-zinc multi-metal solid waste, and uses a bottom blowing reduction furnace for reduction. The oxygen-enriched fuming blowing recovers other valuable metals, but zinc is recovered in the form of zinc oxide ash, and metallic zinc cannot be directly obtained. The presence of zinc oxide, even in small amounts, has a great detrimental effect on the condensation process, covering the zinc liquid with a layer of zinc oxide, making it difficult to gather into large droplets, thus hindering the advancement of the condensation process.

[0076] In line with the above, the most common technical problems in lead and zinc smelting in commonly used technologies include: the need for sintering (the pretreatment process is complex and highly polluting), difficulty in targeted treatment of high-zinc melt (prone to deteriorate furnace conditions), and low direct recovery rate of metallic zinc (mostly recovered in an oxidized state, affecting recovery efficiency).

[0077] It should also be noted that since zinc oxide in high-zinc melts easily combines with iron oxides and silicon dioxide to form stable zinc ferrite and zinc silicate, the free zinc oxide content is small, the activity is low, and it is difficult to reduce. Whether the high-zinc material molten pool smelting process can proceed smoothly and achieve ideal technical and economic indicators depends to a certain extent on the heat and mass transfer of the slag in the molten pool, the slag-metal separation, and the gas penetration process.

[0078] The present invention couples the bed layer 1 and the molten pool 2 to be arranged vertically, and the processing capacity and efficiency of lead-rich and zinc-rich oxide materials are greatly improved. On the one hand, the bed layer material can filter the furnace gas and dust generated by the molten pool smelting, so that the rising first zinc-containing gas and the second zinc-containing gas are purer; on the other hand, the bed layer material fully reacts under the closed reducing atmosphere, including: the first reducing agent is burned under the injection of the first oxygen-rich gas to provide a reducing atmosphere, the unreduced oxides in the bed layer material drip into the molten pool and are reduced under the injection of the second reducing agent and the second oxidant, and the CO generated by the reduction in the molten pool rises into the bed layer material to further reduce the bed layer material. Under the triple reduction conditions, the material enters the capture and recovery device in the form of pure zinc vapor to obtain metallic zinc, and the metallic zinc is efficiently recovered.

[0079] In conjunction with the excellent heat and mass transfer performance brought by the first air inlet 9 and the finely configured spray gun 11 in the above-mentioned lead-zinc-copper refining device, the present invention can process high-zinc melt in a targeted manner with high direct yield and high efficiency without sintering.

[0080] In some embodiments, when the lead-zinc-copper refining device of the present invention is applied to the above-mentioned high-lead-zinc material (the sum of the mass fractions of lead and zinc elements in the oxide material is greater than 30%), the reduction temperature in step S1 is 1200-1400°C, and the reduction time in step S1 is 60-150 minutes; the reduction temperature in step S3 is 1200-1350°C, and the reduction time in step S3 is 30-120 minutes.

[0081] In other embodiments, when the lead, zinc and copper refining device of the present invention is applied to the above-mentioned high-lead and zinc materials, the addition amount of the first reducing agent can be 6-15%, and the injection amount of the second reducing agent is 0.8-2.0 of the mass of the second reducing agent required to reduce all the metal oxides in the melt to be reduced into metal elements.

[0082] In order to facilitate those skilled in the art to further understand the present invention, examples are given below:

[0083] Example 1

[0084] See attached Figure 1 The present invention provides a lead, zinc and copper refining device.

[0085] The lead-zinc-copper refining device is composed of an upper bed layer part 1 and a lower molten pool part 2. A charging cup 7 and a secondary air port are arranged on the upper part of the furnace body 3. The first air supply ports 9 are arranged around the furnace belly 4. The number of the first air supply ports 9 is 10, and the cross-sectional area of ​​each first air supply port 9 can be 100 cm 2The first air inlet 9 is 3 meters away from the top of the bed material, and the angle between the central axis of the first air inlet 9 and the horizontal plane can be 5°. The upper part of the furnace body 3 is also provided with a secondary air inlet and a smoke exhaust port 8, and the smoke exhaust port 8 is connected to the condensation facility. The bed part 1 is built with refractory bricks to form a narrow rectangular space at the bottom. The bed part 1 is provided with a steel plate spray water jacket or a copper water jacket. The bed part 1 is 5 meters high, 3 meters wide and 6 meters long.

[0086] The first air inlet 9 can use oxygen-rich gas as a carrier to spray the first reducing agent (including pulverized coal, bituminous coal, etc.) into the bed material, maintain the temperature of the air inlet area at 1100-1400°C, and reduce the metal oxides in the oxide material.

[0087] The bottom of the lead-zinc-copper refining device is a molten pool 2, which is divided into a reduction zone 5 and a clarification zone 6. An external melt inlet 10 is provided on one side of the reduction zone 5 to collect the external oxidative desulfurized melt. A slag discharge port 12 and a siphon port 13 are provided vertically from top to bottom in the clarification zone 6 at the other end. Opposite horizontally inclined spray guns 11 are provided on both sides of the pool wall oppositely arranged in the extension direction of the molten pool 2. The spray gun 11 is generally facing one side of the clarification zone 6, and the cross-sectional area of ​​the spray gun 11 is 100cm 2 The height of the spray gun 11 from the bottom of the furnace inside the molten pool is 80 cm, which supports the injection of gas, powdered reducing agent, flux, etc. into the molten pool, strongly stirs the molten pool, strengthens the mass transfer and heat transfer of the molten pool, and maintains the temperature of the melt to be reduced at 1300°C. The angle between the first pair of spray guns 11 and the pool wall of the molten pool 2 in the extension direction of the reduction zone 5 is 50°. According to the length extension direction, the angle between the spray gun 11 and the pool wall is continuously increased, and the angle between the pair of spray guns 11 closest to the clarification zone 6 and the pool wall is 90°.

[0088] The molten pool part 2 is a rectangular space surrounded by a copper water jacket, which is 2 meters high, 3 meters wide and 6 meters long.

[0089] Example 2

[0090] See attached Figure 1 The present invention provides an application of a lead, zinc and copper refining device.

[0091] Lead-containing smoke dust, zinc-containing fly ash, hydrometallurgical zinc goethite slag and copper fly ash from a domestic factory were pressed into agglomerates with a composition of 17wt.% lead, 32wt.% zinc, 6wt.% copper, 4wt.% iron, 7wt.% SiO2 and 8wt.% CaO, and then mixed with 12% coke and added to the bed from the sealed material cup 7 at the upper end of the bed portion 1. 800℃ oxygen-enriched 35% hot air was blown in from the air supply port 9 below the bed, and the temperature of the air port area was controlled to be 1300℃ (error ±50℃). The oxide material in the bed was reduced to obtain the first zinc-containing gas and the reduction residue (the reduction residue included liquid lead metal and some unreduced oxides and gangue) under the synergistic reduction action of coke, oxygen-enriched gas and the hot CO-CO2 mixed gas overflowing and rising in the molten pool.

[0092] The reduction residue drips into the molten pool 2. At the same time, the external melt inlet 10 of the lower molten pool 2 adds the lead, zinc, and copper oxidative desulfurization melt, which has the following composition: 26.2wt.% lead, 27.2wt.% zinc, 6.8wt.% copper, 14.4wt.% iron, 0.5wt.% sulfur, 12.3wt.% SiO2, and 3.4wt.% CaO. The reduction residue and the oxidative desulfurization melt converge into the melt to be reduced. Through the spray guns 11 on both sides of the molten pool 2, the reaction flux and the second reducing agent anthracite (wherein the anthracite composition is: 48.5% fixed carbon, 0.75% total sulfur, 33.8% volatile matter, and 16.1% ash) are blown into the melt to be reduced with the oxygen-rich gas with an oxygen concentration of 30% as the carrier, and the temperature of the melt to be reduced in the reduction zone 5 is controlled to be maintained at 1300°C, and the metal oxides such as lead, zinc, and copper to be reduced in the molten pool are continuously reduced, and the slag-making reaction is completed at the same time.

[0093] After the reduction in the molten pool 2, the melt flows into the clarification zone 6. The reduced lead, copper and other alloys are clarified in the clarification zone for 2.5 hours and separated from the slag. The reaction gas escaping from the molten pool is filtered by the material in the bed layer 1 to reduce the dust particle content in the gas phase and obtain the second zinc-containing gas. The first zinc-containing gas and the second zinc-containing gas are captured by the condensation facility to obtain zinc metal. After clarification, the alloy product contains 74.6% lead, 21.6% copper and 2.1% zinc. The copper, lead and zinc contents in the slag are reduced to 0.02%, 0.14% and 3.52% respectively.

[0094] Example 3

[0095] See attached Figure 1 The present invention provides an application of a lead, zinc and copper refining device.

[0096] Recycled copper fly ash, hydrometallurgical zinc-lead-silver slag, and sintering return powder from a domestic factory are pressed into agglomerates with a composition of 15wt.% lead, 27wt.% zinc, 18wt.% copper, 12wt.% iron, 5wt.% SiO2, and 6wt.% CaO, and then mixed with 8% coke and added to the bed from the sealed material cup 7 at the upper end of the bed portion 1. 700℃ oxygen-enriched 45% hot air is blown into the air inlet 9 below the bed, and the temperature of the air inlet area is controlled to be 1250℃ (error ±50℃). The oxide material in the bed is reduced to obtain the first zinc-containing gas and the reduction residue (the reduction residue includes liquid lead metal and some unreduced oxides and gangue) under the synergistic reduction action of coke, oxygen-enriched gas and hot CO-CO2 mixed gas overflowing and rising in the molten pool.

[0097] The reduction residue drips into the molten pool 2. At the same time, the external melt inlet 10 of the lower molten pool 2 adds an oxidative desulfurization melt, which is composed of: 15.5wt.% lead, 30.4wt.% zinc, 14.5wt.% copper, 10.7wt.% iron, 0.8wt.% sulfur, 17.3wt.% SiO2, and 5.3wt.% CaO. The reduction residue and the oxidative desulfurization melt converge into a melt to be reduced. Through the spray guns 11 on both sides of the molten pool 2, the reaction flux and the second reducing agent coke powder are blown into the melt to be reduced with an oxygen-rich gas with an oxygen concentration of 30% as a carrier, and the temperature of the melt to be reduced in the reduction zone 5 is controlled to be maintained at 1250°C, and the metal oxides such as lead, zinc, and copper to be reduced in the molten pool are continuously reduced, and the slag-making reaction is completed at the same time.

[0098] After the reduction in the molten pool 2, the melt flows into the clarification zone 6. The reduced lead, copper and other alloys are clarified in the clarification zone for 2 hours and separated from the slag. The reaction gas escaping from the molten pool is filtered by the material in the bed layer 1 to reduce the dust particle content in the gas phase and obtain the second zinc-containing gas. The first zinc-containing gas and the second zinc-containing gas are captured by the condensation facility to obtain zinc metal. After clarification, the alloy product contains 43.3% lead, 51.9% copper and 3.2% zinc. The copper, lead and zinc contents in the slag are reduced to 0.03%, 0.09% and 3.13% respectively.

[0099] The above technical solutions of the invention are only preferred embodiments of the invention, and do not limit the patent scope of the invention. All equivalent structural changes made by using the contents of the specification and drawings of the invention under the technical concept of the invention, or directly / indirectly applied in other related technical fields are included in the patent protection scope of the invention.

Claims

1. A method for recovering valuable metals using a lead, zinc and copper refining device, characterized in that: The lead, zinc and copper refining device comprises: The bed layer part includes a charge cup, a furnace body and a furnace belly which are arranged in sequence from top to bottom, the charge cup is fixedly installed at one end of the furnace body away from the molten pool part, the furnace body is communicated with the furnace belly, the furnace body is fixedly installed with a smoke exhaust port, and the furnace belly is fixedly installed with a first air supply port; The molten pool part is connected to the end of the furnace belly away from the furnace body, and the molten pool part includes a reduction zone and a clarification zone along the length extension direction. The reduction zone is located at one end of the molten pool part close to the bed layer part. The clarification zone is fixedly installed with a slag discharge port and a siphon port from top to bottom in sequence, and the reduction zone is fixedly installed with a spray gun; The application of the lead, zinc and copper refining device in recovering valuable metals comprises the following steps: S1. The oxide material and the first reducing agent are put into the bed portion from the material cup to form a bed material in the bed portion, and oxygen-rich gas is blown into the furnace belly from the first air supply port. After the bed material is reduced, a reduction residue and a first zinc-containing gas are obtained, wherein the sum of the mass fractions of lead and zinc elements in the oxide material is greater than 30%, wherein the mass fraction of zinc element is 27% or 32%; S2. The reduction residue drips from the bed portion to the molten pool portion to form a melt to be reduced; S3. The spray gun injects a second reducing agent into the molten pool with an oxygen-rich gas as a carrier, and the reduced melt is reduced under the stirring of the second reducing agent to obtain an alloy and slag, and the alloy and slag are separated after standing; Among them, the alloy is discharged from the siphon port and the slag is discharged from the slag discharge port.

2. The method for recovering valuable metals using a lead, zinc and copper refining device according to claim 1, characterized in that: The direction from the reduction zone to the clarification zone is a first direction, the spray gun is fixedly installed on a pool wall extending along the first direction and arranged opposite to the reduction zone, the spray gun is arranged toward the first direction, and the angle between the spray gun and the pool wall increases successively along the first direction.

3. The method for recovering valuable metals using a lead, zinc and copper refining device according to claim 1, characterized in that: A first water jacket structure is fixedly installed on the outer surface of the furnace belly, a second water jacket structure is fixedly installed on the outer surface of the molten pool part, and the inner lining of the bed layer part is built with refractory bricks.

4. The method for recovering valuable metals using a lead, zinc and copper refining device according to claim 1, characterized in that: The first air supply port is tubular and is arranged around a side of the furnace belly away from the furnace body. The first air supply port is fixedly installed on the outer wall of the furnace belly and is connected to the inside of the furnace belly. The number of the first air supply openings is 8 to 24, the angle between the first air supply opening and the cross section of the furnace is ‑15° to 30°, and the cross-sectional area of ​​the first air supply opening is 3 to 120 cm 2 .

5. The method for recovering valuable metals using a lead, zinc and copper refining device according to claim 1, characterized in that: An external melt inlet is arranged at one end of the reduction zone away from the clarification zone.

6. The method for recovering valuable metals using a lead, zinc and copper refining device according to claim 1, characterized in that: The mass fraction of copper element in the oxide material is greater than 5%, the reduction temperature in step S1 is 1050-1350° C., and the reduction time in step S1 is 60-150 min; the reduction temperature in step S3 is 1100-1350° C., and the reduction time in step S3 is 30-120 min.

7. The method for recovering valuable metals using a lead, zinc and copper refining device according to claim 6, characterized in that: The amount of the first reducing agent added is 5-15% of the mass of the oxide material, and the amount of the second reducing agent blown in is 0.6-1.8 of the mass of the second reducing agent required to reduce all the metal oxides in the melt to be reduced into metal elements.

8. The method for recovering valuable metals using a lead, zinc and copper refining device according to claim 1, characterized in that: The reduction temperature in step S1 is 1200-1400° C., and the reduction time in step S1 is 60-150 min; the reduction temperature in step S3 is 1200-1350° C., and the reduction time in step S3 is 30-150 min.

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