CN116026148A - Lead zinc copper refining device and application thereof - Google Patents
Lead zinc copper refining device and application thereof Download PDFInfo
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Abstract
The invention provides a lead zinc copper refining device, which comprises: the bed layer part comprises a material cup, a furnace body and a furnace belly which are sequentially arranged from top to bottom, wherein the material cup is fixedly arranged at one end of the furnace body far away from the molten pool part, the furnace body is communicated with the furnace belly, a smoke outlet is fixedly arranged on the furnace body, and a first air supplementing port is fixedly arranged on the furnace belly; the molten pool part is communicated with one end of the furnace belly, which is far away from the furnace body, and comprises a reduction zone and a clarification zone along the length extension direction, wherein the reduction zone is positioned at one end of the molten pool part, which is close to the bed layer part, the clarification zone is sequentially and fixedly provided with a slag discharge port and a siphon port from top to bottom, and the reduction zone is fixedly provided with a spray gun. The invention can integrally and efficiently cooperatively treat solid and liquid lead zinc copper oxide materials, has remarkable effect and is worthy of popularization.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of resources such as resource environment, metallurgy, urban mineral products and the like, and particularly relates to a lead-zinc-copper refining device and application thereof.
Background
With the further improvement of the requirements of China on solid waste management and recovery, the treatment and recycling recovery of metal-based solid waste are increasingly paid attention to. The pyrometallurgy process has remarkable advantages in the aspects of scale, reduction, harmlessness, comprehensive recovery of resources and the like, particularly represented by molten pool smelting, and the molten pool smelting process improves the production efficiency and economic benefit by strengthening the chemical reaction of furnace gas, furnace burden and melt in the molten pool, and has been widely applied to low-energy consumption and high-efficiency smelting of metals such as copper, nickel, lead and the like. However, the molten pool smelting technology has few reports on the aspects of synchronously reducing and recycling lead, zinc and copper and the like when treating high-zinc melt (Zn% > 20%). The reason for this is mainly the zinc-deficient bath smelting equipment and process.
Because ZnO has higher melting point, the ZnO is difficult to melt and flow at the conventional smelting temperature (1150-1300 ℃) of high-zinc materials, zinc oxide in the high-zinc materials is easy to combine with iron oxide and silicon dioxide to form stable zinc ferrite and zinc silicate, so that the free zinc oxide has low content and low activity and is difficult to reduce, and the development of the molten pool direct zinc smelting technology is restrained for a long time.
For example, the process of oxygen bottom blowing smelting-bottom blowing smelting reduction-oxygen-enriched fuming converting triple furnace developed by Enfei in China is used for treating lead-zinc-containing polymetallic solid waste, the oxygen bottom blowing furnace is used for smelting, desulfurizing and slagging the lead-zinc polymetallic solid waste, the bottom blowing reduction furnace is used for reducing, the oxygen-enriched fuming converting is used for recycling other valuable metals, but zinc is recycled in the form of zinc oxide ash, and metallic zinc cannot be directly obtained.
In addition, lead and copper smelting also has the problems of low lead-zinc-copper direct yield and complex subsequent recovery process outlined in the prior art.
Disclosure of Invention
Aiming at solving the technical problems of low lead zinc copper direct yield and complex subsequent recovery process in the prior art, the invention provides a lead zinc copper refining device, which comprises:
the hearth part comprises a material cup, a furnace body and a furnace belly which are sequentially arranged from top to bottom, the material cup is fixedly arranged at one end of the furnace body, which is far away from the molten pool part, the furnace body is communicated with the furnace belly, the furnace body is fixedly provided with a smoke outlet, and the furnace belly is fixedly provided with a first air supplementing opening;
the molten pool part is communicated with one end of the furnace belly, which is far away from the furnace body, the molten pool part comprises a reduction zone and a clarification zone along the length extension direction, the reduction zone is positioned at one end of the molten pool part, which is close to the bed layer part, the clarification zone is sequentially and fixedly provided with a slag discharge port and a siphon port from top to bottom, and the reduction zone is fixedly provided with a spray gun.
Further, the direction from the reduction zone to the clarification zone is a first direction, the spray gun is fixedly installed on a tank wall which is arranged opposite to the reduction zone along the first direction, the spray gun is arranged towards the first direction, and the included angle between the spray gun and the tank wall is sequentially increased along the first direction.
Further, a first water jacket structure is fixedly arranged on the outer surface of the furnace belly, a second water jacket structure is fixedly arranged on the outer surface of the molten pool part, and the lining of the bed layer part is built by refractory bricks.
Further, the first air supply port is tubular and is arranged around one side of the furnace belly, which is far away from the furnace body, and the first air supply port is fixedly arranged on the outer wall of the furnace belly and is communicated with the interior of the furnace belly;
wherein the number of the first air supply openings is 8-24, the included angle between the first air supply openings and the cross section of the furnace belly is-15-30 degrees, and the cross section area of the first air supply openings is 3-120 cm 2 。
Further, an external melt inlet is arranged at one end of the reduction zone, which is far away from the clarification zone.
The invention also provides an application of the lead zinc copper refining device in recovering valuable metals.
Further, the method comprises the steps of:
s1, throwing an oxidation material into a bed layer part from a material cup, forming the bed layer material in the bed layer part, blowing a first reducing agent taking oxygen-enriched gas as a carrier into a furnace belly from a first air supplementing port, and reducing the bed layer material to obtain a reduction residue and a first zinc-containing gas;
s2, the reduction residues are dripped from the bed layer part to the smelting part to form a melt to be reduced;
s3, the spray gun blows a second reducing agent taking oxygen-enriched gas as a carrier into the molten pool part, the melt to be reduced is reduced under the stirring of the second reducing agent to obtain alloy and slag, and the alloy and slag are layered after standing;
wherein, alloy is discharged from the siphon port, and slag is discharged from the slag discharge port.
The invention also provides application of the lead-zinc-copper refining device in recycling lead-zinc-copper, wherein the mass fraction of copper element in the oxidized material is more than 5%, the reduction temperature in the step S1 is 1050-1350 ℃, and the reduction time in the step S1 is 60-150 min; the reduction temperature in the step S3 is 1100-1350 ℃, and the reduction time in the step S3 is 30-120 min.
Further, the addition amount of the first reducing agent is 5-15% of the mass of the oxidation material, and the bubbling amount of the second reducing agent is 0.6-1.8 of the mass of the second reducing agent required for completely reducing the metal oxides in the melt to be reduced into metal simple substances.
Further, the sum of the mass fractions of lead and zinc in the oxidation materials is more than 30%, the reduction temperature in the step S1 is 1200-1400 ℃, and the reduction time in the step S1 is 60-150 min; the temperature of the reduction in the step S3 is 1200-1350 ℃, and the time of the reduction in the step S3 is 30-150 min.
Compared with the prior art, the invention at least comprises the following advantages:
the lead zinc copper refining device is vertically coupled with the molten pool by the bed layer, so that on one hand, solid materials and liquid materials can be cooperatively treated. And the solid material does not need high-energy consumption and high-pollution pretreatment such as sintering, and has high adaptability and high capacity material treatment capacity.
On the other hand, the invention takes into account the smelting advantages of high reducing capability of the charging post blast furnace and the molten pool smelting furnace in the common technology, so that the application effect of 1+1 & gt2 is achieved, and meanwhile, the limitations in the following common technology are overcome: the smelting of an independent molten pool has the technical defects that smoke dust of furnace gas is large, zinc vapor exists in an oxidation state and the like in the smelting process; the blast reduction of the material column still has the technical defects of low heat utilization rate, high energy consumption and carbon consumption, poor material compatibility and the like. The invention utilizes the bed layer to simultaneously reduce the dust in the furnace, the molten pool and the bed layer to obtain zinc vapor by creatively coupling the bed layer and the molten poolThe gas is filtered and purified, so that the dust rate in the furnace is greatly reduced, and meanwhile, zinc can be efficiently recovered in the form of pure steam. Meanwhile, the heat preservation performance of the bed layer (comprising the bed layer part and the bed layer materials inside the bed layer part) can effectively inhibit Zn (g) low-temperature oxidation side reaction Zn (g) +CO 2 (g) The =zno+co (g) occurs, the closed bed ensures that Zn (g) is not oxidized by external oxygen. And the lead, zinc and copper are integrally and efficiently reduced through linkage of a bed layer and a molten pool.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram of a lead-zinc-copper refining apparatus according to an embodiment of the invention.
Description of the drawings: 1. a bed layer part; 2. a molten pool portion; 3. a furnace body; 4. a furnace belly; 5. a reduction zone; 6. a clarification zone; 7. a material cup; 8. a smoke outlet; 9. a first air supply port; 10. an external melt sink; 11. a spray gun; 12. a slag discharge port; 13. siphon mouth.
Detailed Description
The following description of the embodiments of the present invention will be made in detail and with reference to the accompanying drawings, wherein it is apparent that the embodiments described are only some, but not all embodiments of the present invention. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
Moreover, the technical solutions of the embodiments of the present invention may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the embodiments, and when the technical solutions are contradictory or cannot be implemented, it should be considered that the combination of the technical solutions does not exist, and is not within the scope of protection claimed by the present invention.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, 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 and to which this invention belongs, and any method, apparatus, or material of the prior art similar or equivalent to the methods, apparatus, or materials described in the examples of this invention may be used to practice the invention.
The invention provides a lead zinc copper refining device which comprises a bed layer part 1 and a molten pool part 2.
The bed layer part 1 comprises a material cup 7, a furnace body 3 and a furnace belly 4 which are sequentially arranged from top to bottom, wherein the material cup 7 is fixedly arranged at one end of the furnace body 3, which is far away from the molten pool part 2, the furnace body 3 is communicated with the furnace belly 4, a smoke outlet 8 is fixedly arranged on the furnace body 3, and a first air supplementing opening 9 is fixedly arranged on the furnace belly 4.
The material cup 7 is an openable and closable material feeding device for feeding materials into the lead zinc copper refining device and observing the furnace condition.
The furnace body 3 and the furnace belly 4 can be in a three-dimensional space with wide upper part and narrow lower part. Illustratively, the shaft 3 may be cylindrical and the web 4 may be necked up from top to bottom, with the diameter of the lower cross section of the web 4 being smaller than the diameter of the upper cross section of the web 4. The two can be the internal cavity furnace body with the furnace shell encircling and integrally prefabricated. Wherein the total length of the furnace body 3 and the furnace belly 4 can be 2-10 m, and the diameter of the cross section of the furnace body 3 can be 2-8 m.
In some embodiments, the temperature of the tuyere zone of the first air compensating port 9 can be 1100-1400 ℃, and the outer surface of the furnace belly 4 can be fixedly provided with a first water jacket structure so as to play roles of cooling and relieving the heat load of the furnace body of the lead-zinc-copper refining device.
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 formed by surrounding a plurality of water jackets and is divided into an upper layer and a lower layer, and each water jacket is provided with an independent water inlet and outlet pipe.
In other embodiments, a secondary tuyere may be provided in the shaft 3 to enhance the mixing of the oxidizing material in the furnace while supplementing the oxygen required for combustion in the furnace (i.e., in the lead zinc copper refining apparatus, described below). In addition, the combustion and heat transfer in the furnace can be controlled by adjusting a secondary air ratio in operation.
The first air supply port 9 is a hollow tubular structure communicated with the external spray gun 11, can be fixedly arranged on the furnace belly 4 and arranged around the outer wall of the furnace belly 4, and the number of the first air supply port can be 8-24. The first air supply port 9 can be used for blowing oxygen-enriched gas and reducing agent to regulate the temperature, oxygen concentration and oxygen flow in the furnace.
In some embodiments, the distance between the first air supply port 9 and the top of the bed material can be 1-8 m, and the cross-sectional area of the first air supply port 9 can be 3-120 cm 2 The included angle between the central axis of the first air supply port 9 and the horizontal plane can be-15 degrees or more and alpha or less than 30 degrees.
The smoke outlet 8 can be a hollow tubular structure and is fixedly arranged on the outer wall of the furnace body 3. The end of the smoke outlet 8 far away from the lead-zinc-copper refining device can be fixedly connected with a lead rain/zinc rain condensing device so as to collect and recycle the metal zinc in the first zinc-containing gas and the second zinc-containing gas.
In the specific application, when the oxidation material is thrown onto the material column by the material cup 7 to form a bed material, the bed material forms an arch bridge-shaped bed material with certain pressure resistance on the bed part 1 through the supporting friction of the furnace wall of the furnace belly 4 and the blowing force of the first air supplementing port 9. The reducing agent in the furnace reacts with hot air to generate CO and CO 2 The CO reduces metal oxides in the bed material (i.e., the column) to produce metal. Wherein, the lead-removing compound below the material column surface by about 1000mm is basically reduced into metallic lead, the liquid phase is maintained at high temperature in the furnace, and forms crude lead together with copper, silver, stibium and other metals generated by reduction, gangue slag is melted and moves down to a molten pool part 2 together with the crude lead (the crude lead, gangue and the like are reduction residues).
The molten pool part 2 is communicated with one end of the furnace belly 4, which is far away from the furnace body 3, the molten pool part 2 comprises a reduction zone 5 and a clarification zone 6 along the length extension direction, the reduction zone 5 is positioned at one end of the molten pool part 2, which is close to the bed part 1, the clarification zone 6 is sequentially and fixedly provided with a slag discharge port 12 and a siphon port 13 from top to bottom, and the reduction zone 5 is fixedly provided with a spray gun 11.
The bath portion 2 may be a three-dimensional space having a rectangular cross section. The height of the water heater can be 1-8 m, the width of the water heater can be 2-8 m, and the length of the water heater can be 4-10 m.
The reduction zone 5 is opposite to the bottom of the bed part 1 to bear the reduction residues dropped after the bed material is reduced. The reduction part is fixedly connected with a spray gun 11.
The cross-sectional area of the lance 11 may be 5 to 120cm 2 The height of the spray gun 11 from the bottom of the molten pool part 2 can be 60 cm-2 m; lance 11 may be a horizontally inclined lance 11, lance 11 may be generally oriented to the side of fining zone 6, and may power the flow of the melt to be reduced; the included angle between the spray gun 11 and the furnace wall of the molten pool part 2 can be changed between 35 degrees and 90 degrees according to different positions, one side close to the clarification area 6 is 90 degrees, and the included angle away from the clarification area 6 is sequentially reduced.
In some embodiments, an external melt inlet 10 may be fixedly installed in the reduction zone 5 to collect the external oxidative desulfurization melt, which may be combined with the reduction residue to form the melt to be reduced. The lead-zinc-copper refining device can be used for processing lead-zinc-copper-containing hazardous waste and urban mineral products in a large mixing amount, so that the problems of insufficient original resources and low recycling rate of solid waste resources are effectively solved, and the power-assisted circular economy and the green sustainable development of the metallurgical industry are realized.
In other embodiments, the temperature of the melt to be reduced in the bath portion 2 may be 1100-1350 ℃. A second water jacket structure can be sleeved on the outer wall of the molten pool part 2 to play a role in cooling the furnace wall and protecting the furnace shell.
In a specific application, the reduction zone 5 gathers the externally-collected oxidative desulfurization melt and the reduction residues dropped from the bed material reduction melt to form a melt to be reduced. The melt to be reduced is rapidly reduced with the continuous blowing of the reducing agent under the blowing and stirring of the spray gun 11. After the reduction slagging is finished, the alloy is settled and separated from the slag. The alloy can be discharged from the siphon port 13 for further refining recovery, and the slag can be discharged from the slag discharge port 12 and then enters the fuming furnace for recovery treatment.
In the inventionThe lead-zinc-copper refining device is vertically coupled with the molten pool by utilizing the bed layer, so that on one hand, solid materials and liquid materials can be cooperatively processed, and the device has high compatibility and high capacity material processing capacity; on the other hand, the invention takes into account the smelting advantages of high reducing capability of the charging post blast furnace and the molten pool smelting furnace in the common technology, so that the application effect of 1+1 & gt2 is achieved, and meanwhile, the limitations in the following common technology are overcome: the smelting of an independent molten pool has the technical defects that smoke dust of furnace gas is large, zinc vapor exists in an oxidation state and the like in the smelting process; the blast reduction of the material column still has the technical defects of low heat utilization rate, high energy consumption and carbon consumption, poor material compatibility and the like. According to the invention, the bed layer is creatively coupled with the molten pool, and the zinc vapor reduced by the dust in the furnace, the molten pool and the bed layer simultaneously is filtered and purified by the bed layer, so that the dust rate in the furnace is greatly reduced, and meanwhile, the zinc can be efficiently recovered in the form of pure vapor. Meanwhile, the heat preservation performance of the bed layer (comprising the bed layer part 1 and the bed layer materials inside the bed layer part) can effectively inhibit Zn (g) low-temperature oxidation side reaction Zn (g) +CO 2 (g) The =zno+co (g) occurs, the closed bed ensures that Zn (g) is not oxidized by external oxygen. And the lead, zinc and copper are integrally and efficiently reduced through linkage of a bed layer and a molten pool.
In some embodiments, the direction of the reduction zone 5 to the clarification zone 6 may be a first direction. The spray gun 11 is fixedly installed on the tank wall which is arranged on the reduction zone 5 in a corresponding mode and extends along the first direction, the spray gun 11 of the spray gun 11 is arranged towards the first direction, and the included angle formed by the spray gun 11 and the tank wall is sequentially increased along the first direction.
The spray guns 11 are oppositely arranged at the two sides of the molten pool, support to spray gas, powdery reducing agent, flux and the like into the molten pool, strongly stir the melt to be reduced, strengthen mass and heat transfer of the molten pool part 2 and accelerate the chemical reaction in the melt to be reduced.
In some embodiments, the outer surface of the hearth 4 may be fixedly provided with a first water jacket structure, the outer surface of the molten bath 2 may be fixedly provided with a second water jacket structure, and the lining of the bed portion 1 may be bricked.
The refractory bricks may comprise aluminum-magnesium bricks to play a roleThe furnace body is insulated and the material is protected. The heat preservation performance of the closed bed material is cooperated, so that the Zn (g) low-temperature oxidation side reaction Zn (g) +CO can be effectively inhibited 2 (g) =zno+co (g) occurs, ensuring that Zn (g) is not oxidized by external oxygen.
In some embodiments, the first air compensating port 9 is tubular, and is disposed around a side of the furnace cavity 4 away from the furnace body 3, and the first air compensating port 9 is fixedly mounted on the outer wall of the furnace cavity 4 and is disposed in communication with the interior of the furnace cavity 4;
wherein the number of the first air supply openings 9 is 8-24, the included angle between the first air supply openings 9 and the cross section of the furnace belly 4 is-15-30 degrees, and the cross section area of the first air supply openings 9 is 3-120 cm 2 。
In some embodiments, a melt inlet may be provided at the end of the reduction zone 5 remote from the fining zone 6.
The invention also provides an application of the lead zinc copper refining device in recovering valuable metals.
In some embodiments, the above-described application includes the steps of:
s1, throwing an oxidation material into a bed layer part 1 through a material cup 7, forming the bed layer material in the bed layer part 1, blowing a first reducing agent taking oxygen-enriched gas as a carrier into a furnace belly 4 through a first air supplementing port 9, and reducing the bed layer material to obtain a reduction residue and a first zinc-containing gas.
The oxidation materials can comprise lead-zinc oxidation materials, secondary material blocks of urban mineral products and the like, lead-zinc copper sulphide ore sintering blocks, lead-zinc copper sulphide ore calcine, waste zinc-manganese batteries, waste circuit boards and the like.
S2, the reduction residues are dripped from the bed layer part 1 to a smelting part to form a melt to be reduced.
The reduction residue comprises lead bullion, gangue and the like.
S3, the spray gun 11 blows a second reducing agent taking oxygen-enriched gas as a carrier into the molten pool part 2, the melt to be reduced is reduced under the stirring of the second reducing agent to obtain alloy and slag, and the alloy and the slag are layered after standing;
wherein the alloy is discharged from the siphon port 13, and the slag is discharged from the slag discharge port 12.
The lead zinc copper refining device can be applied to reduction recovery of copper-rich oxidized materials (the mass fraction of copper in the copper-rich oxidized materials is more than 5 percent), and the copper-rich oxidized materials mainly comprise ore copper smoke dust, reclaimed copper smoke dust, copper-containing sludge and the like produced in primary and reclaimed copper smelting (matte smelting, copper matte blowing, blister copper refining and electric furnace copper smelting) processes. Most of the dust and sludge contain valuable metals such as copper, lead, zinc, tin, bismuth, antimony, tin, arsenic, noble metals and the like, and are important secondary resources.
In the prior art, no existing technology for targeted efficient reduction of copper-rich oxidized materials is available, and the copper-rich oxidized materials are usually directly returned to original copper smelting, and ingredients are re-smelted. The direct batching remelting not only increases the circulation quantity of smoke dust in the smelting process, but also reduces the processing capacity of concentrate in a smelting system; the long-term operation can cause that impurity elements can not be opened when the normal operation of an acid making system is influenced, and vicious circle enrichment is carried out in the system, so that the quality of blister copper is influenced, and further the cathode copper impurity exceeds the standard.
If the copper-rich oxidation materials produced in the copper smelting process are treated in a targeted manner, the following steps are: the method of adopting rotary kiln, electric furnace and the like to recover the copper-containing oxidized material by reduction requires higher investment cost and has poor economical efficiency.
The invention utilizes the lead-zinc-copper refining device to pointedly treat the copper-rich oxidized material, efficiently collects and treats secondary resources such as ore copper smoke dust, regenerated copper smoke dust, copper-containing sludge and the like produced in the copper smelting process, skillfully designs the lead-zinc-copper refining device, and can synchronously reduce and recycle metals from the solid/liquid copper-rich oxidized material. The copper-rich oxidized material and oxidized materials such as lead and zinc can be mixed and proportioned, and the lead, the zinc and the copper can be recovered by synergetic reduction in the lead and zinc smelting process.
In some embodiments, when the lead-zinc-copper refining device is applied to the above-mentioned copper-rich lead-zinc oxide material (the mass fraction of copper element in the oxide material is greater than 5%), the reduction temperature in the step S1 is 1050-1350 ℃, and the reduction time in the step S1 is 60-150 min; the reduction temperature in the step S3 is 1100-1350 ℃, and the reduction time in the step S3 is 30-150 min.
In other embodiments, when the lead-zinc-copper refining apparatus of the present invention is applied to the above-mentioned copper-rich material (the mass fraction of copper in the oxidized material is greater than 5%), the amount of the first reducing agent added may be 5-15% of the mass of the oxidized material, and the amount of the second reducing agent blown in may be 0.6-1.8% of the mass of the second reducing agent required for completely reducing the metal oxide in the to-be-reduced melt to the metal simple substance.
The lead-zinc-copper refining device can be applied to reduction recovery of high-lead and zinc materials (the sum of the mass fractions of lead and zinc in oxidized materials is more than 30%).
Because of the high melting point (1975 ℃) of ZnO, the high zinc material is difficult to melt and flow at the conventional smelting temperature (1150-1300 ℃), and the development of the direct zinc smelting technology of a molten pool is restrained for a long time.
In the existing zinc smelting wet smelting, a large amount of waste slag containing iron and zinc is produced in the leaching process, and the waste slag is treated and recovered by a pyrogenic process technology.
The prior zinc smelting pyrometallurgy mainly comprises a sintering-closed blast reduction-fuming process, a Koff Saite lead-zinc combined smelting process and an oxygen bottom blowing smelting-bottom blowing smelting reduction-oxygen-rich fuming converting triple-continuous furnace process. 1) Sintered block blast reduction to directly recycle metallic zinc, and sintering process has high energy consumption and low concentration SO 2 The pollution is heavy, and the popularization of the technology is restricted. 2) The combined smelting process of lead and zinc in the Kelvin technology can only process desulfurated melt with zinc content lower than 18% in industry, and when the zinc content is higher than 18%, the melt is difficult to flow, and the problems of furnace junction and furnace death are easy to occur. 3) The process of oxygen bottom blowing smelting, bottom blowing smelting reduction and oxygen-enriched fuming converting is used for treating lead-zinc-containing multi-metal solid waste, an oxygen bottom blowing furnace is used for smelting, desulfurizing and slagging the lead-zinc multi-metal solid waste, a bottom blowing reduction furnace is used for reduction, oxygen-enriched fuming converting is used for recycling other valuable metals, but zinc is recycled in a zinc oxide ash form, and zinc can not be directly obtained. The existence of zinc oxide, even if the amount is small, has great harm to the condensation process, so that the zinc liquid is covered by a layer of zinc oxide and is difficult to be gathered into a large sizeDroplets impede the progress of the condensation process.
In view of the above, the most common technical problems in the conventional technology for lead-zinc smelting include: sintering is needed, (the pretreatment process is complex and high in pollution), high zinc melt is difficult to treat in a targeted way (the furnace condition is easy to deteriorate), and the direct yield of the metallic zinc is low (the metallic zinc is recovered in an oxidation state to influence the recovery efficiency).
It should be noted that, because zinc oxide in the high zinc melt is easy to combine with iron oxide and silicon dioxide to form stable zinc ferrite and zinc silicate, free zinc oxide has low content and low activity, and is difficult to reduce. The high zinc material molten pool smelting process can be smoothly carried out, achieves ideal technical and economic indexes, and depends on the heat and mass transfer, slag and gold separation and gas permeation processes of slag in a molten pool to a certain extent.
The bed part 1 and the molten pool part 2 are vertically arranged in a coupling way, so that the treatment capacity and the treatment efficiency of lead-rich and zinc-rich oxidation materials are greatly improved, and on one hand, the bed material can filter furnace gas and dust generated by smelting in a molten pool, so that the ascending first zinc-containing gas and the ascending second zinc-containing gas are purer; on the other hand, the bed material fully reacts under the airtight reducing atmosphere, which comprises the following steps: the first reducing agent is combusted under the blowing of the first oxygen-enriched gas to provide a reducing atmosphere, the unreduced oxide in the bed material drops into a molten pool and is reduced under the blowing of the second reducing agent and the second oxidizing agent, and CO generated by reduction in the molten pool rises into the bed material to further reduce the bed material. Under the triple reduction condition, the material enters a trapping and recycling device in the form of pure zinc vapor to obtain metal zinc, and the metal zinc is efficiently recycled.
In cooperation with the excellent heat and mass transfer performance brought by the first air supply port 9 and the finely configured spray gun 11 in the lead-zinc-copper refining device, the invention can process high-zinc melt in a targeted manner with high direct yield and high efficiency on the premise of no sintering.
In some embodiments, when the lead-zinc-copper refining device of the present invention is applied to the above Gao Qianxin material (the sum of mass percentages of lead and zinc in the oxidized material is greater than 30%), the reduction temperature in the step S1 is 1200-1400 ℃, and the reduction time in the step S1 is 60-150 min; the temperature of the reduction in the step S3 is 1200-1350 ℃, and the time of the reduction in the step S3 is 30-120 min.
In other embodiments, when the lead-zinc-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 may be 6-15%, and the bubbling amount of the second reducing agent is 0.8-2.0 of the mass of the second reducing agent required for completely reducing the metal oxides in the melt to be reduced into the metal simple substance.
To facilitate a further understanding of the invention by those skilled in the art, reference is now made to the accompanying drawings, in which:
example 1
Referring to fig. 1, the invention provides a lead zinc copper refining device.
The lead zinc copper refining device consists of an upper bed layer part 1 and a lower molten pool part 2, wherein a material cup 7 and a secondary air port are arranged on the upper part of a furnace body 3, first air supply ports 9 are arranged around the furnace body 4, the number of the first air supply ports 9 is 10, and the cross section area of each first air supply port 9 can be 100cm 2 The position of the first air supply port 9 is 3 meters away from the top of the bed material, and the included angle between the central axis of the first air supply port 9 and the horizontal plane can be 5 degrees. The upper part of the furnace body 3 is also provided with a secondary air port and a smoke exhaust port 8, and the smoke exhaust port 8 is connected with a condensing facility. The bed layer part 1 is built into a rectangular space with a narrow bottom by refractory bricks, the bed layer part 1 is provided with a steel plate spray type water jacket or a copper water jacket, and the height of the bed layer part 1 is 5 meters, the width is 3 meters and the length is 6 meters.
The first air supply port 9 can blow a first reducing agent (including pulverized coal, bituminous coal and the like) into the bed material by taking oxygen-enriched gas as a carrier, and maintain the temperature of the air port area at 1100-1400 ℃ to reduce and oxidize the metal oxide in the material.
The bottom of the lead zinc copper refining device is a molten pool part 2, and the molten pool part 2 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 desulfurization melt. The other end of the clarification area 6 is provided with a slag discharging port 12 and a siphon port 13 from top to bottom in vertical height. Two sides of the pool wall which are oppositely arranged in the extension direction of the pool part 2 are provided with opposite horizontal inclined spray guns 11. The spray gun 11 is generally towards the clarification zone 6 side, the cross-sectional area of the spray gun 11 is 100cm 2 The height of the spray gun 11 from the bottom of the inner furnace of the molten pool is 80cm, the gas, powdery reducer, flux and the like are supported to be sprayed into the molten pool, the molten pool is strongly stirred, the mass and heat transfer of the molten pool are enhanced, and the temperature of the melt to be reduced is maintained at 1300 ℃. The angle between the first pair of spray guns 11 in the extension direction of the reduction zone 5 and the pool wall of the molten pool part 2 is 50 degrees, the angle between the spray guns 11 and the pool wall is continuously increased according to the length extension direction, and the angle between the pair of spray guns 11 closest to the clarification zone 6 and the pool wall is 90 degrees.
The molten pool part 2 is a cuboid space surrounded by a copper water jacket, and the height of the molten pool part is 2 meters, the width of the molten pool part is 3 meters, and the length of the molten pool part is 6 meters.
Example 2
Referring to fig. 1, the present invention provides an application of a lead zinc copper refining device.
The lead-containing smoke dust, zinc-containing ash, zinc hydrometallurgy needle iron slag and copper ash of certain factory in China are pressed into blocks to prepare the components of 17wt.% lead, 32wt.% zinc, 6wt.% copper, 4wt.% iron and SiO 2 The agglomerate of 7wt.% and CaO 8wt.% is mixed with 12% of coke and added to the bed from a closed cup 7 at the upper end of the bed part 1. The oxygen-enriched 35% hot air at 800 ℃ is blown into the air supply port 9 below the bed layer, the temperature of the air port area is controlled to 1300 ℃ (error + -50 ℃), and the bed layer oxidation material overflows rising hot CO-CO in the coke, oxygen-enriched gas and molten pool 2 Under the synergistic reduction of the mixed gas, the first zinc-containing gas and the reduction residue (the reduction residue comprises liquid lead metal and partial unreduced oxide and gangue) are obtained through reduction.
The reduction residue drops into the molten pool part 2, and meanwhile, an external melt converging port 10 of the lower molten pool part 2 is added with lead-zinc-copper-containing oxidative desulfurization melt, and the composition is as follows: 26.2wt.% lead, 27.2wt.% zinc, 6.8wt.% copper, 14.4wt.% iron, 0.5wt.% sulfur, siO 2 12.3wt.% and CaO 3.4wt.%. The reduction residue and the oxidative desulfurization melt are converged into a melt to be reduced. Blowing reaction flux and anthracite as the second reducing agent (wherein the anthracite comprises fixed carbon 48.5%, total sulfur 0.75%, volatile matter 33.8% and ash 16.1%) into the melt to be reduced by using oxygen-enriched gas with oxygen concentration of 30% as a carrier through spray guns 11 on two sides of a molten pool part 2, controlling the temperature of the melt to be reduced in a reduction zone 5 to be maintained at 1300 ℃ for continuously reducing the meltAnd metal oxides such as lead, zinc, copper and the like to be reduced in the pool and simultaneously finish the slag forming reaction.
The melt after the reduction of the molten pool part 2 flows into a clarifying zone 6, the reduced lead-copper alloy and the like are clarified in the clarifying zone for 2.5 hours and separated from slag, and the reaction gas escaping from the molten pool is filtered through the material of the bed part 1, so that the dust particle content in the gas phase is reduced, and the second zinc-containing gas is obtained. The first zinc-bearing gas and the second zinc-bearing gas are captured by a condensing facility to obtain zinc metal. After clarification, the alloy product contains 74.6% of lead, 21.6% of copper, 2.1% of zinc and the contents of copper, lead and zinc in slag are respectively reduced to 0.02%, 0.14% and 3.52%.
Example 3
Referring to fig. 1, the present invention provides an application of a lead zinc copper refining device.
The method comprises the steps of compacting the regenerated copper ash, wet zinc-smelting lead-silver slag and sintering returned powder of a certain factory in China to prepare the powder, wherein the components comprise 15wt.% of lead, 27wt.% of zinc, 18wt.% of copper, 12wt.% of iron and SiO 2 5wt.% of agglomerates and 6wt.% of CaO are mixed with 8% of coke and added to the bed from a closed cup 7 at the upper end of the bed part 1. Oxygen-enriched 45% hot air at 700 ℃ is blown into an air supplementing port 9 below the bed layer, the temperature of an air port area is controlled to be 1250 ℃ (error + -50 ℃), and the bed layer oxidation material overflows rising hot CO-CO in coke, oxygen-enriched gas and a molten pool 2 Under the synergistic reduction of the mixed gas, the first zinc-containing gas and the reduction residue (the reduction residue comprises liquid lead metal and partial unreduced oxide and gangue) are obtained through reduction.
The reduction residue drops into the molten pool part 2, and meanwhile, an external melt converging port 10 of the lower molten pool part 2 is added with an oxidation desulfurization melt, and the composition is as follows: 15.5wt.% lead, 30.4wt.% zinc, 14.5wt.% copper, 10.7wt.% iron, 0.8wt.% sulfur, 17.3wt.% SiO2, 5.3wt.% CaO. The reduction residue and the oxidative desulfurization melt are converged into a melt to be reduced. Blowing reaction flux and second reducing agent coke powder into the melt to be reduced by taking oxygen-enriched gas with the oxygen concentration of 30% as a carrier through spray guns 11 on two sides of a molten pool part 2, controlling the temperature of the melt to be reduced in a reduction zone 5 to be maintained at 1250 ℃, continuously reducing metal oxides such as lead, zinc, copper and the like to be reduced in the molten pool, and simultaneously completing slag-making reaction.
The melt after the reduction of the molten pool part 2 flows into a clarifying zone 6, the reduced lead-copper alloy and the like are clarified in the clarifying zone for 2 hours and separated from slag, and the reaction gas escaping from the molten pool is filtered through the material of the bed part 1, so that the dust particle content in the gas phase is reduced, and the second zinc-containing gas is obtained. The first zinc-bearing gas and the second zinc-bearing gas are captured by a condensing facility to obtain zinc metal. After clarification, the alloy product contains 43.3% of lead, 51.9% of copper, 3.2% of zinc and the contents of copper, lead and zinc in slag are respectively reduced to 0.03%, 0.09% and 3.13%.
In the above technical solution of the present invention, the above is only a preferred embodiment of the present invention, and the patent scope of the present invention is not limited thereto, and all the equivalent structural changes made by the description of the present invention and the content of the drawings or the direct/indirect application in other related technical fields are included in the patent protection scope of the present invention.
Claims (10)
1. A lead zinc copper refining device, characterized by comprising:
the hearth part comprises a material cup, a furnace body and a furnace belly which are sequentially arranged from top to bottom, wherein the material cup is fixedly arranged at one end of the furnace body, which is far away from the molten pool part, the furnace body is communicated with the furnace belly, the furnace body is fixedly provided with a smoke outlet, and the furnace belly is fixedly provided with a first air supplementing port;
the molten pool part is communicated with one end of the furnace belly, which is far away from the furnace body, the molten pool part comprises a reduction zone and a clarification zone along the length extension direction, the reduction zone is positioned at one end of the molten pool part, which is close to the bed layer part, the clarification zone is sequentially and fixedly provided with a slag discharge port and a siphon port from top to bottom, and the reduction zone is fixedly provided with a spray gun.
2. The lead zinc copper refining device according to claim 1, wherein the direction from the reduction zone to the clarification zone is a first direction, the spray gun is fixedly installed on a tank wall extending along the first direction and oppositely arranged in the reduction zone, the spray gun is arranged towards the first direction, and the included angle between the spray gun and the tank wall is sequentially increased along the first direction.
3. The lead zinc copper refining device according to claim 1, wherein a first water jacket structure is fixedly arranged on the outer surface of the furnace belly, a second water jacket structure is fixedly arranged on the outer surface of the molten pool part, and the lining of the bed part is built by refractory bricks.
4. The lead zinc copper refining device according to claim 1, wherein the first air supplementing opening is tubular and is arranged around one side of the furnace belly away from the furnace body, and the first air supplementing opening is fixedly arranged on the outer wall of the furnace belly and communicated with the interior of the furnace belly;
wherein the number of the first air supply openings is 8-24, the included angle between the first air supply openings and the cross section of the furnace belly is-15-30 degrees, and the cross section area of the first air supply openings is 3-120 cm 2 。
5. The lead zinc copper refining apparatus of claim 1, wherein an external melt inlet is provided at an end of the reduction zone remote from the refining zone.
6. Use of a lead zinc copper refining plant according to any one of claims 1 to 5 for recovery of valuable metals.
7. Use of a lead zinc copper refining plant according to claim 6 for the recovery of valuable metals, characterized in that it comprises the steps of:
s1, throwing an oxidation material and a first reducing agent into a bed layer part through a material cup, forming a bed layer material at the bed layer part, blowing oxygen-enriched gas into a furnace belly through a first air supplementing port, and reducing the bed layer material to obtain a reduction residue and first zinc-containing gas;
s2, the reduction residues are dripped from the bed layer part to the smelting part to form a melt to be reduced;
s3, the spray gun blows a second reducing agent into the molten pool part by taking oxygen-enriched gas as a carrier, the melt to be reduced is reduced under the stirring of the second reducing agent to obtain alloy and slag, and the alloy and the slag are layered after standing;
wherein, alloy is discharged from the siphon port, and slag is discharged from the slag discharge port.
8. The application of the lead zinc copper refining device in recycling lead zinc copper according to claim 7, wherein the mass fraction of copper element in the oxidized material is more than 5%, the reduction temperature in the step S1 is 1050-1350 ℃, and the reduction time in the step S1 is 60-150 min; the reduction temperature in the step S3 is 1100-1350 ℃, and the reduction time in the step S3 is 30-120 min.
9. The use of the lead-zinc-copper refining device according to claim 8, wherein the addition amount of the first reducing agent is 5-15% of the mass of the oxidized material, and the bubbling amount of the second reducing agent is 0.6-1.8 of the mass of the second reducing agent required for completely reducing the metal oxides in the melt to be reduced into metal elements.
10. The application of the lead-zinc-copper refining device in recycling lead-zinc-copper according to claim 7, wherein the sum of mass fractions of lead and zinc elements in the oxidized material is more than 30%, the reduction temperature in the step S1 is 1200-1400 ℃, and the reduction time in the step S1 is 60-150 min;
the temperature of the reduction in the step S3 is 1200-1350 ℃, and the time of the reduction in the step S3 is 30-150 min.
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| CN202310107841.1A CN116026148A (en) | 2023-01-29 | 2023-01-29 | Lead zinc copper refining device and application thereof |
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| CN202310107841.1A CN116026148A (en) | 2023-01-29 | 2023-01-29 | Lead zinc copper refining device and application thereof |
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