CN114381606B - Recycling harmless treatment method for intermediate products containing lead and zinc in copper smelting - Google Patents
Recycling harmless treatment method for intermediate products containing lead and zinc in copper smelting Download PDFInfo
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0054—Slag, slime, speiss, or dross treating
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
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Abstract
The invention discloses a recycling harmless treatment method for intermediate products containing lead and zinc in copper smelting. The method comprises the following steps: mixing intermediate products containing lead and zinc produced in the copper smelting process with a vulcanizing agent, adding a reducing agent, and preparing materials, wherein the intermediate products containing lead and zinc comprise one or more of blowing slag, refining slag and smoke dust, and the vulcanizing agent comprises one or more of gypsum slag and pyrite; the reduction and sulfuration are carried out in an oxygen-enriched side-blown smelting furnace, and the obtained products comprise crude lead, copper matte, smelting slag and smoke dust rich in lead and zinc. The invention solves the problems of high copper content in tailings, low ore dressing recovery rate and dangerous waste generation caused by the return of intermediate products to the smelting furnace, improves the recovery rate of valuable metals, and simultaneously effectively treats the dangerous waste such as smoke dust, gypsum slag and the like.
Description
Technical Field
The invention relates to the technical field of copper smelting, in particular to a recycling harmless treatment method for intermediate products containing lead and zinc in copper smelting.
Background
At present, a pyrometallurgical process of 'matte smelting-copper matte blowing-anode refining' is mainly adopted in copper smelting, and intermediate products such as blowing slag, refining slag, smoke dust and the like generated in the current pyrometallurgical process are usually treated by returning to a smelting furnace, but the treatment method has a plurality of problems.
Problems with existing pyrometallurgical processes are described in several respects below.
1) When conventional copper concentrate is treated by the pyrometallurgy process, intermediate materials with higher Cu content such as blowing slag, refining slag, smoke dust and the like are returned to the smelting furnace so as to further recycle Cu. Firstly, when copper concentrate with higher impurity content is treated, pb and the like are enriched in a production system, so that the circulating quantity of intermediate materials such as blowing slag, smoke dust and the like is increased, the quality of products in each section is influenced, and the production cost is increased. Secondly, blowing slag, smoke dust and the like return to the smelting furnace and absorb heat; under the condition that coal is not used as a reducing agent, the blowing slag and the smoke dust float on the surface of the smelting slag in a bulk shape, and are difficult to completely participate in the reaction; because the smelting and slagging reaction is incomplete, more Cu in the melt can be entrained. Furthermore, as the intermediate materials are not fully reacted, the mass form is relatively large, the entrained metal content is relatively high, the oxide form exists in smelting slag mainly, the ore dressing recovery rate is low, the final tailings contain Cu, and the overall Cu recovery rate is reduced.
Aiming at the problem that lead in high-lead copper concentrate is enriched in converting slag, refining slag and smoke dust in the pyrometallurgy process to produce a large amount of high-lead converting slag, high-lead refining slag and high-lead zinc smoke dust, and the high-lead converting slag, the high-lead refining slag and the high-lead zinc smoke dust float on the surface of the smelting slag after returning to a smelting furnace and are difficult to completely participate in the reaction, a certain amount of coke or lump coal is mixed into the smelting furnace in the current production, and the coke or lump coal can reduce high-lead returning materials and supplement heat for the smelting slag, so that the thermodynamic conditions of the smelting slag reaction are enhanced, and the high-lead materials are fully reacted. However, this method has at least the following disadvantages: a) The consumption of coke or lump coal can be increased, the smelting treatment cost is increased, and the carbon consumption and carbon emission indexes are increased; b) Valuable metal lead and zinc cannot be recovered. c) The problem that Pb is enriched in the system to influence the quality of the product cannot be solved.
2) The smoke dust in the copper smelting process is mainly a mixture of smoke dust produced in a smelting process and a blowing process, and the smoke dust has complex chemical components and generally contains Cu, pb, zn, fe, as and other valuable metals. The main harmful elements in the smoke dust are lead, arsenic and the like, and the smoke dust is continuously enriched after being returned to a smelting system, so that the normal production and the product quality of an acid making and electrolysis system can be influenced for a long time. Because smoke belongs to dangerous waste and the accumulated smoke occupies a large area year by year, the accumulated funds are large, enterprises face not little pressure, and some enterprises become important links for restricting the production of the enterprises. At present, the smoke treatment has no relatively mature and reliable process technology, and is a great difficulty to be solved in the copper smelting industry. The fume from each copper smelting plant is either selectively deposited, returned to the system or selected for sale to qualified enterprises for treatment.
Aiming at the treatment of smoke dust, at present, only individual copper smelting enterprises have own treatment systems and all adopt wet treatment processes, and the specific flow is that the smoke dust is subjected to operation procedures of primary water immersion, secondary acid immersion, scrap iron copper removal, iron and arsenic removal, cadmium removal, zinc sulfate crystallization and the like, and valuable metals in the smoke dust are respectively recycled in the forms of sponge copper, electric lead, zinc sulfate and the like. In addition, the smoke dust treatment system adopts a process of leaching smoke dust in two sections, leaching slag is smelted in a blast furnace to obtain crude lead, and then refined lead is obtained through electrolysis; the leaching solution is subjected to electrolytic copper deposition, the electrolytic copper deposition returns to smelting, the liquid is evaporated to crystallize crude zinc sulfate after the electrolytic copper deposition, and the crystallization mother liquor is reduced by sulfur dioxide to deposit arsenic, so that arsenic trioxide is obtained. In the two methods, although the smoke dust is treated, the electrode decoppering cost of the leaching liquid is high, secondary dangerous wastes such as arsenic slag, lead filter cakes and the like can be generated, the treatment process is complex, and the treatment cost is high.
3) The gypsum slag in copper smelting process is the product of lime desulfurization, and its main component is calcium sulfate (CaSO 4 ·2H 2 O), in addition, contains a plurality of heavy metal elements, belongs to dangerous solid waste, and if the dangerous solid waste can not be effectively treated, secondary pollution is caused to the environment and resources, and the dangerous solid waste is mainly pollution to soil, groundwater resources and the like. The output of gypsum slag in the copper smelting industry is very large, and the gypsum slag is required to be subjected to harmless or recycling treatment, so that the significance is great.
Aiming at the problems of the dangerous waste gypsum slag, the main method for domestic treatment of the desulfurization gypsum slag at present comprises the following steps: piling, cement curing, medicament curing and the like. The stockpiling is the most common method for most enterprises at present, but the stockpiling has extremely high requirements on a stockpiling slag yard, and the subsequent maintenance difficulty is quite large; the toxic leaching of waste residues can be reduced to a range meeting the national toxic leaching requirement by cement solidification, but the volume capacity increasing ratio is large, and the treated residues cannot be recycled; the curing of the medicament is poor in adaptability at present, experimental work is only carried out on part of raw materials in a laboratory, and industrial application cannot be realized at present. Therefore, development of new treatment technology for recycling the desulfurized gypsum slag is urgently needed. The desulfurized gypsum slag contains a small amount of heavy metal elements, and the method cannot achieve the purposes of harmlessness, reduction and recycling.
4) The prior art can not recover valuable metals Pb and Zn in copper concentrate, pb and Zn can only be abandoned together with tailings, and the maximization of metal resource recovery can not be realized. This problem will be even more pronounced especially for high Pb, zn copper concentrates.
Aiming at the recovery problem of valuable metals, although a few prior process researches exist in the aspect of recovering Pb and Zn in copper smelting enterprises at present, no successful application cases exist yet, so that the process for recovering the valuable metals Pb and Zn from copper slag needs to be developed.
In summary, at least the following problems exist in the prior art:
1) The blowing slag with high Pb and the high Pb and Zn smoke dust return to the smelting furnace and float on the surface of the smelting slag in a bulk mode, so that the blowing slag with high Pb and the Zn smoke dust are difficult to completely participate in the reaction.
2) The blowing slag with high Pb and the smoke dust with high Pb and Zn float on the surface of the smelting slag, the reaction is incomplete, and more Cu in the melt can be entrained, so that the Cu content of the smelting slag is increased.
3) The smelting slag contains higher Cu, the metal in the unreacted intermediate product mainly exists as oxide, and the ore dressing recovery rate is low. And finally, the Cu content of the tailings is increased, so that the Cu recovery rate of the whole system is reduced.
4) Smoke dust in the copper smelting process belongs to hazardous waste, the treatment process is not mature, and qualified enterprises are usually required to be entrusted for treatment.
5) Impurities such as Pb are enriched in the system, so that the product quality of each process is affected, and the production cost is increased.
6) Gypsum slag in the copper smelting process belongs to dangerous waste, has large storage capacity and needs to be subjected to harmless or recycling treatment.
7) The prior art can not recover valuable metals Pb and Zn in copper concentrate, can only be abandoned together with tailings, and can not realize maximum recovery of metal resources.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a recycling harmless treatment method for intermediate products containing lead and zinc in copper smelting, which is favorable for copper smelting, reduces copper content in tailings, effectively treats hazardous waste, avoids the generation of secondary hazardous waste, improves valuable metal recovery rate and improves economic benefit.
The above object of the present invention is achieved by the following technical solutions:
according to one aspect of the invention, the invention provides a recycling harmless treatment method for copper smelting lead and zinc containing intermediate products, which comprises the following steps:
mixing intermediate products containing lead and zinc produced in the copper smelting process with a vulcanizing agent, adding a reducing agent, and burdening; wherein the intermediate products containing lead and zinc comprise one or more of blowing slag, refining slag, smoke dust and other materials; the vulcanizing agent comprises one or more of gypsum slag, pyrite and other high-sulfur materials;
the reduction and sulfuration are carried out in an oxygen-enriched side-blown smelting furnace, and the obtained products comprise crude lead, copper matte, smelting slag and smoke dust rich in lead and zinc.
Optionally, before the step of mixing the intermediate product containing lead and zinc produced in the copper smelting process with the vulcanizing agent, the method further comprises: a pre-crushing step; wherein the blowing slag is crushed to 5-25 mm in advance, and the refining slag is crushed to 5-25 mm in advance.
Optionally, before the step of mixing the intermediate product containing lead and zinc produced in the copper smelting process with the vulcanizing agent, the method further comprises: and preparing the pellets by adopting a pelletizing process. When the intermediate products containing lead and zinc do not contain smoke dust, preparing the vulcanizing agent into vulcanizing agent pellets, and mixing the vulcanizing agent pellets with the crushed intermediate products containing lead and zinc. When the intermediate products containing lead and zinc contain smoke dust, the vulcanizing agent and the smoke dust are respectively prepared into vulcanizing agent pellets and smoke dust pellets or the vulcanizing agent and the smoke dust are mixed to prepare mixed pellets, and the mixed pellets are mixed with the crushed intermediate products containing lead and zinc except the smoke dust.
Optionally, the reducing agent is one or more of coke, lump coal, semi-coke, graphite powder and anthracite. The ratio of the reducing agent can be 5% -30% (relative to the intermediate material).
Optionally, the vulcanizing agent is one or more of gypsum slag, pyrite and other high-sulfur materials. The vulcanizing agent proportion can be 10% -48% (relative to intermediate materials). Optionally, in the step of reducing and vulcanizing in the oxygen-enriched side-blown smelting furnace, the temperature in the furnace is 1150-1450 ℃, and the oxygen-enriched concentration is 40-85%.
Optionally, the method further comprises: returning the copper matte to a copper smelting system; after the crude lead is cast into ingots, the ingots are sold out; the lead and zinc-enriched fumes are sold as products.
Optionally, the copper matte contains 40-75% of Cu and 12-25% of S, and the temperature of the copper matte is 1150-1300 ℃. Optionally, the Pb content of the crude lead is 90-97%, and the temperature of the crude lead is 900-1000 ℃. Optionally, the Pb-containing and Zn-containing smoke dust contains 20% -50% of Pb and 10% -20% of Zn.
Alternatively, in the method, fe-SiO is used 2 CaO slag type, fe/SiO in the slag 2 CaO is (1-2): 2: (0.5-1), controlling the thickness of the slag layer to be 300-800 mm, and controlling the Cu content of the slag to be 0.8-2.5%.
Optionally, the product also comprises flue gas, the temperature of the flue gas is 1300-1350 ℃, and the flue gas is subjected to secondary combustion at the top of the hearth.
Optionally, when the pellet is prepared by adopting a pelletizing process, the method further comprises the step of adding a binder, wherein the addition amount of the binder is less than 10%.
The invention aims at a recycling harmless treatment method of intermediate products containing lead and zinc in copper smelting, intermediate products produced in the smelting process, such as blowing slag, refining slag, smoke dust and the like, are mixed with vulcanizing agents such as gypsum slag and the like, a proper amount of reducing agent is added, and two processes of reduction and vulcanization are completed in a reduction vulcanizing furnace, such as an oxygen-enriched side-blowing smelting furnace, and two valuable products of crude lead and copper matte and smoke dust rich in lead and zinc and the like are directly produced. The method is more beneficial to copper smelting, reduces the copper content of the tailings, effectively treats hazardous waste, avoids the generation of secondary hazardous waste, improves the recovery rate of valuable metals and improves the economic benefit. The invention realizes the separation of copper and lead in copper smelting intermediate products, at least realizes the separation of copper and lead in the blowing slag, and the copper content of the produced matte is more than or equal to 40%, the lead content of the crude lead is more than or equal to 90%, and the copper content of the slag is less than 2.5%.
Furthermore, the crude lead produced by the method can be cast and sold, the copper matte returns to a copper smelting system, and the smoke dust rich in lead and zinc can be used as a product for sale. The tailings produced by the method belong to common solid wastes, can be further processed, such as beneficiation, deep reduction depletion and the like, so as to recover valuable metals such as copper, lead and the like in the tailings, and can be directly sold or piled after granulating.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1) The invention adopts the hazardous waste gypsum slag as the vulcanizing agent, thereby not only producing copper matte, but also saving the hazardous waste disposal cost.
2) The method can be used for treating high Pb blowing slag, such as 5-30% of blowing slag containing Pb, and avoid the increase of Cu content in the smelting slag caused by returning the blowing slag to a smelting furnace.
3) The method can treat high Pb smoke dust, for example, smoke dust containing Pb more than or equal to 10 percent, and avoid the increase of Cu content in tailings caused by returning the high Pb smoke dust to a smelting furnace.
4) The method can be used for independently treating the high Pb converting slag, and avoids forming bulk converting slag and causing difficult ball milling of a subsequent mineral separation system.
5) The method can be used for independently treating the high Pb smoke dust to avoid forming the bulk smelting slag and causing the difficulty of ball milling of a subsequent mineral separation system.
6) By adopting the method, valuable elements such as Pb, zn and the like are comprehensively recovered, the recovery value of valuable metals is improved, and the economic benefit is better.
Drawings
FIG. 1 is a process flow diagram of a method for the recycling and harmless treatment of copper smelting lead and zinc containing intermediates in an embodiment of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
According to the recycling harmless treatment method for the intermediate products of lead and zinc in copper smelting, one or more of blowing slag, refining slag, smoke dust and the like of lead and zinc produced in the smelting process are mixed with a vulcanizing agent comprising gypsum slag, a reducing agent is added for batching, and two processes of reduction and vulcanization are completed in a reduction vulcanizing furnace such as an oxygen-enriched side blowing smelting furnace, so that products such as valuable products including crude lead and copper matte, smelting slag, smoke dust rich in lead and zinc and the like are directly produced. The crude lead can be cast and sold after being cast, the copper matte can be returned to a copper smelting system, and smoke dust rich in lead and zinc can be used as a product for being sold. The tailings produced by the method, namely smelting slag or reduced sulfation slag, belong to common solid waste, can be further processed, such as beneficiation, deep reduction depletion and the like, so as to recover valuable metals such as copper, lead and the like in the tailings, and can be directly sold or piled. The method effectively treats the dangerous waste gypsum slag, avoids the problems that the copper content of the tailings is high, copper smelting is not easy to carry out and secondary dangerous waste is generated due to the fact that intermediate products return to the smelting furnace, and simultaneously improves the recovery rate of valuable metals and economic benefits.
The intermediate product containing lead and zinc treated by the method can be one or more of blowing slag, refining slag, smoke dust and the like. Fig. 1 schematically shows a process flow of a method for the recycling and harmless treatment of intermediate products containing lead and zinc for copper smelting in an embodiment, which includes blowing slag, refining slag and smoke. As shown in fig. 1, the method for recycling and harmless treatment of the intermediate product containing arsenic and lead for copper smelting provided in this embodiment includes:
collecting smoke dust, conveying the smoke dust to a smoke dust receiving bin through pneumatic conveying, and conveying the smoke dust to a mixing cylinder after metering; gypsum slag produced by the desulfurization working section is collected and sent to a gypsum slag bin, and is sent into a mixing cylinder after being metered; the smoke dust and the gypsum slag are fully mixed in the mixing cylinder, the moisture of the gypsum slag is utilized to fully bond the smoke dust, and finally the mixed material is sent into a ball pressing machine to be pressed into balls, so that the mixed balls are obtained, and the granularity can be 10 mm-30 mm. The gypsum slag produced in the desulfurization working section can be subjected to filter pressing dehydration so that the residual moisture of the gypsum slag adheres to the smoke dust. Optionally, a small amount of binder, such as silica-based bentonite or the like, is added appropriately, depending on the spheroidization conditions, the addition amount of the binder being <10%.
And respectively collecting the blowing slag and the refining slag, feeding the blowing slag and the refining slag to a jaw crusher through a loader, crushing the blowing slag and the refining slag to 5-15 mm to obtain crushed blowing slag and crushed refining slag, and conveying the crushed blowing slag and the crushed refining slag to corresponding bins for temporary storage, wherein the outlet of each bin is provided with a quantitative device.
The reducing agent is transported in a bulk material mode and is self-dumped into a raw material bin for storage, is fed into an intermediate material bin through a loader, and is metered through a vibrating feeder and a quantitative feeder. The reducing agent can be coke or anthracite, or can be lump coal, semi-coke, graphite powder and other reducing agents.
Mixing the mixed pellets, the broken converting slag, the broken refining slag and the reducing agent according to a set proportion, and then adding the mixed pellets, the broken converting slag, the broken refining slag and the reducing agent into a reduction vulcanizing furnace from the top of the furnace through an adhesive tape conveyor for reduction and vulcanization, wherein the reduction vulcanizing furnace can be an oxygen-enriched side-blown smelting furnace, and the oxygen-enriched side-blown smelting furnace can comprise a furnace body, an oxygen-enriched side-blown molten pool, a spray gun and the like, and a lead bullion discharge port, a copper matte discharge port and a slag discharge port are arranged on the furnace body. Wherein, alternatively, the proportion of the vulcanizing agent can be 10% -48% (relative to the intermediate material), and the proportion of the reducing agent can be 5% -30% (relative to the intermediate material), and the proportion is related to the type of the vulcanizing agent, the type of the reducing agent and the actual components of the intermediate material.
Specifically, the oxygen-enriched side-blown smelting furnace is provided with a spray gun, natural gas and oxygen-enriched gas are sprayed into the furnace by adopting the spray gun, and all materials are subjected to reduction and vulcanization reactions rapidly in the furnace. The natural gas is not limited to this, and may be a fuel such as heavy oil, diesel oil, or pulverized coal. The oxygen-enriched gas can be oxygen-enriched air with the oxygen-enriched concentration of 60% -85%, and can be oxygen, air or other gases for providing oxygen. The coke or anthracite is not limited to this, and may be a reducing agent such as lump coal, semi-coke, or graphite powder. The gypsum slag is a vulcanizing agent. When the amount of the melt in the furnace is large, the buffer property is high, and the adjustment is needed, the ratio of the reducing agent in the lower batch material can be adjusted.
In this example, the furnace operating temperature is 1150-1450 ℃, and slag (i.e., reduced sulfidation slag), lead bullion, copper matte, flue gas and smoke dust are finally produced. The slag adopts Fe-SiO 2 CaO slag type, fe/SiO in the slag 2 CaO 1-2: 2: 0.5-1, controlling the thickness of slag layer at 300-800 mm, the slag content Cu at 1250-1450 deg.C. The Cu content of the copper matte is 40-75%, the S content is 12-25%, and the temperature of the copper matte is 1150-1300 ℃. The Pb content of the crude lead is 90-97%, and the temperature of the crude lead is 900-1000 ℃. The smoke dust rich in lead and zinc contains 20-50% of Pb and 10-20% of Zn, and can be used as a product for sale. The flue gas can be cooled, collected into dust and sent to a desulfurization process, the temperature of the flue gas is 1300-1350 ℃, the flue gas is in weak reducing atmosphere, and the flue gas is subjected to secondary combustion at the top of a hearth.
Further, after the reaction, discharging the crude lead from a crude lead discharge port, and casting the crude lead into crude lead ingots for sale; copper matte is discharged from a copper matte discharge port, and returns to a copper smelting system after granulating or casting; discharging the slag from a slag discharge port, and sending the slag to a mineral dressing or depletion furnace for further treatment, or after granulating, selling or discarding the slag; cooling the flue gas by a waste heat boiler, removing dust by an electric dust collector, and then delivering the flue gas to desulfurization treatment; and (5) packaging and selling smoke dust.
In this embodiment, the gypsum slag alone is used as the vulcanizing agent, but the vulcanizing agent is not limited to this, and one or more of the high sulfur materials such as the gypsum slag, the pyrite and the like can be used as the vulcanizing agent, for example, when the sulfur content of the gypsum slag is insufficient, the high sulfur material can be supplemented to supplement the sulfur content of the gypsum slag so as to facilitate the subsequent vulcanization reaction. Further, the vulcanizing agent can be calculated according to the equivalent of sulfur element and slag type flux components required by reduction and vulcanization reaction, so that the blending proportion is determined.
According to the embodiment, through repeated tests on the steps of balling, crushing and the like, analysis on slag, feasibility study on vulcanizing agents, optimization on oxygen-enriched side-blown smelting gas injection parameters and technological condition parameters and the like, the preferred embodiment is finally obtained through repeated tests, copper and lead in copper smelting intermediate products are separated, copper matte copper content is greater than or equal to 40%, lead bullion is greater than or equal to 90%, and copper slag content is less than 2.5%.
The raw materials of the invention are blowing slag, refining slag, smoke dust and the like in the copper smelting industry, and the invention can be applied to copper dross in the lead smelting industry or lead-copper mixed materials and the like in other industries.
The invention is further illustrated by the following examples:
example 1
The vulcanizing agent is gypsum slag, and the vulcanizing agent pellets are prepared by mixing the gypsum slag with 5% silicon-based bentonite and pressing the pellets. Smelting and treating the blowing slag by using an oxygen-enriched side-blown molten pool, wherein the ratio (mass parts) of the blowing slag to the vulcanizing agent pellets to the reducing agent anthracite is 100:35:8, blowing natural gas 25Nm by a spray gun in the furnace 3 /h, oxygen enriched air 50Nm 3 /h (oxygen concentration 70%). The temperature of slag in the furnace is controlled to 1250 ℃, the temperature of matte is controlled to 1250 ℃, and the temperature of lead bullion is controlled to 1150 ℃. The treatment scale is 100t/h of converting slag, 18t/h of copper matte is produced, the copper matte contains Cu=55%, pb=0.99% and S=21%; producing lead bullion 7t/h, wherein the lead bullion contains Pb=92% and Cu=3%; producing smoke dust with the concentration of Pb=38% and Zn=10% at 5 t/h; 84t/h of produced slag, fe/SiO 2 ＝0.9，CaO/SiO 2 =0.6, slag contains cu=1.52% and pb=1.19%.
Example 2
The vulcanizing agent is gypsum slag, and the vulcanizing agent pellets are prepared by mixing the gypsum slag with 8% silicon-based bentonite and pressing the pellets. Smelting and treating the blowing slag by using an oxygen-enriched side-blown molten pool, wherein the ratio (mass parts) of the blowing slag to the vulcanizing agent pellets to the reducing agent anthracite is 100:45:10, blowing natural gas 25Nm by a spray gun in the furnace 3 /h, oxygen enriched air 50Nm 3 /h (oxygen concentration 70%). The slag temperature in the furnace is controlled to 1350 ℃, the matte temperature is 1250 ℃, and the lead bullion temperature is controlled to 1150 ℃. The treatment scale is 100t/h of converting slag, and 16t/h of copper matte is produced, wherein the copper matte contains Cu=65%, pb=3.53% and S=19.8%; producing lead bullion with Pb=92% and Cu=2% at 6.6 t/h; producing smoke dust with the concentration of Pb=57.74% and Zn=10% at 5 t/h; 86.87t/h of produced slag, fe/SiO 2 ＝0.9，CaO/SiO 2 =0.65, slag containing cu=0.52%, containingPb＝0.2％。
Example 3
The vulcanizing agent is gypsum slag and pyrite, wherein the equivalent mass ratio of the added sulfur of the gypsum slag and the pyrite is 1:1. Smelting and treating blowing slag and smoke dust by using an oxygen-enriched side-blown molten pool, wherein the mixture ratio (mass parts) of the blowing slag, gypsum slag mixture pellets (mixed pellets prepared by gypsum slag and smoke dust), pyrite and reductant anthracite is 100:38:10:8, blowing natural gas 25Nm by a spray gun in the furnace 3 /h, oxygen enriched air 50Nm 3 /h (oxygen concentration 70%). The slag temperature in the furnace is controlled to 1350 ℃, the matte temperature is 1250 ℃, and the lead bullion temperature is controlled to 1150 ℃. The treatment scale is 100t/h of converting slag, and 18.9t/h of copper matte is produced, wherein the copper matte contains Cu=55%, pb=2.94%, S=21% and Fe=13%; producing lead bullion with Pb=90% and Cu=3% at 6.8 t/h; 4.6t/h of produced smoke dust, wherein the smoke dust contains Pb= 62.45% and Zn=11%; producing slag 69t/h, fe/SiO 2 ＝0.9～1，CaO/SiO 2 =0.5, slag contains cu=0.5% and pb=0.74%.
The description of the present invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
Claims (7)
1. A recycling harmless treatment method for intermediate products containing lead and zinc in copper smelting is characterized in that the intermediate products containing lead and zinc comprise one or more of blowing slag, refining slag and smoke dust; the vulcanizing agent is one or more of gypsum slag and pyrite; the method comprises the following steps:
collecting gypsum slag produced in a desulfurization working section, collecting smoke dust, mixing the smoke dust after metering with the gypsum slag in a mixing cylinder, bonding the smoke dust by utilizing the moisture of the gypsum slag, and pressing the smoke dust into balls by adopting a ball making process to obtain mixed balls; the granularity of the mixed pellets is 10 mm-30 mm;
mixing blowing slag and/or refining slag which are produced in the copper smelting process and crushed to 5-25 mm, the mixed pellets and a reducing agent; reducing and vulcanizing in an oxygen-enriched side-blown smelting furnace at 1150-1450 deg.c and Fe-SiO 2 CaO slag type, fe/SiO in the slag 2 CaO is (1-2): 2: (0.5-1), controlling the thickness of the slag layer to be 300-800 mm, wherein the obtained product comprises crude lead, copper matte, smelting slag and smoke dust rich in lead and zinc; and the copper content of the smelting slag is 0.8-1%, and the slag temperature is 1250-1450 ℃; copper-sulfur copper content is 40-75%, S content is 12-25%, copper matte temperature is 1150-1300 ℃; lead content of the crude lead is 90-97%, and the temperature of the crude lead is 900-1000 ℃; the smoke rich in Pb and Zn contains Pb 20-50% and Zn 10-20%.
2. The method of claim 1, wherein the step of determining the position of the substrate comprises,
the reducing agent is one or more of coke, lump coal, semi-coke, graphite powder and anthracite;
the addition amount of the reducing agent is 5% -30% of the intermediate product containing lead and zinc.
3. The method of claim 1, wherein the step of determining the position of the substrate comprises,
the addition amount of the vulcanizing agent is 10% -48% of the intermediate product containing lead and zinc.
4. The method according to claim 1, wherein in the step of reducing and sulfidizing in the oxygen-enriched side-blown smelting furnace, the oxygen-enriched concentration is 40-85%.
5. The method as recited in claim 1, further comprising:
returning the copper matte to a copper smelting system;
after the crude lead is cast into ingots, the ingots are sold out;
the lead and zinc-enriched fumes are sold as products.
6. The method of claim 1, wherein the step of determining the position of the substrate comprises,
the product also comprises smoke, the temperature of the smoke is 1300-1350 ℃, and the smoke is subjected to secondary combustion at the top of the hearth.
7. The method of claim 1, further comprising adding a binder when the pellets are produced by a pelletizing process, wherein the binder is added in an amount of <10%.
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| GB925822A (en) * | 1961-04-26 | 1963-05-08 | Nat Smelting Co Ltd | Recovery of copper compounds from lead bullion or low grade drosses |
| RU2114200C1 (en) * | 1996-12-03 | 1998-06-27 | Институт металлургии Уральского отделения РАН | Method for processing lead wastes containing antimony, tin and copper |
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| CN103695650B (en) * | 2013-12-25 | 2016-02-10 | 永州福嘉有色金属有限公司 | A kind of melting waste lead accumulator is containing the method for lead plaster mud |
| CN104404259B (en) * | 2014-11-16 | 2017-01-04 | 中南大学 | The method that Cu, Ni and Co metallurgical slag reclaims valuable metal with gypsum tailings cooperative disposal |
| CN105039701B (en) * | 2015-06-29 | 2017-10-10 | 郴州市金贵银业股份有限公司 | A kind of complicated zinc-rich lead-containing material processing method |
| CN107354299B (en) * | 2017-05-23 | 2019-05-17 | 甘肃中色东方工贸有限公司 | The recoverying and utilizing method of Cu, Pb, Zn, Fe in metal smelt process slag |
| CN109517999A (en) * | 2018-12-05 | 2019-03-26 | 湖南锐异资环科技有限公司 | Side-blowing smelting method for secondary lead-containing material |
| CN109811143A (en) * | 2019-01-08 | 2019-05-28 | 河套学院 | A kind of method of nickel sludge, rich scum, cullet and gypsum tailings cooperative disposal |
| CN110983029B (en) * | 2019-11-18 | 2021-01-29 | 中南大学 | Method for carrying out synergistic vulcanization roasting on lead-zinc smelting slag and gypsum slag |
| CN113355525B (en) * | 2021-04-29 | 2022-07-29 | 中南大学 | Method for processing gold-containing waste residues by synergistic matching of copper smelting slag |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB925822A (en) * | 1961-04-26 | 1963-05-08 | Nat Smelting Co Ltd | Recovery of copper compounds from lead bullion or low grade drosses |
| RU2114200C1 (en) * | 1996-12-03 | 1998-06-27 | Институт металлургии Уральского отделения РАН | Method for processing lead wastes containing antimony, tin and copper |
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