CN114381606A

CN114381606A - Recycling harmless treatment method for copper smelting lead-and zinc-containing intermediate product

Info

Publication number: CN114381606A
Application number: CN202111457588.XA
Authority: CN
Inventors: 陆金忠; 南君芳; 李海春; 张恩华; 祁永峰; 任焱辉; 潘璐; 杜武钊; 李晓霞; 杨宏伟; 曾璐; 张宏斌; 薛红伟
Original assignee: Guotou Jincheng Metallurgical Co ltd; China ENFI Engineering Corp
Current assignee: Guotou Jincheng Metallurgical Co ltd; China ENFI Engineering Corp
Priority date: 2021-12-01
Filing date: 2021-12-01
Publication date: 2022-04-22
Anticipated expiration: 2041-12-01
Also published as: CN114381606B

Abstract

The invention discloses a recycling harmless treatment method for copper smelting lead-and zinc-containing intermediate products. The method comprises the following steps: mixing an intermediate product containing lead and zinc produced in the copper smelting process with a vulcanizing agent, adding a reducing agent, and blending, wherein the intermediate product containing lead and zinc comprises one or more of blowing slag, refining slag and smoke dust, and the vulcanizing agent comprises one or more of gypsum slag and pyrite; reducing and vulcanizing in an oxygen-enriched side-blown smelting furnace to obtain products including crude lead, copper matte, smelting slag and smoke rich in lead and zinc. The invention solves the problems of high copper content of tailings, low ore dressing recovery rate and hazardous waste generation caused by returning the intermediate product to the smelting furnace, improves the recovery rate of valuable metals, and effectively treats hazardous waste such as smoke dust, gypsum slag and the like.

Description

Recycling harmless treatment method for copper smelting lead-and zinc-containing intermediate product

Technical Field

The invention relates to the technical field of copper smelting, in particular to a recycling harmless treatment method for lead and zinc-containing intermediate products in copper smelting.

Background

At present, a pyrometallurgical process of 'matte making smelting-copper matte blowing-anode refining' is mostly adopted for copper smelting, and intermediate products such as blowing slag, refining slag, smoke dust and the like generated in the process of the pyrometallurgical process are usually treated by returning to a smelting furnace, but the treatment method has many problems.

The problems of the prior pyrometallurgical process are described in several respects below.

1) When the conventional copper concentrate is treated by the pyrometallurgical process, intermediate materials with high Cu content, such as blowing slag, refining slag, smoke dust and the like, are returned to the smelting furnace so as to further recover Cu. Firstly, when copper concentrate containing high impurities is treated, Pb and the like can be enriched in a production system, so that the circulation 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, the blowing slag, the smoke dust and the like return to the smelting furnace and can absorb heat; under the condition that coal is not used as a reducing agent, the blowing slag and the smoke dust generally float on the surface of the smelting slag in a lump shape and are difficult to completely participate in the reaction; more Cu in the melt can be entrained due to incomplete smelting slagging reaction. In addition, because the intermediate materials are not completely reacted, the bulk forms are more, the content of entrained metal is higher, the oxide forms exist in the smelting slag mainly, the mineral separation recovery rate is low, the Cu content in the tailings is increased finally, and the overall Cu recovery rate is reduced.

In the process of pyrometallurgy, lead in high-lead copper concentrate is enriched in converting slag, refining slag and smoke dust, a large amount of high-lead converting slag, high-lead refining slag and high-lead zinc smoke dust are produced, and after the high-lead copper concentrate returns to a smelting furnace, the high-lead converting slag and the high-lead zinc smoke dust float on the surface of the smelting slag and are difficult to completely participate in reaction. 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 improved, and the carbon consumption and carbon emission indexes are increased; b) valuable metals of lead and zinc cannot be recovered. c) The problem that the quality of the product is affected by the enrichment of Pb in the system cannot be solved.

2) The smoke dust in the copper smelting process is mainly a mixture of smoke dust produced in the smelting process and the blowing process, the chemical composition of the smoke dust is complex, and the smoke dust generally contains various valuable metals such As Cu, Pb, Zn, Fe, As and the like. The main harmful elements in the smoke dust are lead, arsenic and the like, and the lead, the arsenic and the like are continuously enriched when returning to a smelting system, so that the normal production and the product quality of an acid making and electrolyzing system are influenced for a long time. Because the smoke dust belongs to dangerous waste, the smoke dust amount is accumulated year by year, the occupied area is large, the overstocked capital is large, enterprises face little pressure, and some of the accumulated smoke dust become important links restricting the production of the enterprises. At present, no relatively mature and reliable process technology exists for treating the smoke dust, and the process technology is a great problem to be solved urgently in the copper smelting industry. The smoke dust of each copper smelting plant is either stored in a pile or returned to the system or sold to qualified enterprises for treatment.

Aiming at the treatment of the smoke dust, only individual copper smelting enterprises have own treatment systems at present, and wet treatment processes are adopted, the specific flow is that the smoke dust is subjected to operation procedures of first-stage water leaching, second-stage acid leaching, copper removal by scrap iron, iron and arsenic removal, cadmium removal, zinc sulfate crystallization and the like, and valuable metals are respectively recycled in the forms of sponge copper, electrolytic lead, zinc sulfate and the like. In addition, the smoke dust treatment system adopts a flow of smoke dust two-stage leaching, leaching slag enters a blast furnace to be smelted to obtain crude lead, and then refined lead is obtained through electrolysis; and (3) firstly electrodepositing the leaching solution to remove copper, returning the electrodeposited copper to smelting, evaporating and crystallizing the decoppered solution to obtain crude zinc sulfate, and reducing and depositing arsenic in the crystallized mother solution by using sulfur dioxide to obtain arsenic trioxide. Although the two methods treat the smoke dust, the decoppering cost of the electrode of the leachate is high, secondary hazardous wastes such as arsenic slag, lead filter cakes and the like can be generated, the treatment process is complex, and the disposal cost is high.

3) The gypsum slag in the copper smelting process is a product obtained by using lime method to desulfurize, and the main component of the gypsum slag is calcium sulfate (CaSO)₄·2H₂O), in addition, the heavy metal elements belong to dangerous solid wastes, and if the hazardous solid wastes cannot be effectively treated, secondary pollution is caused to the environment and resources, mainly the pollution to soil, underground water resources and the like. The output of the gypsum slag in the copper smelting industry is very large, and the gypsum slag is urgently required to be subjected to harmless or recycling treatment, so that the significance is great.

Aiming at the problem of the dangerous waste gypsum slag, the current domestic main method for treating the desulfurized gypsum slag comprises the following steps: stacking, 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 stockpiled slag yards and has quite large subsequent maintenance difficulty; the cement solidification can reduce the toxicity leaching of the waste residues to the range meeting the national toxicity leaching requirement, but the volume-increasing ratio is large, and the treated residues can not realize resource utilization; the adaptability of the agent curing is poor at present, experimental work is only carried out in a laboratory aiming at partial raw materials, and industrial application cannot be realized at present. Therefore, the development of a new treatment process for recycling desulfurized gypsum residues is urgently needed. The desulfurized gypsum slag contains a small amount of heavy metal elements, and the method cannot realize the purposes of harmlessness, reduction and recycling.

4) The existing process can not recover valuable metals Pb and Zn in copper concentrate, Pb and Zn can only be discarded together with tailings, and the maximization of metal resource recovery cannot be realized. The problem is more prominent particularly for high Pb, Zn copper concentrate.

In view of the above problems of valuable metal recovery, although some early-stage process researches are carried out in the recovery of Pb and Zn in copper smelting enterprises at present, no successful application cases exist, and therefore, the process for recovering valuable metals Pb and Zn from copper slag needs to be developed urgently.

In summary, the prior art has at least the following problems:

1) the blowing slag with high Pb and the smoke dust with high Pb and Zn return to the smelting furnace and float on the surface of the melting slag in a bulk shape, so that the blowing slag with high Pb and the smoke dust with high Pb and Zn hardly participate in the reaction completely.

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, more Cu in the melt can be carried, and the Cu content of the smelting slag is increased.

3) The smelting slag contains high Cu content, metals in the unreacted intermediate products mainly exist as oxides, and the mineral separation 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) The smoke dust in the copper smelting process belongs to dangerous waste, the treatment process is immature, and qualified enterprises are generally entrusted to carry out treatment.

5) Impurities such as Pb are enriched in the system, which affects the product quality of each process and increases the production cost.

6) The gypsum slag in the copper smelting process belongs to hazardous waste, has large storage capacity and is urgently required to be subjected to harmless or recycling treatment.

7) The existing process can not recover valuable metals Pb and Zn in the copper concentrate, can only be discarded along with tailings, and can not realize the maximum recovery of metal resources.

Disclosure of Invention

Aiming at the problems, the invention aims to provide a recycling harmless treatment method for copper smelting lead-and zinc-containing intermediate products, so as to be beneficial to the copper smelting, reduce the copper content of tailings, effectively treat hazardous wastes, avoid the generation of secondary hazardous wastes, improve the recovery rate of valuable metals and improve the economic benefit.

The above purpose of the invention is realized by the following technical scheme:

according to one aspect of the invention, the invention provides a recycling harmless treatment method for lead and zinc-containing intermediate products in copper smelting, which comprises the following steps:

mixing an intermediate product containing lead and zinc produced in the copper smelting process with a vulcanizing agent, adding a reducing agent, and blending; wherein the intermediate product containing lead and zinc comprises one or more of materials such as blowing slag, refining slag, smoke dust and the like; the vulcanizing agent comprises one or more of gypsum slag, pyrite and other high-sulfur materials;

reducing and vulcanizing in an oxygen-enriched side-blown smelting furnace to obtain products including crude lead, copper matte, smelting slag and smoke 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 the following steps: a pre-crushing step; wherein the blowing slag is pre-crushed to 5-25 mm, and the refining slag is pre-crushed to 5-25 mm.

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 the following steps: preparing the pellets by adopting a pellet making process. When the intermediate product containing lead and zinc does not contain smoke dust, preparing a vulcanizing agent pellet from a vulcanizing agent, and mixing the vulcanizing agent pellet with the crushed intermediate product containing lead and zinc. When the intermediate product containing lead and zinc contains smoke dust, respectively preparing a vulcanizing agent pellet and a smoke dust pellet from the vulcanizing agent and the smoke dust or mixing the vulcanizing agent and the smoke dust to prepare a mixed pellet, and mixing the mixed pellet with the intermediate product containing lead and zinc after crushing except the smoke dust.

Optionally, the reducing agent is one or more of coke, lump coal, semi coke, graphite powder and anthracite. The proportion 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 the intermediate material). Optionally, in the step of reduction and vulcanization 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 includes: returning the copper matte to a copper smelting system; casting the crude lead into ingots and selling the ingots; and selling the smoke rich in lead and zinc as a product.

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 lead and zinc-rich smoke contains 20-50% of Pb and 10-20% of Zn.

Optionally, in the method, Fe-SiO is adopted₂CaO slag type, Fe/SiO in slag₂CaO is (1-2): 2: (0.5-1), controlling the thickness of a slag layer to be 300-800 mm, and controlling the Cu content of the slag to be 0.8-2.5%.

Optionally, the product further 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 pellet preparation process, a binder is added, wherein the addition amount of the binder is less than 10%.

The invention relates to a resource harmless treatment method of lead and zinc-containing intermediate products in copper smelting, which mixes the intermediate products produced in the smelting process, such as blowing slag, refining slag, smoke dust and the like, with vulcanizing agents such as gypsum slag and the like, adds a proper amount of reducing agent, completes two processes of reduction and vulcanization in one reduction vulcanizing furnace, such as an oxygen-enriched side-blowing smelting furnace, and directly produces two valuable products of crude lead and copper matte, smoke dust rich in lead and zinc and the like. The method is more beneficial to the copper smelting, reduces the copper content of the tailings, effectively treats the hazardous waste, avoids the generation of secondary hazardous waste, improves the recovery rate of valuable metals and improves the economic benefit. The method realizes the separation of copper and lead in the copper smelting intermediate product, 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 percent, the lead content of the crude lead is more than or equal to 90 percent, and the copper content of the slag is less than 2.5 percent.

Further, the crude lead produced by the method can be sold after ingot casting, the copper matte is returned to a copper smelting system, and the smoke rich in lead and zinc can be sold as a product. The tailings produced by the method belong to general solid wastes, can be further processed, such as ore dressing or deep reduction and depletion, and the like, so as to recover valuable metals such as copper, lead and the like in the tailings, and can also be directly sold or dumped after being granulated.

Compared with the prior art, the invention has the following advantages and beneficial effects:

1) the method adopts the hazardous waste gypsum slag as the vulcanizing agent, can produce copper matte, and saves the disposal cost of the hazardous waste.

2) The method can be used for treating the high-Pb blowing slag, such as blowing slag containing 5-30% of Pb, and avoid the increase of Cu content in the smelting slag caused by returning the blowing slag to the smelting furnace.

3) The method can treat the high Pb smoke dust, such as the smoke dust with Pb content more than or equal to 10 percent, and avoid the increase of Cu content in the tailings caused by the return of the high Pb smoke dust to the smelting furnace.

4) By adopting the method, the high-Pb smelting slag can be independently treated, and the ball milling difficulty of a subsequent ore dressing system caused by the formation of the bulk smelting slag is avoided.

5) By adopting the method, the high-Pb smoke dust can be independently treated, and the ball milling difficulty of a subsequent ore dressing system caused by the formation of the nodular smelting slag can be avoided.

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 chart of a recycling harmless treatment method for copper smelting lead-and zinc-containing intermediate products in one embodiment of the invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a resource harmless treatment method for copper smelting lead-and zinc-containing intermediate products, which mixes one or more intermediate products of lead-and zinc-containing blowing slag, refining slag, smoke dust and the like produced in the smelting process with a vulcanizing agent comprising gypsum slag, adds a reducing agent, carries out batching, completes two processes of reduction and vulcanization in one reduction vulcanizing furnace such as an oxygen-enriched side-blowing smelting furnace, and directly produces products comprising two valuable products of crude lead and copper matte, smelting slag, smoke dust and the like rich in lead and zinc. Wherein, the crude lead can be sold after ingot casting, the copper matte can be returned to a copper smelting system, and the smoke rich in lead and zinc can be sold as a product. The tailings produced by the invention, namely smelting slag or reduction and vulcanization slag, belongs to general solid wastes, can be further processed, such as ore dressing or deep reduction and depletion, and the like, so as to recover valuable metals such as copper, lead and the like in the tailings, and can also be directly sold or dumped. The method effectively treats the dangerous waste gypsum slag, avoids the problems that the copper content of the tailings is high, the copper smelting is not facilitated to be carried out and secondary dangerous waste is generated because the intermediate product returns to the smelting furnace, improves the recovery rate of valuable metals and improves the economic benefit.

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 recycling and harmlessly treating an intermediate product containing lead and zinc in copper smelting in an embodiment, wherein the intermediate product treated in the embodiment comprises blowing slag, refining slag and smoke dust. As shown in fig. 1, the method for recycling and harmless treatment of an intermediate product containing arsenic and lead in copper smelting provided by this embodiment includes:

collecting smoke dust, conveying the smoke dust to a smoke dust receiving bin through pneumatic conveying, and feeding the smoke dust into a mixing barrel after metering; collecting gypsum slag produced in a desulfurization working section, conveying the gypsum slag to a gypsum slag bin, and feeding the gypsum slag into a mixing barrel after metering; the smoke dust and the gypsum slag are fully mixed in the mixing cylinder, the moisture of the gypsum slag is fully utilized to bond the smoke dust, and finally the mixed material is sent into a ball press to be pressed into balls, so that the mixed balls are obtained, wherein the granularity can be 10-30 mm. The gypsum residue produced in the desulfurization working section can be subjected to filter pressing and dehydration, so that the residual moisture of the gypsum residue can bind the smoke dust. Optionally, a small amount of binder, such as silicon bentonite, is also added appropriately according to the spherical condition, and the addition amount of the binder is less than 10%.

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, conveying the crushed blowing slag and the crushed refining slag to corresponding storage bins for temporary storage, wherein a quantifying device is arranged at an outlet of each storage bin.

The reducing agent is transported in a bulk material mode, is self-unloaded into a raw material bin for storage, is loaded into an intermediate bin through a loader, and is metered through a vibrating feeder and a constant feeder. Wherein, the reducing agent can be coke or anthracite, and certainly can also be reducing agents such as lump coal, semi coke, graphite powder and the like.

The mixed pellets, the crushed converting slag, the crushed refining slag and the reducing agent are mixed according to a set proportion and then are added into a reduction vulcanizing furnace for reduction and vulcanization from the top of the furnace through a belt conveyor, the reduction vulcanizing furnace can be an oxygen-enriched side-blown smelting furnace, the oxygen-enriched side-blown smelting furnace can comprise a furnace body, an oxygen-enriched side-blown smelting bath, a spray gun and the like, and a crude lead discharge port, a copper matte discharge port and a slag discharge port are arranged on the furnace body. Wherein, optionally, the ratio of the vulcanizing agent can be 10-48% (relative to the intermediate material), and the ratio of the reducing agent can be 5-30% (relative to the intermediate material), and the ratio 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 the spray gun, and all materials are subjected to reduction and vulcanization reaction rapidly in the furnace. The natural gas is not limited to this, and may be fuel such as heavy oil, diesel oil, and pulverized coal. The oxygen-enriched air can be oxygen-enriched air with oxygen-enriched concentration of 60% -85%, and can be oxygen, air and other gases for providing oxygen. Coke or anthracite is used as the reducing agent, but the reducing agent is not limited thereto, and may be lump coal, semi coke, graphite powder, or the like. The gypsum residue is a vulcanizing agent. When the quantity of the melt in the furnace is large, the buffer property is high, and the adjustment is needed, the proportion of the reducing agent in the next batch of ingredients can be adjusted.

In the embodiment, the operation temperature in the furnace is 1150-1450 ℃, and slag (namely reduction and vulcanization slag), crude lead, copper matte, flue gas and smoke dust are finally produced. The furnace slag adopts Fe-SiO₂CaO slag type, Fe/SiO in slag₂CaO is 1-2: 2: 0.5-1, controlling the thickness of the slag layer to be 300-800 mm, controlling the slag layer to contain 0.8-1% of Cu, and controlling the slag temperature to be 1250-1450 ℃. The copper matte contains 40-75% of Cu and 12-25% of S, 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 lead and zinc-rich smoke dust contains 20-50% of Pb and 10-20% of Zn, and the smoke dust can be sold as a product. The flue gas can be cooled, collected dust and sent to a desulfurization process, the temperature of the flue gas is 1300-1350 ℃, the flue gas is in a weak reducing atmosphere, and the flue gas is subjected to secondary combustion at the top of a hearth.

Further, after reaction, discharging crude lead from a crude lead discharge port, and casting the crude lead into crude lead ingots for sale; the copper matte is discharged from a copper matte discharge port and returns to a copper smelting system after being granulated or cast; the slag is discharged from a slag discharge port and sent to a mineral separation or depletion furnace for further treatment, or is granulated and sold or discarded; cooling the flue gas by a waste heat boiler, dedusting by an electric dust collector and then desulfurizing; packaging the smoke dust for sale.

In this embodiment, a single gypsum residue is used as the vulcanizing agent, but not limited thereto, and one or more mixtures of gypsum residue, pyrite and other high-sulfur materials may also be used as the vulcanizing agent, for example, when the sulfur content in the gypsum residue is insufficient, the high-sulfur material may be additionally added to supplement the sulfur content in the gypsum residue, so as to facilitate the subsequent vulcanization reaction. Further, the vulcanizing agent can be calculated according to the sulfur element equivalent required by reduction and vulcanization reaction and the slag type flux component, so as to determine the blending proportion.

In the embodiment, the better embodiment is finally obtained by repeatedly testing the steps of balling, crushing and the like, analyzing the slag type, researching the feasibility of the vulcanizing agent, optimizing the blowing parameters and the technological condition parameters of the oxygen-enriched side-blown smelting gas and the like, and the copper and lead in the copper smelting intermediate product are separated, wherein 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%.

It should be noted that the raw materials of the invention are the blowing slag, refining slag, smoke dust and the like in the copper smelting industry, and of course, the invention can also 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 specific examples:

example 1

The vulcanizing agent is gypsum slag, and the vulcanizing agent pellet is prepared by mixing the gypsum slag with 5 percent of silicon bentonite pressed pellets. Smelting and treating the blowing slag by using an oxygen-enriched side-blown molten pool, wherein the ratio (in parts by mass) of the blowing slag, the vulcanizing agent pellets and the reducing agent anthracite is 100: 35: 8, blowing natural gas into the furnace by a spray gun at 25Nm³Per, oxygen-enriched air 50Nm³H (70% oxygen). The temperature of slag in the furnace is controlled to be 1250 ℃, the temperature of copper matte is controlled to be 1250 ℃, and the temperature of lead bullion is controlled to be 1150 ℃. The treatment scale is 100t/h of converting slag, 18t/h of copper matte is produced, the Cu content of the copper matte is 55%, the Pb content is 0.99% and the S content is 21%; 7t/h of crude lead is produced, the Pb content of the crude lead is 92%, and the Cu content of the crude lead is 3%; 5t/h of smoke dust is produced, wherein the content of Pb in the smoke dust is 38 percent, and the content of Zn in the smoke dust is 10 percent; producing 84t/h of slag, Fe/SiO₂＝0.9，CaO/SiO₂The slag contained 1.52% of Cu and 1.19% of Pb, respectively, at 0.6.

Example 2

The vulcanizing agent is gypsum slag, and the vulcanizing agent pellets are prepared by mixing the gypsum slag with 8 percent of silicon bentonite press pellets. Smelting and treating the blowing slag by using an oxygen-enriched side-blown molten pool, wherein the ratio (in parts by mass) of the blowing slag, the vulcanizing agent pellets and the reducing agent anthracite is 100: 45: 10, the natural gas is blown into the furnace by a spray gun at 25Nm³Per, oxygen-enriched air 50Nm³H (70% oxygen). The temperature of slag in the furnace is controlled to 1350 ℃, the temperature of copper matte is controlled to 1250 ℃, and the temperature of lead bullion is controlled to 1150 ℃. The treatment scale is 100t/h of converting slag, 16t/h of copper matte is produced, the Cu content of the copper matte is 65%, the Pb content is 3.53%, and the S content is 19.8%; 6.6t/h of crude lead is produced, the lead content of the crude lead is 92 percent, and the lead content of the crude lead is 2 percent; 5t/h of smoke dust is produced, wherein the content of Pb in the smoke dust is 57.74 percent, and the content of Zn in the smoke dust is 10 percent; produce 86.87t/h, Fe/SiO slag₂＝0.9，CaO/SiO₂The slag contained 0.52% of Cu and 0.2% of Pb, respectively.

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. And (2) smelting the blowing slag and the smoke dust by using an oxygen-enriched side-blown molten pool, wherein the ratio (in parts by mass) of the blowing slag, gypsum slag mixed pellets (mixed pellets prepared from gypsum slag and smoke dust), pyrite and reducer anthracite is 100: 38: 10: 8, blowing natural gas into the furnace by a spray gun at 25Nm³Per, oxygen-enriched air 50Nm³H (70% oxygen). The temperature of slag in the furnace is controlled to 1350 ℃, the temperature of copper matte is controlled to 1250 ℃, and the temperature of lead bullion is controlled to 1150 ℃. The treatment scale is 100t/h of converting slag, 18.9t/h of copper matte is produced, the Cu content of the copper matte is 55%, the Pb content is 2.94%, the S content is 21% and the Fe content is 13%; 6.8t/h of crude lead is produced, the Pb content of the crude lead is 90 percent, and the Cu content of the crude lead is 3 percent; 4.6t/h of smoke dust is produced, the content of Pb in the smoke dust is 62.45%, and the content of Zn in the smoke dust is 11%; producing 69t/h, Fe/SiO of slag₂＝0.9～1，CaO/SiO₂The slag contains 0.5% of Cu and 0.74% of Pb.

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 practitioners skilled in this art. The embodiment was 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

1. A recycling harmless treatment method for copper smelting lead-and zinc-containing intermediate products is characterized by comprising the following steps:

mixing an intermediate product containing lead and zinc produced in the copper smelting process with a vulcanizing agent, adding a reducing agent, and blending; wherein the intermediate product containing lead and zinc comprises one or more of blowing slag, refining slag and smoke dust; the vulcanizing agent comprises one or more of gypsum slag and pyrite;

2. The method according to claim 1, wherein before the step of mixing the intermediate product containing lead and zinc produced in the copper smelting process with a vulcanizing agent, the method further comprises: a pre-crushing step; wherein the blowing slag is pre-crushed to 5-25 mm, and the refining slag is pre-crushed to 5-25 mm.

3. The method of claim 2, wherein the step of mixing the intermediate product containing lead and zinc produced in the copper smelting process with a vulcanizing agent is preceded by the step of: preparing the pellets by adopting a pellet making process; wherein,

when the intermediate product containing lead and zinc does not contain smoke dust, preparing a vulcanizing agent pellet from a vulcanizing agent, and mixing the vulcanizing agent pellet with the crushed intermediate product containing lead and zinc;

when the intermediate product containing lead and zinc contains smoke dust, respectively preparing a vulcanizing agent pellet and a smoke dust pellet from the vulcanizing agent and the smoke dust or preparing a mixed pellet from the vulcanizing agent and the smoke dust by mixing, and mixing with the crushed intermediate product containing lead and zinc except the smoke dust.

4. The method of claim 1,

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 that of the lead-containing and zinc-containing intermediate product.

5. The method of claim 1,

the addition amount of the vulcanizing agent is 10-48% of that of the lead-containing and zinc-containing intermediate product.

6. The method as claimed in claim 1, wherein the reduction and sulfidation are carried out in an oxygen-enriched side-blown smelting furnace at a temperature of 1150 ℃ to 1450 ℃ and an oxygen-enriched concentration of 40% to 85%.

7. The method of claim 1, further comprising:

returning the copper matte to a copper smelting system;

casting the crude lead into ingots and selling the ingots;

and selling the smoke rich in lead and zinc as a product.

8. The method of claim 1,

the copper matte contains 40-75% of Cu and 12-25% of S, 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 lead and zinc-rich smoke dust contains 20-50% of Pb and 10-20% of Zn.

9. The method of claim 1,

in the method, Fe-SiO is adopted₂CaO slag type, Fe/SiO in slag₂CaO is (1-2): 2: (0.5-1), controlling the thickness of a slag layer to be 300-800 mm, and controlling the Cu content of the slag to be 0.8-2.5%;

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.

10. The method of claim 3, wherein the pellet preparation process further comprises adding a binder, wherein the binder is added in an amount of less than 10%.