Method for recovering copper from high-arsenic matte and enriching arsenic and lead
By mixing high-arsenic matte with quartz sand, heating and smelting, and then removing arsenic, the problems of resource waste and arsenic pollution in high-arsenic matte smelting were solved. This enabled the effective recovery and classified utilization of copper, arsenic, and lead, and improved production safety.
Patent Information
- Application Number
- CN202511627250.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-07
- Publication Date
- 2026-01-16
AI Technical Summary
The current technology for treating high-arsenic matte leads to the waste of copper smelting resources and the entry of harmful arsenic into subsequent processing equipment, increasing production risks, and cannot effectively recover valuable metals such as copper, arsenic and lead.
High-arsenic matte was mixed with quartz sand and heated in a smelting furnace. Oxidation and stirring were carried out by introducing natural gas, oxygen and air. Limestone was added to remove arsenic. The temperature was controlled to 950℃. The product was then separated into copper liquid and mixed slag for separate treatment.
It enables the effective recovery of copper, arsenic, and lead, avoids resource waste, reduces the entry of arsenic into subsequent equipment, improves production safety, and achieves the classified recovery and enrichment of valuable metals.
Smart Images
Figure CN121344370A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of metallurgy, in particular to a method for recovering copper and enriching arsenic and lead from high-arsenic copper matte. BACKGROUND
[0002] Copper dross is the product of copper removal by fire method before refining of crude lead. Lead smelting enterprises usually process copper dross to produce copper matte which is sold to copper smelting enterprises to produce pure copper. High-arsenic copper matte refers to the copper matte with high arsenic content.
[0003] For high-arsenic copper matte, when recovered by a copper smelting enterprise, the high-arsenic copper matte is usually directly incorporated into the copper matte smelting line for blowing. However, the copper in the high-arsenic copper matte is high-quality elemental copper and cuprous oxide. Reclaiming the high-arsenic copper matte in the original refining line not only wastes energy due to repeated smelting, but also causes harmful arsenic to enter subsequent treatment equipment with flue gas, which cannot be disposed of specifically and further aggravates the production risk. SUMMARY
[0004] In view of the above problems in the prior art, the present application provides a method for recovering copper and enriching arsenic and lead from high-arsenic copper matte. The method can effectively recover copper, arsenic and lead in high-arsenic copper matte, avoid waste of smelting resources, reduce the entry of harmful arsenic into subsequent treatment equipment, and improve production safety.
[0005] In addition, the present application also provides a performance test method for cement clinker.
[0006] To solve the above technical problems, the present application adopts the following technical solutions:
[0007] A method for recovering copper and enriching arsenic and lead from high-arsenic copper matte, comprising the following steps:
[0008] Step 1) mixing high-arsenic copper matte and quartz sand according to a first set ratio, and then adding them into a smelting furnace;
[0009] Step 2) continuously introducing natural gas and oxygen into the smelting furnace to perform heating and smelting reaction, and continuously blowing air into the smelting furnace to oxidize and stir the materials in the smelting furnace during the heating and smelting reaction, and discharging slag at a set time interval;
[0010] Step 3) after the slagging is completed, adding limestone to remove arsenic, and gradually increasing the temperature in the smelting furnace to 950 DEG C, maintaining the temperature of 950 DEG C in the smelting furnace until the content of arsenic in the materials is less than 1%, at which time the arsenic enters the flue gas to produce flue dust after dust collection;
[0011] Step 4) discharging the copper liquid produced in the above step through a copper channel to form crude copper, and sending the crude copper to an anode furnace for casting plate for electrolysis; the mixed slag produced in the above step is sent to a lead smelting system for treatment, and the flue dust rich in arsenic is sent to an arsenic treatment system for treatment.
[0012] Preferably, step 1) fully mixes the high-arsenic copper concentrate and quartz sand in a first set ratio and then adds them into the smelting furnace, including:
[0013] The amount of quartz sand is 12% to 24% of the amount of high-arsenic copper concentrate.
[0014] Preferably, step 1) fully mixes the high-arsenic copper concentrate and quartz sand in a first set ratio and then adds them into the smelting furnace, including:
[0015] The high-arsenic copper concentrate and quartz sand are continuously added into the smelting furnace, and the first amount of the high-arsenic copper concentrate and quartz sand is half of the total amount, and the remaining high-arsenic copper concentrate and quartz sand are added into the smelting furnace at a speed of 10% of the total amount per hour.
[0016] Preferably, step 1) fully mixes the high-arsenic copper concentrate and quartz sand in a first set ratio and then adds them into the smelting furnace, including:
[0017] The copper content in the high-arsenic copper concentrate is 25% to 35%, the lead content is 4% to 20%, the arsenic content is 5% to 25%, and the iron content is 20% to 40%.
[0018] Preferably, step 2) continuously introduces natural gas and oxygen into the smelting furnace to perform a heating and smelting reaction, and continuously blows air into the smelting furnace to oxidize and stir the materials in the smelting furnace during the heating and smelting reaction, and discharges slag once every set time, including:
[0019] During the heating and smelting reaction, the temperature in the smelting furnace is controlled to be 700°C to 900°C, and the ratio of the introduced natural gas and oxygen is 2.3-3:1.
[0020] Preferably, step 2) continuously introduces natural gas and oxygen into the smelting furnace to perform a heating and smelting reaction, and continuously blows air into the smelting furnace to oxidize and stir the materials in the smelting furnace during the heating and smelting reaction, and discharges slag once every set time, including:
[0021] During the heating and smelting reaction, the air flow is 300-400m 3 / s, and the flow rate of the air introduced into the smelting furnace is 30-40m / s.
[0022] Preferably, step 2) continuously introduces natural gas and oxygen into the smelting furnace to perform a heating and smelting reaction, and continuously blows air into the smelting furnace to oxidize and stir the materials in the smelting furnace during the heating and smelting reaction, and discharges slag once every set time, including:
[0023] During the heating smelting reaction process, air is introduced into the smelting furnace from the bottom and the top of the smelting furnace simultaneously, and the smelting furnace has two air introduction interfaces at the bottom and one air introduction interface at the top, the air introduction interface at the top is arranged at the middle position of the smelting furnace, and the two air introduction interfaces at the bottom are arranged at the two sides of the smelting furnace.
[0024] Preferably, after the slag is discharged in step 3), limestone is added to remove arsenic, and the smelting furnace is gradually heated to 950 DEG C at the same time, and the temperature in the smelting furnace is kept at 950 DEG C until the content of arsenic in the material is less than 1%, at which time the arsenic enters the flue gas and produces fly ash after dust collection, including:
[0025] The amount of limestone added is 8%-28% of the amount of high-arsenic matte.
[0026] Preferably, after the slag is discharged in step 3), limestone is added to remove arsenic, and the smelting furnace is gradually heated to 950 DEG C at the same time, and the temperature in the smelting furnace is kept at 950 DEG C until the content of arsenic in the material is less than 1%, at which time the arsenic enters the flue gas and produces fly ash after dust collection, including:
[0027] Nitrogen is continuously introduced into the smelting furnace, and the nitrogen introduction flow rate is 400-500 m 3 / s, and the flow rate of nitrogen introduced into the smelting furnace is 30-40 m / s.
[0028] Preferably, in step 4), the copper liquid produced in the above steps is discharged through a copper ladle to form crude copper, and the crude copper is sent to the anode furnace for electrolysis; the mixed slag produced in the above steps is sent to the lead smelting system for treatment, and the fly ash rich in arsenic is sent to the arsenic treatment system for treatment, including:
[0029] The content of copper in the crude copper is greater than 95%, and the content of arsenic in the fly ash is greater than 50%.
[0030] In the prior art, high-arsenic matte is generally processed into crude copper in the matte production line, and high-quality matte is processed into anode copper in the crude copper production line, but no matter which process it is integrated into, other valuable metals contained therein will either enter the slag or enter the fly ash, and cannot be recycled and utilized, and harmful arsenic entering the fly ash will reduce the quality of the fly ash, affecting the recycling of the fly ash, and the valuable metals entering the slag cannot be recycled and utilized. The method provided by the present application can be used for targeted recycling of high-arsenic matte treated in a lead smelting enterprise, so that lead, antimony, gold, silver and arsenic can be classified and recycled, realizing deep processing of high-arsenic matte and classified enrichment and extraction of valuable metal elements.
[0031] In addition, the method has the advantages of sulfur-free smelting, no related components of sulfur in the raw materials or addition of the components, no change in the form of sulfur, no generation of sulfur dioxide, and no need for desulfurization treatment in subsequent flue gas treatment. In the process of sulfur-free phase smelting, 85% of lead enters the mixed slag discharged, and 90% of arsenic and antimony enter the generated flue gas, so that classified recycling of various metal elements can be conveniently realized. BRIEF DESCRIPTION OF DRAWINGS
[0032] BRIEF DESCRIPTION OF DRAWINGS Figure 1 A flowchart of the method for recovering copper and enriching arsenic and lead from high-arsenic copper matte according to the present application. DETAILED DESCRIPTION
[0033] In order to make the objectives, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are some embodiments of the present application, rather than all the embodiments. The components of the embodiments of the present application described and shown in the drawings can be arranged and designed in various different configurations. Therefore, the following detailed description of the embodiments of the present application provided in the drawings is not intended to limit the scope of the claimed present application, but only represents selected embodiments of the present application. All other embodiments obtained by those of ordinary skill in the art without creative work based on the embodiments in the present application belong to the scope of protection of the present application.
[0034] It should be noted that the terms "first", "second", and the like in the specification and claims of the present application and the above drawings are used to distinguish similar objects, and do not necessarily have to describe a specific order or sequence. It should be understood that the data thus used can be interchanged under appropriate circumstances, so that the embodiments of the present application described herein can be implemented in an order other than those illustrated or described herein. In addition, the terms "include" and "have" and any variations thereof are intended to cover non-exclusive inclusion, for example, a process, method, system, product or device including a series of steps or units does not have to be limited to those steps or units clearly listed, but can include other steps or units not clearly listed or inherent to the process, method, product or device.
[0035] Furthermore, in describing representative embodiments, the specification can have presented the method and / or process as a particular sequence of steps. However, to the extent that the method or process depends on the particular order of steps, this description should not be construed as limiting since other steps can be performed in other sequences and / or omitted from the method or process. Other steps can also be added to the method and / or process. The particular sequence of steps described should not be construed as limiting. Furthermore, the steps recited in the description of the method and / or process should not be construed as being performed in the order presented, unless explicitly stated as such. Those skilled in the art will be able to recognize, and be able to determine using their own common general knowledge, substitution of steps / operations for one another, and suitable substitution and alteration are considered in the spirit and scope of the present disclosure.
[0036] In the specific embodiment, a method for recovering copper and enriching arsenic and lead from high-arsenic copper matte is proposed, as shown in the accompanying drawings, comprising the following steps: Figure 1
[0037] Step 1) Mix the high-arsenic copper matte and quartz sand in a first set ratio, and then add them into a smelting furnace. The high-arsenic copper matte is a kind of copper matte with high arsenic content. In the specific embodiment, the copper content of the high-arsenic copper matte used is 25% to 35%, the lead content is 4% to 20%, the arsenic content is 5% to 25%, and the iron content is 20% to 40%. The quartz sand is a common non-metallic mineral raw material, and its main component is silicon dioxide (SiO2). It is usually made of natural quartzite or quartzite after crushing, screening, washing and other processes.
[0038] For example, the amount of quartz sand is 12% to 24% of the amount of high-arsenic copper matte. In actual production, the amount of high-arsenic copper matte is generally 110 t to 130 t.
[0039] Specifically, when feeding, the high-arsenic copper matte and the quartz sand are continuously added into the smelting furnace, and the first feeding amount of the high-arsenic copper matte and the quartz sand is half of the total amount. In the specific embodiment, the first feeding amount of the high-arsenic copper matte is between 40 and 60 tons, and the remaining high-arsenic copper matte and quartz sand are added into the smelting furnace at a rate of 10% of the total amount per hour. This feeding method can make the high-arsenic copper matte and the quartz sand fully react, ensure the effect of the subsequent heating and smelting reaction, and thus ensure the effective extraction of each metal element in the final product.
[0040] Step 2) Continuously introduce natural gas and oxygen into the smelting furnace to perform the heating and smelting reaction, and continuously blow air into the smelting furnace to oxidize and stir the materials in the smelting furnace. The slag is discharged every set time during the heating and smelting reaction. In actual implementation, the slag can be discharged every 8 hours, or it can be adjusted adaptively according to the actual reaction of the materials in the smelting furnace, and the time is not fixed during the whole process.
[0041] Specifically, during the heating and smelting reaction, the temperature inside the smelting furnace is controlled at 700℃-900℃, and the ratio of natural gas to oxygen introduced is 2.3-3:1. For example, the natural gas flow rate is 400-500 m³ / h. 3 / h, oxygen flow rate is 200-250m³ / h. 3 / h. The ratio of natural gas to oxygen is set to ensure the reaction process of the heating and smelting reaction.
[0042] Specifically, during the heating and melting reaction, the air flow rate is 300-400 m³ / h. 3 The air flow rate is 30-40 m / s, and the air velocity entering the melting furnace is 30-40 m / s. Air is introduced to oxidize and agitate the material. The air flow rate setting ensures effective oxidation, while the air velocity setting allows the air to impact the material at a high speed, thus agitating it. This agitation ensures that the material at the bottom layer is also fully heated and melted, guaranteeing the overall processing effect.
[0043] More specifically, during the heating and smelting reaction, air is simultaneously introduced into the smelting furnace from both the bottom and the top. There are two air inlet ports at the bottom of the smelting furnace and one air inlet port at the top. The air inlet port at the top of the smelting furnace is located in the middle of the smelting furnace, while the two air inlet ports at the bottom of the smelting furnace are respectively arranged on both sides of the smelting furnace.
[0044] By setting two air inlets at the bottom of the smelting furnace on both sides and one air inlet at the top in the middle, when air is introduced, the air at the top exerts a force on the material from the middle, while the air at the bottom exerts a force on the material from both sides. This ensures that the material at both the bottom and sides of the smelting furnace is effectively impacted by the air. The material on the sides can move towards the middle under the air impact, and the material in the middle can also move to both sides. This ensures that the material in the smelting furnace is fully stirred, thereby ensuring that all materials in the smelting furnace can be effectively heated and smelted, thus improving the recovery of various metal elements in high-arsenic matte.
[0045] Step 3) After the slag is discharged, limestone is added to remove arsenic. At the same time, the temperature inside the smelting furnace is gradually increased to 950°C and maintained at 950°C until the arsenic content in the material is less than 1%. At this time, the arsenic enters the flue gas and is collected by dust collector to produce flue ash.
[0046] For example, the amount of limestone added is 8%-28% of the amount of high-arsenic copper matte. This ensures the effectiveness of arsenic removal using limestone.
[0047] Specifically, in this step, natural gas and oxygen are no longer introduced into the smelting furnace, but nitrogen is continuously introduced into the smelting furnace, so that the atmosphere in the smelting furnace is changed to a weakly oxidizing environment, and the flow rate of the nitrogen introduced into the smelting furnace is 400-500 m 3 / h, and the flow rate of the nitrogen introduced into the smelting furnace is 30-40 m / s. The flow rate of the nitrogen introduced is set so that the smelting furnace can quickly change to a weakly oxidizing environment, and the flow rate of the nitrogen introduced is set so that the nitrogen can play a stirring role on the material in the smelting furnace at this time, so as to ensure the uniformity of the material reaction in this stage of the reaction process. The weakly oxidizing environment is created by introducing nitrogen because, in a weakly oxidizing or reducing atmosphere, arsenic is difficult to be oxidized to a pentavalent state, but exists in the form of trivalent arsenic (As³⁺), thereby generating extremely volatile arsenic trioxide (As2O3), which has a sublimation point of about 193°C and will directly gasify at high temperatures and enter the flue gas, thereby enabling most of the arsenic to volatilize and enter the flue gas to form flue gas for recovery.
[0048] Step 4) The copper liquid generated in the above step is discharged through a copper tapping channel to form crude copper, and the crude copper is sent to a plate casting anode furnace for electrolysis; the mixed slag generated in the above step is sent to a lead smelting system for treatment, and the arsenic-rich soot is sent to an arsenic treatment system for treatment. The crude copper obtained by using the present scheme has a copper content of greater than 95%, the arsenic content in the soot is greater than 50%, and 85% of the lead is concentrated in the mixed slag, thereby concentrating most of the copper, lead, and arsenic in different forms of substances, achieving separate recovery of different metal elements, while avoiding waste of smelting resources and reducing the amount of harmful arsenic entering subsequent treatment equipment, thereby improving production safety.
[0049] Meanwhile, in the present embodiment, the quartz sand is added first and then the limestone is added, which can more effectively form copper liquid from copper, concentrate more than 85% of the lead in the mixed slag, and send more than 90% of the arsenic to the soot.
[0050] In the prior art, high-arsenic copper matte is generally processed into crude copper in a copper matte production line, and high-quality copper matte is processed into anode copper in a crude copper production line. However, no matter which process it is integrated into, other valuable metals contained therein will either enter the slag or enter the soot, and cannot be recycled and utilized. Harmful arsenic entering the soot will reduce the quality of the soot and affect the recycling of the soot, and valuable metals entering the slag cannot be recycled and utilized. The method proposed in the present application can be used to recycle and utilize high-arsenic copper matte processed in a lead smelting enterprise, so that lead, antimony, gold, silver, and arsenic can be classified and recycled for reuse, thereby achieving the purpose of deep processing of high-arsenic copper matte and classified enrichment and extraction of valuable metal elements.
[0051] In addition, the method has the advantages of sulfur-free smelting, no related components of sulfur in the raw materials or addition of the related components of sulfur, no change of the form of sulfur, no generation of sulfur dioxide, no need of desulfurization treatment in the subsequent flue gas treatment. In the process of the sulfur-free phase smelting, 85% of lead enters the discharged mixed slag, 90% of arsenic and antimony enter the generated flue gas, so that the classified recycling of various metal elements can be conveniently realized.
[0052] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit the technical solutions. Those of ordinary skill in the art should understand that modifications or equivalent replacements of the technical solutions of the present application without departing from the purpose and scope of the technical solutions should be covered in the scope of the claims of the present application.
Claims
1. A process for recovering copper and enriching arsenic and lead from high-arsenic copper matte, characterized in that, The method comprises the following steps: Step 1) adding high-arsenic copper and quartz sand into a smelting furnace after mixing them according to a first set ratio; Step 2) continuously feeding natural gas and oxygen into the smelting furnace to perform a heating smelting reaction, and continuously blowing air into the smelting furnace to oxidize and stir the materials in the smelting furnace during the heating smelting reaction, and discharging slag at a set time interval; Step 3) after the slagging is completed, adding limestone to remove arsenic, and gradually increasing the temperature in the smelting furnace to 950 DEG C, keeping the temperature in the smelting furnace at 950 DEG C until the arsenic content in the materials is less than 1%, at which time the arsenic enters the flue gas to produce fly ash after dust collection; Step 4) discharging the copper liquid produced in the above step through a copper channel to form crude copper, and sending the crude copper to an anode furnace for electrolysis; the mixed slag produced in the above step is sent to a lead smelting system for treatment, and the fly ash rich in arsenic is sent to an arsenic treatment system for treatment.
2. The process for recovery of copper and enrichment of arsenic and lead from high arsenic copper matte as claimed in claim 1 wherein, Step 1) adding high-arsenic copper and quartz sand into a smelting furnace after mixing them according to a first set ratio, comprising: The amount of quartz sand is 12% to 24% of the amount of high-arsenic copper.
3. The process for recovery of copper and enrichment of arsenic and lead from high arsenic copper matte as claimed in claim 2 wherein, Step 1) adding high-arsenic copper and quartz sand into a smelting furnace after mixing them according to a first set ratio, further comprising: The high-arsenic copper and the quartz sand are continuously added into the smelting furnace, and the first feeding amount of the high-arsenic copper and the quartz sand is half of the total amount, and the remaining high-arsenic copper and quartz sand are added into the smelting furnace at a speed of 10% of the total amount per hour.
4. The process for recovery of copper and enrichment of arsenic and lead from high arsenic copper concentrate as claimed in claim 1 wherein, Step 1) adding high-arsenic copper and quartz sand into a smelting furnace after mixing them according to a first set ratio; further comprising: The copper content in the high-arsenic copper is 25% to 35%, the lead content is 4% to 20%, the arsenic content is 5% to 25%, and the iron content is 20% to 40%.
5. The process as claimed in claim 1, wherein the copper is recovered from the high arsenic copper matte and the lead is enriched with arsenic. Step 2) continuously feeding natural gas and oxygen into the smelting furnace to perform a heating smelting reaction, and continuously blowing air into the smelting furnace to oxidize and stir the materials in the smelting furnace during the heating smelting reaction, and discharging slag at a set time interval, comprising: During the heating smelting reaction, the temperature in the smelting furnace is controlled to be 700 DEG C to 900 DEG C, and the ratio of the natural gas and the oxygen fed in is 2.3-3:
1.
6. The process for recovery of copper and enrichment of arsenic and lead from high arsenic copper concentrate as claimed in claim 1 wherein, Step 2) continuously feeding natural gas and oxygen into the smelting furnace to perform a heating smelting reaction, and continuously blowing air into the smelting furnace to oxidize and stir the materials in the smelting furnace during the heating smelting reaction, and discharging slag at a set time interval, further comprising: During the heating and smelting process, the air flow rate is 300-400 m 3 / s, and the air flow rate in the smelting furnace is 30-40 m / s.
7. The process as claimed in claim 6, wherein the copper is recovered from the high arsenic copper matte and the lead is enriched with arsenic. Step 2) continuously feeding natural gas and oxygen into the smelting furnace to perform a heating smelting reaction, and continuously blowing air into the smelting furnace to oxidize and stir the materials in the smelting furnace during the heating smelting reaction, and discharging slag at a set time interval, further comprising: During the heating smelting reaction, the air is fed into the smelting furnace from the bottom and the top of the smelting furnace at the same time, and the smelting furnace has two air feeding interfaces at the bottom and one air feeding interface at the top, the air feeding interface at the top is arranged at the middle position of the smelting furnace, and the two air feeding interfaces at the bottom are arranged at the two sides of the smelting furnace.
8. The process for recovery of copper and enrichment of arsenic and lead from high arsenic copper matte as claimed in claim 1 wherein, Step 3) After the slagging is finished, limestone is added to remove arsenic, and the smelting furnace is gradually heated to 950 DEG C. The temperature in the smelting furnace is kept at 950 DEG C until the arsenic content in the material is less than 1%, at which time the arsenic enters the flue gas and produces fly ash after dust collection, including: The amount of limestone added is 8%-28% of the amount of high-arsenic copper.
9. The process for recovery of copper and enrichment of arsenic and lead from high arsenic copper matte as claimed in claim 1 wherein, Step 3) After the slagging is finished, limestone is added to remove arsenic, and the smelting furnace is gradually heated to 950 DEG C. The temperature in the smelting furnace is kept at 950 DEG C until the arsenic content in the material is less than 1%, at which time the arsenic enters the flue gas and produces fly ash after dust collection, including: The nitrogen gas is continuously introduced into the smelting furnace at a flow rate of 400-500 m 3 / s, and the flow rate of the nitrogen gas introduced into the smelting furnace is 30-40 m / s.
10. The process for recovery of copper and enrichment of arsenic and lead from high arsenic copper concentrate as claimed in claim 1 wherein, Step 4) The copper liquid produced in the above steps is discharged through a copper ladle to form crude copper, which is sent to the anode furnace for electrolysis. The mixed slag produced in the above steps is sent to the lead smelting system for treatment, and the fly ash rich in arsenic is sent to the arsenic treatment system for treatment, including: The copper content in the crude copper is greater than 95%, and the arsenic content in the fly ash is greater than 50%.