CN111378844A - Method and system for treating copper-containing sludge - Google Patents

Method and system for treating copper-containing sludge Download PDF

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Publication number
CN111378844A
CN111378844A CN202010342861.3A CN202010342861A CN111378844A CN 111378844 A CN111378844 A CN 111378844A CN 202010342861 A CN202010342861 A CN 202010342861A CN 111378844 A CN111378844 A CN 111378844A
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copper
containing sludge
content
slag
flux
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王云
陈学刚
郭亚光
裴忠冶
祁永峰
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China ENFI Engineering Corp
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China ENFI Engineering Corp
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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
    • 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
    • C22B7/001—Dry processes
    • 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
    • C22B13/00—Obtaining lead
    • C22B13/02—Obtaining lead by dry processes
    • C22B13/025—Recovery from waste materials
    • 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
    • C22B15/0028—Smelting or converting
    • C22B15/0052—Reduction smelting or converting
    • 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
    • C22B15/0056—Scrap treating
    • 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • 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
    • C22B25/00—Obtaining tin
    • C22B25/02—Obtaining tin by dry processes
    • 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
    • C22B25/00—Obtaining tin
    • C22B25/06—Obtaining tin from scrap, especially tin scrap
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a method and a system for treating copper-containing sludge, wherein the method comprises the following steps: drying the copper-containing sludge to obtain dried copper-containing sludge and flue gas; and smelting the dried copper-containing sludge, copper slag, flux or iron tailings and reducing agent to obtain copper matte, tailings and high-temperature flue gas. The method fully utilizes the complementarity of the copper-containing sludge and the copper slag, remarkably reduces the usage amount of the flux and the reducing agent, simultaneously omits a vulcanizing agent, remarkably improves the dilution effect of the copper slag, realizes the resource recycling of various metals such as copper, nickel, lead, zinc, tin and the like in the copper-containing sludge and the copper slag, and also remarkably reduces the solid waste content.

Description

Method and system for treating copper-containing sludge
Technical Field
The invention belongs to the technical field of copper-containing sludge treatment, and particularly relates to a method and a system for treating copper-containing sludge.
Background
The copper-containing sludge after the electroplating process sewage treatment contains a large amount of valuable metal elements (such as copper, nickel, tin and the like), but the sludge produced by different processes has large difference of component types and contents. Generally, sludge with high copper content (10-20 wt%) can enter a blast furnace for reduction smelting after being dried and dehydrated and added with a certain amount of flux, the obtained products such as black copper, matte and the like can enter a main copper smelting process, the copper content of tailings is about 0.8 wt%, and the smelting slag is FeO-SiO2CaO is the main component. In the treatment of low CaSO4When the copper-containing sludge is prepared, only a small amount of flux is added to adjust the composition to obtain the target slag form, but sulfuric acid is usually used in the electroplating process and cheap lime is used for neutralization, so that the sludge generally contains a large amount of calcium sulfate, and for the high-calcium low-silicon low-iron type copper-containing sludge, a large amount of flux such as silica and iron ore needs to be added in the relevant process, the addition amount of the flux exceeds 50% of the total mass of the dry sludge, so that the slag amount is obviously increased, and the copper content in the raw materials can be reduced by adopting a mode of mixing with other high-silicon sludge, the mixing proportion is low, and the treatment capacity is small. Therefore, the existing process for treating the copper-containing sludge with high calcium, low silicon and low iron has large material and energy consumption and poor feasibility.
Slag produced in the bottom blowing copper smelting process is FeO-SiO2Mainly, the copper content is high (about 5 wt%), the dilution treatment is generally carried out by adopting the modes of flotation and electric furnace reduction, the obtained copper matte is returned to be blown, and tailings are piled up or used as building material raw materials. Wherein, the flotation method is adopted, copper slag is required to be slowly cooled, copper concentrate is separated through the processes of crushing, ore grinding, flotation, filter pressing, thickening and the like, and the obtained waste slag contains about 0.3wt percent of copper; the slag is FeO-SiO in the reduction and depletion process of the electric furnace2The binary slag is mainly used, and a fusing agent (such as lime, silica and the like), a reducing agent and the like are added into a molten poolThe obtained tailings contain 0.5-1.0 wt% of copper, but the addition of the flux causes the problems of increased treatment cost, large amount of slag and the like, so the flux is generally added little or not.
In the related technology, there is a process of mixing copper slag, copper-containing sludge and a reducing agent, then carrying out reduction smelting to obtain alloy and ferrochrome slag, and then carrying out electrolysis treatment to recover various valuable metals in the alloy. The copper-containing sludge treated by the process does not contain CaSO basically4Only can treat copper-containing sludge with similar main composition with copper slag, has poor raw material adaptability, and cannot treat high-calcium, low-silicon and low-iron type copper-containing sludge. The process also comprises the steps of premixing the copper-containing sludge, the flux and the reducing agent, and then smelting at high temperature to obtain the metal melt and the copper slag, but the raw materials used in the process hardly contain sulfur and do not generate copper matte, the total consumption mass of the flux and the reducing agent is almost the same as the mass of the treated dry sludge, a large amount of the flux and the reducing agent is consumed, the total amount of slag is increased, and the feasibility is poor.
Therefore, the existing techniques for treating copper-containing sludge are in need of further improvement.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, it is an object of the invention to propose a method and a system for treating copper-containing sludge. The method fully utilizes the complementarity of the copper-containing sludge and the copper slag, remarkably reduces the usage amount of the flux and the reducing agent, simultaneously omits a vulcanizing agent, remarkably improves the dilution effect of the copper slag, realizes the resource recycling of various metals such as copper, nickel, lead, zinc, tin and the like in the copper-containing sludge and the copper slag, and also remarkably reduces the solid waste content.
In one aspect of the invention, a method is provided for treating copper-containing sludge having CaO/SiO therein2>3，Fe/CaO<0.67, according to an embodiment of the invention, the method comprises:
drying the copper-containing sludge to obtain dried copper-containing sludge and flue gas;
and smelting the dried copper-containing sludge, copper slag, flux and reducing agent to obtain copper matte, tailings and high-temperature flue gas.
According to the method for treating the copper-containing sludge, disclosed by the embodiment of the invention, the dried copper-containing sludge and the copper slag are matched for use, and the flux or the iron tailings and the reducing agent are supplemented, so that FeO and SiO in the copper slag2CaSO in copper-containing sludge4FeO-SiO can be formed under the combined action of the reducing agent and the flux or the iron tailings2The sulfur element in the copper-containing sludge can promote Cu, Ni, Sn and the like in the copper slag and the copper-containing sludge to be enriched into copper matte, so that the produced copper matte can enter a main process of copper smelting to be used, the copper content in the obtained tailings can be reduced to be below 0.5 wt%, the copper matte can be used as a building material raw material, and the obtained smoke dust is rich in lead, zinc and tin, and is beneficial to subsequent recycling. Therefore, the method fully utilizes the complementarity of the copper-containing sludge and the copper slag, remarkably reduces the usage amount of a fusing agent and a reducing agent, simultaneously omits a vulcanizing agent, remarkably improves the dilution effect of the copper slag, realizes the resource recycling of various metals such as copper, nickel, lead, zinc, tin and the like in the copper-containing sludge and the copper slag, obtains the matte with the grade of 40-60%, has the copper recovery rate of over 96%, has the contents of copper, nickel, lead, zinc and tin in the tailings respectively lower than 0.5 wt%, 0.1 wt%, 0.6 wt% and 0.3 wt%, also remarkably reduces the total mass of solid waste, and obtains the tailings with the mass only accounting for 40-60% of the total mass of the copper-containing sludge and the copper slag. In the embodiment of the invention, the iron tailings can be used for replacing the flux, and the iron tailings are solid wastes, wherein SiO is contained in the solid wastes2The iron tailings instead of the flux can provide a new treatment way for the solid waste of the iron tailings and is also beneficial to the adjustment of slag components.
In addition, the method for treating copper-containing sludge according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the copper-containing sludge has a TFe content of 2 to 10 wt%, a CaO content of 15 to 30 wt%, and SiO2Is 0-5 wt% of Al2O3Is 0-3 wt%, and the content of Cu is more than10 wt%, Ni content of 0-0.5 wt%, Sn content of 0-1 wt%, S content greater than 10 wt%, and C content of 2-10 wt%, based on copper-containing sludge dry basis.
In some embodiments of the present invention, the mass ratio of the copper-containing sludge to the copper slag and the flux reducer is 100: 10-50: 2-10: 5-10, or the mass ratio of the copper-containing sludge to the copper slag, the iron tailings and the reducing agent is 100: 10-50: 5-30: 5-10, based on the copper-containing sludge dry basis;
in some embodiments of the invention, the sum of the mass of the flux and the reductant is no more than 15% of the sum of the mass of the copper-containing sludge and the copper slag, the mass of the copper-containing sludge being on a wet basis.
In some embodiments of the invention, the copper slag is bottom-blown copper smelting slag.
In some embodiments of the invention, the content of TFe in the copper slag is 35-45 wt%, the content of CaO is 0-5 wt%, and SiO is220-30 wt%, MgO 0-3 wt%, Al2O30-5 wt%, Cu 1-5 wt%, Pb 0-1 wt%, Zn 0-5 wt%, and S1-3 wt%.
In some embodiments of the invention, the reductant is selected from at least one of coal, coke.
In some embodiments of the invention, the flux is silica.
In some embodiments of the invention, the content of TFe in the iron tailings is 10-20 wt%, the content of CaO is 1-5 wt%, and SiO is250-75 wt%, MgO 1-5 wt%, Al2O3The content of (B) is 1-10 wt%.
In some embodiments of the invention, the CaO/SiO in the tailings2＝0.7-1.1，Fe/SiO2＝0.5-1.2，Fe3+/Fe2+＝0.09-0.11。
In some embodiments of the invention, the temperature of the smelting process is 1250-.
In some embodiments of the present invention, the method for treating copper-containing sludge further comprises: and using the high-temperature flue gas for drying the copper-containing sludge.
In some embodiments of the present invention, the method for treating copper-containing sludge further comprises: and carrying out dust collection treatment on the flue gas so as to obtain the smoke dust containing lead, zinc and tin.
In a further aspect of the invention, the invention proposes a system suitable for use in the above method for treating copper-containing sludge, which system comprises, according to an embodiment of the invention:
the drying device is provided with a copper-containing sludge inlet, a dried copper-containing sludge outlet and a flue gas outlet;
the smelting device is provided with a dried copper-containing sludge inlet, a copper slag inlet, a flux or iron tailing inlet, a reducing agent inlet, an ice copper outlet, a tailing outlet and a high-temperature flue gas outlet, and the dried copper-containing sludge inlet is connected with the dried copper-containing sludge outlet.
According to the system for treating the copper-containing sludge, disclosed by the embodiment of the invention, the copper-containing sludge and the copper slag are matched for use, and the flux or the iron tailings and the reducing agent are supplemented, so that FeO and SiO in the copper slag2CaSO in copper-containing sludge4FeO-SiO can be formed under the combined action of the reducing agent and the flux or the iron tailings2The sulfur element in the copper-containing sludge can promote Cu, Ni, Sn and the like in the copper slag and the copper-containing sludge to be enriched into copper matte, so that the produced copper matte can enter a main process of copper smelting to be used, the copper content in the obtained tailings can be reduced to be below 0.5 wt%, the copper matte can be used as a building material raw material, and the obtained smoke dust is rich in lead, zinc and tin, and is beneficial to subsequent recycling. Therefore, the system fully utilizes the complementarity of the copper-containing sludge and the copper slag, remarkably reduces the usage amount of the flux and the reducing agent, simultaneously omits a vulcanizing agent, remarkably improves the dilution effect of the copper slag, realizes the resource recycling of various metals such as copper, nickel, lead, zinc, tin and the like in the copper-containing sludge and the copper slag, the grade of the obtained matte is 40-60%, the copper recovery rate exceeds 96%, and the contents of copper, nickel, lead, zinc and tin in the tailings are respectively lower than 0.5 wt%, 0.1 wt%, 0.6 wt% and 0.3 wt%. Further, the system only connects the drying device withThe smelting device is used in combination for treating the copper-containing sludge, so that the equipment investment and the operation cost are obviously reduced.
In addition, the system for treating copper-containing sludge according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the high temperature flue gas outlet is connected to the drying device.
In some embodiments of the present invention, the above system for treating copper-containing sludge further comprises: the dust collecting device is provided with a smoke inlet and a smoke outlet containing lead, zinc and tin, and the smoke inlet is connected with the smoke outlet.
In some embodiments of the invention, the drying device is selected from at least one of a rotary kiln, a tunnel kiln.
In some embodiments of the invention, the smelting apparatus is a lean electric furnace.
In some embodiments of the invention, the dust collecting device is a multi-stage dust removing apparatus.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a method of treating copper-containing sludge according to one embodiment of the present invention;
FIG. 2 is a schematic flow diagram of a method of treating copper-containing sludge according to yet another embodiment of the present invention;
FIG. 3 is a schematic flow diagram of a method of treating copper-containing sludge according to yet another embodiment of the present invention;
FIG. 4 is a side view of a system configuration for treating copper-containing sludge according to one embodiment of the present invention;
FIG. 5 is a side view of a system configuration for treating copper-containing sludge according to yet another embodiment of the present invention;
FIG. 6 is a top view of the system for treating copper-containing sludge of FIG. 5;
fig. 7 is a side view of the structure of a system for treating copper-containing sludge according to yet another embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In one aspect of the invention, a method is provided for treating copper-containing sludge containing CaO/SiO therein2>3，Fe/CaO<0.67 that the sludge containing copper is high calcium, low silicon, low iron type sludge containing copper, and Cu, Fe, Ca, S, C in the sludge containing copper are mainly sulfate (CuSO) respectively4) Ferrous silicate (Fe)2SiO4) Calcium sulfate (CaSO)4) Sulfate (SO)4 2-) Organic material (C)xHyOz) The form exists. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: drying the copper-containing sludge
In the step, the copper-containing sludge is dried to reduce the moisture in the copper-containing sludge, so that dried copper-containing sludge and flue gas are obtained. Before drying, the copper-containing sludge may be subjected to a pretreatment, such as a press filtration or an air drying step, to primarily remove water from the copper-containing sludge. Further, the moisture content of the copper-containing sludge used for the drying process is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, it may be about 30 wt%. Therefore, the energy consumption during drying treatment is saved, the energy consumption of pretreatment is not too high, and the overall energy consumption is reduced. Further, the temperature of the drying treatment is not particularly limited, and can be selected by those skilled in the art according to actual needs, such as 600 ℃.
According to an embodiment of the present invention, the content of each component in the copper-containing sludge is not particularly limited, and for example, the content of TFe may be 2 to 10 wt%, the content of CaO may be 15 to 30 wt%, and SiO may be2May be contained in an amount of 0 to 5 wt%, Al2O3May be present in an amount of 0-3 wt.%, may be present in an amount of more than 10 wt.%, may be present in an amount of 0-0.5 wt.%, may be present in an amount of 0-1 wt.%, may be present in an amount of more than 10 wt.%, and may be present in an amount of 2-10 wt.%, based on the copper-containing sludge on a dry basis.
S200: smelting the dried copper-containing sludge, copper slag, flux or iron tailings and reducing agent
In the step, the dried copper-containing sludge, copper slag, flux or iron tailings and reducing agent are smelted so as to obtain copper matte, tailings and high-temperature flue gas. The inventor finds that FeO and SiO in the copper slag in the smelting process2CaSO in copper-containing sludge4FeO-SiO can be formed under the combined action of the reducing agent and the flux2The sulfur element in the copper-containing sludge can promote Cu, Ni, Sn and the like in the copper slag and the copper-containing sludge to be enriched into copper matte, so that the produced copper matte can enter a main process of copper smelting to be used, the copper content in the obtained tailings can be reduced to be below 0.5 wt%, the copper matte can be used as a building material raw material, and the obtained smoke dust is rich in lead, zinc and tin, and is beneficial to subsequent recycling. Namely, the smelting fully utilizes the complementarity of the copper-containing sludge and the copper slag, obviously reduces the usage amount of the flux and the reducing agent, and simultaneously saves the sulfurThe diluting effect of the copper slag is obviously improved by the aid of the agent, resource recycling of copper, nickel, lead, zinc, tin and other metals in the copper-containing sludge and the copper slag is realized, the grade of the obtained matte is 40-60%, the copper recovery rate exceeds 96%, and the contents of copper, nickel, lead, zinc and tin in tailings are respectively lower than 0.5 wt%, 0.1 wt%, 0.6 wt% and 0.3 wt%. In the embodiment of the invention, the iron tailings can be used for replacing the flux, and the iron tailings are solid wastes, wherein SiO is contained in the solid wastes2The iron tailings instead of the flux can provide a new treatment way for the solid waste of the iron tailings and is also beneficial to the adjustment of slag components.
According to an embodiment of the present invention, the mass ratio of the copper-containing sludge to the copper slag, the flux or the iron tailings, and the reductant is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the mass ratio of the copper-containing sludge to the copper slag, the flux, and the reductant may be 100: 10-50: 2-10: 5-10, or the mass ratio of the copper-containing sludge to the copper slag, the iron tailings and the reducing agent can be 100: 10-50: 5-30: 5-10 based on the copper-containing sludge dry basis. Specifically, for example, the mass ratio of the copper-containing sludge to the copper slag, the flux and the reducing agent may be 100: 10/20/30/40/50: 2/4/6/8/10: 5/6/7/8/9/10, or the mass ratio of the copper-containing sludge to the copper slag, the iron tailings and the reducing agent can be 100: 10/20/30/40/50: 5/10/15/20/25/30: 5/6/7/8/9/10. Further, the sum of the mass of the flux and the reducing agent can be not more than 15% of the sum of the mass of the copper-containing sludge and the mass of the copper slag, and the copper-containing sludge is calculated by wet materials. The inventor finds that the usage amount of the flux and the reducing agent is obviously reduced due to complementarity of the copper-containing sludge and the components in the copper slag, the problem of solid-waste capacity increase caused by the proportion of a large amount of the flux is avoided, and the tailing slag type can be optimized under the condition of the usage amount of the flux to reduce the copper content in the tailing. Specifically, the usage amount of the flux and the reducing agent can be selectively added according to the content of each component in the copper-containing sludge and the copper slag so as to promote the recovery of valuable metal elements.
According to another embodiment of the invention, the copper slag can be bottom-blown copper smelting slag to realize the reutilization of solid wastes, and the copperFe in the slag is mainly FeO and Fe3O4In the form of (1), Cu being predominantly Cu2S and metallic Cu. Further, the contents of the respective components in the copper slag are not particularly limited, and for example, the content of TFe in the copper slag may be 35 to 45 wt%, the content of CaO may be 0 to 5 wt%, and SiO may be2May be 20-30 wt%, MgO may be 0-3 wt%, Al2O3May be contained in an amount of 0 to 5 wt%, Cu may be contained in an amount of 1 to 5 wt%, Pb may be contained in an amount of 0 to 1 wt%, Zn may be contained in an amount of 0 to 5 wt%, and S may be contained in an amount of 1 to 3 wt%. The copper slag and the copper-containing sludge are smelted together, and the components in the copper slag can be complementary with the components in the copper-containing sludge to form FeO-SiO2And the CaO ternary slag system can promote Cu, Ni, Sn and the like in the copper slag and the copper-containing sludge to be enriched into the copper matte, so that the copper content in the obtained tailings can be reduced to be below 0.5 wt%, and the obtained smoke dust is rich in lead, zinc and tin.
According to still another embodiment of the present invention, the specific type of the reducing agent, the flux or the iron tailings is also not particularly limited, such as the reducing agent may be selected from at least one of coal and coke, and the flux may be silica. The inventor finds that the reducing agent can promote calcium sulfate to be reduced into CaS, and Fe in copper slag exists in the reducing agent in the smelting process2O3Can react with CaS, 2CaS + Fe2O3And the produced FeS enters into a matte phase, and CaO and SiO in the flux or iron tailings2The combination forms calcium silicate, so that the alkalinity of the slag can be adjusted, and the melting property of the slag is improved. Further, the content of each component in the iron tailings is not particularly limited, and for example, the content of TFe may be 10 to 20 wt%, the content of CaO may be 1 to 5 wt%, and SiO2May be contained in an amount of 50 to 75 wt%, MgO may be contained in an amount of 1 to 5 wt%, and Al2O3The content of (B) may be 1 to 10 wt%. In the embodiment of the invention, the iron tailings are adopted to replace the flux, and the iron tailings are solid wastes, wherein SiO is contained in the solid wastes2The iron tailings instead of the flux can provide a new treatment way for the solid waste of the iron tailings and is also beneficial to the adjustment of slag components.
According to another embodiment of the invention, the method for treating the copper-containing sludge is adopted, and the ratio of CaO/SiO in the obtained tailings is controlled by controlling the proportion of the raw materials2＝0.7-1.1，Fe/SiO2＝0.5-1.2，Fe3+/Fe2+0.09-0.11. The inventor finds that in the component range, the slag has better properties, mainly reflected in that the melting point of the slag is lower, the viscosity is lower, the smelting temperature can be reduced, the separation of the slag and the matte is facilitated, and the dissolving content of copper in the slag is lower.
According to yet another embodiment of the invention, the temperature of the smelting process may be 1250-. Specifically, during the smelting treatment, the temperature near the high-temperature flue gas outlet can be controlled to be in a higher range, such as 1250-.
According to the method for treating the copper-containing sludge provided by the embodiment of the invention, the copper-containing sludge and the copper slag are matched and used, and the flux and the reducing agent are supplemented, so that FeO and SiO in the copper slag2CaSO in copper-containing sludge4FeO-SiO can be formed under the combined action of the reducing agent and the flux2The sulfur element in the copper-containing sludge can promote Cu, Ni, Sn and the like in the copper slag and the copper-containing sludge to be enriched into copper matte, so that the produced copper matte can enter a main process of copper smelting to be used, the copper content in the obtained tailings can be reduced to be below 0.5 wt%, the copper matte can be used as a building material raw material, and the obtained smoke dust is rich in lead, zinc and tin, and is beneficial to subsequent recycling. Therefore, the method fully utilizes the complementarity of the copper-containing sludge and the copper slag, remarkably reduces the usage amount of the flux and the reducing agent, simultaneously omits a vulcanizing agent, remarkably improves the dilution effect of the copper slag, realizes the resource recycling of various metals such as copper, nickel, lead, zinc, tin and the like in the copper-containing sludge and the copper slag, the grade of the obtained matte is 40-60%, the copper recovery rate exceeds 96%, and the contents of copper, nickel, lead, zinc and tin in the tailings are respectively lower than 0.5 wt%, 0.1 wt%, 0.6 wt% and 0.3 wt%.
According to an embodiment of the present invention, referring to fig. 2, in order to recover heat of the high temperature flue gas, promote heat utilization of the process, and reduce drying energy consumption of the copper-containing sludge, the method for treating the copper-containing sludge further includes: the high temperature flue gas is used for drying the copper-containing sludge.
According to an embodiment of the present invention, referring to fig. 3, the method for treating copper-containing sludge further includes:
s300: the flue gas is subjected to dust collection treatment
In the step, the flue gas is subjected to dust collection treatment so as to obtain the smoke dust containing lead, zinc and tin. The inventor finds that the high-temperature flue gas obtained by smelting is rich in lead, zinc and tin, the high-temperature flue gas can be subjected to waste heat recovery and dust collection treatment to obtain smoke dust with lead, zinc and tin contents respectively higher than 5 wt%, 30 wt% and 20 wt%, and the smoke dust can be used for lead, zinc and tin smelting, so that resource waste is avoided, and the benefit is increased.
In a further aspect of the invention, the invention proposes a system suitable for use in the above method for treating copper-containing sludge containing CaO/SiO2>3，Fe/CaO<0.67 that the sludge containing copper is high calcium, low silicon, low iron type sludge containing copper, and Cu, Fe, Ca, S, C in the sludge containing copper are mainly sulfate (CuSO) respectively4) Ferrous silicate (Fe)2SiO4) Calcium sulfate (CaSO)4) Sulfate (SO)4 2-) Organic material (C)xHyOz) The form exists. Referring to fig. 4, the system includes, according to an embodiment of the present invention: a drying device 100 and a melting device 200.
According to an embodiment of the invention, the drying apparatus 100 has a copper-containing sludge inlet 101, a dried copper-containing sludge outlet 102 and a flue gas outlet 103 and is adapted to subject the copper-containing sludge to a drying process in order to obtain dried copper-containing sludge and flue gas. It should be noted that the specific type of the drying device is not particularly limited, and may be selected from at least one of a rotary kiln and a tunnel kiln. Further, before drying, the copper-containing sludge may be pretreated, such as by press filtration and air drying, to primarily remove water from the copper-containing sludge. Further, the moisture content of the copper-containing sludge used for the drying process is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, it may be about 30 wt%. Therefore, the energy consumption during drying treatment is saved, the energy consumption of pretreatment is not too high, and the overall energy consumption is reduced. Further, the temperature of the drying treatment is not particularly limited, and can be selected by those skilled in the art according to actual needs, such as 600 ℃.
According to an embodiment of the present invention, the content of each component in the copper-containing sludge is not particularly limited, and for example, the content of TFe may be 2 to 10 wt%, the content of CaO may be 15 to 30 wt%, and SiO may be2May be contained in an amount of 0 to 5 wt%, Al2O3May be present in an amount of 0-3 wt.%, may be present in an amount of more than 10 wt.%, may be present in an amount of 0-0.5 wt.%, may be present in an amount of 0-1 wt.%, may be present in an amount of more than 10 wt.%, and may be present in an amount of 2-10 wt.%, based on the copper-containing sludge on a dry basis.
According to the embodiment of the invention, the smelting device 200 is provided with a dried copper-containing sludge inlet 201, a copper slag inlet 202, a flux inlet 203, a reducing agent inlet 204, an ice copper outlet 205, a tailings outlet 206 and a high-temperature flue gas outlet 207, wherein the dried copper-containing sludge inlet 201 is connected with the dried copper-containing sludge outlet 102 and is suitable for smelting the dried copper-containing sludge, copper slag, a flux and a reducing agent so as to obtain ice copper, tailings and high-temperature flue gas. The inventor finds that FeO and SiO in the copper slag in the smelting process2CaSO in copper-containing sludge4FeO-SiO can be formed under the combined action of the reducing agent and the flux2The sulfur element in the copper-containing sludge can promote Cu, Ni, Sn and the like in the copper slag and the copper-containing sludge to be enriched into copper matte, so that the produced copper matte can enter a main process of copper smelting to be used, the copper content in the obtained tailings can be reduced to be below 0.5 wt%, the copper matte can be used as a building material raw material, and the obtained smoke dust is rich in lead, zinc and tin, and is beneficial to subsequent recycling. Namely, the smelting fully utilizes the complementarity of the copper-containing sludge and the copper slag, obviously reduces the usage amount of the flux and the reducing agent, simultaneously omits a vulcanizing agent, obviously improves the dilution effect of the copper slag, and realizes the copper, nickel and lead in the copper-containing sludge and the copper slagAnd the resource recycling of various metals such as zinc, tin and the like, the grade of the obtained matte is 40-60%, the copper recovery rate exceeds 96%, and the contents of copper, nickel, lead, zinc and tin in the tailings are respectively lower than 0.5 wt%, 0.1 wt%, 0.6 wt% and 0.3 wt%. It should be noted that the specific type of smelting unit is not particularly limited, and may be a lean electric furnace. The electric cleaning furnace equipment has small occupied area and high treatment efficiency.
Further, in order to recover the heat of the high temperature flue gas, promote the heat utilization of the process, and reduce the drying energy consumption of the copper-containing sludge, referring to fig. 5 and 6, the high temperature flue gas outlet 207 may be connected to the drying device 100.
According to an embodiment of the present invention, the mass ratio of the copper-containing sludge to the copper slag, the flux and the reductant is not particularly limited, and can be selected by those skilled in the art according to actual needs, for example, the mass ratio of the copper-containing sludge (on a dry basis) to the copper slag, the flux and the reductant may be 100: 10-50: 2-10: 5-10, in particular, it may be, for example, 100: 10/20/30/40/50: 2/4/6/8/10: 5/6/7/8/9/10, or the mass ratio of the copper-containing sludge (calculated by dry basis) to the copper slag, the iron tailings and the reducing agent can be 100: 10-50: 5-30: 5-10, in particular, it may be, for example, 100: 10/20/30/40/50: 5/10/15/20/25/30: 5/6/7/8/9/10. Further, the sum of the mass of the flux and the reducing agent may be not more than 15% of the sum of the mass of the copper-containing sludge and the mass of the copper slag, the copper-containing sludge being on a wet basis. The inventor finds that the usage amount of the flux and the reducing agent is obviously reduced due to complementarity of the copper-containing sludge and the components in the copper slag, the problem of solid-waste capacity increase caused by the proportion of a large amount of the flux is avoided, and the tailing slag type can be optimized under the condition of the usage amount of the flux to reduce the copper content in the tailing. Specifically, the usage amount of the flux and the reducing agent can be selectively added according to the content of each component in the copper-containing sludge and the copper slag so as to promote the recovery of valuable metal elements.
According to another embodiment of the invention, the copper slag can be bottom-blown copper smelting slag to realize the reutilization of solid wastes, and the Fe in the copper slag is mainly FeO and Fe3O4In the form of (1), Cu being predominantly Cu2S and metallic Cu. Further, each of the copper slagThe contents of the components are not particularly limited, and for example, the content of TFe in the copper slag may be 35 to 45 wt%, the content of CaO may be 0 to 5 wt%, and SiO2May be 20-30 wt%, MgO may be 0-3 wt%, Al2O3May be contained in an amount of 0 to 5 wt%, Cu may be contained in an amount of 1 to 5 wt%, Pb may be contained in an amount of 0 to 1 wt%, Zn may be contained in an amount of 0 to 5 wt%, and S may be contained in an amount of 1 to 3 wt%. The copper slag and the dried copper-containing sludge are smelted together, and the components in the copper slag can be complementary with the components in the copper-containing sludge to form FeO-SiO2And the CaO ternary slag system can promote Cu, Ni, Sn and the like in the copper slag and the copper-containing sludge to be enriched into the copper matte, so that the copper content in the obtained tailings can be reduced to be below 0.5 wt%, and the obtained smoke dust is rich in lead, zinc and tin.
According to still another embodiment of the present invention, the specific types of the reducing agent and the flux are not particularly limited, and for example, the reducing agent may be at least one selected from coal and coke, and the flux may be silica. The inventor finds that the reducing agent can promote calcium sulfate to be reduced into CaS, and Fe in copper slag exists in the reducing agent in the smelting process2O3Can react with CaS, 2CaS + Fe2O3And the produced FeS enters into a matte phase, and CaO and SiO in the flux or iron tailings2The combination forms calcium silicate, so that the alkalinity of the slag can be adjusted, and the melting property of the slag is improved. Further, the content of each component in the iron tailings is not particularly limited, and for example, the content of TFe may be 10 to 20 wt%, the content of CaO may be 1 to 5 wt%, and SiO2May be contained in an amount of 50 to 75 wt%, MgO may be contained in an amount of 1 to 5 wt%, and Al2O3The content of (B) may be 1 to 10 wt%. In the embodiment of the invention, the iron tailings are adopted to replace the flux, and the iron tailings are solid wastes, wherein SiO is contained in the solid wastes2The iron tailings instead of the flux can provide a new treatment way for the solid waste of the iron tailings and is also beneficial to the adjustment of slag components.
According to another embodiment of the invention, the copper-containing sludge is treated by controlling the ratio of raw materials to obtain tailingsMedium CaO/SiO2＝0.7-1.1，Fe/SiO2＝0.5-1.2，Fe3+/Fe2+0.09-0.11. The inventor finds that in the component range, the slag has better properties, mainly reflected in that the melting point of the slag is lower, the viscosity is lower, the smelting temperature can be reduced, the separation of the slag and the matte is facilitated, and the dissolving content of copper in the slag is lower.
According to yet another embodiment of the invention, the temperature of the smelting process may be 1250-. Specifically, during the smelting treatment, the temperature of the high-temperature flue gas outlet accessory can be controlled in a higher range, such as 1250-. For example, when the smelting device is a impoverishment furnace, the high-temperature flue gas outlet, the dried copper-containing sludge inlet, the copper slag inlet, the flux inlet and the reducing agent inlet are all positioned in the charging area of the impoverishment furnace, the matte outlet and the tailing outlet are positioned at the discharge end of the impoverishment furnace, and the impoverishment furnace adopts electrode supplementary heating, so that the temperature control in the impoverishment furnace becomes possible, the recovery rate of valuable metals can be improved through temperature control, the smelting effect is improved, and the smelting energy consumption is reduced.
According to the system for treating the copper-containing sludge, disclosed by the embodiment of the invention, the copper-containing sludge and the copper slag are matched for use, and the fluxing agent and the reducing agent are supplemented, so that FeO and SiO in the copper slag2CaSO in copper-containing sludge4FeO-SiO can be formed under the combined action of the reducing agent and the flux2The sulfur element in the copper-containing sludge can promote Cu, Ni, Sn and the like in the copper slag and the copper-containing sludge to be enriched into copper matte, so that the produced copper matte can enter a main process of copper smelting to be used, the copper content in the obtained tailings can be reduced to be below 0.5 wt%, the copper matte can be used as a building material raw material, and the obtained smoke dust is rich in lead, zinc and tin, and is beneficial to subsequent recycling. Therefore, the system fully utilizes the complementarity of the copper-containing sludge and the copper slag, remarkably reduces the using amount of the flux and the reducing agent, simultaneously omits a vulcanizing agent, remarkably improves the dilution effect of the copper slag, and realizes the copper, nickel and lead in the copper-containing sludge and the copper slagAnd the resource recycling of various metals such as zinc, tin and the like, the grade of the obtained matte is 40-60%, the copper recovery rate exceeds 96%, and the contents of copper, nickel, lead, zinc and tin in the tailings are respectively lower than 0.5 wt%, 0.1 wt%, 0.6 wt% and 0.3 wt%. Further, the system only combines the drying device with the smelting device for treating the copper-containing sludge, so that the equipment investment and the operation cost are obviously reduced.
According to an embodiment of the present invention, referring to fig. 7, the system for treating copper-containing sludge further includes: dust collecting apparatus 300.
According to the embodiment of the invention, the dust collecting device 300 is provided with a flue gas inlet 301 and a smoke outlet 302 containing lead, zinc and tin, wherein the flue gas inlet 301 is connected with the flue gas outlet 103 and is suitable for carrying out dust collecting treatment on flue gas so as to obtain the smoke containing lead, zinc and tin. The inventor finds that smoke dust with lead, zinc and tin contents respectively higher than 5 wt%, 30 wt% and 20 wt% can be obtained after waste heat recovery and dust collection treatment of high-temperature smoke gas obtained by smelting, and the smoke dust can be used for lead-zinc-tin smelting, so that resource waste is avoided, and benefits are increased. It should be noted that the specific type of the dust collecting device is not particularly limited, and may be a multi-stage dust removing apparatus. A conventional dry dust removal device is generally adopted and commonly used together with a plurality of dust removal devices, a cyclone dust remover is adopted for coarse dust removal, and electric dust removal is adopted for the rear section.
It should be noted that the above-mentioned features and advantages of the method for treating copper-containing sludge are also applicable to the system for treating copper-containing sludge, and are not described in detail herein.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
In the raw materials used in the examples of the present application:
the water content of the copper-containing sludge is 30 percent, the dry basis component comprises 6.39 weight percent of TFe, 6.61 weight percent of FeO, 0.12 weight percent of MgO, 19.88 weight percent of CaO and SiO2Is 1.87 wt%, Al2O31.28 wt%, Cu 15.18 wt%, Ni 0.2 wt%, Sn0.5 wt%, S content 15.17 wt%, C content 4.85 wt%.
The copper slag is the slag of the bottom blowing smelting furnace, wherein the content of TFe is 44.57 wt%, the content of FeO is 31.99 wt%, the content of CaO is 3.29 wt%, and SiO223.82 wt%, MgO 1.42 wt%, Al2O32.29 wt%, Cu 4.25 wt%, Pb 0.41 wt%, Zn 2.44 wt%, and S1.46 wt%.
The content of TFe in the iron tailings is 12.18 wt%, the content of CaO is 4.83 wt%, and the content of SiO is273.29 wt%, MgO 3.24 wt%, Al2O3The content of (B) was 6.12 wt%.
Example 1
Drying copper-containing sludge with the water content of 30% at 600 ℃ by using a rotary kiln, continuously feeding the obtained copper-containing sludge after drying the thermal-state material into a melting pool of a dilution furnace, and adding 30% of copper slag, 10% of silica and 8% of crushed coal (the total adding amount of the flux silica and the reducing agent crushed coal is 10.41% of the total mass of the solid waste copper-containing sludge and the copper slag) by the total weight of the copper-containing sludge (calculated by dry basis), wherein the copper-containing sludge is calculated by wet materials, namely the ratio of the flux and the reducing agent crushed coal to the total mass of the solid waste is (10% (flux) + 8% (reducing agent crushed coal))/(100% (copper-containing sludge dry basis) + 70% + 30% (copper slag))/(10.41%), controlling the temperature of the feeding position in the dilution furnace to 1250-, the tailings are general solid wastes which can be used as building material raw materials, high-temperature flue gas is sent to a rotary kiln to be dried back to copper-containing sludge, the flue gas obtained by the rotary kiln is subjected to dust collection treatment to obtain flue gas containing lead, zinc and tin, and the content of lead, zinc and tin in the flue gas is respectively 8.53 wt% (more than 5%), 43.05 wt% (more than 30%) and 31.75 wt% (more than 20%).
And (3) processing results: 10 ten thousand tons of copper-containing sludge (dry basis) and 3 ten thousand tons of bottom blowing smelting slag are treated annually to produce 3.7 ten thousand tons of copper matte (matte grade is 44%), 5.5 ten thousand tons of tailings (the tailings contain 0.28 wt% of copper, 0.3 wt% of zinc, 0.15 wt% of tin, and less than 0.1 wt% of nickel and lead, and the tailingsMedium CaO/SiO2＝1.09，Fe/SiO2＝0.76，Fe3+/Fe2+0.1. ) The copper recovery rate of the whole process is 98.94 percent.
Example 2
Drying copper-containing sludge with the water content of 30% at 600 ℃ by using a rotary kiln, continuously feeding the obtained copper-containing sludge after drying the thermal-state material into a dilution electric furnace molten pool, adding copper slag accounting for 15% of the total weight of the copper-containing sludge (calculated by dry basis), iron tailings accounting for 25% of the total weight of the copper-containing sludge and the iron tailings accounting for 5.47% of the total weight of the solid waste copper-containing sludge, the copper slag and the iron tailings, and adding the copper-containing sludge accounting for wet materials, wherein the proportion of the reducing agent crushed coal to the total weight of the solid waste is 10% (reducing agent crushed coal)/(100% (copper-containing sludge dry basis), 70% + 15% (copper slag) + 25% (iron tailings)) -5.47%), controlling the temperature of the feeding position in the dilution electric furnace to 1250-, the tailings are general solid wastes which can be used as building material raw materials, high-temperature flue gas is sent to a rotary kiln to be dried back to copper-containing sludge, the flue gas obtained by the rotary kiln is subjected to dust collection treatment to obtain flue gas containing lead, zinc and tin, and the content of lead, zinc and tin in the flue gas is respectively 6.29 wt% (more than 5%), 31.89 wt% (more than 30%) and 45.15 wt% (more than 20%).
And (3) processing results: 10 ten thousand tons of copper-containing sludge (dry basis) and 1.5 ten thousand tons of bottom blowing smelting slag and 2.5 ten thousand tons of iron tailings are treated annually to produce 2.6 ten thousand tons of copper matte (matte grade 59 percent), 6.5 ten thousand tons of tailings (the tailings contain 0.25 weight percent of copper, 0.2 weight percent of zinc, 0.25 weight percent of tin and less than 0.1 weight percent of nickel and lead), and CaO/SiO in the tailings2＝1.00，Fe/SiO2＝0.68，Fe3+/Fe2+0.1. ) The copper recovery rate in the whole process is 96.98 percent.
Example 3
Drying copper-containing sludge with the water content of 30% at 600 ℃ by using a rotary kiln, continuously feeding the obtained copper-containing sludge after drying the thermal-state material into a melting pool of a dilution furnace, adding copper slag accounting for 45% of the total weight of the copper-containing sludge (calculated by dry basis), 10% of silica and 5% of crushed coal (the total adding amount of the flux silica and the reducing agent crushed coal is 7.98% of the total weight of the solid waste copper-containing sludge and the copper slag), and adding the copper-containing sludge accounting for wet materials, wherein the proportion of the flux and the reducing agent crushed coal accounting for the total weight of the solid waste is (10% (flux) + 5% (reducing agent crushed coal))/(100% (copper-containing sludge dry basis) + 70% + 45% (copper slag))/(7.98%), controlling the temperature of the feeding position in the dilution furnace to 1250-, the tailings are general solid wastes which can be used as building material raw materials, high-temperature flue gas is sent to a rotary kiln to be dried back to the copper-containing sludge, the flue gas obtained by the rotary kiln is subjected to dust collection treatment to obtain flue gas containing lead, zinc and tin, and the content of lead, zinc and tin in the flue gas is respectively 12.84 wt% (more than 5%), 49.79 wt% (more than 30%) and 20.70 wt% (more than 20%).
And (3) processing results: 10 ten thousand tons of copper-containing sludge (dry basis) and 4.5 ten thousand tons of bottom blowing smelting slag are treated annually to produce 2.75 ten thousand tons of copper matte (matte grade is 60 percent), 8.6 ten thousand tons of tailings (the tailings contain 0.4 weight percent of copper, 0.6 weight percent of zinc, 0.3 weight percent of tin, and the content of nickel and lead is lower than 0.1 weight percent, and CaO/SiO in the tailings2＝0.72，Fe/SiO2＝1.17，Fe3+/Fe2+0.1. ) The copper recovery rate of the whole process is 96.53 percent.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. Method for treating copper-containing sludge containing CaO/SiO2>3，Fe/CaO<0.67, characterized by comprising:
drying the copper-containing sludge to obtain dried copper-containing sludge and flue gas;
and smelting the dried copper-containing sludge, copper slag, flux or iron tailings and reducing agent to obtain copper matte, tailings and high-temperature flue gas.
2. The method according to claim 1, characterized in that the copper-containing sludge has a TFe content of 2-10 wt.%, a CaO content of 15-30 wt.%, and SiO2Is 0-5 wt% of Al2O3The content of (A) is 0-3 wt%, the content of Cu is more than 10 wt%, the content of Ni is 0-0.5 wt%, the content of Sn is 0-1 wt%, the content of S is more than 10 wt%, and the content of C is 2-10 wt%, based on the copper-containing sludge dry basis.
3. The method according to claim 1 or 2, wherein the mass ratio of the copper-containing sludge to the copper slag, the flux and the reducing agent is 100: 10-50: 2-10: 5-10, or the mass ratio of the copper-containing sludge to the copper slag, the iron tailings and the reducing agent is 100: 10-50: 5-30: 5-10, based on the copper-containing sludge dry basis;
optionally, the sum of the mass of the flux and the mass of the reducing agent is not more than 15% of the sum of the mass of the copper-containing sludge and the mass of the copper slag, and the mass of the copper-containing sludge is calculated by wet materials;
optionally, the copper slag is bottom-blown copper smelting slag;
optionally, the content of TFe in the copper slag is 35-45 wt%, the content of CaO is 0-5 wt%, and SiO is220-30 wt%, MgO 0-3 wt%, Al2O3Is 0-5 wt%, and the content of Cu is1-5 wt%, Pb content of 0-1 wt%, Zn content of 0-5 wt%, and S content of 1-3 wt%;
optionally, the reducing agent is selected from at least one of coal and coke;
optionally, the flux is silica;
optionally, the content of TFe in the iron tailings is 10-20 wt%, the content of CaO is 1-5 wt%, and SiO250-75 wt%, MgO 1-5 wt%, Al2O3The content of (B) is 1-10 wt%;
optionally, CaO/SiO in the tailings2＝0.7-1.1，Fe/SiO2＝0.5-1.2，Fe3+/Fe2+＝0.09-0.11。
4. The method as claimed in claim 1, wherein the temperature of the smelting process is 1250-.
5. The method of claim 1, further comprising: and using the high-temperature flue gas for drying the copper-containing sludge.
6. The method of claim 5, further comprising: and carrying out dust collection treatment on the flue gas so as to obtain the smoke dust containing lead, zinc and tin.
7. A system adapted for use in a method of treating copper-containing sludge according to any one of claims 1 to 6, comprising:
the drying device is provided with a copper-containing sludge inlet, a dried copper-containing sludge outlet and a flue gas outlet;
the smelting device is provided with a dried copper-containing sludge inlet, a copper slag inlet, a flux or iron tailing inlet, a reducing agent inlet, an ice copper outlet, a tailing outlet and a high-temperature flue gas outlet, and the dried copper-containing sludge inlet is connected with the dried copper-containing sludge outlet.
8. The system of claim 7, wherein the high temperature flue gas outlet is connected to the drying device.
9. The system of claim 8, further comprising:
the dust collecting device is provided with a smoke inlet and a smoke outlet containing lead, zinc and tin, and the smoke inlet is connected with the smoke outlet.
10. The system of claim 9, wherein the drying device is selected from at least one of a rotary kiln, a tunnel kiln;
optionally, the smelting device is a lean electric furnace;
optionally, the dust collecting device is a multi-stage dust removing device.
CN202010342861.3A 2020-04-27 2020-04-27 Method and system for treating copper-containing sludge Pending CN111378844A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114836630A (en) * 2022-03-29 2022-08-02 中国恩菲工程技术有限公司 Method and system for cooperatively treating hazardous waste containing copper by copper concentrate
CN115261628A (en) * 2022-08-29 2022-11-01 广东飞南资源利用股份有限公司 Method for preparing low-iron copper nickel matte by directly smelting copper-nickel-containing sludge
CN117385178A (en) * 2023-10-24 2024-01-12 韶关鹏瑞环保科技有限公司 Comprehensive treatment process of complex multi-metal electronic electroplating sludge

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114836630A (en) * 2022-03-29 2022-08-02 中国恩菲工程技术有限公司 Method and system for cooperatively treating hazardous waste containing copper by copper concentrate
CN115261628A (en) * 2022-08-29 2022-11-01 广东飞南资源利用股份有限公司 Method for preparing low-iron copper nickel matte by directly smelting copper-nickel-containing sludge
CN115261628B (en) * 2022-08-29 2023-10-20 广东飞南资源利用股份有限公司 Method for preparing low-iron copper nickel matte by direct smelting of copper-nickel-containing sludge
CN117385178A (en) * 2023-10-24 2024-01-12 韶关鹏瑞环保科技有限公司 Comprehensive treatment process of complex multi-metal electronic electroplating sludge
CN117385178B (en) * 2023-10-24 2024-05-07 广东鹏瑞环保资源股份有限公司 Comprehensive treatment process of complex multi-metal electronic electroplating sludge

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