CN110004351B - Production system of copper-containing steel - Google Patents

Production system of copper-containing steel Download PDF

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Publication number
CN110004351B
CN110004351B CN201910432644.0A CN201910432644A CN110004351B CN 110004351 B CN110004351 B CN 110004351B CN 201910432644 A CN201910432644 A CN 201910432644A CN 110004351 B CN110004351 B CN 110004351B
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copper
furnace
slag
reduction
sedimentation
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CN110004351A (en
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高永亮
李兵
尉克俭
李东波
黎敏
郭亚光
王雪亮
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China ENFI Engineering Corp
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China ENFI Engineering Corp
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/52—Manufacture of steel in electric furnaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/064—Dephosphorising; Desulfurising
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/068—Decarburising
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/072—Treatment with gases
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/10—Handling in a vacuum
    • 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
    • C22B11/00—Obtaining noble metals
    • C22B11/02—Obtaining noble metals by dry processes
    • C22B11/021—Recovery of noble metals from waste materials
    • C22B11/023—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/0054—Slag, slime, speiss, or dross treating
    • 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
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • 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

Abstract

The disclosure provides a production system of copper-containing steel, which comprises a heating and sedimentation furnace, a reduction furnace, an electric furnace, a refining device and a forming device, wherein the heating and sedimentation furnace comprises a heating and reduction region and a sedimentation region, the heating and reduction region is communicated with the bottom of the sedimentation region, and a material outlet of the sedimentation region comprises a first liquid outlet and a first slag outlet; the material inlet of the reduction furnace is communicated with the first slag hole of the sedimentation zone, and the material outlet of the reduction furnace comprises a second liquid outlet and a second slag hole; the material inlet of the electric furnace is communicated with the second liquid outlet of the reduction furnace; the material inlet of the refining device is communicated with the material outlet of the electric furnace; the material inlet of the forming device is communicated with the material outlet of the refining device. The production system disclosed by the invention is used for producing copper-containing steel, has higher recovery rate and low production cost, can realize extraction of valuable elements, fully utilizes iron and copper in copper slag, can obtain copper-containing steel with higher added value, and has good industrial application prospect.

Description

Production system of copper-containing steel
Technical Field
The present disclosure relates to the field of metallurgy, and in particular to a copper-containing steel production system.
Background
Copper slag is metallurgical slag discharged from a copper smelting furnace in the process of pyrometallurgy copper smelting, and is a eutectic formed by mutually melting various oxides in furnace burden and fuel. At present, the annual emission of China exceeds 1000 ten thousand tons, and copper slag with the quantity exceeding 1.2 hundred million tons is piled nationwide, and the copper slag becomes industrial solid waste with a large quantity in the metallurgical industry. Although the copper slag contains Fe, cu, zn, pb, co, ni and other valuable metals and Au, ag and other small amounts of noble metals, most of the copper slag is piled up in a slag field, so that the copper slag occupies land, pollutes the environment and causes huge waste of resources. If the iron and copper in the copper slag are fully utilized, the contradiction between the supply and demand of the iron ore and the copper ore can be relieved to a certain extent; and if a small amount of noble metal contained in the copper slag is effectively extracted, the economic benefit can be better improved. Therefore, the comprehensive utilization of the copper slag has important strategic significance and market prospect, and is an important approach for sustainable development of the current copper smelting industry.
However, current research on copper slag utilization technology has focused on both copper alone utilization and iron alone utilization. The method has the advantages that the research on the extraction of noble metals in copper slag and the simultaneous utilization of copper and iron in slag is less, and certain defects exist. For example, chinese patent application 200910163234.7 discloses a method for extracting iron by inert gas injection, which avoids heat loss, but only considers the recovery of iron alone, does not consider the recovery and utilization of noble metals and copper, and does not consider impurities present in iron. Both chinese patent applications 201010167157.5 and 201010216133.4 improve the process of refining iron on the basis of the aforementioned patent applications, but the problem of recovery of noble metals and copper is still not considered. Although the problem of copper recovery is considered in chinese patent application 201110380257.0, the chlorine salt added in the process may have pollution problems. Furthermore, the above is considered to separate the use of iron and copper, and copper-containing steels such as weathering steel, copper-containing stainless steel, copper-containing antimicrobial stainless steel, and the like are not considered to be produced from copper and iron. Patent application number 201410345197.2 proposes to produce copper-containing antimicrobial stainless steel from copper slag, but does not consider the extraction of noble metals, and adds an oxidation process to perform pre-desulfurization treatment before the reduction process, increasing the process flow and production cost.
It is noted that the information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
It is a primary object of the present disclosure to overcome at least one of the above-mentioned drawbacks of the prior art, and to provide a copper-containing steel production system that rationally utilizes copper slag resources to produce copper-containing steel with high efficiency and at low cost.
In order to achieve the above purpose, the present disclosure adopts the following technical scheme:
The present disclosure provides a copper-containing steel production system comprising: the device comprises a heating and sedimentation furnace, a reduction furnace, an electric furnace, a refining device and a forming device, wherein the heating and sedimentation furnace comprises a heating and reduction region and a sedimentation region, the heating and reduction region is communicated with the bottom of the sedimentation region, and a material outlet of the sedimentation region comprises a first liquid outlet and a first slag outlet; the material inlet of the reduction furnace is communicated with the first slag hole of the sedimentation zone, and the material outlet of the reduction furnace comprises a second liquid outlet and a second slag hole; the material inlet of the electric furnace is communicated with the second liquid outlet of the reduction furnace; the material inlet of the refining device is communicated with the material outlet of the electric furnace; the material inlet of the forming device is communicated with the material outlet of the refining device.
According to one embodiment of the present disclosure, the top, bottom and/or side of the heated settling furnace is provided with a first injection port.
According to one embodiment of the present disclosure, a partition plate is provided between the heating reduction zone and the sedimentation zone, and a gap is provided between the partition plate and the bottom of the heating sedimentation furnace, so that the heating reduction zone and the sedimentation zone are two parts communicating with each other at the bottom.
According to one embodiment of the present disclosure, a stirring device is provided in the reduction furnace.
According to one embodiment of the present disclosure, the side, bottom and/or top of the reduction furnace is provided with a second injection port.
According to one embodiment of the disclosure, the reduction furnace is further provided with a flue gas outlet, which is connected to the flue gas recovery processing device.
According to one embodiment of the disclosure, a molten iron pretreatment device is further communicated between the reduction furnace and the electric furnace, the second liquid outlet of the reduction furnace is communicated with the material inlet of the molten iron pretreatment device, and the material outlet of the molten iron pretreatment device is communicated with the material inlet of the electric furnace.
According to one embodiment of the present disclosure, when the copper-containing steel is weathering steel, the refining apparatus includes a ladle refining furnace and a vacuum refining furnace which are sequentially communicated.
According to one embodiment of the present disclosure, when the copper-containing steel is copper-containing antimicrobial stainless steel, the refining apparatus includes a ladle refining furnace, an argon oxygen refining furnace, and a vacuum oxygen blowing decarburization furnace that are sequentially communicated.
According to the technical scheme, the copper-containing steel production system provided by the disclosure has the advantages and positive effects that:
The production system of the copper-containing steel provided by the disclosure can be used for producing the copper-containing steel. The production system firstly provides a heating sedimentation furnace which is provided with a heating reduction zone and a sedimentation zone, most of precious metals in copper slag and copper matte can be settled and separated by adopting the heating sedimentation furnace, the recovered precious metals can directly bring economic benefit, the copper matte can return to a copper smelting process, copper is fully utilized, a large amount of sulfur is taken away, a good foundation is laid for the subsequent steelmaking process, and the desulfurization process and desulfurization cost can be reduced. In addition, the production system of the present disclosure further adopts a reduction furnace to simultaneously recycle iron and copper, and has high efficiency and low cost. The production system disclosed by the invention is used for producing copper-containing steel, has higher recovery rate and low production cost, can realize extraction of valuable elements, fully utilizes iron and copper in copper slag, can obtain copper-containing steel with higher added value, and has good industrial application prospect.
Drawings
FIG. 1 is a schematic view of a production system for copper-containing steel according to one embodiment of the present disclosure;
fig. 2 is a flow chart of a process for producing copper-containing steel according to one embodiment of the present disclosure.
Wherein, the drawings are as follows:
100: heating sedimentation furnace
101: Heating reduction zone
102: Sedimentation zone
103: Partition board
200: Reduction furnace
300: Electric stove
400: Refining device
401: Ladle refining furnace (LF furnace)
402: Vacuum refining furnace (RH furnace)
403: Argon oxygen refining furnace (AOD furnace)
404: Vacuum oxygen decarburization furnace (VOD furnace)
500: Forming device
501: Continuous casting machine
502: Heating furnace
503: Hot rolling mill
600: Tundish
700: Molten iron pretreatment device
Detailed Description
The present disclosure is described below by way of specific embodiments with reference to the accompanying drawings, but the present disclosure is not limited to the following embodiments. The endpoints of the ranges and any values disclosed in this disclosure are not limited to the precise range or value, and such range or value should be understood to encompass values approaching those range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and should be considered as specifically disclosed herein.
Copper slag is industrial solid waste with a large quantity in the metallurgical industry, contains Fe, cu, zn, pb, co, ni and other valuable metals and Au, ag and other small amounts of noble metals, but most of copper slag is piled up in a slag field, so that the copper slag occupies land, pollutes the environment and causes huge waste of resources. The copper slag compositions obtained by different smelting processes have certain differences, and the ranges of the copper slag compositions are shown in table 1.
TABLE 1 chemical composition of slag/%
TFe TCu Fe3O4 SiO2 Al2O3 CaO S Au*
29～45 0.45～3.0 1～20 25～40 ≤10 ≤10 0.6～2.8 <0.5
* The unit is g/t
As shown in Table 1, the copper slag contains 29% -45% of iron, while the average grade of all iron ores in the iron-making industry in China is only 29.1%, and a large amount of imported external ores are needed to be matched with the copper slag for sintering and pelletizing; at present, the exploitation grade of many copper ores in China is only 0.2% -0.3%, and the copper content in copper slag is more than 0.5%. If the iron and copper in the copper slag are fully utilized, the contradiction between the supply and demand of the iron ore and the copper ore can be relieved to a certain extent.
The iron in the copper slag mainly exists in the forms of ferric silicate (2 FeO, siO 2) and magnetite (Fe 3O4), most of the iron is ferric silicate, and the copper mainly exists in the forms of Cu 2 S, cuO and Cu. Since iron in copper slag exists mainly in the form of fayalite, it is difficult to effectively recover the weak magnetic mineral fayalite by a conventional magnetic separation method. To recycle the iron in the copper slag, the 2FeO, siO 2, in the copper slag is firstly converted into Fe 3O4, and then the Fe is recycled by a magnetic separation method. This method has many disadvantages such as failure to recover noble metals, cooling of the high-temperature copper slag and then high-temperature roasting (the temperature of the copper slag is typically 1200 ℃), great waste of heat, low iron recovery, and the like. The wet extraction, ore dressing separation and the like have the defects of complex process, high cost, incapability of realizing industrialization and the like. Although copper slag can also be used for preparing glass ceramics, mineral wool and producing cement, precious iron and copper, and other metal resources are wasted greatly. At present, the research on the utilization technology of copper slag is mainly focused on two aspects of utilization of single copper or utilization of single iron. The method has the advantages that the research on the extraction of noble metals in copper slag and the simultaneous utilization of copper and iron in slag is less, and certain defects exist.
To this end, the present disclosure provides a production system of copper-containing steel, by which copper-containing steel is produced. Wherein fig. 1 representatively illustrates a schematic diagram of a production system for copper-containing steel in accordance with an embodiment of the present disclosure; fig. 2 representatively illustrates a process flow diagram for producing copper-containing steel in accordance with an embodiment of the present disclosure. The production system of the copper-containing steel of the present disclosure will be further described with reference to fig. 1 and 2. Those skilled in the art will readily appreciate that the production system of the present disclosure may be generalized for other colored slag systems as well. Various modifications, additions, substitutions, deletions, or other changes may be made to the following embodiments, which should remain within the principles of the copper-containing steel production process set forth in the present disclosure.
Referring to fig. 1, in the present embodiment, a copper-containing steel production system includes: the method for producing copper-containing steel is specifically described below with reference to the system for producing copper-containing steel by heating and settling furnace 100, reduction furnace 200, electric furnace 300, refining apparatus 400, and forming apparatus 500:
as shown in fig. 1 and 2, the method for producing copper-containing steel includes a sedimentation treatment, a melt reduction treatment, a steelmaking treatment, a refining treatment, and a forming treatment, and is specifically described as follows:
(1) Sedimentation treatment
The foregoing heat and sedimentation furnace 100 is used for sedimentation treatment, and the heat and sedimentation furnace 100 includes a heat reduction zone 101 and a sedimentation zone 102, and in some embodiments, a partition 103 is disposed between the heat reduction zone 101 and the sedimentation zone 102, and a gap is formed between the partition 103 and the bottom of the heat and sedimentation furnace 100, so that the heat reduction zone 101 and the sedimentation zone 102 are two parts with bottom communicating. The material outlet of the settling zone 102 comprises a first liquid outlet and a first slag outlet (not shown).
Firstly, copper slag to be treated is placed in a heating reduction zone 101 to be heated to 1300-1600 ℃, sedimentation treatment is carried out in a sedimentation zone 102, sedimentation separation can be completed in the sedimentation zone 102 due to different densities of the copper slag and copper matte, noble metals contained in the copper slag and the copper matte are discharged from a first liquid outlet together in a liquid state, and high-temperature slag after sedimentation treatment is discharged from a first slag outlet. And (3) extracting the noble metal, and recycling the copper and sulfur after extracting the noble metal, for example, returning to a converting furnace for copper smelting. Through the sedimentation treatment, 85% -95% of copper matte and 85% -95% of noble metal are separated from copper slag, so that the sulfur content of the copper slag is reduced, conditions are created for further reducing copper-containing molten iron, and the desulfurization process flow and the desulfurization cost are reduced.
In some embodiments, the copper slag to be treated may be tapped high temperature copper slag at a temperature of 1100 ℃ to 1300 ℃ that is transferred through tundish 600 into the heated reduction zone 101 of the heated settler 100. The waste heat of the high-temperature copper slag can be fully utilized by directly utilizing the high-temperature copper slag, and the requirements of energy conservation and emission reduction are met.
In some embodiments, the top, bottom, and/or sides of the heated settling furnace 100 are provided with first nozzles. The first injection port is provided with a lance for injecting a reducing gas, such as natural gas, oil, carbon monoxide, or the like, into the heated settling furnace 100. According to the position where the first blowing openings are arranged, the blowing mode can be top blowing, bottom blowing, side blowing or compound blowing modes, and one or more first blowing openings can be arranged at different positions. The blowing pressure can be 100kPa to 1000kPa, and continuous blowing can be performed. The advantages of using the injected reducing gas are: the heat of the heating sedimentation furnace can be provided by jetting the reducing gas, so that the cost for improving the temperature is lower; in addition, as the injected gas is reducing gas, the formed reducing atmosphere can reduce ferroferric oxide (Fe 3O4) contained in the copper slag to be treated into ferrous oxide (FeO), thereby reducing the viscosity of the copper slag and being beneficial to the sedimentation separation. However, the heating method of the present disclosure is not limited thereto, and for example, heating may be performed by an electrode method. In addition, in some embodiments, after the copper slag to be treated flows into the sedimentation zone after being heated to a certain temperature, electrodes can be used for continuing heating so as to maintain the temperature in the furnace, and thus the sedimentation separation treatment process is completed.
(2) Melt reduction treatment
The melting reduction treatment is performed using the aforementioned reduction furnace 200. Wherein, the material inlet of the reduction furnace 200 is connected to the first slag hole of the settling zone 102, and the material outlet of the reduction furnace 200 includes a second liquid outlet and a second slag hole (not shown).
Transferring the settled copper slag into the reduction furnace 200, adding a slag former, heating to a molten state in the reduction furnace 200, and then blowing a reducing agent into the reduction furnace 200 to perform a smelting reduction reaction to obtain copper-containing molten iron and slag. Wherein the high-temperature copper-containing molten iron flows out from the second liquid outlet and enters a steelmaking process; slag is discharged through the second slag hole. In some embodiments, the reduction furnace 200 is further provided with a flue gas outlet connected to a flue gas recovery treatment device that specifically treats and recovers flue gas during reduction, as well as harmful elements. Through the steps, iron and copper are reduced, and metals with lower melting points such as zinc (Zn) enter the flue gas to be recovered. The main chemical reactions that occur during the melt reduction process are as follows:
Cu2S+CaO+C＝2Cu+CaS+CO (1)
Fe2SiO4+2CaO+2C＝2Fe+Ca2SiO4+2CO (2)
Fe3O4+4C＝3Fe+4CO (3)
2[P]+5(FeO)+4(CaO)＝(4CaO·P2O5)+[Fe] (4)
[FeS]+(CaO)＝(CaS)+(FeO) (5)
CuO+C＝Cu+CO (6)
in some embodiments, the temperature of the melt reduction reaction is 1450 ℃ to 1750 ℃.
In some embodiments, one or more second injection ports are provided at the side, bottom and/or top of the reduction furnace 200, for example, the reduction furnace shown in fig. 1 is a side-blown furnace, and a plurality of second injection ports are provided. When the materials in the reduction furnace 200 are in a molten state after reaching the temperature range, the reducing agent is injected into the reduction furnace 200 through the second injection port by using the spray gun, wherein the reducing agent is selected from one or more of pulverized coal, carbon monoxide, natural gas, hydrogen and tar, and preferably, the injected pulverized coal is mainly used, so that compared with other technical cost is lower. The addition amount of the reducing agent is determined according to the ratio of the carbon content C in the reducing agent to the iron content Fe x+ in the settled copper slag by mass ratio, the ratio is controlled between 1.2 and 2.8, and X is 2 or 3.
In some embodiments, a stirring device (not shown) may be further added to the reduction furnace 200 to stir the molten material, or to blow inert gas, so as to improve the kinetic conditions of the reaction and increase the reaction rate. Wherein, the inert gas can be nitrogen (N 2) or argon (Ar), and the blowing pressure is 100 kPa-1000 kPa.
In some embodiments, the slag former comprises calcium oxide, and optionally calcium carbonate may be added, which may be thermally decomposed to produce calcium oxide for slag formation. The addition amount of the slag former is determined according to the alkalinity R, wherein:
Wherein MgO and SiO 2 are both from copper slag after sedimentation treatment, the range of alkalinity R is controlled between 1.0 and 2.5, ω (CaO)% represents the mass fraction of CaO, ω (MgO)% represents the mass fraction of MgO, and ω (SiO 2)% represents the mass fraction of SiO 2.
In some embodiments, small amounts of calcium fluoride (CaF 2) may be added to the slag former in order to allow better progress of the melting reaction. With the increase of the addition amount of the calcium oxide, the viscosity of the copper slag is increased, so that the contact surface of the calcium oxide and the copper slag is reduced, the reduction condition is deteriorated, the reaction rate is reduced, the addition of the CaF 2 can damage the silicon oxygen tetrahedron structure of silicate ions in the slag, the viscosity of the slag is reduced, the contact area is increased, and the dynamic condition of the reduction reaction is improved. Preferably, the calcium fluoride is added in an amount of 8-20% of the total amount of the slag former in percentage by mass.
In the field, a reduction furnace is commonly used for smelting copper, and the reduction furnace is further adopted for smelting copper and iron simultaneously, so that iron oxides in copper slag are reduced to iron, copper oxides are reduced to copper, the copper and the iron are comprehensively utilized, the recovery rate is high, and the production cost is reduced. The sulfur content in the copper slag is low after reduction sedimentation treatment, so that the desulfurization burden is greatly reduced; because the melting point of zinc, lead, arsenic and the like is low, the zinc, lead, arsenic and the like enter smoke in the reduction process and can be recovered through a set system, and the smoke is discharged into the atmosphere after being treated; in addition, the produced slag can also be used for producing cement, mineral wool, for paving and the like.
(3) Steelmaking and refining process
Alloying the copper-containing molten iron to obtain copper-containing molten steel, and refining the copper-containing molten steel to obtain refined molten steel. Specifically, the copper-containing molten iron after the above-described melt reduction reaction is transferred to the electric furnace 300, subjected to electric furnace steelmaking treatment, and then transferred to the refining apparatus 400 to be subjected to refining treatment. Wherein, the material inlet of the electric furnace 300 is communicated with the second liquid outlet of the reduction furnace 200, and the material inlet of the refining device 400 is communicated with the material outlet of the electric furnace.
In some embodiments, a molten iron pretreatment device 700 is further communicated between the reduction furnace 200 and the electric furnace 300 to perform a molten iron pretreatment process. Wherein, the second liquid outlet of the reduction furnace 200 is communicated with the material inlet of the molten iron pretreatment device 700, and the material outlet of the molten iron pretreatment device 700 is communicated with the material inlet of the electric furnace 300. Specifically, the content of C, si, mn, S, P, cu and the like is detected on line before steelmaking by copper-containing molten iron. If the Si, P and S contents are not satisfactory, further molten iron pretreatment is needed, comprising: desilication, dephosphorization and desulfurization, or directly adding ferroalloy and scrap steel for component adjustment. Wherein the pretreatment of molten iron is carried out by a process commonly used in the art. In the present disclosure, the pretreated copper-containing molten iron requires, in mass percent: the silicon content is 0.45-0.85%, the phosphorus content is less than 0.15%, and the sulfur content is 0.05-0.07%. After meeting the steel-making requirements, alloying treatment is carried out according to different steel grades. Wherein the alloying treatment is carried out by a process commonly used in the art.
The component requirements of copper-containing steel are met through molten iron pretreatment or adding ferroalloy and scrap steel to adjust the components in the steelmaking process. The composition of copper can be adjusted through an alloying link in the steelmaking process, copper-containing steel with different requirements is smelted, and the capability of producing various copper-containing steels is realized. In the steelmaking process, various copper-containing steels are smelted by adjusting copper or other alloys such as chromium, nickel and the like, and the steel type components can be adjusted according to market conditions.
The copper-containing steel related by the disclosure comprises weathering resistant steel, copper-containing stainless steel, copper-containing antibacterial stainless steel and other steel types, and the technical routes are different due to different production steel types. The smelting process is carried out after qualified copper-containing molten steel is smelted, namely, the external refining process is a steelmaking process which is to pour the molten steel into a ladle or a special container for deoxidization, desulfurization, decarburization, degassing, removing nonmetallic inclusion and adjusting the composition and the temperature of the molten steel so as to achieve the further smelting purpose. The refining apparatus 400 includes a ladle refining furnace (LF furnace) 401 for desulfurizing, deoxidizing, removing inclusions, alloying; a vacuum refining furnace (RH furnace) 402 for dehydrogenation, decarburization, deoxidation; an argon oxygen refining furnace (AOD furnace) 403 for rapid decarburization and avoiding oxidation of chromium is suitable for stainless steel smelting. The vacuum oxygen decarburization furnace (VOD oven) 404 easily removes carbon and nitrogen in molten steel to a low level under vacuum conditions, and is suitable for stainless steel smelting. Specifically:
In some embodiments, where the copper-containing steel is weathering steel, the refining apparatus 400 includes a ladle refining furnace and a vacuum refining furnace (LF-RH furnace) in series. After refining, the weathering steel contains 0.12 to 0.21 mass percent of carbon, 0.2 to 2.0 mass percent of silicon, 0.7 to 2.0 mass percent of manganese, no more than 0.036 mass percent of sulfur, no more than 0.034 mass percent of phosphorus, 0.10 to 0.40 mass percent of copper and less than 0.2 mass percent of aluminum.
In some embodiments, where the copper-containing steel is copper-containing antimicrobial stainless steel, the refining apparatus 400 includes a ladle refining furnace, an argon oxygen refining furnace, and a vacuum oxygen decarburization furnace (LF furnace-AOD furnace-VOD furnace) in sequential communication. Wherein the copper-containing antimicrobial stainless steel comprises austenitic copper-containing antimicrobial stainless steel, ferritic copper-containing antimicrobial stainless steel or martensitic copper-containing antimicrobial stainless steel.
When the obtained copper-containing steel is austenitic copper-containing antibacterial stainless steel or ferrite copper-containing antibacterial stainless steel, the carbon content in the austenitic copper-containing antibacterial stainless steel or ferrite copper-containing antibacterial stainless steel is not more than 0.07%, the silicon content is not more than 1.00%, the manganese content is not more than 2.00%, the phosphorus content is not more than 0.035%, the sulfur content is not more than 0.03%, the nickel content is 8.00% -11.00%, the chromium content is 17.00% -19.00%, and the copper content is 1.50% -4.00% after refining is completed.
When the obtained copper-containing steel is martensitic copper-containing antibacterial stainless steel, after refining, the martensitic copper-containing antibacterial stainless steel contains 0.16-0.35% of carbon, not more than 1.00% of silicon, not more than 2.00% of manganese, not more than 0.035% of phosphorus, not more than 0.03% of sulfur, not more than 0.60% of nickel, 12.00-14.00% of chromium and 2.50-4.00% of copper.
(4) And (3) forming:
After refining, the refined molten steel is subjected to forming treatment by adopting a forming device 500, wherein the forming device 500 comprises a continuous casting machine 501, a heating furnace 502, a hot rolling mill 503 and the like, and means such as continuous casting, hot rolling, heat treatment, cold rolling and the like are sequentially carried out to prepare a qualified copper-containing steel product. The hot rolling process parameters of the copper-containing steel are as follows: the heating temperature is 1150-1300 ℃; the initial temperature of the coarse bundling is 950-1100 ℃; finish rolling starting temperature, 930-1050 ℃; finish rolling finishing temperature is 800-1000 ℃; the coiling temperature is 650-830 ℃. Wherein, the production of the cold-rolled stainless steel plate strip is not simple cold rolling, annealing, acid washing, grinding and the like are required before cold rolling, and flattening, straightening, shearing, stacking and the like are required after cold rolling.
The present disclosure is described in detail with reference to the following examples, but the scope of the present disclosure is not limited by the following examples. Example 1:
(1) And (3) extracting noble metals and copper matte through sedimentation treatment:
Firstly, transferring high-temperature copper slag (TFe：41.65％、TCu：1.32％、Fe3O4：11.2％、SiO2：28.9％、Al2O3：1.45％、CaO：2.56％、S：1.16％、Au：0.45g/t) at 1180 ℃ into a heating reduction zone in a heating sedimentation furnace through a tundish, providing heat by side blowing natural gas and reducing Fe 3O4, wherein the blowing pressure is 150kPa, and the mode is side blowing, so that the temperature is increased to 1380 ℃; the copper slag after temperature rise flows into a sedimentation zone, the temperature is raised by an electrode and kept at 1380 ℃, and a sedimentation process is started, wherein the process is a continuous process; 85% of copper and 85% of noble metal can be recovered in the sedimentation process; the recovered copper matte re-enters the copper smelting process, and the rest copper slag enters the smelting reduction process.
(2) Smelting reduction iron making to obtain copper-containing molten iron:
Flowing the settled high-temperature copper slag into a reducing furnace, and then adding a certain amount of CaO and CaCO 3, wherein CaCO 3 is thermally decomposed to obtain CaO, and the CaO which is initially added are used as a slag former; the addition amount of CaO and CaCO 3 is calculated by the alkalinity, and the alkalinity of the embodiment is 1.2; the addition amount of CaF 2 is 10% of the slag former; the furnace temperature was raised to 1480 ℃ by means of electrode heating. When the materials in the reduction furnace and the slag former are in a molten state, coal dust is sprayed into a molten pool, and the adding amount is 1.5 in a ratio of C/Fe x+ (x=2, 3). After the blowing is finished, nitrogen is blown into the molten pool, and the position of the spray gun is changed during the blowing period, so that the stirring achieves the optimal effect; the stirring device is added to make the interface reaction of the slag and the iron more complete and the reaction speed faster. And after the reaction is finished, separating slag and iron to obtain copper-containing molten iron. Performing C, si, mn, S, P, cu component detection on the copper-containing molten iron; and (3) carrying out pretreatment of Si, P and S molten iron, and then sending the molten iron into an electric furnace for steelmaking process.
(3) Steelmaking treatment, refining treatment and molding treatment:
Alloying according to the component requirements of smelting weathering steel, and after alloying is finished, entering an LF furnace-RH furnace for impurity removal; and then carrying out continuous casting flow, hot rolling flow and heat treatment to obtain weather-resistant steel with qualified quality, wherein the components of the weather-resistant steel are C:0.16%, si:046%, mn:1.0%, S:0.02%, P:0.08%, cu:0.32%, al:0.08%.
Example 2:
(1) And (3) extracting noble metals and copper matte through sedimentation treatment:
Firstly, transferring high-temperature copper slag (TFe：41.50％、TCu：1.30％、Fe3O4：12.0％、SiO2：27.8％、Al2O3：1.50％、CaO：2.60％、S：1.14％、Au：0.48g/t) at 1200 ℃ into a heating reduction zone in a heating sedimentation furnace through a tundish, providing heat and reducing Fe 3O4 by spraying natural gas, wherein the spraying pressure is 500kPa, and the mode is top blowing, so that the temperature is increased to 1400 ℃; the copper slag after temperature rise flows into a sedimentation zone, the temperature is raised and kept at 1400 ℃ by using an electrode, and a sedimentation process is started, wherein the process is a continuous process; 88% of copper and 90% of noble metal in the sedimentation process can be recovered; the recovered copper matte re-enters the copper smelting process, and the rest copper slag enters the smelting reduction process.
(2) Smelting reduction iron making to obtain copper-containing molten iron:
flowing the settled high-temperature copper slag into a reducing furnace, and then adding a certain amount of CaO and CaCO 3, wherein CaCO 3 is thermally decomposed to obtain CaO, and the CaO which is initially added are used as a slag former; the addition amount of CaO and CaCO 3 is calculated by the alkalinity, and the alkalinity of the embodiment is 1.4; the addition amount of CaF 2 is 12% of the slag former; the furnace temperature was raised to 1560 c by means of electrode heating. When the furnace burden and the slag former are in a molten state, natural gas is blown into a molten pool, and the addition amount is 1.9 in a ratio of C/Fe x+ (x=2, 3). After the blowing is finished, argon is blown into the molten pool, and the position of a spray gun is changed during the blowing period, so that the stirring achieves the optimal effect; the stirring device is added to make the interface reaction of the slag and the iron more complete and the reaction speed faster. And after the reaction is finished, separating slag and iron to obtain copper-containing molten iron. Performing C, si, mn, S, P, cu component detection on the copper-containing molten iron; and (3) carrying out pretreatment of Si, P and S molten iron, and then sending the molten iron into an electric furnace for steelmaking process.
(3) Steelmaking treatment, refining treatment and molding treatment:
Alloying according to the component requirements of smelting copper-containing antibacterial stainless steel, and after alloying is finished, entering an LF furnace-AOD furnace-VOD furnace for impurity removal; then carrying out continuous casting flow-hot rolling flow-heat treatment, wherein the heating temperature is 1200 ℃; the initial temperature of the coarse bundling is 1050 ℃; finish rolling starting temperature, 980 ℃; finish rolling finishing temperature, 850 ℃; coiling temperature, 700 ℃. The copper-containing antibacterial stainless steel with qualified quality is obtained, and the components are C:0.20%, si:0.5%, mn:1.2%, P:0.05%, S:0.008%, ni:0.60%, cr:13.00%, cu:2.6%.
Example 3:
(1) And (3) extracting noble metals and copper matte through sedimentation treatment:
Firstly, transferring high-temperature copper slag (TFe：40.95％、TCu：1.28％、Fe3O4：13.0％、SiO2：26.9％、Al2O3：1.33％、CaO：2.66％、S：1.09％、Au：0.46g/t) at 1250 ℃ into a heating reduction zone in a heating sedimentation furnace through a tundish, and heating the copper slag by an electrode mode to raise the temperature to 1500 ℃; the copper slag after temperature rise flows into a sedimentation zone, the temperature is raised by an electrode and kept at 1500 ℃, and a sedimentation process is started, wherein the process is a continuous process; 90% of copper and 85% of noble metal can be recovered in the sedimentation process; the recovered copper matte re-enters the copper smelting process, and the rest copper slag enters the smelting reduction process.
(2) Smelting reduction iron making to obtain copper-containing molten iron:
Flowing the settled high-temperature copper slag into a reducing furnace, and then adding a certain amount of CaO and CaCO 3, wherein CaCO 3 is thermally decomposed to obtain CaO, and the CaO which is initially added are used as a slag former; the addition amount of CaO and CaCO 3 is calculated by the alkalinity, and the alkalinity of the embodiment is 2.0; the addition amount of CaF 2 is 15% of the slag former; the furnace temperature was raised to 1600 c by means of electrode heating. When the furnace burden and the slag former are in a molten state, coal dust is injected into a molten pool, and the addition amount is 2.0 in a ratio of C/F x+ (x=2, 3). After the blowing is finished, nitrogen is blown into the molten pool, and the position of the spray gun is changed during the blowing period, so that the stirring achieves the optimal effect; the stirring device is added to make the interface reaction of the slag and the iron more complete and the reaction speed faster. And after the reaction is finished, separating slag and iron to obtain copper-containing molten iron. Performing C, si, mn, S, P, cu component detection on the copper-containing molten iron; adding ferroalloy and scrap steel to adjust the components to meet the component requirements, and then sending the steel into an electric furnace to carry out steelmaking flow.
(3) Steelmaking treatment, refining treatment and molding treatment:
Alloying according to the component requirements of smelting weathering steel, and after alloying is finished, entering an LF furnace-RH furnace for impurity removal; and then carrying out continuous casting flow, hot rolling flow and heat treatment to obtain weather-resistant steel with qualified quality, wherein the components of the weather-resistant steel are C:0.15%, si:044%, mn:1.2%, S:0.01%, P:0.07%, cu:0.33%, al:0.07%.
Example 4:
(1) And (3) extracting noble metals and copper matte through sedimentation treatment:
Firstly, transferring high-temperature copper slag (TFe：40.89％、TCu：1.02％、Fe3O4：13.4％、SiO2：28.6％、Al2O3：1.46％、CaO：2.70％、S：1.07％、Au：0.44g/t) at 1280 ℃ into a heating reduction zone in a heating sedimentation furnace through a tundish, providing heat and reducing Fe 3O4 by spraying carbon monoxide, wherein the spraying pressure is 1000kPa, and the mode is top-blowing, so that the temperature is increased to 1600 ℃; the copper slag after temperature rise flows into a sedimentation zone, the temperature is raised and kept at 1600 ℃ by using an electrode, and a sedimentation process is started, wherein the process is a continuous process; 93% of copper and 90% of noble metal can be recovered in the sedimentation process; the recovered copper matte re-enters the copper smelting process, and the rest copper slag enters the smelting reduction process.
(2) Smelting reduction iron making to obtain copper-containing molten iron:
Flowing the settled high-temperature copper slag into a smelting reduction furnace, and then adding a certain amount of CaO and CaCO 3, wherein CaCO 3 is thermally decomposed to obtain CaO, and the CaO which is initially added are used as a slag former; the addition amount of CaO and CaCO 3 is calculated by the alkalinity, and the alkalinity of the embodiment is 2.4; the addition amount of CaF 2 is 18% of the slag former; the furnace temperature was raised to 1700 ℃ by means of electrode heating. When the furnace burden and the slag former are in a molten state, coal dust is sprayed into a molten pool, and the adding amount is 2.6 in a ratio of C/Fe x+ (x=2, 3). After the blowing is finished, nitrogen is blown into the molten pool, and the position of the spray gun is changed during the blowing period, so that the stirring achieves the optimal effect; the stirring device is added to make the interface reaction of the slag and the iron more complete and the reaction speed faster. And after the reaction is finished, separating slag and iron to obtain copper-containing molten iron. Performing C, si, mn, S, P, cu component detection on the copper-containing molten iron; adding ferroalloy and scrap steel to adjust the components to meet the component requirements, and then sending the steel into an electric furnace to carry out steelmaking flow.
(3) Steelmaking treatment, refining treatment and molding treatment:
Alloying according to the component requirements of smelting copper-containing antibacterial stainless steel, and after alloying is finished, entering an LF furnace-AOD furnace-VOD furnace for impurity removal; then carrying out continuous casting flow-hot rolling flow-heat treatment, wherein the heating temperature is 1250 ℃; the initial temperature of coarse bundling is 1040 ℃; finish rolling starting temperature, 970 ℃; finish rolling finishing temperature, 830 ℃; coiling temperature, 680 ℃. The copper-containing antibacterial stainless steel with qualified quality is obtained, and the components are C:0.05%, si:0.45%, mn:1.5%, P:0.007%, S:0.006%, ni:10.00%, cr:138.00%, cu:2.8%.
In conclusion, the production system disclosed by the invention is used for producing copper-containing steel, the recovery rate is higher, the production cost is low, the extraction of valuable elements can be realized, the iron and copper in copper slag are fully utilized, the copper-containing steel with higher added value can be obtained, and the production system has good industrial application prospect.
It should be noted by those skilled in the art that the embodiments described in this disclosure are merely exemplary and that various other substitutions, modifications and improvements may be made within the scope of this disclosure. Thus, the present disclosure is not limited to the above-described embodiments, but is only limited by the claims.

Claims (7)

1. A system for producing copper-containing steel, comprising:
The heating sedimentation furnace comprises a heating reduction zone and a sedimentation zone, wherein the heating reduction zone is communicated with the bottom of the sedimentation zone, and a material outlet of the sedimentation zone comprises a first liquid outlet and a first slag outlet;
placing copper slag to be treated in a heating reduction zone, heating to 1300-1600 ℃, carrying out sedimentation treatment in a sedimentation zone, discharging noble metals contained in the copper slag and copper matte together in a liquid state from a first liquid outlet, and discharging high-temperature slag after sedimentation treatment from the first slag outlet;
The material inlet of the reduction furnace is communicated with the first slag hole of the sedimentation zone, and the material outlet of the reduction furnace comprises a second liquid outlet and a second slag hole;
the material inlet of the electric furnace is communicated with the second liquid outlet of the reduction furnace;
the material inlet of the refining device is communicated with the material outlet of the electric furnace;
the material inlet of the forming device is communicated with the material outlet of the refining device;
The top, the bottom and/or the side edges of the heating sedimentation furnace are provided with first blowing openings; the first blowing opening is provided with a spray gun for blowing reducing gas to the heating sedimentation furnace;
the side, bottom and/or top of the reduction furnace are provided with second blowing openings; and when the materials in the reduction furnace are in a molten state, blowing a reducing agent into the reduction furnace through the second blowing opening by using a spray gun.
2. The production system of claim 1, wherein a partition is provided between the heated reduction zone and the settling zone, and the partition has a gap with the bottom of the heated settling furnace such that the heated reduction zone and the settling zone are two parts in bottom communication.
3. The production system according to claim 1, wherein a stirring device is provided in the reduction furnace.
4. The production system according to claim 1, wherein the reduction furnace is further provided with a flue gas outlet, the flue gas outlet being connected to a flue gas recovery processing device.
5. The production system of claim 1, wherein a molten iron pretreatment device is further communicated between the reduction furnace and the electric furnace, a second liquid outlet of the reduction furnace is communicated with a material inlet of the molten iron pretreatment device, and a material outlet of the molten iron pretreatment device is communicated with a material inlet of the electric furnace.
6. The production system of claim 1, wherein when the copper-containing steel is weathering steel, the refining apparatus comprises a ladle refining furnace and a vacuum refining furnace which are sequentially communicated.
7. The production system of claim 1, wherein when the copper-containing steel is copper-containing antimicrobial stainless steel, the refining device comprises a ladle refining furnace, an argon oxygen refining furnace and a vacuum oxygen blowing decarburization furnace which are sequentially communicated.
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