CN110016571B - Copper-containing cast iron production system - Google Patents

Copper-containing cast iron production system Download PDF

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Publication number
CN110016571B
CN110016571B CN201910432643.6A CN201910432643A CN110016571B CN 110016571 B CN110016571 B CN 110016571B CN 201910432643 A CN201910432643 A CN 201910432643A CN 110016571 B CN110016571 B CN 110016571B
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copper
furnace
slag
sedimentation
reduction
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CN110016571A (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
    • C21C1/00—Refining of pig-iron; Cast iron
    • C21C1/08—Manufacture of cast-iron
    • 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
    • C22B15/0028—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
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/08—Making cast-iron alloys
    • 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 present disclosure provides a production system comprising copper-containing cast iron: the heating sedimentation furnace comprises a heating reduction zone and a sedimentation zone, 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; 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 smelting furnace is communicated with the second liquid outlet of the reduction furnace; and the material inlet of the casting device is communicated with the material outlet of the smelting furnace. The production system is used for producing copper-containing cast iron, has high recovery rate and low production cost, can realize extraction of valuable elements, and fully utilizes iron and copper in copper slag; the copper-containing corrosion-resistant cast iron can be obtained by adding alloys such as manganese, silicon, copper, chromium, nickel and molybdenum, so that the value of the product can be greatly improved, and the economic benefit is improved.

Description

Copper-containing cast iron production system
Technical Field
The invention relates to the field of metallurgy, in particular to a production system of copper-containing cast iron.
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.
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. There are many methods for recovering copper in slag, mainly including pyrogenic depletion, wet extraction, mineral separation, etc. However, current research on copper slag utilization technology has focused on both copper alone utilization and iron alone utilization. For extracting metals in copper slag, the beneficiation method is widely applied, but the recycling utilization rate is low; the recovery rate of the pyrometallurgical metal is high, but the treatment cost is high; wet treatment is potentially secondary and costly. Although the copper slag can also be used for preparing microcrystalline glass and mineral wool; the method is used for producing cement, and precious iron and copper, and other metal resources are wasted greatly.
With the progress of technology, people have new knowledge of the influence of copper on the performance of steel, and the copper is not stopped from generating 'copper embrittlement' hazard, and copper has a plurality of beneficial effects in steel, such as improving corrosion resistance, strength, impact resistance and the like. If copper and iron in the copper slag can be effectively utilized and the beneficial influence of copper on iron is exerted, a new way for efficiently utilizing the copper slag is provided.
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 iron extraction process based on the previous patents, but the recovery of noble metals and copper is still not considered. Although China patent application 201110380257.0 considers the problem of copper recovery, the addition of chloride salts in the process still has the problem of pollution. Chinese patent application 201410345197.2 proposes to produce copper-containing antibacterial stainless steel by using copper slag, but the extraction of noble metals is not considered, and the process for preparing the copper-containing antibacterial stainless steel is complex, not easy to realize and has higher utilization cost. Chinese patent application 20151201607. X proposes to prepare copper-containing cast iron from copper-containing slag, but it is also to extract noble metals (Zn, ag, au, etc.), and does not treat impurities in copper-containing molten iron, so that its product does not meet the requirements.
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 system for producing copper-containing cast iron by rational utilization of copper slag resources, in order to produce copper-containing cast iron efficiently and at low cost.
In order to achieve the above purpose, the present disclosure adopts the following technical scheme:
The present disclosure provides a production system of copper-containing cast iron, comprising: the heating sedimentation furnace comprises a heating reduction zone and a sedimentation zone, 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; 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 smelting furnace is communicated with the second liquid outlet of the reduction furnace; and the material inlet of the casting device is communicated with the material outlet of the smelting furnace.
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 present disclosure, the smelting furnace is an electric furnace or an induction furnace.
According to the technical scheme, the copper-containing cast iron production system provided by the disclosure has the advantages and positive effects that:
The copper-containing cast iron production system provided by the disclosure can be used for producing copper-containing cast iron. The production system 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 separated by sedimentation through 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, and a good foundation is laid for the subsequent entering of cast iron process. In addition, the production system further adopts the reduction furnace to simultaneously recycle iron and copper, and has high efficiency and low cost. The copper-containing cast iron is produced by the production system, the smelting difficulty is greatly reduced, the copper-containing corrosion-resistant cast iron can be obtained by adding alloys such as manganese (Mn), silicon (Si), copper (Cu), chromium (Cr), nickel (Ni), molybdenum (Mo) and the like, the value of a product can be greatly improved, and the economic benefit is improved.
Drawings
FIG. 1 is a schematic view of a production system of copper-containing cast iron according to one embodiment of the present disclosure;
fig. 2 is a flow chart of a process for producing copper-containing cast iron according to one embodiment of the present disclosure.
Wherein reference numerals are as follows:
100: heating sedimentation furnace
101: Heating reduction zone
102: Sedimentation zone
103: Partition board
200: Reduction furnace
300: Smelting furnace
400: Casting device
500: Tundish
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 cast iron by which copper-containing cast iron 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 copper-containing cast iron 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 cast iron production system includes: the production method of copper-containing cast iron is specifically described below with reference to the production system of copper-containing cast iron by means of the heat sedimentation furnace 100, the reduction furnace 200, the smelting furnace 300, and the casting apparatus 400:
as shown in fig. 1 and 2, the production method of copper-containing cast iron of the present disclosure includes a sedimentation treatment, a melt reduction treatment, a smelting treatment, and a casting treatment, and specifically includes the following:
(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 1300-1500 ℃, 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% -96% of copper matte and 85% -96% 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 500 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.
In some embodiments, an inert gas may also be injected into the settling zone 102, wherein the inert gas is selected from nitrogen or argon, and the pressure of the injected inert gas is 100kPa to 1000kPa. The copper matte can collide and grow up by blowing in inert gas and stirring in the sedimentation process, which is more beneficial to sedimentation.
(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 smelting 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 1400 ℃ to 1650 ℃.
In some embodiments, one or more second injection ports are provided at the side or top or bottom 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 1.1 and 2.9, 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 1.1 and 2.6, 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. After the smelting reduction reaction treatment, the sulfur content in the copper slag is low, 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) Smelting treatment
Placing the copper-containing molten iron subjected to the smelting reduction reaction in a smelting furnace 300, adding an auxiliary agent, and heating to perform smelting treatment; wherein the material inlet of the smelting furnace 300 is communicated with the second liquid outlet of the reduction furnace 200.
In some embodiments, the smelting furnace 300 may be an electric furnace or an induction furnace. The auxiliary agent includes, but is not limited to, one or more of scrap steel, carburant, desulfurizing agent, dephosphorizing agent, ferromanganese, ferrosilicon or inoculant. The composition of the copper-containing molten iron is adjusted by the auxiliary agent so as to meet the composition requirement of the cast pig iron. The smelting temperature is not too high or too low, and the smelting temperature suitable for producing copper-containing cast iron is 1300-1580 ℃.
(4) Casting treatment
The casting process includes placing the copper-containing molten iron after the smelting process into the casting apparatus 400 for casting molding. Wherein the material inlet of the casting device 400 is communicated with the material outlet of the smelting furnace 300.
In some embodiments, the casting temperature is 1280-1500 ℃, and the casting treatment mode can be sand casting or special casting, and the special casting can be investment casting, gypsum type precision casting, ceramic type precision casting, lost foam casting, metal type casting, pressure casting, low pressure casting, differential pressure casting, vacuum suction casting, extrusion casting, centrifugal casting, continuous casting, semi-continuous casting, shell casting, graphite type casting, electroslag casting and the like. But the present disclosure is not limited thereto.
In some embodiments, the methods of the present disclosure may produce copper-containing corrosion resistant cast iron. Specifically, alloying of different components can be performed according to the requirements of different copper-containing corrosion-resistant cast irons on copper, manganese, silicon, chromium, nickel, molybdenum and the like during smelting treatment. Specifically, it may include: adding one or more of pure copper, ferromanganese alloy, ferrosilicon alloy, ferrochrome alloy, ferronickel alloy or ferromolybdenum alloy into a smelting furnace in the smelting treatment process. The copper-containing corrosion-resistant cast iron can be produced by changing the carbon content, the carbon content of the copper-containing corrosion-resistant cast iron can be controlled below 2.11 percent by mass percent, and other contents are realized by adding copper, manganese, silicon, chromium, nickel, molybdenum and the like.
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) Sedimentation treatment for extracting noble metal and copper matte
Firstly, transferring high-temperature copper slag (TFe：42.65％、TCu：1.12％、Fe3O4：16.2％、SiO2：25.9％、Al2O3：1.35％、CaO：2.66％、S：1.26％、Au：0.48g/t) at 1130 ℃ 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 180kPa, and the mode is side blowing, so that the temperature is increased to 1380 ℃; then the copper slag flows into a sedimentation zone through a baffle plate, and the copper matte grows up by blowing nitrogen, wherein the blowing pressure is 180kPa, and the mode is side blowing; raising the temperature by using the electrode to keep the temperature at 1380 ℃, and starting a sedimentation process, wherein the process is a continuous process; 87% of copper and 88% of noble metal can be recovered in the sedimentation process; the recovered copper matte re-enters a copper smelting process; and the rest copper slag enters a smelting reduction flow.
(2) Smelting reduction iron making to obtain copper-containing molten iron
Flowing the settled high-temperature copper slag into a reduction furnace, and then adding a certain amount of slag former CaO; the addition amount of the slag former 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 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 1.6 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.
(3) Smelting and casting processes
Transferring the copper-containing molten iron into an electric furnace for smelting treatment. The composition of the copper-containing molten iron is adjusted by scrap steel, carburant, desulfurizing agent, dephosphorizing agent, ferromanganese alloy and ferrosilicon alloy to meet the composition requirement of cast pig iron. Further, the temperature is raised to 1500 ℃, alloying is realized by adding pure copper, ferrochrome, ferronickel, ferromolybdenum and the like, and then casting treatment is carried out. Wherein the casting temperature in the casting treatment is 1300 ℃.
The copper-containing cast iron finally obtained comprises the following components: c:3.2%, si:1.6%, mn:0.7%, S:0.12%, P:0.02%, cu:1.2%, mo:0.5%.
Example 2:
(1) Sedimentation treatment for extracting noble metal and copper matte
Firstly, transferring high-temperature copper slag (TFe：50.45％、TCu：1.2％、Fe3O4：12.2％、SiO2：26.9％、Al2O3：1.15％、CaO：2.86％、S：1.36％、Au：0.43g/t) at 1200 ℃ 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 160kPa, and the mode is side blowing, so that the temperature is increased to 1440 ℃; then the copper matte flows into a sedimentation area through a baffle plate, and is grown up by blowing nitrogen gas, wherein the blowing pressure is 160kPa, and the mode is side blowing; maintaining the temperature at 1440 ℃ with the electrodes, and starting the sedimentation process, wherein the process is a continuous process; 90% of copper and 90% of noble metal can be recovered in the sedimentation process; the recovered copper matte re-enters a copper smelting process; and the rest copper slag enters a smelting reduction flow.
(2) Smelting reduction iron making to obtain copper-containing molten iron
Flowing the settled high-temperature copper slag into a reduction furnace, and then adding a certain amount of slag former CaO; the addition amount of the slag former is calculated by the alkalinity, and the alkalinity of the embodiment is 1.8; the addition amount of CaF 2 is 15% of the slag former; the furnace temperature was raised to 1520 ℃ 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 1.7 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.
(3) Smelting and casting processes
Transferring the copper-containing molten iron into an electric furnace for smelting treatment. The composition of the copper-containing molten iron is adjusted by scrap steel, carburant, desulfurizing agent, dephosphorizing agent, ferromanganese alloy and ferrosilicon alloy to meet the composition requirement of cast pig iron. Further, the temperature was raised to 1550 ℃, alloying was achieved by adding pure copper, ferrochrome, ferronickel, ferromolybdenum, etc., and then casting treatment was performed, wherein the casting temperature was 1380 ℃.
The final copper-containing cast iron comprises the following components: c:3.3%, si:2.2%, mn:0.6%, S:0.04%, P:0.08%, cu:4.5%, ni:1.8%, cr:0.8%.
Example 3:
(1) Sedimentation treatment for extracting noble metal and copper matte
Firstly, transferring high-temperature copper slag (TFe：48.45％、TCu：1.3％、Fe3O4：15.2％、SiO2：28.9％、Al2O3：1.33％、CaO：2.88％、S：1.66％、Au：0.42g/t) at 1100 ℃ 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 250kPa in a mode of side blowing, and the temperature is increased to 1500 ℃; then the copper matte flows into a sedimentation area through a baffle plate, and is grown up by blowing nitrogen gas, wherein the blowing pressure is 250kPa, and the mode is side blowing; raising the temperature by using the electrode to maintain the temperature at 1500 ℃, and starting a sedimentation process, wherein the process is a continuous process; 92% of copper and 90% of noble metal can be recovered in the sedimentation process; the recovered copper matte re-enters a copper smelting process; and the rest copper slag enters a smelting reduction flow.
(2) Smelting reduction iron making to obtain copper-containing molten iron
Flowing the settled high-temperature copper slag into a reduction furnace, and then adding a certain amount of slag former CaO; the addition amount of the slag former is calculated by the alkalinity, and the alkalinity of the embodiment is 2.0; the addition amount of CaF 2 is 14% of the slag former; the furnace temperature was raised to 1580 ℃ 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 1.8 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.
(3) Smelting and casting processes
Transferring the copper-containing molten iron into an electric furnace for smelting treatment. The composition of the copper-containing molten iron is adjusted by scrap steel, carburant, desulfurizing agent, dephosphorizing agent, ferromanganese alloy and ferrosilicon alloy to meet the composition requirement of cast pig iron. Further, the temperature was raised to 1580 ℃, alloying was achieved by adding pure copper, ferrochrome, ferronickel, ferromolybdenum, etc., and then casting treatment was performed, wherein the casting temperature was 1400 ℃.
The final copper-containing cast iron comprises the following components: c:0.11%, si:0.22%, mn:0.8%, S:0.01%, P:0.01%, cu:1.2%, ni:1.6%, cr:0.2%, V:0.1%.
Example 4:
(1) Sedimentation treatment for extracting noble metal and copper matte
Firstly, transferring high-temperature copper slag (TFe：51.45％、TCu：1.5％、Fe3O4：14.2％、SiO2：25.6％、Al2O3：1.23％、CaO：2.38％、S：1.36％、Au：0.42g/t) at 1200 ℃ 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 240kPa, and the mode is side blowing, so that the temperature is increased to 1400 ℃; then the copper matte flows into a sedimentation zone through a baffle plate, and is grown up by blowing nitrogen gas, wherein the blowing pressure is 240kPa, and the mode is side blowing; maintaining the temperature at 1400 ℃ by using the electrode, and starting a sedimentation process, wherein the process is a continuous process; 92% of copper and 93% of noble metal can be recovered in the sedimentation process; the recovered copper matte re-enters a copper smelting process; and the rest copper slag enters a smelting reduction flow.
(2) Smelting reduction iron making to obtain copper-containing molten iron
Flowing the settled high-temperature copper slag into a reduction furnace, and then adding a certain amount of slag former CaO; the addition amount of the slag former is calculated by the alkalinity, and the alkalinity of the embodiment is 1.8; the addition amount of CaF 2 is 16% of the slag former; the furnace temperature was raised to 1570 c 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 1.6 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.
(3) Smelting and casting processes
Transferring the copper-containing molten iron into an electric furnace for smelting treatment. The composition of the copper-containing molten iron is adjusted by scrap steel, carburant, desulfurizing agent, dephosphorizing agent, ferromanganese alloy and ferrosilicon alloy to meet the composition requirement of cast pig iron. Further, the temperature was raised to 1570 ℃, alloying was achieved by adding pure copper, ferrochrome, ferronickel, ferromolybdenum, etc., and then casting treatment was performed, wherein the casting temperature was 1390 ℃.
The final copper-containing cast iron comprises the following components: c:0.12%, si:0.28%, mn:0.7%, S:0.02%, P:0.01%, cu:1.3%, ni:1.7%, cr:0.3%, V:0.13%.
In conclusion, the copper-containing cast iron production system disclosed by the invention is high in recovery rate and low in production cost, not only can realize extraction of valuable elements, but also fully utilizes iron and copper in copper slag; in addition, the copper-containing corrosion-resistant cast iron can be obtained by adding alloys such as manganese, silicon, copper, chromium, nickel, molybdenum and the like, so that the value of the product can be greatly improved, and the economic benefit is improved.
It will be appreciated by persons skilled in the art that the embodiments described herein are merely exemplary and that various other alternatives, modifications and improvements may be made within the scope of the invention. Thus, the present invention is not limited to the above-described embodiments, but only by the claims.

Claims (5)

1. A system for producing copper-containing cast iron, 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 1300-1500 ℃, carrying out sedimentation treatment in a sedimentation zone, discharging noble metals contained in the copper slag and copper matte from a first liquid outlet in a liquid state, 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 smelting furnace is communicated with the second liquid outlet of the reduction furnace; and
The material inlet of the casting device is communicated with the material outlet of the smelting furnace;
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 the smelting furnace is an electric furnace or an induction furnace.
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Publication number Priority date Publication date Assignee Title
CN103614607A (en) * 2013-09-12 2014-03-05 昆明理工大学 Method for preparing stainless steel raw materials through smelting reduction of hot copper slags under action of nickel-containing materials
CN103757170A (en) * 2013-12-13 2014-04-30 金川集团股份有限公司 Method for injection reduction extraction of iron from nickel smelting furnace slag
CN104164531A (en) * 2013-09-11 2014-11-26 襄阳康捷飞龙电气有限公司 Method for producing cast iron by adopting converter blowing smelting and purification
CN107699702A (en) * 2017-10-10 2018-02-16 东北大学 A kind of method that valuable component is reclaimed by cupric slag
CN210012885U (en) * 2019-05-23 2020-02-04 中国恩菲工程技术有限公司 Production system of copper-containing cast iron

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104164531A (en) * 2013-09-11 2014-11-26 襄阳康捷飞龙电气有限公司 Method for producing cast iron by adopting converter blowing smelting and purification
CN103614607A (en) * 2013-09-12 2014-03-05 昆明理工大学 Method for preparing stainless steel raw materials through smelting reduction of hot copper slags under action of nickel-containing materials
CN103757170A (en) * 2013-12-13 2014-04-30 金川集团股份有限公司 Method for injection reduction extraction of iron from nickel smelting furnace slag
CN107699702A (en) * 2017-10-10 2018-02-16 东北大学 A kind of method that valuable component is reclaimed by cupric slag
CN210012885U (en) * 2019-05-23 2020-02-04 中国恩菲工程技术有限公司 Production system of copper-containing cast iron

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