CN109971967B - Method for recovering valuable metal from copper smelting converting furnace slag - Google Patents
Method for recovering valuable metal from copper smelting converting furnace slag Download PDFInfo
- Publication number
- CN109971967B CN109971967B CN201910208457.4A CN201910208457A CN109971967B CN 109971967 B CN109971967 B CN 109971967B CN 201910208457 A CN201910208457 A CN 201910208457A CN 109971967 B CN109971967 B CN 109971967B
- Authority
- CN
- China
- Prior art keywords
- copper
- cobalt
- smelting
- converting
- slag
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
- B03C1/30—Combinations with other devices, not otherwise provided for
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0056—Scrap treating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/025—Obtaining nickel or cobalt by dry processes with formation of a matte or by matte refining or converting into nickel or cobalt, e.g. by the Oxford process
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recovering valuable metals from copper smelting converting furnace slag, which comprises the steps of pouring a hot converting furnace slag melt of copper pyrometallurgical smelting into a smelting furnace through a slag ladle or a chute, adding a reducing agent, copper concentrate and a slag forming agent into the smelting furnace, and smelting to obtain a cobalt matte melt and a furnace slag melt; crushing, grinding and magnetically separating the cobalt matte solid to obtain a cobalt concentrate with higher cobalt content and a copper concentrate with low cobalt and high copper content; the copper concentrate with low cobalt and high copper is sent to a copper smelting furnace of a copper smelting plant, the copper in the copper concentrate is recycled by adopting the existing copper smelting technology to produce a copper product, and the cobalt in the copper concentrate is further enriched in converting furnace slag to form the recycling of the cobalt and the copper. The method has the advantages of low smelting temperature, low energy consumption, high metal recovery rate, fine granularity of the obtained cobalt concentrate, high cobalt content, low silicon content and easy subsequent treatment of products, and can smelt the copper concentrate while recovering valuable metals in the copper smelting converting furnace slag.
Description
Technical Field
The invention relates to the technical field of comprehensive recovery of valuable metals in smelting slag in the non-ferrous metal metallurgy industry, in particular to a method for recovering valuable metals from copper smelting converting slag.
Background
In the copper pyrometallurgy process, 50-70% of cobalt and nickel brought by copper concentrate enter the converting furnace slag after undergoing the matte making smelting-converting process. Particularly, copper concentrate produced by African countries such as Congo (gold), Zanbia and the like and northwest China of China has high cobalt and nickel content, the total content of nickel and cobalt is about 0.5-1.2%, and cobalt is enriched in converting slag in the copper smelting process. The main mineral phase of the converting furnace slag for smelting the cobalt-and nickel-containing copper concentrate consists of fayalite and a small amount of magnetite, the mass content of iron is usually 40-55%, and SiO is2The mass content is usually 20-35%, and the total content of cobalt and nickel is about 0.5-4%And contains 2 to 10% of copper. Wherein copper is mainly mechanically entrained into the slag phase in the form of sulfides and metallic copper, while cobalt and nickel are mainly present in the fayalite and magnetite phases in an oxidized state and in lattice-substituted form.
The main application of the method for recovering nickel, cobalt and copper in the cobalt and nickel-containing converting furnace slag in the copper smelting production process is a pressure leaching method, a reduction smelting method and the like.
1. A pressure acid leaching method: the valuable metals in the slag are recovered by adopting an oxygen pressure acid leaching method. Under the condition that the temperature is about 160-250 ℃, the using amount of sulfuric acid is 40-70% of the mass of raw slag, the oxygen partial pressure is controlled to be 0.3-0.6 MPa, valuable metals such as cobalt, nickel and copper in the converting slag are leached into a solution, iron is dissolved out under the condition of oxygen pressure and is oxidized and hydrolyzed into hematite precipitate, and selective leaching of the valuable metals is realized, the leaching rate of copper is more than 90%, the leaching rate of cobalt is 70-85%, and the leaching rate of nickel is 60-80%. However, the pressure acid leaching method uses acid-resistant high-pressure equipment, and the equipment investment and maintenance cost are large; because the blowing furnace slag has low content of valuable metals, the material handling capacity is large, and the production operation cost is high.
2. A reduction smelting method: at the smelting temperature of about 1500 ℃, reducing agent and slagging constituent are added to reduce cobalt, nickel and copper in the slag into metal state to form alloy with iron, the alloy and the slag are layered, the formed alloy phase is discharged from a furnace, alloy particles are obtained after water quenching, and the separation and purification of the cobalt, the nickel and the copper are realized by adopting leaching-impurity removal. The method for treating the copper smelting slag has the following defects:
1) the alloy obtained by reduction smelting has high melting point (the melting point is 1400-1550 ℃), high operation temperature and high energy consumption, but the copper converting furnace slag is FeO-SiO with lower melting point2A slag-tying type, wherein a large amount of slag former is required to be added for realizing high-temperature smelting;
2) reduction smelting, high iron reduction rate and large addition amount and consumption of a reducing agent;
3) the alloy produced by reduction smelting has a coarse granularity after water quenching, the granularity is generally more than 2mm, and the alloy has high toughness and is difficult to crush and grind;
4) the smelting temperature and the addition amount of the reducing agent are high, so that the silicon content in the alloy obtained by reduction is high, silicon is easy to form silica gel in the subsequent wet leaching and separating process of cobalt and copper, and the difficulty is increased for the leaching process.
In conclusion, a reasonable and effective method for recovering cobalt, nickel and copper in the cobalt-nickel containing converting furnace slag in the copper smelting production process is still lacked.
Disclosure of Invention
The invention aims to provide a method for recovering valuable metals from copper smelting converting slag.
The purpose of the invention is realized by the following technical scheme:
the method for recovering valuable metals from copper smelting converting slag comprises the following steps:
step one, pouring the hot converting furnace slag melt of the copper pyrometallurgy into a smelting furnace through a slag ladle or a chute, and adding a reducing agent, copper concentrate and a slagging agent into the smelting furnace;
step two, the smelting temperature is 1200-1350 ℃, and the smelting time is 15-300 minutes (preferably 30-120 minutes), so that a cobalt matte melt, a slag melt and flue gas are obtained;
and step three, placing the cobalt matte discharged in the step two into a copper clad with heat preservation through a chute, controlling the cooling rate of 1-5 ℃/min, slowly cooling to the surface temperature of 700-1000 ℃, then pouring the uncondensed matte melt on the upper layer in the copper clad into a copper smelting converting furnace by a travelling crane for converting, pouring the obtained converting slag into a smelting furnace by a slag ladle, forming the recycling recovery of cobalt and nickel, and converting the copper into crude copper by converting. Naturally or forcibly cooling the condensed cobalt matte solid in the copper cladding to about 100-200 ℃, and pouring out the cobalt matte solid by adopting a travelling crane;
and step four, crushing the cobalt matte solid produced in the step three by using a crusher and grinding the cobalt matte solid by using a ball mill until the granularity of-0.074 mm accounts for 60-95%, and magnetically separating ore pulp by using a magnetic separator. In the magnetic separation process, the upper part is cobalt concentrate with high cobalt content, which contains 5-20% of Co, 1-10% of Ni, 8-25% of Cu, 40-70% of Fe, 10% of S, 1.5% of Si and 80% of granularity of-0.074 mm. In the magnetic separation process, copper concentrate with low cobalt and high copper is selected as the lower part, and the copper concentrate contains 0.1-1.0% of Co and 45-50% of Cu;
and step five, sending the copper concentrate produced in the step four to a copper smelting furnace of a copper smelting plant, recovering copper in the copper concentrate to produce a copper product by adopting the existing copper smelting technology, and further enriching cobalt in converting furnace slag to form the recycling of the cobalt and the copper.
According to the technical scheme provided by the invention, the method for recovering valuable metals from the copper smelting converting slag provided by the embodiment of the invention has the advantages of low smelting temperature, low energy consumption and high metal recovery rate, the obtained cobalt concentrate has fine granularity, high cobalt content and low silicon content, the subsequent treatment of the product is easy, and the copper concentrate can be smelted while the valuable metals in the copper smelting converting slag are recovered.
Drawings
FIG. 1 is a schematic flow chart of a method for recovering valuable metals from copper smelting converting slag according to an embodiment of the present invention.
Detailed Description
The embodiments of the present invention will be described in further detail below. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to the person skilled in the art.
The method for recovering valuable metals from copper smelting converting slag of the invention has the preferred embodiment that:
the method comprises the following steps:
step one, pouring the hot converting furnace slag melt of the copper pyrometallurgy into a smelting furnace through a slag ladle or a chute, and adding a reducing agent, copper concentrate and a slagging agent into the smelting furnace;
step two, the smelting temperature is 1200-1350 ℃, and the smelting time is 15-300 minutes (preferably 30-120 minutes), so that a cobalt matte melt, a slag melt and flue gas are obtained;
and step three, placing the cobalt matte discharged in the step two into a copper clad with heat preservation through a chute, controlling the cooling rate of 1-5 ℃/min, slowly cooling to the surface temperature of 700-1000 ℃, then pouring the uncondensed matte melt on the upper layer in the copper clad into a copper smelting converting furnace by a travelling crane for converting, pouring the obtained converting slag into a smelting furnace by a slag ladle, forming the recycling recovery of cobalt and nickel, and converting the copper into crude copper by converting. Naturally or forcibly cooling the condensed cobalt matte solid in the copper cladding to about 100-200 ℃, and pouring out the cobalt matte solid by adopting a travelling crane;
and step four, crushing the cobalt matte solid produced in the step three by using a crusher and grinding the cobalt matte solid by using a ball mill until the granularity of-0.074 mm accounts for 60-95%, and magnetically separating ore pulp by using a magnetic separator. In the magnetic separation process, the upper part is cobalt concentrate with high cobalt content, which contains 5-20% of Co, 1-10% of Ni, 8-25% of Cu, 40-70% of Fe, 10% of S, 1.5% of Si and 80% of granularity of-0.074 mm. In the magnetic separation process, copper concentrate with low cobalt and high copper is selected as the lower part, and the copper concentrate contains 0.1-1.0% of Co and 45-50% of Cu;
and step five, sending the copper concentrate produced in the step four to a copper smelting furnace of a copper smelting plant, recovering copper in the copper concentrate to produce a copper product by adopting the existing copper smelting technology, and further enriching cobalt in converting furnace slag to form the recycling of the cobalt and the copper.
The reducing agent is at least one of granular coke, charcoal or anthracite; the copper concentrate is copper concentrate or copper-cobalt concentrate containing 15-30% of sulfur; the slagging agent is at least one of quicklime, limestone, dolomite or quartz sand.
The dosage of the reducing agent is 1-10% (preferably 2-4%) of the total mass of the converting furnace slag, the dosage of the copper concentrate is 10-45% (preferably 20-35%) of the total mass of the converting furnace slag, and the dosage of the slag-forming agent is 0.1-20% of the total mass of the converting furnace slag.
The smelting furnace comprises a closed submerged arc electric furnace and/or a rotary furnace.
And the converting furnace slag is poured into a smelting furnace through a slag ladle or a chute, an auxiliary material reducing agent, copper concentrate and a slagging agent are uniformly fed from the top of the smelting furnace through a conveyor, a storage bin and a feeding metering scale respectively, and an auxiliary material layer with the thickness of 0.5-1.2 m is formed on the upper layer of a melt in the smelting furnace.
And discharging the cobalt matte discharged from the smelting furnace into a copper clad with heat insulation or placing the copper clad into an intermediate frequency furnace to slowly cool the copper clad to the surface temperature of 700-1000 ℃, taking out the copper clad, and pouring the uncondensed matte into a converting furnace for converting.
And (4) producing a cobalt matte melt in the second step, directly adopting a casting machine to cast and cool to form a cobalt matte solid, and putting the cobalt matte solid into the fourth step to produce a cobalt concentrate with higher cobalt content and a copper concentrate with lower cobalt content.
The cobalt matte solid produced in the third step is an aggregate in which Fe-Co-Ni-Cu alloy particles are embedded in matte.
Crushing the cobalt matte solid produced in the third step, wherein the crushing comprises a crushing system consisting of crushing and screening, and the granularity of crushed discharged materials is controlled to be 5-15 mm; the ore grinding system is formed by combining a ball mill, a classifier and a magnetic separator, and the ore grinding granularity is controlled to be 60-95% at-0.074 mm;
the wet magnetic separator comprises a magnetic separation system consisting of a plurality of magnetic separators.
And D, directly adding the copper concentrate produced in the fourth step into a converting furnace of a copper smelting plant for converting to produce blister copper after pelletizing by a pelletizer, and enriching cobalt and nickel in converting furnace slag.
The method for recovering valuable metals from the copper smelting converting furnace slag not only has low smelting temperature, low energy consumption and high metal recovery rate, but also can obtain the cobalt concentrate with fine granularity, high cobalt content, low silicon content and easy subsequent treatment of products, and can also smelt the copper concentrate while recovering the valuable metals from the copper smelting converting furnace slag.
The specific embodiment is as follows:
firstly, the method for recovering valuable metals from copper smelting converting furnace slag provided by the invention mainly aims at cobalt-and nickel-containing converting furnace slag produced in the copper pyrometallurgical industry, wherein the total mass percent of cobalt and nickel is 0.5-4%, the mass percent of copper is 2-10%, the mass percent of Fe is 40-55%, and the mass percent of SiO is2The mass percentage is 20-35%. However, in practice, the converting slag is hot molten slag discharged from the converting furnace during the converting process. The method for recovering valuable metals from copper smelting converting slag provided by the present invention will be described in detail.
As shown in fig. 1, a method for recovering valuable metals from copper smelting converting slag includes the steps of:
step one, pouring the hot converting furnace slag of the copper pyrometallurgical smelting into a smelting furnace through a slag ladle or a chute, and adding a reducing agent, copper concentrate and a slagging agent into the smelting furnace. Wherein the reducing agent is at least one of granular coke, charcoal or anthracite; the copper concentrate is copper concentrate or copper-cobalt concentrate containing 15-30% of sulfur; the slagging agent is at least one of lime, limestone, dolomite or quartz sand. The dosage of the reducing agent is 1-10% (preferably 2-4%) of the total mass of the converting furnace slag, the dosage of the copper concentrate is 10-45% (preferably 20-35%) of the total mass of the converting furnace slag, and the dosage of the slag-forming agent is 0-20% of the total mass of the converting furnace slag.
And step two, carrying out low-temperature reduction vulcanization smelting on the hot converting furnace slag to be smelted, the reducing agent, the copper concentrate and the slag former by using a smelting furnace, wherein the smelting temperature is 1200-1350 ℃, and the smelting time is 15-300 minutes (preferably 30-120 minutes), so that a cobalt matte melt, a furnace slag melt and flue gas are obtained. The blowing furnace slag to be smelted is poured into the smelting furnace through a slag ladle or a chute, an auxiliary material reducing agent, copper concentrate and a slagging agent are respectively conveyed into a storage bin (namely a feeding buffer storage bin at the top of the smelting furnace) of the smelting furnace through a conveyor (for example, the conveyor can adopt a belt conveyor or a bucket elevator in the prior art, or can select a conveyor capable of conveying powder and granules in the prior art according to terrain arrangement), the feeding rate of the auxiliary material entering the smelting furnace is controlled according to the input amount of the blowing furnace slag and the residence time of the smelting material through a storage bin feeding metering scale, and an auxiliary material layer with the thickness of 0.5-1.2 m is formed on the upper layer of a melt in the smelting furnace. In the reduction vulcanization smelting process, cobalt and nickel in the converting furnace slag are reduced, part of iron is reduced to be in a metal state, and the cobalt, the nickel and the copper are collected to form Fe-Co-Ni-Cu alloy; and smelting the copper concentrate and capturing copper in the converting furnace slag to form copper matte, and forming a molten mutual solution with a lower melting point with the copper matte and the Fe-Co-Ni alloy, namely the cobalt matte. The cobalt matte melt is separated by the density difference with the slag melt, the density of the cobalt matte melt is larger than that of the slag melt, the cobalt matte melt sinks at the lower part of a molten pool of the smelting furnace, therefore, the cobalt matte melt can be periodically discharged from a lower discharge port of the smelting furnace through a chute, the slag melt can be periodically discharged from a higher discharge port of the smelting furnace through the chute, and the flue gas is discharged from a top flue of the smelting furnace, so that the recovery rate of cobalt is more than 95%, the recovery rate of nickel is more than 92%, and the recovery rate of copper is more than 95%. In practical application, the smelting furnace preferably adopts a submerged arc closed electric furnace, and is matched with facilities such as a transformer, a rectifier, an electrode lifting device, a furnace body structure, a heat insulation material, a furnace top cover plate, a dust gas collecting hood, a furnace body cooling system, a cobalt and ice copper discharging port and chute, a slag discharging port and chute, a flue gas discharging port and the like.
And step three, placing the cobalt matte discharged in the step two into a copper clad with heat preservation through a chute, controlling the cooling rate of 1-5 ℃/min, slowly cooling to the surface temperature of 700-1000 ℃, then pouring the uncondensed matte melt on the upper layer in the copper clad into a copper smelting converting furnace by a travelling crane for converting, pouring the obtained converting slag into a smelting furnace by a slag ladle, forming the recycling recovery of cobalt and nickel, and converting the copper into crude copper by converting. And naturally or forcibly cooling the condensed cobalt matte solid in the copper cladding to about 100-200 ℃, and pouring out the cobalt matte solid by adopting a travelling crane.
And step four, crushing the cobalt matte solid produced in the step three by using a crusher and grinding the cobalt matte solid by using a ball mill until the granularity of-0.074 mm accounts for 60-95%, and magnetically separating ore pulp by using a magnetic separator. In the magnetic separation process, the upper part is cobalt concentrate with high cobalt content, which contains 5-20% of Co, 1-10% of Ni, 8-25% of Cu, 40-70% of Fe, 10% of S, 1.5% of Si and 80% of granularity of-0.074 mm. In the magnetic separation process, the part of the copper concentrate with low cobalt and high copper is selected, and the copper concentrate contains 0.1-1.0% of Co and 45-50% of Cu.
And step five, sending the copper concentrate produced in the step four to a copper smelting furnace of a copper smelting plant, recovering copper in the copper concentrate to produce a copper product by adopting the existing copper smelting technology, and further enriching cobalt in converting furnace slag to form the recycling of the cobalt and the copper.
The scientific principle of the invention is as follows:
fe in the converting slag of copper pyrometallurgical method is mainly Fe3O4And 2 FeO. SiO2The form exists; co and Ni mainly exist in an iron oxide crystal phase in an oxidation state and a homogeneous phase; cu is mainly stored in the form of metallic copper and copper sulfideAt this point.
The reduction-vulcanization smelting is to reduce Co and Ni into a metallic state by adopting a reducing agent, reduce part of Fe into a metallic state and trap cobalt, nickel and copper to form Fe-Co-Ni-Cu alloy; meanwhile, copper concentrate is used for capturing copper in converting furnace slag to form matte in the smelting process; the matte has low melting point and good fluidity, and forms a metallized cobalt matte mutual solution with lower melting point with Fe-Co-Ni-Cu alloy formed by reduction in slag, and the metallized cobalt matte mutual solution is separated from the slag and discharged. After the cobalt matte mutual solution is discharged, the alloy is precipitated and grows in the slow cooling process, and magnetic Fe-Co-Ni-Cu alloy particles are formed. After cooling, the alloy and the matte are dissociated by crushing and ore grinding, and the Fe-Co-Ni-Cu alloy is enriched by a magnetic separation method, so that the separation of cobalt, nickel and copper is realized. The main chemical reactions are as follows:
CoO+C＝Co+CO
NiO+C＝Ni+CO
Fe3O4+C＝3FeO+CO
FeO+C＝Fe+CO
Fe+CoO＝Co+FeO
Fe+NiO＝Ni+FeO
Fe+Fe3O4＝4FeO
Fe(L)+Co(L)+Ni(L)+Cu(L)＝Fe-Co-Ni-Cu(L alloy)
CuFeS2+2Fe3O4+3SiO2＝CuFeS(matte)+3(2FeO·SiO2)+SO2
CuFeS(matte)+Fe-Co-Ni-Cu(L alloy)＝CuFeS-(Fe-Co-Ni-Cu)(L mutual solution)
CuFeS-(Fe-Co-Ni-Cu)(mutual solution)＝CuFeS(S)+Fe-Co-Ni-Cu(S alloy)
Compared with the prior art, the method for recovering valuable metals from the copper smelting thermal state converting slag provided by the invention at least has the following technical effects:
(1) the invention adopts the smelting furnace to directly treat the hot converting furnace slag for copper smelting, fully utilizes the heat energy of the hot converting furnace slag, has lower smelting energy consumption, and reduces the energy consumption by 1 compared with the traditional smelting00～200kwh/tSlag。
(2) The invention adopts low-temperature reduction vulcanization to treat the copper smelting converting furnace slag, is suitable for the existing copper smelting converting furnace slag type, has low consumption of slag former, and reduces the smelting temperature.
(3) According to the invention, the cobalt matte melt is placed in the copper cladding for slow cooling, part of the condensed part returns to the converting furnace for converting, and a converting furnace converting and electric furnace smelting circulating system is formed, so that copper is converted into crude copper, cobalt and nickel enter converting furnace slag to return to the reduction electric furnace, copper is recovered, cobalt and nickel are recycled, and the recovery rate of cobalt and nickel is improved.
(4) The invention has low smelting reduction degree, small alloy particles formed in the smelting furnace and difficult layering of alloy and matte in the furnace.
(5) The cobalt matte structure obtained by smelting is characterized in that iron-cobalt alloy particles are embedded in the matte, the fineness of the alloy particles is generally about-0.074 mm, and the structure is easy to crush and grind and is more beneficial to the subsequent refining and purification of cobalt and nickel.
(6) The cobalt matte obtained after low-temperature smelting is slowly cooled by copper cladding, so that alloy particles further grow up, and the separation of copper, cobalt and nickel in the subsequent magnetic separation process is facilitated.
(7) According to the invention, the separation of cobalt, nickel and copper in the cobalt matte obtained by smelting is realized by crushing, ore grinding and magnetic separation, the cobalt content of the obtained cobalt concentrate is up to 5-20%, the Si content is lower than 1.5%, the copper content is 8-25%, and the proportion of the granularity of-0.074 mm is more than 80%, so that the subsequent cobalt refining and purification are facilitated.
(8) The invention not only can comprehensively recover cobalt, nickel and copper in the copper smelting converting furnace slag, the cobalt recovery rate is more than or equal to 95 percent, the nickel recovery rate is more than or equal to 92 percent, and the copper recovery rate is more than or equal to 95 percent, but also can smelt copper concentrate.
In order to more clearly show the technical scheme and the technical effects provided by the invention, the method for recovering valuable metals from copper smelting converting slag provided by the invention is described in detail by specific examples.
Example 1
A method for recovering valuable metals from copper smelting converting slag adopts converting slag of a certain copper smelting plant of Zaizabeth as a raw material, and the main element components of the converting slag are shown in the following table 1:
table 1:
| element(s) | Co | Ni | Cu | SiO2 | Fe |
| Content/% | 2.20 | 0.44 | 10.56 | 20.16 | 52.99 |
The method comprises the following steps: 5kg of the copper smelting converting furnace slag is melted by a submerged arc electric furnace, then 0.2kg of anthracite, 1.25kg of copper concentrate containing 15 percent of Cu and 25 percent of S respectively and 0.25kg of quartz sand are uniformly mixed and added into the electric furnace for continuous smelting, the smelting temperature is controlled to 1350 ℃, the temperature is kept for 90min, then the mixture is slowly cooled to 800 ℃ at the cooling rate of 3 ℃/min and then is naturally cooled to normal temperature, and thus the cobalt matte and the furnace slag which are separated are obtained. Crushing cobalt matte, ball-milling until the granularity is-0.074 mm and accounts for 80%, and magnetically separating the ball-milled slurry by a wet magnetic separator.
Respectively taking the smelting slag and the cobalt concentrate obtained by magnetic separation for element detection, wherein the contents of Co, Ni and Cu in the smelting slag are respectively 0.11%, 0.06% and 0.48%, and the slag recovery rates are respectively Co 97.25%, Ni 92.5% and Cu 97.5%; the cobalt concentrate obtained by magnetic separation comprises 13.5% of Co, 2.5% of Ni, 15.4% of Cu and 0.5% of Si.
Example 2
A method for recovering valuable metals from blowing slag of copper smelting adopts the blowing slag of a Congo copper smelting plant as a raw material, and the main element components of the blowing slag are shown in the following table 1:
table 2:
| element(s) | Co | Ni | Cu | SiO2 | Fe |
| Content/% | 1.32 | 0.38 | 5.48 | 24.10 | 48.85 |
The method comprises the following steps: and 5kg of the copper smelting converting furnace slag is melted by a submerged arc electric furnace, then 0.15kg of coke and 1.5kg of copper concentrate containing 25 percent and 15 percent of Cu and S respectively are uniformly mixed and added into the electric furnace for continuous smelting, the smelting temperature is controlled to be 1300 ℃, the temperature is kept for 120min, then the mixture is slowly cooled to 700 ℃ at the cooling rate of 2 ℃/min and then is naturally cooled to the normal temperature, and thus the cobalt matte and the furnace slag which are separated are obtained. Crushing cobalt matte, ball-milling until the granularity is-0.074 mm and accounts for 85%, and magnetically separating the ball-milled slurry by a wet magnetic separator.
Respectively taking the smelting slag and the cobalt concentrate obtained by magnetic separation for element detection, wherein the contents of Co, Ni and Cu in the smelting slag are respectively 0.12%, 0.05% and 0.41%, and the slag recovery rates are respectively Co 95.00%, Ni 92.76% and Cu 95.89%; the cobalt concentrate obtained by magnetic separation comprises 10.5% of Co, 2.5% of Ni, 13.6% of Cu and 0.4% of Si.
Example 3
A method for recovering valuable metals from copper smelting converting slag adopts converting slag of a certain copper smelting plant in Yunnan as a raw material, and the main element components of the converting slag are shown in the following table 1:
table 3:
| element(s) | Co | Ni | Cu | SiO2 | Fe |
| Content/% | 0.92 | 0.21 | 3.52 | 23.46 | 47.62 |
The method comprises the following steps: 5kg of the copper smelting converting furnace slag is firstly melted by a submerged arc electric furnace, then 0.125kg of charcoal and 1.75kg of copper concentrate containing 20 percent and 21 percent of Cu and S respectively are uniformly mixed and then added into the electric furnace for continuous smelting, the smelting temperature is controlled at 1250 ℃, the temperature is kept for 180min, then the mixture is slowly cooled to 850 ℃ at the cooling rate of 2 ℃/min and then is naturally cooled to the normal temperature, and finally the separated cobalt matte and the furnace slag are obtained. Crushing cobalt matte, ball-milling until the granularity is-0.074 mm and accounts for 90%, and magnetically separating the ball-milled slurry by a wet magnetic separator.
Respectively taking the smelting slag and the cobalt concentrate obtained by magnetic separation for element detection, wherein the contents of Co, Ni and Cu in the smelting slag are respectively 0.08%, 0.03% and 0.32%, and the slag recovery rates are respectively Co 95.22%, Ni 92.14% and Cu 95.00%; the cobalt concentrate obtained by magnetic separation comprises 9.8% of Co, 1.8% of Ni, 16.9% of Cu and 0.3% of Si.
In conclusion, the embodiment of the invention has the advantages of low smelting temperature, low addition of the slag former, high comprehensive recovery rate of cobalt, nickel and copper, high cobalt and nickel content of the obtained cobalt concentrate, and capability of smelting and processing the copper concentrate.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A method for recovering valuable metals from copper smelting converting slag is characterized by comprising the following steps:
step one, pouring the hot converting furnace slag melt of the copper pyrometallurgy into a smelting furnace through a slag ladle or a chute, and adding a reducing agent, copper concentrate and a slagging agent into the smelting furnace;
step two, smelting at the temperature of 1200-1350 ℃ for 15-300 minutes to obtain a cobalt matte melt, a slag melt and flue gas;
thirdly, placing the cobalt matte discharged in the second step into a copper clad with heat preservation through a chute, controlling the cooling rate of 1-5 ℃/min to slowly cool the cobalt matte to the surface temperature of 700-1000 ℃, then pouring the uncondensed matte melt on the upper layer in the copper clad into a copper smelting converting furnace through a travelling crane for converting, pouring the obtained converting slag into a smelting furnace through a slag ladle for recycling cobalt and nickel, converting copper into blister copper, naturally or forcibly cooling the condensed cobalt matte solid in the copper clad to 100-200 ℃, and pouring the cobalt matte solid by the travelling crane;
step four, crushing the cobalt matte solid produced in the step three by using a crusher and grinding the solid by using a ball mill until the granularity of-0.074 mm accounts for 60-95%, magnetically separating the ore pulp by using a magnetic separator, wherein the upper part in the magnetic separation process is cobalt concentrate with higher cobalt content, the cobalt concentrate contains 5-20% of Co, 1-10% of Ni, 8-25% of Cu, 40-70% of Fe, 10% of S and 1.5% of Si, the granularity of-0.074 mm accounts for more than 80%, and the lower part in the magnetic separation process is copper concentrate with low cobalt and high copper, the cobalt matte solid contains 0.1-1.0% of Co and 45-50% of Cu;
and step five, sending the copper concentrate produced in the step four to a copper smelting furnace of a copper smelting plant, recovering copper in the copper concentrate to produce a copper product by adopting the existing copper smelting technology, and further enriching cobalt in converting furnace slag to form the recycling of the cobalt and the copper.
2. The method for recovering valuable metals from copper smelting converting slag according to claim 1, wherein the reducing agent is at least one of granular coke, charcoal or anthracite; the copper concentrate is copper concentrate or copper-cobalt concentrate containing 15-30% of sulfur; the slagging agent is at least one of quicklime, limestone, dolomite or quartz sand.
3. The method for recovering valuable metals from copper smelting converting slag according to claim 1, wherein the amount of the reducing agent is 1-10% of the total mass of the converting slag, the amount of the copper concentrate is 10-45% of the total mass of the converting slag, and the amount of the slag former is 0.1-20% of the total mass of the converting slag.
4. The method for recovering valuable metals from copper smelting converting slag according to claim 3, wherein the amount of the reducing agent is 2-4% of the total mass of the converting slag, and the amount of the copper concentrate is 20-35% of the total mass of the converting slag.
5. The method for recovering valuable metals from copper smelting converting slag according to claim 1, wherein the smelting furnace comprises a closed submerged arc furnace and/or a rotary furnace, the converting slag is poured into the smelting furnace through a slag ladle or a chute, auxiliary reducing agents, copper concentrates and slag formers are respectively and uniformly fed from the top of the smelting furnace through a conveyor, a storage bin and a feeding metering scale, and an auxiliary material layer with the thickness of 0.5-1.2 m is formed on the upper layer of a melt in the smelting furnace.
6. The method for recovering valuable metals from copper smelting converting furnace slag according to claim 1, characterized in that cobalt matte discharged from the smelting furnace is discharged into copper clad with heat preservation or the copper clad is put into an intermediate frequency furnace to be slowly cooled to the surface temperature of 700-1000 ℃, the copper clad is taken out, and the uncondensed matte is poured into a converting furnace for converting.
7. The method for recovering valuable metals from copper smelting converting slag according to claim 1, wherein in the second step, the smelting time is 30-120 minutes, a cobalt matte melt is produced, a casting machine is directly adopted for casting and cooling to form a cobalt matte solid, and the cobalt matte solid is put into the fourth step to produce a cobalt concentrate with higher cobalt content and a copper concentrate with lower cobalt content.
8. The method for recovering valuable metals from copper smelting converting slag according to claim 1, wherein the cobalt matte solid produced in the third step is an aggregate of Fe-Co-Ni-Cu alloy particles embedded in matte.
9. The method for recovering valuable metals from copper smelting converting slag according to claim 1, wherein the crushing of the cobalt matte solid produced in the third step comprises a crushing system consisting of crushing and screening, and the granularity of the crushed discharge is controlled to be 5-15 mm; the ore grinding comprises an ore grinding system formed by combining a ball mill, a classifier and a magnetic separator, and the ore grinding grain size of-0.074 mm is controlled to be 60-95%;
the wet magnetic separator comprises a magnetic separation system consisting of a plurality of magnetic separators.
10. The method for recovering valuable metals from the copper smelting converting slag according to the claim 1, wherein the copper concentrate produced in the fourth step is directly added into a converting furnace of a copper smelting plant for converting to produce blister copper after being pelletized by a pelletizer, and cobalt and nickel are enriched in the converting slag.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910208457.4A CN109971967B (en) | 2019-03-19 | 2019-03-19 | Method for recovering valuable metal from copper smelting converting furnace slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910208457.4A CN109971967B (en) | 2019-03-19 | 2019-03-19 | Method for recovering valuable metal from copper smelting converting furnace slag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109971967A CN109971967A (en) | 2019-07-05 |
| CN109971967B true CN109971967B (en) | 2020-08-21 |
Family
ID=67079533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910208457.4A Active CN109971967B (en) | 2019-03-19 | 2019-03-19 | Method for recovering valuable metal from copper smelting converting furnace slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109971967B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11926884B2 (en) * | 2019-11-27 | 2024-03-12 | Umicore | Pyrometallurgical process for recovering nickel, manganese, and cobalt |
| CN110845163A (en) * | 2019-12-19 | 2020-02-28 | 沈阳有色金属研究院有限公司 | Copper slag aggregate and preparation method and application thereof |
| CN111455194A (en) * | 2020-04-24 | 2020-07-28 | 金川集团股份有限公司 | Method for reducing copper content in PS converter slag |
| CN113481376B (en) * | 2021-05-31 | 2022-09-06 | 金川集团股份有限公司 | Method for sorting, recovering and treating copper and nickel in copper smelting furnace slag |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE495631A (en) * | 1949-05-13 | |||
| US4036636A (en) * | 1975-12-22 | 1977-07-19 | Kennecott Copper Corporation | Pyrometallurgical process for smelting nickel and nickel-copper concentrates including slag treatment |
| FI119774B (en) * | 2007-06-20 | 2009-03-13 | Outotec Oyj | Process for the treatment of cobalt-containing copper concentrate |
| CN101838739B (en) * | 2009-07-21 | 2012-03-14 | 中国恩菲工程技术有限公司 | Electrothermal impoverishment process for copper smelting slag |
| CN102925717B (en) * | 2012-11-28 | 2014-08-13 | 昆明冶金研究院 | Novel technology for comprehensively recovering copper and cobalt from cobalt-copper concentrate |
| CN103725896A (en) * | 2013-12-13 | 2014-04-16 | 金川集团股份有限公司 | Copper-nickel sulfide ore concentrate smelting method through pyrometallurgy |
| CN106399682A (en) * | 2016-09-23 | 2017-02-15 | 中国恩菲工程技术有限公司 | Method for extracting valuable metal from copper, cobalt and nickel sulfide |
| CN109201312B (en) * | 2018-08-23 | 2020-12-04 | 北京矿冶科技集团有限公司 | Dressing and smelting treatment method for copper oxide cobalt ore containing pumice |
-
2019
- 2019-03-19 CN CN201910208457.4A patent/CN109971967B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109971967A (en) | 2019-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109971967B (en) | Method for recovering valuable metal from copper smelting converting furnace slag | |
| US11952288B2 (en) | Method for producing battery-grade nickel sulfate by using laterite nickel ore | |
| CN110004352B (en) | Method for preparing copper-chromium-containing wear-resistant cast iron by utilizing reduction of molten depleted copper slag | |
| WO2019071792A1 (en) | Production method based on smelting reduction of slag containing zinc and iron | |
| WO2019071798A1 (en) | Method for producing smelting slag from nickel | |
| WO2019071793A1 (en) | Method for recovering valuable component from slag containing copper | |
| WO2019071796A1 (en) | Method for recovering valuable components from mixed slag containing nickel and iron | |
| WO2019071791A1 (en) | Method for smelting reduction production of zinc smelting slag | |
| CN111424167A (en) | Method for treating laterite-nickel ore | |
| US20070283785A1 (en) | Process for recovery of iron from copper slag | |
| CN111378851A (en) | System and method for treating laterite-nickel ore | |
| WO2019071794A1 (en) | Method for recovering valuable components from mixed slag containing copper and iron | |
| WO2019071795A1 (en) | Manufacturing method using copper-containing slag | |
| WO2009129653A1 (en) | A comprehensive recovery and utilization process for laterite-nickel ore | |
| WO2019071790A1 (en) | Method for recovering valuable components from mixed slag containing zinc and iron | |
| CN110106433B (en) | Comprehensive utilization method of molten depleted copper slag and zinc slag | |
| WO2019071797A1 (en) | Method for producing mixed slag containing nickel and iron | |
| WO2019071787A1 (en) | Method for recovering valuable components from smelting slag containing nickel | |
| CN110106347B (en) | Treatment method for applying copper smelting waste residues to sintering | |
| CN111172384B (en) | Method for reducing, enriching and recycling nickel and cobalt from nickel and cobalt multi-metal oxide ore | |
| CN112359227B (en) | Method for extracting cobalt from pyrometallurgical nickel smelting process | |
| CN102002598B (en) | Method for recovering copper and cobalt from cobalt-containing copper converter slag | |
| CN102220479A (en) | Beneficiation method for comprehensive recovery of valuable metals from sulfuric acid residues through chlorination and segregation | |
| CN111763820B (en) | Slag modified reducing agent, preparation method thereof and method for recycling iron by using slag waste heat | |
| CN101967571A (en) | Method for using red-soil nickel ore to produce nickel-iron alloy in tunnel kiln-electric furnace |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |