CN111979423B - Method for reinforced recovery of valuable metals in copper smelting slag by using gypsum slag - Google Patents
Method for reinforced recovery of valuable metals in copper smelting slag by using gypsum slag Download PDFInfo
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- 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
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- C22B15/00—Obtaining copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract
The invention discloses a method for strengthening and recovering valuable metals in copper smelting slag by using gypsum slag, which comprises the following steps: (1) uniformly mixing gypsum residues and a carbonaceous reducing agent, and granulating or tabletting to obtain mixed granules or mixed tablets; (2) adding the obtained mixed granules or mixed flakes into the high-temperature copper smelting slag; (3) and (3) slowly cooling the mixture obtained in the step (2) to obtain slowly-cooled slag. Compared with the prior art, the method has the advantages of low energy consumption, high metal recovery rate, low cost, simple flow, simple materials, easy realization of industrial application and very high industrial application prospect and value.
Description
Technical Field
The invention belongs to the technical field of metallurgical engineering, chemical engineering and industrial solid waste resource utilization, and relates to a method for strengthening and recovering valuable metals in copper smelting slag by using gypsum slag.
Background
Pyrometallurgical copper smelting typically involves matte smelting, matte converting, anode refining and anode casting to produce an anode plate for use in electrorefining. The process can produce smelting furnace slag with the mass 3-4 times that of the metal copper, and the smelting furnace slag mainly comprises FexO、SiO2、CaO、MgO、ZnO、Al2O3And the oxide components simultaneously contain a small amount of valuable metals such As Cu, Ni and Ag and a certain amount of harmful elements such As As and Pb. The blowing slag and the pyrometallurgical refining slag generally contain high copper, but have small amount and can be used for returning treatment.
The smelting slag is the smelting slag with the largest volume in a copper smelting plant and is also the main mode of material open circuit, and the main phase of the copper smelting slag is fayalite (2 FeO. SiO)2) Magnetic iron oxide (Fe)3O4) And oxide eutectic glass body, and the main chemical elements include Fe, O, Si, Ca, Zn, Al, Mg, Pb, S, As, etcIn addition, the slag contains a certain amount of Cu, Au, Ag and S, and also contains valuable metals such as Ni, Co and the like under special conditions, and the recovery of the relevant valuable metals from the slag can not only improve the resource utilization rate, but also reduce the adverse effect of the smelting slag on the ecological environment. The copper smelting slag generally contains 1-6 wt% of Cu and valuable metals such as Ag and the like, and needs to be further recovered. At present, two common processes are used for recovering valuable metals such as copper, slag slow cooling-grinding flotation is the process with higher metal recovery rate at present, flotation slag concentrate returns to a smelting system, and beneficiation tailings generally contain about 0.3wt% of copper and serve as byproducts for making cement by external sale; the valuable metals can also be recovered by adopting an electric furnace slag dilution and smelting process, the obtained electric furnace final slag contains about 0.5wt% of copper, the obtained electric furnace final slag is sold as a basic building auxiliary material or a rust remover after water quenching and granulation, and at present, the slag slow cooling-grinding and floating ore dressing process is mostly adopted in the copper enterprises in China.
In the production practice of various oxygen-enriched intensified smelting technologies at present, the reaction temperature is generally controlled to be 1180-1320 ℃ in the smelting stage, and the oxygen potential of a system is controlled to be 10-8～10-9atm, Fe/SiO in slag2The mass ratio is 1.00-1.90, and Fe in slag3O4The content is 5-32 wt%, and the slag contains 1-6 wt% of copper.
In the treatment of the smelting slag, valuable metals such as Au, Ag and the like mostly follow Cu migration, and the phase form and the reaction rule of copper in the slag are considered heavily. Slag copper content of the smelting slag after dilution, clarification and separation by an electric furnace is about 0.5-0.8 wt%; the copper content of the tailings after slow cooling and grinding flotation separation is about 0.3 wt%. Compared with the prior art, the slow cooling-grinding-floating ore dressing technical route in the two industrial technical routes can obtain higher copper (valuable metal) recovery rate, but the technical limit still exists, and the copper content in the tailings is close to the boundary grade of the exploitation of the oxidized copper ore. Under the condition of increasingly deficient resources, the method has great significance for further strengthening the recovery of metals such as Cu and the like in the smelting slag.
The occurrence form of copper in the smelting slag has important influence on the selection and the recovery effect of a copper recovery process route, and the process mineralogy research of the slow cooling slag shows that the copper has three existence forms in the smelting slag, namely sulfide forms including Cu2S、CuFeS2And secondly in oxide form, including CuO, Cu2O、Cu2O·Fe2O3And the like, and finally a small amount of metal copper dispersed particles. Production practice and scientific research show that the production of high-grade matte can cause the slag to contain Fe3O4The slag viscosity is increased when the slag content is higher, the separation condition of matte and slag is worse, and the copper content of slag is increased.
CN101491789A discloses a mineral separation process of mixing and binding three copper smelting processes of a flash furnace, a converter and a dilution furnace, wherein a mineral separation method is adopted to recover copper in mixed slag, but the recovery of oxidation-state valuable metals is found to be difficult, and the comprehensive recovery rate of metals is low.
The electric furnace dilution is a method for strengthening and recycling smelting slag copper, which is widely applied, high-temperature smelting slag is added into a dilution electric furnace through a chute independently or together with copper matte, the temperature of the electric furnace is controlled to be 1200-1400 ℃, the slag discharge is completed after the temperature is kept for a certain time, the slag is sold after water quenching, and the copper matte is discharged from a matte port after being accumulated to a certain amount. The impoundment of small particle copper matte is mainly completed in the electric cleaning furnace, and a proper amount of reducing agent is added. However, the process scheme has higher cost and more copper is lost along with the electric furnace slag. CN104404259A is an improvement of a dilution process of a common electric furnace, and discloses a method for recovering valuable metals by the cooperative treatment of copper nickel cobalt smelting slag and gypsum slag, wherein N is carried2The method has the advantages that the sulfur content of the slag is improved through the gypsum, the copper in the slag is favorably converted into matte, but the method has the defects of high energy consumption, high residual Cu content in the slag, lower comprehensive recovery rate of the metal than a slow cooling-flotation process, complex material, long preparation flow, dependence on the dilution electric furnace, limited application and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the method for strengthening and recovering the valuable metals in the copper smelting slag by utilizing the gypsum slag, which has the advantages of low energy consumption, high metal recovery rate, low cost, simple process, simple materials and easy realization of industrial application.
In order to solve the technical problems, the invention adopts the following technical scheme.
A method for strengthening and recovering valuable metals in copper smelting slag by using gypsum slag comprises the following steps:
(1) uniformly mixing gypsum residues and a carbonaceous reducing agent, and granulating or tabletting to obtain mixed granules or mixed tablets;
(2) adding the obtained mixed granules or mixed flakes into the high-temperature copper smelting slag;
(3) and (3) slowly cooling the mixture obtained in the step (2) to obtain slowly-cooled slag.
In the method for reinforced recovery of valuable metals in copper smelting slag by using gypsum slag, preferably, in the step (3), the slow cooling speed is 1-10 ℃/min.
In the method for reinforced recovery of valuable metals in copper smelting slag by using gypsum slag, the mass ratio of the gypsum slag to the carbonaceous reducing agent in the step (1) is preferably 1: 1-5: 1.
In the method for reinforced recovery of valuable metals in copper smelting slag by using gypsum slag, the mass of the gypsum in the mixed granules or mixed tablets is preferably 2-6 times of the copper content in the high-temperature copper smelting slag.
According to the method for strengthening and recovering valuable metals in the copper smelting slag by using the gypsum slag, the temperature of the high-temperature copper smelting slag is preferably 1180-1320 ℃.
In the method for intensively recovering valuable metals from copper smelting slag by using gypsum slag, preferably, the gypsum slag is gypsum slag generated by a waste acid treatment system of a copper smelting plant or desulfurized gypsum slag generated by treatment of tail gas and circular collected flue gas.
In the method for strengthening and recovering valuable metals in copper smelting slag by using gypsum slag, preferably, the carbonaceous reducing agent is one or more of pulverized coal, carbon powder and petroleum coke.
In the method for intensively recovering valuable metals from copper smelting slag by using gypsum slag, preferably, the copper smelting slag is one or more of flash smelting slag, oxygen-enriched bottom blowing smelting slag, Osmant top blowing smelting slag, Vanecov side blowing smelting slag and silver furnace smelting slag.
In the method for strengthening and recovering the valuable metals in the copper smelting slag by using the gypsum slag, the granulation or tabletting method is preferably agglomeration type granulation, extrusion type granulation or mechanical tabletting.
In the method for reinforced recovery of valuable metals in copper smelting slag by using gypsum slag, the steps (2) and (3) are preferably carried out in a slag ladle.
Compared with the prior art, the invention has the advantages that:
1. the existing recovery treatment process of valuable metals in copper smelting slag generally has the defects of high residual Cu content in tailings, high energy consumption, low Cu recovery rate and the like. The inventors have found that the prior art slow cooling-flotation and electric furnace depletion valuable metal recovery is limited during the treatment of copper smelting slag due to the dispersion of fine mineral particles and the chemical dissolution of copper oxides. The inventor has carried out a great deal of research and innovatively provides a reinforced recovery process of valuable metals in copper smelting slag, gypsum slag and a carbonaceous reducing agent are granulated and then directly added into high-temperature copper slag, gypsum reduction and smelting slag ore phase recombination are completed in the slag slow cooling process, dissolved copper oxide is separated out in the slow cooling process, CaS formed by reduction induces ore phase recombination of copper, the particle size and the proportion of sulfide copper and metallic copper are improved, the system is slowly cooled to room temperature by controlling the cooling speed, gypsum is reduced and decomposed by the self heat of the slag in the slow cooling process, the generated CaS is transferred to a slag main body, the phase form of valuable metals such as copper in the slag is transformed, and slow cooling slag which is easy to break, easy to dissociate and high in selectivity is generated.
2. The method can complete the recovery of valuable metals in the high-temperature smelting copper slag by directly utilizing the heat of the high-temperature smelting copper slag without additionally heating, greatly reduces the energy consumption, does not need specific equipment, has simple process, obtains the slow cooling slag which is easy to crush and dissociate and has high selectivity, and improves the recovery rate of the valuable metals and the Cu because the Cu content in the tailings is lower than that in the tailings of the existing various copper smelting slag treatment and recovery processes after simple subsequent mineral separation.
3. The process of the invention completes the relevant reaction in the slow cooling stage of the slag, strengthens the recovery process of valuable metals, and can be directly applied to production.
4. According to the process, the cooling speed of the system is further controlled to be 1-10 ℃/min, so that sulfide particles are continuously formed and slowly grow, the residual rate of Cu in tailings is favorably reduced, the residual rate of Cu in the tailings is as low as below 0.2wt.%, even as low as below 0.15wt.%, the recovery rate of Cu can be effectively improved, and the obtained slowly-cooled slag is easy to break and dissociate and high in selectivity, and is convenient for subsequent mineral separation.
5. The process of the invention is favorable for fully reducing the gypsum by further controlling the adding proportion of the gypsum slag, the reducing agent and the slag, and completes the phase recombination of the copper under the condition of sufficient vulcanizing agent CaS.
6. Copper is in the form of micro-fine particles in slag, even in the form of micro-particles and sub-micro-particles distributed in gaps or lattices of other minerals, so that slag must be ground to dissociate copper mineral monomers, generally, copper mineral particles with the particle size of over 45 mu m can be effectively and economically dissociated, and particles with the particle size of over 45 mu m are not easy to dissociate and are uneconomical. The slow cooling slag obtained by the process comprises an Fe-O-Si-Ca slag phase and a sulfide phase with the size of more than 50 mu m, and an obvious boundary line exists between the Fe-O-Si-Ca slag phase and the sulfide phase, so that the slow cooling slag is beneficial to the dissociation of mineral monomers and the efficient recovery of valuable metals such as Cu and the like in sulfide flotation.
Drawings
FIG. 1 is a photograph of a sample of a gradually-cooled slag obtained in example 1.
FIG. 2 is a comparison XRD of the raw slag quench and the quench slag obtained in example 1.
FIG. 3 is a SEM test result of the slow-cooling slag obtained in example 1.
FIG. 4 is a photograph of a sample of the gradually-cooled slag obtained in example 2.
FIG. 5 is a comparison XRD of the raw slag quench and the quench slag obtained in example 2.
FIG. 6 is a SEM test result of the slow-cooling slag obtained in example 2.
FIG. 7 is a photograph of a sample of a gradually-cooled slag obtained in example 3.
FIG. 8 is a comparison XRD of the raw slag quench and the quench slag obtained in example 3.
FIG. 9 is a SEM test result chart of the gradually-cooled slag obtained in example 3.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The gypsum slag and the carbonaceous reducing agent are mixed in proportion, and then the mixture is pelletized (granulated or tabletted) and dried for later use. Adding the mixed particle groups into high-temperature smelting slag, completing reductive decomposition of gypsum through the heat of the slag, transferring the generated CaS to a slag main body, converting the phase form of valuable metals such as copper in the slag, controlling the cooling speed to slowly cool the system to room temperature, and generating the slow-cooling slag which is easy to crush, easy to dissociate and high in selectivity.
The invention relates to a method for strengthening and recovering valuable metals in copper smelting slag by using gypsum slag, which comprises the following steps:
(1) uniformly mixing gypsum slag and a carbonaceous reducing agent in proportion, and granulating (pelletizing/tabletting) to obtain mixed granules;
(2) adding the obtained mixed granules into high-temperature copper molten slag (high-temperature copper smelting slag);
(3) and (3) slowly cooling the mixture obtained in the step (2) to obtain slowly-cooled slag.
In the step (3), the cooling speed is 1-10 ℃/min.
In the step (1), the proportion of the gypsum slag and the solid carbonaceous reducing agent is calculated according to a chemical reaction, and the mass ratio of the gypsum slag to the carbonaceous reducing agent is 1: 1-5: 1.
And (3) measuring the adding amount of the mixed particle group in the step (2) according to the copper content of the furnace slag, and controlling the adding amount of gypsum in the particle group to be 2-6 times, preferably 2-5 times of the copper content of the furnace slag.
The temperature of the high-temperature copper molten slag is the industrial production slag discharge temperature, and is generally 1180-1320 ℃.
The gypsum slag is gypsum waste slag generated by a waste acid treatment system of a copper smelting plant, or desulfurized gypsum slag generated by treating tail gas and ring-collected flue gas.
The carbonaceous reducing agent is one or more of pulverized coal, carbon powder and petroleum coke.
The copper smelting slag is one or more of flash smelting slag, oxygen-enriched bottom blowing smelting slag, Osmant top blowing smelting slag, Vanecov side blowing smelting slag and silver furnace smelting slag.
The granulating or tabletting method in the step (1) comprises agglomeration type granulating, extrusion type granulating or mechanical tabletting and the like.
The slow cooling operation can be carried out in various atmospheres, for example, in an air atmosphere or an inert gas atmosphere, and the steps (2) and (3) are preferably carried out in a slag ladle in the process.
The raw materials used in the examples of the present invention are as follows, and it should be noted that the raw materials of the copper smelting slag, the gypsum slag and the reducing agent used in the present invention are not limited to the following raw materials.
Copper smelting slag:
a flash copper smelting plant in China generates 65% grade matte, and the chemical composition (wt%) of smelting furnace slag is as follows: fe 39.86, SiO2 31.26、CaO 3.27、Al2O32.31, Cu 1.41, Ni 0.01, Co 0.01 and (Ag + Au) 3.15g/t, which is marked as smelting slag A; 69 percent grade matte is generated in certain domestic oxygen-enriched bottom blowing copper smelting plant, and the chemical composition (wt%) of the slag of a smelting furnace is Fe 46.56 and SiO2 27.56、CaO 1.27、Al2O32.61, Cu 3.25, Ni 0.02, Co 0.01, (Ag + Au) 5.29g/t, and is marked as smelting slag B.
Gypsum slag:
the waste acid treatment gypsum slag of a certain domestic copper smelting plant comprises the following chemical components in percentage by weight: ca 29.52, S7.94, As 8.56, F4.45, C2.13, Zn 1.01 and Cu 0.23 which are marked As gypsum residue A; a certain domestic copper smelting plant adopts a limestone-gypsum method to treat acid making tail gas to generate gypsum slag, and the chemical composition (wt%) of the gypsum slag is as follows: ca 22.52, S15.53, Mg 1.51, Si 0.34, Al 0.01, Fe 0.01, and is marked as gypsum residue B.
Reducing agent:
the powdered coal in the carbonaceous fuel is provided by a reagent supplier and has the chemical composition (wt%): c79.16, H5.11, S2.85, N1.32 and marked as a reducing agent A; the carbon powder in the carbonaceous fuel is provided by a reagent supplier and has the following chemical composition (wt%): c87.37, H3.71, S1.47, N0.13, marked as reductant B.
Example 1
The invention relates to a method for strengthening and recovering valuable metals in copper smelting slag by using gypsum slag, which comprises the following steps:
(1) mixing the gypsum residue A and the reducing agent B according to the mass ratio of 5: 1, granulating, controlling the particle size of the granules to be about 1mm, and drying the granules for later use.
(2) In N2Adding 2g of material particles into 20g of the smelting slag A at the temperature of 1250 ℃ in the atmosphere, and then slowly cooling to room temperature at the cooling speed of 4 ℃/min to obtain the slowly-cooled slag.
In this example, since the laboratory operation was performed and the melting slag A was a cooled slag taken from a factory, it was necessary to set 20g of the melting slag A in N2Melting at 1250 ℃ in an atmosphere; in the actual treatment process, the slag generated in the industrial copper smelting process is high-temperature smelting slag, the temperature is 1180-1320 ℃, so the slag can be directly treated without heating, a 20-50 t slag ladle is usually adopted, the internal slag is an oxygen-free environment naturally, a protective atmosphere is not specially adopted, even if the slag ladle is not used, the slag ladle can be protected by an inert atmosphere, the cost is reduced, the slag ladle can also be used in an air atmosphere, the molten slag is in a molten state, the reaction between the molten slag, gypsum slag and a reducing agent is a solid-liquid reaction, only a small amount of samples on the surface can be oxidized, and the whole body cannot be substantially influenced, so the industrial application has no special requirement on the atmosphere; the laboratory cases use a small sample size and therefore require a protective atmosphere.
In the actual industrial process, slag is discharged from a furnace in the copper smelting process, the slag is fed into slag discharge in the cooling process in a slag ladle, the reduction vulcanization process is completed by utilizing heat in slow cooling of the slag, and then valuable metal recovery is enhanced.
The slow cooling slag sample obtained in the embodiment is shown in figure 1, slag is completely melted and deposited at the bottom of a cast iron crucible, and the loose structure on the surface of the sample is CO generated by reaction2And the like. XRD (X-ray diffraction) detection is carried out on the original slag direct slow-cooling sample and the slow-cooling slag obtained in example 1, the obtained result is shown in figure 2, metallographic samples are prepared on the sample, analysis is carried out through SEM, and the obtained result is shown in figure 3.
As shown in the XRD detection result of fig. 2, in the nitrogen atmosphere, the main phase obtained after melting-slow cooling of the melting slag a is ferrous silicate and ferrous oxide; CaSO was not detected in the slow-cooling slag samples obtained by the process of this example4Or the diffraction peak of the phase C and the like shows that the reduction reaction is carried out more completely, in the embodiment, in a laboratory environment, the reduction vulcanization reaction is an oxygen-free reaction, inert atmosphere such as nitrogen or argon is adopted, the gypsum and carbon can react more completely, the diffraction peak intensity of ferrous silicate in the sample is obviously reduced, the dissolution of the fayalite slag structure is corresponded, and the Cu appears simultaneously5FeS4、Cu5FeS6And (4) waiting for diffraction peaks of sulfides and Fe alloy, wherein the substances can be effectively recovered in the subsequent beneficiation stage.
The SEM picture detection result in figure 3 shows that the grain sizes of Cu-Fe-S matte particles and Fe-S sulfides are both larger than 100 mu m, and the Cu-Fe-S matte particles and the Fe-S sulfides can be efficiently recovered in sulfide flotation; meanwhile, the sulfide and the Fe-O-Si-Ca slag phase have an obvious boundary line, which is beneficial to the dissociation of mineral monomers. And EDS test is performed on the points in the figure 3, and the obtained EDS detection result shows that the chemical composition (wt%) of the Cu-Fe-S matte phase is as follows: cu 54.3, Fe 18.38, S26.82, Si 0.12 and Ca 0.01; the chemical composition (wt%) of the Fe-O-Si-Ca slag phase is as follows: fe 64.92, SiO2 31.24、CaO 2.76、Al2O3 0.21、Cu 0.14。
Example 2
The invention relates to a method for strengthening and recovering valuable metals in copper smelting slag by using gypsum slag, which comprises the following steps:
(1) and uniformly mixing the gypsum residue B and the reducing agent A according to the mass ratio of 3: 1, and tabletting under the pressure of 2 Mpa.
(2) Taking 20g of smelting slag B in N2Heating to 1200 ℃ in the atmosphere, adding 3g of gypsum for tabletting, slowly cooling to room temperature, and controlling the cooling speed to be 10 ℃/min to obtain the slow-cooling slag.
The obtained sample is shown in FIG. 4, slag is completely melted and deposited at the bottom of the cast iron crucible, and the loose structure on the surface of the sample is generated by CO generated by reaction2And the like. XRD (X-ray diffraction) detection is carried out on the original slag directly slow-cooling sample and the slow-cooling slag obtained in example 2, the obtained result is shown in figure 5, metallographic samples are prepared on the sample, analysis is carried out through SEM, and the obtained result is shown in figure 6.
The XRD detection result in fig. 5 shows that, in the nitrogen atmosphere, the main phase obtained after melting-slow cooling of the smelting slag B is also ferrous silicate and ferrous oxide; CaSO was not detected in the slow-cooling slag samples obtained by the process of this example4Or C, the reduction reaction of the gypsum is relatively thorough, the intensity of the diffraction peak of ferrous silicate in the sample is obviously reduced, and the Cu appears simultaneously corresponding to the decomposition of the fayalite slag structure5FeS4、Cu5FeS6And diffraction peaks of sulfides and Fe alloy are obtained, and the substances can be effectively recovered in the beneficiation stage.
The SEM picture detection result in FIG. 6 shows that the grain size of Cu-Fe-S matte is larger than 100 μm, which is beneficial to the high-efficiency recovery of valuable metals such as Cu in sulfide flotation; meanwhile, the sulfide and the Fe-O-Si-Ca slag phase have an obvious boundary line, which is beneficial to the dissociation of mineral monomers. And EDS test is performed on the points in the graph 6, and the obtained EDS detection result shows that the chemical composition (wt%) of the Cu-Fe-S matte phase is as follows: cu 51.36, Fe 18.82, S29.06, Si 0.08; the chemical composition (wt%) of the Fe-O-Si-Ca slag phase is as follows: fe 63.86, SiO2 32.33、CaO 0.56、Cu 0.11。
Example 3
The invention relates to a method for strengthening and recovering valuable metals in copper smelting slag by using gypsum slag, which comprises the following steps:
(1) and pelletizing the gypsum slag B and the reducing agent B according to the mass ratio of 1: 1, and controlling the diameter of the pellets to be 2 mm.
(2) Taking 20g of smelting slag A in N2Heating to 1250 ℃ in the atmosphere, adding 4g of pellet particles, slowly cooling to room temperature, and controlling the cooling speed to be 2 ℃/min to obtain the slow-cooling slag.
The obtained sample is shown in FIG. 7, slag is completely melted and deposited at the bottom of the cast iron crucible, and the loose structure on the surface of the sample is generated by CO generated by reaction2And the like. XRD (X-ray diffraction) detection is carried out on the original slag direct slow-cooling sample and the slow-cooling slag obtained in example 3, the obtained result is shown in figure 8, metallographic samples are prepared on the sample, analysis is carried out through SEM, and the obtained result is shown in figure 9.
The XRD detection result in FIG. 8 shows that CaSO is not detected in the slow-cooling slag sample obtained by the process of this example4Or C, which shows that the gypsum is decomposed more thoroughly, the intensity of the diffraction peak of ferrous silicate in the sample is obviously reduced, and the Cu appears simultaneously corresponding to the decomposition of the fayalite slag structure5FeS4And diffraction peaks of sulfide and Fe alloy are obtained, and the substances can be effectively recovered in the beneficiation stage.
As shown in the SEM picture detection result in FIG. 9, the particle size of Cu-Fe-S matte is larger than 50 μm, which is beneficial to the high-efficiency recovery of valuable metals such as Cu in sulfide flotation; meanwhile, the sulfide and the Fe-O-Si-Ca slag phase have an obvious boundary line, which is beneficial to the dissociation of mineral monomers. And EDS test was performed on the points in FIG. 9, and the obtained EDS test result showed that the chemical composition (wt%) of the Cu-Fe-S matte phase was: cu 57.51, Fe 15.33, S26.55, Si 0.11; the chemical composition (wt%) of the Fe-O-Si-Ca slag phase is as follows: fe 66.12, SiO2 30.75、CaO 2.56、Cu 0.09。
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (8)
1. A method for strengthening and recovering valuable metals in copper smelting slag by using gypsum slag is characterized by comprising the following steps:
(1) uniformly mixing gypsum residues and a carbonaceous reducing agent, and granulating or tabletting to obtain mixed granules or mixed tablets;
(2) adding the obtained mixed granules or mixed flakes into the high-temperature copper smelting slag; the mass of gypsum in the mixed granules or the mixed tablets is 2-6 times of the copper content in the high-temperature copper smelting slag;
(3) slowly cooling the mixture obtained in the step (2) to obtain slowly-cooled slag; the slow cooling speed is 1-10 ℃/min.
2. The method for reinforced recovery of valuable metals in copper smelting slag by using gypsum slag as claimed in claim 1, wherein in the step (1), the mass ratio of gypsum slag to carbonaceous reducing agent is 1: 1-5: 1.
3. The method for strengthening and recovering the valuable metals in the copper smelting slag by using the gypsum slag as claimed in claim 1 or 2, wherein the temperature of the high-temperature copper smelting slag is 1180-1320 ℃.
4. The method for the enhanced recovery of valuable metals from copper smelting slag according to claim 1 or 2, wherein the gypsum slag is gypsum slag generated by a waste acid treatment system of a copper smelting plant or desulfurized gypsum slag generated by tail gas and annular collection flue gas treatment.
5. The method for the enhanced recovery of valuable metals from copper smelting slag by using gypsum slag as claimed in claim 1 or 2, wherein the carbonaceous reducing agent is one or more of pulverized coal, carbon powder and petroleum coke.
6. The method for the enhanced recovery of valuable metals from copper smelting slag according to claim 1 or 2, wherein the copper smelting slag is one or more of flash smelting slag, oxygen-enriched bottom blowing smelting slag, Osmant top blowing smelting slag, Vanecov side blowing smelting slag and silver furnace smelting slag.
7. The method for strengthening and recovering the valuable metals in the copper smelting slag by using the gypsum slag as claimed in claim 1 or 2, wherein the granulating or tabletting method is agglomeration type granulating, extrusion type granulating or mechanical tabletting.
8. The method for enhanced recovery of valuable metals from copper smelting slag using gypsum slag according to claim 1 or 2, wherein the steps (2) and (3) are performed in a slag ladle.
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| CN87107380A (en) * | 1986-11-06 | 1988-06-22 | 佛罗里达磷酸盐研究院 | Desulfurization of gypsum |
| JP5042586B2 (en) * | 2006-10-16 | 2012-10-03 | 新日本製鐵株式会社 | Powder granulation method using desulfurized slag |
| CN104694706A (en) * | 2015-03-23 | 2015-06-10 | 新疆中合大正商贸有限公司 | Application process of calcium oxide carbon balls to LF steel-making |
| CN106367613A (en) * | 2016-08-25 | 2017-02-01 | 阳谷祥光铜业有限公司 | Copper matte blowing and slagging process |
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| CN87107380A (en) * | 1986-11-06 | 1988-06-22 | 佛罗里达磷酸盐研究院 | Desulfurization of gypsum |
| JP5042586B2 (en) * | 2006-10-16 | 2012-10-03 | 新日本製鐵株式会社 | Powder granulation method using desulfurized slag |
| CN104694706A (en) * | 2015-03-23 | 2015-06-10 | 新疆中合大正商贸有限公司 | Application process of calcium oxide carbon balls to LF steel-making |
| CN106367613A (en) * | 2016-08-25 | 2017-02-01 | 阳谷祥光铜业有限公司 | Copper matte blowing and slagging process |
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