CN110408791B - Method for reducing self-vulcanizing roasting pretreatment of jarosite slag - Google Patents
Method for reducing self-vulcanizing roasting pretreatment of jarosite slag Download PDFInfo
- Publication number
- CN110408791B CN110408791B CN201910686659.XA CN201910686659A CN110408791B CN 110408791 B CN110408791 B CN 110408791B CN 201910686659 A CN201910686659 A CN 201910686659A CN 110408791 B CN110408791 B CN 110408791B
- Authority
- CN
- China
- Prior art keywords
- roasting
- iron
- reduction
- slag
- jarosite 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
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0066—Preliminary conditioning of the solid carbonaceous reductant
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
-
- 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
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/0052—Reduction smelting or converting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B58/00—Obtaining gallium or indium
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for reducing auto-vulcanization roasting pretreatment of jarosite slag, which comprises the following steps: (1) mixing the jarosite slag with a reducing agent, and carrying out solid-solid reduction and sulfur fixation roasting on the obtained mixture to reduce metal sulfate in the jarosite slag into metal sulfide to obtain a reduction roasting product; (2) and (2) carrying out reduction, vulcanization and roasting on the reduction roasting product obtained in the step (1), so that iron sulfide and heavy metal oxide in the reduction roasting product react to generate iron simple substance and heavy metal sulfide, the iron oxide is reduced into metallic iron, and aggregation and growth of Fe and heavy metal sulfide are realized at the same time, thus obtaining the reduction, vulcanization and roasting product. The pretreatment method can realize the fixation of sulfur, the sulfuration conversion of heavy metals and the metallization of iron to the maximum extent, and is favorable for recovering valuable components through flotation and magnetic separation respectively.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a method for pretreating jarosite slag by reducing auto-vulcanization roasting.
Background
The iron vitriol slag is iron sediment slag obtained by removing iron by an iron vitriol method in the smelting process of manganese, zinc, copper, nickel, cobalt and the like, and is ammonium or alkali metal at a certain temperature and acidityFe in solution in the presence of ions3+The iron vitriol crystal formed by ion precipitation has the maximum yield in the zinc smelting process. Since the yellow potassium jarosite method iron removal industrial application is first carried out by non-ferrous metal smelting plants in Liuzhou city in Guangxi in 1985, more than ten plants such as Shanxi commercial Rockwell smelting plant, northwest lead-zinc smelting plant and Guangxi guest smelting plant are successively used for zinc smelting iron removal by the jarosite method in China. At present, the quantity of the iron vitriol slag in China exceeds 3000 million tons, and the iron vitriol slag is increased at a speed of more than 100 million tons every year, and the quantity is extremely large. The jarosite slag (wet base) usually contains 25 to 30% of Fe, 8 to 12% of S, and In addition, valuable metals such as Zn, Pb, Cu, Ni, Cd, Ag, and In. Because the zinc slag contains heavy metals, contains 30-50% of water, is unstable and is not easy to accumulate, the ferroalumen slag is typical dangerous solid waste, the requirement on a slag storage is very strict, the environmental protection tax is paid according to 1000/t for the ferroalumen slag accumulation, and the expenditure is enough to make many zinc smelting enterprises difficult to continue.
At present, a large number of scientific researchers at home and abroad make extensive studies on treatment of jarosite slag. Mainly adopts a pyrogenic process treatment process of desulfurization, reduction and magnetic separation. The technical idea for treating the jarosite slag by the traditional pyrogenic process technology is as follows: firstly, oxidizing, roasting and desulfurizing, so that sulfur compounds in the jarosite slag are quickly decomposed into sulfur dioxide or sulfur trioxide gas, and the sulfur compounds are ensured not to react with iron, lead and zinc to generate sulfides; metal oxides such as lead, zinc and the like in the desulfurized material are reduced and volatilized, and are recovered in the flue gas; and magnetically separating the reduced product to obtain metal iron powder and tailings.
For example, chinese patent document (CN 107254585a) discloses a method for recovering zinc, indium, iron, and gallium from jarosite, which comprises mixing jarosite slag with additives, pelletizing, oxidizing, roasting, desulfurizing, adding a reducing agent, directly reducing to reduce the indium and zinc in the jarosite slag into metal, volatilizing and enriching the metal into smoke dust, cooling, crushing, magnetically separating the slag to obtain metalized pellets, melting the metalized pellets, and separating the slag liquid to obtain gallium-rich molten iron. The sulfur content of the alum slag is low during the desulfurization roasting, and the low-concentration SO generated during the desulfurization roasting2The gas can meet the acid making requirement after being enriched by adopting the ionic liquid, and the cost is high; and alsoThe original pellets need to be cooled and magnetically separated and then melted at high temperature, the process is complex, the energy consumption is high, the cost is high, and elements such as Cu, Ag, Ni and Co which are difficult to volatilize enter reduced iron in the reduction and volatilization process, so that a large amount of valuable metals are lost, and the recovery of the valuable metals is insufficient.
Chinese patent publication No. (CN 106544460A) discloses a method and a system for treating iron vitriol slag, the method comprises the steps of mixing the iron vitriol slag with a carbonaceous reducing agent and an additive, feeding the mixture into an annular radiation furnace, respectively passing through a drying zone, a decomposition zone and a reduction zone to realize the drying and desulfurization of the iron vitriol slag, the reduction and volatilization of zinc and lead and the metallization of iron, and magnetically separating the roasted product to obtain iron ore concentrate2The decomposition of the iron vitriol is carried out in the weak reducing atmosphere, and the removal rate of sulfur in a decomposition zone is only about 70 percent, so the volatilization effect of lead and zinc during reduction and volatilization is poor.
In general, the existing pyrogenic process treatment process has certain application when the content of elements such as In and the like In the iron vitriol slag is very high, but the practical process limits incomplete desulfurization, high content of heavy metal sulfide, ineffective separation In the magnetic separation process and low iron taste, SO that the problems of good iron recycling, high-efficiency recovery of other metals and SO In the process cannot be effectively solved2Secondary tailings and leachate are polluted, and the like, so that the method is not popularized in a large area.
The technology carries out reduction roasting-magnetic separation experimental research on jarosite slag to produce magnetite with iron content of 58.72%, metallic zinc is dispersed in concentrate and tailings, and sulfur is dispersed in roasting gas, magnetic separation concentrate and magnetic separation tailings2The tail gas and the magnetic separation tailings are subjected to secondary pollution, and the application prospect is not good.
Liu super, etc. research the microwave heating sulfating roasting technology, under the optimized sulfating roasting and water leaching technological conditions, the leaching rates of Fe, Zn, In, Cu, Ag and Cd respectively reach 89.4%, 80.7%, 85.1%, 90.7%, 61.3% and 48.8%, and Pb is basically PbSO4The form of the extract is enriched in the leaching residueIn the method, iron and other valuable metals are leached out simultaneously, the separation of iron and other metals in the solution is difficult to be thorough, an effective iron recycling way is lacked, and the application prospect is limited.
Although the treatment technology of the jarosite slag is widely researched, no economically feasible treatment method can realize the recycling of iron and other valuable metals simultaneously and does not bring secondary pollution, and the jarosite slag with huge amount is hardly effectively treated and is completely stockpiled, thereby seriously restricting the development of the zinc and other metal industries.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for pretreating jarosite slag by reducing auto-vulcanization roasting, which can immobilize valuable components to the maximum extent and is beneficial to recovering the valuable components through physical separation.
Theoretically, if the technical idea opposite to the pyrometallurgical treatment process of desulfurization-reduction-magnetic separation is adopted, namely, the reducing agent is adopted to carry out self-vulcanization on the metal in the jarosite slag, and then the valuable components in the reduced slag are subjected to flotation and magnetic separation, SO is avoided2The release of the iron vitriol slag can realize the full-scale utilization of the iron vitriol slag. The principal chemical reactions involved in theory:
1、KFe3(SO4)2(OH)6＝1/2Fe2(SO4)3+Fe2O3+1/2K2SO4+3H2O
2、Fe2(SO4)3+6C＝3/2FeS2+1/2Fe+6CO2(g)
3、ZnSO4+2C＝ZnS+2CO2(g)
4、PbSO4+2C＝PbS+2CO2(g)
5、Ag2SO4+2C＝Ag2S+2CO2(g)
6、CuSO4+2C＝CuS+2CO2(g)
7、ZnO+1/2FeS2+1/2C＝ZnS+1/2Fe+1/2CO2(g)
8、ZnFe2O4+1/2FeS2+2C＝ZnS+5/2Fe+2CO2(g)
9、ZnSiO3+1/2FeS2+1/2C＝ZnS+1/2Fe+SiO2+1/2CO2(g)
10、PbO+1/2FeS2+1/2C＝PbS+1/2Fe+1/2CO2(g)
11、CuO+1/2FeS2+1/2C＝CuS+1/2Fe+1/2CO2(g)
12、Fe2O3+1.5C＝2Fe+1.5CO2(g)
13、AgO+1/4FeS2+1/2C＝1/2Ag2S+1/4Fe+1/2CO2(g)
14、In2O3+1.5C＝2In+1.5CO2(g)
however, since there are many valuable metals in the iron vitriol slag, the self-sulfurization conditions of each metal are different, and the metal sulfate is easily decomposed into sulfur dioxide and metal oxide, and is limited by the process, the actual reaction does not proceed toward the above-mentioned ideal reaction. Therefore, the recycling degree of the jarosite slag is low, and high-grade valuable metal ore and iron ore concentrate are difficult to obtain.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for reducing auto-vulcanization roasting pretreatment jarosite slag comprises the following steps:
(1) mixing the jarosite slag with a reducing agent, and carrying out solid-solid reduction and solid sulfur roasting on the obtained mixture to reduce metal sulfate in the jarosite slag into metal sulfide to obtain a reduction and solid sulfur roasting product;
(2) and (2) carrying out reduction, vulcanization and roasting on the reduction roasting product obtained in the step (1), so that iron sulfide and heavy metal oxide in the reduction and sulfur fixation roasting product react to generate iron simple substance and heavy metal sulfide, iron oxide is reduced to metallic iron, and aggregation and growth of Fe and heavy metal sulfide grains are realized to obtain the reduction, vulcanization and roasting product.
The technical idea of the invention is as follows: firstly, reducing metal sulfate in the jarosite slag into metal sulfide by a solid-solid reduction solid sulfur roasting process, and preventing the metal sulfate from being decomposed into metal oxide and sulfur dioxide; (ii) a The iron sulfide generated by reduction can participate in the next vulcanization reaction as a vulcanizing agent;
the main reactions in this step are:
1、KFe3(SO4)2(OH)6＝1/2Fe2(SO4)3+Fe2O3+1/2K2SO4+3H2O；
2、Fe2(SO4)3+6C＝3/2FeS2+1/2Fe+6CO2(g)；
3、ZnSO4+2C＝ZnS+2CO2(g)；
4、PbSO4+2C＝PbS+2CO2(g)；
5、Ag2SO4+2C＝Ag2S+2CO2(g)；
6、CuSO4+2C＝CuS+2CO2(g)；
then the iron sulfide and the metal oxide in the reduction roasting product react to generate iron simple substance and metal sulfide through a reduction vulcanization roasting process, the iron oxide is reduced to metallic iron, and the indium is reduced to ln or ln2O volatilizes and then is oxidized into ln in the flue gas2O3The iron-containing magnetic iron-containing composite material is enriched in smoke dust, the generation of low-melting-point compounds is promoted through the interaction of process coordination and additives, a liquid phase channel is formed in the reaction process, the iron simple substance and the metal sulfide are separated, and the aggregation and growth of crystal grains are promoted, so that favorable conditions are created for flotation and magnetic separation.
The main reactions in this step are:
7、ZnO+1/2FeS2+1/2C＝ZnS+1/2Fe+1/2CO2(g)；
8、ZnFe2O4+1/2FeS2+2C＝ZnS+5/2Fe+2CO2(g)；
9、ZnSiO3+1/2FeS2+1/2C＝ZnS+1/2Fe+SiO2+1/2CO2(g)；
10、PbO+1/2FeS2+1/2C＝PbS+1/2Fe+1/2CO2(g)；
11、CuO+1/2FeS2+1/2C＝CuS+1/2Fe+1/2CO2(g)；
12、Fe2O3+1.5C＝2Fe+1.5CO2(g)；
13、AgO+1/4FeS2+1/2C＝1/2Ag2S+1/4Fe+1/2CO2(g)；
14、In2O3+1.5C＝2In+1.5CO2(g)
by the step-by-step reduction reaction, the metals in the jarosite slag can be vulcanized, converted and fixed to the maximum extent, and SO is avoided2Release of (1); zinc, lead and the like in the slag are converted into metal sulfides, silver is converted into sulfides or simple substances, and indium is volatilized and enriched in smoke dust; directly reducing iron into metallic iron, and obtaining metallic sulfide and metallic iron particles which are easy to be recovered by flotation or magnetic separation, so that after separation, the concentrate and iron concentrate of heavy metal with high recovery rate and high grade can be obtained; after other gangue components in the iron vitriol slag are activated at high temperature in the roasting link, the mineral dressing tailings can be directly used for producing building materials, so that the full-scale utilization of the iron vitriol slag can be realized.
The reduction and auto-vulcanization process of the jarosite slag mainly utilizes metal and sulfur contained in the jarosite slag, and realizes auto-vulcanization under the condition of carbon reduction, wherein zinc, lead and copper are converted into a vulcanization state, silver is converted into a vulcanization state or a metal state, iron is converted into a metal state, indium is volatilized and enriched in smoke dust, sulfur oxides are basically not released in the whole reaction process, a sulfur fixing reagent is not required to be added, and efficient self-immobilization is realized.
Preferably, in the step (1), the solid-solid reduction and sulfur-fixation roasting is carried out in a nitrogen protection atmosphere or an oxygen-free atmosphere, the roasting temperature is 400-600 ℃, and the roasting time is 30-90 min.
The iron oxide in the jarosite slag can be reduced into metal, the sulfates of lead, zinc, copper and iron can be reduced into metal sulfides, and the silver compound can be reduced into metal or metal sulfides by reduction roasting under the low-temperature condition. The reaction temperature is too low, so that the reaction time is too long, and the reduction of the metal sulfate is insufficient; the reaction temperature is too high, the metal sulfate is easy to decompose, and the fixation of sulfur is not facilitated.
Preferably, in the step (2), the reduction, vulcanization and roasting is performed in a nitrogen protective atmosphere or an oxygen-free atmosphere, the roasting temperature is 800-1100 ℃, and the roasting time is 60-120 min.
Carrying out vulcanization roasting under the high-temperature condition, so that iron sulfide generated in the reduction roasting process reacts with residual lead, zinc and copper oxides in the slag, the lead, zinc and copper oxides are vulcanized and converted into sulfide, the iron sulfide is converted into metal, and indium in the slag is volatilized; in addition, the high-temperature environment is favorable for liquid phase generation, separation of metal and sulfide and aggregation growth of crystal grains. If the high-temperature roasting temperature is too low, the indium volatilization rate is low, the liquid phase amount is small, and the aggregation and growth of metal iron grains and metal sulfide grains are not facilitated; if the roasting temperature is too high, the energy consumption is high, the hardness of roasted product slag is high, and the crushing and sorting difficulty is high.
In the method for pretreating jarosite slag by reduction auto-sulfidation roasting, it is preferable that in the step (1), an additive for promoting the formation of a liquid phase channel is added to the mixture.
The additive for promoting the formation of the liquid phase channel mainly provides a liquid phase medium, on one hand, the solid phase reaction of the jarosite slag and the carbonaceous reducing agent is promoted, the reaction efficiency is improved, on the other hand, the reaction temperature can be reduced, and the purpose of reducing the energy consumption is achieved.
In the method for reducing and roasting the pretreated jarosite slag by auto-sulfidation roasting, in the step (1), the reducing agent is preferably a carbonaceous reducing agent, and the additive for promoting the formation of the liquid phase channel is sodium carbonate or sodium chloride.
In the method for pretreating jarosite slag by reducing auto-vulcanization roasting, in the step (1), the mass ratio of the jarosite slag, the reducing agent and the additive for promoting the formation of the liquid phase channel in the mixture is preferably 100: 10-20: 5-10.
When the mass of the carbonaceous reducing agent exceeds 20% of the mass of the jarosite slag, the utilization rate of carbon is low, and a large amount of residual carbon is adsorbed in the flotation stageFlotation reagents are not beneficial to flotation separation; when the mass of the carbonaceous reducing agent is less than 10 percent of that of the jarosite slag, carbon powder is gradually consumed in the later reduction, vulcanization and roasting process, the oxygen partial pressure of a reaction system is increased, zinc, lead, silver and iron in the roasting slag are oxidized, and SO can be caused2Release, which is not beneficial to the sulfuration conversion of heavy metal, the volatilization of indium, the fixation of sulfur and the metallization of iron; and because the reduction vulcanization roasting effect is poor, the vulcanization rate is low, the amount of liquid phase formed in the roasting process is small, heavy metal sulfide and iron grains in a roasted product are fine, and the flotation and magnetic separation recovery are difficult.
The additive for promoting the formation of the liquid phase channel is preferably sodium carbonate, when the mass of the sodium carbonate exceeds 10% of the mass of the iron vanadium slag, the cost is increased, the oxygen potential of a reaction system is increased, the heavy metal vulcanization and iron metallization are not facilitated, and when the mass of the sodium carbonate is less than 5% of the mass of the iron vanadium slag, the liquid phase generation and the growth of metal sulfide and iron crystal grains are not facilitated.
In addition, the research of the applicant shows that the generation and growth of zinc sulfide, lead sulfide and metallic iron grains can be promoted by adopting sodium chloride instead of sodium carbonate as an additive, but toxic chlorine gas can be released; the adoption of sodium sulfate as an additive can generate a large amount of akermanite which is not beneficial to the vulcanization of metal zinc.
In the method for pretreating jarosite slag by reduction auto-vulcanization roasting, the preferred jarosite slag is at least one of jarosite slag, jarosite slag and jarosite slag.
In the method for pretreating jarosite slag by reduction auto-vulcanization roasting, preferably, the carbonaceous reducing agent is at least one of stone tar powder, coke powder, activated carbon powder, carbon black powder, graphite powder and charcoal powder.
In the method for pretreating jarosite slag by reduction auto-sulfidation roasting, in step (1), before the reduction roasting, the method further comprises the step of pelletizing the obtained mixture to obtain a mixture consisting of particles with diameters smaller than 50 mm. When the diameter of the pressed ball is more than 50mm, the ball is extruded and thermally expanded in the kiln to be scattered.
The method for pretreating jarosite slag by reduction auto-sulfidation roasting preferably further comprises recovering indium from the flue gas in step (2).
Compared with the prior art, the invention has the advantages that:
1. according to the technical scheme, the method can volatilize and enrich indium in the dangerous waste iron alum slag existing in a large amount in the existing nonferrous metallurgy industry through reduction-self-vulcanizing roasting, the indium is recovered, heavy metal sulfate or oxide of lead and zinc is converted into metal sulfide, a silver compound is converted into metal or metal sulfide, and iron sulfate or iron oxide is reduced into metallic iron. The zinc and lead after reduction, vulcanization and roasting have extremely high vulcanization rate and extremely high metal rate of silver and iron, thereby creating favorable conditions for the recovery of valuable metals in the jarosite slag by a flotation method and a magnetic separation method. And the fixation rate of the sulfur reaches more than 95 percent, the sulfur in the slag is basically fixed in the form of metal sulfide instead of being volatilized into the flue gas, and the low-concentration SO in the conventional pyrogenic process roasting process is eliminated2The treatment cost and the secondary pollution.
2. The technical scheme of the invention has the advantages of mild process conditions, environmental protection, simple operation and low cost, and is beneficial to industrial production.
Drawings
FIG. 1 is a temperature-Gibbs free energy diagram of the relevant reaction during the roasting process of reducing solid sulfur.
FIG. 2 is a temperature-Gibbs free energy diagram of the relevant reaction during the reduction-sulfidation calcination process of the present invention.
Detailed Description
The invention is further described below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
Example 1:
the method takes a certain sodium jarosite slag as a raw material, and the contents of zinc, lead, iron, sulfur, silver and indium in the jarosite slag are respectively 4.07 percent, 1.96 percent, 22.47 percent, 13.52 percent, 74g/t and 300 g/t. The jarosite slag is dried and ground to be less than 74 mu m, and then is mixed and pressed into balls with 15 percent of charcoal powder (the fixed carbon content is 73 percent) and 5 percent of sodium carbonate by a mixer to obtain mixed balls with the diameter of less than 50 mm.
100kg of the mixed spheres are taken and put into a rotary kiln, and the temperature is raised to 450 ℃ and kept for 90min to carry out reduction sulfur fixation roasting reaction. The main reactions in this process are:
1、KFe3(SO4)2(OH)6＝1/2Fe2(SO4)3+Fe2O3+1/2K2SO4+3H2O；
2、Fe2(SO4)3+6C＝3/2FeS2+1/2Fe+6CO2(g)；
3、ZnSO4+2C＝ZnS+2CO2(g)；
4、PbSO4+2C＝PbS+2CO2(g)；
5、Ag2SO4+2C＝Ag2S+2CO2(g)；
6、CuSO4+2C＝CuS+2CO2(g)；
FIG. 1 is a temperature-Gibbs free energy diagram of the above reaction during the reduction sulfur fixation roasting process of the present example.
Then, the temperature is continuously increased to 1000 ℃, and the temperature is kept for 60min to carry out the reduction vulcanization roasting reaction. The main reactions in this process are:
7、ZnO+1/2FeS2+1/2C＝ZnS+1/2Fe+ 1/2CO2(g)；
8、ZnFe2O4+1/2FeS2+2C＝ZnS+5/2Fe+2CO2(g)；
9、ZnSiO3+1/2FeS2+1/2C＝ZnS+1/2Fe+SiO2+1/2CO2(g)；
10、PbO+1/2FeS2+1/2C＝PbS+1/2Fe+ 1/2CO2(g)；
11、CuO+1/2FeS2+1/2C＝CuS+1/2Fe+ 1/2CO2(g)；
12、Fe2O3+1.5C＝2Fe+1.5CO2(g)；
13、AgO+1/4FeS2+1/2C＝1/2Ag2S+1/4Fe+ 1/2CO2(g)；
14、In2O3+1.5C＝2In+1.5CO2(g)
FIG. 2 is a Gibbs free energy diagram showing the temperature of the above reaction during the reduction vulcanization calcination of this example.
And after the heat preservation is finished, naturally cooling to room temperature, taking out the roasting slag, sampling, and calculating the volatilization rate of indium in the jarosite slag, the fixation rate of sulfur, and the vulcanization conversion rate or metallization rate of zinc, lead, iron and silver. The results show that the indium volatilization rate, the zinc, lead and silver vulcanization conversion rates are respectively 95.47%, 92.28%, 86.15% and 33.26%, the silver and iron metallization rates are respectively 63.16% and 84.64%, the sulfur fixation rate is 97.32%, and the rest of zinc, lead, silver and iron in the roasting slag are respectively present as sphalerite, simple substance lead, silver silicate and ferrous sulfide.
The obtained roasted product is finely ground by a ball mill until the grain size is-0.074 mm and accounts for 80 percent, and lead, zinc and silver are recovered by adopting a lead-zinc preferential flotation process. During lead mineral flotation, sodium sulfide is used as an inhibitor of iron sulfide, zinc sulfate is used as an inhibitor of zinc sulfide ore, ethidium and ammonium nitrate are used as combined agents to serve as collecting agents, and a coarse-fine-three-sweep closed flotation process flow is carried out to obtain lead concentrate containing 41.7% of lead, the recovery rate is 82.3%, the content of silver is 835g/t, and the recovery rate is 89.7%; during zinc flotation, lime is adopted to adjust the pH value to 10.5, copper sulfate is adopted as an activating agent, lime is adopted as an inhibitor, butyl xanthate is adopted as a collecting agent, and a coarse-fine-twice-sweep closed-loop test is carried out to obtain zinc concentrate containing 57.4% of zinc and the recovery rate of 84.8%. After the flotation tailings are subjected to primary low-intensity magnetic separation, iron ore concentrate containing 72.6% of iron and having a recovery rate of 84.5% is obtained.
Lime comparative example 1:
the method takes a certain sodium jarosite slag as a raw material, and the contents of zinc, lead, iron, sulfur, silver and indium in the jarosite slag are respectively 4.07 percent, 1.96 percent, 22.47 percent, 13.52 percent, 74g/t and 300 g/t. Drying and grinding the jarosite slag to be less than 74 mu m, mixing the jarosite slag with 15% of charcoal powder (the fixed carbon content is 73%) and 5% of sodium carbonate by a mixer, pressing the materials into balls to obtain mixed balls with the diameter of less than 50mm, taking 100kg of the mixed balls, putting the mixed balls into a rotary kiln, heating to 750 ℃, roasting at constant temperature for 120min, naturally cooling to room temperature, taking out the roasted slag, sampling, and calculating the indium volatilization rate, the sulfur fixation rate, the zinc, lead, iron and silver vulcanization conversion rate or metallization rate in the jarosite slag. The results showed that the indium volatilization rate, the zinc, lead and silver sulfidation conversion rates were 45.47%, 63.24%, 73.15% and 33.26%, respectively, the silver and iron metal rates were 63.16% and 64.64%, respectively, and the sulfur fixation rate was 73.68%.
And finely grinding the obtained roasted product by a ball mill to enable the roasted product to be-0.074 mm and account for 80%, and recovering lead, zinc and silver by adopting a lead-zinc preferential flotation process. During lead mineral flotation, sodium sulfide is used as an inhibitor of iron sulfide, zinc sulfate is used as an inhibitor of zinc sulfide ore, ethidium and ammonium nitrate combined reagent is used as a collecting agent, and a coarse-fine-three-fine-sweeping closed flotation process flow is carried out to obtain lead concentrate containing 14.3% of lead, the recovery rate of 22.5% of lead, 765g/t of silver and 80.2% of lead; during zinc flotation, lime is adopted to adjust the pH value to 10.5, copper sulfate is adopted as an activating agent, lime is adopted as an inhibitor, butyl xanthate is adopted as a collecting agent, and a coarse-fine-twice-sweep closed-loop test is carried out to obtain zinc concentrate containing 23.6% of zinc and the recovery rate of 32.3%. After the flotation tailings are subjected to primary low-intensity magnetic separation, iron ore concentrate with iron content of 50.6% and recovery rate of 64.5% is obtained.
Compared with the embodiment, because only one-stage roasting is adopted, a large amount of metal sulfate is decomposed to release SO2 during reduction roasting, which is not beneficial to sulfur fixation and heavy metal reduction vulcanization; and because the reduction vulcanization temperature is low, the liquid phase generation amount of a reaction system is insufficient, so that metal sulfides and iron grains in a roasted product are fine, and flotation and magnetic separation are not facilitated.
Example 2:
taking certain jarosite slag as a raw material, wherein the content of zinc, lead, iron, sulfur, silver and indium in the jarosite slag is respectively 3.25%, 2.36%, 26.36%, 14.52%, 112g/t and 270g/t, drying and grinding the jarosite slag to be below 74 microns, then mixing the jarosite slag with 18% of coke powder (the fixed carbon content is 87%) and 10% of sodium carbonate by using a mixer and pressing the mixture into balls to obtain mixed balls with the diameter of less than 50mm, taking 100kg of the mixed balls, putting the mixed balls into a rotary kiln, heating to 600 ℃, keeping the temperature for 60min, then continuing heating to 1100 ℃, keeping the temperature for 60min, naturally cooling to room temperature after the heat preservation is finished, taking out the roasted slag, sampling, and calculating the indium volatilization rate, the sulfur fixation rate, the zinc, lead, iron and silver vulcanization conversion rate or metallization rate. The results show that the indium volatilization rate, the zinc, lead and silver vulcanization conversion rates are respectively 96.52%, 95.64%, 78.35% and 27.53%, the silver and iron metal rates are respectively 70.14% and 88.52%, the sulfur fixation rate is 95.23%, and the rest zinc, lead, silver and iron in the roasting slag are respectively present as sphalerite, simple substance lead, silver silicate and ferrous sulfide.
The obtained roasted product is finely ground by a ball mill until the grain size is-0.074 mm and accounts for 85 percent, and lead, zinc and silver are recovered by adopting a lead-zinc preferential flotation process. During lead mineral flotation, sodium sulfide is used as an inhibitor of iron sulfide, zinc sulfate is used as an inhibitor of zinc sulfide ore, ethidium and ammonium nitrate combined reagent is used as a collecting agent, and a coarse-fine-three-sweep closed flotation process flow is carried out to obtain lead concentrate containing 44.7% of lead, the recovery rate of 83.2%, silver and 1123g/t and the recovery rate of 91.3%; during zinc flotation, lime is adopted to adjust the pH value to 10.5, copper sulfate is adopted as an activating agent, lime is adopted as an inhibitor, butyl xanthate is adopted as a collecting agent, and a coarse-fine-twice-sweep closed-loop test is carried out to obtain the zinc concentrate containing 56.8 percent of zinc and the recovery rate of 88.4 percent. After the flotation tailings are subjected to primary low-intensity magnetic separation, iron ore concentrate containing 81.3% of iron and having a recovery rate of 87.6% is obtained.
Comparative example 2:
taking certain jarosite slag as a raw material, wherein the contents of zinc, lead, iron, sulfur, silver and indium in the jarosite slag are respectively 3.25%, 2.36%, 26.36%, 14.52%, 112g/t and 270g/t, drying and grinding the jarosite slag to be below 74 microns, then mixing the jarosite slag and 18% of coke powder (the fixed carbon content is 87%) by using a mixer and pressing the mixture into balls to obtain mixed balls with the diameter of less than 50mm, taking 100kg of the mixed balls, putting the mixed balls into a rotary kiln, heating to 600 ℃, keeping the temperature for 30min, then continuously raising the temperature to 1000 ℃, keeping the temperature for 120min, naturally cooling to room temperature after the heat preservation is finished, taking out the roasted slag, sampling, and calculating the indium volatilization rate, the fixed rate of sulfur, the vulcanization conversion rate or the metallization rate of zinc, lead, iron and silver in the jarosite slag. The results show that the volatilization rate of indium, the vulcanization conversion rates of zinc, lead and silver are respectively 94.48%, 90.28%, 75.07% and 30.86%, the metallization rates of silver and iron are respectively 65.35% and 70.26%, the fixation rate of sulfur is 92.41%, and the rest zinc, lead, silver and iron in the roasting slag are respectively present as sphalerite, simple substance lead, silver silicate and ferrous sulfide.
And finely grinding the obtained roasted product by a ball mill to be-0.074 mm accounting for 85%, and recovering lead, zinc and silver by adopting a lead-zinc preferential flotation process. During lead mineral flotation, sodium sulfide is used as an inhibitor of iron sulfide, zinc sulfate is used as an inhibitor of zinc sulfide ore, ethidium and ammonium nitrate combined reagent is used as a collecting agent, and a coarse-fine-three-sweep closed flotation process flow is adopted to obtain lead concentrate containing 32.5% of lead, the recovery rate is 63.2%, the silver content is 865g/t, and the recovery rate is 76.8%; during zinc flotation, lime is adopted to adjust the pH value to 10.5, copper sulfate is adopted as an activating agent, lime is adopted as an inhibitor, butyl xanthate is adopted as a collecting agent, and a coarse-fine-twice-sweep closed-loop test is carried out to obtain zinc concentrate containing 41.3 percent of zinc and the recovery rate of 68.2 percent. The flotation tailings are subjected to primary low-intensity magnetic separation to obtain iron ore concentrate containing 64.2% of iron and having a recovery rate of 71.3%.
In the comparative example, although the vulcanization conversion rate of lead and zinc and the metallization rate of iron are high, because a sodium carbonate additive is not added during the reduction vulcanization roasting, the liquid phase amount in the reduction vulcanization roasting process is small, and sulfides and metal grains cannot be aggregated and grown, so that the metal sulfide particles and the metal particles in the roasted product have small embedded particle size, and the flotation and magnetic separation effects are poor.
Example 3:
taking silver iron vitriol slag from Hunan as raw material, the content of zinc, lead, iron, sulfur, silver and indium in the vitriol slag is respectively 8.75%, 4.47%, 20.35%, 15.76%, 656g/t and 425 g/t. Drying and grinding the jarosite slag to below 74 mu m, mixing the jarosite slag with 20% graphite powder (the fixed carbon content is 93%) below 74 mu m and 10% sodium carbonate by a mixer, pressing the materials into balls to obtain mixed balls with the diameter of less than 50mm, putting 100kg of the mixed balls into a rotary kiln, heating to 450 ℃, keeping the temperature for 90min, then continuing to raise the temperature to 850 ℃, keeping the temperature for 120min, naturally cooling to room temperature after the heat preservation is finished, taking out the roasted slag, sampling, and calculating the volatilization rate of indium in the jarosite slag, the fixation rate of sulfur, the vulcanization conversion rate of zinc, lead, iron and silver or the metallization rate. The results show that the volatilization rate of indium, the sulfidation conversion rates of zinc, lead and silver are 82.78%, 96.16%, 86.26% and 74.46%, the metal rates of silver and iron are 10.52% and 73.32%, respectively, the fixation rate of sulfur is 94.82%, and the rest of zinc, lead, silver and iron in the roasting slag are respectively present as sphalerite, simple substance lead, silver silicate and ferrous sulfide.
The obtained roasted product is finely ground by a ball mill until the grain size is-0.074 mm and accounts for 85 percent, and lead, zinc and silver are recovered by adopting a lead-zinc preferential flotation process. During lead mineral flotation, sodium sulfide is used as an inhibitor of iron sulfide, zinc sulfate is used as an inhibitor of zinc sulfide ore, ethidium and ammonium nitrate combined reagent is used as a collecting agent, and a coarse-fine-three-sweep closed flotation process flow is adopted to obtain lead concentrate containing 46.7% of lead, the recovery rate is 81.6%, the content of silver is 7623g/t, and the recovery rate is 93.3%; during zinc flotation, lime is adopted to adjust the pH value to 10.5, copper sulfate is adopted as an activating agent, lime is adopted as an inhibitor, butyl xanthate is adopted as a collecting agent, and a coarse-fine-twice-sweep closed-loop test is carried out to obtain zinc concentrate containing 67.8% of zinc and the recovery rate of 86.2%. After the flotation tailings are subjected to primary low-intensity magnetic separation, iron ore concentrate containing 68.3% of iron and having a recovery rate of 82.2% is obtained.
Comparative example 3:
taking silver iron vitriol slag from Hunan as raw material, the content of zinc, lead, iron, sulfur, silver and indium in the vitriol slag is respectively 8.75%, 4.47%, 20.35%, 15.76%, 656g/t and 425 g/t. Drying and grinding the jarosite slag to below 74 mu m, mixing the jarosite slag with 25% graphite powder (with fixed carbon content of 93%) below 74 mu m and 10% sodium carbonate by a mixer, pressing the mixture into balls with the diameter of less than 50mm, putting 100kg of the mixed balls into a rotary kiln, heating to 700 ℃, keeping the temperature for 90min, continuing heating to 1200 ℃, keeping the temperature for 120min, naturally cooling to room temperature after the heat preservation is finished, taking out the roasting slag, sampling, and calculating the volatilization rate of indium in the jarosite slag, the fixation rate of sulfur, the vulcanization conversion rate of zinc, lead, iron and silver or the metallization rate. The results show that the volatilization rate of indium, the sulfidation conversion rates of zinc, lead and silver are respectively 96.43%, 76.43%, 54.53% and 13.46%, the metal rates of silver and iron are respectively 80.56% and 93.72%, and the fixation rate of sulfur is 73.72%, and most of lead and zinc are reduced to metal and volatilized into smoke dust due to the overhigh temperature and overlarge carbon ratio of the reduction-sulfidation roasting.
And finely grinding the obtained roasted product by a ball mill to be-0.074 mm accounting for 85%, and recovering lead, zinc and silver by adopting a lead-zinc preferential flotation process. During lead mineral flotation, sodium sulfide is used as an inhibitor of iron sulfide, zinc sulfate is used as an inhibitor of zinc sulfide ore, ethidium and ammonium nitrate combined reagent is used as a collecting agent, and a coarse-fine-three-sweep closed flotation process flow is adopted to obtain lead concentrate containing 28.2% of lead, the recovery rate is 81.6%, the silver content is 11346g/t, and the recovery rate is 95.3%; during zinc flotation, lime is adopted to adjust the pH value to 10.5, copper sulfate is adopted as an activating agent, lime is adopted as an inhibitor, butyl xanthate is adopted as a collecting agent, and a coarse-fine-twice-sweep closed-loop test is carried out to obtain zinc concentrate containing 32.8% of zinc and the recovery rate of 85.2%. After the flotation tailings are subjected to primary low-intensity magnetic separation, iron ore concentrate containing 84.3% of iron and having a recovery rate of 90.2% is obtained.
Because the carbon proportion is too high, a large amount of graphite powder is left in the reduction-vulcanization roasting product, a large amount of flotation reagents are adsorbed during flotation, and meanwhile, the graphite powder can adsorb a large amount of fine-grained particles, so that the selectivity in the flotation process is poor, the concentrate grade is low, and the reagent consumption is large; in addition, the roasting temperature is too high, the hardness of the roasted product is high, and the crushing and ore grinding are difficult.
The above description is only for the preferred embodiment of the present application and should not be taken as limiting the present application in any way, and although the present application has been disclosed in the preferred embodiment, it is not intended to limit the present application, and those skilled in the art should understand that they can make various changes and modifications within the technical scope of the present application without departing from the scope of the present application, and therefore all the changes and modifications can be made within the technical scope of the present application.
Claims (9)
1. A method for reducing auto-vulcanization roasting pretreatment jarosite slag is characterized by comprising the following steps:
(1) mixing the jarosite slag with a reducing agent, and carrying out solid-solid reduction and solid sulfur roasting on the obtained mixture to reduce metal sulfate in the jarosite slag into metal sulfide to obtain a reduction and solid sulfur roasting product;
(2) carrying out reduction, vulcanization and roasting on the reduction roasting product obtained in the step (1), so that iron sulfide and heavy metal oxide in the reduction and sulfur fixation roasting product react to generate iron simple substance and heavy metal sulfide, iron oxide is reduced to metallic iron, and aggregation and growth of Fe and heavy metal sulfide grains are realized respectively at the same time, thus obtaining the reduction, vulcanization and roasting product;
in the step (1), the solid-solid reduction sulfur fixation roasting is carried out in an oxygen-free atmosphere, the roasting temperature is 400-600 ℃, and the roasting time is 30-90 min;
in the step (2), the reduction vulcanization roasting is carried out in an oxygen-free atmosphere, the roasting temperature is 800-1000 ℃, and the roasting time is 60-120 min.
2. The method for reducing auto-sulfidation roasting pre-treatment of jarosite slag as recited in claim 1, wherein in step (1), the mixture further comprises adding an additive for promoting the formation of liquid phase channels.
3. The method for reducing self-vulcanizing roasting pre-treating jarosite slag as recited in claim 2, wherein in the step (1), the reducing agent is a carbonaceous reducing agent, and the additive for promoting the formation of liquid phase channels is sodium carbonate or sodium chloride.
4. The method for reducing self-vulcanizing roasting pretreatment of jarosite slag as claimed in claim 3, wherein in the step (1), the mass ratio of the jarosite slag, the reducing agent and the additive for promoting the formation of the liquid phase channel in the mixture is 100: 10 to 20: 5 to 10.
5. The method of claim 4, wherein the jarosite slag is at least one of jarosite slag, and sillimanite slag.
6. The method of claim 4, wherein the carbonaceous reducing agent is at least one of stone tar powder, coke powder, activated carbon powder, carbon black powder, graphite powder and charcoal powder.
7. The method for reducing self-vulcanizing roasting pre-treating jarosite slag as claimed in any one of claims 1 to 6, wherein in the step (1), before the reducing roasting, the method further comprises the step of subjecting the obtained mixture to ball pressing to obtain a mixture consisting of particles with diameters of less than 50 mm.
8. The method for pretreating jarosite slag by reductive auto-sulfidation roasting according to any one of claims 1 to 6, further comprising recovering indium from the flue gas of step (2).
9. The method for reducing self-vulcanizing roasting pretreatment of jarosite slag according to any one of claims 1 to 6, wherein the oxygen-free atmosphere is a nitrogen atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910686659.XA CN110408791B (en) | 2019-07-29 | 2019-07-29 | Method for reducing self-vulcanizing roasting pretreatment of jarosite slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910686659.XA CN110408791B (en) | 2019-07-29 | 2019-07-29 | Method for reducing self-vulcanizing roasting pretreatment of jarosite slag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110408791A CN110408791A (en) | 2019-11-05 |
| CN110408791B true CN110408791B (en) | 2021-07-02 |
Family
ID=68363610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910686659.XA Active CN110408791B (en) | 2019-07-29 | 2019-07-29 | Method for reducing self-vulcanizing roasting pretreatment of jarosite slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110408791B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112194171A (en) * | 2020-09-01 | 2021-01-08 | 珠海格力绿色再生资源有限公司 | Novel process for reducing ash content of pyrolysis carbon black and recovering beneficial components |
| CN114317954A (en) * | 2021-12-31 | 2022-04-12 | 上海大学 | Method for cooperatively treating and utilizing stainless steel pickling sludge and blast furnace dust |
| CN115433825B (en) * | 2022-08-16 | 2023-11-07 | 湖南中邦再生资源科技有限公司 | Comprehensive recovery method of iron and sulfur in waste lithium battery |
-
2019
- 2019-07-29 CN CN201910686659.XA patent/CN110408791B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110408791A (en) | 2019-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110408791B (en) | Method for reducing self-vulcanizing roasting pretreatment of jarosite slag | |
| CN110983061B (en) | Method for cooperative recycling of lead-zinc smelting slag and jarosite slag | |
| CN101348859B (en) | Method for comprehensively recovering gold, iron and sulphur resource from gold-containing sulfurous iron ore | |
| CN110983029B (en) | Method for carrying out synergistic vulcanization roasting on lead-zinc smelting slag and gypsum slag | |
| CN102517439B (en) | Method for selectively roasting and separating tin, zinc and arsenic in compound iron ore containing tin, zinc and arsenic | |
| CN115386738B (en) | Method for producing high nickel matte by reducing, vulcanizing and smelting laterite-nickel ore | |
| CN107012328A (en) | A kind of high ferro zinc leaching residue clean utilization method | |
| CN106731629B (en) | Method for removing sulfur, arsenic and mercury by using copper smelting plant tailing slag slurry | |
| CN103103344A (en) | Dressing-smelting combined treatment method for sulfate-containing lead-zinc smelting slags | |
| CN111118303A (en) | Method for preparing zinc hypoxide by oxygen pressure leaching of zinc smelting solid waste slag | |
| CN106222397A (en) | A kind of utilize pyrite sulfidation roasting smithsonite and the method for Zn accumulation galvanized iron | |
| Yang et al. | A novel process for Fe recovery and Zn, Pb removal from a low-grade pyrite cinder with high Zn and Pb contents | |
| CN111996364B (en) | Method for recovering gold from cyanidation tailings and synchronously magnetizing iron | |
| CN110453079B (en) | Method for efficiently recovering silver in lead-silver slag by melting-fuming method | |
| CN108950195B (en) | Method for extracting valuable metals from zinc concentrate oxidizing slag by using chlorine-containing wastewater | |
| CN115094245B (en) | Method for synchronously recycling cobalt and iron from low-cobalt multi-metal sulfide ore | |
| CN114774676B (en) | Method for enriching metal and material for refining metal | |
| Swamy et al. | Enrichment of the manganese to iron ratio of ferruginous low-grade manganese ore using solid reductant | |
| CN116179871A (en) | Method for enriching nickel and cobalt by low-carbon reduction, vulcanization and roasting of laterite-nickel ore | |
| US4135913A (en) | Thermal concentration of non-ferrous metal values in sulfide minerals | |
| CN104017997A (en) | Copper recycling process of copper casting scum by utilizing biological dump leaching | |
| CN110373539B (en) | Method for strengthening gold enrichment of refractory gold ore by direct smelting | |
| CN106756093A (en) | A kind of modified floatation and recovery of lead zinc method in difficult zinc oxide material heat chemistry surface | |
| CN1156588C (en) | Sulfurizing reduction and roasting and voltizing dearsenication method for copper-zine-cobalt material | |
| CN111979423B (en) | Method for reinforced recovery of valuable metals in copper smelting slag by using gypsum slag |
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 |