CN110564964A - Dressing and smelting combined process for efficiently utilizing copper-zinc ore - Google Patents
Dressing and smelting combined process for efficiently utilizing copper-zinc ore Download PDFInfo
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- CN110564964A CN110564964A CN201910986759.4A CN201910986759A CN110564964A CN 110564964 A CN110564964 A CN 110564964A CN 201910986759 A CN201910986759 A CN 201910986759A CN 110564964 A CN110564964 A CN 110564964A
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- 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
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
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- 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
- C22B15/0002—Preliminary treatment
- C22B15/0004—Preliminary treatment without modification of the copper constituent
- C22B15/0008—Preliminary treatment without modification of the copper constituent by wet processes
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- 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
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- 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
- C22B15/0063—Hydrometallurgy
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- 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
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- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
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- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to a dressing-smelting combined process for efficiently utilizing copper-zinc ores, wherein in a dressing stage, copper-zinc mixed ore raw ores are subjected to crushing, ore grinding, grading and other processes to reach proper granularity, and then mixed flotation is utilized to obtain copper-zinc mixed concentrates with high recovery rate; and then, in the copper-zinc separation stage, carrying out size mixing and reagent removal treatment on the copper-zinc bulk concentrate obtained in the step, and preparing for bioleaching or chemical leaching. According to the used leaching method, the potential, the pH value, the ore pulp concentration, the temperature, the leaching agent ratio, the species and the concentration of leaching microorganisms of the leaching system are regulated and controlled, and the selective leaching of zinc in the copper-zinc bulk concentrate is finally realized. Obtaining copper concentrate and leachate containing zinc ions; finally, the metal copper and the metal zinc are finally obtained through wet or fire metallurgy process treatment. The process has the advantages of simple flow, complete technology, high comprehensive recovery rate, thorough copper and zinc separation and lower cost, and is beneficial to realizing industrial application.
Description
Technical Field
The invention relates to efficient separation and extraction of metal copper and zinc in a copper-zinc mixed ore in the fields of mineral processing and wet metallurgy, in particular to a process for effectively separating copper minerals and zinc minerals in the copper-zinc mixed ore to obtain leachate containing zinc ions and copper concentrate, and finally obtaining metal zinc and metal copper.
Background
In the field of mineral processing and smelting, copper and zinc separation is a difficult problem which troubles the industry for a long time. In nature, copper and zinc are mainly present in the form of sulfides. Flotation is commonly used in the mineral processing field to separate sulphide ores from oxidised ores (most gangue minerals) based on differences in their hydrophilicity and hydrophobicity. However, non-ferrous metal minerals often exist as co-associated polymetallic complex sulfide deposits, wherein copper sulfide minerals are often co-associated with zinc sulfide minerals. During the flotation process, the activation of the copper ions in the pulp on the surface of the zinc sulfide mineral reduces the difference of the surface hydrophobicity of the copper sulfide mineral and the zinc sulfide mineral, so that the copper and the zinc are difficult to separate by using the flotation method. Thus, even up to 10% by mass of zinc is present in the copper concentrate obtained industrially. The residual zinc in the copper concentrate is separated in the form of soot during the pyrometallurgical copper smelting, the soot needs to be collected and treated, the process is complex, the cost is high, otherwise, the zinc resource waste is faced, and the price of the copper concentrate is reduced. Therefore, the development of an effective copper-zinc separation process has wide industrial application prospects.
In industrial production, the most common copper-zinc separation method is the preferential flotation method. The method is used for floating useful minerals one by one in an easy-to-first-difficult sequence according to the difference of floatability of the useful minerals. The method requires that the raw ore grade is high, the difference of the floatability of the copper ore and the zinc ore in the raw ore is large, but the method has poor effect on poor ores and the situation that the floatability of the zinc ore after copper ion activation is similar to that of the copper ore. In addition, the preferential flotation method requires longer flotation time, more flotation machines, higher cost in ore grinding sections, and higher production cost due to the consumption of a large amount of inhibitors and activators. Therefore, as high-grade mineral products are reduced in nature, the properties of the mineral are more complex, and the copper-zinc separation by a preferential flotation method is more and more limited.
In addition to the most common methods of preferential flotation, methods such as mixed flotation, partial preferential-mixed flotation, iso-flotation, and thermal flotation are also used industrially. The ultimate goal of these processes is to separate the copper and zinc ores by flotation. Among them, the bulk concentrates of copper and zinc obtained by bulk flotation, partial preferential bulk flotation and iso-floatable processes often require further grinding to fully dissociate copper ores and zinc ores, and require a large amount of inhibitors and activators, which undoubtedly increases the cost. The heating flotation is to inhibit the floatability of zinc minerals by utilizing the temperature rise, and the consumption of a large amount of energy is an obvious defect.
At present, although the dressing and smelting combined process is also applied in industry, the processes comprise roasting desulfurization-acid leaching process, pressure leaching process, chlorination roasting water leaching and the like, and the aim is to simultaneously extract copper and zinc in the bulk concentrate obtained by flotation, the roasting, pressure and other methods consume a large amount of energy, and the obtained leachate still needs copper and zinc separation.
In order to solve the problem that the copper-zinc mixed ore is difficult to separate by using a flotation method, in order to reduce the zinc content in the copper concentrate and improve the quality of the copper concentrate, in order to utilize metal zinc in the copper-zinc mixed ore as resources and to realize copper-zinc separation by using an efficient method, a new process needs to be developed to realize the purposes.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a dressing-smelting combined process for efficiently utilizing copper-zinc ores, which skillfully realizes the separation of copper and zinc in copper-zinc mixed ores by utilizing a (biological) hydrometallurgy method. The method solves the industrial problem of copper-zinc separation, and the required copper-zinc bulk concentrate can be obtained by a simple equal-floatability (mixed flotation) method, thereby shortening the flotation flow and reducing the medicament use and energy consumption. The process has the advantages of simple flow, complete technology, high comprehensive recovery rate, thorough copper-zinc separation and low cost, and is favorable for realizing industrial application.
The invention adopts the following technical scheme for solving the technical problems: a dressing and smelting combined process for efficiently utilizing copper-zinc ores comprises the following steps:
(1) Crushing and screening the copper-zinc mixed ore to obtain fine ore with qualified granularity;
(2) Grinding and grading the fine ore to obtain ore pulp meeting the requirement of flotation granularity;
(3) Carrying out copper-zinc mixed flotation on the ore pulp to obtain copper-zinc mixed concentrate;
(4) Leaching zinc from the copper-zinc mixed ore concentrate by adopting biological or chemical selectivity, and performing solid-liquid separation to obtain low-zinc high-grade copper concentrate and a zinc-containing leachate;
(5) Purifying, concentrating, cooling and crystallizing the zinc-containing leachate to obtain a zinc sulfate product; or purifying, extracting and electrodepositing the zinc-containing leachate to obtain a zinc plate;
(6) Returning residual liquid generated by the crystallization and the extraction in the step (5) to the step (4) for mixed pulping after adding a chemical oxidant or oxidizing by microorganisms;
(7) Smelting, converting and oxidizing the high-grade copper concentrate to obtain metal copper; or roasting, leaching and electrodepositing the high-grade copper concentrate to obtain the metal copper.
Preferably, in the step (1), the copper-zinc mixed ore mainly contains copper sulfide minerals and zinc sulfide minerals, the copper grade is more than or equal to 0.4%, and the zinc grade is more than or equal to 2%.
Preferably, in the step (1), the qualified fine ore has a grain size of 13mm or less.
Preferably, in the step (2), the feeding granularity conforming to flotation is-200 meshes or more and 65%.
Preferably, in the step (3), the flotation is copper-zinc mixed flotation.
preferably, in the step (4), the biological selective leaching is selected, and the copper-zinc mixed ore concentrate is subjected to size mixing and reagent removal treatment to obtain mixed ore concentrate pulp; then adjusting the pH value of the ore pulp by using dilute sulfuric acid, adding ore leaching bacteria, and stirring and leaching.
Preferably, the concentration of the ore pulp of the bulk concentrate is 1-30%, the pH of the ore pulp is adjusted to 1.0-2.5 by using dilute sulfuric acid, the total iron concentration is controlled to be 0.1-1.0mol/L, and the bacteria concentration is controlled to be not less than 107Stirring at 15-200rpm, controlling the temperature of the leaching system at 30-80 deg.C, controlling the leaching potential at 600-790mV relative to the saturated silver/silver chloride electrode, and leaching for 1-5 days.
Preferably, the ore leaching bacteria are one or more of acidithiobacillus ferrooxidans, leptospirillum ferrooxidans and leptospirillum ferrophilis.
Preferably, in the step (4), chemoselective leaching is selected, and the copper-zinc mixed ore concentrate is subjected to size mixing and reagent removal treatment to obtain mixed ore concentrate pulp; then dilute sulphuric acid is used for adjusting the pH value of the ore pulp, an oxidant is added, and then stirring leaching is carried out.
As a further preference, the oxidant is Fe3+Oxygen and halogen element simple substance, nitrate, persulfate, permanganate, oxyacid of chlorine and salt thereof, and peroxide; the concentration of the mixed concentrate ore pulp is 1-30%, the pH of the ore pulp is adjusted to be 0.5-2.5, the leaching potential is controlled to be 810-1000mV relative to a saturated silver/silver chloride electrode, the stirring speed is 15-1000rpm, the temperature of a leaching system is controlled to be 30-100 ℃, and the leaching time is 1-48 hours.
Compared with the prior art, the invention has the following advantages: 1. the used dressing and smelting combined process has no strict requirement on the grade of raw ore and is beneficial to the treatment of lower-grade mineral resources; 2. the flotation-smelting combined process efficiently utilizing the copper-zinc ores utilizes the mixed flotation method, avoids the defects of long process and large reagent consumption of the current common copper-zinc separation flotation process, simplifies the flotation process and reduces the consumption of the flotation reagent; 3. the copper-zinc sulfide ore is subjected to mixed flotation, so that the use of an inhibitor is avoided, and the recovery rate of the copper-zinc sulfide ore can reach over 90 percent; 3. the copper-zinc bulk concentrate obtained in the process flow does not need high-temperature heating pretreatment and pressurization treatment in the subsequent copper-zinc separation stage, so that a large amount of energy is saved, and the cost is low; 4. the process flow of the invention utilizes a (biological) hydrometallurgy method, realizes the purpose of separating copper and zinc by selectively dissolving out zinc, has no strict requirements on the grade and quality of the copper-zinc bulk concentrate obtained by flotation, and allows the copper-zinc bulk concentrate and other easily soluble minerals to be separated out together with the iron sulfide minerals and the like in the equal floatable (bulk flotation) stage; 5. the process has the advantages of simple flow, complete technology, high comprehensive recovery rate, thorough copper and zinc separation and lower cost, and is beneficial to realizing industrial application.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is further described below by combining the specific drawings and the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, the invention provides a dressing and smelting combined process for efficiently utilizing copper-zinc ores, which comprises the following steps: crushing and screening the copper-zinc mixed ore to obtain fine ore with qualified granularity; grinding and grading the fine ore to obtain ore pulp meeting the requirement of flotation granularity; carrying out copper-zinc mixed flotation on the ore pulp to obtain copper-zinc mixed concentrate, and mixing the copper-zinc mixed concentrate with water for size mixing; then leaching zinc by adopting biological or chemical selectivity, and performing solid-liquid separation to obtain low-zinc high-grade copper concentrate and zinc-containing leachate; purifying, concentrating, cooling and crystallizing the zinc-containing leachate to obtain a zinc sulfate product; or purifying, extracting and electrodepositing the zinc-containing leachate to obtain a zinc plate; the raffinate generated by the crystallization and the extraction is returned to the mixed pulping after being oxidized by adding a chemical oxidant or microorganisms; smelting, converting and oxidizing the high-grade copper concentrate to obtain metal copper; or roasting, leaching and electrodepositing the high-grade copper concentrate to obtain the metal copper.
Example 1
The method selects copper-zinc mixed ore mainly containing copper sulfide minerals and zinc sulfide minerals, and the copper grade is more than or equal to 0.4 percent, and the zinc grade is more than or equal to 2 percent. Crushing and screening the copper-zinc mixed ore to obtain fine ore with qualified granularity of less than or equal to 13mm, and grinding and grading the fine ore until the proportion of-200 meshes is more than or equal to 65%. And carrying out copper-zinc mixed flotation on the fine ore to obtain copper-zinc mixed concentrate. In the copper-zinc mixed ore concentrate of the embodiment, the copper grade is 4.23% (recovery rate 91.39%), and the zinc grade is 4.95% (recovery rate 92.51%). The copper-zinc bulk concentrate and water are mixed and size-mixed, and are processed by size mixing and reagent removal to reach the concentration of 10 percent of ore pulp, so that the bioleaching is conveniently carried out. Controlling the pH value of the ore pulp to be between 1.0 and 2.5 by using dilute sulfuric acid, controlling the reaction temperature of a leaching system to be between 40 and 55 ℃, and adding Fe2(SO4)3And Fe3(SO4)2The total iron concentration is controlled to be 0.2mol/L, wherein the Fe3+And Fe2+the ratio is equal to 8, Acidithiobacillus ferrooxidans is added, and the bacterial concentration is controlled to be not less than 107The copper and the zinc are separated by stirring per milliliter at the stirring speed of 150rpm, controlling the temperature of a leaching system to be 30-80 ℃, controlling the leaching potential to be 600-790mV relative to a saturated silver/silver chloride electrode, and the leaching time to be 2 days. In the embodiment, the zinc-containing leachate with the zinc recovery rate of 96.17 percent is obtained; cu is dissolved out by 2.77 percent, and the zinc content of the obtained copper concentrate is only 0.26 percent. Purifying, concentrating, cooling and crystallizing the zinc-containing leachate to obtain a zinc sulfate product; or purifying, extracting and electrodepositing the zinc-containing leachate to obtain a zinc plate; the raffinate generated by the crystallization and the extraction is returned to the mixed pulping after being oxidized by adding a chemical oxidant or microorganisms; smelting, converting and oxidizing the high-grade copper concentrate to obtain metal copper; or roasting, leaching and electrodepositing the high-grade copper concentrate to obtain the metal copper.
Example 2
The copper-zinc mixed ore concentrate obtained in example 1 had a copper grade of 4.23% (recovery rate of 91.39%) and a zinc grade of 4.95% (recovery rate of 92.51%). Mixing the copper-zinc bulk concentrate with water, pulping, and removing the chemicalsthe concentration of the ore pulp is regulated to be 30 percent, so that the chemical leaching is conveniently carried out. Controlling the pH value of the ore pulp to be between 0.5 and 2.5 by using dilute sulfuric acid, controlling the reaction temperature of a leaching system to be 60 ℃, and adding an oxidant Fe2(SO4)3The total iron concentration of the initial addition is controlled to be 0.6mol/L, the leaching potential is controlled to be 810-1000mV relative to a saturated silver/silver chloride electrode, and the stirring speed is 500 rpm. After 2 hours, the zinc-containing leachate with the zinc recovery rate of 96.35% is obtained in the embodiment; cu is dissolved out by 1.98 percent, and the zinc content of the obtained copper concentrate is only 0.22 percent. Purifying, concentrating, cooling and crystallizing the zinc-containing leachate to obtain a zinc sulfate product; or purifying, extracting and electrodepositing the zinc-containing leachate to obtain a zinc plate; the raffinate generated by the crystallization and the extraction is returned to the mixed pulping after being oxidized by adding a chemical oxidant or microorganisms; smelting, converting and oxidizing the high-grade copper concentrate to obtain metal copper; or roasting, leaching and electrodepositing the high-grade copper concentrate to obtain the metal copper.
example 3
The copper-zinc mixed ore concentrate obtained in example 1 had a copper grade of 4.23% (recovery rate of 91.39%) and a zinc grade of 4.95% (recovery rate of 92.51%). The copper-zinc bulk concentrate and water are mixed and size-mixed, and are subjected to size mixing and reagent removal treatment to reach the concentration of 20% of ore pulp, so that chemical leaching is conveniently carried out. The pH value of the ore pulp is controlled between 0.5 and 2.5 by using dilute sulfuric acid, the reaction temperature of a leaching system is controlled to be 70 ℃, the leaching potential is controlled to be 810-1000mV relative to a saturated silver/silver chloride electrode by adding an oxidant potassium perchlorate, and the stirring speed is 500 rpm. After 2 hours, the zinc-containing leachate with the zinc recovery rate of 94.95% is obtained in the embodiment; cu is dissolved out by 2.07 percent, and the zinc content of the obtained copper concentrate is only 0.31 percent. Purifying, concentrating, cooling and crystallizing the zinc-containing leachate to obtain a zinc sulfate product; or purifying, extracting and electrodepositing the zinc-containing leachate to obtain a zinc plate; the raffinate generated by the crystallization and the extraction is returned to the mixed pulping after being oxidized by adding a chemical oxidant or microorganisms; smelting, converting and oxidizing the high-grade copper concentrate to obtain metal copper; or roasting, leaching and electrodepositing the high-grade copper concentrate to obtain the metal copper.
Example 4
The copper-zinc mixed ore concentrate obtained in example 1 had a copper grade of 20.23% (recovery rate of 95.66%) and a zinc grade of 8.85% (recovery rate of 91.47%). The copper-zinc bulk concentrate and water are mixed and size-mixed, and are processed by size mixing and reagent removal to reach 5% of pulp concentration, so that bioleaching is conveniently carried out. Controlling the pH value of ore pulp between 1.0-2.5 by using dilute sulfuric acid, controlling the reaction temperature of a leaching system to be 30-40 ℃, and adding Fe2(SO4)3And Fe3(SO4)2The total iron concentration of the initial charge is controlled to be 0.2mol/L, wherein the Fe3+And Fe2+the ratio is equal to 6, ferrous oxide leptospira micrantha is added to leach the ore, the concentration of the bacteria is controlled to be not less than 107the leaching potential is controlled to be 600-790mV relative to a saturated silver/silver chloride electrode, and the separation of copper and zinc is carried out, and the stirring speed is 200 rpm. After 3 days, the zinc-containing leachate with the zinc recovery rate of 95.81% is obtained in the embodiment; cu is only dissolved out by 3.43 percent, and the zinc content of the leaching slag (copper concentrate) is only 0.47 percent. Purifying, concentrating, cooling and crystallizing the zinc-containing leachate to obtain a zinc sulfate product; or purifying, extracting and electrodepositing the zinc-containing leachate to obtain a zinc plate; the raffinate generated by the crystallization and the extraction is returned to the mixed pulping after being oxidized by adding a chemical oxidant or microorganisms; smelting, converting and oxidizing the high-grade copper concentrate to obtain metal copper; or roasting, leaching and electrodepositing the high-grade copper concentrate to obtain the metal copper.
Example 5
Copper-zinc bulk concentrate was obtained as in example 1, and the copper grade in the copper-zinc bulk concentrate of this example was 20.23% (recovery 95.66%) and the zinc grade was 8.85% (recovery 91.47%). The copper-zinc bulk concentrate and water are mixed and size-mixed, and are subjected to size mixing and reagent removal treatment to reach the concentration of 20% of ore pulp, so that chemical leaching is conveniently carried out. The pH value of the ore pulp is controlled between 0.5 and 2.5 by dilute sulphuric acid, the reaction temperature of a leaching system is controlled to be 80 ℃, the leaching potential is controlled to be 810-1000mV relative to a saturated silver/silver chloride electrode by adding an oxidant potassium permanganate, and the stirring speed is 1000 rpm. After 2 hours, the zinc-containing leachate with the zinc recovery rate of 93.20% is obtained in the embodiment; cu is only dissolved out by 2.93 percent, and the zinc content of the obtained leaching slag (copper concentrate) is only 0.76 percent. Purifying, concentrating, cooling and crystallizing the zinc-containing leachate to obtain a zinc sulfate product; or purifying, extracting and electrodepositing the zinc-containing leachate to obtain a zinc plate; the raffinate generated by the crystallization and the extraction is returned to the mixed pulping after being oxidized by adding a chemical oxidant or microorganisms; smelting, converting and oxidizing the high-grade copper concentrate to obtain metal copper; or roasting, leaching and electrodepositing the high-grade copper concentrate to obtain the metal copper.
Example 6
The copper-zinc mixed ore concentrate obtained in example 1 had a copper grade of 20.23% (recovery rate of 95.66%) and a zinc grade of 8.85% (recovery rate of 91.47%). The copper-zinc bulk concentrate and water are mixed and size-mixed, and are subjected to size mixing and reagent removal treatment to reach the concentration of 10% of ore pulp, so that chemical leaching is conveniently carried out. The pH value of the ore pulp is controlled between 0.5 and 2.5 by using dilute sulphuric acid, the reaction temperature of a leaching system is controlled to be 80 ℃, the leaching potential is controlled to be 810-1000mV relative to a saturated silver/silver chloride electrode by adding an oxidant potassium nitrate, and the stirring speed is 1000 rpm. After 2 hours, the zinc-containing leachate with the zinc recovery rate of 94.17% is obtained in the embodiment; cu is only dissolved out by 2.79 percent, and the zinc content of the obtained leaching slag (copper concentrate) is only 0.65 percent. Purifying, concentrating, cooling and crystallizing the zinc-containing leachate to obtain a zinc sulfate product; or purifying, extracting and electrodepositing the zinc-containing leachate to obtain a zinc plate; the raffinate generated by the crystallization and the extraction is returned to the mixed pulping after being oxidized by adding a chemical oxidant or microorganisms; smelting, converting and oxidizing the high-grade copper concentrate to obtain metal copper; or roasting, leaching and electrodepositing the high-grade copper concentrate to obtain the metal copper.
Example 7
The copper-zinc mixed ore concentrate obtained in example 1 had a copper grade of 10.71% (recovery rate of 94.19%) and a zinc grade of 13.46% (recovery rate of 92.67%). The copper-zinc bulk concentrate and water are mixed and size-mixed, and are processed by size mixing and reagent removal to reach the concentration of 10 percent of ore pulp, so that the bioleaching is conveniently carried out. Controlling the pH value of ore pulp to be 1.0-2.5 by using dilute sulfuric acid, controlling the reaction temperature of a leaching system to be 55-80 ℃, and adding Fe2(SO4)3And Fe3(SO4)2The total iron concentration of the initial charge is controlled to be 0.4mol/L, wherein the Fe3+And Fe2+The ratio is equal to 5, the leptospira siderophila is added for leaching, and the bacterial concentration is controlled to be not less than 107The leaching potential is controlled to be 600-790mV relative to a saturated silver/silver chloride electrode, and the stirring speed is 150 rpm. After 2 days, the zinc-containing leachate with the zinc recovery rate of 94.55% is obtained in the embodiment; cu is only dissolved out by 3.10 percent, and the zinc content of the leaching slag (copper concentrate) is only 0.99 percent. Purifying, concentrating, cooling and crystallizing the zinc-containing leachate to obtain a zinc sulfate product; or purifying, extracting and electrodepositing the zinc-containing leachate to obtain a zinc plate; the raffinate generated by the crystallization and the extraction is returned to the mixed pulping after being oxidized by adding a chemical oxidant or microorganisms; smelting, converting and oxidizing the high-grade copper concentrate to obtain metal copper; or roasting, leaching and electrodepositing the high-grade copper concentrate to obtain the metal copper.
Example 8
The copper-zinc mixed ore concentrate obtained in example 1 had a copper grade of 10.71% (recovery rate of 94.19%) and a zinc grade of 13.46% (recovery rate of 92.67%). The copper-zinc bulk concentrate and water are mixed and size-mixed, and are processed by size mixing and reagent removal to reach the concentration of 30 percent of ore pulp, so that the chemical leaching is conveniently carried out. The pH value of the ore pulp is controlled between 0.5 and 2.5 by dilute sulphuric acid, the reaction temperature of a leaching system is controlled to be 75 ℃, the leaching potential is controlled to be 810-1000mV relative to a saturated silver/silver chloride electrode by adding an oxidant hydrogen peroxide, and the stirring speed is 1000 rpm. After 24 hours, the zinc-containing leachate with 95.31% zinc recovery rate is obtained in the embodiment; the Cu is only dissolved out by 2.15 percent, and the leached slag (copper concentrate) contains 13.37 percent of copper and 0.68 percent of zinc. Purifying, concentrating, cooling and crystallizing the zinc-containing leachate to obtain a zinc sulfate product; or purifying, extracting and electrodepositing the zinc-containing leachate to obtain a zinc plate; the raffinate generated by the crystallization and the extraction is returned to the mixed pulping after being oxidized by adding a chemical oxidant or microorganisms; smelting, converting and oxidizing the high-grade copper concentrate to obtain metal copper; or roasting, leaching and electrodepositing the high-grade copper concentrate to obtain the metal copper.
Example 9
the copper-zinc mixed ore concentrate obtained in example 1 had a copper grade of 10.71% (recovery rate of 94.19%) and a zinc grade of 13.46% (recovery rate of 92.67%). The copper-zinc bulk concentrate and water are mixed and size-mixed, and are processed by size mixing and reagent removal to reach the concentration of 30 percent of ore pulp, so that the chemical leaching is conveniently carried out. The pH value of the ore pulp is controlled between 0.5 and 2.5 by using dilute sulfuric acid, the reaction temperature of a leaching system is controlled to be 75 ℃, the leaching potential is controlled to be 810-1000mV relative to a saturated silver/silver chloride electrode by regulating and controlling the concentration of dissolved oxygen, and the stirring speed is 1000 rpm. After 48 hours, the zinc-containing leachate with 96.19 percent of zinc recovery rate is obtained in the embodiment; only 1.01 percent of Cu is dissolved out, and leached slag (copper concentrate) contains 13.77 percent of copper and only 0.66 percent of zinc. Purifying, concentrating, cooling and crystallizing the zinc-containing leachate to obtain a zinc sulfate product; or purifying, extracting and electrodepositing the zinc-containing leachate to obtain a zinc plate; the raffinate generated by the crystallization and the extraction is returned to the mixed pulping after being oxidized by adding a chemical oxidant or microorganisms; smelting, converting and oxidizing the high-grade copper concentrate to obtain metal copper; or roasting, leaching and electrodepositing the high-grade copper concentrate to obtain the metal copper.
The invention can realize the high-efficiency utilization of the copper-zinc mixed ore in the fields of mineral processing and (biological) wet metallurgy. The process provided by the invention can avoid the copper-zinc separation by utilizing a flotation process, and can finally realize the copper-zinc separation by using a more energy-saving and efficient (biological) hydrometallurgical process and selective leaching of zinc. The problem that the traditional process is difficult to realize the separation of copper and zinc is solved, the quality of copper concentrate is improved, and the high-efficiency recycling of zinc is realized. The process flow is simple and is beneficial to realizing industrial application.
while there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be understood by those skilled in the art that the invention is not limited by the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (10)
1. A dressing and smelting combined process for efficiently utilizing copper-zinc ores comprises the following steps:
(1) crushing and screening the copper-zinc mixed ore to obtain fine ore with qualified granularity;
(2) Grinding and grading the fine ore to obtain ore pulp meeting the requirement of flotation granularity;
(3) carrying out copper-zinc mixed flotation on the ore pulp to obtain copper-zinc mixed concentrate;
(4) Leaching zinc from the copper-zinc mixed ore concentrate by adopting biological or chemical selectivity, and performing solid-liquid separation to obtain low-zinc high-grade copper concentrate and a zinc-containing leachate;
(5) Purifying, concentrating, cooling and crystallizing the zinc-containing leachate to obtain a zinc sulfate product; or purifying, extracting and electrodepositing the zinc-containing leachate to obtain a zinc plate;
(6) Returning residual liquid generated by the crystallization and the extraction in the step (5) to the step (4) for mixed pulping after adding a chemical oxidant or oxidizing by microorganisms;
(7) smelting, converting and oxidizing the high-grade copper concentrate to obtain metal copper; or roasting, leaching and electrodepositing the high-grade copper concentrate to obtain the metal copper.
2. The process according to claim 1, wherein in the step (1), the copper-zinc mixed ore mainly contains copper sulfide minerals and zinc sulfide minerals, the copper grade is more than or equal to 0.4%, and the zinc grade is more than or equal to 2%.
3. The process according to claim 1, wherein the qualified fine ore has a grain size of 13mm or less in step (1).
4. The process of claim 1, wherein in step (2), the feed size for flotation is-200 mesh ≥ 65%.
5. The process of claim 1, wherein in step (3), the flotation is copper-zinc bulk flotation.
6. The process of claim 1, wherein in the step (4), the copper-zinc mixed ore concentrate is subjected to size mixing and reagent removal treatment by using bioselective leaching to obtain mixed ore concentrate pulp; then adjusting the pH value of the ore pulp by using dilute sulfuric acid, adding ore leaching bacteria, and stirring and leaching.
7. The process of claim 6 wherein the concentration of the mixed concentrate pulp is 1-30%, the pulp pH is adjusted to 1.0-2.5 with dilute sulfuric acid, the total iron concentration is controlled to 0.1-1.0mol/L, and the bacteria concentration is controlled to not less than 107Stirring at 15-200rpm, controlling the temperature of the leaching system at 30-80 deg.C, controlling the leaching potential at 600-790mV relative to the saturated silver/silver chloride electrode, and leaching for 1-5 days.
8. The process according to claim 6, wherein the leaching bacteria is one or more of Acidithiobacillus ferrooxidans, Leptospira ferrooxidans and Leptospira ferrooxidans.
9. the process of claim 1, wherein in the step (4), chemoselective leaching is selected, and the copper-zinc mixed ore concentrate is subjected to size mixing and reagent removal treatment to obtain mixed ore concentrate pulp; then dilute sulphuric acid is used for adjusting the pH value of the ore pulp, an oxidant is added, and then stirring leaching is carried out.
10. The process of claim 9, the oxidant being Fe3+Oxygen and halogen element simple substance, nitrate, persulfate, permanganate, oxyacid of chlorine and salt thereof, and peroxide; the concentration of the mixed concentrate ore pulp is 1-30%, the pH of the ore pulp is adjusted to be 0.5-2.5, the leaching potential is controlled to be 810-1000mV relative to a saturated silver/silver chloride electrode, the stirring speed is 15-1000rpm, the temperature of a leaching system is controlled to be 30-100 ℃, and the leaching time is 1-48 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112176198A (en) * | 2020-09-07 | 2021-01-05 | 中南大学 | Selective leaching agent and deep separation method of complex copper-zinc mineral resources |
| CN113798049A (en) * | 2021-07-27 | 2021-12-17 | 烟台市金奥环保科技有限公司 | Comprehensive recovery method of gold-containing and antimony-containing cyanidation tailings |
| CN115074527A (en) * | 2022-05-27 | 2022-09-20 | 中国恩菲工程技术有限公司 | Method for treating copper-zinc mixed ore |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112176198A (en) * | 2020-09-07 | 2021-01-05 | 中南大学 | Selective leaching agent and deep separation method of complex copper-zinc mineral resources |
| CN113798049A (en) * | 2021-07-27 | 2021-12-17 | 烟台市金奥环保科技有限公司 | Comprehensive recovery method of gold-containing and antimony-containing cyanidation tailings |
| CN115074527A (en) * | 2022-05-27 | 2022-09-20 | 中国恩菲工程技术有限公司 | Method for treating copper-zinc mixed ore |
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