CN109055717B - Method for regulating and controlling high-iron sphalerite oxidation dissolution by using bornite - Google Patents

Method for regulating and controlling high-iron sphalerite oxidation dissolution by using bornite Download PDF

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CN109055717B
CN109055717B CN201811186516.4A CN201811186516A CN109055717B CN 109055717 B CN109055717 B CN 109055717B CN 201811186516 A CN201811186516 A CN 201811186516A CN 109055717 B CN109055717 B CN 109055717B
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bornite
iron
iron sphalerite
sphalerite
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CN109055717A (en
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赵红波
吕鑫
张艳军
张伊升
孟晓宇
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Central South University
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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
    • C22B1/00—Preliminary treatment of ores or scrap
    • 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
    • C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
    • 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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Abstract

The invention provides a method for regulating and controlling the oxidation and dissolution of high-iron sphalerite by utilizing bornite, which is characterized in that the high-iron sphalerite is ground, and under a chemical system, the ground bornite is added and the proper proportion and the chemical conditions of a solution are controlled; in a biological system, mineral leaching microorganisms are cultured, domesticated and inoculated, and proper mineral proportion and solution chemical conditions are controlled; can selectively strengthen or inhibit the oxidative dissolution of the high-iron sphalerite. The invention has the advantages that in the (biological) hydrometallurgy system, when the high-iron sphalerite exists as a target mineral, the leaching of the high-iron sphalerite can be enhanced or inhibited selectively by regulation and control, so that the synergistic or step-by-step leaching of multi-metal complex minerals is realized; when the high-iron sphalerite is used as a non-target mineral or a gangue mineral, the leaching of elements such as zinc, iron and the like in the high-iron sphalerite can be inhibited through regulation and control, so that the trouble of metal ions generated by leaching of the high-iron sphalerite on the recovery of other valuable metals is avoided, and the recovery and utilization of the bornite can be enhanced.

Description

Method for regulating and controlling high-iron sphalerite oxidation dissolution by using bornite
Technical Field
The invention relates to the technical field of biological hydrometallurgy and mineral processing, in particular to a method for regulating and controlling the oxidation and dissolution of high-iron sphalerite by utilizing bornite.
Background
Zinc is a very important metal resource, and zinc ore is divided into zinc sulfide ore and zinc oxide ore according to the different minerals contained in the zinc ore, and the zinc sulfide ore is mainly divided into sphalerite and sphalerite, wherein the sphalerite accounts for a considerable proportion. The high-iron sphalerite with high iron content in the sphalerite is a zinc-containing resource rich in reserves on the earth and is the most important mineral raw material for extracting zinc.
Zinc can be produced by two basic ways, and the production ways are divided into pyrometallurgy and hydrometallurgy. The main processes of traditional pyrometallurgy of zinc are roasting, reductive distillation and rectification. The problems of high energy consumption, low efficiency, large pollution and the like are gradually replaced by hydrometallurgy. Smelting tool by wet smelting technique compared with fire methodHas the advantages of environment and economy, low cost and strong applicability, and is regarded as a technology with great application prospect for treating metal minerals. The zinc hydrometallurgy mainly comprises four main steps of roasting, leaching, electrolysis and electrodeposition, namely ZnO and SO which are easy to dissolve are generated in the roasting process of zinc sulfide ores2After leaching and purification treatment, electrolysis is carried out, thus obtaining the required high-grade zinc product. When zinc ore is treated by a conventional wet zinc smelting method, a large amount of zinc ferrite which is difficult to dissolve is generated in the roasting process, and the zinc is difficult to leach during leaching, so that the recovery rate of zinc is low. In addition, the conventional wet zinc smelting process has the defects of high energy consumption, environmental pollution, complicated working procedures and the like.
The zinc plants of Terel, Canada, Timins, Del, Germany, and Hadamson Bay mining, Canada, use oxygen pressure leaching. The process comprises the steps of material preparation, pressure leaching, flash evaporation, cooling and sulfur recovery. In the roasting-combined operation, one-section oxygen pressure leaching is adopted; when the zinc concentrate is completely treated, two-stage oxygen pressure leaching is adopted. Compared with the traditional metallurgical process, the oxygen pressure leaching process has wide adaptability and high zinc recovery rate. But the operation conditions are quite harsh, and higher temperature and pressure are required, and the requirements on equipment are higher.
Zinc concentrate developed by the finnoclada plant, norwegian oda, korea temperate plant was leached with sulphuric acid at atmospheric pressure. The technology takes iron as a catalyst of sulfide, sulfur in the sulfide is reduced into elemental sulfur in the reaction, the leaching rate of zinc is up to 90%, the slag yield is low, and the atmospheric pollution is almost 0. And the leaching residue is also treated by a hot acid-jarosite process or a goethite method. The process has low requirements on equipment and low cost, but can not realize the selective leaching of iron and zinc, and further removes iron in the later period. In addition, the process has high temperature requirements and the leaching efficiency is low.
The traditional acid method zinc smelting process has the defects of high acid consumption, difficult impurity separation, complex flow, difficult process control and the like. The equipment for smelting zinc by alkaline leaching-electrolysis method is not easy to corrode, the solid-liquid separation is simple and convenient, the leaching solution is easy to purify, and the leaching rate of iron is very low. However, the zinc-containing waste slag often contains impurities such as tungsten, tin, molybdenum, chlorine and the like, and the crystallization state, the current efficiency and the zinc quality of zinc precipitated in the electrodeposition process are seriously influenced.
The microbial leaching technology has low cost, small investment, simple flow and little environmental pollution, and the high-iron sphalerite treated by the biological metallurgy technology can realize the high-efficiency separation of metals such as zinc, iron and the like and simultaneously avoid the generated SO2Thereby polluting the environment. However, microbial leaching biotechnology has problems such as a long process cycle, a low leaching rate, a low dissolution rate of zinc, and the like, which limit its large-scale application.
In the actual smelting process, the high-iron sphalerite is often associated with other gangue minerals, so that the leaching of the high-iron sphalerite needs to be regulated and controlled: when the high-iron sphalerite exists as a target mineral, the leaching of valuable metal Zn needs to be enhanced; when the high-iron sphalerite exists as a non-target mineral or a gangue mineral, the dissolution of the high-iron sphalerite is often required to be inhibited, so that the trouble of impurity ions on the recovery of other valuable metals is avoided. In addition, the comprehensive utilization of complex polymetallic ores usually needs to adopt step leaching to selectively regulate and control the leaching of the high-iron sphalerite.
Meanwhile, mining produces a large amount of acid mine wastewater (AMD) containing heavy metal ions, which causes serious pollution to the environment. The zinc ions, iron ions and sulfuric acid generated by the oxidation and dissolution of the high-iron sphalerite are one of the important sources of acid mine wastewater, and the wastewater rich in the substances erodes other minerals in the flowing process, so that the environmental pollution is great.
Therefore, how to regulate and control the oxidative dissolution of the high-iron sphalerite by using the bornite in the hydrometallurgy field and AMD becomes a current technical problem.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for regulating and controlling the oxidative dissolution of the sphalerite, which has the advantages of low price, high efficiency, simplicity and easy operation.
The invention provides an in-situ regulation method, which can selectively strengthen the leaching of zinc element in the high-iron sphalerite or effectively inhibit the dissolution of the zinc element in the high-iron sphalerite by regulating the proportion range of the existing bornite and the high-iron sphalerite and the chemical conditions of related solutions.
The invention adopts the following technical scheme for solving the technical problems: a method for regulating and controlling the oxidation and dissolution of high-iron sphalerite by utilizing bornite comprises the following steps:
(1) respectively crushing and grinding the high-iron sphalerite and the bornite to obtain high-iron sphalerite powder and bornite powder;
(2) mixing the high-iron sphalerite powder and the bornite powder, and putting into a sterile 9K culture medium;
(3) and adjusting the temperature, the pH value and the oxidation-reduction potential of the sterile 9K culture medium, and then stirring and dissolving to obtain a zinc-containing solution.
Preferably, in the step (1), the iron content in the high-iron sphalerite is 12-18%.
Preferably, in the step (1), the high-iron sphalerite and the bornite raw ore are ground to-0.074 mm, which accounts for more than 80% by adopting dry grinding.
Preferably, in the step (2), when the dissolution of the high-iron sphalerite is promoted, the mixing ratio of the high-iron sphalerite to the bornite is 5000: 1-1000: 1; when the dissolution of the high-iron sphalerite is inhibited, the mixing ratio of the high-iron sphalerite to the bornite is 5: 1-1: 5.
preferably, in step (2), the formulation of the sterile 9K medium is: (NH)4)2SO43.0g/L, KCl is 0.1g/L, K2HPO4Is 0.5g/L, MgSO40.5g/L, Ca (NO)3)2Is 0.01 g/L.
Further, in the step (3), the temperature is adjusted to be between 20 and 50 ℃, and 0.1 to 0.5mol/L H is used2SO4Adjusting the pH value to 1.5-2.0, stirring at 150-200 rpm, and maintaining the oxidation-reduction potential at 350-600 mV vs.
More preferably, in the step (3), 1-5% of acidithiobacillus ferrooxidans is inoculated to the sterile 9K culture medium; the temperature is adjusted to 20 ℃ to 50 ℃ and 0.1 mol/L H mol/0.5 mol/78 mol2SO4Adjusting the pH value to 1.0-3.0, stirring at 150-200 rpm, maintaining the oxidation-reduction potential at 200-500mV vs.Ag/AgCl。
Further, the acidophilic thiobacillus ferrooxidans is domesticated and cultured in a 9K culture medium containing high-iron sphalerite and bornite.
Further, culturing the bacteria-containing culture medium at 20-50 ℃ and stirring speed of 100-500 rpm.
Further, the number of viable cells was measured by a hemacytometer at a regular time every day when the bacterial concentration reached 108～109And (4) finishing acclimatization when the strain/ml is reached, removing filter residues, and centrifuging to obtain the acclimatized and cultured acidithiobacillus ferrooxidans.
Compared with the prior art, the invention has the following advantages: aiming at complex multi-metal minerals, the leaching of the high-iron sphalerite can be enhanced and the dissolution of zinc elements and iron elements in the high-iron sphalerite can be selectively inhibited by regulating the proportion of the bornite to the high-iron sphalerite and the chemical conditions of the solution: when the high-iron sphalerite exists as a target mineral, the leaching of valuable metal zinc can be enhanced; when the high-iron sphalerite exists as a non-target mineral or a gangue mineral, the dissolution of the high-iron sphalerite can be inhibited, and the trouble brought by impurity ions to the recovery of other valuable metals is avoided. In addition, in the complex multi-metal mineral step-by-step (biological) leaching method, the leaching sequence of the high-iron sphalerite can be selectively controlled, and the effect of leaching different minerals step by step is achieved; the leaching effect can be further improved in a biological system, the leaching rate of zinc can reach more than 95%, and the method is suitable for high-iron sphalerite with different iron contents. In the aspect of preventing and treating acid mine wastewater (AMD), the invention can effectively inhibit the dissolution of zinc and iron elements in the high-iron sphalerite by regulating and controlling the proportion of the porphyrite to the high-iron sphalerite, the chemical conditions of the solution and other parameters, control the generation of the acid mine wastewater from the source, reduce heavy metal ions in the wastewater, reduce the wastewater treatment cost and improve the economic benefit. The method is simple, low in cost and has a prospect of large-scale application.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific 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.
And (3) preparing a sterile 9K culture medium, wherein the formula of the sterile 9K culture medium is as follows: (NH)4)2SO43.0g/L, KCl is 0.1g/L, K2HPO4Is 0.5g/L, MgSO40.5g/L, Ca (NO)3)2Is 0.01 g/L.
Domestication and culture of acidophilic thiobacillus ferrooxidans: acclimatizing and culturing acidophilic thiobacillus ferrooxidans in a 9K culture medium containing high-iron sphalerite and bornite, placing the culture medium containing bacteria into a shake flask for culture, wherein the culture temperature is 20-50 ℃, the rotation speed of a shaking table is 100 plus materials and 500rpm, counting the number of living cells by a blood counting plate method every day when in culture, and when the concentration of bacteria can reach 108～109And (4) finishing acclimatization when the strain/ml is reached, removing filter residues, and centrifuging to obtain the acclimatized and cultured acidithiobacillus ferrooxidans.
In the embodiment, the high-iron sphalerite with the iron content of 12-18% is adopted.
Examples 1-6 are directed to the controlled and enhanced chemical dissolution of kesterite and the biological dissolution of Acidithiobacillus ferrooxidans.
Examples 7-12 are directed to the control of inhibition of chemical dissolution of kesterite and biological dissolution of thiobacillus ferrooxidans containing acidophilic acid.
Example 1:
respectively crushing the high-iron sphalerite and the bornite, and then carrying out dry grinding and ore grinding to grind the high-iron sphalerite and the bornite raw ore to the grain size of-0.074 mm, wherein the grain size is more than 80%, so as to obtain high-iron sphalerite powder and the bornite powder. The high-iron sphalerite powder and the bornite powder are prepared according to the mixture ratio of 1200: 1 mixing, putting into a sterile 9K culture medium, adjusting the dissolution temperature to 30 ℃, stirring at 150-200 rpm, and using 0.1-0.5mol/L H2SO4Controlling the pH value to be 1.5-2.0, maintaining the oxidation-reduction potential to be 350-600 mV vs. Ag/AgCl in the reaction process, wherein the dissolving time is 10 days, and the dissolution rate of zinc is 15.33%. When the high-iron sphalerite is dissolved alone, the zinc dissolution rate is 7.69% on the 10 th day. The ratio of the high-iron sphalerite to the bornite is 1200: 1 ratio of zinc dissolution to zinc dissolution aloneThe high-iron sphalerite decomposition is relatively improved by 99.3 percent. The embodiment is aseptic chemical dissolution, and can remarkably enhance and promote the dissolution of the high-iron sphalerite.
Example 2:
respectively crushing the high-iron sphalerite and the bornite, and then carrying out dry grinding and ore grinding to grind the high-iron sphalerite and the bornite raw ore to the grain size of-0.074 mm, wherein the grain size is more than 80%, so as to obtain high-iron sphalerite powder and the bornite powder. The high-iron sphalerite powder and the bornite powder are mixed according to the mixture ratio of 2500: 1, mixing, putting into a sterile 9K culture medium, adjusting the dissolution temperature to 20 ℃, stirring at the speed of 150-200 rpm, and using 0.1-0.5mol/L H2SO4Controlling the pH value to be 1.5-2.0, maintaining the oxidation-reduction potential to be 350-600 mV vs. Ag/AgCl in the reaction process, wherein the dissolving time is 10 days, and the dissolution rate of zinc is 15.51%. When the high-iron sphalerite is dissolved alone, the zinc dissolution rate is 7.69% on the 10 th day. The ratio of the high-iron sphalerite to the bornite is 2500: the zinc dissolution rate of 1 is relatively improved by 101.7 percent compared with the method for singly dissolving the high-iron sphalerite. The embodiment is aseptic chemical dissolution, and can remarkably enhance and promote the dissolution of the high-iron sphalerite.
Example 3:
respectively crushing the high-iron sphalerite and the bornite, and then carrying out dry grinding and ore grinding to grind the high-iron sphalerite and the bornite raw ore to the grain size of-0.074 mm, wherein the grain size is more than 80%, so as to obtain high-iron sphalerite powder and the bornite powder. The high-iron sphalerite powder and the bornite powder are mixed according to the proportion of 5000: 1, mixing, putting into a sterile 9K culture medium, adjusting the dissolution temperature to 50 ℃, stirring at 150-200 rpm, and adding 0.1-0.5mol/L H2SO4Controlling the pH value to be 1.5-2.0, maintaining the oxidation-reduction potential to be 350-600 mV vs. Ag/AgCl in the reaction process, wherein the dissolving time is 10 days, and the dissolution rate of zinc is 16.58%. When the high-iron sphalerite is dissolved alone, the zinc dissolution rate is 7.69% on the 10 th day. The ratio of the high-iron sphalerite to the bornite is 5000: the zinc dissolution rate of 1 is relatively improved by 115.6 percent compared with the method for singly dissolving the high-iron sphalerite. The embodiment is aseptic chemical dissolution, and can remarkably enhance and promote the dissolution of the high-iron sphalerite.
Example 4:
respectively crushing the high-iron sphalerite and the bornite, and then grinding the high-iron sphalerite and the bornite by dry grindingGrinding the raw ore of the marmatite and the bornite until the grain size is-0.074 mm and accounts for more than 80 percent to obtain the high-iron marmatite powder and the bornite powder. The high-iron sphalerite powder and the bornite powder are prepared according to the mixture ratio of 1200: 1, mixing, putting into a sterile 9K culture medium, inoculating 1-5% of acidithiobacillus ferrooxidans into the sterile 9K culture medium, adjusting the dissolving temperature to 30 ℃, and using 0.1-0.5mol/L H2SO4Adjusting the pH value to 1.0-3.0, stirring at 150-200 rpm, maintaining the oxidation-reduction potential at 200-500 mV vs. On the 10 th day, the zinc dissolution rate was 98.9%. When the high-iron sphalerite is dissolved separately, the dissolution rate of zinc is 92.8% on the 10 th day of dissolution. The ratio of the high-iron sphalerite to the bornite is 1200: the zinc dissolution rate of 1 is improved by 6.10 percent compared with the method for singly dissolving the high-iron sphalerite. The embodiment is the biological dissolution with bacteria, and can obviously enhance the dissolution of the high-iron sphalerite.
Example 5:
respectively crushing the high-iron sphalerite and the bornite, and then carrying out dry grinding and ore grinding to grind the high-iron sphalerite and the bornite raw ore to the grain size of-0.074 mm, wherein the grain size is more than 80%, so as to obtain high-iron sphalerite powder and the bornite powder. The high-iron sphalerite powder and the bornite powder are mixed according to the ratio of 1700: 1, mixing, putting into a sterile 9K culture medium, inoculating 1-5% of acidithiobacillus ferrooxidans into the sterile 9K culture medium, adjusting the dissolving temperature to 20 ℃, and using 0.1-0.5mol/L H2SO4Adjusting the pH value to 1.0-3.0, stirring at 150-200 rpm, maintaining the oxidation-reduction potential at 200-500 mV vs. On the 10 th day, the zinc dissolution rate was 98.8%. When the high-iron sphalerite is dissolved separately, the dissolution rate of zinc is 92.8% on the 10 th day of dissolution. The ratio of the high-iron sphalerite to the bornite is 1700: the zinc dissolution rate of 1 is improved by 6.00 percent compared with the method for singly dissolving the high-iron sphalerite. The embodiment is the biological dissolution with bacteria, and can obviously enhance the dissolution of the high-iron sphalerite.
Example 6:
respectively crushing the high-iron sphalerite and the bornite, and then carrying out dry grinding and ore grinding to grind the high-iron sphalerite and the bornite raw ore to the grain size of-0.074 mm, wherein the grain size is more than 80%, so as to obtain high-iron sphalerite powder and the bornite powder. The high-iron sphalerite powder and the bornite powder are mixed according to the mixture ratio of 2500: 1 mixing, and putting into a sterile environmentInoculating 1-5% acidithiobacillus ferrooxidans into 9K culture medium, regulating dissolving temperature to 50 deg.C, and using 0.1-0.5mol/L H2SO4Adjusting the pH value to 1.0-3.0, stirring at 150-200 rpm, maintaining the oxidation-reduction potential at 200-500 mV vs. On the 10 th day, the zinc dissolution rate was 97.8%. When the high-iron sphalerite is dissolved separately, the dissolution rate of zinc is 92.8% on the 10 th day of dissolution. The ratio of the high-iron sphalerite to the bornite is 2500: the zinc dissolution rate of 1 is improved by 5.00 percent compared with the method for singly dissolving the high-iron sphalerite. The embodiment is the biological dissolution with bacteria, and can obviously enhance the dissolution of the high-iron sphalerite.
Example 7:
respectively crushing the high-iron sphalerite and the bornite, and then carrying out dry grinding and ore grinding to grind the high-iron sphalerite and the bornite raw ore to the grain size of-0.074 mm, wherein the grain size is more than 80%, so as to obtain high-iron sphalerite powder and the bornite powder. The high-iron sphalerite powder and the bornite powder are mixed according to the proportion of 3: 1 mixing, putting into a sterile 9K culture medium, adjusting the dissolution temperature to 30 ℃, stirring at 150-200 rpm, and using 0.1-0.5mol/L H2SO4Controlling the pH value to be 1.5-2.0, maintaining the oxidation-reduction potential to be 350-600 mV vs. Ag/AgCl in the reaction process, wherein the dissolving time is 14 days, and the dissolution rate of zinc is 3.10%. When the high-iron sphalerite is dissolved alone, the zinc dissolution rate is 11.0% on day 14. The ratio of the high-iron sphalerite to the bornite is 3: the zinc dissolution rate of 1 is relatively reduced by 71.8 percent compared with that of the high-iron sphalerite dissolved alone. The embodiment is aseptic chemical dissolution, and can obviously inhibit the dissolution of the high-iron sphalerite.
Example 8:
respectively crushing the high-iron sphalerite and the bornite, and then carrying out dry grinding and ore grinding to grind the high-iron sphalerite and the bornite raw ore to the grain size of-0.074 mm, wherein the grain size is more than 80%, so as to obtain high-iron sphalerite powder and the bornite powder. Mixing the high-iron sphalerite powder and the bornite powder according to the proportion of 1: 1, mixing, putting into a sterile 9K culture medium, adjusting the dissolution temperature to 20 ℃, stirring at the speed of 150-200 rpm, and using 0.1-0.5mol/L H2SO4Controlling the pH value to be 1.5-2.0, maintaining the oxidation-reduction potential to be 350-600 mV vs. Ag/AgCl in the reaction process, wherein the dissolving time is 14 days, and the dissolution rate of zinc is 2.38%. When an orderThe high-iron sphalerite is dissolved separately, and the dissolution rate of zinc is 11.0% on day 14. The ratio of the high-iron sphalerite to the bornite is 1: the zinc dissolution rate of 1 is reduced by 78.4 percent compared with that of the high-iron sphalerite dissolved alone. The embodiment is aseptic chemical dissolution, and can obviously inhibit the dissolution of the high-iron sphalerite.
Example 9:
respectively crushing the high-iron sphalerite and the bornite, and then carrying out dry grinding and ore grinding to grind the high-iron sphalerite and the bornite raw ore to the grain size of-0.074 mm, wherein the grain size is more than 80%, so as to obtain high-iron sphalerite powder and the bornite powder. Mixing the high-iron sphalerite powder and the bornite powder according to the proportion of 1: 3 mixing, putting into a sterile 9K culture medium, adjusting the dissolution temperature to 50 ℃, stirring at the speed of 150-200 rpm, and using 0.1-0.5mol/L H2SO4Controlling the pH value to be 1.5-2.0, maintaining the oxidation-reduction potential to be 350-600 mV vs. Ag/AgCl in the reaction process, wherein the dissolving time is 14 days, and the dissolution rate of zinc is 2.32%. When the high-iron sphalerite is dissolved alone, the zinc dissolution rate is 11.0% on day 14. The ratio of the high-iron sphalerite to the bornite is 1: the zinc dissolution rate of 3 is reduced by 78.9 percent compared with that of the zinc blende which is singly dissolved. The embodiment is aseptic chemical dissolution, and can obviously inhibit the dissolution of the high-iron sphalerite.
Example 10:
respectively crushing the high-iron sphalerite and the bornite, and then carrying out dry grinding and ore grinding to grind the high-iron sphalerite and the bornite raw ore to the grain size of-0.074 mm, wherein the grain size is more than 80%, so as to obtain high-iron sphalerite powder and the bornite powder. The high-iron sphalerite powder and the bornite powder are mixed according to the proportion of 3: 1, mixing, putting into a sterile 9K culture medium, inoculating 1-5% of acidithiobacillus ferrooxidans into the sterile 9K culture medium, adjusting the dissolving temperature to 30 ℃, and using 0.1-0.5mol/L H2SO4Adjusting the pH value to 1.0-3.0, stirring at 150-200 rpm, maintaining the oxidation-reduction potential at 200-500 mV vs. On the 8 th day, the zinc dissolution rate is 80.5%. When the high-iron sphalerite is dissolved separately and the dissolution day 8 is up, the zinc dissolution rate is 89.8%. The ratio of the high-iron sphalerite to the bornite is 3: the zinc dissolution rate of 1 is reduced by 9.8 percent compared with that of the zinc blende with high iron which is dissolved separately. The embodiment is the biological dissolution with bacteria, and can obviously inhibit the dissolution of the high-iron sphalerite.
Example 11:
respectively crushing the high-iron sphalerite and the bornite, and then carrying out dry grinding and ore grinding to grind the high-iron sphalerite and the bornite raw ore to the grain size of-0.074 mm, wherein the grain size is more than 80%, so as to obtain high-iron sphalerite powder and the bornite powder. Mixing the high-iron sphalerite powder and the bornite powder according to the proportion of 1: 1, mixing, putting into a sterile 9K culture medium, inoculating 1-5% of acidithiobacillus ferrooxidans into the sterile 9K culture medium, adjusting the dissolving temperature to 20 ℃, and using 0.1-0.5mol/L H2SO4Adjusting the pH value to 1.0-3.0, stirring at 150-200 rpm, maintaining the oxidation-reduction potential at 200-500 mV vs. On the 8 th day, the zinc dissolution rate is 84.7%. When the high-iron sphalerite is dissolved separately and the dissolution day 8 is up, the zinc dissolution rate is 89.8%. The ratio of the high-iron sphalerite to the bornite is 1: the zinc dissolution rate of 1 is reduced by 5.10 percent compared with the zinc blende which is singly dissolved. The embodiment is the biological dissolution with bacteria, and can obviously inhibit the dissolution of the high-iron sphalerite.
Example 12:
respectively crushing the high-iron sphalerite and the bornite, and then carrying out dry grinding and ore grinding to grind the high-iron sphalerite and the bornite raw ore to the grain size of-0.074 mm, wherein the grain size is more than 80%, so as to obtain high-iron sphalerite powder and the bornite powder. Mixing the high-iron sphalerite powder and the bornite powder according to the proportion of 1: 3 mixing, putting into a sterile 9K culture medium, inoculating 1-5% of acidithiobacillus ferrooxidans into the sterile 9K culture medium, adjusting the dissolving temperature to 50 ℃, and using 0.1-0.5mol/L H2SO4Adjusting the pH value to 1.0-3.0, stirring at 150-200 rpm, maintaining the oxidation-reduction potential at 200-500 mV vs. On the 8 th day, the zinc dissolution rate is 83.0%. When the high-iron sphalerite is dissolved separately and the dissolution day 8 is up, the zinc dissolution rate is 89.8%. The ratio of the high-iron sphalerite to the bornite is 1: 3, the zinc dissolution rate is reduced by 6.80 percent compared with the zinc blende which is singly dissolved. The embodiment is the biological dissolution with bacteria, and can obviously inhibit the dissolution of the high-iron sphalerite.
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 (9)

1. A method for regulating and controlling the oxidation and dissolution of high-iron sphalerite by utilizing bornite comprises the following steps:
(1) respectively crushing and grinding the high-iron sphalerite and the bornite to obtain high-iron sphalerite powder and bornite powder;
(2) mixing the high-iron sphalerite powder and the bornite powder, and putting into a sterile 9K culture medium;
(3) adjusting the temperature, the pH value and the oxidation-reduction potential of the sterile 9K culture medium, and then stirring and dissolving to obtain a zinc-containing solution; in the step (2), when the dissolution of the high-iron sphalerite is promoted, the mixing ratio of the high-iron sphalerite to the bornite is 5000: 1-1000: 1; when the dissolution of the high-iron sphalerite is inhibited, the mixing ratio of the high-iron sphalerite to the bornite is 5: 1-1: 5.
2. the method according to claim 1, wherein in the step (1), the iron content in the high-iron sphalerite is 12-18%.
3. The method as claimed in claim 1, wherein in step (1), the high-iron sphalerite and the bornite raw ore are stone-ground to-0.074 mm in proportion to 80% or more by dry grinding.
4. The method of claim 1, wherein in step (2), the sterile 9K medium is formulated as: (NH)4)2SO43.0g/L, KCl is 0.1g/L, K2HPO4Is 0.5g/L, MgSO40.5g/L, Ca (NO)3)2Is 0.01 g/L.
5. The method of claim 4, wherein in step (3), the adjusting is performedThe temperature is 20-50 ℃, and the content of the active carbon is 0.1-0.5 mol/LH2SO4Adjusting the pH value to 1.5-2.0, stirring at 150-200 rpm, and maintaining the oxidation-reduction potential at 350-600 mVvs.
6. The method according to claim 4, wherein in the step (3), 1-5% of Acidithiobacillus ferrooxidans is inoculated into the sterile 9K culture medium; the temperature is adjusted to 20 ℃ to 50 ℃ and 0.1 mol/L H mol/0.5 mol/78 mol2SO4Adjusting the pH value to 1.0-3.0, stirring at 150-200 rpm, and maintaining the oxidation-reduction potential at 200-500 mV vs.
7. The method of claim 6, wherein said Acidithiobacillus ferrooxidans is acclimatized in 9K medium containing high-iron sphalerite and bornite.
8. The method as claimed in claim 7, wherein the culture medium containing the bacteria is cultured under stirring at 20-50 ℃ and at a stirring speed of 100-500 rpm.
9. The method of claim 8, wherein the viable cell count is measured by a hemocytometer at a time of day when the bacteria concentration reaches 108～109And (4) finishing acclimatization when the strain/ml is reached, removing filter residues, and centrifuging to obtain the acclimatized and cultured acidithiobacillus ferrooxidans.
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