CN115161476B - Method for reducing concentration of ferric acid in secondary copper sulfide ore biological heap leaching system - Google Patents
Method for reducing concentration of ferric acid in secondary copper sulfide ore biological heap leaching system Download PDFInfo
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Abstract
The invention relates to a method for utilizing valuable elements in a secondary copper sulfide ore biological heap leaching system, belonging to the field of nonferrous metal smelting. The iron concentration in the heap leaching copper qualified liquid or raffinate is reduced by using a hematite iron removal process, sulfuric acid in the solution is transferred from a water phase to an organic phase by using an organic extractant which can selectively extract sulfuric acid without extracting metal ions such as copper, ferrous iron and the like, dilute sulfuric acid with higher purity is obtained after water back extraction of the loaded organic phase, and the solution with reduced iron acid concentration enters a copper extraction-electrodeposition system to produce cathode copper or returns to the heap leaching system.
Description
Technical Field
The invention belongs to the field of nonferrous metal smelting, and particularly relates to a method for utilizing valuable elements in a secondary copper sulfide ore biological heap leaching system.
Background
The biological heap leaching-extraction-electrodeposition process is used as a process for treating low-grade ore, has the advantages of high resource utilization efficiency, short process flow, low production cost, small pollution and the like, is more and more valued by people, is particularly widely applied to treating low-grade secondary copper sulfide ores, and is adopted in nearly 20 secondary copper sulfide ores mines worldwide at present.
Pyrite is often associated in the secondary copper sulphide ore, and in the biological heap leaching process of the secondary copper sulphide ore, the pyrite generates ferric iron and sulfuric acid through oxidation reaction, and the heat released by oxidation and the generated ferric iron promote leaching of the secondary copper sulphide ore. However, if the secondary copper sulphide ore contains more pyrite and less gangue is consumed, the oxidation of pyrite can cause excessive accumulation of ferric acid in the system along with the continuous circulation of the solution in the system, and the factors such as acid return extraction, alum precipitation and acid production can aggravate the situation of excessive acid in the system, thereby bringing adverse effects to the subsequent extraction-electrowinning production. Firstly, if the acid concentration of the qualified liquid entering the extraction is too high, the extraction efficiency is reduced, the copper transfer quantity is reduced, and finally the cathode copper yield is limited; secondly, the iron concentration of the qualified liquid is too high, so that the iron content in the electro-deposition liquid is too high, the current efficiency is seriously affected, and the production cost is too high. The heap leaching system chemically reacts as follows:
(1) Chalcocite leaching-copper extraction process
Chalcocite oxidation: cu (Cu) 2 S+5O 2 +H 2 SO 4 ＝2CuSO 4 +H 2 O
Leaching chalcocite: cu (Cu) 2 S+2Fe 2 (SO 4 ) 3 ＝2CuSO 4 +4FeSO 4 +S
Extracting and acid returning: cuSO 4 +2HR＝CuR 2 +H 2 SO 4
(2) Pyrite oxidation acid-producing and iron-producing process
Pyrite oxidation: 4FeS 2 +15O 2 +2H 2 O＝2Fe 2 (SO 4 ) 3 +2H 2 SO 4
Fe 3+ Alum formation: 3Fe 3+ +2SO4 2- +7H 2 O＝(H 3 O)Fe 3 (SO 4 ) 2 (OH) 6 ↓+5H +
In practice, the method of neutralizing lime or limestone is generally adopted to reduce the iron acidity in the system after the raffinate is partially opened, but the method has high cost on one hand and the generated neutralization slag has huge influence on the environment on the other hand. In the method for realizing iron balance by utilizing the formation of iron vitriol in the biological metallurgy process (CN 101984095A), a method for controlling the concentration of acid and iron in a heap leaching system is proposed, so that iron is precipitated in a heap, raffinate is neutralized by limestone to neutralize free acid and then returned to a storage yard for spraying, a large amount of neutralized slag can be generated, the defects of occupied space for storage, environmental pollution, copper metal loss entrainment and the like exist, and the iron vitriol covers the surface of the ore to prevent copper minerals from leaching out; the method for regulating acid and iron in a copper sulfide ore biological heap leaching system (CN 107354298B) proposes that limestone with certain granularity and thickness is paved on the upper layer after the leaching of each layer of heap leaching units is completed, and the concentration of the acid and the iron in the heap leaching system is regulated by controlling the thickness of a limestone layer, but the method can only regulate the concentration of the acid and the iron in the system to a certain degree in the initial stage, and the limestone consumption and the passivation of the limestone surface and sulfuric acid can not play a corresponding role any more along with the progress of heap leaching.
Disclosure of Invention
First, the technical problem to be solved
The invention aims to solve the technical problems that: how to provide a method for reducing the concentration of acid iron in a secondary copper sulphide ore biological heap leaching system, which is used for solving the problems of excessive accumulation of acid iron in the secondary copper sulphide ore heap leaching system and excessive acid in the system caused by acid return extraction.
(II) technical scheme
In order to solve the technical problems, the invention provides a method for reducing the concentration of ferric acid in a secondary copper sulfide ore biological heap leaching system, which comprises the following steps:
step 1: introducing sulfur dioxide into qualified liquid or raffinate of the heap leaching system, starting a stirrer to promote the sulfur dioxide to be fully mixed with the solution, and controlling the aeration speed to be 10-100L/L Liquid and its preparation method H, reacting for 2-4 h, and adding the qualified liquid or raffinateFe 3+ Reduction of Fe 2+ ；
Step 2: controlling Fe in qualified liquid or raffinate 2+ The reaction time in the oxidizing hydrolysis process is 1-4h, the reaction temperature is 180-200 ℃, the oxygen partial pressure is 400-500 kPa, and Fe 2+ Generating solid-phase hematite slag after oxidative hydrolysis to realize copper-iron separation, discharging the solid-phase hematite slag out of a heap leaching system, and mainly reacting as follows:
2FeSO 4 +0.5O 2 +2H 2 O＝Fe 2 O 3 ↓+2H 2 SO 4 (1)；
step 3: preparing an extract liquid by tri (2-ethylhexyl) amine, sulfonated kerosene and isomeric tridecanol according to a certain proportion, adopting a three-stage countercurrent extraction procedure and fully stirring and mixing the solution after iron removal in the step 2, so that sulfuric acid in the solution after iron removal is extracted from a water phase to an organic phase, setting three-stage back extraction, selecting water as a back extraction agent, fully stirring and mixing a load organic phase generated by extraction with water, and enabling acid in the load phase to enter the water phase to obtain a dilute acid solution, wherein the reflection equation is as follows;
step 4: and (3) clarifying and separating the solution after the back extraction in the step (3), and then delivering the solution with the reduced concentration of the obtained ferric acid to a copper extraction-electrodeposition system to produce cathode copper or returning the solution to a heap leaching system, wherein the obtained dilute acid solution is discharged from the heap leaching system.
Wherein, the preparation proportion of each reagent in the extract liquid in the step 3 is as follows:
the configuration proportion of the tri (2-ethylhexyl) amine is 40% -50%;
the preparation proportion of the sulfonated kerosene is 10% -20%;
the configuration proportion of the isomerism tridecanol is 35% -40%.
The method comprises the steps of carrying out water back extraction on a loaded organic phase at a given temperature to obtain a recovered product pure dilute sulfuric acid solution, and recycling the regenerated organic phase, wherein the back extraction reaction is the reverse process of reaction formulas (2) and (3) in the step 3.
Wherein, in the step 3, when water is used as a stripping agent, the stripping temperature is 20-30 ℃.
Wherein, the extraction conditions in the extraction mode are that the temperature is 30 ℃, and the ratio of A/O=1:2-1:3 is subjected to 3-level extraction.
Wherein the back extraction condition in the extraction mode is that the temperature is 30 ℃, and the ratio of A/O=2:1-1:1 is subjected to 3-stage back extraction.
The iron removal and extraction method is suitable for the field of hydrometallurgy biological heap leaching or other technical fields requiring adjustment of the iron content of solution acid in a system.
(III) beneficial effects
Compared with the prior art, the invention has the following beneficial effects:
1) The invention reduces the iron concentration of the solution or raffinate of the heap leaching system through the hematite iron removal process, and has high iron removal efficiency without additives.
2) The invention reduces the acidity of the solution of the heap leaching system by a solvent extraction method, is beneficial to producing qualified liquid with low acidity, and ensures the copper transfer quantity in the extraction process.
3) Compared with the traditional neutralization method, the method can effectively avoid the generation and treatment cost of the neutralization slag, and does not introduce other impurity elements.
Drawings
FIG. 1 is a flow chart of the method of the present invention.
Detailed Description
For the purposes of clarity, content, and advantages of the present invention, a detailed description of the embodiments of the present invention will be described in detail below with reference to the drawings and examples.
To solve the above technical problems, this embodiment provides a method for reducing the concentration of ferric acid in a secondary copper sulfide heap bioleaching system, as shown in fig. 1, which includes the following steps:
step 1: sulfur dioxide is introduced into qualified liquid or raffinate of the heap leaching system,starting the stirrer to promote the full mixing of sulfur dioxide and solution, and controlling the aeration speed to be 10-100L/L Liquid and its preparation method H, reacting for 2-4 h, and adding Fe in qualified liquid or raffinate 3+ Reduction of Fe 2+ ；
Step 2: controlling Fe in qualified liquid or raffinate 2+ The reaction time in the oxidizing hydrolysis process is 1-4h, the reaction temperature is 180-200 ℃, the oxygen partial pressure is 400-500 kPa, and Fe 2+ Generating solid-phase hematite slag after oxidative hydrolysis to realize copper-iron separation, discharging the solid-phase hematite slag out of a heap leaching system, and mainly reacting as follows:
2FeSO 4 +0.5O 2 +2H 2 O＝Fe 2 O 3 ↓+2H 2 SO 4 (1)；
step 3: preparing an extract liquid by tri (2-ethylhexyl) amine, sulfonated kerosene and isomeric tridecanol according to a certain proportion, adopting a three-stage countercurrent extraction procedure and fully stirring and mixing the solution after iron removal in the step 2, so that sulfuric acid in the solution after iron removal is extracted from a water phase to an organic phase, setting three-stage back extraction, selecting water as a back extraction agent, fully stirring and mixing a load organic phase generated by extraction with water, and enabling acid in the load phase to enter the water phase to obtain a dilute acid solution, wherein the reflection equation is as follows;
step 4: and (3) clarifying and separating the solution after the back extraction in the step (3), and then delivering the solution with the reduced concentration of the obtained ferric acid to a copper extraction-electrodeposition system to produce cathode copper or returning the solution to a heap leaching system, wherein the obtained dilute acid solution is discharged from the heap leaching system.
Wherein, the preparation proportion of each reagent in the extract liquid in the step 3 is as follows:
the configuration proportion of the tri (2-ethylhexyl) amine is 40% -50%;
the preparation proportion of the sulfonated kerosene is 10% -20%;
the configuration proportion of the isomerism tridecanol is 35% -40%.
The method comprises the steps of carrying out water back extraction on a loaded organic phase at a given temperature to obtain a recovered product pure dilute sulfuric acid solution, and recycling the regenerated organic phase, wherein the back extraction reaction is the reverse process of reaction formulas (2) and (3) in the step 3.
Wherein, in the step 3, when water is used as a stripping agent, the stripping temperature is 20-30 ℃.
Wherein, the extraction conditions in the extraction mode are that the temperature is 30 ℃, and the ratio of A/O=1:2-1:3 is subjected to 3-level extraction.
Wherein the back extraction condition in the extraction mode is that the temperature is 30 ℃, and the ratio of A/O=2:1-1:1 is subjected to 3-stage back extraction.
The iron removal and extraction method is suitable for the field of hydrometallurgy biological heap leaching or other technical fields requiring adjustment of the iron content of solution acid in a system.
Example 1
In order to solve the technical problems, the invention provides a method for utilizing valuable elements in a secondary copper sulphide ore biological heap leaching system, as shown in figure 1, the treated high-acid iron qualified liquid contains 3.7g/l copper, 8.6g/l acid concentration and 14.7g/l iron, and the specific process operation, control conditions and test results are as follows:
(1)Fe 3+ and (3) reduction process control: sulfur dioxide is introduced into the qualified liquid, stirring is started to promote the mixture to be fully mixed with the solution, and the aeration speed is controlled to be 50-80L/(L- Liquid and its preparation method H), reaction time 2.5h.
(2)Fe 2+ And (3) controlling an oxidation hydrolysis process: controlling the reaction temperature to be 180 ℃ and the operating condition of oxygen partial pressure of 400kPa, the reaction time is 4h, fe 2+ Oxidizing and hydrolyzing to obtain solid-phase hematite slag (Fe) 2 O 3 )。
(3) Preparing an extract: the extractant consists of an amine extractant, a diluent and a phase regulator, and the formula is 40% of tri (2-ethylhexyl) amine (TEHA), 20% of sulfonated kerosene and 40% of isomeric tridecanol.
(4) And adopting a countercurrent extraction procedure to fully stir and mix the qualified liquid and the extract liquid. The extraction conditions were 3-stage extraction at 30℃compared with A/O=1:3. The back extraction condition is that water is used as a back extraction agent, the temperature is 30 ℃, and the ratio of A/O=1:1 is subjected to 3-stage back extraction. The stripping temperature was 30 ℃.
(5) Test results: the iron removal rate is 90%, the produced hematite slag contains 59% of iron, less than 0.5% of copper and less than 2% of sulfur, and can be used as raw materials for iron making or cement production after treatment; the total extraction rate of sulfuric acid is more than 90 percent, the total back extraction rate is more than 94 percent, the mass concentration of the outlet aqueous phase acid is about 6g/L, the mass concentration of the product acid is about 7g/L, and the product acid is pure sulfuric acid solution after 3-stage extraction and 3-stage back extraction.
Example 2
Referring to FIG. 1, the high-acid iron qualified liquid treated by the method contains 5.1g/l copper, 13.5g/l acid and 32g/l iron, and the specific process operation, control conditions and test results are as follows:
(1)Fe 3+ and (3) reduction process control: sulfur dioxide is introduced into the qualified liquid, stirring is started to promote the mixture to be fully mixed with the solution, the aeration speed is controlled to be 50-80L/(L-liquid.h), and the reaction time is 3.5h.
(2)Fe 2+ And (3) controlling an oxidation hydrolysis process: controlling the reaction temperature to be 190 ℃ and the operating condition of oxygen partial pressure of 400kPa, the reaction time is 3h, fe 2+ Oxidizing and hydrolyzing to obtain solid-phase hematite slag (Fe) 2 O 3 )。
(3) Preparing an extract: the extractant consists of an amine extractant, a diluent and a phase regulator, and the formula is 45% of tri (2-ethylhexyl) amine (TEHA), 20% of sulfonated kerosene and 35% of isomeric tridecanol.
(4) And adopting a countercurrent extraction procedure to fully stir and mix the qualified liquid and the extract liquid. The extraction conditions were 3-stage extraction at 30℃compared with A/O=1:2. The back extraction condition is that water is used as a back extraction agent, the temperature is 30 ℃, and the ratio of A/O=1:1 is subjected to 3-stage back extraction. The stripping temperature was 30 ℃.
(5) Test results: the iron removal rate is 91%, the produced hematite slag contains 61% of iron, less than 0.5% of copper and less than 2% of sulfur, and the hematite slag can be used as raw materials for iron making or cement production after being treated; the total extraction rate of sulfuric acid is more than 90 percent, the total back extraction rate is more than 95 percent, the mass concentration of the outlet aqueous phase acid is about 8g/L, the mass concentration of the product acid is about 12g/L, and the product acid is pure sulfuric acid solution after 3-stage extraction and 3-stage back extraction.
Example 3
Referring to FIG. 1, the high-acid iron qualified liquid treated by the method contains 7.2g/l copper, 23g/l acid concentration and 49g/l iron, and the specific process operation, control conditions and test results are as follows:
(1)Fe 3+ and (3) reduction process control: sulfur dioxide is introduced into the qualified liquid, stirring is started to promote the mixture to be fully mixed with the solution, the aeration speed is controlled to be 60-100L/(L-liquid.h), and the reaction time is 4h.
(2)Fe 2+ And (3) controlling an oxidation hydrolysis process: controlling the reaction temperature to be 200 ℃ and the operating condition of oxygen partial pressure of 400kPa, the reaction time is 2h, fe 2+ Oxidizing and hydrolyzing to obtain solid-phase hematite slag (Fe) 2 O 3 )。
(3) Preparing an extract: the extractant consists of an amine extractant, a diluent and a phase regulator, and the formula is 50% of tri (2-ethylhexyl) amine (TEHA), 10% of sulfonated kerosene and 40% of isomeric tridecanol.
(4) And adopting a countercurrent extraction procedure to fully stir and mix the qualified liquid and the extract liquid. The extraction conditions were 3-stage extraction at 30℃compared with A/O=1:2. The back extraction condition is that water is used as a back extraction agent, the temperature is 30 ℃, and the ratio of A/O=2:1 is subjected to 3-stage back extraction. The stripping temperature was 30 ℃.
(5) Test results: the iron removal rate is 92%, the produced hematite slag contains 65% of iron, less than 0.5% of copper and less than 2% of sulfur, and the hematite slag can be used as raw materials for iron making or cement production after being treated; the total extraction rate of sulfuric acid is more than 90 percent, the total back extraction rate is more than 94 percent, the mass concentration of the outlet aqueous phase acid is about 9g/L, the mass concentration of the product acid is about 20g/L, and the product acid is pure sulfuric acid solution after 3-stage extraction and 3-stage back extraction.
Example 4
Referring to FIG. 1, the treated high acid iron raffinate of the present invention contains copper 1.64g/l, acid concentration 17g/l, iron concentration 37g/l, and specific process operations, control conditions and test results are as follows:
(1)Fe 3+ and (3) reduction process control: sulfur dioxide is introduced into the qualified liquid, stirring is started to promote the mixture to be fully mixed with the solution, the aeration speed is controlled to be 60-100L/(L-liquid.h), and the reaction time is 3.5h.
(2)Fe 2+ And (3) controlling an oxidation hydrolysis process: controlling the reaction temperature to be 200 ℃ and the operating condition of oxygen partial pressure of 400kPa, the reaction time is 2h, fe 2+ Oxidizing and hydrolyzing to obtain solid-phase hematite slag (Fe) 2 O 3 )。
(3) Preparing an extract: the extractant consists of an amine extractant, a diluent and a phase regulator, and the formula is 45% of tri (2-ethylhexyl) amine (TEHA), 20% of sulfonated kerosene and 35% of isomeric tridecanol.
(4) And adopting a countercurrent extraction procedure to fully stir and mix the qualified liquid and the extract liquid. The extraction conditions were 3-stage extraction at 30℃compared with A/O=1:2. The back extraction condition is that water is used as a back extraction agent, the temperature is 30 ℃, and the ratio of A/O=1:1 is subjected to 3-stage back extraction. The stripping temperature was 30 ℃.
(5) Test results: the iron removal rate is 92%, the produced hematite slag contains iron 64%, copper less than 0.5% and sulfur less than 2%, and the hematite slag can be used as raw materials for iron making or cement production after being treated; the total extraction rate of sulfuric acid is more than 90 percent, the total back extraction rate is more than 95 percent, the mass concentration of the outlet aqueous phase acid is about 9g/L, the mass concentration of the product acid is about 15g/L, and the product acid is pure sulfuric acid solution after 3-stage extraction and 3-stage back extraction.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and variations could be made by those skilled in the art without departing from the technical principles of the present invention, and such modifications and variations should also be regarded as being within the scope of the invention.
Claims (7)
1. A method for reducing the concentration of ferric acid in a secondary copper sulphide ore bioleaching system comprising the steps of:
step 1: introducing sulfur dioxide into qualified liquid or raffinate of the heap leaching system, starting a stirrer to promote the sulfur dioxide to be fully mixed with the solution, and controlling the aeration speed to be 10-100L/L- Liquid and its preparation method H, reacting for 2-4 h, and adding Fe in qualified liquid or raffinate 3+ Reduction of Fe 2+ ；
Step 2: controlling Fe in qualified liquid or raffinate 2+ The reaction time in the oxidizing hydrolysis process is 1-4h, the reaction temperature is 180-200 ℃, the oxygen partial pressure is 400-500 kPa, and Fe 2+ Generating solid-phase hematite slag after oxidative hydrolysis to realize copper-iron separation, discharging the solid-phase hematite slag out of a heap leaching system, and mainly reacting as follows:
2FeSO 4 +0.5O 2 +2H 2 O＝Fe 2 O 3 ↓+2H 2 SO 4 (1)；
step 3: preparing an extract liquid by tri (2-ethylhexyl) amine, sulfonated kerosene and isomeric tridecanol according to a certain proportion, adopting a three-stage countercurrent extraction procedure and fully stirring and mixing the solution after iron removal in the step 2, so that sulfuric acid in the solution after iron removal is extracted from a water phase to an organic phase, setting three-stage back extraction, selecting water as a back extraction agent, fully stirring and mixing a load organic phase generated by extraction with water, and enabling acid in the load phase to enter the water phase to obtain a dilute acid solution, wherein the reflection equation is as follows;
step 4: and (3) clarifying and separating the solution after the back extraction in the step (3), and then delivering the solution with the reduced concentration of the obtained ferric acid to a copper extraction-electrodeposition system to produce cathode copper or returning the solution to a heap leaching system, wherein the obtained dilute acid solution is discharged from the heap leaching system.
2. The method for reducing the concentration of ferric acid in a secondary copper sulphide ore heap bioleaching system according to claim 1, wherein the reagents in the extract of step 3 are arranged in the following proportions:
the configuration proportion of the tri (2-ethylhexyl) amine is 40% -50%;
the preparation proportion of the sulfonated kerosene is 10% -20%;
the configuration proportion of the isomerism tridecanol is 35% -40%.
3. The method for reducing the concentration of ferric acid in a secondary copper sulphide ore bioleaching system according to claim 2, wherein the pure dilute sulfuric acid solution of the recovered product is obtained by back-extracting the loaded organic phase with water at a given temperature, and the regenerated organic phase is recycled, and the back-extraction reaction is the reverse process of the reactions of the formulas (2) and (3) in the step 3.
4. A method for reducing the concentration of ferric acid in a secondary copper sulphide ore heap bioleaching system as claimed in claim 3 wherein the stripping temperature in step 3 is in the range 20 to 30 ℃ when water is used as stripping agent.
5. The method for reducing the concentration of ferric acid in a secondary copper sulphide ore heap bioleaching system according to claim 4 wherein the extraction conditions in the extraction mode are 3-stage extraction at a temperature of 30 ℃ compared with a/o=1:2 to 1:3.
6. The method for reducing the concentration of ferric acid in a secondary copper sulphide ore bioleaching system according to claim 5, wherein the stripping condition in the extraction mode is that the temperature is 30 ℃, and the ratio of A/O=2:1-1:1 is subjected to 3-stage stripping.
7. The method for reducing the concentration of iron acid in a secondary copper sulphide ore heap bioleaching system according to claim 6 wherein the iron removal and extraction method is applicable to the field of hydrometallurgical heap bioleaching or other technical fields in which the degree of iron acid in solution in the system is to be mediated.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2210090A1 (en) * | 1971-03-05 | 1972-09-28 | Cominco Ltd., Vancouver, British Columbia (Kanada) | Process for the extraction of copper and sulfur from copper-iron sulfides |
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| WO2024016522A1 (en) | 2024-01-25 |
| CN115161476A (en) | 2022-10-11 |
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