CN1511962A - Compound leaching agent and leaching method for leaching out copper pyrite using compound leaching agent - Google Patents
Compound leaching agent and leaching method for leaching out copper pyrite using compound leaching agent Download PDFInfo
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- CN1511962A CN1511962A CNA021590834A CN02159083A CN1511962A CN 1511962 A CN1511962 A CN 1511962A CN A021590834 A CNA021590834 A CN A021590834A CN 02159083 A CN02159083 A CN 02159083A CN 1511962 A CN1511962 A CN 1511962A
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Abstract
The compound leaching agent consists of leaching agent, oxidant, pH regulator and ore pulp potential controlling agent. Decomposing copper pyrite with the compound leaching agent has leaching temperature of 20-120 deg.c, leaching pressure of normal pressure, ore granularity of 30-200 mesh, leaching time of 3-240 hr, molar ratio between the leaching agent and the oxidant determined by the Cu, Fe and S content in the copper pyrite and ore pulp potential of 300-500 mV. The present invention has the advantages of no need of high temperature and high pressure apparatus, lower impurity content in leached liquid, less leaching agent loss, easy separation of copper and impurity, circular use of the leaching agent, low cost and less pollution. Using the leaching agent can obtain three products including metal copper, iron red and sulfur.
Description
Technical Field
The invention relates to a chalcopyrite leaching method, in particular to a composite leaching agent and a leaching method for leaching chalcopyrite by using the same.
Background
The existing forms of copper ores in the nature can be divided into three main categories: sulphide ores, oxide ores and native copper. Because copper has strong thiophilic property, 80 percent of copper ores are sulfide ores, 20 percent of copper ores are oxide ores, and the native copper is very rare. The oxidized ore and the natural ore are easy to leach, the sulphide ore is difficult, the chalcopyrite is one of the most difficult to leach in the sulphide ore, and the reserve is the largest copper ore, so the research on the leaching technology of the chalcopyrite is very important.
Various processing techniques have been used for a long time for industrial production, for example, the pressure ammonia leaching method for processing chalcopyrite is called an Abbe method; a Krey process which is a pressure acid leaching process; roasting-leaching-electrodeposition; bacterial methods for tailings processing, and the like. Also as disclosed in the latest patent 95113004.8, publication 97182088.0, the leaching agents for the ammonia process are ammonium carbonate and ammonium hydroxide, and the pressure acid leach process uses ferric chloride, cupric chloride, sodium chloride and hydrochloric acid.
The above methods all have problems that the production conditions are difficult to control, a high-pressure reaction kettle is required and the processing cost is high.
Disclosure of Invention
In order to overcome the defects of the prior processing method, the invention provides a method for leaching chalcopyrite by using a composite leaching agent, and achieves the aim of realizing a wet leaching method of chalcopyrite with high selectivity, simple operation process and high yield.
In order to achieve the purpose, the technical scheme of the invention is to provide a composite leaching agent which comprises four components, namely a leaching agent, an oxidant, a pH regulator and a pulp potential control agent.
The invention also provides a leaching method for leaching the chalcopyrite by using the composite leaching agent, which decomposes the chalcopyrite by using the aqueous solution of the composite leaching agent, wherein the leaching temperature of the method is between 20 and 120 ℃; the leaching pressure is normal pressure; the granularity of the ore is between 30 and 200 meshes; the leaching time is 3 to 240 hours; according to the content of copper, iron and sulfur in the chalcopyrite, the molar ratio of the ingredients to the leaching agent and the oxidant in the composite leaching agent is 1: 1-6; the mol ratio of iron to oxygen is 1: 1.5-3; the mol ratio of the sulfur to the oxygen is 1: 1-1.5; pulp potential: 300mv-500 mv.
The method has the advantages that the reactor of the method does not need high-temperature and high-pressure equipment, the manufacturing and the production are simple, the impurity content in the leaching solution is low, the loss of the leaching agent in the leaching process is low, the separation of copper and impurities is easy, and the like, and the leaching agent can be recycled, thereby reducing the production cost and the environmental pollution; the leaching agent can be used for leaching chalcopyrite (CuFeS)2) Three elements in the alloy become three products, namely goldBelongs to copper, iron oxide red and sulfur, and achieves the purpose of comprehensive utilization. The technology can be used for processing the beneficiated concentrate powder (the fineness is less than 100 meshes) and processing the raw ore which is not beneficiated, so that the production cost can be greatly reduced.
Detailed Description
The composite leaching agent and the leaching method for leaching chalcopyrite by using the composite leaching agent are described by combining with the examples.
The invention provides a composite leaching agent and a leaching method for leaching chalcopyrite by using the same.
The leaching agent in the composite leaching agent is ammonium carbonate, ammonium nitrate, ammonium chloride and air.
The oxidant in the composite leaching agent is air, oxygen, manganese dioxide and ammonium persulfate.
The pH regulator in the composite leaching agent is nitric acid, hydrochloric acid, sulfuric acid, ammonium hydroxide and ammonium carbonate.
The slurry potential control agent in the composite leaching agent is ferric chloride, ferric sulfate, ammonium chlorate and ammonium perchlorate.
At least one component of each of the four components of the composite leaching agent is combined into an acidic formula, an alkaline formula or a neutral formula to leach out copper.
The acidic formula of the compound leaching agent is ammonium chloride, ferric chloride, hydrochloric acid, oxygen or air; or ammonium sulfate, ferric sulfate, ammonium persulfate, sulfuric acid, manganese dioxide; the pH value of both leaching reactions is 0.5-3.
The neutral formula of the compound leaching agent is ammonium chloride, ammonium carbonate, ammonium chlorate and ammonium perchlorate, and the pH value is 5.5-8.
The alkaline formula of the composite leaching agent comprises ammonium nitrate, ammonium hydroxide, ammonium chlorate and oxygen, and the PH value is 9-12.
The leaching method for leaching the chalcopyrite by using the composite leaching agent is to decompose the chalcopyrite by using the aqueous solution of the composite leaching agent, and the leaching temperature of the method is between 20 and 120 ℃; the leaching pressure is normal pressure; the granularity of the ore is between 30 and 200 meshes; the leaching time is 3 to 240 hours; according to the content of copper, iron and sulfur in the chalcopyrite, the molar ratio of the ingredients to the leaching agent and the oxidant in the composite leaching agent is 1: 1-6; the mol ratio of iron to oxygen is 1: 1.5-3; the mol ratio of the sulfur to the oxygen is 1: 1-1.5; pulp potential: 300mv-500 mv.
The working principle and the implementation process of the composite leaching agent and the leaching method for leaching the chalcopyrite by using the composite leaching agent are as follows:
the composite leaching agent is a composite solvent with high selectivity, as is known, copper ores are symbiotic with a large amount of gangue, and the components of the copper ores are variable and different in different regions, such as calcite, dolomite, feldspar and Fe2O3、FeS、SiO2Paragenic ores and the like are very common, and are difficult to completely remove even through mineral separation, and in any case, raw ores are leached, so that a large amount of leaching agent is inevitably consumed by the conventional method, and a large amount of impurities enter leachate, which brings difficulty to post-processing. Several kinds of ores in Yunnan province of China such as Zhongdian Hongshan ore (chalcopyrite), Cedar terrace (chalcopyrite), Jintunite (bornite), Castanea sativa slope copper ore (chalcopyrite), Dongchua copper ore (oxidized ore, chalcocite, bornite), and Dayuye copper ore (Fanghua chalcopyrite), which basically reflect the existing forms of chalcopyrite.
The compound leaching agent can achieve the purpose of high selectivity only by aiming at different formulas of sulphide ores (chalcopyrite, bornite, chalcocite and copper blue) and gangue components with different ore compositions, so that the compound leaching agent is prepared into a selective compound formula aiming at different ore compositions, and one formula cannot achieve an ideal target for all ores.
If the ore is an alkaline ore (ore with high content of alkaline earth metals) and Fe2O3High minerals, formulations with a PH near neutral are referred to as neutral or alkaline formulations. If the ore is sandstone ore (SiO)2High calcium and low magnesium ores) then a formulation with an acidic PH, called an acidic formulation, may be used.
The substances of different formulas are different, but all the substances comprise four groups of substances with different functions, namely leaching agent, oxidant, pH regulator and pulp potential regulator. The leaching agent is used for changing copper into a soluble copper complex compound to enter a solution to be separated from other impurities; the oxidant is a substance necessary for satisfying the oxidation-reduction reaction, so that S in the chalcopyrite is changed into S DEG to lose two electrons and is transferred to the oxidant, and simultaneously, the iron is changed into ferric oxide or ferric salt, thereby achieving the aim of completing the oxidation reaction; the PH regulator is mainly used for enabling the reaction to be carried out at a certain PH value so as to maintain the reaction speed, prevent impurities from entering the solution and reduce the amount of the impurities in the solution; the potential regulator is used to stabilize the optimal oxidation-reduction potential value in the whole reaction system, ensure the reaction to be carried out in a better environment, and control the pulp potential to be 300-500 mv, thus achieving the necessary condition for accelerating (or maintaining) the reaction speed.
The leaching agent in the formula of the composite leaching agent is mainly a plurality of substances with special affinity to copper, and mainly comprises: ammonium salts such as ammonium carbonate, ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium persulfate, and the like, which form stable complexes with copper, leach the copper out.
The oxidant is mainly air (O)2)、MnO2And ammonium persulfate. Their effect is to make S in chalcopyrite＝When the temperature changes to S DEG, the iron is changed to iron oxide, and the following oxidation-reduction reaction occurs:
the pH regulator mainly comprises nitric acid, hydrochloric acid, sulfuric acid, ammonium hydroxide and ammonium carbonate, and is mainly used for controlling the pH in the reaction system.
The ore pulp potential regulator comprises ferric chloride, ferric sulfate, ammonium chlorate and ammonium perchlorate.
At least one of the four groups of substances with different functions is extracted, and then a compound leaching agent formula is formed, the compound leaching agent is used for leaching ores formed by different minerals, and is applicable to any type of chalcopyrite, four components of the compound leaching agent formula are mutually dependent and mutually promoted, and a set of compound leaching agent which is effective to the chalcopyrite is formed by organically matching different substances, can be divided into neutral, acidic and alkaline formulas due to different pH values, and is used for leaching copper in different copper ores, and the comprehensive reaction formula is as follows:
x: is acid radical
In addition to the leaching agent, the reaction conditions are essential to be matched during the process of leaching the chalcopyrite, such as reaction time, reaction temperature, the size of ore particles, stirring degree and the like. The leaching rate of copper increases with the reaction time and increases with the temperature. The reaction speed is related to the particle size of the ore, and the finer the particles, the faster the speed, and vice versa; the reaction speed is high when the temperature is high and is slow when the temperature is low, which is related to the reaction temperature.
Reaction temperature: if the formula is alkaline, the temperature is generally controlled to be 20-70 ℃;
if the formula is neutral, the temperature is generally controlled to be 70-120 ℃;
in the case of acidic formulations, the temperature is generally controlled at 50-100 ℃.
Ore particles: if stirring and leaching, generally controlling the particle size to be about 200 meshes;
if the soaking is carried out in a tank, the size is generally controlled to be about 5-30 meshes.
Leaching time: if the leaching is carried out by stirring, the leaching rate can reach 90-98 percent in 5-8 hours generally;
if the leaching is carried out in a tank (without stirring), the leaching rate can reach 88-98 percent in 3-10 days.
With the time being prolonged, the leaching rate can reach more than 98 percent.
The working process of the wet leaching method of the chalcopyrite is described by combining the examples:
the composite lixiviant formulation is formulated differently according to the mineral composition of the ore, and may be an alkaline ore, a neutral or alkaline formulation (e.g. example 3), a sandy ore (i.e. an ore with high SiO 2) an acidic formulation (e.g. examples 1-2), or a mixed ore a neutral formulation (e.g. example 4).
Example 1 (acidic formulation)
Weighing 100 g of chalcopyrite powder containing 22.2% of copper, the fineness of 100-; and rinsing the leached slag to separate slag, and then separating to obtain iron oxide red and sulfur, wherein the weight is as follows: 20 g of iron oxide red and 12 g of sulfur. Ferric chloride is used to control the pulp potential to be 350 mv.
If a tank leaching mode is adopted, the reaction time is generally 3-10 days, and the leaching rate is 88-98%.
Example 2 (acid formulation)
Weighing 100 g of chalcopyrite powder containing 30% of copper and 200 meshes of fineness, respectively adding 74.8 g of ammonium sulfate, ammonium persulfate, ferric sulfate, 47 g of manganese dioxide, sulfuric acid and 25L of air, wherein the PH value is less than 3, the liquid-solid ratio is 5: 1, and the reaction temperature is as follows: stirring and leaching at 100-120 deg.c and normal pressure for 3 hr, filtering and washing to obtain 1300ml filtrate, copper concentration 22.61 g/l and copper leaching rate 98%. Ammonium persulfate and ferric sulfate are used for controlling the potential of the ore pulp to be 350 mv.
If a tank leaching mode is adopted, the reaction time is generally 3-10 days, and the leaching rate is 88-98%.
Example 3 (alkaline formulation)
300 g of mineral powder containing 11.4 percent of copper and 200 meshes of fineness are weighed, 34.4 g of ammonium nitrate, 26.8 g of ammonium chlorate, 26.8 g of ammonium perchlorate and ammonium hydroxide are respectively added, the PH value is more than 9, the reaction temperature is 60 ℃, the pressure is normal, the liquid-solid ratio is 3: 1, the reaction time is 9 hours, and 1200ml of filter-washing solution with the concentration of 25.65 g/L and the leaching rate of 90 percent is obtained by filtering and washing. The ammonium chlorate controls the electric potential of the ore pulp to be 500 mv.
If the leaching mode is tank leaching, the reaction time is 3-10 days generally, and the leaching rate is 70-90%.
Example 4 (neutral formulation)
Weighing 100 g of chalcopyrite powder containing 26% of copper, the fineness of 100-. The leaching rate was 91%. Ammonium chlorate controlling the pulp potential: 500 mv.
Example 5
Weighing 1kg of ore containing 1% of copper and raw ore without mineral dressing and having fineness of 5-20mm, loading into a cylindrical glass cylinder with external heat preservation, heating the leachate (as in example 1) to 30 ℃, adding the leachate from the bottom of the cylinder, gradually immersing ore particles, then adding a certain amount of leachate every 5 hours, displacing the original liquid, allowing the original liquid to flow out from the upper part of the cylinder, continuously adding and flowing out, soaking for 5 days, then displacing and washing with water, completely displacing the leachate, obtaining 670ml of leachate and washing water altogether, analyzing the copper content of the leachate to be 5.89 g/l, and continuously leachingfor 10 days, wherein the leaching rate is 88%. The leaching rate reaches 98 percent. Pulp potential: 300mv-500 mv.
Claims (10)
1. A composite leaching agent is characterized in that the composite leaching agent consists of four components, namely a leaching agent, an oxidant, a pH regulator and a pulp potential control agent.
2. The composite leaching agent as claimed in claim 1, wherein the leaching agent is ammonium carbonate, ammonium nitrate, ammonium chloride, air.
3. The composite leaching agent according to claim 1, wherein the oxidant is air, oxygen, manganese dioxide, ammonium persulfate.
4. The composite leaching agent as claimed in claim 1, wherein the pH regulator is nitric acid, hydrochloric acid, sulfuric acid, ammonium hydroxide, ammonium carbonate.
5. The composite leaching agent according to claim 1, wherein the ore pulp potential control agent is ferric chloride, ferric sulfate, ammonium chlorate or ammonium perchlorate.
6. The composite leaching agent according to the claim 1 to 5, wherein at least one component of each of the four components of the composite leaching agent is combined into an acidic formulation or an alkaline formulation or a neutral formulation to leach copper.
7. The composite leaching agent according to claim 6, wherein the acidic formula of the composite leaching agent is ammonium chloride, ferric chloride, hydrochloric acid, oxygen or air; or ammonium sulfate,ferric sulfate, ammonium persulfate, sulfuric acid, manganese dioxide; the pH value of both leaching reactions is 0.5-3.
8. The composite leaching agent according to claim 6, wherein the neutral formula of the composite leaching agent is ammonium chloride, ammonium carbonate, ammonium chlorate and ammonium perchlorate, and the pH is 5.5-8.
9. The composite leaching agent according to claim 6, wherein the alkaline formula of the composite leaching agent is ammonium nitrate, ammonium hydroxide, ammonium chlorate and oxygen, and the pH is 9-12.
10. A leaching method for leaching chalcopyrite by using a composite leaching agent is characterized in that the chalcopyrite is decomposed by using an aqueous solution of the composite leaching agent, and the leaching temperature of the method is between 20 and 120 ℃; the leaching pressure is normal pressure; the granularity of the ore is between 30 and 200 meshes; the leaching time is 3 to 240 hours; according to the content of copper, iron and sulfur in the chalcopyrite, the molar ratio of the ingredients to the leaching agent and the oxidant in the composite leaching agent is 1: 1-6; the mol ratio of iron to oxygen is 1: 1.5-3; the mol ratio of the sulfur to the oxygen is 1: 1-1.5; pulp potential: 300mv-500 mv.
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| CNB021590834A CN1320137C (en) | 2002-12-31 | 2002-12-31 | Compound leaching agent and leaching method for leaching out copper pyrite using compound leaching agent |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101586186B (en) * | 2009-06-19 | 2012-07-25 | 昆明理工大学 | Method for leaching chalcopyrite and corresponding leaching agent |
| CN102703701A (en) * | 2012-06-20 | 2012-10-03 | 昆明理工大学 | Method for treating cupric oxide or zinc oxide ores by adopting agitation ammonia leaching and infiltration basin ammonia leaching in combination |
| CN105755283A (en) * | 2016-03-08 | 2016-07-13 | 江西理工大学 | Method for selectively leaching valuable metals in laterite-nickel ore by aid of chloride |
| CN106676280A (en) * | 2017-01-19 | 2017-05-17 | 昆明理工大学 | Leaching method for sulfide-oxide mixed copper ore |
| CN106755999A (en) * | 2016-12-21 | 2017-05-31 | 武汉理工大学 | A kind of microwave reinforced leaching method of chalcopyrite |
| CN115000239A (en) * | 2022-05-11 | 2022-09-02 | 中南大学 | Method for preparing precursor solution of copper-zinc-tin-sulfur-selenium film solar cell by acid leaching of brass |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081239C (en) * | 1997-03-03 | 2002-03-20 | 明特克公司 | Processf or the leaching of chalcopyrite |
| CN1058056C (en) * | 1997-07-28 | 2000-11-01 | 中国科学院化工冶金研究所 | Process of chlorine complexing oxidation method for slective leaching nickel cobalt copper sulfurized ore |
| US6319389B1 (en) * | 1999-11-24 | 2001-11-20 | Hydromet Systems, L.L.C. | Recovery of copper values from copper ores |
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2002
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101586186B (en) * | 2009-06-19 | 2012-07-25 | 昆明理工大学 | Method for leaching chalcopyrite and corresponding leaching agent |
| CN102703701A (en) * | 2012-06-20 | 2012-10-03 | 昆明理工大学 | Method for treating cupric oxide or zinc oxide ores by adopting agitation ammonia leaching and infiltration basin ammonia leaching in combination |
| CN102703701B (en) * | 2012-06-20 | 2014-07-30 | 昆明理工大学 | Method for treating cupric oxide or zinc oxide ores by adopting agitation ammonia leaching and infiltration basin ammonia leaching in combination |
| CN105755283A (en) * | 2016-03-08 | 2016-07-13 | 江西理工大学 | Method for selectively leaching valuable metals in laterite-nickel ore by aid of chloride |
| CN106755999A (en) * | 2016-12-21 | 2017-05-31 | 武汉理工大学 | A kind of microwave reinforced leaching method of chalcopyrite |
| CN106755999B (en) * | 2016-12-21 | 2018-11-23 | 武汉理工大学 | A kind of microwave reinforced leaching method of chalcopyrite |
| CN106676280A (en) * | 2017-01-19 | 2017-05-17 | 昆明理工大学 | Leaching method for sulfide-oxide mixed copper ore |
| CN106676280B (en) * | 2017-01-19 | 2019-04-12 | 昆明理工大学 | A kind of leaching method of oxygen-sulfur mixed copper ore |
| CN115000239A (en) * | 2022-05-11 | 2022-09-02 | 中南大学 | Method for preparing precursor solution of copper-zinc-tin-sulfur-selenium film solar cell by acid leaching of brass |
| CN115000239B (en) * | 2022-05-11 | 2024-02-23 | 中南大学 | Method for preparing copper zinc tin sulfur selenium film solar cell precursor solution by acid leaching brass |
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