CN112280980B - Method for regulating and controlling potential of biological heap leaching system - Google Patents

Method for regulating and controlling potential of biological heap leaching system Download PDF

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CN112280980B
CN112280980B CN202011239278.6A CN202011239278A CN112280980B CN 112280980 B CN112280980 B CN 112280980B CN 202011239278 A CN202011239278 A CN 202011239278A CN 112280980 B CN112280980 B CN 112280980B
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copper
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CN112280980A (en
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蓝碧波
黄怀国
江城
王春
巫銮东
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Zijin Mining Group Co Ltd
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    • 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
    • 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
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
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Abstract

The invention relates to a method for regulating and controlling potential of a biological heap leaching system, which comprises the following stepsThe method comprises the steps of a biological heap leaching system, and taking measures of regulating the amount of piled ore, intermittently spraying and leaching in the middle and later stages, controlling the turnover rate of spraying liquid and sealing the heap for controlling the potential at 600-700 mV, wherein crushing-heaping is sequentially carried out, secondary copper sulfide ore is firstly crushed to-30 mm-50 mm, heaping is carried out, the heap height is 10-12 m, and then the amount of piled ore is increased or reduced according to the actually measured potential of the biological heap leaching system so as to regulate the potential; leaching at the early stage, and after the arrangement of a spraying pipeline, continuously spraying raffinate serving as spraying liquid to a building pile, wherein the spraying strength is 30-50L/h.m2Controlling the turnover rate of the spraying liquid until the leaching rate of copper reaches 40-50%; leaching in the middle and later periods, intermittently spraying the ore heap leached in the previous period, controlling the turnover rate of a spraying liquid, and leaching the ore in the biological heap after leaching copper twice to obtain an old ore heap; and (4) sealing and isolating, namely sealing and isolating the lower-layer old ore pile by using a film after three layers of pile covering and copper leaching are finished. Has the advantages of simple process control, no need of adding medicament, low production cost, environmental protection and the like.

Description

Method for regulating and controlling potential of biological heap leaching system
Technical Field
The invention relates to a method for regulating and controlling potential of a biological heap leaching system, which is suitable for application in the mining and metallurgy industry.
Background
The 'biological heap leaching-extraction-electrodeposition' process has the remarkable advantages of low cost, low energy consumption and the like, and becomes a preferred process for low-grade secondary copper sulfide ore. At present, nearly 20 mines in the world adopt the process. The first ten thousand-ton biological copper extraction mine in China is put into production in the copper mine of the purple Jinshan in 2005, low-grade resources which are difficult to utilize in the traditional process are fully utilized, and good economic benefits are obtained. However, in the practical process of copper leaching, pyrite in the ore is also oxidized, and because the content of pyrite is much higher than that of copper minerals, the acid and iron generation amount in the biological heap leaching process is large, and the environmental protection cost is high.
Chalcocite (Cu)2S) is the main existing form of copper in the secondary copper sulphide ore. The leaching of the chalcocite in the acidic high-speed rail medium is carried out in two stages: first stage leach kineticsMainly by oxidant Fe3+Diffusion control from solution to mineral surface, leaching rate and oxidant Fe3+The concentration is in direct proportion and enough high Fe is kept3+The Cu can be leached out quickly by concentration2The first copper in S; the second stage leaching is controlled by chemical reaction, is strongly related to temperature and is related to Fe in the spray liquid3+The concentration is weakly correlated. The oxidation power of the pyrite is controlled by the oxidation-reduction potential of the system, the oxidation rate of the pyrite is slow when the oxidation-reduction potential is low, and the oxidation rate of the pyrite is accelerated when the oxidation-reduction potential is high.
How to control the oxidation-reduction potential of a biological heap leaching system at a lower level is a key for controlling the oxidation of pyrite and a key technical problem to be solved in the biological heap leaching process of secondary copper sulfide ores. The redox potential in solution is mainly associated with Fe3+And Fe2+Molar concentration ratio of [ Fe ]3+]/[Fe2+]Related to, Fe3+The higher the concentration, the higher the redox potential. In the process of biological heap leaching, leaching microorganisms (such as thiobacillus ferrooxidans) can greatly accelerate Fe2+The oxidation rate of the biological heap leaching system is improved.
The currently disclosed methods for controlling the redox potential in the heap bioleaching process are mainly two: the method for controlling the oxidation-reduction potential in the biological heap leaching process is disclosed by Chinese patent CN 101984094B, and the method for controlling the oxidation-reduction potential is provided, namely the total sulfate concentration is controlled to be 220-260 g/L, so that sulfur-oxidizing bacteria are in superiority, the activity of iron-oxidizing bacteria is inhibited, and the oxidation-reduction potential is controlled to be 650-720 mV, so that the oxidation of pyrite is inhibited, and the defects that the total sulfate concentration is controlled to be too high, the feasibility in industrial production is not large, the total sulfate concentration is controlled to be too high, and the feasibility in industrial production is not large are overcome; the other is a chalcopyrite bioleaching method disclosed in Chinese patent CN110527830A, which proposes that a surfactant and/or an isothiazolinone bactericide is added into a chalcopyrite bioleaching system to inhibit the activity of microorganisms and control the oxidation process of the microorganisms to ferrous so as to adjust the potential of a leaching solution, and the defects that the activity of the microorganisms is difficult to accurately control, the environment is not friendly and the like exist.
Therefore, the method for regulating and controlling the potential of the biological heap leaching system is urgent and has great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for regulating and controlling the oxidation-reduction potential of a secondary copper sulfide ore heap bioleaching system. The method can control the potential to be 600-700 mV relative to the standard hydrogen electrode potential (Vs. SHE), and can effectively inhibit the oxidation of pyrite without adding any medicament.
The task of the invention is completed by the following technical scheme:
1. the method for regulating and controlling the potential of the biological heap leaching system comprises the biological heap leaching system and is characterized by also comprising the steps of regulating the amount of ore entering a heap, intermittently spraying and leaching in the middle and later periods, controlling the turnover rate of a spraying liquid and sealing the heap for controlling the potential at 600-700 mV, wherein the specific process steps and conditions are as follows:
a. crushing-stacking: crushing the secondary copper sulfide ore to-30 mm to-50 mm, stacking, wherein the stacking height is 10-12 m, and increasing or decreasing the stacking ore amount according to the actually measured potential height of a biological heap leaching system so as to adjust the potential;
b. early leaching: after the arrangement of the spraying pipelines, raffinate is used as spraying liquid to continuously spray the building pile for early leaching, and the spraying strength is 30-50L/h.m2Simultaneously controlling the turnover rate of the spraying liquid until the leaching rate of copper reaches 40-50% to obtain the previous copper leaching liquid;
c. leaching at the middle and later stages: intermittently spraying the ore heap leached in the previous stage by using raffinate as spraying liquid, and simultaneously controlling the turnover rate of the spraying liquid to obtain copper leaching liquid in the middle and later stages, wherein the biological heap leached ore after copper leaching twice is an old ore heap;
d. pile sealing and isolation: in the biological heap leaching process, after three layers of heap are covered and copper leaching is finished, the lower layer old ore heap is sealed and isolated by using a film.
Compared with the prior art, the invention has the following advantages and effects:
(1) the process is simple to control, and the potential of the biological heap leaching system can be controlled within a target range by adjusting the amount of piled ore, the turnover rate of spraying liquid and the spraying system according to the potential change trend of the biological heap leaching system.
(2) No need of adding medicament and low production cost.
(3) The environmental protection benefit is good. Effectively inhibits the oxidation of pyrite while realizing the high-efficiency leaching of copper, generates less acid and iron, and greatly reduces the neutralization cost of wastewater and the amount of neutralized slag.
Drawings
FIG. 1 is a process flow diagram of a method for regulating potential of a biological heap leaching system according to the present invention.
The present invention is described in further detail below with reference to the attached drawings.
Detailed Description
2. As shown in figure 1, the method for regulating and controlling the potential of the biological heap leaching system comprises the biological heap leaching system, and is characterized by also comprising the steps of regulating the amount of ore entering a heap, intermittently spraying and leaching in the middle and later periods, controlling the turnover rate of a spraying liquid and sealing the heap for controlling the potential to be 600-700 mV, wherein the specific process steps and conditions are as follows:
a. crushing-stacking: crushing the secondary copper sulfide ore to-30 mm to-50 mm, stacking, wherein the stacking height is 10-12 m, and increasing or decreasing the stacking ore amount according to the actually measured potential height of a biological heap leaching system so as to adjust the potential;
b. early leaching: after the arrangement of the spraying pipelines, raffinate is used as spraying liquid to continuously spray the building pile for early leaching, and the spraying strength is 30-50L/h.m2Simultaneously controlling the turnover rate of the spraying liquid until the leaching rate of copper reaches 40-50% to obtain the previous copper leaching liquid;
c. leaching at the middle and later stages: intermittently spraying the ore heap leached in the previous stage by using raffinate as spraying liquid, and simultaneously controlling the turnover rate of the spraying liquid to obtain copper leaching liquid in the middle and later stages, wherein the biological heap leached ore after copper leaching twice is an old ore heap;
d. pile sealing and isolation: in the biological heap leaching process, after three layers of heap are covered and copper leaching is finished, the lower layer old ore heap is sealed and isolated by using a film.
The method of the invention may further be:
and c, performing an extraction-electrodeposition process on the copper leaching solution in the step b and the step c to obtain the cathode copper and the raffinate.
And (c) returning a part of the raffinate to the early stage leaching in the step b and the middle and later stage leaching in the step c to be used as spraying liquid.
And (4) the residual raffinate enters a neutralization process, is neutralized by lime to pH 6-9, and is discharged.
The membrane is a geomembrane or a PE membrane, and can prevent pyrite in an old ore heap from being oxidized continuously.
The intermittent spraying is carried out for 1 day, and the spraying is stopped for 3-5 days, so that the spraying strength in the middle and later leaching stages can be reduced, and the oxidation of pyrite is inhibited, thereby reducing the concentration of iron ions in the solution and reducing the number of leaching microorganisms.
The term "stacking" as used herein means that the leached slag on the bottom mat is not removed after the leaching of the ore is finished, and the ore is continuously stacked above the bottom mat for spray leaching; the 'seal pile isolation' is to isolate the old ore pile after the lower layer copper leaching is finished by utilizing a geomembrane or a PE film (polyethylene film), so as to fundamentally prevent the pyrite in the old pile from being continuously oxidized; "controlling the amount of ore piled" means controlling the amount of ore piled and sprayed over a period of time (e.g. daily, weekly), mainly using the copper minerals and Fe in the ore3+Reacting, namely reducing the potential of a biological heap leaching system, and properly increasing the amount of piled ore when the potential is higher under the condition of maintaining stable production, and conversely, properly reducing the amount of piled ore; the 'control of the turnover rate of the spray liquid' is to control the retention time of the spray liquid outside the ore heap or in the solution pool, when the spray liquid is stored in the solution pool, Fe can be accelerated due to the existence of a large amount of ore leaching microorganisms2+Oxidizing to raise the solution potential, wherein the longer the retention time is, the higher the solution potential is; the intermittent spraying system is adopted in the middle and later stage leaching process of the ore, the spraying strength of the ore in the later stage of leaching is reduced through intermittent spraying, and the oxidation of pyrite is inhibited, so that the concentration of iron ions in the solution is reduced, and the number of leaching microorganisms is reduced, which is based on Fe2+Is oxidized into Fe3+Can provide necessary energy for the propagation of the mineral leaching microorganisms.
Example 1
The copper grade in certain secondary copper sulfide ore is 0.40 percent, copper minerals mainly comprise chalcocite and copper blue, and a small amount of refractory copper minerals such as copper-sulfur-arsenic ore and the like; the content of the pyrite is high (4-8%), and copper minerals and the pyrite are in close symbiosis; the gangue minerals are mainly quartz, and the acid-consuming gangue content is low. After the copper ore is crushed to minus 50mm which is more than or equal to 85 percent, heaping the copper ore and stacking the copper ore by 10 meters. After the spray pipeline is arranged, the raffinate is utilized to carry out section continuous spraying, and the spraying strength is 35L/h.m2. And (4) after the copper leaching rate reaches 50%, entering a middle and later stage leaching stage, and carrying out intermittent spraying for 1 day and leisure time for 3 days. And (4) the copper leaching solution enters an extraction-electrodeposition process to produce cathode copper. The turnaround period (average residence time in the solution pool) for the raffinate was 24 h. After three layers of the pile are leached, the old ore pile at the lower layer is sealed and piled and isolated by the geomembrane. The amount of the ore piled in a certain time range is properly adjusted according to the potential of the heap leaching system. The potential of the heap leaching system is controlled within the range of 670-690 mV. Leaching the ore heap for 7-8 months, wherein the copper content of leaching residues is less than 0.08%, the copper leaching rate is more than 80%, and the pyrite oxidation rate is 5%. 1000 ten thousand tons of ore are processed annually, and the neutralization cost of open-circuit raffinate is 3000 ten thousand yuan/year.
Example 2
The copper grade in certain secondary copper sulfide ore is 0.40 percent, copper minerals mainly comprise chalcocite and copper blue, and a small amount of refractory copper minerals such as copper-sulfur-arsenic ore and the like; the content of the pyrite is high (4-8%), and copper minerals and the pyrite are in close symbiosis; the gangue minerals are mainly quartz, and the acid-consuming gangue content is low. After the copper ore is crushed to minus 50mm which is more than or equal to 85 percent, heaping the copper ore and stacking the copper ore by 10 meters. After the spray pipeline is arranged, the raffinate is utilized to carry out section continuous spraying, and the spraying strength is 35L/h.m2. And (4) after the leaching rate of copper reaches 50%, entering a middle and later stage leaching stage, and carrying out intermittent spraying for 1 day and leisure time for 5 days. And (4) the copper leaching solution enters an extraction-electrodeposition process to produce cathode copper. The turnaround period (average residence time in the solution pool) for the raffinate was 12 h. After three layers of the pile are leached, the PE film is used for sealing and isolating the old ore pile at the lower layer. According to heap leaching systemsThe potential is used for properly adjusting the amount of the piled ore within a certain time range. The potential of the heap leaching system is controlled within the range of 640-660 mV. Leaching the ore heap for 7-8 months, wherein the copper content of leaching residues is less than 0.08%, the copper leaching rate is more than 80%, and the pyrite oxidation rate is 3%. 1000 ten thousand tons of ore are processed annually, and the neutralization cost of open-circuit raffinate is 1800 ten thousand yuan per year.
Comparative example
The copper grade in certain secondary copper sulfide ore is 0.40 percent, copper minerals mainly comprise chalcocite and copper blue, and a small amount of refractory copper minerals such as copper-sulfur-arsenic ore and the like; the content of the pyrite is high (4-8%), and copper minerals and the pyrite are in close symbiosis; the gangue minerals are mainly quartz, and the acid-consuming gangue content is low. After the copper ore is crushed to minus 40mm which is more than or equal to 85 percent, heaping the copper ore and stacking the copper ore by 12 meters. After the arrangement of the spray pipelines, raffinate is utilized for continuous spraying. The leachate enters an extraction-electrodeposition process to produce cathode copper. And no extra measure is taken to regulate and control the potential of the heap leaching system, and the potential of the heap leaching system is 850-900 mV. Leaching the ore heap for 7-8 months, wherein the copper content of leaching residues is less than 0.07%, the copper leaching rate is greater than 82%, and the pyrite oxidation rate is 20%. 1000 million tons of ore are processed annually, and the neutralization cost of open-circuit raffinate is 1.2 million yuan/year.
The technical and economic indicators of the examples and the comparative examples are shown in Table 1.
TABLE 1 comparison of technical and economic indicators between examples and comparative examples
Figure BDA0002767882950000071
Figure BDA0002767882950000081
As described above, the present invention can be preferably realized. The above embodiments are only preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments, and other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent replacements within the protection scope of the present invention.

Claims (6)

1. The method for regulating and controlling the potential of the biological heap leaching system comprises the biological heap leaching system and is characterized by also comprising the steps of regulating the amount of ore entering a heap, intermittently spraying and leaching in the middle and later periods, controlling the turnover rate of a spraying liquid and sealing the heap for controlling the potential at 600-700 mV, wherein the specific process steps and conditions are as follows:
a. crushing-stacking: crushing the secondary copper sulfide ore to-30 mm to-50 mm, stacking, wherein the stacking height is 10-12 m, and increasing or decreasing the stacking ore amount according to the actually measured potential height of a biological heap leaching system so as to adjust the potential;
b. early leaching: after the arrangement of the spraying pipelines, raffinate is used as spraying liquid to continuously spray the building pile for early leaching, and the spraying strength is 30-50L/h.m2Simultaneously controlling the turnover rate of the spraying liquid until the leaching rate of copper reaches 40-50% to obtain the previous copper leaching liquid;
c. leaching at the middle and later stages: intermittently spraying the ore heap leached in the previous stage by using raffinate as spraying liquid, and simultaneously controlling the turnover rate of the spraying liquid to obtain copper leaching liquid in the middle and later stages, wherein the biological heap leached ore after copper leaching twice is an old ore heap;
d. pile sealing and isolation: in the biological heap leaching process, after three layers of heap are covered and copper leaching is finished, the lower layer old ore heap is sealed and isolated by using a film.
2. The method as set forth in claim 1, characterized in that said copper leachate from steps b and c is subjected to an extraction-electrodeposition step to produce a product cathode copper and a raffinate.
3. The process as set forth in claim 2, characterized in that a portion of said raffinate is returned to the pre-leaching in step b and the post-middle leaching in step c as a spray.
4. The method as set forth in claim 2 or 3, characterized in that the raffinate is neutralized with lime to pH 6-9 and discharged.
5. The method of claim 1, wherein the membrane is a geomembrane or PE membrane that prevents further oxidation of pyrite in the old heap.
6. The method as set forth in claim 1, wherein the intermittent spraying is performed for 1 day, and the spraying is stopped for 3 to 5 days, so that the spraying intensity in the middle and later leaching stages can be reduced, and the oxidation of pyrite can be inhibited, thereby reducing the concentration of iron ions in the solution and reducing the number of leaching microorganisms.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
ES2204340A1 (en) * 1999-10-28 2004-04-16 Mintek A method of operating a bioleach process with control of redox potential
CN107267755A (en) * 2017-07-03 2017-10-20 紫金矿业集团股份有限公司 A kind of method of secondary copper sulfide mineral biological dump leaching
CN107299224A (en) * 2017-07-03 2017-10-27 紫金矿业集团股份有限公司 A kind of method of copper sulfide mineral biological heap leaching system envelope heap isolation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2204340A1 (en) * 1999-10-28 2004-04-16 Mintek A method of operating a bioleach process with control of redox potential
CN107267755A (en) * 2017-07-03 2017-10-20 紫金矿业集团股份有限公司 A kind of method of secondary copper sulfide mineral biological dump leaching
CN107299224A (en) * 2017-07-03 2017-10-27 紫金矿业集团股份有限公司 A kind of method of copper sulfide mineral biological heap leaching system envelope heap isolation

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