CN114277259A - Method for regulating and controlling acidity of solution in secondary copper sulfide ore heap leaching system - Google Patents
Method for regulating and controlling acidity of solution in secondary copper sulfide ore heap leaching system Download PDFInfo
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- CN114277259A CN114277259A CN202111529532.0A CN202111529532A CN114277259A CN 114277259 A CN114277259 A CN 114277259A CN 202111529532 A CN202111529532 A CN 202111529532A CN 114277259 A CN114277259 A CN 114277259A
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Abstract
The invention relates to a method for regulating and controlling the acidity of a solution in a secondary copper sulfide ore heap leaching system, belonging to the field of hydrometallurgy heap leaching, and the method comprises the following steps: crushing limestone; after being buffered by a storage bin, limestone particles are uniformly fed into a ball mill, water is added into the ball mill, and the concentration of limestone pulp is adjusted to 15% -30%; pumping the limestone pulp subjected to ball milling to a hydrocyclone for sorting through a delivery pump, pumping the stirred limestone pulp and raffinate discharged from a second-stage extraction tank to a neutralization reaction tank through a liquid continuous stirrer, and automatically interlocking and starting a slurry delivery pump when the pH value of a solution in the neutralization reaction tank is 1.2-1.5; the invention is beneficial to improving the utilization rate of limestone, and simultaneously, through online monitoring of the pH value, the free acid in the system is accurately neutralized, the generation of ferric iron precipitate is reduced, and the consumption of limestone is reduced, so that the amount of neutralized slag is reduced, and the loss caused by copper entrained by the ferric hydroxide colloid is reduced.
Description
Technical Field
The invention belongs to the field of hydrometallurgy heap leaching, and particularly relates to a method for regulating and controlling the acidity of a solution in a secondary copper sulfide ore heap leaching system.
Background
As a process for treating low-grade ores, the 'biological heap leaching-extraction-electrodeposition' process has the advantages of high efficiency in resource utilization, short process flow, low production cost, small pollution and the like, is increasingly emphasized by people, is particularly widely applied to treatment of low-grade secondary copper sulfide ores, and is adopted in more than 20 secondary copper sulfide ore mines in the world at present.
Pyrite is often associated in the secondary copper sulfide ore, and in the biological heap leaching process of the secondary copper sulfide ore, the pyrite is subjected to oxidation reaction to generate ferric iron and sulfuric acid, and the leaching of the secondary copper sulfide ore is promoted by the heat released by oxidation and the generated ferric iron. However, if the associated pyrite in the secondary copper sulfide ore is more and the acid-consuming gangue is less, the oxidation of pyrite can cause the accumulation of excessive iron in the system with the continuous circulation of the solution in the system, which causes adverse effects on the subsequent extraction electrodeposition, and the conditions of excessive acid in the system can be aggravated by the reasons of acid return by extraction, acid production by alum precipitation, and the like.
In general production practice, the acidity in the system is usually reduced by adopting a method for neutralizing raffinate with lime or limestone, but the traditional neutralization method is often relatively extensive, the utilization rate of lime or limestone is not high, a large amount of neutralization slag can be generated, and a large amount of neutralization slag carries away a large amount of copper, so that loss is caused; the method is also a method for accurately and efficiently regulating and controlling the acidity of the solution in the secondary copper sulfide ore heap leaching system by adding crushed limestone into crushed ore, but in the actual operation of the method, sulfuric acid can firstly react with the limestone to cause the delay of copper leaching, and can not play a corresponding role along with the consumption and passivation of the limestone; a method for regulating acid and iron in a copper sulfide ore heap bioleaching system (CN107354298B) proposes that limestone with certain granularity and thickness is paved on the upper layer after leaching of each layer of heap leaching units is finished, and the concentration of iron in the heap leaching system is regulated by controlling the thickness of the limestone layer.
Disclosure of Invention
Technical problem to be solved
The technical problem to be solved by the invention is as follows: how to provide a method for regulating and controlling the acidity of a solution in a secondary copper sulfide ore heap leaching system, which is used for solving the problems that the utilization rate of limestone in the system is low, a large amount of neutralization slag is generated, and a large amount of copper is taken away by the large amount of neutralization slag, so that loss is caused.
(II) technical scheme
In order to solve the technical problem, the invention provides a method for regulating and controlling the acidity of a solution in a secondary copper sulfide ore heap leaching system, which comprises the following steps:
step 1: limestone is crushed in a first section and a second section until the requirement of the granularity of the feed of the ball mill is met;
step 2: after the crushed limestone particles are buffered by a storage bin, the limestone particles are uniformly fed into a ball mill through a spiral feeder;
step 3, continuing ball milling the broken limestone particles until the particle size meets the sorting requirement of the hydrocyclone, adding water into the ball mill, and adjusting the concentration of limestone pulp to 15-30%;
and 4, step 4: pumping the limestone pulp subjected to ball milling to a hydrocyclone through a delivery pump for sorting, returning the coarse-fraction limestone pulp to a ball mill for continuous ball milling, and pumping the fine-fraction limestone pulp to a stirring tank;
and 5: pumping the stirred limestone ore pulp and raffinate discharged from the second-stage extraction tank to a neutralization reaction tank through a liquid continuous stirrer, so that the acid content in the raffinate participating in the reaction is matched with the limestone content;
step 6: monitoring the pH value in real time through an online pH meter, and automatically interlocking and starting a slurry delivery pump when the pH value of a solution in a neutralization reaction tank is 1.2-1.5;
and 7: and (4) pumping the slurry obtained after the neutralization reaction in the step (6) to a rake thickener through a slurry delivery pump, discharging the liquid solution after overflowing to a raffinate pool, and discharging the solid neutralized slag to a heap leaching field in a dispersed mode.
Wherein, the feeding granularity of the ball mill in the step 1 is required to be 12.5mm of the particle size P80 of limestone particles.
Wherein, the sorting requirement of the hydrocyclone is that the particle size P80 of limestone particles is 0.15 mm.
And (3) adding a flocculating agent during concentration by the rake concentrator in the step (7) to accelerate the coagulation of solid particles.
(III) advantageous effects
Compared with the prior art, the invention has the following beneficial effects: according to the method for the full-flow uninterrupted neutralization, the limestone is crushed and ball-milled, the neutralization reaction interface is enlarged, compared with the traditional neutralization method, the utilization rate of the limestone is improved, meanwhile, the pH value is monitored on line, free acid in a system is neutralized accurately, ferric iron precipitation is reduced, the consumption of the limestone is reduced, the amount of neutralization slag is reduced, and the loss caused by copper entrained by ferric hydroxide colloid is reduced.
Drawings
FIG. 1 is a flow chart of the method of the present invention.
Detailed Description
In order to make the objects, contents, and advantages of the present invention clearer, the following detailed description of the embodiments of the present invention will be made in conjunction with the accompanying drawings and examples.
A method for regulating and controlling the acidity of a solution in a secondary copper sulfide ore heap leaching system comprises the following steps:
step 1: limestone is crushed in a first section and a second section until the requirement of the granularity of the feed of the ball mill is met;
step 2: after the crushed limestone particles are buffered by a storage bin, the limestone particles are uniformly fed into a ball mill through a spiral feeder;
step 3, continuing ball milling the broken limestone particles until the particle size meets the sorting requirement of the hydrocyclone, adding water into the ball mill, and adjusting the concentration of limestone pulp to 15-30%;
and 4, step 4: pumping the limestone pulp subjected to ball milling to a hydrocyclone through a delivery pump for sorting, returning the coarse-fraction limestone pulp to a ball mill for continuous ball milling, and pumping the fine-fraction limestone pulp to a stirring tank;
and 5: pumping the stirred limestone ore pulp and raffinate discharged from the second-stage extraction tank to a neutralization reaction tank through a liquid continuous stirrer, so that the acid content in the raffinate participating in the reaction is matched with the limestone content;
step 6: monitoring the pH value in real time through an online pH meter, and automatically interlocking and starting a slurry delivery pump when the pH value of a solution in a neutralization reaction tank is 1.2-1.5;
and 7: and (4) pumping the slurry obtained after the neutralization reaction in the step (6) to a rake thickener through a slurry delivery pump, discharging the liquid solution after overflowing to a raffinate pool, and discharging the solid neutralized slag to a heap leaching field in a dispersed mode.
Wherein, the feeding granularity of the ball mill in the step 1 is required to be 12.5mm of the particle size P80 of limestone particles.
Wherein, the sorting requirement of the hydrocyclone is that the particle size P80 of limestone particles is 0.15 mm.
And (3) adding a flocculating agent during concentration by the rake concentrator in the step (7) to accelerate the coagulation of solid particles.
Example 1
Copper sulfate and sulfuric acid with CaCO3The reaction equation is shown below (with quicklime CaO, slaked lime Ca (OH)2The same theory of reaction, but no obvious CO2Production):
CaCO3+H2SO4+H2O→CaSO4·2H2O+CO2
Fe2(SO4)3+3CaCO3+5H2O→3CaSO4·2H2O+Fe(OH)3+3CO2
HSO4 -and HCO3 -Possibly as an intermediate product, while the fe (iii) hydrolysis precipitation and the vanadium-forming precipitation also reduce the fe (iii) concentration in the solution.
1mol of calcium carbonate consumes 1mol of acid, i.e. 100g of calcium carbonate consumes 98g of sulfuric acid.
3mol of calcium carbonate consumes 2mol of Fe (III), i.e. 300g of calcium carbonate consumes 112g of Fe (III).
From the above equation, it follows: (1) the calcium carbonate required to neutralize fe (iii) per unit mass is about 2.6 times as much as the sulfuric acid per unit mass, which greatly increases the cost of neutralization;
(2) the amount of neutralization slag generated per mole of Fe (III) is about 2 times as much as that of sulfuric acid, and Fe (OH) is generated3The copper is always in colloid state, and a large amount of solution is taken away during precipitation, so that the copper loss is greatly increased;
(3) fe (III) can be helpful for chalcocite leaching to a certain extent, and the great reduction of the concentration of Fe (III) can cause adverse effect on the leaching rate;
(4) with the increase of the pH value of the system after neutralization, part of Fe (III) can precipitate in the interior of a storage yard, and Fe (III) reaches a certain equilibrium concentration;
(5) the effect of Fe (III) on the electrodeposition efficiency can be reduced by washing in the extraction-electrodeposition scheme.
Due to H2SO4Compared with Fe2(SO4)3Has stronger reactivity, so CaCO is in the system3Will take precedence over H2SO4Carrying out reaction; because the pH value of Fe (III) precipitation is related to the concentration, the concentration of Fe (III) in the system is higher, and the concentration is inevitable and part of CaCO3The reaction often occurs when the pH value reaches about 1.7, and the precipitation is complete when the pH value reaches about 3.0.
Therefore, the amount of calcium carbonate required by the neutralization reaction can be calculated, the amount of calcium carbonate participating in the reaction and the pH value of the feed liquid after the neutralization reaction can be controlled, and the pH value of the reaction can be adjusted to accurately regulate and control Fe (III) precipitation. Therefore, the method only treats free acid in the solution of the heap leaching system.
The copper concentration is high, and the formation of gypsum can cause large copper loss; gypsum precipitates in the first-stage extraction tank E1 and the second-stage extraction tank E2, and particularly the second-stage extraction tank E2 is high in temperature, so that the solubility of gypsum is reduced, entrainment is increased, and subsequent extraction is influenced.
In the burma certain secondary copper sulfide ore project, cathode copper is produced by adopting a 'biological heap leaching-extraction-electrodeposition' process, in the initial production stage, because a sulfuric acid adding starting mode is adopted when the ore to be piled is started to spray, and the ore to be piled mainly takes low-clay hard ore, the percolation performance is good, the system can produce acid only, the acidity of the spray liquid reaches 15gpl in one year, the iron concentration reaches 20gpl, the iron concentration is rapidly improved, and the production efficiency of an extraction electrodeposition workshop is influenced. In order to reduce the iron concentration of the system and ensure the efficient operation of the electrowinning extraction plant, the project starts to start a neutralization plant to neutralize the raffinate, and the neutralization plant actually operates for 12 months. Historical monthly throughput averages 3000 neutralization raffinates per day and 90000 neutralization raffinates per month. The average acid concentration before raffinate neutralization was 13.09gpl and the average acid concentration after neutralization was 1.42 gpl. The comparison of the monthly neutralization treatment capacity with the same loss rate shows that the copper loss rate is in negative correlation with the neutralization treatment capacity, the monthly treatment capacity exceeds ten thousand squares, and the copper loss rate is about 10 percent. The total iron concentration before and after neutralization was essentially unchanged, only the acid was neutralized. A total of 1.49 million tons limestone and 1.18 million tons of neutralized acid were consumed during the operation of the neutralization plant, with an average 1.26 kg limestone for neutralization per kg of acid, an average solids percentage of the lime slurry of 15.85%, resulting in 3.06 kg of neutralized slag (67.31% moisture), which contains an average of 0.45% copper. The neutralization raffinate 111.35 ten thousand squares was accumulated during the operation, and limestone (CaCO3) was consumed by 1.49 ten thousand tons to generate 3.24 ten thousand tons of neutralization slag. Along with the change of the properties of the ores piled on the heap, the acidity of the heap leaching system is reduced due to the massive piling of clay ores, and the average acidity of intermediate liquid in the system is reduced to 7.3gpl after the neutralization workshop runs for one year, so that the operation of the neutralization workshop is stopped.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (4)
1. A method for regulating and controlling the acidity of a solution in a secondary copper sulfide ore heap leaching system is characterized by comprising the following steps of:
step 1: limestone is crushed in a first section and a second section until the requirement of the granularity of the feed of the ball mill is met;
step 2: after the crushed limestone particles are buffered by a storage bin, the limestone particles are uniformly fed into a ball mill through a spiral feeder;
step 3, continuing ball milling the broken limestone particles until the particle size meets the sorting requirement of the hydrocyclone, adding water into the ball mill, and adjusting the concentration of limestone pulp to 15-30%;
and 4, step 4: pumping the limestone pulp subjected to ball milling to a hydrocyclone through a delivery pump for sorting, returning the coarse-fraction limestone pulp to a ball mill for continuous ball milling, and pumping the fine-fraction limestone pulp to a stirring tank;
and 5: pumping the stirred limestone ore pulp and raffinate discharged from the second-stage extraction tank to a neutralization reaction tank through a liquid continuous stirrer, so that the acid content in the raffinate participating in the reaction is matched with the limestone content;
step 6: monitoring the pH value in real time through an online pH meter, and automatically interlocking and starting a slurry delivery pump when the pH value of a solution in a neutralization reaction tank is 1.2-1.5;
and 7: and (4) pumping the slurry obtained after the neutralization reaction in the step (6) to a rake thickener through a slurry delivery pump, discharging the liquid solution after overflowing to a raffinate pool, and discharging the solid neutralized slag to a heap leaching field in a dispersed mode.
2. The method for regulating the acidity of a solution in a secondary copper sulfide ore heap leaching system as claimed in claim 1, wherein the feed particle size requirement of the ball mill in step 1 is limestone particle size P80-12.5 mm.
3. The method for regulating the acidity of a solution in a secondary copper sulfide ore heap leaching system as claimed in claim 1 wherein the hydrocyclone classification requirement is that the limestone particle size P80 be 0.15 mm.
4. The method for regulating the acidity of a solution in a secondary copper sulfide ore heap leaching system as claimed in claim 1, wherein a flocculating agent is added to accelerate the coagulation of solid particles during the concentration in the rake thickener in step 7.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060188427A1 (en) * | 2005-02-04 | 2006-08-24 | Kappes Daniel W | Apparatus and methods for reaction of limestone with sulfate solution |
| US20100120104A1 (en) * | 2008-11-06 | 2010-05-13 | John Stuart Reed | Biological and chemical process utilizing chemoautotrophic microorganisms for the chemosythetic fixation of carbon dioxide and/or other inorganic carbon sources into organic compounds, and the generation of additional useful products |
| CN101715493A (en) * | 2007-05-18 | 2010-05-26 | 塞瑟尔有限公司 | Process for precious metal recovery from a sulphide ore or concentrate or other feed material |
| CN107354298A (en) * | 2017-07-03 | 2017-11-17 | 紫金矿业集团股份有限公司 | A kind of method of copper sulfide mineral biological heap leaching system regulation and control acid and iron |
| CN107858531A (en) * | 2017-12-01 | 2018-03-30 | 云南驰宏资源综合利用有限公司 | A kind of high-arsenic antimony thick bismuth improves the method and device of bismuth direct yield when refining |
| CN207266826U (en) * | 2017-08-14 | 2018-04-24 | 华电电力科学研究院 | A kind of slurries system of agstone slurrying |
-
2021
- 2021-12-14 CN CN202111529532.0A patent/CN114277259A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060188427A1 (en) * | 2005-02-04 | 2006-08-24 | Kappes Daniel W | Apparatus and methods for reaction of limestone with sulfate solution |
| CN101715493A (en) * | 2007-05-18 | 2010-05-26 | 塞瑟尔有限公司 | Process for precious metal recovery from a sulphide ore or concentrate or other feed material |
| US20100120104A1 (en) * | 2008-11-06 | 2010-05-13 | John Stuart Reed | Biological and chemical process utilizing chemoautotrophic microorganisms for the chemosythetic fixation of carbon dioxide and/or other inorganic carbon sources into organic compounds, and the generation of additional useful products |
| CN107354298A (en) * | 2017-07-03 | 2017-11-17 | 紫金矿业集团股份有限公司 | A kind of method of copper sulfide mineral biological heap leaching system regulation and control acid and iron |
| CN207266826U (en) * | 2017-08-14 | 2018-04-24 | 华电电力科学研究院 | A kind of slurries system of agstone slurrying |
| CN107858531A (en) * | 2017-12-01 | 2018-03-30 | 云南驰宏资源综合利用有限公司 | A kind of high-arsenic antimony thick bismuth improves the method and device of bismuth direct yield when refining |
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