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CN113088690A - Method for stirring and leaching high-alkaline gangue low-grade copper oxide ore - Google Patents

Method for stirring and leaching high-alkaline gangue low-grade copper oxide ore Download PDF

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CN113088690A
CN113088690A CN202110359960.7A CN202110359960A CN113088690A CN 113088690 A CN113088690 A CN 113088690A CN 202110359960 A CN202110359960 A CN 202110359960A CN 113088690 A CN113088690 A CN 113088690A
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leaching
copper oxide
oxide ore
edta
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肖发新
彭宇
张亚博
李康博
孙树臣
涂赣峰
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Northeastern University China
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
    • C22B3/1608—Leaching with acyclic or carbocyclic agents
    • C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

本发明提供一种高碱性脉石低品位氧化铜矿搅拌浸出的方法，该矿物中钙、镁所形成的碱性脉石约占矿石中总矿物的15％～55％，普遍存在含钙镁高、氧化率高、泥含量高及品位低的“三高一低”特征，是一种典型的难处理氧化铜矿。难以采用常规酸浸工艺及浮选富集，氨浸搅拌浸出是目前工业上实现该铜矿资源回收的主要方法。然而，生产实践表明，该方法存在着氨水浓度高、作业环境差、浸出时间长、设备维修比较困难、管道腐蚀比较严重的问题。本发明提供一种含EDTA或EDTA盐的水溶液搅拌浸出高碱性脉石低品位氧化铜矿的方法，浸出过程对环境友好，操作简便、且铜浸出率高，具有广阔的应用前景。The invention provides a method for stirring and leaching high alkaline gangue low-grade copper oxide ore. The alkaline gangue formed by calcium and magnesium in the mineral accounts for about 15% to 55% of the total minerals in the ore. It is a typical refractory copper oxide ore with the "three highs and one low" characteristics of high magnesium, high oxidation rate, high mud content and low grade. It is difficult to adopt conventional acid leaching process and flotation enrichment. Ammonia leaching and stirring leaching are the main methods to realize the recovery of copper ore resources in industry. However, production practice shows that this method has the problems of high ammonia concentration, poor working environment, long leaching time, difficult equipment maintenance and serious pipeline corrosion. The invention provides a method for stirring and leaching high-alkaline gangue low-grade copper oxide ore with an aqueous solution containing EDTA or EDTA salt.

Description

Method for stirring and leaching high-alkaline gangue low-grade copper oxide ore
Technical Field
The invention belongs to the technical field of ore dressing metallurgy, and relates to a method for stirring and leaching high-alkaline gangue low-grade copper oxide ore.
Background
The global copper oxide ore accounts for more than 10% of the basic reserves of the world copper ore resources, 25% of the total annual copper metal yield is extracted from the copper oxide ore, the proportion of the copper oxide ore is also increased year by year, the upper parts of most of copper ore deposits in China are covered with oxidation zones, meanwhile, a considerable number of independent large and medium copper oxide ore deposits are also arranged, the copper oxide ore accounts for more than 25% of the copper ore resources in China, and the copper oxide ore is recycled as the copper sulfide resources are continuously depleted and depleted, so that the copper oxide ore is one of the important subjects of mineral dressing and metallurgy work.
The high-alkaline gangue type low-grade copper oxide ore is a typical copper oxide ore and is mainly distributed in Congo (gold), Zanbia and the like in foreign aspects; the domestic distribution is mainly in areas such as Xinjiang, Yunnan, Sichuan and inner Mongolia, for example: yunnan Dongchuan copper oxide ore, Sichuan Leshan copper oxide ore and sandstone copper oxide ore in Xinjiang region.
The high-alkaline gangue low-grade copper oxide ore generally has the characteristics of high calcium and magnesium content, high oxidation rate, high mud content and low grade, namely three highs and one lowness. The copper in the ore is low in grade and is mixed with various metals, such as: the calcium, magnesium, aluminum and other impurity metals, wherein the alkaline gangue formed by the calcium and the magnesium accounts for about 15 to 55 percent of the total minerals in the ore, and is the main reason of high alkalinity of the ore. The minerals in the ore are mainly oxides, and the oxidation rate of the ore is high, such as: about 60% of ores of the Dongchuan Toudan copper oxide ore are oxidized, mainly free copper oxide, and about 20% of combined copper oxide in the ores. In addition, the raw ore contains a certain proportion of copper sulfide ore, mainly secondary copper sulfide ore and hardly contains primary copper sulfide ore. The oxide minerals mainly comprise malachite, cuprite and chalcopyrite; copper sulphide ores are mainly chalcocite and copper blue. The mineral embedded particle size is very fine, the mineral with the particle diameter less than 40 mu m accounts for about 40 percent of the total amount of the mineral, wherein the minimum particle size can reach 0.7-2.5 mu m, and the fine particles are embedded in the high-calcium magnesium basic gangue to cause the structure of the mineral to be extremely complicated. In addition, the deposit size is small, which is not beneficial to large-scale mining.
The high-alkaline gangue copper oxide ore is a typical refractory copper oxide ore due to the inherent characteristics of 'three high and one low'. The traditional copper oxide ore treatment methods are acid leaching, flotation and ammonia leaching. However, if the conventional acid leaching process is adopted for the mineral, the acid consumption is high, the economic benefit is low, a large amount of calcium sulfate generated in the leaching process is adsorbed on a mineral pile to cause hardening, and the subsequent solution permeation effect is seriously deteriorated. If a direct flotation method is adopted, the consumption of an activating agent in the flotation process is increased, in addition, the sorting is extremely unfavorable due to the embedded granularity of superfine minerals and the complex ore structure, most of malachite and pinto pumice which are absolutely dominant in quantity in copper minerals are embedded in gangue by the superfine particles, and the grinding fineness of the copper minerals cannot be separated by monomers, so that the ore treatment is difficult. Meanwhile, for the high-alkaline gangue type low-grade copper oxide ore, the recovery difficulty of the sulfuration flotation is higher. When the ammonia leaching method is used for treating the minerals, metals such as calcium, magnesium and the like can be effectively prevented from being mixed into the solution, and meanwhile, the stable complex ions generated by copper and ammonia in the minerals are guaranteed to be immersed into the solution. Therefore, ammonia leaching agitation leaching is the main method for industrially realizing the recovery of the copper ore resource at present.
However, ammonia leaching stirring production practices show that the method has the problems of high ammonia water concentration, poor working environment, long leaching time, difficult equipment maintenance and severe pipeline corrosion, and the ammonia leaching process needs to be carried out in a closed container to reduce ammonia consumption and environmental pollution, so that the requirement on equipment is high; if high temperature leaching is used, the pressure of the reaction system must be increased to increase the ammonia concentration in the leachate. Therefore, the research on the novel environment-friendly high-alkalinity low-grade copper oxide ore agitation leaching technology has important significance for the high-efficiency utilization of the copper ore resource.
Disclosure of Invention
The invention aims to provide a stirring leaching method for high-alkaline gangue low-grade copper oxide ore with high calcium and magnesium content, fine ore granularity and high oxidation rate based on the defects of the prior treatment technology. In the scheme, the aqueous solution containing EDTA or EDTA salt is used for stirring and leaching the high-alkaline gangue low-grade copper oxide ore, no irritant gas is emitted in the experimental process, the environment is friendly, the airtight operation is not needed, the operation is simple and convenient, and the high-alkaline gangue low-grade copper oxide ore is effectively recycled.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for stirring and leaching high-alkaline gangue low-grade copper oxide ore comprises the following steps:
(1) grinding: crushing and grinding the copper oxide ore;
(2) preparing a leaching agent: dissolving EDTA or EDTA salt in water as leaching agent;
(3) leaching: mixing the EDTA or EDTA salt solution prepared in the step (2) with the copper oxide ore powder ground in the step (1), and stirring;
(4) and (3) filtering: and (4) filtering and separating the copper oxide ore powder leached in the step (3) to obtain a filtrate, namely the copper leaching solution.
Furthermore, in the high-alkaline gangue low-grade copper oxide ore, the mass fraction of alkaline gangue formed by calcium and magnesium in the total ore minerals is 15-55% (the content of CaO and MgO), and the mass fraction of copper in the total ore minerals is 0.4-2.7%.
Furthermore, in the step (1), after the copper oxide ore is ground, the powder with the granularity of 80 μm accounts for more than 90% of the total mass of the powder.
In the step (2), the EDTA salt is one of disodium ethylenediaminetetraacetate (edta.2 Na), tetrasodium ethylenediaminetetraacetate (edta.4 Na) and dipotassium ethylenediaminetetraacetate (edta.2K), preferably edta.2 Na.
Further, in the step (2), the molar concentration of EDTA or EDTA salt is 0.02-1 mol/L, preferably 0.15-0.3 mol/L.
Further, in the step (3), the leaching temperature is 5-90 ℃, and preferably 20-40 ℃.
Further, in the step (3), the liquid-solid volume-to-mass ratio (mL: g) is 1:1 to 10:1, preferably 2:1 to 4: 1.
Further, in the step (3), the stirring speed is 50-1000 r/min, preferably 200-400 r/min.
Further, in the step (3), the leaching time is 0.5-10 hours, preferably 1-4 hours.
The adopted ethylene diamine tetraacetic acid and salts thereof (EDTA and EDTA salt for short) are a wide ammonia-hydroxyl complex, are easy to dissolve in water, can easily form a complex with copper ions, and are environment-friendly; after EDTA and EDTA salt are dissolved in water, the pH value of the solution is about 4.5, and the solution is weakly acidic. Therefore, the invention adopts the aqueous solution containing EDTA and EDTA salt to leach the high-alkalinity low-grade copper oxide ore.
The reaction equation which may occur in the process of leaching the high-alkaline low-grade copper oxide ore by EDTA is as follows:
malachite leaching reaction:
Cu2(OH)2CO3+2C10H14N2Na2O8＝2C10H12CuN2Na2O8+CO2↑+3H2O (1)
and (3) carrying out copper blue ore leaching reaction:
Cu3(CO3)2(OH)2+3C10H14N2Na2O8＝3C10H12CuN2Na2O8+2CO2↑+4H2O (2)
copper hematite leaching reaction:
Figure BDA0003005146260000031
leaching reaction of chalcocite:
Figure BDA0003005146260000032
copper blue leaching reaction:
Figure BDA0003005146260000033
compared with the prior art, the invention has the beneficial effects that: the invention provides a method for leaching high-alkalinity gangue low-grade copper oxide ore by aqueous solution containing EDTA or EDTA salt. The whole operation can be carried out at room temperature, no sealing is needed, no irritant gas is generated, and the method has the characteristics of environmental friendliness, simplicity and convenience in operation, high copper leaching rate and wide application prospect.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The copper oxide ore comprises the following components in percentage by mass: SiO 2256.12％，CaO 18.38％，MgO 11.67％，A12O38.52％，Fe2O31.39%, CuO 1.28%, and the other 2.64%.
Drying and crushing copper oxide ore, grinding until the powder with the granularity of 80 mu m accounts for more than 90 percent of the total mass of the powder, weighing 50g of copper oxide ore powder, placing the copper oxide ore powder into a three-mouth flask, adding 0.1mol/L EDTA & 2Na aqueous solution, uniformly mixing, stirring and leaching under the conditions of stirring speed of 200r/min, reaction temperature of 25 ℃ and liquid-solid volume-mass ratio (mL: g) of 5:1, filtering after 2h to obtain leachate, and detecting the copper content in the leachate.
By the process, the leaching rate of the obtained copper is 82.7%.
Example 2
The copper oxide ore comprises the following components in percentage by mass: SiO 2256.12％，CaO 18.38％，MgO 11.67％，A12O38.52％，Fe2O31.39%, CuO 1.28%, and the other 2.64%.
Drying and crushing copper oxide ore, grinding until the powder with the granularity of 80 mu m accounts for more than 90 percent of the total mass of the powder, weighing 50g of copper oxide ore powder, placing the copper oxide ore powder into a three-mouth flask, adding 0.2mol/L of EDTA (ethylene diamine tetraacetic acid) aqueous solution, uniformly mixing, stirring and leaching under the conditions that the stirring speed is 400r/min, the reaction temperature is 30 ℃, and the liquid-solid volume-mass ratio (mL: g) is 3:1, filtering after 3 hours to obtain leachate, and detecting the copper content in the leachate.
By the process, the leaching rate of the obtained copper is 86.7%.
Example 3
The copper oxide ore comprises the following components in percentage by mass: SiO 2256.12％，CaO18.38％，MgO 11.67％，A12O38.52％，Fe2O31.39%, CuO 1.28%, and the other 2.64%.
Drying and crushing copper oxide ore, grinding until the powder with the granularity of 80 mu m accounts for more than 90 percent of the total mass of the powder, weighing 50g of copper oxide ore powder, placing the copper oxide ore powder into a three-mouth flask, adding 0.3mol/L EDTA & 2Na aqueous solution, uniformly mixing, stirring and leaching under the conditions of stirring speed of 500r/min, reaction temperature of 50 ℃ and liquid-solid volume-to-mass ratio (mL: g) of 8:1, filtering after 2 hours to obtain leachate, and detecting the copper content in the leachate.
By the process, the leaching rate of the obtained copper is 88.4%.
Example 4
The copper oxide ore comprises the following components in percentage by mass: SiO 2238.87％，CaO28.15％，MgO24.36％，A12O33.43％，Fe2O31.52%, CuO2.08%, and the other 1.59%.
Drying and crushing copper oxide ore, grinding until the powder with the granularity of 80 mu m accounts for more than 90 percent of the total mass of the powder, weighing 50g of copper oxide ore powder, placing the copper oxide ore powder into a three-mouth flask, adding 0.02mol/L EDTA-4 Na aqueous solution, uniformly mixing, stirring and leaching under the conditions of stirring speed of 700r/min, reaction temperature of 5 ℃ and liquid-solid volume-to-mass ratio (mL: g) of 10:1, filtering after 6h to obtain leachate, and detecting the copper content in the leachate.
By the process, the leaching rate of the obtained copper is 75.1%.
Example 5
The copper oxide ore comprises the following components in percentage by mass: SiO 2256.12％，CaO18.38％，MgO11.67％，A12O38.52％，Fe2O31.39%, CuO1.28%, and the other 2.64%.
Drying and crushing copper oxide ore, grinding until the powder with the granularity of 80 mu m accounts for more than 90 percent of the total mass of the powder, weighing 50g of copper oxide ore powder, placing the copper oxide ore powder into a three-mouth flask, adding 0.7mol/L EDTA-2K aqueous solution, uniformly mixing, stirring and leaching under the conditions of stirring speed of 200r/min, reaction temperature of 25 ℃ and liquid-solid volume-to-mass ratio (mL: g) of 1:1, filtering after 0.5h to obtain leachate, and detecting the copper content in the leachate.
By the process, the leaching rate of the obtained copper is 78.4%.
Example 6
The copper oxide ore comprises the following components in percentage by mass: SiO 2256.12％，CaO 18.38％，MgO 11.67％，A12O38.52％，Fe2O31.39%, CuO 1.28%, and the other 2.64%.
Drying and crushing copper oxide ore, grinding until the powder with the granularity of 80 mu m accounts for more than 90 percent of the total mass of the powder, weighing 50g of copper oxide ore powder, placing the copper oxide ore powder into a three-mouth flask, adding 0.5mol/L EDTA & 2Na aqueous solution, uniformly mixing, stirring and leaching under the conditions of stirring speed of 300r/min, reaction temperature of 40 ℃ and liquid-solid volume-to-mass ratio (mL: g) of 3:1, filtering after 4 hours to obtain leachate, and detecting the copper content in the leachate.
By the process, the leaching rate of the obtained copper is 89.6%.
Example 7
The copper oxide ore comprises the following components in percentage by mass: SiO 2267.28％，CaO9.21％，MgO7.49％，A12O38.67％，Fe2O32.78%, CuO0.74%, and the other 3.83%.
Drying and crushing copper oxide ore, grinding until the powder with the granularity of 80 mu m accounts for more than 90 percent of the total mass of the powder, weighing 50g of copper oxide ore powder, placing the copper oxide ore powder into a three-mouth flask, adding 0.12mol/L EDTA & 2Na aqueous solution, uniformly mixing, stirring and leaching under the conditions that the stirring speed is 50r/min, the reaction temperature is 10 ℃, and the liquid-solid volume-mass ratio (mL: g) is 2:1, filtering after 1h to obtain leachate, and detecting the copper content in the leachate.
By the process, the leaching rate of the obtained copper is 74.8%.
Example 8
The copper oxide ore comprises the following components in percentage by mass: SiO 2247.91％，CaO20.73％，MgO18.78％，A12O31.52％，Fe2O33.39%, CuO3.29%, and the other 4.38%.
Drying and crushing copper oxide ore, grinding until the powder with the granularity of 80 mu m accounts for more than 90 percent of the total mass of the powder, weighing 50g of copper oxide ore powder, placing the copper oxide ore powder into a three-mouth flask, adding 1mol/L EDTA & 2Na aqueous solution, uniformly mixing, stirring and leaching under the conditions of stirring speed of 1000r/min, reaction temperature of 90 ℃ and liquid-solid volume-mass ratio (mL: g) of 2:1, filtering after 10 hours to obtain leachate, and detecting the copper content in the leachate.
By the process, the leaching rate of the obtained copper is 96.7%.
Example 9
The copper oxide ore comprises the following components in percentage by mass: SiO 22 47.91％，CaO 20.73％，MgO 18.78％，A12O31.52％，Fe2O33.39%, CuO3.29%, and the other 4.38%.
Drying and crushing copper oxide ore, grinding until the powder with the granularity of 80 mu m accounts for more than 90 percent of the total mass of the powder, weighing 50g of copper oxide ore powder, placing the copper oxide ore powder into a three-mouth flask, adding 0.15mol/L EDTA-2 Na aqueous solution, uniformly mixing, stirring and leaching under the conditions of stirring speed of 300r/min, reaction temperature of 40 ℃ and liquid-solid volume-to-mass ratio (mL: g) of 4:1, filtering after 8 hours to obtain leachate, and detecting the copper content in the leachate.
By the process, the leaching rate of the obtained copper is 95.9%.
Example 10
The copper oxide ore comprises the following components in percentage by mass: SiO 22 47.91％，CaO 20.73％，MgO 18.78％，A12O3 1.52％，Fe2O33.39%, CuO3.29%, and the other 4.38%.
Drying and crushing copper oxide ore, grinding until the powder with the granularity of 80 mu m accounts for more than 90 percent of the total mass of the powder, weighing 50g of copper oxide ore powder, placing the copper oxide ore powder into a three-mouth flask, adding 0.25mol/L EDTA-2 Na aqueous solution, uniformly mixing, stirring and leaching under the conditions of stirring speed of 400r/min, reaction temperature of 40 ℃ and liquid-solid volume-to-mass ratio (mL: g) of 4:1, filtering after 4 hours to obtain leachate, and detecting the copper content in the leachate.
By the process, the leaching rate of the obtained copper is 92.4%.
Example 11
The copper oxide ore comprises the following components in percentage by mass: SiO 22 47.91％，CaO 20.73％，MgO 18.78％，A12O3 1.52％，Fe2O33.39%, CuO3.29%, and the other 4.38%.
Drying and crushing copper oxide ore, grinding until the powder with the granularity of 80 mu m accounts for more than 90 percent of the total mass of the powder, weighing 50g of copper oxide ore powder, placing the copper oxide ore powder into a three-mouth flask, adding 0.15mol/L EDTA & 2Na aqueous solution, uniformly mixing, stirring and leaching under the conditions of stirring speed of 300r/min, reaction temperature of 25 ℃ and liquid-solid volume-mass ratio (mL: g) of 6:1, filtering after 2h to obtain leachate, and detecting the copper content in the leachate.
By the process, the leaching rate of the obtained copper is 89.2%.
Comparative example 1
The copper oxide ore comprises the following components in percentage by mass: SiO 2256.12％，CaO18.38％，MgO11.67％，A12O38.52％，Fe2O31.39%, CuO1.28%, and the other 2.64%.
Drying and crushing copper oxide ore, grinding until the powder with the granularity of 80 mu m accounts for more than 90 percent of the total mass of the powder, weighing 50g of copper oxide ore powder, placing the copper oxide ore powder into a three-neck flask, adding 1.2mol/L ammonia water to 0.6mol/L ammonium sulfate mixed aqueous solution (the ammonia-ammonium ratio is 2:1), uniformly mixing, and stirring and leaching under a closed condition, wherein: stirring at 500r/min, reacting at 50 deg.C, and liquid-solid volume-to-mass ratio (mL: g) of 8:1, filtering for 2 hr to obtain leachate, and detecting copper content in the leachate.
By the process, the leaching rate of the obtained copper is 88.1%.
Comparative example 2
The copper oxide ore comprises the following components in percentage by mass: SiO 22 38.87％，CaO28.15％，MgO24.36％，A12O33.43％，Fe2O31.52%, CuO2.08%, and the other 1.59%.
Drying and crushing copper oxide ore, grinding until the powder with the granularity of 80 mu m accounts for more than 90 percent of the total mass of the powder, weighing 50g of copper oxide ore powder, placing the copper oxide ore powder into a three-neck flask, adding 2mol/L ammonia water to 1.2mol/L ammonium chloride mixed aqueous solution (the ammonia-ammonium ratio is 1:1), uniformly mixing, and stirring and leaching under a closed condition, wherein: stirring at 700r/min, reacting at 5 deg.C, and liquid-solid volume-to-mass ratio (mL: g) of 10:1, filtering for 6 hr to obtain leachate, and detecting copper content in the leachate.
By the process, the leaching rate of the obtained copper is 75.8%.
Comparative example 3
The copper oxide ore comprises the following components in percentage by mass: SiO 2267.28％，CaO9.21％，MgO7.49％，A12O38.67％，Fe2O32.78%, CuO0.74%, and the other 3.83%.
Drying and crushing copper oxide ore, grinding until the powder with the granularity of 80 mu m accounts for more than 90 percent of the total mass of the powder, weighing 50g of copper oxide ore powder, placing the copper oxide ore powder into a three-neck flask, adding 1.2mol/L ammonia water to 0.6mol/L ammonium sulfate mixed aqueous solution (the ammonia-ammonium ratio is 2:1), uniformly mixing, and stirring and leaching under a closed condition, wherein: stirring at 50r/min, reacting at 10 deg.C, and liquid-solid volume-to-mass ratio (mL: g) of 2:1, filtering for 1 hr to obtain leachate, and detecting copper content in the leachate.
By the process, the leaching rate of the obtained copper is 75.3%.
Comparative example 4
The copper oxide ore comprises the following components in percentage by mass: SiO 2247.91％，CaO20.73％，MgO18.78％，A12O31.52％，Fe2O33.39%, CuO3.29%, and the other 4.38%.
Drying and crushing copper oxide ore, grinding until the powder with the granularity of 80 mu m accounts for more than 90 percent of the total mass of the powder, weighing 50g of copper oxide ore powder, placing the copper oxide ore powder into a three-neck flask, adding 1.2mol/L ammonia water and 1.2mol/L ammonium carbonate mixed aqueous solution (the ammonia-ammonium ratio is 1:1), uniformly mixing, and stirring and leaching under a closed condition, wherein: stirring at 300r/min, reacting at 40 deg.C, and liquid-solid volume-to-mass ratio (mL: g) of 4:1, filtering for 8 hr to obtain leachate, and detecting copper content in the leachate.
By the process, the leaching rate of the obtained copper is 95.2%.
According to the embodiments 1-11, the EDTA or EDTA salt aqueous solution is really effective in stirring and leaching the high-alkalinity gangue low-grade copper oxide ore, and the leaching rate is high. Through comparison of the example 3 with the comparative example 1, the example 4 with the comparative example 2, the example 7 with the comparative example 3, and the example 9 with the comparative example 4, for different types of alkaline gangue low-grade copper oxide ores, the copper leaching rate of EDTA or EDTA saline solution agitation leaching is close to that of ammonia leaching, but the EDTA or EDTA saline solution agitation leaching can be operated at room temperature, no pungent odor is generated in the leaching process, the method is environment-friendly, does not need to be carried out under a closed condition, and is simple and convenient to operate, so that the method has a wide application prospect.
The technical idea of the present invention is described in the above technical solutions, and the protection scope of the present invention is not limited thereto, and any changes and modifications made to the above technical solutions according to the technical essence of the present invention belong to the protection scope of the technical solutions of the present invention.

Claims (10)

1. A method for stirring and leaching high-alkaline gangue low-grade copper oxide ore is characterized by comprising the following steps:
(1) grinding: crushing and grinding the copper oxide ore;
(2) preparing a leaching agent: dissolving EDTA or EDTA salt in water as leaching agent;
(3) leaching: mixing the EDTA or EDTA salt solution prepared in the step (2) with the copper oxide ore powder ground in the step (1), and stirring;
(4) and (3) filtering: and (4) filtering and separating the copper oxide ore powder leached in the step (3) to obtain a filtrate, namely the copper leaching solution.
2. The method for agitation leaching of high-alkaline gangue low-grade copper oxide ore according to claim 1, characterized in that in the high-alkaline gangue low-grade copper oxide ore, the mass fraction of alkaline gangue formed by calcium and magnesium in the total ore minerals is 15-55%, and the mass fraction of copper in the total ore minerals is 0.4-2.7%.
3. The method for agitation leaching of high alkaline gangue low grade copper oxide ore according to claim 1, characterized in that in step (1), after grinding of the copper oxide ore, the powder with 80 μm particle size accounts for more than 90% of the total mass of the powder.
4. The method for agitation leaching of high alkaline gangue low grade copper oxide ore according to claim 1, wherein in the step (2), the EDTA salt is one of disodium ethylene diamine tetraacetic acid (EDTA-2 Na), tetrasodium ethylene diamine tetraacetic acid (EDTA-4 Na) and dipotassium ethylene diamine tetraacetic acid (EDTA-2K).
5. The method for agitation leaching of the high alkaline gangue low-grade copper oxide ore according to claim 1, wherein in the step (2), the molar concentration of EDTA or EDTA salt in the leaching agent is 0.02-1 mol/L.
6. The method for agitation leaching of the high alkaline gangue low-grade copper oxide ore according to claim 1, wherein in the step (2), the leaching agent is disodium ethylene diamine tetraacetate (EDTA-2 Na) with a molar concentration of 0.15-0.3 mol/L.
7. The method for agitation leaching of the high-alkaline gangue low-grade copper oxide ore according to claim 1, wherein in the step (3), the leaching temperature is 5-90 ℃, and the liquid-solid volume-to-mass ratio (mL: g) is 1: 1-10: 1.
8. The method for agitation leaching of the high-alkaline gangue low-grade copper oxide ore according to claim 1, wherein in the step (3), the leaching temperature is 20-40 ℃, and the liquid-solid volume-to-mass ratio (mL: g) is 2: 1-4: 1.
9. The method for agitation leaching of the high alkaline gangue low-grade copper oxide ore according to claim 1, wherein in the step (3), the agitation speed is 50-1000 r/min, and the leaching time is 0.5-10 h.
10. The method for agitation leaching of the high alkaline gangue low-grade copper oxide ore according to claim 1, wherein in the step (3), the agitation speed is 200-400 r/min, and the leaching time is 1-4 h.
CN202110359960.7A 2021-04-02 2021-04-02 Method for stirring and leaching high-alkaline gangue low-grade copper oxide ore Pending CN113088690A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634070A (en) * 1969-07-29 1972-01-11 Us Interior Process for recovery of copper and other metals from source materials
US4443268A (en) * 1981-11-12 1984-04-17 The Dow Chemical Company Process for removing copper and copper oxide encrustations from ferrous surfaces
CN1084895A (en) * 1992-09-30 1994-04-06 武汉市冶炼科研所 Process for treating low-grade copper slag or copper oxide ore by ammonia leaching precipitation method
CN1718786A (en) * 2005-07-25 2006-01-11 方建军 Normal temperature normal pressure ammonia infusion-extraction-electrodeposition-slag infusion flotation of copper oxide green ore
CN102600984A (en) * 2012-03-20 2012-07-25 昆明理工大学 Processing method of copper oxide ore containing calcium magnesium gangue
CN109355498A (en) * 2018-11-22 2019-02-19 长春黄金研究院有限公司 A kind of process of low grade copper oxide ore recycling copper
CN111500860A (en) * 2020-04-26 2020-08-07 郑州大学 Process method for recovering copper from low-grade copper oxide ore

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634070A (en) * 1969-07-29 1972-01-11 Us Interior Process for recovery of copper and other metals from source materials
US4443268A (en) * 1981-11-12 1984-04-17 The Dow Chemical Company Process for removing copper and copper oxide encrustations from ferrous surfaces
CN1084895A (en) * 1992-09-30 1994-04-06 武汉市冶炼科研所 Process for treating low-grade copper slag or copper oxide ore by ammonia leaching precipitation method
CN1718786A (en) * 2005-07-25 2006-01-11 方建军 Normal temperature normal pressure ammonia infusion-extraction-electrodeposition-slag infusion flotation of copper oxide green ore
CN102600984A (en) * 2012-03-20 2012-07-25 昆明理工大学 Processing method of copper oxide ore containing calcium magnesium gangue
CN109355498A (en) * 2018-11-22 2019-02-19 长春黄金研究院有限公司 A kind of process of low grade copper oxide ore recycling copper
CN111500860A (en) * 2020-04-26 2020-08-07 郑州大学 Process method for recovering copper from low-grade copper oxide ore

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Application publication date: 20210709