CN1026335C - Hydrometallurgical method for recovering copper from copper oxide ore - Google Patents

Hydrometallurgical method for recovering copper from copper oxide ore Download PDF

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CN1026335C
CN1026335C CN92101545A CN92101545A CN1026335C CN 1026335 C CN1026335 C CN 1026335C CN 92101545 A CN92101545 A CN 92101545A CN 92101545 A CN92101545 A CN 92101545A CN 1026335 C CN1026335 C CN 1026335C
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copper
leaching
extraction
oxide ore
copper oxide
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CN1076494A (en
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尹才硚
蒋训雄
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Beijing General Research Institute of Mining and Metallurgy
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Beijing General Research Institute of Mining and Metallurgy
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    • 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
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Abstract

The invention relates to a hydrometallurgical method for recovering copper from copper oxide ores. It is characterized by adopting NH3-NH4F (or NH)3-NH4HF2) The new technology as leaching agent system replaces the traditional ammonia leaching method NH3-(NH4)CO3Or NH3-(NH4)2SO4The present high-temp. reduction roasting-normal-pressure ammonia leaching is changed into direct normal-pressure ammonia leaching, which is combined with extraction and electrowinning to form a new technological process for treating said ore. The method has the characteristics of short flow, simple and convenient operation, low energy consumption, short leaching time, high leaching rate and the like, can be used for selectively recovering copper from copper oxide ores, and is particularly suitable for treating copper-containing oresRefractory copper oxide ore with high alkaline gangue.

Description

Metallurgical method for recovering copper from copper oxide ore by wet process
The present invention relates to from copper oxide ore, reclaim the warm therapy metallurgical technology of copper, particularly from copper oxide ore, optionally leach the extract technology of copper.The present invention can be used for reclaiming copper from copper oxide ore.Be particularly suited for handling and contain the high copper oxide ore of basic gangue.
Copper oxide ore also is being mingled with a small amount of secondary copper sulfide and chalcopyrite usually by free copper oxide (also claim free cupric oxide), forms in conjunction with cupric oxide, and wherein free copper oxide leaches easily, in conjunction with cupric oxide and the difficult leaching of cupric sulfide.The gangue of copper oxide ore also divides two classes, and a class is a basic gangue, and as calcite, rhombspar etc., another kind of is acid gangue, as quartz.The Wet-process metallurgy method of handling copper oxide ore both at home and abroad is divided into pickling process and ammonia leaching process, and wherein ammonia leaching process is divided into reducing roasting-normal pressure ammonia leaching process and pressure ammonia leaching method again.That ammonia leaching process has is good to selective copper, the leach liquor foreign matter content is few, and that leaching agent consumes is low, advantage such as etching apparatus not.It is reducing roasting one normal pressure ammonia leaching-extraction-electrodeposition that the main at present ammonia that adopts soaks the principle technical process, be about under 700～780 ℃ condition, the copper oxide reduction in the ore be become metallic copper behind the grinde ore, then calcining sneaked into by the amount of certain liquid-solid ratio NH is housed with reductive agent 3-(NH 4) 2CO 3In the leaching vat of leaching agent, carry out normal pressure and leached 2～4 hours under the air agitation condition, through liquid-solid separation, get filter residue (discarding) and copper-containing solution, cupric liquid is through extracting to such an extent that purified cupric rich solution send electrodeposition to get metallic copper again.This reducing roasting one normal pressure ammonia soaks the method that reclaims copper, needs through the prereduction of high temperature pyrogenic process, and the energy consumption height, facility investment is big, and is especially when handling the low-grade refractory copper oxide ore, difficult to keep a foothold economically.
The objective of the invention is to seek that a kind of technical process is short, energy consumption is low, the Wet-process metallurgy method of the processing cupric oxide ore of reduced investment, particularly to containing the Wet-process metallurgy method of the refractory copper oxide ore that copper grade is low, basic gangue content is high.
Fig. 1 is a method technological process block-diagram of the present invention.
The invention is characterized in cupric oxide ore is adopted NH3-NH 4F or NH3-NH 4HF 2The leachate that (or other fluoride salt such as NaF, KF etc.) are made into carries out direct normal pressure ammonia and soaks, and consists of the method that reclaims copper with extraction, electrodeposition operation. Steep cencentration can be controlled [NH3]/[F -]=30/17.5～90/52.5(grams per liter). Optium concentration is [NH3]/[F -]=60/35(grams per liter).
Technical process of the present invention is earlier the cupric oxide ore fragmentation to be finely ground to-0.074 millimeter to account for more than 75%, and under condition of normal pressure, 20～50 ℃ of temperature are with NH then 3+ NH 4F(or NH 3+ NH 4HF 2) solution makes leaching agent, its concentration [NH 3]/[F -]=30/17.5～90/52.5(grams per liter), optimum concn [NH 3]/[F -]=60/35(grams per liter), liquid-solid ratio is 1.5: 1～2: 1, leaches in airtight container for stirring, after 0.5～1.5 hour, carries out liquid-solid separation, and slag discards, and keeps its leach liquor.Then with LIX54(or other copper extractants) make extraction agent, kerosene is made thinner and is formed organic phase, in extractor with the selective copper in the leach liquor be extracted on the organic phase, be rich in NH 3+ NH 4F(or NH 3+ NH 4HF 2) raffinate turn back to the leaching system again and recycle the organic phase H of load copper as leaching agent 2SO 4Solution is made strippant, in stripper copper is entered the anti-stripping agent under organic phase is stripped, and obtains to be rich in the purified copper sulfate strip liquor of copper, and organic phase is returned again and made extraction agent.Strip liquor is carried out conventional insoluble anode electrolysis (being electrodeposition method), and its electrodeposition process condition is identical with existing factory, makes high-quality electro deposited copper behind the electrodeposition, is rich in the vitriolic electric effusion that gives up and returns and make strippant.Three reagent closed cycle systems are arranged in technical process of the present invention, reagent can be used on stream again and again repeatedly, thereby both reduced the reagent consumption of technology, reduced the pollution of producing again to surrounding environment, reagent loss in the process gives quantitative replenishing respectively in each recycle system.
Method of the present invention is owing to adopted NH 3-NH 4F or NH 3-NH 4HF 2Make the leaching system of leaching agent, replaced traditional NH 3-(NH 4) 2CO 3Or NH 3-(NH 4) 2SO 4The leaching system of leaching agent has realized reclaiming the target that copper adopts direct normal pressure ammonia to soak from copper oxide ore.Compare with traditional reducing roasting-normal pressure ammonia leaching-extraction-electrodeposition process flow process, saved high temperature fire reduction calcining process, have that technical process is short, easy and simple to handle, energy consumption is low, reduced investment, be easy to realize characteristics such as suitability for industrialized production.
Example: raw material is certain copper oxide ore of China, its main chemical constitution (%): Cu0.58, Fe3.75, Mn0.25, S0.085, Al 2O 31.32, CaO24.74, MgO15.42, SiO 218.05.The thing phase composite (%) of copper: free copper oxide 46.73, in conjunction with cupric oxide 28.04, secondary copper sulfide 20.56, chalcopyrite 4.67.
Leach
Processing condition: raw material granularity-0.074 millimeter accounts for 90%, the leaching agent system is NH 3-NH 4HF 2, [NH 3]/[F -]=60/35(grams per liter) Gu, normal pressure, 30 ℃, 50 ℃ of temperature, liquid /=2/1(milliliter/gram), 1 hour time.
Operation steps: take by weighing test portion (being raw material) 100 gram earlier and pour preprepared 500 millimeters into and add a cover in the there-necked flask, subsequently there-necked flask is inserted in the thermostat water bath, load onto agitator, take by weighing purity then and be 98% ammonium bifluoride (NH 4HF 2) 10.6 grams, to measure concentration be that 25% 39 milliliters of strong aquas, water (ordinary tap water) are poured in the flask respectively for 155 milliliters, starting agitator stirs, about 300 rev/mins of stirring velocity, and clock immediately, take out after one hour and filter, filtrate is measured with graduated cylinder, and filter residue filters with 100～200 ml water drip washing, washing lotion also with the graduated cylinder metering, is sent to chemical analysis together with filtrate and washing lotion after filter residue oven dry, weighing, the division and is measured copper content.
Leach the result: the leaching yield of copper is 81.38% under 30 ℃ of temperature, be 84.49% under 50 ℃ of temperature.
Extraction
Processing condition: leach liquor contains the Cu=2.4 grams per liter, and organic phase is formed 10%(V/V) LIX54+260# solvent kerosene, compare O/A=1/1, secondary, room temperature, mixing time 6 minutes.
The percentage extraction of copper is more than 99%, and raffinate contains the Cu=0.005 grams per liter
Strip
Processing condition: load organic phases contains the Cu=2.4 grams per liter, and strippant is the electrodeposition waste liquid, contains H 2SO 4150 grams per liters, contain the Cu35 grams per liter, compare O/A=5/1, secondary, mixing time 5 minutes, room temperature,
The stripping rate of copper is 99%
Electrodeposition
Processing condition: the electrode materials anode is that Pb-Sb alloy sheets, anode are that stainless steel plate (SUS316), electric effusion are anti-stripping agent, 2 volts of bath voltages, current density 200 peace/rice 2, room temperature.
The electrodeposition rate of recovery of copper more than 99%, current efficiency 98%, electrolytic copper purity 99.95% reach the quality of one-level copper.

Claims (2)

1, a kind of extraction, electrodeposition operation of comprising handled the Wet-process metallurgy method that copper oxide ore reclaims copper, and its inventive features is cupric oxide ore is adopted NH 3-NH 4E or NH 3-NH 4HF 2The leach liquor that (or other fluorochemical salt such as NaF, KF etc.) are made into carries out direct normal pressure ammonia and soaks, and constitutes the method that reclaims copper with extraction, electrodeposition operation.
2, method according to claim 1, its normal pressure ammonia soaking technology condition is:
A. the leaching agent concentration of Cai Yonging is [NH 3]/[F -]=30/17.5～90/52.5(grams per liter), optimum concn [NH 3]/[F -]=60/35(grams per liter);
B. ore grain size accounts for more than 75% for-0.074 millimeter;
C. liquid-solid ratio is 1.5: 1～2: 1;
D. extraction time is 0.5～1.5 hour;
E. extraction temperature is 20～50 ℃;
F. stirring intensity requires the pulp solids particle to be even suspension flow state.
CN92101545A 1992-03-13 1992-03-13 Hydrometallurgical method for recovering copper from copper oxide ore Expired - Fee Related CN1026335C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN92101545A CN1026335C (en) 1992-03-13 1992-03-13 Hydrometallurgical method for recovering copper from copper oxide ore

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Application Number Priority Date Filing Date Title
CN92101545A CN1026335C (en) 1992-03-13 1992-03-13 Hydrometallurgical method for recovering copper from copper oxide ore

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CN1076494A CN1076494A (en) 1993-09-22
CN1026335C true CN1026335C (en) 1994-10-26

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1047800C (en) * 1997-03-23 1999-12-29 尹国宗 Simple method and apparatus for obtaining Cu, Ni and Co from ore by wet metallurgy
CN100342042C (en) * 2002-08-15 2007-10-10 北京有色金属研究总院 Acid balance method in biometallugical process
CN101812587B (en) * 2010-04-09 2011-11-30 紫金矿业集团股份有限公司 Wet method lixiviating method for copper-contained tailings
CN102021325B (en) * 2010-12-14 2012-07-04 深圳市格林美高新技术股份有限公司 Method for respectively leaching copper and cobalt from copper and cobalt concentrate
CN102534658B (en) * 2012-03-01 2014-07-23 崔海林 Method for preparing electrolytic copper fast with copper ore
CN105018724A (en) * 2014-04-30 2015-11-04 天津开发区均诚纸业有限公司 Copper ore processing technology
CN104862478B (en) * 2015-05-13 2017-01-11 广州市吉池环保科技有限公司 Regeneration method of waste extraction agent for alkaline solution copper extraction and application thereof
CN106399698A (en) * 2016-10-27 2017-02-15 北京科技大学 Method for recovering copper and aluminum from copper clad aluminum bar processing waste

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