CN102776369A - Iron removing method in process for extracting-electrowinning copper metal by using high-iron and low-copper material liquid - Google Patents

Iron removing method in process for extracting-electrowinning copper metal by using high-iron and low-copper material liquid Download PDF

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Publication number
CN102776369A
CN102776369A CN2012102675623A CN201210267562A CN102776369A CN 102776369 A CN102776369 A CN 102776369A CN 2012102675623 A CN2012102675623 A CN 2012102675623A CN 201210267562 A CN201210267562 A CN 201210267562A CN 102776369 A CN102776369 A CN 102776369A
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copper
iron
organic phase
organic phases
extraction
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张仪
张新普
金正聪
杨德学
孔令洪
陈国清
孙鸿明
甘静
於友清
左志国
王冲
顾尚昆
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YUNNAN DIQING MINING DEVELOP CO Ltd
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YUNNAN DIQING MINING DEVELOP CO Ltd
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Abstract

The invention provides an iron removing method in a process for extracting-electrowinning copper metal by using a high-iron and low-copper material liquid. The method comprises a sulfuric acid heap leaching and stirring leaching step and a step of extracting copper from a leaching solution, and is characterized in that after the copper is extracted, the remaining loaded organic phase is treated by the following steps: the loaded organic phase is added with a washing solution with sulfuric acid content of 8 to 10 g/l, and is stirred and mixed until the content of iron ions in the washing solution is less than 0.5g/l to obtain the loaded organic phase from which iron ions are removed; electric tail washings: the volume ratio of the loaded organic phase from which iron ions are removed is 1:2 to 3, the loaded organic phase is reextracted with the electric tail washings containing 180 to 200g/l sulfuric acid, so that copper ions are enriched in a reextraction solution for producing electro-deposit copper; and the remaining solution is an extractant-containing regenerated organic phase, and then the solution is sent to a primary extraction process for extracting copper. The content of iron ions is reduced by more than 10 times, and simultaneously calcium, magnesium and other impurities are also washed and removed; the quality of electrolysed copper is improved, the situation that lugs of cathode copper do not fall off is ensured, the hidden dangers of solution leaking and electricity leaking caused by damage to an electrowinning tank are eliminated, the washing solution is not discharged, and the environmental protection is favorable.

Description

The method for removing iron of the low copper feed liquid extraction-electrowinning copper process of high ferro
?
Technical field
The present invention relates to the low copper feed liquid extraction-electrodeposition of a kind of high ferro and produce the method for removing iron of metallic copper process, belong to mine special exploitation mode, belong to technical field of wet metallurgy.
Background technology
For Fe 2O 3And the high copper oxide ore of FeO content; In with sulfuric acid dump leaching and agitation leach production process; There is a large amount of iron ions to be entered into feed liquid by leaching; The high ferro feed liquid is carried in the process of copper in extraction, and iron ion can be carried secretly by physics and get in the strip liquor (being electric effusion), causes problems such as the fracture of cathode copper hangers, power consumption rise, electro deposited copper is off quality in the electro deposited copper production process.The copper oxide ore of Deqen in Yunnan Province mining industry electrolytic copper factory and office reason is because Fe in the ore 20 3Content is up to 20～27%, and FeO content reaches 3～5%, and with sulfuric acid dump leaching and agitation leach ore, when producing electro deposited copper, part iron can get in the leach liquor with the form dissolving of ferric sulphate and ferrous sulfate, makes sulphuric leachate contain Cu 2+0.5～1.0g/l, Fe 3+5～10g/l, Fe 2+1～3g/l; When extracting copper, carried secretly and get into strip liquor (electric effusion), and in the electro deposited copper Production Flow Chart, build up rising, cause in the electric effusion iron ion content increasingly high, reach 10～15g/l, have a strong impact on the operation of electrodeposition ordinary production by physics.Especially iron concentration is than the standard max (Fe ≦ 3g/l) exceed 3～5 times of industry permission; Cause the serious copper hangers phenomenon of rupture of appearance in the electrodeposition production process; Current efficiency is seriously on the low side! and ≦ 60%); The electrodeposition power consumption also exceeds more than 2 times than same column criterion (2000kw.h/tcu) and (reaches 4228kw.h/tcu), causes bigger influence for enterprise's electrodeposition production operation and operation control.
Summary of the invention
In order thoroughly to solve bottleneck problems such as above-mentioned cathode copper hangers ruptures, power consumption rises, electro deposited copper is off quality; The present invention provides the low copper feed liquid extraction-electrodeposition of a kind of high ferro to produce the method for removing iron in the metallic copper process; After being applied to production practice, can effectively improve the problem of iron ion influence in the electrolytic copper factory electro deposited copper production process.
Iron ion in electrodeposition flow process source mainly is that organic phase has produced the part feed liquid when ferric ion feed liquid is mixed and carries secretly with containing in the extraction process; After these are carried liquid secretly and get into the reextraction operation with organic phase; Got in the electric effusion by the strip liquor washing, cause iron ion constantly to raise through continuous accumulation.All there is this design defect in traditional extraction, if the iron ion content height will be carried secretly entering electric effusion flow process in the leach liquor.The key of therefore, dealing with problems will be blocked the direct channel that iron ion gets into electric effusion exactly.
The present invention realizes through following technical proposal: the method for removing iron of the low copper feed liquid extraction-electrowinning copper process of a kind of high ferro; It comprises sulfuric acid dump leaching and agitation leach step; Leach liquor is carried out the step of extracting copper, it is characterized in that load organic phases remaining behind the extracting copper is through following processing:
A, in load organic phases, to add sulfuric acid content be the washings of 8～10g/l; Mix iron ion content to washings when being lower than 0.5g/l; Obtain removing the load organic phases of iron ion, washings send and leaches step and use, or sends to laundry and wash collecting tank and recycle as washings;
B, by electric tail washings: load organic phases=1:2～3 volume ratios of removing iron ion; Load organic phases with the removal iron ion of steps A; Strip with containing 180～200g/l vitriolic electricity tail washings; Make the cupric ion enrichment in the strip liquor as the electric effusion of producing electro deposited copper, surplus liquid is the regeneration organic phase that contains extraction agent;
C, with the regeneration organic phase of step B, send the single extraction operation to carry out extracting copper;
D, send the electrodeposition operation, produce electro deposited copper the electric effusion of step B.
The load organic phases that the load organic phases of said steps A produces for the single extraction process, the load organic phases that produces when perhaps behind single extraction, carrying out reextraction again.
The washing of said steps A is in conventional wash trough, to mix washing by what routine was carried out.
Said step B to contain 180～200g/l vitriolic electricity tail washings be the electrodeposition tail washings that produces in the electro deposited copper production process.
The reextraction of said step B is on routine reextraction equipment, the process of mixing phase-splitting.
The extraction of said step C is on conventional extraction equipment, presses the copper leach liquor: organic phase=1:1 volume ratio, the process of mixing phase-splitting.
The electrodeposition of said step D is the copper electrodeposition that on conventional electrodeposition equipment, is undertaken by insoluble anode.
The present invention compared with prior art has advantage and effect: adopt such scheme, the iron ion of carrying secretly in the organic phase is washed separates out, the content that makes iron ion bring electric effusion into has reduced more than 10 times; Other impurity such as calcium, magnesium also are washed and remove simultaneously; Help improving the electrolytic copper quality product, guarantee that the hangers obscission no longer takes place cathode copper, stop the electrodeposition cell body and damage leakage, the electric leakage hidden danger that produces; Guarantee safe production, effectively reduce electrodeposition Workshop Production personnel labor.Washings can return and leach step usefulness again, or recycles as washings, and the washing cost is lower, does not efflux washing composition, environmentally safe.Organic phase can keep certain cleanliness factor for a long time, can accelerate organic phase and water and carry out phase-splitting, reduces the organic phase entrainment loss; Obviously reduce kerosene and extraction agent consumption; Electrodeposition current efficiency can be brought up to more than 90%, and the electrodeposition power consumption can drop to below the 2500kw.h/ ton copper, ton copper economize on electricity 1728kwh; Ton copper reduces cost 1036.8 yuan, and the electrolytic copper production cost obviously reduces.That the present invention drops into is low, technology is simple, easy to operate, de-ironing efficiency is high, cost is low; Be fit to improving and optimizating of all traditional copper extraction; The copper wet method acid immersion technical process high to the raw material iron content, that detrimental impurity content is high can both be suitable for, and guarantees that electro deposited copper production carries out smoothly.
Description of drawings
Fig. 1 is electro deposited copper technological process of production figure;
Fig. 2 is a process flow sheet of the present invention.
Embodiment
The present invention done further describe.
Embodiment 1
Present embodiment adopts two extracting systems respectively leach liquor to be extracted, and contains a large amount of Fe in the handled copper mine stone 2O 3And the FeO composition, after conventional acidleach, agitation leach, Fe 2O 3By H 2SO 4Dissolving generates Fe 3(SO 4) 2, FeO is by H 2SO 4Dissolving generates FeSO 4, when routine is carried out extracting copper, part Fe 3+And Fe 2+Carried secretly in the entering load organic phases, this load organic phases carried out following processing:
A, in load organic phases, to add sulfuric acid content be the washings of 8g/l, mixes the iron ion content of washing organic phase to washings when being lower than 0.5g/l, obtains removing the load organic phases of iron ion, and washings send ore to leach step and uses;
B, by electric tail washings: load organic phases=1:2 volume ratio of removing iron ion; Load organic phases with the removal iron ion of steps A; Strip with containing 180g/l vitriolic electricity tail washings; Make the cupric ion enrichment in the strip liquor as the electric effusion of producing electro deposited copper, surplus liquid is the regeneration organic phase that contains extraction agent;
C, send the single extraction operation to carry out copper extraction the regeneration organic phase of step B;
D, the electric effusion of step B is carried out conventional electrodeposition, electro deposited copper.
Embodiment 2
Present embodiment adopts two extracting systems respectively leach liquor to be extracted, and contains a large amount of Fe in the handled ore 2O 3And the FeO composition, after conventional acidleach, agitation leach, Fe 2O 3By H 2SO 4Dissolving generates Fe 3(SO 4) 2, FeO is by H 2SO 4Dissolving generates FeSO 4, after conventional extraction, the part Fe in the solution 3+And Fe 2+When extraction, carried secretly in the entering load organic phases, this load organic phases carried out following processing:
A, in load organic phases, to add acid content be the washings of 10g/l, and the iron ion content that mixes in washing organic phase to the washings is lower than 0.5g/l, obtains removing the load organic phases of iron ion, and washings is sent to laundry and washed collecting tank and recycle as washings;
B, by electric tail washings: load organic phases=1:3 volume ratio of removing iron ion; Load organic phases with the removal iron ion of steps A; Strip with containing 200g/l vitriolic electricity tail washings; Make the cupric ion enrichment in the strip liquor as the electric effusion of producing electro deposited copper, surplus liquid is the regeneration organic phase that contains extraction agent;
C, send the single extraction operation to carry out copper extraction the regeneration organic phase of step B;
D, the electric effusion of step B is carried out conventional electrodeposition, electro deposited copper.
After embodiment 1,2 washing deironing, make iron ion reduce by 80%～90%, promptly iron ion content when not washing 1/5～1/10.Therefore, the iron concentration in the electrolytic copper factory electric effusion is reduced to below the 3g/l, current efficiency can be promoted to more than 90%, can reduce the electrodeposition production cost of electrolytic copper factory.Specific as follows:
(1) reduces cost
The electrodeposition power consumption is reduced in the 2500kwh/ ton copper, and ton copper economize on electricity 1728kwh reduces production costs 1036.8 yuan.If calculate by producing 2000 tons of copper per year, 345.6 ten thousand kwh that can economize on electricity in year practice thrift 207.36 ten thousand yuan of the electricity charge, the better economic benefit of creation.
(2) reduce foreign matter content
After increasing the washing iron removal step, can effectively control iron ion and carried secretly into electric effusion, other impurity such as calcium, magnesium also can be washed and remove, and help promoting the electrolytic copper quality product.
(3) avoid the fracture of electro deposited copper hangers
After increasing the washing iron removal step, can guarantee that disconnected ear obscission no longer takes place cathode copper, stop effectively to reduce electrodeposition Workshop Production personnel labor because of the electrodeposition cell body damages the leakage electric leakage hidden danger that produces.
(4) cleanliness factor of raising organic phase
After increasing the washing iron removal step, organic phase can keep certain cleanliness factor for a long time, can accelerate organic phase and water clarification phase-splitting, reduces the organic phase entrainment loss, can reduce kerosene and extraction agent consumption.
Comparative Examples
Embodiment 1 gained load organic phases after the prior art back extraction, is entrained in the electric effusion by strip liquor again, and along with constantly carrying out of dump leaching-extraction-electrodeposition production, the iron concentration that accumulates in the electric effusion is increasingly high, Fe in the electric effusion 3+Concentration is higher than 10g/l, far exceeds 3～5 times of industry standard permission mxm. (3g/l); Fe 3+In the electrodeposition production process,, can dissolve cathodic metal copper, Fe with metallic copper generation oxidizing reaction 3+Be reduced to Fe 2+, cause cathodic current to be consumed.Fe 3+Be converted into Fe from negative electrode electron gain generation reduction reaction 2+, the Fe of formation 2+Again can by dissolved oxygen in the solution (from the air or anode) reoxidize and be Fe 3+This redox reaction circulates in the electrodeposition flow process and carries out; Constantly consume the electrodeposition electric energy, unit electrodeposition power consumption reaches 4228kwh, surpasses the twice of industry standard electrodeposition power consumption (2000kwh); Ton copper electrodeposition power consumption cost up to 2536.80 yuan (this ore deposit electricity price be 0.6 yuan/kwh), exceed 1336.80 yuan than industry standard.If calculate by producing 2000 tons of copper per year, year current consumption has more 445.6 ten thousand kwh than industry standard, and a year power consumption cost increases by 267.36 ten thousand yuan.
Fe in the solution 3+Metallic copper is had stronger corrodibility, and making negative electrode Cu oxidation dissolution is Cu 2+Get into liquid, copper coin hangers position is little because of thickness, Fe 3+Rupture after the concentration oxidation corrosion, cause copper coin to come off and fall in the Winning cell, breaks in production needs to return electrodeposition production behind the riveting ear again.Strengthened labour intensity, the disconnected backwardness of a large amount of copper coins causes the Winning cell preservative coat damaged, contains sour electric effusion and leaks the corrosion cell body, produces leaky, causes current efficiency to reduce, and production cost rises, electrolytic copper quality iron content rising etc.

Claims (5)

1. the method for removing iron of the low copper feed liquid extraction-electrowinning copper process of a high ferro, it comprises sulfuric acid dump leaching and agitation leach step, and leach liquor is carried out the step of extracting copper, it is characterized in that extracting copper after remaining load organic phases pass through following processing:
A, in load organic phases, to add sulfuric acid content be the washings of 8～10g/l; Mix iron ion content to washings when being lower than 0.5g/l; Obtain removing the load organic phases of iron ion, washings send and leaches step and use, or sends to laundry and wash collecting tank and recycle as washings;
B, by electric tail washings: load organic phases=1:2～3 volume ratios of removing iron ion; Load organic phases with the removal iron ion of steps A; Strip with containing 180～200g/l vitriolic electricity tail washings; Make the cupric ion enrichment in the strip liquor as the electric effusion of producing electro deposited copper, surplus liquid is the regeneration organic phase that contains extraction agent;
C, with the regeneration organic phase of step B, send the single extraction operation to carry out extracting copper;
D, send the electrodeposition operation, produce electro deposited copper the electric effusion of step B.
2. the method for removing iron of the low copper feed liquid extraction-electrowinning copper process of high ferro as claimed in claim 1; It is characterized in that the load organic phases of the load organic phases of said steps A, the load organic phases that produces when perhaps behind single extraction, carrying out reextraction again for the generation of single extraction process.
3. the method for removing iron of the low copper feed liquid extraction-electrowinning copper process of high ferro as claimed in claim 1, the washing that it is characterized in that said steps A are in conventional wash trough, to mix washing by what routine was carried out.
4. the method for removing iron of the low copper feed liquid extraction-electrowinning copper process of high ferro as claimed in claim 1, it is characterized in that said step B to contain the electric tail washings of 180～200g/l vitriolic be the electrodeposition tail washings that produces in the electro deposited copper production process.
5. the method for removing iron of the low copper feed liquid extraction-electrowinning copper process of high ferro as claimed in claim 1, the extraction that it is characterized in that said step C is on conventional extraction equipment, presses the copper leach liquor: organic phase=1:1 volume ratio, the process of mixing phase-splitting.
CN2012102675623A 2012-07-30 2012-07-30 Iron removing method in process for extracting-electrowinning copper metal by using high-iron and low-copper material liquid Pending CN102776369A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106283109A (en) * 2016-08-18 2017-01-04 紫金矿业集团股份有限公司 The processing method of high ferro electrodeposition lean solution during a kind of wet-milling processing
CN110669946A (en) * 2019-11-07 2020-01-10 万宝矿产有限公司 Extraction method of iron-rich and high-impurity copper leaching solution
CN113337714A (en) * 2021-05-12 2021-09-03 浙江天能新材料有限公司 Method for purifying and removing iron from electrodeposited copper anolyte

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WO2001061058A1 (en) * 2000-02-18 2001-08-23 Cognis Corporation Process for recovery of metals from metal-containing ores
WO2003014422A1 (en) * 2001-08-07 2003-02-20 Cognis Corporation Improvements in solvent extraction processes for metal recovery
CN1566377A (en) * 2003-06-18 2005-01-19 北京有色金属研究总院 Combined heap leaching process for copper ore
CN101195861A (en) * 2007-12-20 2008-06-11 金川集团有限公司 Method for separating copper from nickel and cobalt solution
CN101457299A (en) * 2007-12-10 2009-06-17 北京有色金属研究总院 Wet processing process of high mud cupric oxide mine at high-cold area

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
WO2001061058A1 (en) * 2000-02-18 2001-08-23 Cognis Corporation Process for recovery of metals from metal-containing ores
WO2003014422A1 (en) * 2001-08-07 2003-02-20 Cognis Corporation Improvements in solvent extraction processes for metal recovery
CN1566377A (en) * 2003-06-18 2005-01-19 北京有色金属研究总院 Combined heap leaching process for copper ore
CN101457299A (en) * 2007-12-10 2009-06-17 北京有色金属研究总院 Wet processing process of high mud cupric oxide mine at high-cold area
CN101195861A (en) * 2007-12-20 2008-06-11 金川集团有限公司 Method for separating copper from nickel and cobalt solution

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106283109A (en) * 2016-08-18 2017-01-04 紫金矿业集团股份有限公司 The processing method of high ferro electrodeposition lean solution during a kind of wet-milling processing
CN106283109B (en) * 2016-08-18 2018-08-24 紫金矿业集团股份有限公司 The processing method of high ferro electrodeposition lean solution during a kind of wet-milling processing
CN110669946A (en) * 2019-11-07 2020-01-10 万宝矿产有限公司 Extraction method of iron-rich and high-impurity copper leaching solution
CN113337714A (en) * 2021-05-12 2021-09-03 浙江天能新材料有限公司 Method for purifying and removing iron from electrodeposited copper anolyte

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Application publication date: 20121114