CN100554452C - Method for extracting copper from copper-containing sulfide ore by wet process - Google Patents
Method for extracting copper from copper-containing sulfide ore by wet process Download PDFInfo
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- CN100554452C CN100554452C CNB2008101325378A CN200810132537A CN100554452C CN 100554452 C CN100554452 C CN 100554452C CN B2008101325378 A CNB2008101325378 A CN B2008101325378A CN 200810132537 A CN200810132537 A CN 200810132537A CN 100554452 C CN100554452 C CN 100554452C
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Abstract
The invention relates to a method for extracting copper from copper-containing sulphide ore by a wet method, which is characterized by comprising the following steps: (1) under the catalytic action of chloride ions, leaching copper-containing sulphide ore by using an acidic aqueous solution containing ferric ions, and separating ore pulp into two parts of supernatant and underflow after settling; (2) sending the supernatant to an anode chamber of a diaphragm electrolytic cell, and carrying out anodic oxidation reaction on ferrous ions in the supernatant to generate ferric ions, and returning the ferric ions to the step (1) to be used as leachate; performing oxidation and iron removal leaching on the bottom flow, and performing solid-liquid separation; (3) sending the solution obtained by solid-liquid separation after the bottom flow in the step (2) is leached by oxidation and iron removal to a cathode chamber of a diaphragm electrolytic cell for electrodeposition to produce electrolytic copper, and returning the cathode waste liquid to the step (1) for leaching; the leached slag is oxidized and leached with copper under the catalysis of chloride ions, and the leached copper is recovered by extraction-electrodeposition. The method has the advantages of short flow, low investment, low electrowinning power consumption, wide raw material application range, easy process operation, high copper recovery rate, environmental friendliness and the like.
Description
Technical field
A kind ofly contain the method that the copper sulfurized ore wet method is extracted copper, relate to a kind ofly from containing copper sulfurized ore, particularly wet method is extracted the method for copper in the chalcopyrite.
Background technology
Wet method is carried copper technology and is started from the sixties in last century, mainly handles copper oxide ore and secondary sulphide ore, and the copper that accounts for present world wide production 20% greatly extracts from these resources with leaching-extraction-electrodeposition technology.The copper ore concentrates that with the chalcopyrite is essential mineral is the main raw material of coppersmith industry, at present industrial traditional pyrometallurgical smelting process, i.e. " melting-blowing-refining " technologies of also almost all adopting of this raw material.So, the dominant position that copper smelting by pyrometallurgy is still produced in occupation of present copper.But there is following shortcoming in copper smelting by pyrometallurgy: (1) investment cost height, must carry out scale operation; (2) copper smelting by pyrometallurgy factory produces SO
2There is problem of environmental pollution in flue gas; (3) for remote mine or economically less developed region, copper smelting by pyrometallurgy produces a large amount of sulfuric acid to be difficult to handle; (4) copper smelting by pyrometallurgy has comparatively strict requirement to the grade and the foreign matter content of copper ore concentrates, and Technological adaptability is poor.Along with reducing gradually with difficult ore, copper mine stone mining grade increases, along with the enhancing of people's environmental consciousness, to SO
2Etc. the common concern of objectionable impurities contaminate environment, countries in the world are paid attention to the wet type copper smelting Study on Technology day by day, and attempting hydrometallurgical technology is expanded to processing is the copper ore concentrates of essential mineral with the chalcopyrite.
In recent years, the full wet method extractive technique of cupric sulphide concentrate has been carried out big quantity research both at home and abroad, and existing technology with potential prospects for commercial application mainly contains following several:
1.CLEAR technology
CLEAR technology is with ferric chloride Solution leaching chalcopyrite concentrate, leaching is divided into two sections, first section is leached not blowing air, utilizes the reductibility of new chalcopyrite that second section ferric ion and cupric ion that leaches in the leach liquor that obtains is reduced to ferrous ion and cuprous ion; Second section leaching be one section slag with under the electrolytic solution of anode electrolytic cell oxidation situation, react at continuous bubbling air, copper is leached, and makes iron oxydrolysis precipitation; One section leach liquor is directly sent to electrodeposition, adopts septate electrolyzer, and cuprous ion is reduced into copper powder in the cathodic area.Positive column Red copper oxide ion and ferrous ion.Therefore the power consumption of electro deposited copper is more much lower than electrodeposition from copper-bath.
CLEAR technology in last century the eighties carried out commerical test, prove that flow process is feasible, but because copper products is of low quality, need reason such as refining again to fail to realize industrial applications.
2.Cymet technology
Cymet technology is the technology that copper-sulphide ores is handled in a kind of villaumite system in-pulp electrolysis, and its core is two electrolyzers, and one is the middle copper electrolysis cells that separates with semi-permeable membranes, the cathodic area electro deposited copper, and the positive column iron protoxide ion leaches sulphide ores simultaneously.Catholyte behind the decopper(ing) enters another electrolytic iron groove, cathodic area electrodeposition iron, positive column oxidation regeneration ferric sesquichloride.The ore pulp that ferric sesquichloride solution produces with the copper electrolysis cells positive column returns to and leaches operation, the leaching chalcopyrite.This technology runs into fluctuation of service and the not high problem of quality product equally, fails to apply industrial.
3.Intec technology
The Intec copper-extracting process is a kind of chloride media copper-extracting process, and leaching agent contains 30g/l Cu
2+, 280g/lNaCl and 28g/l NaBr, technical process is four sections leaching-bivalent cupric ion reduction-purification-electrodeposition.It is low that Intec technology leaches temperature of reaction, need not pressurize, and need not extract, and the copper powder quality of generation is better, and therefore, its progress extremely is concerned by people.
4.Placer Dome technology
Placer Dome technology is a kind of high temperature, high pressure total oxygen extract technology, and at 210～220 ℃, under the leaching condition of oxygen partial pressure 0.7MPa, the sulphur major part in the ore is oxidized to SO
4 2-This technology is fit to handle the low ore of sulfur-bearing, and being not suitable for handling with the chalcopyrite is the copper ore concentrates of essential mineral, because the sulphur major part in the ore is oxidized to SO
4 2-, system's sulfuric acid is superfluous serious.
5.CESL technology
CESL pressurization leaching-out technique is to be proposed by Canadian Ke Mingke (Cominco) Engineering Service company limited in 1992, adopts two sections leachings, and first section adds small amount of hydrochloric acid pressure oxidation leaching with dilute sulphuric acid under 150 ℃, and leach liquor contains Cl
-: 12g/l, Cu
2+: 15～20g/l, the acid amount that control adds, making one section leaching endpoint pH is 2.3～3.5, copper is converted into Basic Chrome Sulphate.Second section normal pressure leaches, and extraction temperature is 40 ℃, and the sulphur major part in the ore is oxidized to elementary sulfur and enters in the leached mud, after one section leach liquor extracts, evaporates, returns one section leaching, and two sections leach liquors are produced electrolytic copper through extraction-electrodeposition.
6.AAC-UBC technology
AAC-UBC technology is at first carried out fine grinding with ore, requires grinding fineness to reach-10 μ m and accounts for 80%, leaches 2～4h after the fine grinding under the oxygen partial pressure of 150 ℃ and 700kPa.Leach liquor neutralizes through lime, and extraction-electrodeposition is produced electrolytic copper then.
7.Gordon technology
The acid ferrum sulfuricum oxydatum solutum of Gordon process using directly leaches copper glance, and the ferrous ion that will be reduced in leaching process with oxygen is oxidized to ferric ion again.Leach liquor is produced electrolytic copper through extraction-electrodeposition method.This technology is fit to handle copper glance, is difficult to handle chalcopyrite.
8. two electrodeposition processes of copper manganese
Yunnan Copper Industry Science and Technology Development Co., Ltd. in 2002 have proposed a kind of hydrometallurgical processes of copper ore concentrates, and its technical process is: the copper ore concentrates-oxidation leaching-iron purification-two-way electrodeposition-electrolytic copper of copper manganese.
Existing wet type copper smelting technology can be divided into two classes: a class is a sulfate system; Another kind of is the villaumite system.
In existing sulfate system wet type copper smelting technology, under middle cold condition, leach chalcopyrite, the leaching yield of copper is often undesirable, leaches chalcopyrite under hot conditions, and the most of sulphur in the ore is oxidized to sulfate radical, causes system sulfuric acid superfluous greatly.The electrolytic deposition process anodic reaction is normally emitted the reaction of oxygen in sulfate system:
4OH
-＝O
2+2H
2O+4e
The anodic reaction of electrodeposition is consumed energy in vain not only, and causes acid mist, degradation manipulation environment for the electrodeposition workshop.
In the villaumite system, chalcopyrite can leach under comparatively gentle condition more fully, the electrodeposition reaction product of anode can be used for leaching in the villaumite system, energy utilization rate is very high, but electro deposited copper is a copper powder in the villaumite system, the villaumite system is to many reasons such as equipment corrosion are serious, and villaumite system wet type copper smelting technology also is difficult to for the moment industrialization promotion.
Summary of the invention
The purpose of this invention is to provide a kind of technology that can overcome the copper ore concentrates wet type copper smelting of above-mentioned drawback; this technology has less investment, copper smelting recovery height, production cost is low, environment protection good, the method that contains copper sulfurized ore wet method extraction copper of technology easy handling.
The object of the present invention is achieved like this.
A kind of method that contains copper sulfurized ore wet method extraction copper is characterized in that the step of leaching process comprises:
(1) under catalytic action of chloride ions, contain copper sulfurized ore with the acidic aqueous solution leaching that contains ferric ion, ore pulp is divided into supernatant liquor and underflow two portions after sedimentation;
(2) supernatant liquor is sent the diaphragm sell anolyte compartment ferrous ion in the supernatant liquor is returned step (1) through anodic oxidation reactions generation ferric ion and make leach liquor; With underflow solid-liquid separation after iron removal by oxidation leaches;
(3) cathode compartment of the solution of step (2) underflow solid-liquid separation after iron removal by oxidation leaches being delivered to diaphragm sell carries out electrodeposition production electrolytic copper, and the negative electrode waste liquid returns step (1) and leaches; Copper is wherein leached in leached mud further oxidation under catalytic action of chloride ions, and the copper of leaching reclaims through extraction-electrodeposition.
A kind of method that the copper sulfurized ore wet method is extracted copper that contains of the present invention, it is characterized in that leaching used acidic aqueous solution in the described step (1) is sulfuric acid system, sulfuric acid concentration ranges contains the chlorion of catalytic amount at 30～300g/l in the solution, concentration range is 0.1～10g/l.
A kind of method that the copper sulfurized ore wet method is extracted copper that contains of the present invention is characterized in that extraction temperature is 60～130 ℃ in the described step (1); Extraction time is 1～8 hour, the solid mass ratio of leach liquor 4: 1～8: 1.
A kind of method that the copper sulfurized ore wet method is extracted copper that contains of the present invention is characterized in that oxygenant that the underflow in the described step (2) leaches through iron removal by oxidation is a kind of in oxygen, air, hydrogen peroxide, the Sodium Persulfate, and extraction temperature is 80～180 ℃.
A kind of method that the copper sulfurized ore wet method is extracted copper that contains of the present invention, it is characterized in that the leached mud in the described step (3) leaches with the further oxidation of the solution of chloride ion-containing, leaching process adds a kind of oxygenant that is selected from oxygen, air, hydrogen peroxide, sodium chlorate or the clorox, the concentration of leach liquor chlorion is 10～150g/l, extraction temperature is 80～140 ℃, and the copper of leaching is reclaimed with extraction-electrodeposition method.
A kind of method that contains copper sulfurized ore wet method extraction copper, copper ore concentrates carries out airtight leaching, iron removal by oxidation leaching and electrodeposition with ferric sulphate solution in the presence of the chlorion of catalytic amount in sulfate system, two sections leached muds leach with the solution oxide that contains chlorion, the 3rd section leach liquor is through extraction, the aqueous sulfuric acid back extraction makes this part copper be transformed into sulfate system and is convenient to electrodeposition.
First section is leached the used oxygenant of copper sulfide concentrate is the Fe that anodic oxidation reactions produces in the electrolytic deposition process
3+, Fe
3+Can constantly regenerate in electrolytic deposition process, therefore, compare with other copper sulfide concentrate sulfate system wet type copper smelting technology, this technology can reduce the consumption of oxygenant greatly.
With the chalcopyrite is the copper sulfide concentrate of essential mineral, leaches reaction to be:
CuFeS
2+4Fe
3+＝Cu
2++5Fe
2++2S
As can be seen, the iron ion in leaching process in the solution can constantly increase, and can tend towards stability in order to ensure the total system iron concentration, need set up iron removal step from reaction formula.Can adopt three kinds of deironing schemes: (1) all supernatant liquors carry out the part deironing; (2) get the deironing of part supernatant liquor; (3) underflow (leached mud and part leach liquor) deironing.These three kinds of schemes can both realize the de-ferrous effect of expecting.For being the copper sulfide concentrate of essential mineral with the chalcopyrite, the leaching of 1mol chalcopyrite needs the 4mol electronics at least, and electrodeposition 1mol copper only needs the 2mol electronics on the sulfuric acid system negative electrode, so being leached, chalcopyrite thoroughly also needs supplemental oxidant, iron removal also needs additional oxidizer, so this process choice underflow deironing scheme, and deironing and oxidation leached to merge a step be that iron removal by oxidation leaches (two sections leachings).
The oxygenant of second section leaching can be used oxygen, air, hydrogen peroxide or Sodium Persulfate or the like, the most Jing Ji oxygenant yes oxygen or air; Second section extraction temperature scope is 80～180 ℃, and preferable temperature range is 100～150 ℃; The oxygen partial pressure scope is 0.02～1.0MPa; Extraction time 1～6 hour.
Electrolyzer separates cathode compartment and anolyte compartment with anion-exchange membrane, and the electrode reaction of positive column is: Fe
2+=Fe
3++ e, its standard potential E
0=0.771V; The electrode reaction in cathodic area is: Cu
2++ 2e=Cu, its standard potential E
0=0.337V, the difference of two standard potentials is 0.434V, this technology bath voltage is 1.0～1.4V (bath voltage mainly is made of the volts lost of anodic-cathodic potential difference, electrolytic solution volts lost and film), obviously low than the Winning cell voltage 2.2V of traditional precipitated oxygen, so this technology can significantly reduce the electrodeposition power consumption.In addition, in electrolytic deposition process, do not produce acid, help whole wet type copper smelting system held acid balance, reduce lime consumption.
Method of the present invention, the characteristics of technical process are: flow process weak point, less investment, electrodeposition power consumption are low, the raw material wide accommodation, be easy to technological operation, copper recovery is high and environmentally friendly etc.
Description of drawings
Fig. 1 is the process flow sheet of the inventive method.
Embodiment
A kind of method that contains copper sulfurized ore wet method extraction copper, the step of leaching process comprises:
(1) under catalytic action of chloride ions, contain copper sulfurized ore with the acidic aqueous solution leaching that contains ferric ion, ore pulp is divided into supernatant liquor and underflow two portions after sedimentation;
(2) supernatant liquor is sent the diaphragm sell anolyte compartment ferrous ion in the supernatant liquor is returned step (1) through anodic oxidation reactions generation ferric ion and make leach liquor; With underflow solid-liquid separation after iron removal by oxidation leaches;
(3) cathode compartment of the solution of step (2) underflow solid-liquid separation after iron removal by oxidation leaches being delivered to diaphragm sell carries out electrodeposition production electrolytic copper, and the negative electrode waste liquid returns step (1) and leaches; Copper is wherein leached in leached mud further oxidation under catalytic action of chloride ions, and the copper of leaching reclaims through extraction-electrodeposition.
Method of the present invention, under a small amount of catalytic action of chloride ions, contain copper sulfurized ore with the acidic aqueous solution leaching that contains ferric ion, ore pulp is divided into supernatant liquor and underflow two portions after sedimentation, supernatant liquor is recycled to the diaphragm sell anolyte compartment, and the ferrous ion in the solution of positive column returns to leach through anodic oxidation reactions generation ferric ion makes oxygenant; Underflow is solid-liquid separation after iron removal by oxidation leaches, and the cathode compartment that solution is delivered to Winning cell carries out electrodeposition production electrolytic copper, and the negative electrode waste liquid returns one section leaching.The leached mud further oxidation leaching of the solution of chloride ion-containing copper wherein, the copper of this part leaching reclaims through extraction-electrodeposition.
The main purpose of first section leaching is in leaching process, utilizes the reductibility of sulphide ores that the ferric ion in the solution is reduced to ferrous ion, so first section leaching process need not lead to oxygen or air.First section acidic substance that leach used acidic aqueous solution is mainly sulfuric acid, and the free sulfuric acid concentration range contains the chlorion of catalytic amount at 30～300g/l in the solution, and concentration range is 0.1～10g/l.First section extraction temperature scope is 60～130 ℃.Extraction time is 1～8 hour.
Ferric ion in leaching process in the solution is as oxygenant, oxidation contains copper sulfurized ore, make copper immerse solution, sulphur mainly is oxidized to elemental sulfur, ferric ion then is reduced to ferrous ion, ferrous ion is oxidized to ferric ion again on the anode of electrolytic deposition process, liquid is used for leaching after anolyte compartment's electrolysis.For chalcopyrite is the copper ore concentrates of essential mineral, because leaching with exhaustive oxidation, the quantity not sufficient of ferric ion that forms electrolytic deposition process contains copper sulfurized ore, in order further to leach copper, guarantee that simultaneously the solution iron content of whole circulation system keeps balance, after one section leaching was dense, underflow carried out iron removal by oxidation and leaches.
Second section leach to need oxidizer, as oxygen, air, hydrogen peroxide, Sodium Persulfate or the like, and Jing Ji oxygenant yes oxygen or air the most, second section extraction temperature scope is 80～180 ℃.
After two sections leachings; common some copper in the leached mud; in order to obtain the ideal yield; two sections leached muds leach with the further oxidation of the solution of chloride ion-containing, and the 3rd section leaching process needs oxidizer, as oxygen, air, hydrogen peroxide, sodium chlorate or clorox or the like; comparatively Jing Ji oxygenant is oxygen, air or sodium chlorate; the concentration of leach liquor chlorion is 10～150g/l, and extraction temperature is 80～140 ℃, and the copper of leaching is reclaimed with extraction-electrodeposition method.Electrolyzer is divided into cathode compartment and anolyte compartment with anion-exchange membrane, in the positive column, and Fe
2+Be oxidized to Fe
3+In the cathodic area, Cu
2+Become the electrolytic copper plate by electrodeposition, sulfate ion in the cathode chamber solution can see through anion-exchange membrane and enter the anolyte compartment, and the positively charged ion in the anolyte compartment can not see through anion-exchange membrane, thereby avoids ferric ion to enter cathode compartment, guarantees that electrolytic deposition process obtains higher current efficiency.
Embodiment 1
Add 100g levigated 1# copper ore concentrates toward the vertical lining titanium of GSA type 2L autoclave, concentrate cupric: iron 14.17%: sulphur 31.63%: 32.19%, 600ml leach liquor, leach liquor main component: free H
2SO
4: 60g/L, Cu
2+: 15g/L, Fe
3+35g/L is heated to 110 ℃, extraction time 4h, and after reaction finished, ore pulp was dense, and electrolyzer anode chamber's oxidation is sent in dense overflow, and thickened underflow enters the next stage iron removal by oxidation and leaches, underflow density 33%.Airtight normal pressure extracting stage Cu leaching yield 42%, iron leaching yield 25%.Leach liquor contains Cu30g/L, Fe40g/L.
One section airtight normal pressure leaches thickened underflow and electrodeposition catholyte and enters two sections oxygen and press deironing to leach, be reflected in the vertical lining titanium of the GSA type 2L autoclave and carry out, liquid-solid mass ratio 6: 1, be heated to 130 ℃, extraction time 2h, aerating oxygen in the reaction process, after reaction finishes, slurry filtration, leach liquor send electric tank cathode chamber electrodeposition, and leached mud send strengthens the leaching of oxidation extracting stage.Oxygen is pressed deironing extracting stage Cu leaching yield 45%, the total leaching yield 68% of Cu, and iron enters in the slag with the pyrrhosiderite form in the leach liquor, Fe＜2g/L in the solution.
The oxygen pressure is removed scum and is advanced to strengthen the oxidation extracting stage, liquid-solid mass ratio 8: 1, Cu 0.5g/L in the leach liquor, Fe＜5g/L, Cl
-15g/L, 95 ℃ of extraction temperatures, blowing air in the leaching process, extraction time 3h.After reaction finished, slurry filtration was stored up after the leached mud washing, and leach liquor send extraction.Strengthen oxidation extracting stage Cu leaching yield 92%, the total leaching yield of Cu＞97%, iron leaching yield 8%.
Strengthen the BK992 extraction agent 3 stage countercurrents extraction that the Cu in the oxidation leach liquor develops with the Beijing Mine and Metallurgy General Inst, copper percentage extraction 99%, load organic phases is used 180g/LH after 2 grades of washings
2SO
4Back extraction, organic phase is returned extraction section after 3 grades of back extractions, and liquid send the electrodeposition operation to produce cathode copper after the back extraction.The omnidistance yield of flow process copper reaches more than 92%.
Embodiment 2
One section airtight normal pressure leaching test condition: 130 ℃ of extraction temperatures, extraction time 6h, the solid mass ratio of leach liquor 4: 1, leach liquor main component: free H
2SO
4: 250g/L, Cu
2+: 15g/L, Fe
3+35g/L, other are with example 1, airtight normal pressure extracting stage Cu leaching yield 45%, iron leaching yield 36%.Leach liquor contains Cu40g/L, Fe50g/L.
Two sections oxygen are pressed deironing leaching test condition: extraction temperature: 170 ℃, and extraction time 4h, bubbling air in the reaction process, other are with example 1, and oxygen is pressed deironing extracting stage Cu leaching yield 25%, the total leaching yield 70% of Cu, iron enters in the slag in the leach liquor, Fe＜2g/L in the solution.
Strengthen oxidation leaching test condition for three sections: 130 ℃ of extraction temperatures, the solid mass ratio of leach liquor 4: 1, Cu 0.5g/L in the leach liquor, Fe＜5g/L, Cl
-120g/L, extraction time 2h adds the strong oxidizer hydrogen peroxide, and other are with example 1.Strengthen oxidation extracting stage Cu leaching yield 92%, the total leaching yield of Cu＞97%, iron leaching yield 8%.
Embodiment 3
One section airtight normal pressure leaching test condition: 80 ℃ of extraction temperatures, extraction time 4h, the solid mass ratio of leach liquor 6: 1, leach liquor main component: free H
2SO
4: 180g/L, Cu
2+: 15g/L, Fe
3+35g/L, other are with example 1, airtight normal pressure extracting stage Cu leaching yield 40%, iron leaching yield 25%.
Two sections oxygen are pressed deironing leaching test condition: extraction temperature: 80 ℃, extraction time 3h feeds hydrogen peroxide in the reaction process, other are with example 1, and oxygen is pressed deironing extracting stage Cu leaching yield 25%, the total leaching yield 70% of Cu, iron enters in the slag with the pyrrhosiderite form in the leach liquor, Fe＜2g/L in the solution.
Strengthen oxidation leaching test condition for three sections: 110 ℃ of extraction temperatures, the solid mass ratio of leach liquor 6: 1, Cu 0.5g/L in the leach liquor, Fe＜5g/L, Cl
-60g/L, extraction time 4h adds the strong oxidizer sodium chlorate, and other are with example 1.Strengthen oxidation extracting stage Cu leaching yield 92%, the total leaching yield of Cu＞97%, iron leaching yield 8%.
Embodiment 4
One section airtight normal pressure leaching test condition: 100 ℃ of extraction temperatures, extraction time 3h, the solid mass ratio of leach liquor 6: 1, leach liquor main component: free H
2SO
4: 100g/L, Cu
2+: 15g/L, Fe
3+35g/L, other are with example 1, airtight normal pressure extracting stage Cu leaching yield 40%, iron leaching yield 25%.
Two sections oxygen are pressed deironing leaching test condition: extraction temperature: 150 ℃, extraction time 3h feeds Sodium Persulfate in the reaction process, other are with example 1, and oxygen is pressed deironing extracting stage Cu leaching yield 25%, the total leaching yield 70% of Cu, iron enters in the slag with the pyrrhosiderite form in the leach liquor, Fe＜2g/L in the solution.
Strengthen oxidation leaching test condition for three sections: 110 ℃ of extraction temperatures, the solid mass ratio of leach liquor 6: 1, Cu 0.5g/L in the leach liquor, Fe＜5g/L, Cl
-30g/L, extraction time 4h adds the strong oxidizer clorox, and other are with example 1.Strengthen oxidation extracting stage Cu leaching yield 92%, the total leaching yield of Cu＞97%, iron leaching yield 8%.
Claims (5)
1. one kind contains the method that the copper sulfurized ore wet method is extracted copper, it is characterized in that leaching process comprises:
(1) under catalytic action of chloride ions, contain copper sulfurized ore with the acidic aqueous solution leaching that contains ferric ion, ore pulp is divided into supernatant liquor and underflow two portions after sedimentation;
(2) supernatant liquor is sent the diaphragm sell anolyte compartment ferrous ion in the supernatant liquor is returned step (1) through anodic oxidation reactions generation ferric ion and make leach liquor; With underflow solid-liquid separation after iron removal by oxidation leaches;
(3) cathode compartment of the solution of step (2) underflow solid-liquid separation after iron removal by oxidation leaches being delivered to diaphragm sell carries out electrodeposition production electrolytic copper, and the negative electrode waste liquid returns step (1) and leaches; Copper is wherein leached in leached mud further oxidation under catalytic action of chloride ions, and the copper of leaching reclaims through extraction-electrodeposition.
2. a kind of method that the copper sulfurized ore wet method is extracted copper that contains according to claim 1, it is characterized in that leaching used acidic aqueous solution in the described step (1) is sulfuric acid system, sulfuric acid concentration ranges is at 30～300g/l, the chlorion that contains catalytic amount in the solution, concentration range are 0.1～10g/l.
3. a kind of method that the copper sulfurized ore wet method is extracted copper that contains according to claim 1 is characterized in that extraction temperature is 60～130 ℃ in the described step (1); Extraction time is 1～8 hour.
4. a kind of method that the copper sulfurized ore wet method is extracted copper that contains according to claim 1, it is characterized in that oxygenant that the underflow in the described step (2) leaches through iron removal by oxidation is a kind of in oxygen, air, hydrogen peroxide, the Sodium Persulfate, extraction temperature is 80～180 ℃, extraction time 1～4h.
5. a kind of method that the copper sulfurized ore wet method is extracted copper that contains according to claim 1, it is characterized in that the leached mud in the described step (3) leaches with the further oxidation of the solution of chloride ion-containing, leaching process adds a kind of oxygenant that is selected from oxygen, air, hydrogen peroxide, sodium chlorate or the clorox, the concentration of leach liquor chlorion is 10～150g/l, extraction temperature is 80～140 ℃, the solid mass ratio of leach liquor 3: 1～8: 1, extraction time 1～4h, the copper of leaching is reclaimed with extraction-electrodeposition method.
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