CN104232924B - A kind of Copper Ores acid leaching liquor carry copper method for removing iron - Google Patents
A kind of Copper Ores acid leaching liquor carry copper method for removing iron Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 133
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 131
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 238000000034 method Methods 0.000 title claims abstract description 75
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 63
- 238000002386 leaching Methods 0.000 title claims abstract description 52
- 239000002253 acid Substances 0.000 title claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 85
- 230000008569 process Effects 0.000 claims abstract description 46
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 22
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 238000004070 electrodeposition Methods 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 239000002893 slag Substances 0.000 claims abstract description 13
- 229960004643 cupric oxide Drugs 0.000 claims abstract description 10
- 238000005204 segregation Methods 0.000 claims abstract description 10
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 10
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 10
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical group [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000605 extraction Methods 0.000 claims abstract description 7
- 238000005342 ion exchange Methods 0.000 claims abstract description 6
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 4
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims abstract description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910001447 ferric ion Inorganic materials 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 230000004044 response Effects 0.000 claims description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 229910052569 sulfide mineral Inorganic materials 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- -1 iron ion Chemical class 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000032258 transport Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052935 jarosite Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000009867 copper metallurgy Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000004763 sulfides Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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Abstract
A kind of Copper Ores acid leaching liquor of disclosure carry copper method for removing iron, carry out wet method dump leaching including by mixing after broken to secondary cupric oxide ore and secondary copper sulfide ore；Carry out shower-bubble type with dilute sulfuric acid, obtain faintly acid leachate；Leachate carries copper by extraction or ion exchange, obtains copper segregation liquid and lean copper liquid；Copper segregation liquid electrodeposition is obtained tough cathode；Lean copper liquid High Temperature High Pressure continuous deferrization under oxidizing atmosphere, the ore pulp obtained is through being filtrated to get bloodstone slag, and stockyard circulating leaching is sent in the part lean copper acidified oxidation of liquid.The present invention utilizes iron ion and copper-sulphide ores that redox occurs in heap leaching process, in heap leaching solution, iron ion mainly exists with ferrous ion form, the step of reduction ferrous ion is eliminated for the follow-up copper that carries, adopt high temperature and high pressure method deironing, the product quantity of slag is little, environmental protection pressure is little, and scum can utilize by secondary；The sulphuric acid produced in iron removal does not need to neutralize, and directly returns dump leaching and recycles, comprehensively utilizes effective.
Description
Technical field
The present invention relates to the processing method of Copper Ores acid leaching liquor in wet type copper smelting process, what be specifically related to a kind of Copper Ores acid leaching liquor carries copper method for removing iron.
Background technology
Low-grade refractory selects secondary cupric oxide ore and secondary sulphide ore in traditional wet type copper smelting process, the extract technologies such as dump leaching, post leaching, drill traverse are adopted to be leached by copper therein, leachate obtains copper-rich liquid send to electrodeposition operation through extraction, back extraction operation, and in raffinate, substantial amounts of ferrum and other impurity needs could qualified discharge or reuses after processing.The conventional oxidation adopted neutralizes deironing and jarosite process deironing method, is required for consuming substantial amounts of oxidant and nertralizer, and the quantity of slag is big and copper is more with the loss of slag, and investment and production cost are higher, and the subsequent treatment difficulty of slag, environmental protection pressure is bigger.
Summary of the invention
The technical problem to be solved in the present invention: put forward the drawbacks described above of liquid method for removing iron after copper for conventional wet copper metallurgy, it is provided that the Copper Ores acid leaching liquor that a kind of copper leaching rate is high, production cost is low, efficiency is high carry copper method for removing iron.
The technical solution used in the present invention:
A kind of Copper Ores acid leaching liquor carry copper method for removing iron, comprise the following steps:
(1) dump leaching: collect the low-grade secondary cupric oxide ore and secondary copper sulfide mineral that produce in Copper Ores wet smelting process, secondary cupric oxide ore and secondary copper sulfide ore are crushed, and in the ratio mix homogeneously of 0.2 ~ 5:1, transports stockyard wet method dump leaching to；Do leaching agent with dilute sulfuric acid and carry out shower-bubble type, obtain the faintly acid leachate of cupric 0.2 ~ 10g/L, iron content 0.5 ~ 30g/L, pH1 ~ 3, leachate is sent to and puies forward copper process；
Dominant response formula is as follows:
Cu2(OH)2CO3+4H+=2Cu2++CO2+3H2O
Cu2O+2H+=Cu2++Cu+H2O
Cu+2Fe3+=Cu2++2Fe2+
Cu2O+2H++2Fe3+=2Cu2++H2O+2Fe2+
CuO+2H+=Cu2++H2O
CuSiO3·2H2O+2H++(n-3)H2O=Cu2++SiO2·nH2O
Cu2S+4Fe3+=2Cu2++S0+4Fe2+
CuS+2Fe3+=Cu2++2Fe2++S0
4Fe2++O2+4H+=4Fe3++2H2O
(2) copper process is put forward: leachate is undertaken carrying copper by extraction or ion exchange, obtains cupric 30 ~ 60g/L, the iron content copper segregation liquid lower than 500mg/L, obtains lean copper liquid simultaneously；Copper segregation liquid is sent to electrodeposition operation electrodeposition and obtains tough cathode；Lean copper liquid is delivered to rear liquid storage tank, it is sent to stockyard through complex acid oxidation processes to leach, when the ferrous iron content in lean copper liquid reaches 10 ~ 35g/L, ferric iron content 1 ~ 10g/L, lean for part copper liquid is delivered to iron removal step, make the iron concentration in system stable in the scope of 10 ~ 30g/L；
Copper electrodeposition dominant response formula:
Negative electrode: Cu2++2e=Cu
Anode: 4OH—=O2+2H2O+4e
(3) iron removal step: lean copper liquid is after filtering and impurity removing, more than steam preheating to 90 DEG C, by force (forcing) pump, lean copper liquid is squeezed into reactor, under oxidizing atmosphere, carry out High Temperature High Pressure continuous deferrization reaction, iron removal maintains temperature of reaction kettle 150 ~ 220 DEG C, pressure 1.0 ~ 2.0MPa, response time 2 ~ 5h, obtains ore pulp after reaction, ore pulp is through being filtrated to get bloodstone slag, after gained deironing, liquid storage tank after liquid return, returns dump leaching operation after complex acid oxidation processes.
Dominant response formula is as follows:
4Fe2++O2+4H+=4Fe3++2H2O
Fe2(SO4)3+3H2O=Fe2O3+3H2SO4
As the further optimization to technique scheme, the present invention takes techniques below measure:
Carrying in copper process and iron removal step, the oxidant adopted during complex acid oxidation processes is air, oxygen enrichment, pure oxygen, hydrogen peroxide, manganese dioxide or potassium permanganate, and the acidity after complex acid is at 25 ~ 80g/L.
Putting forward copper process also to include, by the electrodeposition waste liquid complex acid oxidation processes of electrodeposition operation, being circulated subsequently into dump leaching, after complex acid, acidity is 25 ~ 80g/L, ferric iron content 5 ~ 15g/L, total iron content 10 ~ 30g/L.
Iron removal step enters ferrous ion concentration 10 ~ 30g/L, ferric ion concentration 1 ~ 10g/L, copper ion concentration 0.2g/L ~ 10g/L, pH value 1 ~ 3 in the lean copper liquid of reactor.
The measuring of the lean copper liquid of part wherein delivering to iron removal step is the 5% ~ 40% of lean copper liquid total amount.
After the deironing obtained, liquid is containing Cu0.47-1.14g/L, Fe2+0.58-0.7g/L、Fe3+1.1-1.3g/L, sulphuric acid 25-50g/L.
The present invention, compared with traditional handicraft, has the advantage that
1, the present invention makes full use of the redox that iron ion and copper-sulphide ores occur in heap leaching process, iron ion in heap leaching solution is mainly existed with ferrous ion form, the step of reduction ferrous ion is eliminated for the attached copper that carries of follow-up extraction or ion-exchange absorption, lean copper liquid can directly adopt High Temperature High Pressure deironing simultaneously, good iron removal effect, step simplifies, it is easy to operation.
2, traditional copper hydrometallurgy method for removing iron adopts oxidation neutralisation or jarosite process deironing, and oxidant consumption is big, and copper recovery is low, and the quantity of slag is big, and environmental protection pressure is big；Comparing with traditional method, the present invention has the advantages such as oxidant consumption is little, copper leaching rate is high, reaction is fast, the product quantity of slag is little, is conducive to environmental protection.
3, the present invention adopts High Temperature High Pressure deironing, can reduce the loss of copper in solution, and the product quantity of slag is little, and environmental protection pressure is little, and scum can as iron-smelting raw material or as the raw material producing the pigment such as iron oxide red, iron oxide yellow simultaneously, it is achieved that the secondary of scum utilizes, and turns waste into wealth.
4, a large amount of sulphuric acid used in iron removal of the present invention need not neutralize, and can return to dump leaching and recycles, saved sulphuric acid, advantageously reduce production cost, comprehensively utilizes effective.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the present invention.
Detailed description of the invention
The technological process carrying copper method for removing iron of Copper Ores acid leaching liquor, referring to Fig. 1, main processes is: Copper Ores crushes hybrid reactor lixiviate copper electrodeposition tough cathode, lean copper liquid High Temperature High Pressure deironing scum.Aided process: the oxidation of lean copper liquid ferrum, the follow-up washing process of scum, electrodeposition effluent purifying etc..
Embodiment 1:A kind of Copper Ores acid leaching liquor carry copper method for removing iron, comprise the following steps:
(1) dump leaching: collect the low-grade secondary cupric oxide ore and secondary copper sulfide mineral that produce in Copper Ores wet smelting process, it is broken into respectively the fragment of 10-30mm size, then in secondary cupric oxide ore and copper-sulphide ores 0.2 ~ 5:1 ratio mix homogeneously (specifically press copper, ferrum, the proportioning of three kinds of elements of sulfur and determine), transport stockyard to and carry out wet method dump leaching；Do leaching agent shower-bubble type with dilute sulfuric acid, obtain the faintly acid leachate of cupric 0.2 ~ 10g/L, ferrum 0.5 ~ 30g/L, pH1 ~ 3；The leachate obtained is sent to and puies forward copper process；
(2) put forward copper process: leachate is carried copper by extracting process, obtain cupric 30 ~ 60g/L, the iron content copper segregation liquid lower than 500mg/L, obtain lean copper liquid simultaneously；Copper segregation liquid is sent to electrodeposition operation electrodeposition and obtains the tough cathode of purity 99.99%；Lean copper liquid is sent to stockyard after complex acid oxidation processes and leaches, when the ferrous iron content in lean copper liquid is 10 ~ 35g/L, ferric iron content 1 ~ 10g/L, the lean copper liquid of part is delivered to iron removal step deironing and (is determined according to circular flow, system bulk and ferrum leaching rate, the lean copper liquid measure returned is generally the 5% ~ 40% of total lean copper liquid, the present embodiment takes 15%), iron concentration controls in suitable scope (10 ~ 30g/L) the most at last；
(3) iron removal step: by lean copper liquid more than steam preheating to 90 DEG C, is squeezed into by force (forcing) pump and carries out High Temperature High Pressure continuous deferrization in reactor, maintains temperature of reaction kettle 150 ~ 220 DEG C, pressure 1.0 ~ 2.0MPa, response time 2 ~ 5h；The ore pulp that will generate after reacting discharges reactor, enters flash tank and reclaims heat, filters ore pulp and obtains scum, obtain bloodstone slag through pressure filter filter pressing scum under normal pressure, and after the deironing obtained, liquid storage tank after liquid return, returns dump leaching after complex acid oxidation processes.
After the deironing obtained after reaction in liquid, containing Cu2+0.47g/L、Fe2+0.7g/L、Fe3+1.1g/L, sulphuric acid 25g/L, obtain scum 49.4g, and iron content 55.2%, cupric 0.17% in scum, deironing rate is 88.6%.
Described carry in copper process and iron removal step, during lean copper liquid complex acid oxidation processes, oxidant adopts air, oxygen enrichment, pure oxygen, hydrogen peroxide, manganese dioxide or potassium permanganate, concrete grammar stirs 1-3 hour for being slowly added to by oxidant in reactive tank, oxidant adds excessive 10% than normal, institute's acid adding is dilute sulfuric acid, and the acidity after complex acid is at 25 ~ 80g/L.
Scum is outer after washing etc. processes to be sold, as iron-smelting raw material, it is possible to as the raw material of the pigment product such as iron oxide red, iron oxide yellow；Liquid is reused in whole technological process, closed cycle.
Embodiment 2:Copper Ores acid leaching liquor carry copper method for removing iron, operation, with example 1, is different in that:
(1) dump leaching: according to the ratio mix homogeneously of secondary cupric oxide ore and copper-sulphide ores 0.2 ~ 1, transports stockyard to and carries out wet method dump leaching；Do leaching agent shower-bubble type with dilute sulfuric acid, obtain the faintly acid leachate of cupric 0.2 ~ 3g/L, ferrum 0.5 ~ 10g/L, pH1 ~ 3；The leachate obtained is sent to and puies forward copper process；
(2) put forward copper process: leachate carries copper by extracting process, obtain cupric 30 ~ 60g/L, the iron content copper segregation liquid lower than 500mg/L；Lean copper liquid after extraction is containing Cu0.5g/L, Fe2+14.3g/L、Fe3+1.1g/L, pH1.2, lean copper liquid is sent to iron removal step；
(3) iron removal step: by lean copper liquid through steam preheating to 90-98 DEG C, is squeezed into by force (forcing) pump and carries out High Temperature High Pressure continuous deferrization in reactor, during lean copper liquid deironing: reaction temperature 170 DEG C, reaction pressure 1.2MPa, partial pressure of oxygen 0.25MPa, response time 3h；Obtain after deironing in liquid: containing Cu0.74g/L, Fe2+0.58g/L、Fe3+1.3g/L, sulphuric acid 35g/L；Obtain scum 63.7g, iron content 56.3%, cupric 0.21%, deironing rate 90.6% in scum.
By the electrodeposition waste liquid after purification and liquid, the oxidation of lean copper liquid mixing complex acid after deironing, circulating subsequently into dump leaching operation, the acidity after complex acid is at 25 ~ 80g/L, ferric iron content 5 ~ 15g/L；The leachate obtained is sent to again and puies forward copper process.During complex acid oxidation processes, oxidant adopts pure oxygen, is passed into by pure oxygen in reactive tank and stirs 1-3 hour, and institute's acid adding is dilute sulfuric acid, and the acidity after complex acid is at 25 ~ 80g/L.
Embodiment 3:Copper Ores acid leaching liquor carry copper method for removing iron, operation, with example 1, is different in that:
(1) dump leaching: according to the ratio mix homogeneously of secondary cupric oxide ore and copper-sulphide ores 3 ~ 5:1, transports stockyard to and carries out wet method dump leaching；Do leaching agent shower-bubble type with dilute sulfuric acid, obtain the faintly acid leachate of cupric 5 ~ 10g/L, ferrum 10 ~ 30g/L, pH1 ~ 3；
(2) copper process is put forward: it is attached that leachate dump leaching obtained carries out ion-exchange absorption by resin, obtains cupric 30 ~ 60g/L, the iron content copper segregation liquid lower than 500mg/L；The lean copper liquid obtained is containing Cu1.2g/L, Fe2+23.7g/L、Fe3+0.8g/L, pH3.0, lean copper liquid is sent to iron removal step；
Lean copper liquid is sent to stockyard after complex acid oxidation processes and leaches, when the ferrous iron content in lean copper liquid is 10 ~ 35g/L, ferric iron content 5 ~ 10g/L, the lean copper liquid of part delivers to iron removal step deironing, amount is total amount the 35% of the lean copper liquid of return, by stable for iron concentration in the scope of 20 ~ 30g/L；
(3) iron removal step: by lean copper liquid more than steam preheating to 90 DEG C, reaction temperature 175 DEG C, reaction pressure 1.2MPa, partial pressure of oxygen 0.2MPa, response time 3.5h during deironing, obtain liquid after deironing, wherein containing Cu1.14g/L, Fe2+0.6g/L、Fe3+1.2g/L, sulphuric acid 40g/L, obtain scum 74.2g, iron content 61.4%, cupric 0.22%, deironing rate 92.8% in scum.
Liquid after electrodeposition waste liquid after purification, deironing and lean copper liquid together being mixed complex acid oxidation, circulates subsequently into dump leaching operation, the acidity after complex acid is at 25 ~ 80g/L, ferric iron content 5 ~ 15g/L；The leachate obtained is sent to and puies forward copper process.During complex acid oxidation, oxidant adopts hydrogen peroxide, is slowly added to by oxidant in reactive tank and stirs 1-3 hour, and oxidant adds excessive 10% than normal, and institute's acid adding is dilute sulfuric acid, and the acidity after complex acid is at 40 ~ 80g/L.
Embodiment 4:Copper Ores acid leaching liquor carry copper method for removing iron, operation, with example 3, is different in that:
Leachate dump leaching obtained carries out ion exchange by resin absorption, and the lean copper liquid obtained is containing Cu0.7g/L, Fe2+26.6g/L、Fe3+1.1g/L, pH2.4, lean copper liquid sends to iron removal step；
During lean copper liquid deironing, reaction temperature 185 DEG C, reaction pressure 1.5MPa, partial pressure of oxygen 0.3MPa, response time 3.0h, obtain liquid after deironing, wherein containing Cu0.63g/L, Fe2+0.55g/L、Fe3+1.2g/L, sulphuric acid 45g/L, obtain scum 95.3g, slag iron content 54.7%, Copper in Slag 0.18%, deironing rate 93.84%.
Embodiment 5:Copper Ores acid leaching liquor carry copper method for removing iron, operation, with example 3, is different in that:
The exchange of resin absorption ion sent to by leachate dump leaching obtained, and lean copper liquid is containing Cu1.0g/L, Fe2+31.3g/L、Fe3+1.0g/L, pH2.5, after absorption, liquid sends to iron removal step；
Lean copper liquid deironing, reaction temperature 200 DEG C, reaction pressure 1.75MPa, partial pressure of oxygen 0.2MPa, response time 4h, obtain liquid after deironing, wherein containing Cu0.92g/L, Fe2+0.65g/L、Fe3+1.1g/L, sulphuric acid 50g/L, obtain scum 106.2g, iron content 58.2%, cupric 0.19%, deironing rate 94.7% in scum.
Enumerated above is only presently preferred embodiments of the present invention; it is not offered as any pro forma restriction to the present invention; all on the basis of technical solution of the present invention design, any amendment that those skilled in the art make or equivalent replace, belong to protection scope of the present invention.
Claims (3)
1. Copper Ores acid leaching liquor carry a copper method for removing iron, it is characterized in that: the method comprises the following steps:
(1) dump leaching: collect the low-grade secondary cupric oxide ore and secondary copper sulfide mineral that produce in Copper Ores wet smelting process, will
Secondary cupric oxide ore and secondary copper sulfide ore crush, and in the ratio mix homogeneously of 0.2 ~ 5:1, transport stockyard wet method dump leaching to；Do leaching agent with dilute sulfuric acid and carry out shower-bubble type, obtain the faintly acid leachate of cupric 0.2 ~ 10g/L, iron content 0.5 ~ 30g/L, pH1 ~ 3, leachate is sent to and puies forward copper process；
(2) copper process is put forward: leachate is undertaken carrying copper by extraction or ion exchange, obtains cupric 30 ~ 60g/L, the iron content copper segregation liquid lower than 500mg/L, obtains lean copper liquid simultaneously；Copper segregation liquid is sent to electrodeposition operation electrodeposition and obtains tough cathode；Lean copper liquid is delivered to rear liquid storage tank, it is sent to stockyard through complex acid oxidation processes to leach, when the ferrous iron content in lean copper liquid reaches 10 ~ 35g/L, ferric iron content 1 ~ 10g/L, lean for part copper liquid is delivered to iron removal step, make the iron concentration in system stable in the scope of 10 ~ 30g/L；The measuring of the lean copper liquid of part wherein delivering to iron removal step is the 5% ~ 40% of lean copper liquid total amount；
(3) iron removal step: lean copper liquid is after filtering and impurity removing, more than steam preheating to 90 DEG C, by force (forcing) pump, lean copper liquid is squeezed into reactor, under oxidizing atmosphere, carry out High Temperature High Pressure continuous deferrization reaction, course of reaction maintains temperature of reaction kettle 150 ~ 220 DEG C, pressure 1.0 ~ 2.0MPa, response time 2 ~ 5h, obtaining ore pulp after reaction, ore pulp is through being filtrated to get bloodstone slag
After gained deironing, liquid storage tank after liquid return, returns dump leaching operation after complex acid oxidation processes；
Described carrying in copper process and iron removal step, the oxidant adopted during complex acid oxidation processes is air, pure oxygen, hydrogen peroxide, manganese dioxide or potassium permanganate, and the acidity after complex acid is at 25 ~ 80g/L；
The described copper process that carries also includes, by the electrodeposition waste liquid complex acid oxidation processes of electrodeposition operation, being circulated subsequently into dump leaching, and after complex acid, acidity is 25 ~ 80g/L, ferric iron content 5 ~ 15g/L, total iron content 10 ~ 30g/L.
2. according to claim 1 carry copper method for removing iron, it is characterised in that: described iron removal step enters ferrous ion concentration 10 ~ 30g/L, ferric ion concentration 1 ~ 10g/L, copper ion concentration 0.2g/L ~ 10g/L, pH value 1 ~ 3 in the lean copper liquid of reactor.
3. according to any one of claim 1-2, carry copper method for removing iron, it is characterised in that: containing Cu0.47-1.14g/L, Fe in liquid after described deironing2+0.58-0.7g/L、Fe3+1.1-1.3g/L, sulphuric acid 25-50g/L.
Priority Applications (1)
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| CN104962740A (en) * | 2015-07-15 | 2015-10-07 | 长沙有色冶金设计研究院有限公司 | Method for preventing deposition and scaling of hematite iron removal reactor |
| CN105779773B (en) * | 2016-04-20 | 2017-11-17 | 广东省稀有金属研究所 | A kind of method that ambrose alloy iron is separated from electroplating sludge |
| 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 |
| CN106967888A (en) * | 2017-05-19 | 2017-07-21 | 伍继斌 | A kind of Copper Ores refine auxiliary agent and the Copper Ores refinement method based on the refinement auxiliary agent |
| CN112662892B (en) * | 2020-12-15 | 2022-06-14 | 衢州华友钴新材料有限公司 | High-pressure nickel-iron doped separation method for pickle liquor |
| CN114622247B (en) * | 2021-04-23 | 2024-04-26 | 东莞市盛德电解设备科技有限公司 | Copper extraction process of ore low-concentration acid leaching solution |
| CN115161476B (en) * | 2022-07-20 | 2023-06-02 | 万宝矿产有限公司 | Method for reducing concentration of ferric acid in secondary copper sulfide ore biological heap leaching system |
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