CN104232924A - Copper extraction and iron removal method of copper ore acid leaching liquid - Google Patents
Copper extraction and iron removal method of copper ore acid leaching liquid Download PDFInfo
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- CN104232924A CN104232924A CN201410494688.3A CN201410494688A CN104232924A CN 104232924 A CN104232924 A CN 104232924A CN 201410494688 A CN201410494688 A CN 201410494688A CN 104232924 A CN104232924 A CN 104232924A
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- copper
- liquid
- iron
- leaching
- poor
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 239000010949 copper Substances 0.000 title claims abstract description 146
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 133
- 239000007788 liquid Substances 0.000 title claims abstract description 89
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 69
- 238000002386 leaching Methods 0.000 title claims abstract description 56
- 239000002253 acid Substances 0.000 title claims abstract description 43
- 238000000605 extraction Methods 0.000 title claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002893 slag Substances 0.000 claims abstract description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005751 Copper oxide Substances 0.000 claims abstract description 10
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 10
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 9
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 238000005342 ion exchange Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000004070 electrodeposition Methods 0.000 claims description 15
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 8
- 238000005204 segregation Methods 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical group [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- 230000032258 transport Effects 0.000 claims description 4
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 3
- 238000013467 fragmentation Methods 0.000 claims description 3
- 238000006062 fragmentation reaction Methods 0.000 claims description 3
- 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
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 229910001447 ferric ion Inorganic materials 0.000 claims description 2
- -1 iron ions Chemical class 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000002950 deficient Effects 0.000 abstract 3
- 229910000365 copper sulfate Inorganic materials 0.000 abstract 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract 2
- 125000004122 cyclic group Chemical group 0.000 abstract 2
- 229910052595 hematite Inorganic materials 0.000 abstract 1
- 239000011019 hematite Substances 0.000 abstract 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 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
- 229910052935 jarosite Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000009867 copper metallurgy Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000004763 sulfides Chemical group 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a copper extraction and iron removal method of copper ore acid leaching liquid. The method comprises the following steps: breaking secondary copper oxide ore and secondary copper sulfate ore, mixing and performing wet-process dump leaching; using dilute sulphuric acid as a leaching agent for conducting spraying and leaching to obtain faintly acid leaching liquid; extracting copper from the leaching liquid through extraction or ion exchange to obtain copper-rich liquid and copper-deficient liquid; electrodepositing the copper-rich liquid to obtain cathode copper; performing high-temperature high-pressure continuous iron removal on the copper-deficient liquid in an oxidizing atmosphere to obtain ore pulp, filtering to obtain hematite slag, acidifying and oxidizing part of the copper-deficient liquid, and feeding to a stock dump for cyclic leaching. According to the method, iron ions and the copper sulfate ore are subjected to oxidative reduction in the dump leaching process; iron ions in the dump leaching liquid mainly exist in the form of divalent iron ions, so that the step of reducing divalent iron ions is removed for subsequent copper extraction; iron is removed by a high-temperature high-pressure process, so that the slag yield is low, the environmental protection pressure is small, and the iron slag can be reutilized; sulfuric acid generated in the iron removal process does not need to be neutralized and directly returns to the stock dump for cyclic leaching, so that the comprehensive utilization effect is good.
Description
Technical field
The present invention relates to the treatment process 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 copper 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 wherein, leach liquor obtains rich copper liquid send to electrodeposition operation through extraction, back extraction operation, and iron a large amount of in raffinate and other impurity could qualified discharge or reuses after needing process.The conventional oxidation neutralized ex iron that adopts and jarosite process are except iron processes, and all need to consume a large amount of oxygenants and neutralizing agent, the quantity of slag is large and copper is more with the loss of slag, investment and production cost higher, the subsequent disposal difficulty of slag, environmental protection pressure is larger.
Summary of the invention
The technical problem to be solved in the present invention: the above-mentioned defect carrying liquid method for removing iron after copper for conventional wet copper metallurgy, what provide the Copper Ores acid leaching liquor that a kind of copper leaching rate is high, production cost is low, efficiency is high carries copper method for removing iron.
The technical solution used in the present invention:
Copper Ores acid leaching liquor carry a copper method for removing iron, comprise the following steps:
(1) dump leaching: collect the low-grade secondary copper oxide ore and secondary copper sulfide mineral that produce in Copper Ores wet smelting process, by secondary copper oxide ore and secondary copper sulfide ore fragmentation, and mixes in the ratio of 0.2 ~ 5:1, transports stockyard wet method dump leaching to; Do leaching agent with dilute sulphuric acid and carry out shower-bubble type, obtain the slightly acidic leach liquor of cupric 0.2 ~ 10g/L, iron content 0.5 ~ 30g/L, pH1 ~ 3, leach liquor is sent to and puies forward copper process;
Principal reaction formula is as follows:
Cu
2(OH)
2CO
3+4H
+=2Cu
2++CO
2+3H
2O
Cu
2O+2H
+=Cu
2++Cu+H
2O
Cu+2Fe
3+=Cu
2++2Fe
2+
Cu
2O+2H
++2Fe
3+=2Cu
2++H
2O+2Fe
2+
CuO+2H
+=Cu
2++H
2O
CuSiO
3·2H
2O+2H
++(n-3)H
2O=Cu
2++SiO
2·nH
2O
Cu
2S+4Fe
3+=2Cu
2++S
0+4Fe
2+
CuS+2Fe
3+=Cu
2++2Fe
2++S
0
4Fe
2++O
2+4H
+=4Fe
3++2H
2O
(2) copper process is put forward: leach liquor is undertaken carrying copper by extraction or ion-exchange, obtains cupric 30 ~ 60g/L, iron content lower than the copper segregation liquid of 500mg/L, obtains poor copper liquid simultaneously; Copper segregation liquid is sent to electrodeposition operation electrodeposition and obtains cathode copper; Poor copper liquid is delivered to rear liquid storage tank, be sent to stockyard through complex acid oxide treatment to leach, when the ferrous iron content in poor copper liquid reaches 10 ~ 35g/L, ferric iron content 1 ~ 10g/L, poor for part copper liquid is delivered to iron removal step, make the iron concentration in system be stabilized in the scope of 10 ~ 30g/L;
Copper electrodeposition principal reaction formula:
Negative electrode: Cu
2++ 2e=Cu
Anode: 4OH
-=O
2+ 2H
2o+4e
(3) iron removal step: poor copper liquid is after filtration after removal of impurities, more than steam preheating to 90 DEG C, by force (forcing) pump, poor copper liquid is squeezed into reactor, under oxidizing atmosphere, carry out the reaction of High Temperature High Pressure continuous deferrization, in iron removal, maintain temperature of reaction kettle 150 ~ 220 DEG C, pressure 1.0 ~ 2.0MPa, reaction times 2 ~ 5h, obtains ore pulp after reaction, and ore pulp obtains rhombohedral iron ore slag after filtration, after gained deironing, liquid returns rear liquid storage tank, returns dump leaching operation after complex acid oxide treatment.
Principal reaction formula is as follows:
4Fe
2++O
2+4H
+=4Fe
3++2H
2O
Fe
2(SO
4)
3+3H
2O=Fe
2O
3+3H
2SO
4
As the further optimization to technique scheme, the present invention takes following technical measures:
Carry in copper process and iron removal step, the oxygenant adopted during complex acid oxide treatment is air, oxygen enrichment, pure oxygen, hydrogen peroxide, Manganse Dioxide or potassium permanganate, and the acidity after complex acid is at 25 ~ 80g/L.
Put forward copper process also to comprise the electrodeposition waste liquid complex acid oxide treatment of electrodeposition operation, then enter dump leaching and circulate, after complex acid, acidity is 25 ~ 80g/L, ferric iron content 5 ~ 15g/L, total iron content 10 ~ 30g/L.
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 poor copper liquid of reactor is entered in iron removal step.
The amount wherein delivering to the part poor copper liquid of iron removal step is 5% ~ 40% of poor copper liquid total amount.
After the deironing obtained, liquid is containing Cu0.47-1.14g/L, Fe
2+0.58-0.7g/L, Fe
3+1.1-1.3g/L, sulfuric acid 25-50g/L.
the present invention, compared with traditional technology, has the following advantages:
1, the present invention makes full use of the redoxomorphism 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, for the step that copper eliminates reduction ferrous ion is put forward in follow-up extraction or ion-exchange absorption, poor copper liquid can directly adopt High Temperature High Pressure deironing simultaneously, good iron removal effect, step simplifies, easy handling.
2, traditional copper hydrometallurgy method for removing iron adopts oxidation neutralisation or jarosite process deironing, and oxygenant consumption is large, and copper recovery is low, and the quantity of slag is large, and environmental protection pressure is large; Compare with traditional method, the present invention has the advantages such as oxygenant 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 be used as iron-smelting raw material or as the raw material producing the pigment such as iron oxide red, iron oxide yellow, achieves the second stage employ of scum, turn waste into wealth simultaneously.
4, a large amount of sulfuric acid used in iron removal of the present invention do not need neutralization, can return dump leaching recycle, save sulfuric acid, are conducive to reducing production cost, fully utilize effective.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
The technical process carrying copper method for removing iron of Copper Ores acid leaching liquor, see Fig. 1, main processes is: Copper Ores fragmentation mixing---dump leaching---carry copper---electrodeposition---cathode copper, poor copper liquid---High Temperature High Pressure deironing---scum.Aided process: the oxidation of poor copper liquid iron, the follow-up washing process of scum, electrodeposition effluent purifying etc.
embodiment 1:copper Ores acid leaching liquor carry a copper method for removing iron, comprise the following steps:
(1) dump leaching: collect the low-grade secondary copper 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 mix (specifically determining by the proportioning of copper, iron, sulphur three kinds of elements) in the ratio of secondary copper oxide ore and copper-sulphide ores 0.2 ~ 5:1, transporting stockyard to carries out wet method dump leaching; Do leaching agent shower-bubble type with dilute sulphuric acid, obtain the slightly acidic leach liquor of cupric 0.2 ~ 10g/L, iron 0.5 ~ 30g/L, pH1 ~ 3; The leach liquor obtained is sent to and puies forward copper process;
(2) put forward copper process: leach liquor is carried copper by extracting process, obtain cupric 30 ~ 60g/L, iron content lower than the copper segregation liquid of 500mg/L, obtain poor copper liquid simultaneously; Copper segregation liquid is sent to the cathode copper that electrodeposition operation electrodeposition obtains purity 99.99%; Poor copper liquid is sent to stockyard and leaches after complex acid oxide treatment, when the ferrous iron content in poor copper liquid is 10 ~ 35g/L, ferric iron content 1 ~ 10g/L, the poor copper liquid of part is delivered to iron removal step deironing and (is determined according to circular flow, system bulk and iron leaching yield, the poor copper liquid measure returned is generally 5% ~ 40% of total poor copper liquid, the present embodiment gets 15%), iron concentration controls in suitable scope (10 ~ 30g/L) the most at last;
(3) iron removal step: by poor copper liquid more than steam preheating to 90 DEG C, squeezed in reactor carry out High Temperature High Pressure continuous deferrization by force (forcing) pump, maintains temperature of reaction kettle 150 ~ 220 DEG C, pressure 1.0 ~ 2.0MPa, reaction times 2 ~ 5h; The ore pulp generated after reaction is discharged reactor, and enter flash drum and reclaim heat, filter ore pulp under normal pressure and obtain scum, obtain rhombohedral iron ore slag through pressure filter press filtration scum, after the deironing obtained, liquid returns rear liquid storage tank, after complex acid oxide treatment, return dump leaching.
After the deironing obtained after reaction in liquid, containing Cu
2+0.47g/L, Fe
2+0.7g/L, Fe
3+1.1g/L, sulfuric acid 25g/L, obtain scum 49.4g, and iron content 55.2%, cupric 0.17% in scum, deironing rate is 88.6%.
Describedly carry in copper process and iron removal step, during poor copper liquid complex acid oxide treatment, oxygenant adopts air, oxygen enrichment, pure oxygen, hydrogen peroxide, Manganse Dioxide or potassium permanganate, concrete grammar stirs 1-3 hour for slowly being added in reactive tank by oxygenant, oxygenant adds excessive 10% than normal, institute's acid adding is dilute sulphuric acid, and the acidity after complex acid is at 25 ~ 80g/L.
Scum is outer after the process such as washing to be sold, and as iron-smelting raw material, also can be used as the raw material of the pigment product such as iron oxide red, iron oxide yellow; Liquid is reused in whole technical process, closed cycle.
embodiment 2:copper Ores acid leaching liquor carry copper method for removing iron, operation is with example 1, and difference is:
(1) dump leaching: mix according to the ratio of secondary copper 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 sulphuric acid, obtain the slightly acidic leach liquor of cupric 0.2 ~ 3g/L, iron 0.5 ~ 10g/L, pH1 ~ 3; The leach liquor obtained is sent to and puies forward copper process;
(2) put forward copper process: leach liquor carries copper by extracting process, obtain cupric 30 ~ 60g/L, iron content lower than the copper segregation liquid of 500mg/L; Poor copper liquid after extraction is containing Cu0.5g/L, Fe
2+14.3g/L, Fe
3+1.1g/L, pH1.2, poor copper liquid is sent to iron removal step;
(3) iron removal step: by poor copper liquid through steam preheating to 90-98 DEG C, squeezed in reactor by force (forcing) pump and carry out High Temperature High Pressure continuous deferrization, during poor copper liquid deironing: temperature of reaction 170 DEG C, reaction pressure 1.2MPa, oxygen partial pressure 0.25MPa, reaction times 3h; To obtain after deironing in liquid: containing Cu0.74g/L, Fe
2+0.58g/L, Fe
3+1.3g/L, sulfuric acid 35g/L; Obtain scum 63.7g, iron content 56.3%, cupric 0.21% in scum, deironing rate 90.6%.
By purification after electrodeposition waste liquid be oxidized with liquid, poor copper liquid mixing complex acid after deironing, then enter dump leaching operation circulate, the acidity after complex acid at 25 ~ 80g/L, ferric iron content 5 ~ 15g/L; The leach liquor obtained is sent to again and puies forward copper process.During complex acid oxide treatment, oxygenant adopts pure oxygen, and passed in reactive tank by pure oxygen and stir 1-3 hour, institute's acid adding is dilute sulphuric 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 is with example 1, and difference is:
(1) dump leaching: mix according to the ratio of secondary copper 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 sulphuric acid, obtain the slightly acidic leach liquor of cupric 5 ~ 10g/L, iron 10 ~ 30g/L, pH1 ~ 3;
(2) put forward copper process: leach liquor dump leaching obtained carries out ion-exchange absorption by resin, obtain cupric 30 ~ 60g/L, iron content lower than the copper segregation liquid of 500mg/L; The poor copper liquid obtained is containing Cu1.2g/L, Fe
2+23.7g/L, Fe
3+0.8g/L, pH3.0, poor copper liquid is sent to iron removal step;
Poor copper liquid is sent to stockyard and leaches after complex acid oxide treatment, when the ferrous iron content in poor copper liquid is 10 ~ 35g/L, ferric iron content 5 ~ 10g/L, the poor copper liquid of part delivers to iron removal step deironing, the amount of the poor copper liquid returned is 35% of total amount, is stabilized in by iron concentration in the scope of 20 ~ 30g/L;
(3) iron removal step: by poor copper liquid more than steam preheating to 90 DEG C, temperature of reaction 175 DEG C, reaction pressure 1.2MPa, oxygen partial pressure 0.2MPa, reaction times 3.5h during deironing, obtain liquid after deironing, wherein containing Cu1.14g/L, Fe
2+0.6g/L, Fe
3+1.2g/L, sulfuric acid 40g/L, obtain scum 74.2g, iron content 61.4%, cupric 0.22% in scum, deironing rate 92.8%.
By the electrodeposition waste liquid after purification, liquid and poor copper liquid together mix complex acid oxidation after deironing, then enter the circulation of dump leaching operation, the acidity after complex acid at 25 ~ 80g/L, ferric iron content 5 ~ 15g/L; The leach liquor obtained is sent to and puies forward copper process.During complex acid oxidation, oxygenant adopts hydrogen peroxide, is slowly added in reactive tank by oxygenant and stirs 1-3 hour, and oxygenant adds excessive 10% than normal, and institute's acid adding is dilute sulphuric 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 is with example 3, and difference is:
Leach liquor dump leaching obtained carries out ion-exchange by resin absorption, and the poor copper liquid obtained is containing Cu0.7g/L, Fe
2+26.6g/L, Fe
3+1.1g/L, pH2.4, poor copper liquid sends to iron removal step;
During poor copper liquid deironing, temperature of reaction 185 DEG C, reaction pressure 1.5MPa, oxygen partial pressure 0.3MPa, reaction times 3.0h, obtains liquid after deironing, wherein containing Cu0.63g/L, Fe
2+0.55g/L, Fe
3+1.2g/L, sulfuric 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 is with example 3, and difference is:
Resin absorption ion-exchange sent to by leach liquor dump leaching obtained, and poor copper liquid is containing Cu1.0g/L, Fe
2+31.3g/L, Fe
3+1.0g/L, pH2.5, after absorption, liquid sends to iron removal step;
The deironing of poor copper liquid, temperature of reaction 200 DEG C, reaction pressure 1.75MPa, oxygen partial pressure 0.2MPa, reaction times 4h, obtains liquid after deironing, wherein containing Cu 0.92g/L, Fe
2+0.65g/L, Fe
3+1.1g/L, sulfuric acid 50g/L, obtain scum 106.2g, iron content 58.2%, cupric 0.19% in scum, deironing rate 94.7%.
Citedly above be only preferred embodiment of the present invention; do not represent any pro forma restriction of the present invention; all on the basis of technical solution of the present invention design, any amendment that those skilled in the art do or equivalent replacement, all belong to protection scope of the present invention.
Claims (6)
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 copper oxide ore and secondary copper sulfide mineral that produce in Copper Ores wet smelting process, by secondary copper oxide ore and secondary copper sulfide ore fragmentation, and mixes in the ratio of 0.2 ~ 5:1, transports stockyard wet method dump leaching to; Do leaching agent with dilute sulphuric acid and carry out shower-bubble type, obtain the slightly acidic leach liquor of cupric 0.2 ~ 10g/L, iron content 0.5 ~ 30g/L, pH1 ~ 3, leach liquor is sent to and puies forward copper process;
(2) copper process is put forward: leach liquor is undertaken carrying copper by extraction or ion-exchange, obtains cupric 30 ~ 60g/L, iron content lower than the copper segregation liquid of 500mg/L, obtains poor copper liquid simultaneously; Copper segregation liquid is sent to electrodeposition operation electrodeposition and obtains cathode copper; Poor copper liquid is delivered to rear liquid storage tank, be sent to stockyard through complex acid oxide treatment to leach, when the ferrous iron content in poor copper liquid reaches 10 ~ 35g/L, ferric iron content 1 ~ 10g/L, poor for part copper liquid is delivered to iron removal step, make the iron concentration in system be stabilized in the scope of 10 ~ 30g/L;
(3) iron removal step: poor copper liquid is after filtration after removal of impurities, more than steam preheating to 90 DEG C, by force (forcing) pump, poor copper liquid is squeezed into reactor, under oxidizing atmosphere, carry out the reaction of High Temperature High Pressure continuous deferrization, in reaction process, maintain temperature of reaction kettle 150 ~ 220 DEG C, pressure 1.0 ~ 2.0MPa, reaction times 2 ~ 5h, obtains ore pulp after reaction, and ore pulp obtains rhombohedral iron ore slag after filtration, after gained deironing, liquid returns rear liquid storage tank, returns dump leaching operation after complex acid oxide treatment.
2. according to claim 1ly carry copper method for removing iron, it is characterized in that: described in carry in copper process and iron removal step, the oxygenant adopted during complex acid oxide treatment is air, oxygen enrichment, pure oxygen, hydrogen peroxide, Manganse Dioxide or potassium permanganate, and the acidity after complex acid is at 25 ~ 80g/L.
3. according to claim 2ly carry copper method for removing iron, it is characterized in that: described in put forward copper process and also comprise the electrodeposition waste liquid complex acid oxide treatment of electrodeposition operation, then enter dump leaching and circulate, after complex acid, acidity is 25 ~ 80g/L, ferric iron content 5 ~ 15g/L, total iron content 10 ~ 30g/L.
4. according to claim 1ly carry copper method for removing iron, it is characterized in that: in described iron removal step, enter 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 poor copper liquid of reactor.
5. according to claim 1ly carry copper method for removing iron, it is characterized in that: the amount wherein delivering to the part poor copper liquid of iron removal step is 5% ~ 40% of poor copper liquid total amount.
6. according to any one of claim 1-5, carry copper method for removing iron, it is characterized in that: after described deironing in liquid containing Cu0.47-1.14g/L, Fe
2+0.58-0.7g/L, Fe
3+1.1-1.3g/L, sulfuric acid 25-50g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410494688.3A CN104232924B (en) | 2014-09-25 | 2014-09-25 | A kind of Copper Ores acid leaching liquor carry copper method for removing iron |
Applications Claiming Priority (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 |
| CN105779773A (en) * | 2016-04-20 | 2016-07-20 | 广东省稀有金属研究所 | Method for separating nickel, copper and iron from electroplating sludge |
| 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 |
| 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 |
| CN112662892A (en) * | 2020-12-15 | 2021-04-16 | 衢州华友钴新材料有限公司 | High-pressure nickel-iron doped separation method for pickle liquor |
| CN114622247A (en) * | 2021-04-23 | 2022-06-14 | 东莞市盛德电解设备科技有限公司 | Copper extraction process for low-concentration acid leaching solution of ore |
| WO2024016522A1 (en) * | 2022-07-20 | 2024-01-25 | 万宝矿产有限公司 | Method for reducing acid and iron concentrations in secondary copper sulfide ore bio-heap leaching system |
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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 |
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| 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 |
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| CN112662892A (en) * | 2020-12-15 | 2021-04-16 | 衢州华友钴新材料有限公司 | High-pressure nickel-iron doped separation method for pickle liquor |
| 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 |
| CN114622247A (en) * | 2021-04-23 | 2022-06-14 | 东莞市盛德电解设备科技有限公司 | Copper extraction process for low-concentration acid leaching solution of ore |
| 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 |
| WO2024016522A1 (en) * | 2022-07-20 | 2024-01-25 | 万宝矿产有限公司 | Method for reducing acid and iron concentrations in secondary copper sulfide ore bio-heap leaching system |
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