CN102864313A - Smelting method of natural copper mine - Google Patents
Smelting method of natural copper mine Download PDFInfo
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- CN102864313A CN102864313A CN2011101882227A CN201110188222A CN102864313A CN 102864313 A CN102864313 A CN 102864313A CN 2011101882227 A CN2011101882227 A CN 2011101882227A CN 201110188222 A CN201110188222 A CN 201110188222A CN 102864313 A CN102864313 A CN 102864313A
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- copper
- slag
- natural
- blister
- anode
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 239
- 239000010949 copper Substances 0.000 title claims abstract description 122
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 120
- 238000003723 Smelting Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000002893 slag Substances 0.000 claims abstract description 106
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 52
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 34
- 229910052742 iron Inorganic materials 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012141 concentrate Substances 0.000 claims abstract description 18
- 230000002829 reductive effect Effects 0.000 claims abstract description 18
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 14
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 13
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 13
- 239000004571 lime Substances 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 38
- 239000003500 flue dust Substances 0.000 claims description 30
- 238000002844 melting Methods 0.000 claims description 29
- 230000008018 melting Effects 0.000 claims description 29
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 28
- 239000003546 flue gas Substances 0.000 claims description 28
- 229960004643 cupric oxide Drugs 0.000 claims description 22
- 238000000926 separation method Methods 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 16
- 238000005352 clarification Methods 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000009423 ventilation Methods 0.000 claims description 8
- 238000007499 fusion processing Methods 0.000 claims description 7
- 230000005484 gravity Effects 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 9
- 239000005751 Copper oxide Substances 0.000 abstract description 8
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000000779 smoke Substances 0.000 abstract 1
- 239000004071 soot Substances 0.000 abstract 1
- 239000008151 electrolyte solution Substances 0.000 description 12
- 239000000571 coke Substances 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 9
- 239000000428 dust Substances 0.000 description 9
- 238000009434 installation Methods 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000003610 charcoal Substances 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 6
- 235000011613 Pinus brutia Nutrition 0.000 description 6
- 241000018646 Pinus brutia Species 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 210000000078 claw Anatomy 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910021653 sulphate ion Inorganic materials 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 5
- 150000002739 metals Chemical group 0.000 description 4
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 3
- 241000784732 Lycaena phlaeas Species 0.000 description 3
- 241001062472 Stokellia anisodon Species 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000012946 outsourcing Methods 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a smelting method of natural copper mine. According to weight, 95-105 parts of copper concentrate, 35-45 parts of iron-bearing slag, 1-5 parts of lime and 0-10 parts of soot are smashed and mixed to prepare particles. The particles are smelted through reduction at high temperature and separated naturally to obtain smoke, rough slag and a first part of crude copper. The temperature of the crude copper is kept at the temperature of 1150-1250 DEG C, and the crude copper is cleared to be separated naturally to obtain slag, copper matte and a second part of crude copper, and the first part of crude copper and the second part of crude copper are combined to obtain total crude copper. The total crude copper is smelted, ventilated and oxidized, and silica is added to make slag to obtain copper oxide and remained slag. The remained slag is separated, a reduction agent is added, and the copper oxide is fully reduced and smelted to obtain anode copper. The anode copper is used as an anode, an electrolytic copper plate is used as a cathode, and electrolytic copper is obtained after fully electrolysis in acidic electrolysis liquid. The technological process is simple, low in production cost and small in environment pollution. The obtained electrolytic copper is good in quality, copper content is 99.95%, and comprehensive recovery rate is 96%.
Description
Technical field
The present invention relates to a kind of smelting process of natural copper mine, more specifically, relate to the method for the natural copper mine smelting that a kind of copper exists with the elemental metals form.
Background technology
The positive copper mine of fiber crops is the natural copper mine of domestic contrast uniqueness, and copper is different with the form that sulfide exists in copper wherein and the common copper mine, mainly is that the form with elemental metals copper exists; The content of sulphur and iron is also very low in the copper mine.Present copper mine smelting technique mainly be for copper with the common copper mine that sulphided form exists, there is no the independent smelting process that is suitable for the natural copper mine that copper exists with the elemental metals form.Smelt numb positive copper mine if use for the traditional technology of common copper mine, copper content is higher in the waste of fusion process, and the copper recovery of whole technique is low.
Summary of the invention
The technical problem to be solved in the present invention is, this problem of independent smelting process for not being suitable at present the natural copper mine that copper exists with the elemental metals form provides a kind of smelting process that is suitable for this type of natural copper mine.
The technical problem to be solved in the present invention realizes by following proposal: a kind of smelting process of natural copper mine is provided, and the method may further comprise the steps:
(1) batching: copper ore concentrates, iron slag, lime and flue dust are fully pulverized and are mixed, and obtain initial material, and wherein the parts by weight of copper ore concentrates, iron slag, lime and flue dust are respectively 95～105,35～45,1～5 and 0～10;
(2) granulate: with described initial material granulation;
(3) high temperature reduction melting: after described particle dehydrated, abundant melting and natural separation obtained flue gas, thick slag and first part's blister copper under the reducing atmosphere;
(4) insulation clarification: will described thick slag after 7～8h is clarified in 1150～1250 ℃ of insulations, obtain slag, matte and second section blister copper through natural separation, the first part's blister copper that then described second section blister copper and step (3) is made merges and obtains total blister copper;
(5) further retailoring: after described total blister copper fusing, the ventilation oxidation also adds the silica slag making, makes cupric oxide and surplus slag; Add reductive agent after separating described surplus slag, described cupric oxide makes anode copper through abundant melting; Wherein, described reductive agent is preferably the combination of at least a and charcoal of pine tree or diesel oil;
(6) electrolytic refining: take described anode copper as anode, electrolytic copper foil is negative electrode, fully electrolysis makes electrolytic copper in acid electrolyte.
In the smelting process of above-mentioned natural copper mine, described method also comprises collects the described flue gas that produces in the described step (3), and described flue gas is through precipitating the flue dust that obtains in the described initial material.
In the smelting process of above-mentioned natural copper mine, the parts by weight of copper ore concentrates, iron slag, lime and flue dust are respectively 98～102,38～42,2～4 and 0～8 in the described initial material.
In the smelting process of above-mentioned natural copper mine, in described step (2), described particle is spheroidal particle, and the diameter of described spheroidal particle is 30～45mm.
In the smelting process of above-mentioned natural copper mine, in described step (3), described abundant melting refers at 1300～1400 ℃ of lower melting 2.5～3.5h.
In the smelting process of above-mentioned natural copper mine, in described step (5), described abundant melting refers at 1300～1400 ℃ of lower melting 19～20h.
In the smelting process of above-mentioned natural copper mine, in described step (6), it is that 58～65 ℃, voltage are that 0.2～0.3V, current density are 200～240A/m that described abundant electrolysis refers in temperature
2Lower electrolysis; Cupric concentration in the described acid electrolyte is that 40～45g/L, sulfuric acid concentration are 150～200g/L.
In the smelting process of above-mentioned natural copper mine, the natural separation of described flue gas, thick slag and first part's blister copper is to realize by the difference of specific gravity between them in the high temperature reduction fusion process, and wherein first part's blister copper is deposited on the bottom.
In the smelting process of above-mentioned natural copper mine, the natural separation of described slag, matte and second section blister copper is to realize by the difference of specific gravity between them in the insulation clarifying process, and wherein the second section blister copper is deposited on the bottom.
Implement the smelting process of natural copper mine of the present invention, can obtain following beneficial effect: ferrosilicon ratio is greater than 15 in the copper ore concentrates, and the iron slag that adds suitable proportion during batching (comprises Fe
2O
3, Fe
3O
4With FeS etc.), can regulate the ferrosilicon ratio in the initial material, satisfy the slag making needs in the high temperature reduction fusion process; Simultaneously in the high temperature reduction fusion process, the incomplete combustion of the coke by q.s keeps strongly reducing atmosphere, so that the Fe in the thick slag that produces during melting
3O
4Be reduced to FeO fully, and and SiO
2Slag making realizes separating, and guarantees that the rate of recovery of blister copper is not less than 96.5%; Adopt the technique of high temperature reduction melting, thick slag insulation clarification, total further retailoring of blister copper and anode copper electrorefining to make to contain copper grade to be not less than 99.95% electrolytic copper, comprehensive recovery is not less than 96%.High and the final electrolytic copper quality of metal of the present invention (total blister copper, anode copper and the electrolytic copper) rate of recovery is good, and technical process is simple, the production run cost is low, and because SO in present method
2Discharging little, environmental pollution is little.
Embodiment
The natural copper mine that adopts among the present invention is the special copper ore concentrates that copper exists with elemental metals copper form, and the iron that wherein comprises and the content of sulphur are also very low, and ferrosilicon ratio is greater than 15.The concrete composition of such copper ore concentrates and mass percent separately are: Cu 28-30%, Fe 2%, S 1%, SiO
234%, CaO 6.5%, Al
2O
35.5%, MgO 1%, H
2O 13% etc.Therefore, in the smelting process of copper mine, in order to satisfy the slag making needs, usually allocate the iron slag of suitable proportion in the copper ore concentrates into, so that the slag type that the slag making reaction is carried out smoothly and obtained wishing in the smelting process.Here used iron slag is the product behind the sulfurous iron ore process fluidized bed roasting, and in the strong oxidizing atmosphere of fluidized bed roasting, the Fe element in the iron slag is Fe substantially
2O
3And Fe
3O
4State; In the incomplete situation of roasting, there is a small amount of FeS.Here said " the slag type of hope " refers to that the slag type is controlled to be SiO
240-42%, Fe 24-25%, CaO 9-11%.
Below by specific embodiment, the present invention is described in further details, it should be understood that and use the purpose of following examples to be more fully to explain and open the present invention, and the scope that does not limit the present invention in any way.
Embodiment 1:
The flue dust that by rotary conveyor parts by weight is respectively 100,40,3 and 7 copper ore concentrates, iron slag, lime and outsourcing is transported to respectively in the mixing pan, mixes after fully pulverizing, and obtains initial material; Should change in the apparatus for making pearl ball by initial material, each material is bonded together equably, make the spheroidal particle that diameter is 35mm; By rotary conveyor spheroidal particle is transported in the smelting furnace, after dehydrating, carbonate in the spheroidal particle, sulphate decomposition, further, in the high-temperature zone of smelting furnace at 1350 ℃, because the various material meltings of the incomplete combustion spheroidal particle of coke also are reduced, obtain respectively flue gas behind the melting 3h, comprise thick slag and first part's blister copper of part copper; Adopt dust arrester installation to collect flue gas, flue gas is back to the flue dust that obtains in the batch bin through fully obtaining flue dust after the precipitation, uses when preparing burden next time; Thick slag is changed in the electrothermal front bed, behind 1200 ℃ of insulation clarification 8h, obtain slag, matte and second section blister copper through the gravity natural separation, discharge slag from top slag blanket relief outlet, obtain the second section blister copper from row's copper mouth of bottom, then the first part's blister copper that makes in the smelting furnace and the second section blister copper that makes merging are obtained total blister copper herein; By charging machine described total blister copper is changed over to reverberatory furnace, 1350 ℃ of lower fusings, the ventilation oxidation obtains cupric oxide, add the silica slag making and manually will remain slag and from reverberatory furnace, claw, the surplus slag of realization separates with cupric oxide, then add the abundant reductive copper oxide of pine tree and charcoal, behind reverberatory smelting 20h, obtain anode copper; Described anode copper is changed in the electrolyzer, take described anode copper as anode, electrolytic copper foil is negative electrode, fully electrolysis makes electrolytic copper in the acid electrolyte of sulfur acid copper, and wherein each parameter setting of electrolyzer is as follows: temperature 60 C, bath voltage 0.2V, current density 220A/m
2, sulfuric acid concentration 180g/L among the electrolytic solution cupric concentration 42g/L, electrolytic solution; Among the embodiment in 1 prepared blister copper, anode copper and electrolytic copper contain copper grade and be respectively 92%, 98.8% and 99.96%.
Adopt the smelting process among the embodiment 1, further the purpose of the thick slag of insulation clarification is after the high temperature reduction melting, realize the separation of the copper of the part that comprises in the thick slag, and then improve on the one hand the rate of recovery of blister copper, make on the other hand the requirement that copper grade satisfies discharging that contains in the thick slag.Wherein, the weight percent that makes matte, blister copper after the insulation clarification and contain the very low slag of copper grade is respectively 14%, 6% and 80%.
Among the embodiment 1, the thick slag and the slag in the electrothermal front bed that obtain in the smelting furnace all are preferably three component system slag FeOSiO
2CaO, its concrete forming process relates generally to following reaction:
3Fe
2O
3+CO＝2Fe
3O
4+CO
2
FeS+16Fe
2O
3＝11Fe
3O
4+2SO
2
Fe
3O
4+CO＝3FeO+CO
2
2FeO+SiO+CaO＝2FeO·SiO
2·CaO
In electrothermal front bed, blister copper, matte (are respectively 8.6g/cm from slag because the proportion of self is different
3, 5.5g/cm
3And 3.7g/cm
3) and realize natural separation, wherein, slag is discharged from top slag blanket relief outlet; Blister copper sinks to the bottom, and discharges from row's copper mouth.Here need to prove Fe
3O
4Be magnetic oxide, if amount of coke is not enough in the fusion process, the reducing atmosphere that its incomplete combustion produces is inadequate, the Fe that produces in the smelting furnace
3O
4In electrothermal front bed, may enter matte, the viscosity of matte is increased.During the insulation clarification, after the blister copper fusing, when passing matte in the process bottom it is being deposited into, blister copper may be mixed in the matte, causes the rate of recovery of blister copper to reduce.Therefore, among the present invention, in order to guarantee the rate of recovery of blister copper, in smelting furnace, by the amount of control coke, guarantee the content of C in the furnace gas by its incomplete combustion, thereby keep the strongly reducing atmosphere in the smelting furnace, to guarantee Fe
3O
4Can be reduced to FeO fully, then with SiO
2Slag making and effective separation.
Among the embodiment 1, adopt dust arrester installation to collect the flue gas that produces in the smelting furnace, flue gas is through obtaining the material identical with flue dust composition in the initial material after the abundant precipitation, also be in the smelting furnace flue gas through collection with precipitation after the flue dust that obtains can when batching next time, recycle, wherein the composition of flue dust and content separately are Cu 8-15%, Fe16-20%, S 2-3%, SiO
226-30%, CaO 4-6%, Al
2O
37-8%, MgO 1%.Particularly, when using method of the present invention to smelt copper mine first, the flue dust in the initial material is the outsourcing flue dust, and the content that composition reaches separately satisfies above-mentioned requirements; Subsequently in the situation that the flue dust output is arranged, during batching in described ratio add an amount of, adopt flue gas that above-mentioned dust arrester installation the collects flue dust through obtaining after the abundant precipitation, to guarantee the comprehensive recovery of whole fusion process.Certainly, when using method of the present invention to smelt copper mine first, also can not add flue dust in the initial material, only need suitably to improve the add-on of copper ore concentrates, to guarantee that the stove material contains copper grade; This will further specify by following examples.
Embodiment 2:
By rotary conveyor parts by weight are respectively 102,40 and 2 copper ore concentrates, iron slag and lime and are transported to respectively in the mixing pan, mix after fully pulverizing, obtain initial material; Should change in the apparatus for making pearl ball by initial material, each material is bonded together equably, make the spheroidal particle that diameter is 38mm; By rotary conveyor spheroidal particle is transported in the smelting furnace, after dehydrating, carbonate in the spheroidal particle, sulphate decomposition, further, in the high-temperature zone of smelting furnace at 1300 ℃, because the various material meltings of the incomplete combustion spheroidal particle of coke also are reduced, obtain respectively flue gas behind the melting 3.5h, comprise thick slag and first part's blister copper of part copper; Adopt dust arrester installation to collect flue gas, flue gas is back to the flue dust that obtains in the batch bin through fully obtaining flue dust after the precipitation, uses when preparing burden next time; Thick slag is changed in the electrothermal front bed, behind 1150 ℃ of insulation clarification 7h, obtain slag, matte and second section blister copper through the gravity natural separation, discharge slag from top slag blanket relief outlet, obtain the second section blister copper from row's copper mouth of bottom, then the first part's blister copper that makes in the smelting furnace and the second section blister copper that makes merging are obtained total blister copper herein; By charging machine described total blister copper is changed over to reverberatory furnace, 1350 ℃ of lower fusings, the ventilation oxidation obtains cupric oxide, add the silica slag making and manually will remain slag and from reverberatory furnace, claw, the surplus slag of realization separates with cupric oxide, then add the abundant reductive copper oxide of pine tree and charcoal, behind reverberatory smelting 19h, obtain anode copper; Described anode copper is changed in the electrolyzer, take described anode copper as anode, electrolytic copper foil is negative electrode, fully electrolysis makes electrolytic copper in the acid electrolyte of sulfur acid copper, and wherein each parameter setting of electrolyzer is as follows: 58 ℃ of temperature, bath voltage 0.25V, current density 220A/m
2, sulfuric acid concentration 170g/L among the electrolytic solution cupric concentration 45g/L, electrolytic solution; Among the embodiment in 2 prepared blister copper, anode copper and electrolytic copper contain copper grade and be respectively 93%, 98.5% and 99.95%.
Embodiment 3:
The flue dust that by rotary conveyor parts by weight is respectively 100,38,4 and 6 copper ore concentrates, iron slag, lime and outsourcing is transported to respectively in the mixing pan, mixes after fully pulverizing, and obtains initial material; Should change in the apparatus for making pearl ball by initial material, each material is bonded together equably, make the spheroidal particle that diameter is 45mm; By rotary conveyor spheroidal particle is transported in the smelting furnace, after dehydrating, carbonate in the spheroidal particle, sulphate decomposition, further, in the high-temperature zone of smelting furnace at 1300 ℃, because the various material meltings of the incomplete combustion spheroidal particle of coke also are reduced, obtain respectively flue gas, thick slag and first part's blister copper behind the melting 2.5h; Thick slag is changed in the electrothermal front bed, behind 1150 ℃ of insulation clarification 7.5h, be met slag, matte and the second section blister copper of emission request through natural separation, discharge slag from top slag blanket relief outlet, obtain the second section blister copper from row's copper mouth of bottom, then the first blister copper that makes in the smelting furnace and the second section blister copper that makes merging are obtained total blister copper herein; By charging machine described total blister copper is changed over to reverberatory furnace, 1400 ℃ of lower fusings, the ventilation oxidation obtains cupric oxide, add the silica slag making and manually will remain slag and from reverberatory furnace, claw, the surplus slag of realization separates with cupric oxide, then add the abundant reductive copper oxide of diesel oil and charcoal, behind reverberatory smelting 19h, obtain anode copper; Described anode copper is changed in the electrolyzer, take described anode copper as anode, electrolytic copper foil is negative electrode, fully electrolysis makes electrolytic copper in the acid electrolyte of sulfur acid copper, and wherein each parameter setting of electrolyzer is as follows: 58 ℃ of temperature, bath voltage 0.25V, current density 240A/m
2, sulfuric acid concentration 200g/L among the electrolytic solution cupric concentration 40g/L, electrolytic solution; Among the embodiment in 3 prepared blister copper, anode copper and electrolytic copper contain copper grade and be respectively 90%, 98.5% and 99.95%.
Embodiment 4:
By rotary conveyor parts by weight are respectively the flue dust that obtains in the dust arrester installation among 98,42,4 and 8 copper ore concentrates, iron slag, lime and the embodiment 1 and are transported to respectively in the mixing pan, mix after fully pulverizing, obtain initial material; Should change in the apparatus for making pearl ball by initial material, each material is bonded together equably, make the spheroidal particle that diameter is 30mm; By rotary conveyor spheroidal particle is transported in the smelting furnace, after dehydrating, carbonate in the spheroidal particle, sulphate decomposition, further, in the high-temperature zone of smelting furnace at 1400 ℃, because the various material meltings of the incomplete combustion spheroidal particle of coke also are reduced, obtain respectively flue gas, thick slag and first part's blister copper behind the melting 3.5h; Adopt dust arrester installation to collect flue gas, flue gas is back to the flue dust that obtains in the batch bin through fully obtaining flue dust after the precipitation, uses when preparing burden next time; Thick slag is changed in the electrothermal front bed, behind 1250 ℃ of insulation clarification 7h, be met slag, matte and the second section blister copper of emission request through natural separation, discharge slag from top slag blanket relief outlet, obtain the second section blister copper from row's copper mouth of bottom, then the first part's blister copper that makes in the smelting furnace and the second section blister copper that makes merging are obtained total blister copper herein; By charging machine described total blister copper is changed over to reverberatory furnace, 1300 ℃ of lower fusings, the ventilation oxidation obtains cupric oxide, add the silica slag making and manually will remain slag and from reverberatory furnace, claw, the surplus slag of realization separates with cupric oxide, then add the abundant reductive copper oxide of diesel oil, pine tree and charcoal, behind reverberatory smelting 19.5h, obtain anode copper; Described anode copper is changed in the electrolyzer, take described anode copper as anode, electrolytic copper foil is negative electrode, fully electrolysis makes electrolytic copper in the acid electrolyte of sulfur acid copper, and wherein each parameter setting of electrolyzer is as follows: 65 ℃ of temperature, bath voltage 0.3V, current density 200A/m
2, sulfuric acid concentration 150g/L among the electrolytic solution cupric concentration 45g/L, electrolytic solution; Among the embodiment in 4 prepared blister copper, anode copper and electrolytic copper contain copper grade and be respectively 94%, 98.6% and 99.95%.
Embodiment 5:
By rotary conveyor parts by weight are respectively 105,35 and 5 copper ore concentrates, iron slag and lime and are transported to respectively in the mixing pan, mix after fully pulverizing, obtain initial material; Should change in the apparatus for making pearl ball by initial material, each material is bonded together equably, make the spheroidal particle that diameter is 40mm; By rotary conveyor spheroidal particle is transported in the smelting furnace, after dehydrating, carbonate in the spheroidal particle, sulphate decomposition, further, in the high-temperature zone of smelting furnace at 1350 ℃, because the various material meltings of the incomplete combustion spheroidal particle of coke also are reduced, obtain respectively flue gas, thick slag and first part's blister copper behind the melting 3h; Adopt dust arrester installation to collect flue gas, flue gas is back to the flue dust that obtains in the batch bin through fully obtaining flue dust after the precipitation, uses when preparing burden next time; Thick slag is changed in the electrothermal front bed, behind 1250 ℃ of insulation clarification 8h, be met slag, matte and the second section blister copper of emission request through natural separation, discharge slag from top slag blanket relief outlet, obtain the second section blister copper from row's copper mouth of bottom, then the first part's blister copper that makes in the smelting furnace and the second section blister copper that makes merging are obtained total blister copper herein; By charging machine described total blister copper is changed over to reverberatory furnace, 1300 ℃ of lower fusings, the ventilation oxidation obtains cupric oxide, add the silica slag making and manually will remain slag and from reverberatory furnace, claw, the surplus slag of realization separates with cupric oxide, then add the abundant reductive copper oxide of diesel oil, pine tree and charcoal, behind reverberatory smelting 20h, obtain anode copper; Described anode copper is changed in the electrolyzer, take described anode copper as anode, electrolytic copper foil is negative electrode, fully electrolysis makes electrolytic copper in the acid electrolyte of sulfur acid copper, and wherein each parameter setting of electrolyzer is as follows: 58 ℃ of temperature, bath voltage 0.25V, current density 240A/m
2, sulfuric acid concentration 180g/L among the electrolytic solution cupric concentration 42g/L, electrolytic solution; Among the embodiment in 5 prepared blister copper, anode copper and electrolytic copper contain copper grade and be respectively 90%, 98.5% and 99.95%.
Embodiment 6:
By rotary conveyor parts by weight are respectively the flue dust that obtains in the dust arrester installation among 95,45,1 and 10 copper ore concentrates, iron slag, lime and the embodiment 1 and are transported to respectively in the mixing pan, mix after fully pulverizing, obtain initial material; Should change in the apparatus for making pearl ball by initial material, each material is bonded together equably, make the spheroidal particle that diameter is 35mm; By rotary conveyor spheroidal particle is transported in the smelting furnace, after dehydrating, carbonate in the spheroidal particle, sulphate decomposition, further, in the high-temperature zone of smelting furnace at 1400 ℃, because the various material meltings of the incomplete combustion spheroidal particle of coke also are reduced, obtain respectively flue gas, thick slag and first part's blister copper behind the melting 3h; Adopt dust arrester installation to collect flue gas, flue gas is back to the flue dust that obtains in the batch bin through fully obtaining flue dust after the precipitation, uses when preparing burden next time; Thick slag is changed in the electrothermal front bed, behind 1250 ℃ of insulation clarification 7.5h, be met slag, matte and the second section blister copper of emission request through natural separation, discharge slag from top slag blanket relief outlet, obtain the second section blister copper from row's copper mouth of bottom, then the first part's blister copper that makes in the smelting furnace and the second section blister copper that makes merging are obtained total blister copper herein; By charging machine described total blister copper is changed over to reverberatory furnace, 1350 ℃ of lower fusings, the ventilation oxidation obtains cupric oxide, add the silica slag making and manually will remain slag and from reverberatory furnace, claw, the surplus slag of realization separates with cupric oxide, then add the abundant reductive copper oxide of diesel oil, pine tree and charcoal, behind reverberatory smelting 19h, obtain anode copper; Described anode copper is changed in the electrolyzer, take described anode copper as anode, electrolytic copper foil is negative electrode, fully electrolysis makes electrolytic copper in the acid electrolyte of sulfur acid copper, and wherein each parameter setting of electrolyzer is as follows: temperature 60 C, bath voltage 0.2V, current density 210A/m
2, sulfuric acid concentration 180g/L among the electrolytic solution cupric concentration 42g/L, electrolytic solution; Among the embodiment in 6 prepared blister copper, anode copper and electrolytic copper contain copper grade and be respectively 92%, 98.6% and 99.95%.
Claims (9)
1. the smelting process of a natural copper mine is characterized in that, may further comprise the steps:
(1) batching: copper ore concentrates, iron slag, lime and flue dust are fully pulverized and are mixed, and obtain initial material, and wherein the parts by weight of copper ore concentrates, iron slag, lime and flue dust are respectively 95 ~ 105,35 ~ 45,1 ~ 5 and 0 ~ 10;
(2) granulate: with described initial material granulation;
(3) high temperature reduction melting: after described particle dehydrated, abundant melting and natural separation obtained flue gas, thick slag and first part's blister copper under the reducing atmosphere;
(4) insulation clarification: will described thick slag after 7 ~ 8 h are clarified in 1150 ~ 1250 ℃ of insulations, obtain slag, matte and second section blister copper through natural separation, the first part's blister copper that then described second section blister copper and step (3) is made merges and obtains total blister copper;
(5) further retailoring: after described total blister copper fusing, the ventilation oxidation also adds the silica slag making, makes cupric oxide and surplus slag; Add reductive agent after separating described surplus slag, described cupric oxide makes anode copper through abundant melting;
(6) electrolytic refining: take described anode copper as anode, electrolytic copper foil is negative electrode, fully electrolysis makes electrolytic copper in acid electrolyte.
2. the smelting process of natural copper mine according to claim 1 is characterized in that, described method also comprises collects the described flue gas that produces in the described step (3), and described flue gas is through precipitating the flue dust that obtains in the described initial material.
3. the smelting process of natural copper mine according to claim 1 and 2 is characterized in that, the parts by weight of copper ore concentrates, iron slag, lime and flue dust are respectively 98 ~ 102,38 ~ 42,2 ~ 4 and 0 ~ 8 in the described initial material.
4. the smelting process of natural copper mine according to claim 1 and 2 is characterized in that, in described step (2), described particle is spheroidal particle, and the diameter of described spheroidal particle is 30 ~ 45 mm.
5. the smelting process of natural copper mine according to claim 1 and 2 is characterized in that, in described step (3), described abundant melting refers at 1300 ~ 1400 ℃ of lower melting 2.5 ~ 3.5 h.
6. the smelting process of natural copper mine according to claim 1 and 2 is characterized in that, in described step (5), described abundant melting refers at 1300 ~ 1400 ℃ of lower melting 19 ~ 20 h.
7. the smelting process of natural copper mine according to claim 1 and 2 is characterized in that, in described step (6), it is that 58 ~ 65 ℃, voltage are that 0.2 ~ 0.3 V, current density are 200 ~ 240 A/m that described abundant electrolysis refers in temperature
2Lower electrolysis; Cupric concentration in the described acid electrolyte is that 40 ~ 45 g/L, sulfuric acid concentration are 150 ~ 200 g/L.
8. the smelting process of natural copper mine according to claim 1 and 2, it is characterized in that, the natural separation of described flue gas, thick slag and first part's blister copper is to realize by the difference of specific gravity between them in the high temperature reduction fusion process, and wherein first part's blister copper is deposited on the bottom.
9. the smelting process of natural copper mine according to claim 1 and 2, it is characterized in that, the natural separation of described slag, matte and second section blister copper is to realize by the difference of specific gravity between them in the insulation clarifying process, and wherein the second section blister copper is deposited on the bottom.
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| CN112030002A (en) * | 2020-09-10 | 2020-12-04 | 江西理工大学 | Method for producing blister copper by directly oxygen-enriched smelting from waste circuit boards |
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| CN102864313B (en) | 2014-02-05 |
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Effective date of registration: 20160811 Address after: Lu Jia Ping Zhen Jiu Qu 419413 Huaihua city of Hunan Province, Mayang Miao Autonomous County Bay (Mayang copper mine) Patentee after: HUNAN SENXIN MINING INDUSTRY GROUP CO.,LTD. Address before: 419413 Huaihua City, Hunan province Mayang Miao Autonomous County jouquwan Patentee before: HUNAN HUAYANG COPPER INDUSTRY Co.,Ltd. |
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Effective date of registration: 20180709 Address after: 419413 Hunan Huaihua Mayang Miao Autonomous County Lujia Ping Town, 9 Qu Wan copper mine. Patentee after: Mayang Hua Sen Mining Co.,Ltd. Address before: 419413 Hunan Huaihua Mayang Miao Autonomous County Lujia Ping Town Qu Jiu Wan (formerly Mayang copper mine) Patentee before: HUNAN SENXIN MINING INDUSTRY GROUP CO.,LTD. |
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