CN101619399B - Method for selectively leaching voluble metal in copper refinery cinder - Google Patents
Method for selectively leaching voluble metal in copper refinery cinder Download PDFInfo
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- CN101619399B CN101619399B CN2009103046114A CN200910304611A CN101619399B CN 101619399 B CN101619399 B CN 101619399B CN 2009103046114 A CN2009103046114 A CN 2009103046114A CN 200910304611 A CN200910304611 A CN 200910304611A CN 101619399 B CN101619399 B CN 101619399B
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- copper
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- cobalt
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- 229910052802 copper Inorganic materials 0.000 title claims abstract description 59
- 239000010949 copper Substances 0.000 title claims abstract description 59
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000002386 leaching Methods 0.000 title claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 40
- 239000002184 metal Substances 0.000 title claims abstract description 40
- 239000003818 cinder Substances 0.000 title abstract 3
- 239000002893 slag Substances 0.000 claims abstract description 66
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 24
- 239000010941 cobalt Substances 0.000 claims abstract description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- 239000011701 zinc Substances 0.000 claims abstract description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000000839 emulsion Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000003483 aging Methods 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 4
- 238000007873 sieving Methods 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 25
- 239000000920 calcium hydroxide Substances 0.000 claims description 13
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 13
- 238000007670 refining Methods 0.000 claims description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical group CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 26
- 239000010703 silicon Substances 0.000 abstract description 24
- 238000003723 Smelting Methods 0.000 abstract description 23
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000004927 fusion Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000004513 sizing Methods 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 238000005345 coagulation Methods 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 6
- -1 iron ion Chemical class 0.000 description 6
- 229940037003 alum Drugs 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000001698 pyrogenic effect Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ANFIEGWCRSNVFS-UHFFFAOYSA-N [Na].OCl(=O)=O Chemical compound [Na].OCl(=O)=O ANFIEGWCRSNVFS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- YCODVQGTXLFHGU-UHFFFAOYSA-M sodium sulfuric acid chlorate Chemical compound Cl(=O)(=O)[O-].[Na+].S(O)(O)(=O)=O YCODVQGTXLFHGU-UHFFFAOYSA-M 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- 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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for selectively leaching voluble metal in copper refinery cinder, which comprises the steps of crushing, acid fusion, size mixing and ageing, and the concrete steps are as follows: crushing and sieving the copper refinery cinder, and adding an oxidizer in slag; then stirring and leaching the mixture with 0.5-1.5 mol/L dilute sulphuric acid; after leaching, adding a size mixing agent which is calvital emulsion to neutralize excessive acid in the neutralization reaction; controlling the pH value of the reaction end point to 1.6-2.3; ageing the leaching agent; and carrying out filtering and washing to obtain filtrate containing the leached valuable metal. The method can effectively leach out copper, cobalt and zinc, inhibit the dissolution of silicon and ferrum to the maximum extent and obtain filter residue with favorable filtering performance. The method has simple and convenient size mixing scheme, less equipment investment, low raw material and small environment pollution, changes copper smelting waste residue into developable resources and has huge environment and economic benefits.
Description
Technical field
The invention belongs to environment protection and non-ferrous metallurgy technology field, relate to the method that the valuable metal selectivity leaches in the copper refining slag, this method can suppress the wherein leaching of silicon, iron by selectivity leaching valuable metal (cobalt, copper, zinc) simultaneously.
Background technology
Produced the waste residue that contains a certain amount of valuable metal in a large number in the pyrogenic process smelting copper process, the long-term accumulation of a large amount of waste residues will cause environmental pollution, also will cause the huge waste of resource in addition, the present invention is primarily aimed at the pyrometallurgical smelting slag of African copper mine, and the valuable metal in the method recovery slag that use selectivity normal pressure leaches is cobalt especially.Normal association cobalt in the copper mine of Africa, so be rich in cobalt in the pyrometallurgical smelting slag of copper, also contain a certain amount of zinc, copper etc. in addition.In recent years, along with African copper mine is progressively developed, the comprehensive reutilization of the rich cobalt copper smelting slag of this class has become the focus of social concerns.Analysis revealed, the content of cobalt in addition, contains copper 1-3%, zinc 1-7% up to 4-10% in the slag.Cobalt is widely used in fields such as battery, machinery, chemical industry, aerospace as a kind of rare metal, and in recent years, along with the widespread use of lithium cell, the demand of cobalt increases severely, and reclaims cobalt and have important economic benefit and environmental benefit from copper smelting slag.
How valuable metal cobalt in the copper smelting-furnace slag, zinc exist with olivine structural, part copper exists with simple substance or sulfide state, owing to contain a large amount of silicon, iron in the slag, directly adopt acidleach will cause a large amount of silica gel strippings, influence the dissolution efficiency of valuable metal, produce the very big slurry of stickiness simultaneously, influence follow-up filtration step.In addition, contain a large amount of iron in the slag, behind the molten sample, iron enters solution, sepn process easily forms colloidal iron hydroxide and adsorbs valuable metal and cause the rate of recovery low, so must suppress the stripping of silicon and iron in leaching process when industrial treatment copper smelting slag, promptly reaches the purpose that selectivity leaches.(Hydrometallurgy such as A.N.Banza, 2002 (67): 63-69) propose when high copper silicon smelting slag is handled in acidleach, add hydrogen peroxide and suppress the silica gel generation, but at high temperature a large amount of decomposing hydrogen dioxide solution, the add-on that makes hydrogen peroxide is 3-5 a times of theoretical amount, because hydrogen peroxide costs an arm and a leg, the production cost height is difficult to this technology is carried out industrialization; (MineralsEngineering such as Ewa Rudnik, 2009 (22): 88-95) African copper smelting slag is carried out reducing roasting earlier and obtain alloy, the method that adopts electrolysis ammonia to soak again leaches cobalt, copper, avoided the stripping of silica gel in the acidleach process, but this procedure energy consumption is big, gained alloy poor selectivity.
Summary of the invention
The purpose of this invention is to provide the method that the valuable metal selectivity leaches in the copper refining slag, solve that copper smelting slag colloid in leaching process produces and the leaching that causes not exclusively, problem such as strainability difference, realize optionally leaching cobalt in the slag, zinc, copper and suppress the leaching of silicon, iron.。
For achieving the above object, technical scheme of the present invention is:
The method that the valuable metal selectivity leaches in a kind of copper refining slag, it is characterized in that, processing step is: with the copper refining slag through pulverizing and sieving, the slag powder particle size of control gained is less than 74 microns, add oxygenant in the slag powder, described oxygenant is Manganse Dioxide, potassium permanganate, oxymuriate; Adopting concentration then is the dilute sulphuric acid agitation leach of 0.5-1.5mol/L, and liquid-solid ratio is 8-20 (a ml/g powder), and extraction temperature is 60-95 ℃; , after the leaching, add again and size mixing the agent calcium hydroxide emulsion with acid excessive in the neutralization reaction process, control is sized mixing temperature 75-100 ℃, control reaction end pH is 1.4-3.0, and ageing leach liquor, filtration, washing more promptly contains the valuable metal of leaching in the filtrate of gained.
Described valuable metal comprises cobalt, zinc, copper.
Siliceous 12-30%, iron 15-30%, cobalt 2-12%, copper 1-2% in the described copper refining slag.
Described oxygenant is a sodium chlorate, and addition is that slag powder per ton adds 0.06-0.15 ton sodium chlorate, if uses oxygenant as Manganse Dioxide, potassium permanganate also can, addition is a slag powder interpolation 0.1-0.25 ton per ton.
Described extraction time is 0.5-5 hour.
The present invention to copper smelting slag carry out oxidation acid leaching, neutralization is sized mixing, filters, is washed, iron in the good filter cake of strainability and the gained filtrate, silicone content are very low.
Concrete grammar is: copper smelting slag is through crushing screening, the control particle diameter is less than 74mm, in the slag powder, add oxygenant (slag per ton adds 0.06-0.15 ton sodium chlorate), adopting concentration then is dilute sulphuric acid (liquid-solid ratio 8-20) agitation leach of 0.5-1.5mol/L, extraction temperature is 75-100 ℃, extraction time 0.5-5 hour, slowly add excessive acid in agent (calcium hydroxide emulsion) the neutralization reaction process of sizing mixing again, sized mixing time 2-4 hour, control reaction end pH is 1.6-2.3, and ageing is (after precipitation is complete, allow the precipitation that just generates place for some time with mother liquor, this process is called " ageing ") leach liquor, filter washing, cobalt, a leaching yield about 98% of zinc, a leaching yield of copper is about 89%, and the silicon leaching yield is less than 3.6%, and the leaching yield of iron is less than 0.02%.Solution did not have jelly when this method was handled copper smelting slag, and strainability is good, and gained filtrate can obtain cobalt, zinc, copper products respectively through subsequent disposal such as purification and impurity removals.
The present invention is according to principle: this copper smelting slag lixiviation process adopts Wet technique to reach transformation and three targets of ferrosilicon colloidal coagulation of the stripping of valuable metal in the slag, siloxane bond.Find that after tested slag is in the acidleach process, siloxane bond has precedence over the metal oxygen bond rupture and makes silicon enter solution with ionic forms, a large amount of silicon dissolves in liquid phase and very easily produces colloid, hinder valuable metal leaching process and strainability, the present invention adopts the scheme of adding oxygenant chloric acid sodium can suppress the stripping of silica gel, change and leach system status, reduce leach liquor viscosity, can guarantee effective stripping of valuable metal in the slag, the existence of sodium chlorate simultaneously impels that the iron ion of stripping becomes the alum precipitation in the sulfuric acid system, adhered to the ihleite precipitation of valuable metal hardly and made iron level reduction in the filtrate, process adding calcium hydroxide emulsion makes iron ion remaining in the solution be hydrolyzed into ironic hydroxide owing to size mixing, the process of sizing mixing makes iron glue and the silica gel generation coagulation that electrically neutralizes, viscosity reduces, a large amount of silicon are separated out with the silica solid form, control suitable reaction end pH simultaneously and can reach smooth and easy filtering purpose.The use of agent calcium hydroxide of the sizing mixing excess acid in the leaching system that not only neutralized, simultaneously owing to calcium hydroxide, the sl. sol. characteristics of calcium sulfate make the adding of the agent of sizing mixing can not roll up impurity ion content, and because the character of calcium hydroxide emulsion, its adding can not cause the violent change of pH values of pulp, make and exist slag acid dissolving to grab iron ion in the leaching system to become alum to analyse the acid base equilibrium of acid, help into the carrying out of alum process.In sum, the leaching system is leaching agent with sulfuric acid, sodium chlorate is an additive, calcium hydroxide is the agent of sizing mixing that neutralizes, leaching is grabbed the process of grabbing filtration, washing of sizing mixing and will be obtained being rich in valuable metal and only contain the very filtrate of minor amount of silicon, iron, and additive can not make the impurity in the filtrate introduce in a large number with the adding of the agent of sizing mixing.
Advantage of the present invention and effect:
Compare with the method that now can look into about handling high silicon, iron copper smelting slag recovery valuable metal, the present invention has following advantage:
The present invention adopts pure wet method dissolving-out technology, does not need slag is carried out the pyrogenic process pre-treatment, has farthest saved the energy, reduces the pyrogenic process exhaust gas discharging, pollutes little;
The present invention adopts to leach and grabs the process integration of sizing mixing, and whole leaching is all carried out in same reactor with the process of sizing mixing, and need not more exchange device, reduces the non-productive operation expense;
Method environmental friendliness used herein, no noxious gas emission, whole process is all carried out under normal pressure, and operational danger is little, and cost is low;
The present invention has good selectivity to leach effect to valuable metals such as cobalt, zinc, copper, suppressed the stripping of silicon, iron simultaneously largely, for follow-up wet separation valuable metal provides the good premise condition;
The present invention has facilitated the coagulation of silica gel, iron glue effectively, and gained filter pulp strainability is good, and filter cake easily washs;
The present invention use calcium hydroxide emulsion be size mixing agent when facilitating iron, silicon coagulation effectively slag acid dissolving grab iron ion and become alum to analyse the acid base equilibrium of acid, can not cause iron ion to be hydrolyzed to the phenomenon of flocks because of local alkali overrich, use this agent low price of sizing mixing, filtration washing process silicon, iron are difficult for anti-molten.
It is the slag that main body contains valuable metal that the present invention is primarily aimed at behind the pyrometallurgical smelting with the olivine structural, and this method can leach copper, cobalt, zinc effectively, and farthest suppresses the stripping of silicon, iron, and obtains the good filter residue of strainability.When the present invention contains the copper smelting slag of a large amount of silicon, iron in processing, do not need the pyrogenic process pre-treatment, the leaching scheme is only used sulfuric acid and sodium chlorate, suppresses the formation of silica gel, facilitates that silicon changes precipitation of silica in the system.The process of sizing mixing is used cheap calcium hydroxide emulsion, utilize the characteristic of calcium cpd to make the leaching system exist suitable iron ion to become the sedimentary acid base equilibrium of alum, under the situation of minimum introducing foreign ion, be implemented in the colloidal coagulation of silicon, iron, obtain the good ore pulp of strainability, after filtration, after the washing, a leaching yield about 98% of cobalt, zinc, leaching yield of copper all about 89%, the silicon leaching yield is less than 3.6%, and the leaching yield of iron can be carried out Separation and Recovery to various valuable metals by traditional wet processing less than the 0.02%. leach liquor.This leaching grabs that the scheme of sizing mixing is easy and simple to handle, and facility investment is little, the raw material cheapness, and environmental pollution is little, has realized that change copper smelting waste residue is developable resource, has huge environmental benefit and economic benefit.
Description of drawings
Fig. 1 is that the valuable metal selectivity leaches flow process in the copper refining slag.
Embodiment
Embodiment 1
Contain 1.6%Cu from African copper smelting slag I, 1.2%Co, 6.7%Zn, 21%Fe, 18%Si, material phase analysis must distribute with wustite, silicate form by this slag metal.This slag was ground 100 mesh sieves, every 100kg slag adds the 7kg sodium chlorate, use 0.7mol/L sulfuric acid, liquid-solid ratio control 10: 1, mechanical stirring, 75 ℃ of temperature of reaction leach 3 hours reaction times, the employing calcium hydroxide emulsion is sized mixing, size mixing 3 hours time, control terminal point pH is 2.1,95 ℃ of ageings 0.5 hour, filter, hot wash, strainability is good, and copper, cobalt, zinc leaching rate are respectively 90.1%, 98.2%, 98.1%, silicon, iron leaching yield are lower than 3.5%, 0.02%, and producing the quantity of slag is the 216.4kg/100kg slag.
Embodiment 2
Contain 15.4%Si, 28.4%Fe, 4.0%Co, 1.4%Cu, 1.7%Zn, Al3.22%, 0.05%Ni from African copper smelting slag II, this slag metal of material phase analysis exists with silicate, wustite form.80 mesh sieves were ground in this ore deposit, every 100kg slag adds the 10kg sodium chlorate, use 0.5mol/L sulfuric acid, liquid-solid ratio 15: 1, mechanical stirring, 95 ℃ of temperature of reaction leach 2 hours reaction times, size mixing with calcium hydroxide emulsion, size mixing 2.5 hours time, 1.9,95 ℃ of ageings of control endpoint pH 0.5 hour are filtered, hot wash, strainability is good, and copper, cobalt, zinc leaching rate are respectively 89.3%, 98.1%, 98.0%, and aluminium, silicon, iron leaching yield are lower than 31%, 3.3%, to produce the quantity of slag be the 186.3kg/100kg slag to 0.1%..
As known from the above examples, the method that adopts the neutralization of interpolation sodium chlorate sulfuric acid system leaching-calcium hydroxide emulsion to size mixing can leach the valuable metal in the copper smelting slag effectively, facilitate the transformation of silicon in the slag, make iron, silicon not form colloid and effectively coagulation be the good precipitation of strainability, it is few that this precipitation is adsorbed with the valency amount of metal, can be with attached to the metal ion wash-out that soaks in the slag by simple washing, the leaching yield of cobalt, zinc is about 98%, the leaching yield of copper is about 90%, and silicon, iron leaching yield are lower than 3.6%, 0.02%.This method uses pure Wet technique to finish the leaching of valuable metal in the copper smelting tailings, and cost is little, and it is good to leach selectivity, helps further wet separation.Therefore the present invention overcome easily generate silica gel in the existing copper smelting slag wet processing scheme, be difficult for filtering, bottleneck that recovery rate of valuable metals is low.
Claims (4)
1. the method that the valuable metal selectivity leaches in the copper refining slag, it is characterized in that, processing step is: with the copper refining slag through pulverizing and sieving, the slag powder particle size of control gained is less than 74 microns, add oxygenant in the slag powder, described oxygenant is Manganse Dioxide, potassium permanganate or oxymuriate; Adopting concentration then is the dilute sulphuric acid agitation leach of 0.5-1.5mol/L, and liquid-solid ratio is the 8-20ml/g powder, and extraction temperature is 60-95 ℃; After the leaching, add and size mixing the agent calcium hydroxide emulsion with acid excessive in the neutralization reaction process, control is sized mixing temperature 75-100 ℃, and control reaction end pH is 1.4-3.0, ageing leach liquor, filtration, washing more promptly contains the valuable metal of leaching in the filtrate of gained;
Described valuable metal comprises cobalt, zinc and copper.
2. the method that the valuable metal selectivity leaches in the copper refining slag according to claim 1 is characterized in that siliceous 12-30%, iron 15-30%, cobalt 2-12% and copper 1-2% in the described copper refining slag.
3. the method that the valuable metal selectivity leaches in the copper refining slag according to claim 1, it is characterized in that, when described oxygenant is sodium chlorate, addition is that slag powder per ton adds 0.06-0.15 ton sodium chlorate, when using oxygenant as Manganse Dioxide or potassium permanganate, addition is that slag powder per ton adds the 0.1-0.25 ton.
4. the method that leaches according to valuable metal selectivity in each described copper refining slag of claim 1～3 is characterized in that described extraction time is 0.5-5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103046114A CN101619399B (en) | 2009-07-21 | 2009-07-21 | Method for selectively leaching voluble metal in copper refinery cinder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103046114A CN101619399B (en) | 2009-07-21 | 2009-07-21 | Method for selectively leaching voluble metal in copper refinery cinder |
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Families Citing this family (14)
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| CN102465202B (en) * | 2010-11-12 | 2013-10-23 | 深圳市格林美高新技术股份有限公司 | Cobalt copper sulfide ore processing method |
| CN103436712B (en) * | 2013-07-31 | 2014-12-10 | 山东国大黄金股份有限公司 | Method for increasing leaching rate of copper in difficult-to-treat mineral |
| CN103757410A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Leaching method of nickel cobalt lithium manganate waste battery positive-negative electrode mixed material |
| CN103740941B (en) * | 2014-01-01 | 2016-03-02 | 桂林理工大学 | A kind of method leaching copper, zinc and lead from high indium oxygen powder acid leaching residue |
| CN104988311B (en) * | 2015-04-23 | 2018-01-12 | 兰州金川新材料科技股份有限公司 | A kind of method for improving the high silicon cobalt raw material lysate rate of filtration |
| WO2016178040A1 (en) | 2015-05-05 | 2016-11-10 | Arcelormittal | Method for the treatment of iron-containing sludge |
| CN105018745B (en) * | 2015-07-29 | 2017-09-22 | 昆明理工大学 | A kind of method for cooperateing with coordination to reclaim zinc in oxysulphied zinc ore |
| CN109082533A (en) * | 2018-08-01 | 2018-12-25 | 昆明理工大学 | A kind of method that acidolysis curing-oxygen hydrothermal conversion recycles iron in copper smelting slag |
| CN110835692A (en) * | 2019-10-16 | 2020-02-25 | 厦门钨业股份有限公司 | Method for improving leaching solution of cobalt sulfate |
| CN110564959B (en) * | 2019-10-17 | 2021-05-04 | 中南大学 | Method for selectively removing zinc from zinc-containing copper concentrate by using chemical oxidant |
| CN111961850B (en) * | 2020-09-11 | 2021-06-08 | 长沙海创金源工程技术有限公司 | Treatment method of copper-cobalt ore |
| CN114405979A (en) * | 2021-12-20 | 2022-04-29 | 荆门市格林美新材料有限公司 | Cobalt-nickel tailing treatment method |
| CN114517258A (en) * | 2022-01-11 | 2022-05-20 | 云南云铜锌业股份有限公司 | Two-stage zinc hydrometallurgy leaching method for improving copper recovery rate |
| CN115874062A (en) * | 2022-11-30 | 2023-03-31 | 新疆有色金属研究所 | Efficient acid-mixing curing leaching process for non-ferrous metal copper smelting slag |
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