CN1094460A - Directly electrolytic extraction of electrolytic copper by copper sulfide ore - Google Patents
Directly electrolytic extraction of electrolytic copper by copper sulfide ore Download PDFInfo
- Publication number
- CN1094460A CN1094460A CN93104763A CN93104763A CN1094460A CN 1094460 A CN1094460 A CN 1094460A CN 93104763 A CN93104763 A CN 93104763A CN 93104763 A CN93104763 A CN 93104763A CN 1094460 A CN1094460 A CN 1094460A
- Authority
- CN
- China
- Prior art keywords
- copper
- electrolytic
- electrolyzer
- positive column
- electrolytic copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
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
Abstract
The direct electrolysis of various copper mines is produced electrolytic copper and is belonged to chemistry and field of metallurgy.It is characterized in that utilization reduction back, positive column liquid electricity chlorination leaching copper mine, and meet the one-level electrolytic copper of GB466-82 standard in cathodic area while electrodeposition output.The present invention utilizes a kind of fluidization electrolyzer of special construction can handle single copper-sulphide ores, many metals copper-sulphide ores that complicated copper mine and leaded zinc are higher, and its Production Flow Chart is simple, and comprehensive energy consumption is low, and is pollution-free, and is easy to industrial implementation.
Description
The invention belongs to chemistry and field of metallurgy.
From copper-sulphide ores produce the commodity electrolytic copper, commercial run adopts pyrogenic process production more.For improving the environmental pollution that pyrogenic process is produced, work out the technology of multiple wet production metallic copper.China emtallurgy research total institute is at " non-ferrous metal (smelt " " the 6th phase in 1981 delivered through improved Dextec one step copper-smelting method.This method owing to the catholyte quality can not get guaranteeing and reports and use membranous performance, thereby also can only get copper powder.The weak point of this method is:
(1). the chalcopyrite pre-treatment is only in order suitably to improve Cu
+Concentration, avoid anolyte to be recycled directly to the cathodic area;
(2). catholyte iron-holder height, Cu
+/ Σ Cu ratio is low, the Cu of anolyte compartment
2+May penetrate into cathode compartment;
(3). can not directly obtain electrolytic copper.
" containing the research of arsenical copper concentrate hydrometallurgy new process " that China's Guizhou Polytechnical College was delivered on " non-ferrous metal (smelting) " the 3rd phase in 1981, though obtain electrolytic copper at cathode compartment, but spread to negative electrode owing to adopt asbestos diaphragm to keep away unavoidable impurity cationic, thereby electrolytic copper quality can only reach GB466-82 secondary electrolytic copper standard, simultaneously, the anolyte compartment only is used for CuCl during electrolysis
2Leaching agent regeneration, and leaching plant costliness.
The purpose of this invention is to provide a kind of both pollution-freely, can directly produce electrolytic copper again, and flow process is short, the novel process that cost is low, novel method from copper-sulphide ores.
Feature of the present invention is to leach part mantoquita in the copper-sulphide ores with the chloride solution reduction, and remaining copper is leached by electric chlorination in the anode electrolytic cell district of special construction, and at cathodic area while electrodeposition, meets the one-level electrolytic copper that GB466-82 requires to produce.
Suitable treatment granularity of the present invention contains Pb ≯ 20% less than 0.88mm, the various copper-sulphide ores of Zn ≯ 5%, As ≯ 1.0%.
Preparation method of the present invention is that copper-sulphide ores is reduced in the reducing bath of chloride solution is housed earlier, and solution is put into the cathodic area of electrolyzer, the electrodeposition copper that produces electrolysis; The slag that produces in the reducing bath is put into the anode electrolytic cell district that fills chloride solution leach, produce anolyte and slag, anolyte is returned repeat said process in the reducing bath again.Its main chemical reactions (former grain mineral are example with the copper glance) is as follows:
Reduction is leached and is carried out in the fluidization steel basin of furans glass reinforced plastic lining, steam heating, and according to the difference of raw material grade, the leaching agent main component is: Cu
2+60～90g/L, Fe
3+8～12g/L, Cl
-150～350g/L, H
+0.3～0.8mol/L; 80～110 ℃ of extraction temperatures, liquid-solid ratio 3～8: 1 leaches acid eventually regulates PH=1.5～3.0.Reduction ore pulp filtered while hot, and the acid chloride solution countercurrent washing filter residue of the heat of usefulness.Wash water reclaims iron and U-Ramin MC, and filter residue adds the anode electrolytic cell district, and reducing solution adds cathode compartment.
Electrolyzer is isolated positive column and cathodic area with the ion-exchange cavity block, and material is a furans glass reinforced plastic, and structure as shown in Figure 1.Can the monomer electrolyzer be combined into required series according to industrial scale.Anolyte compartment's ore pulp stirs with the jetting type pump, steam heating.
Fig. 1 is the direct electrolyzer of copper-sulphide ores, and it is by furans glass steel tank (1), anolyte compartment (2), film frame (3), cathode compartment (4) ion-exchange cavity block (5), upflow tube (6), liquid-inlet pipe (7), jet agitator (8) is formed.
According to the difference of feedstock property, the technical conditions that anode chamber's electricity chlorination is leached are: L/S=4～8, H+0.5～1.0mol/L，Cl
-150～250g/L uses graphite anode, Dλ＝150～350A/m
2 The slag cupric is lower than 0.5%, and total leaching rate is all greater than 98.5%.
Reducing solution in the technical conditions of cathode chamber is: Σ Cu25～110g/L, Cu+/ΣCu＞90%，Fe
2+＜8g/L，D
k＝100～159A/m
2，V
Groove=1.2～1.8V makes negative electrode with starting sheet. Cathode copper surface compact, light, chemical composition reach the GB466-82 primary standard, cathode efficiency 85～90%, direct current consumption 600～900kwh/tCu.
Compared with the prior art the present invention has following advantage:
(1). the chlorine that produces on the graphite anode when directly adopting electrolysis is made chlorinating agent, and the chlorination current potential is high, and the slag cupric easily is down to below 0.5%, and the while is without the regenerative process of leaching agent;
(2). owing to adopt resistance little, select the barrier film of the good ion-exchange cavity block of through performance, can guarantee that cathode chamber direct electrowinning monovalence copper obtains the cathode copper product.
(3). adjust PH during reduction simultaneously except Fe, As, then pickling allows Fe, As open a way, and has guaranteed the quality of catholyte.
(4) technological process is simple, the cupprous anode energy consumption of having utilized simultaneously of electrodeposition, and comprehensive energy consumption is low.
(5) a kind of electrolytic cell and reasonable combination thereof with special construction, and the use of acidproof, heatproof, diaphragm material that intensity is good have solved industrialized plant issue.
Example 1:
Get and contain Cu29.8%, Fe22.15%, S30.18%, granularity copper sulfide concentrate 300g, with consisting of Cu less than 0.088mm
2+72.5g/L, Fe
3+10.2g/L, Cl
-287g/L, H
+0.5mol/L villaumite leaching agent (the quite composition of positive column electricity chloridizing leach solution), in the 2L there-necked flask, reduce, 103 ± 1 ℃ of controlled temperature, L/S=5, reduced liquid filter the back and add the cathodic area.Reducing slag after the washing adds the positive column and leaches leaching condition L/S=5, Cl
-287g/L, H
+0.5mol/L, D
λ205A/M
2, 80 ± 2 ℃ of temperature; The condition of cathodic area electrodeposition is D
k=120A/m
2Bath voltage 1.3～1.7V, behind the time 24h, positive column slag cupric reaches 0.43% by analysis, negative electrode gets electrolytic copper 89g(and removes beginning utmost point copper sheet weight), the surface compact light, chemical ingredients reaches one-level electrolytic copper standard among the GB466-82,99.96%Cu, cathode efficiency 86.37% direct current consumption 733kwh/tCu.
Example 2 is got and is contained Cu12.38% pb17.45%, Zn4.5%, many metals copper-sulphide ores 300g of S22.08%, and granularity is less than 0.088mm, with consisting of Cu
2+64.30g/L, Fe
3+8.33g/L, Cl
-218g/l, H
+0.3mol/L villaumite leaching agent liquid isolate pbCl through crystallisation by cooling
2Send into the cathodic area of electrolyzer behind the solid; The positive column leaching condition that the reduction leached mud is sent into electrolyzer is L/S=6, Cl
-218g/L, H
+0.3mol/L, D
λ155A/M
2, 78 ± 1 ℃ of temperature; Cathodic area electrodeposition condition is D
K=90A/M
2, bath voltage 1.1～1.5V, time 24h, it is positive column slag cupric Cu0.47% as a result, negative electrode gets electrolytic copper 36.96g(and removes beginning utmost point copper sheet amount), the surface compact light, chemical ingredients reaches one-level electrolytic copper standard among the GB466-84,99.95%, cathode efficiency 88.4%, direct current consumption 620kwh/tCu.
Claims (3)
1, a kind of hydrometallurgical is got the method for electrolytic copper, is gone on foot by direct electrolysis one and finishes, and it is characterized in that:
I) copper-sulphide ores reduces in the groove of chloride solution is housed earlier, leaches slag and solution two portions product;
Cathodic area, the electrodeposition of ii) solution of output in the reducing bath the being put into electrolyzer copper that produces electrolysis is put into the slag of output in the groove electric tank cathode district that fills villaumite liquid simultaneously and is leached;
Iii) the leach liquor with anode electrolytic cell district output repeats above-mentioned steps.
2, hydrometallurgical as claimed in claim 1 is got the method for electrolytic copper, it is characterized in that controlling electrolytic technical qualification to be:
ⅰ) positive column: L/S=4～8, H
+0.5～1.0mol/L, Cl
-150～250g/L, graphite anode, D
A=150～350A/M
2;
ⅱ) cathodic area: Σ Cu25～110g/L, Cu
+/ Σ Cu＞90%, copper sheet is made negative electrode, D
k=100～150A/m
2,
=1.2～1.8V.
3, a kind of claim 1,2 described hydrometallurgical of realizing are got the electrolyzer of the method for electrolytic copper, it is characterized in that:
ⅰ) adopt the ion-exchange cavity block to be isolated between the positive column of described electrolyzer and the cathodic area;
ⅱ) be provided with the jet agitator in the bottom of the positive column of described electrolyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93104763A CN1034957C (en) | 1993-04-24 | 1993-04-24 | Directly electrolytic extraction of electrolytic copper by copper sulfide ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93104763A CN1034957C (en) | 1993-04-24 | 1993-04-24 | Directly electrolytic extraction of electrolytic copper by copper sulfide ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1094460A true CN1094460A (en) | 1994-11-02 |
| CN1034957C CN1034957C (en) | 1997-05-21 |
Family
ID=4985353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93104763A Expired - Fee Related CN1034957C (en) | 1993-04-24 | 1993-04-24 | Directly electrolytic extraction of electrolytic copper by copper sulfide ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1034957C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206835A (en) * | 2011-05-19 | 2011-10-05 | 广州鸿葳科技股份有限公司 | Acid etchant online electrolytic recycling device and etchant regenerating method |
| CN105506670A (en) * | 2015-12-18 | 2016-04-20 | 阳谷祥光铜业有限公司 | Device for copper electrolysis or copper electrodeposition, and running method |
| CN110106531A (en) * | 2019-06-14 | 2019-08-09 | 安徽工业大学 | A kind of molten-salt electrolysis copper sulfide synchronizes the method for preparing metallic copper and sulphur |
| CN113088722A (en) * | 2021-03-17 | 2021-07-09 | 磨名言 | Method for electrolytically recovering copper from copper sulfide ore |
| WO2024045447A1 (en) * | 2022-09-02 | 2024-03-07 | 昆明理工大学 | Electrochemical metallurgy method for extracting metal and sulfur from metal sulfide |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3673061A (en) * | 1971-02-08 | 1972-06-27 | Cyprus Metallurg Process | Process for the recovery of metals from sulfide ores through electrolytic dissociation of the sulfides |
| CN1017167B (en) * | 1989-03-20 | 1992-06-24 | 重庆钢铁研究所 | Direct electrolytic refining of copper scrap by stainless steel anode frame |
| CN2047266U (en) * | 1989-03-25 | 1989-11-08 | 航天工业部第七○三研究所 | Equipment for copper or silver electrolytic-recovering from dilute solution |
| US5196095A (en) * | 1990-04-03 | 1993-03-23 | Henkel Corporation | Process for recovering a metal from an aqueous solution comprising a mixture of metal chlorides |
-
1993
- 1993-04-24 CN CN93104763A patent/CN1034957C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206835A (en) * | 2011-05-19 | 2011-10-05 | 广州鸿葳科技股份有限公司 | Acid etchant online electrolytic recycling device and etchant regenerating method |
| CN105506670A (en) * | 2015-12-18 | 2016-04-20 | 阳谷祥光铜业有限公司 | Device for copper electrolysis or copper electrodeposition, and running method |
| CN110106531A (en) * | 2019-06-14 | 2019-08-09 | 安徽工业大学 | A kind of molten-salt electrolysis copper sulfide synchronizes the method for preparing metallic copper and sulphur |
| CN110106531B (en) * | 2019-06-14 | 2021-12-07 | 安徽工业大学 | Method for synchronously preparing metal copper and sulfur by electrolyzing copper sulfide through molten salt |
| CN113088722A (en) * | 2021-03-17 | 2021-07-09 | 磨名言 | Method for electrolytically recovering copper from copper sulfide ore |
| WO2024045447A1 (en) * | 2022-09-02 | 2024-03-07 | 昆明理工大学 | Electrochemical metallurgy method for extracting metal and sulfur from metal sulfide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1034957C (en) | 1997-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100594265C (en) | Method for producing electrolytic nickel using various nickel-containing raw material | |
| CN101838736B (en) | Wet separation method for valuable metals in purified liquid cobalt slags of wet zinc smelting system | |
| AU2016318302B2 (en) | Optimized ore processing using molten salts for leaching and thermal energy source | |
| CN101451198A (en) | Method for recovering zinc and lead from waste electrolysis anode sludge | |
| US3764490A (en) | Method of recovering metals | |
| CN109055755A (en) | A kind for the treatment of process of high-copper argentiferous material | |
| CN112458280A (en) | Method for extracting valuable metals by leaching low grade nickel matte with acidic etching solution | |
| CN105200242B (en) | A kind of method that cadmium is reclaimed from containing arsenic refining lead oxygen bottom blown furnace cigarette ash | |
| CN1239720C (en) | Method for producing high purity metal zinc from zinc oxide ore | |
| CN104711426B (en) | A kind of useless methods of the target through reducing electroextraction indium tin of ITO | |
| JPH07505443A (en) | Electrochemical system for recovery of metals from metal compounds | |
| CN109957655A (en) | A kind of give up from ITO extracts the process of indium and tin in target | |
| CN107475752A (en) | Clean metallurgy method and device for low-temperature molten salt electrolysis of tin dross | |
| CN104532295A (en) | Recycling technology for valuable metals in electrolytic zinc leach residues and electrolytic cell adopted by same | |
| PL111879B1 (en) | Method of recovery of copper from diluted acid solutions | |
| CN1094460A (en) | Directly electrolytic extraction of electrolytic copper by copper sulfide ore | |
| CN1034231C (en) | Prodn. of zinc by complex compound electrolysis | |
| CN112481505B (en) | Method for preparing basic zinc chloride by using high-chlorine smelting soot | |
| CN1173077C (en) | Method for producing antimony by electrolyzing antimony-containing sulfide mineral pulp | |
| CN1094762A (en) | One-step Zn smelting technique by suspension electrolysis of ZnS | |
| CN1042752C (en) | Method for extracting bismuth from bismuth sulfide ore pulp through electrolysis | |
| CN1284869C (en) | Method for leaching valuable metals from ocean polymetallic nodules | |
| CA1071136A (en) | Method for the electrolytic recovery of sb, as, hg and/or sn | |
| CN105112679A (en) | Method for recycling copper and bismuth from bismuth slag | |
| US1808547A (en) | Copper extraction process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |