CN105063361A - Method for comprehensively recovering valuable metal from copper anode slime - Google Patents
Method for comprehensively recovering valuable metal from copper anode slime Download PDFInfo
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Abstract
The invention belongs to the technical field of non-ferrous metal metallurgy, and provides a method for comprehensively recovering valuable metal from copper anode slime. The method comprises the following steps that 1, the copper anode slime is added to a selenium-containing acid solution, hydrochloric acid is added, the liquid-solid ratio is controlled to be 2-5:1, primary leaching is carried out, primary leaching residues are added to the selenium-containing acid solution, and compressed air is introduced for secondary leaching; 2, primary leach liquor and secondary leach liquor obtained in the step 1 are evenly mixed, neutralizing is carried out two times, lime is added to two-time post-neutralization liquor for sedimentation, copper-containing sediment residues and post-sedimentation liquor are obtained in a filtering mode, dilute sulphuric acid is added to the post-sedimentation liquor to adjust pH to 5-7, nano zero-valent iron is added to control potential for a reaction, and filtering is carried out; and 3, primary neutralizing residues obtained in the step 2 are leached three times through a sodium hydroxide solution, sulfuric acid and a mixed solution of sodium hydroxide and sodium sulphide, and leach liquor of three times is subjected to air oxidation and concentration and crystallization to obtain sodium antimonite.
Description
Technical field
The invention belongs to non-ferrous metal metallurgy technical field, be specifically related to a kind of method reclaiming valuable metal from Copper Anode Slime.
Background technology
Copper anode mud is the product of electrolytic refining course of copper, comprises gold and silver, platinum metals, copper, selenium, tellurium, arsenic, antimony, bismuth, nickel, tin, lead and silicon-dioxide etc. containing principal element.The object of the process anode sludge reclaims the valuable metals such as Au Ag Pt Pd wherein and selenium, tellurium, antimony, bismuth, tin.Current employing prior art process copper anode mud synthetical recovery valuable metal technique wherein all have some limitations.Based on this present situation, the present invention intends developing the copper anode mud comprehensively recovering valuable metal novel process that a kind of synthetical recovery is effective, simple to operate, be easy to commercial application.
Summary of the invention
In order to overcome the deficiencies in the prior art, the present invention proposes a kind of method reclaiming the method for valuable metal from Copper Anode Slime, the method has the features such as flow process is short, simple to operate, the rate of recovery of metal is high, production cost is low, environmental pollution is little, simultaneously, utilize the inventive method that the leaching reagent in technical process can be made can to obtain recycle to greatest extent, wastewater discharge is few, good in economic efficiency.
The object of the invention is to be achieved through the following technical solutions.Reclaim a method for valuable metal from Copper Anode Slime, comprise the following steps:
(1) join copper anode mud containing in selenium acidic solution, add hydrochloric acid, control liquid-solid ratio is 2 ~ 5:1, temperature of reaction 60 ~ 90 DEG C, and chlorine ion concentration 100 ~ 140g/L in 2 ~ 5 hours reaction times, once leaches, and obtains a leach liquor and a leached mud; Add in a leached mud containing in selenium acidic solution, pass into pressurized air and carry out secondary leaching, control liquid-solid ratio 3 ~ 6:1, temperature of reaction 60 ~ 90 DEG C, in 2 ~ 5 hours reaction times, carries out secondary leaching, obtains secondary leach liquor and secondary leached mud;
(2) by a leach liquor of step (1) gained and secondary leach liquor Homogeneous phase mixing, add NaOH regulate pH of mixed be 1.5 ~ 2, in 0.5 ~ 2 hour reaction times, once neutralize, once neutralized rear liquid and once in and slag; Once after neutralization liquid to add NaOH regulator solution pH be 3 ~ 3.5, in 0.5 ~ 2 hour reaction times, carry out Two-step neutralization, obtain liquid and Two-step neutralization slag after Two-step neutralization; After Two-step neutralization, liquid adds lime and precipitates, and controlling terminal pH is 8 ~ 10, filters and obtains liquid after cupric precipitation slag and precipitation; After precipitation, liquid adds dilute sulphuric acid adjustment pH is 5 ~ 7, adds nano zero valence iron controlling potential and reacts, filter; Filtrate, again after oxidation and aeration process, returns production system reuse;
(3) by step (2) gained once in and slag add sodium hydroxide solution and once leach; One time leached mud carries out secondary leaching with sulfuric acid again; Secondary leached mud joins sodium hydroxide and sodium sulphite mixing solutions carries out three leachings, filters and obtains three leach liquors and three leached muds; Three times leach liquor obtains sodium antimonate after atmospheric oxidation, condensing crystal process.
In the present invention, described is 0.5 ~ 5g/L, H containing selenium in selenium acidic solution
2sO
4be 200 ~ 350/L, chlorion is 20 ~ 30g/L.
In the present invention, the pulp of the secondary leached mud vitriol oil carried out sulfurization roasting after 0.5 ~ 1 hour, and maturing temperature is 500 ~ 700 DEG C, and roasting time is 2 ~ 3 hours; Flue gas absorption tower is stirred 8 ~ 12 hours under normal temperature after absorbing through three grades, filters and obtains thick selenium and containing selenium acidic solution, return leaching process reuse containing selenium acidic solution.
Two-step neutralization slag in step of the present invention (2) returns bismuth recovery system and carries out synthetical recovery process.
The invention has the beneficial effects as follows: 1, adopt copper anode mud sulphuric leaching technique, realize the high efficiency separation of impurity copper bismuth antimony arsenic in the anode sludge, be conducive to the extraction of subsequent handling rare precious metal; Being reused containing selenium acid waste liquid 2, in treatment process, is conducive to the rate of recovery improving selenium, decreases the treatment capacity of waste water simultaneously; 3, the copper selenium antimony bismuth etc. in copper anode mud obtains efficient recovery, and the rate of recovery is high, environmental friendliness, is applicable to industrial applications; The advantage such as 4, have that technological process is simple, technical indicator is stable, labour intensity is little and production cost is low.
Embodiment
The present invention's raw material used is the anode sludge of copper electrolyzing refining output, comprises gold and silver, platinum metals, copper, selenium, tellurium, arsenic, antimony, bismuth, nickel, tin, lead and silicon-dioxide etc. containing element.Its main chemical compositions is roughly (mass percent): Cu2 ~ 25%, Au0.05 ~ 0.8%, Ag2 ~ 15%, Sb1 ~ 15%, Bi1 ~ 10%, As3 ~ 8%, selenium 2 ~ 8%, tellurium 1 ~ 6%, Pb1 ~ 15%, Sn0.2 ~ 8.
Reclaim a method for valuable metal from Copper Anode Slime, specifically comprise following technological process:
(1) join copper anode mud containing in selenium acidic solution, add concentrated hydrochloric acid, control liquid-solid ratio is 2 ~ 5:1, temperature of reaction is 60 ~ 90 DEG C, and chlorine ion concentration is 100 ~ 140g/L, and the reaction times is 2 ~ 5 hours, once leach, filter, obtain a leach liquor and a leached mud; A leach liquor is containing Cu20 ~ 35g/L, Sb20 ~ 30g/L, Bi10 ~ 20g/L;
Join containing in selenium acidic solution by an above-mentioned leached mud, the pressurized air passing into 0.3 ~ 0.5MPa carries out secondary leaching, control liquid-solid ratio is 3 ~ 6:1, temperature of reaction is 60 ~ 90 DEG C, reaction total time is 2 ~ 5 hours, wherein pass into 0.5 ~ 2 hour pressurized air time, filter, obtain secondary leached mud and secondary leach liquor; Secondary leach liquor is containing Cu50 ~ 70g/L, Sb4 ~ 8g/L, Bi2 ~ 6g/L;
Described is 0.5 ~ 5g/L, H containing selenium in selenium acidic solution
2sO
4be 200 ~ 350g/L, chlorion is 20 ~ 30g/L; After above-mentioned two sections are leached, in copper anode mud, Cu, Sb, Bi leaching yield reaches 55%, 85%, more than 88% respectively;
98% vitriol oil pulp of secondary leached mud was carried out sulfurization roasting after 0.5 ~ 1 hour, and maturing temperature is 500 ~ 700 DEG C, and roasting time is 2 ~ 3 hours, and secondary leached mud and vitriol oil mass ratio are 0.8 ~ 1.2; Calcining send precious metal abstraction process recovery Gold, Silver, Platinum, Palladium tellurium copper etc. wherein; Described calcining is less than 0.1% containing selenium; Flue gas absorption tower is stirred 8 ~ 12 hours under normal temperature after absorbing through three grades, filters, and obtains, containing the thick selenium of selenium more than 85% with containing selenium acidic solution, returning above-mentioned leaching process reuse containing selenium acidic solution;
(2) by a leach liquor in step (1) and secondary leach liquor Homogeneous phase mixing, add NaOH and regulate pH of mixed to be 1.5 ~ 2, react 0.5 ~ 2 hour, once neutralize; Described once in and slag containing Sb20 ~ 45%, Cu5 ~ 10%, Bi1 ~ 5%;
Once after neutralization, liquid adds NaOH adjustment pH is 3 ~ 3.5, reacts 0.5 ~ 2 hour, carries out Two-step neutralization; Sb5 ~ 10%, Cu4 ~ 10%, Bi10 ~ 16% in described Two-step neutralization slag; Two-step neutralization slag returns bismuth recovery system and carries out synthetical recovery process;
After Two-step neutralization, liquid adds lime and precipitates, and controlling reaction end pH is 8 ~ 10, filters and is precipitated liquid after slag and precipitation; Described precipitation slag cupric is 20 ~ 25%, precipitates rear liquid cupric 50 ~ 80mg/L, containing arsenic 30 ~ 50mg/L;
After precipitation, liquid adds dilute sulphuric acid adjustment pH is 5 ~ 7, adds nano zero valence iron and keeps current potential at-500 ~-600mV, react after 2 hours, filter; Filtrate, again after oxidation and aeration process, returns production system reuse;
(3) by step (2) once in and slag join sodium hydroxide solution and once leach, filter and obtain a leached mud and a leach liquor; A leaching condition is sodium hydroxide 40 ~ 60g/L, temperature of reaction 70 ~ 90 DEG C, liquid-solid ratio 3 ~ 6:1,2 ~ 5 hours reaction times;
One time leached mud carries out secondary leaching with sulfuric acid again, filters and obtains secondary leached mud and secondary leach liquor; Described secondary leaching condition is sulfuric acid 80 ~ 100g/L, temperature of reaction 70 ~ 90 DEG C, liquid-solid ratio 3 ~ 6:1,2 ~ 5 hours reaction times;
Secondary leached mud joins sodium hydroxide and sodium sulphite mixing solutions carries out three leachings, filters and obtains three leach liquors and three leached muds; Three times described leaching conditions are naoh concentration 40 ~ 60g/L, sodium sulphite concentration 140 ~ 180g/L, temperature of reaction 70 ~ 90 DEG C, liquid-solid ratio 3 ~ 6:1,2 ~ 5 hours reaction times; Three times leach liquor obtains sodium antimonate product after atmospheric oxidation, condensing crystal process; Three leached muds return bismuth recovery system and carry out synthetical recovery process.
embodiment 1:
(1) copper anode mud is joined containing in selenium acidic solution, add 30% concentrated hydrochloric acid once to leach, control liquid-solid ratio is 2:1, temperature of reaction is 70 DEG C, chlorine ion concentration is 120g/L, filter after 3 hours reaction times, a leach liquor is containing Cu25.9g/L, Sb25.6g/L, Bi14.6g/L, Te0.03g/L, Se<0.5g/L; Secondary leaching is carried out containing in selenium acidic solution by adding in a leached mud, control liquid-solid ratio is 3:1, temperature of reaction is 70 DEG C, pass into 0.4MPa pressurized air after 1 hour, continue reaction to filter after 2 hours, Cu65.2g/L, Sb5.7g/L, Bi3.9g/L, Te0.27g/L, Se<0.5g/L in secondary leach liquor; Described is 3.5g/L, H containing selenium in selenium acidic solution
2sO
4for 266g/L, chlorion is 28.5g/L; After two sections are leached, in copper anode mud, Cu, Sb, Bi leaching yield is respectively: 56%, 88%, 90%; Be 0.9 according to secondary leached mud and vitriol oil mass ratio, add 98% vitriol oil pulp and joined in rotary kiln by secondary leached mud after 0.5 hour and carry out sulfurization roasting, maturing temperature is 500 ~ 700 DEG C, and roasting time is 2 hours; The calcining of output is containing selenium 0.06%; The absorption of three grades, flue gas absorption tower, after stirring 10 hours again, filters and obtains, containing the thick selenium of selenium 88% with containing selenium acidic solution, returning above-mentioned leaching process reuse containing selenium acidic solution under normal temperature.
(2) by an above-mentioned leach liquor and secondary leach liquor Homogeneous phase mixing, add NaOH regulate pH of mixed be 1.5 ~ 2, react after 1 hour filter, obtain once in and slag contain Sb38.6%, Cu6.8%, Bi1.7%; Once after neutralization, liquid adds NaOH adjustment pH of mixed is 3 ~ 3.5, and react after 1 hour and filter, the Two-step neutralization slag obtained is containing Sb6.1%, Cu4.8%, Bi14.4%; After Two-step neutralization, liquid adds lime and precipitates, and controlling terminal pH is 8 ~ 10, filters liquid after the precipitation slag and precipitation obtaining cupric 22%; After precipitation, liquid adds dilute sulphuric acid adjustment pH is 5 ~ 7, adds nano zero valence iron and keeps current potential-500 ~-600mV, react after 2 hours and filter; Filtrate, again after oxidation and aeration process, returns production system reuse; Two-step neutralization slag reduction smelting in reverberatory furnace synthetical recovery bismuth, antimony, copper.
(3) will once in and slag add sodium hydroxide solution and once leach, leaching condition is sodium hydroxide 50g/L, temperature of reaction 80 DEG C, liquid-solid ratio 4:1,3 hours reaction times; Filtration obtains a leached mud and a leach liquor; One time leached mud carries out secondary leaching with sulfuric acid again, and leaching condition is sulfuric acid 100g/L, temperature of reaction 80 DEG C, liquid-solid ratio 3:1,3 hours reaction times; Filtration obtains secondary leached mud and secondary leach liquor; Secondary leached mud joins sodium hydroxide and sodium sulphite mixing solutions carries out three leachings, and three leaching conditions are naoh concentration 40g/L, sodium sulphite concentration 160g/L, temperature of reaction 80 DEG C, liquid-solid ratio 4:1,3 hours reaction times; Filtration obtains three leach liquors and three leached muds; Three times leach liquor obtains containing antimony 48.3% sodium antimonate after atmospheric oxidation, condensing crystal process; Three leached mud reduction smelting in reverberatory furnace synthetical recovery bismuths, antimony, copper.
embodiment 2:
(1) copper anode mud is joined containing in selenium acidic solution, add 30% concentrated hydrochloric acid once to leach, control liquid-solid ratio is 3:1, temperature of reaction is 70 DEG C, chlorine ion concentration is 130g/L, reaction times is filter after 4 hours, Cu34.1g/L, Sb28.5g/L, Bi15.0g/L, Te0.02g/L, Se<0.5g/L in a leach liquor; Secondary leaching is carried out containing in selenium acidic solution by adding in a leached mud, control liquid-solid ratio is 3:1, temperature of reaction is 70 DEG C, pass into the pressurized air of 0.4MPa after 1.5 hours, continue reaction to filter after 3 hours, secondary leach liquor is containing Cu54.7g/L, Sb6.5g/L, Bi5.1g/L, Te0.34g/L, Se<0.5g/L; Wherein containing selenium in selenium acidic solution is 2.9g/L, H
2sO
4for 320g/L, chlorion is 25.3g/L; After two sections are leached, in copper anode mud, Cu, Sb, Bi leaching yield is respectively: 60%, 90%, 91%; Be 0.8 according to secondary leached mud and vitriol oil mass ratio, add 98% vitriol oil pulp and joined in rotary kiln by secondary leached mud after 1 hour and carry out sulfurization roasting, maturing temperature is 500 ~ 700 DEG C, and roasting time is 2.5 hours; The absorption of three grades, flue gas absorption tower, after stirring 12 hours again, filters and obtains, containing the thick selenium of selenium 87% with containing selenium acidic solution, returning above-mentioned leaching process reuse containing selenium acidic solution under normal temperature; The calcining of output is containing selenium 0.07%.
(2) by an above-mentioned leach liquor and secondary leach liquor Homogeneous phase mixing, add NaOH regulate pH of mixed be 1.5 ~ 2, react after 1 hour filter, obtain once in and slag contain Sb43.8%, Cu8.5%, Bi1.2%; Once after neutralization, liquid adds NaOH adjustment pH of mixed is 3 ~ 3.5, and react after 1 hour and filter, the Two-step neutralization slag obtained is containing Sb8.6%, Cu5.2%, Bi15.3%; After Two-step neutralization, liquid adds lime and precipitates, and controlling terminal pH is 8 ~ 10, filters liquid after the precipitation slag and precipitation obtaining cupric 24.2%; After precipitation, liquid adds dilute sulphuric acid adjustment pH is 5 ~ 7, adds nano zero valence iron and keeps current potential after-500 ~-600mV reacts 2 hours, filter; Filtrate, again after oxidation and aeration process, returns production system reuse; Two-step neutralization slag reduction smelting in reverberatory furnace synthetical recovery bismuth, antimony, copper.
(3) will once in and slag add sodium hydroxide solution and once leach, leaching condition is sodium hydroxide 40g/L, temperature of reaction 80 DEG C, liquid-solid ratio 3:1,4 hours reaction times; Filtration obtains a leached mud and a leach liquor; One time leached mud carries out secondary leaching with sulfuric acid again, and leaching condition is sulfuric acid 90g/L, temperature of reaction 80 DEG C, liquid-solid ratio 5:1,3 hours reaction times; Filtration obtains secondary leached mud and secondary leach liquor; Secondary leached mud joins sodium hydroxide and sodium sulphite mixing solutions carries out three leachings, and three leaching conditions are naoh concentration 50g/L, sodium sulphite concentration 150g/L, temperature of reaction 80 DEG C, liquid-solid ratio 3:1,4 hours reaction times; Filtration obtains three leach liquors and three leached muds; Three times leach liquor obtains containing antimony 47.5% sodium antimonate after atmospheric oxidation, condensing crystal process; Three leached mud reduction smelting in reverberatory furnace synthetical recovery bismuths, antimony, copper.
embodiment 3
(1) copper anode mud is joined containing in selenium acidic solution, add 30% concentrated hydrochloric acid once to leach, control liquid-solid ratio is 5:1, temperature of reaction is 80 DEG C, chlorine ion concentration is 140g/L, reaction times is filter after 4 hours, Cu29.3g/L, Sb26.7g/L, Bi15.5g/L, Te0.03g/L, Se<0.5g/L in a leach liquor; Secondary leaching is carried out containing in selenium acidic solution by adding in a leached mud, control liquid-solid ratio is 6:1, temperature of reaction is 90 DEG C, pass into the pressurized air of 0.3MPa after 2 hours, continue reaction to filter after 3 hours, secondary leach liquor is containing Cu67.6g/L, Sb5.8g/L, Bi5.0g/L, Te0.41g/L, Se<0.5g/L; Wherein containing selenium in selenium acidic solution is 4.8g/L, H
2sO
4for 340g/L, chlorion is 24.5g/L; After two sections are leached, in copper anode mud, Cu, Sb, Bi leaching yield is respectively: 58%, 92%, 90%; Be 0.8 according to secondary leached mud and vitriol oil mass ratio, add 98% vitriol oil pulp and joined in rotary kiln by secondary leached mud after 1 hour and carry out sulfurization roasting, maturing temperature is 500 ~ 700 DEG C, and roasting time is 2.5 hours; The absorption of three grades, flue gas absorption tower, after stirring 12 hours again, filters and obtains, containing the thick selenium of selenium 88% with containing selenium acidic solution, returning above-mentioned leaching process reuse containing selenium acidic solution under normal temperature; The calcining of output is containing selenium 0.07%.
(2) by an above-mentioned leach liquor and secondary leach liquor Homogeneous phase mixing, add NaOH regulate pH of mixed be 1.5 ~ 2, react after 1 hour filter, obtain once in and slag contain Sb39.5%, Cu6.6%, Bi1.5%; Once after neutralization, liquid adds NaOH adjustment pH of mixed is 3 ~ 3.5, and react after 1 hour and filter, the Two-step neutralization slag obtained is containing Sb8.6%, Cu7.3%, Bi13.5%; After Two-step neutralization, liquid adds lime and precipitates, and controlling terminal pH is 8 ~ 10, filters liquid after the precipitation slag and precipitation obtaining cupric 23.2%; After precipitation, liquid adds dilute sulphuric acid adjustment pH is 5 ~ 7, adds nano zero valence iron and keeps current potential after-500 ~-600mV reacts 2 hours, filter; Filtrate, again after oxidation and aeration process, returns production system reuse; Two-step neutralization slag reduction smelting in reverberatory furnace synthetical recovery bismuth, antimony, copper.
(3) will once in and slag add sodium hydroxide solution and once leach, leaching condition is sodium hydroxide 60g/L, temperature of reaction 80 DEG C, liquid-solid ratio 5:1,5 hours reaction times; Filtration obtains a leached mud and a leach liquor; One time leached mud carries out secondary leaching with sulfuric acid again, and leaching condition is sulfuric acid 90g/L, temperature of reaction 80 DEG C, liquid-solid ratio 4:1,3 hours reaction times; Filtration obtains secondary leached mud and secondary leach liquor; Secondary leached mud joins sodium hydroxide and sodium sulphite mixing solutions carries out three leachings, and three leaching conditions are naoh concentration 50g/L, sodium sulphite concentration 140g/L, temperature of reaction 80 DEG C, liquid-solid ratio 3:1,4 hours reaction times; Filtration obtains three leach liquors and three leached muds; Three times leach liquor obtains containing antimony 47.5% sodium antimonate after atmospheric oxidation, condensing crystal process; Three leached mud reduction smelting in reverberatory furnace synthetical recovery bismuths, antimony, copper.
Claims (4)
1. reclaim a method for valuable metal from Copper Anode Slime, it is characterized in that comprising the following steps:
Join copper anode mud containing in selenium acidic solution, add hydrochloric acid, control liquid-solid ratio is 2 ~ 5:1, temperature of reaction 60 ~ 90 DEG C, and chlorine ion concentration 100 ~ 140g/L in 2 ~ 5 hours reaction times, once leaches, and obtains a leach liquor and a leached mud; Add in a leached mud containing in selenium acidic solution, pass into pressurized air and carry out secondary leaching, control liquid-solid ratio 3 ~ 6:1, temperature of reaction 60 ~ 90 DEG C, in 2 ~ 5 hours reaction times, carries out secondary leaching, obtains secondary leach liquor and secondary leached mud;
By a leach liquor of step (1) gained and secondary leach liquor Homogeneous phase mixing, add NaOH regulate pH of mixed be 1.5 ~ 2, in 0.5 ~ 2 hour reaction times, once neutralize, once neutralized rear liquid and once in and slag; Once after neutralization liquid to add NaOH regulator solution pH be 3 ~ 3.5, in 0.5 ~ 2 hour reaction times, carry out Two-step neutralization, obtain liquid and Two-step neutralization slag after Two-step neutralization; After Two-step neutralization, liquid adds lime and precipitates, and controlling terminal pH is 8 ~ 10, filters and obtains liquid after cupric precipitation slag and precipitation; After precipitation, liquid adds dilute sulphuric acid adjustment pH is 5 ~ 7, adds nano zero valence iron controlling potential and reacts, filter; Filtrate, again after oxidation and aeration process, returns production system reuse;
(3) by step (2) gained once in and slag add sodium hydroxide solution and once leach; One time leached mud carries out secondary leaching with sulfuric acid again; Secondary leached mud joins sodium hydroxide and sodium sulphite mixing solutions carries out three leachings, filters and obtains three leach liquors and three leached muds; Three times leach liquor obtains sodium antimonate after atmospheric oxidation, condensing crystal process.
2. a kind of method reclaiming valuable metal from Copper Anode Slime according to claim 1, is characterized in that, described is 0.5 ~ 5g/L, H containing selenium in selenium acidic solution
2sO
4be 200 ~ 350/L, chlorion is 20 ~ 30g/L.
3. a kind of method reclaiming valuable metal from Copper Anode Slime according to claim 1, it is characterized in that, the pulp of the secondary leached mud vitriol oil carried out sulfurization roasting after 0.5 ~ 1 hour, and maturing temperature is 500 ~ 700 DEG C, and roasting time is 2 ~ 3 hours; Flue gas absorption tower is stirred 8 ~ 12 hours under normal temperature after absorbing through three grades, filters and obtains thick selenium and containing selenium acidic solution, return leaching process reuse containing selenium acidic solution.
4. a kind of method reclaiming valuable metal from Copper Anode Slime according to claim 1, it is characterized in that, the Two-step neutralization slag in step (2) returns bismuth recovery system and carries out synthetical recovery process.
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