CN1027977C

CN1027977C - Treatment method of high arsonium lead anode mud wet process

Info

Publication number: CN1027977C
Application number: CN92104421A
Authority: CN
Inventors: 胡绪铭; 谢斌
Original assignee: KUNMING NOBLE METAL INST CHINA NONFERROUS METAL INDUSTRY GENERAL Co
Current assignee: KUNMING NOBLE METAL INST CHINA NONFERROUS METAL INDUSTRY GENERAL Co
Priority date: 1992-06-02
Filing date: 1992-06-02
Publication date: 1995-03-22
Anticipated expiration: 2007-06-02
Also published as: CN1079510A

Abstract

The present invention relates to a wet treating method for high arsonic lead anode mud. In the method, material is put into in hydrochloric acid media and chlorine is introduced for controlling potential chlorination residue can be treated by a sodium hydroxide solution, and then, pure silver and pure gold are obtained by a fire method and electrolysis; the silver can be extracted by a wet method or a fire method after the gold is extracted by the wet method; tellurium ore concentrate is deposited by reduction or by catalytic reduction by filling SO2 into chlorination liquid; arsenic is recovered by a distillation method.; antimony is recovered from residue liquid after distillation by a hydrolysis method; mother liquor obtained by hydrolyzing the antimony is used for neutralizing the deposit so as to obtain bismuth ore concentrate; the mother liquor of deposited bismuth is oxidized and then is used for neutralizing the deposited so as to obtain copper concentrate; the recovery rates of the gold and the silver are 99%, the recovery rates of the antimony and the bismuth are from 90% to 96%, and the recovery rate of copper is from 90% to 98%.

Description

Treatment method of high arsonium lead anode mud wet process

Treatment method of high arsonium lead anode mud wet process the invention relates to precious metals metallurgy.

The present invention is the improvement invention of Chinese patent application application number 89103853.1 patent applications.Plumbous positive mud is one of main raw material that extracts silver and gold, and traditional pyrogenic processing method is: lead anode gets precious metals containing lead through retailoring, and the precious metals containing lead oxidation refining gets slightly silver, and thick silver-colored electrolysis gets product silver.The shortcoming of pyrogenic process is silver-colored direct yield lower (85～90%), and part silver is dispersed in flue dust and the slag, and the valency that has in the slag does not have the plain comprehensive difficulty that reclaims, and the As in the flue dust, Sb still do not have desirable separation method, easily cause environmental pollution." extracting precious metal from the anode sludge " (patent No. CN85106670 of people such as the bear Zong Guo of Kunming Institute of Precious Metals invention with the CONTROLLED POTENTIAL method, applying date 85.8.31), propose with the method for CONTROLLED POTENTIAL method from lead, antimony, nickel anode extraction precious metal, more effective to the enrichment of precious metals metallurgy process, separate precious metal; But this method leaching condition is stronger to equipment corrosion, to the extraction of silver not deeply, the comprehensive recovery of copper, antimony, bismuth, arsenic is not related to." a kind of method of lead anode slurry wet processing " (application number 89103853 of people such as the Hu Xuming of Kunming Institute of Precious Metals invention, applying date 89.6.3) a lead anode slurry wet processing general flow has been proposed, silver-colored, golden direct yield height (Ag96～98%, Au～98%), antimony, bismuth, copper also can comprehensively reclaim, but further separating of arsenic and antimony, bismuth, copper is also undesirable, particularly contains the high lead anode slurry of arsenic.

The objective of the invention is on " a kind of method of lead anode slurry wet processing " basis of people such as Hu Xuming invention, wet processing process to anode mud with high As and Pb (arsenic content 10～40%) further improves, solve the difficult problem of separating of arsenic and antimony in the leach liquor, bismuth, copper, propose both to have made all comprehensive recovery of arsenic and antimony, bismuth, copper, it is minimum to take into account the gold and silver loss again, the technical qualification that the rate of recovery is high.

Method provided by the present invention, be that said anode mud with high As and Pb is placed 3～5N hydrochloric acid medium, best 4NHCl medium, solid: liquid=1: 4～8, under best 1: 4～6 conditions, 10～50 ℃ of temperature, best 15～20 ℃, the oxidation reduction potential control that feeding chlorine makes system is at 360～450mv, and best 380～400mv carries out selectivity and leaches, the enrichment of gained leach liquor arsenic, antimony, bismuth, copper, tellurium, gold and silver have small part to enter solution (Au～2%, Ag～1%), afterwards step recovery: slag has been slagged tap enrichment silver, gold, after can handling with sodium hydroxide solution, the method-electrorefining of starting to exchange fire gets fine silver, gold; After also can wet gold extraction again with wet method or pyrogenic process desilver; Chloridizing leach solution feeds SO ₂Gas reduces or adds a small amount of KI again and carries out catalytic reduction, makes Sb ^{+ 5}→ Sb ^{+ 3}, As ^{+ 5}→ As ^{+ 3}, tellurium precipitate reduction, chloridizing with controlled voltage leach the gold of loss and silver is over half and tellurium coprecipitation enters the tellurium concentrate, and control reduction terminal point is As ^{+ 5}→ As ^{+ 3}～100%(connects distillation) or＞70%(do not distill); The mother liquor of precipitate reduction pound is 100～110 ℃ of temperature, and distill under normal pressure best≤107 ℃, and arsenic distills out with water and HCl with the AsCl3 form, and condensation is reclaimed.Distillation mother liquor or tellurium precipitate reduction mother liquor add water hydrolysis antimony 40～50 ℃ of temperature, get antimony concentrate.Heavy antimony mother liquor adds sodium carbonate solution at～40 ℃ to be handled to pH2～4, precipitated bismuth.Feed chlorine oxidation in the heavy bismuth mother liquor, make Cu ^{+ 1}Complete oxidation is Cu ^{+ 2}, then in temperature～50 ℃, add milk of lime with sodium hydroxide solution and be neutralized to pH7～9, precipitated copper and residue arsenic, copper ore concentrates.Process indicator: Au, Ag total yield～99%, antimony, bismuth 90～96%, copper 90～98%, heavy copper raffinate pH7～9, Cu, Bi, Sb content＜1mg/l, As0.5mg/l reaches emission standard.

The advantage of method is: 1, gold and silver rate of recovery height, the gold and silver that are lost in the chloridizing with controlled voltage leach liquor are recovered in again in the tellurium concentrate, make total recovery～99% of gold and silver.2, arsenic removal distillation is more thorough, and hydrochloric acid can reclaim with appropriate mode, makes in the hydrolysis and the alkaline consumption of bismuth, copper reduces.3, antimony, bismuth, copper comprehensive recovery height (to concentrate rate of recovery antimony, bismuth 90～96%, copper 90～98%).4, corrodibility is little, and equipment solves well.5, if adopt the simple and easy method that does not distill arsenic of this law proposition, method is simple, but simplified apparatus.

Embodiment

Example 1, content are (weight %): Au0.03, Pb10.24, Cu3.40, Bi8.46, Sb33.12, Te0.38, the low golden anode mud with high As and Pb of As17.15 is at 4HNCl, temperature～20 ℃, solid: under liquid=1: 5 condition, feed the chlorine CONTROLLED POTENTIAL and leach at 380～420mv, can be with the tellurium leaching of the arsenic 98% or more, antimony, bismuth, copper and about 80%; Hydrochloric acid leachate adds a small amount of KI and feeds the gaseous sulfur dioxide reduction, and tellurium deposition rate＞99%, the gold and silver (Au～2%, Ag～1.4%) that enter leach liquor when chloridizing with controlled voltage leaches respectively has～and 50% co-precipitation enters the tellurium concentrate; Heavy tellurium mother liquor (As(+3)/As is total=and～90%, Sb(+3)/and Sb is total=and 100%) under normal pressure, 102～107 ℃ of arsenic removal distillations of temperature, contain the arsenic phlegma and can use sulfide precipitation, store up with the red arsenic form, hydrochloric acid returns leaching usefulness, or the phlegma condensing crystal is produced commodity As ₂O ₃, steaming raffinate with 40～50 ℃ of hot water hydrolytic precipitation antimony, heavy antimony mother liquor adds the sodium carbonate solution precipitated bismuth in 40～50 ℃, behind the logical chlorine oxidation of heavy bismuth mother liquor, in 40 ℃ of hydro-oxidation sodium solutions and an amount of milk of lime pH=7～9 that neutralize, precipitated copper and remain arsenic.To the concentrate rate of recovery: antimony, bismuth＞96%, copper＞98%.Heavy copper raffinate pH=8 contains Cu, Bi, Sb＜1mg/l, and As0.5mg/l reaches emission standard.

The hydrochloric acid leached mud contains Cu＜0.3%, Bi＜0.05%, Sb＜0.9%, As＜0.08%, Pb=40%, Au～0.115%, Ag～24.6%, after can handling with sodium hydroxide solution, the method-electrorefining of starting to exchange fire gets product silver, gold, after also can wet gold extraction again with wet method or pyrogenic process desilver, gold and silver total recovery～99%.

Example 2, content (weight %) are: Au0.014, Ag11.85, Pb14.70, Cu1.87, Sb20.66, Bi11.48, Te0.46, the low golden anode mud with high As and Pb of As13.46, by example 1 condition CONTROLLED POTENTIAL chlorination, the amount that gold and silver enter leach liquor is respectively～2% ,～1%; Leach liquor adds a small amount of KI ventilation body SO ₂Reduction, tellurium deposition rate＞96%, the tellurium concentrate is advanced in each 50% co-precipitation of gold and silver that enters the chloridizing with controlled voltage leach liquor; Heavy tellurium mother liquor (As(+3)/As is total=and～80%, Sb(+3)/and Sb is total=and～98%) hydrolytic precipitation antimony, reclaim bismuth, copper by example 1 identical step process then.Antimony concentrate contains Sb70.1%, As1.1%, antimony direct yield 73%, arsenic scatter coefficient 1.61%; The bismuth concentrate contains Bi54.3%, As0.13%, bismuth direct yield 91%, arsenic scatter coefficient 0.2%; Copper ore concentrates contains Cu1.51%, As12.7%, copper direct yield 90%, arsenic scatter coefficient～75%; Heavy copper raffinate contains Cu4.2mg/l, Sb2.0mg/l, Bi5.0mg/l, As0.5mg/l after the high ferro dearsenification.Chloridizing with controlled voltage leached mud composition is similar to example 1, and after can handling with sodium hydroxide solution, the method-electrorefining of starting to exchange fire gets product silver, gold; Also can extract silver, gold and silver total yield 99% with wet method or pyrogenic process again behind the wet gold extraction.

Method of the present invention can also be used to contain the flue dust and the copper anode mud of arsenic, antimony, the enrichment process of goldmud from cyanide processing except that being used for the lead anode slurry processing.

Claims

1, treatment method of high arsonium lead anode mud wet process is characterized in that:

A, the lead anode slurry material is placed 3～5N hydrochloric acid medium, solid: under the condition of liquid=1: 4～8, temperature feeds chlorine for 10～50 ℃ makes the oxidation reduction potential control of system carry out the selectivity leaching at 360～450Mv, the enrichment of gained solution arsenic, antimony, bismuth, copper, tellurium, the enrichment of gained leached mud silver, golden, after the sodium hydroxide solution processing, the method-electrorefining of starting to exchange fire gets product silver, gold; Or behind the wet gold extraction again with wet method or pyrogenic process desilver;

B, A, gained leach liquor are fed SO ₂Gas reduces or adds a small amount of KI again and carries out catalytic reduction, makes Sb ^{+ 5}→ Sb ^{+ 3}, As ^{+ 5}→ As ^{+ 3}, the sulphur precipitate reduction, the gold and silver co-precipitation of A, leaching loss enters the tellurium concentrate;

C, B, gained solution are distilled for 100～110 ℃ in temperature, and condensation is reclaimed arsenic and is got AsC13, HCl;

D, with C, gained vinasse or B, gained solution 40～50 ℃ of temperature, add water hydrolysis antimony, antimony concentrate;

E, with D, gained solution in temperature～50 ℃, add sodium carbonate solution neutralization precipitation bismuth, the control endpoint pH is 2～4;

F, E, gained solution are fed chlorine oxidation, making 1 valency copper complete oxidation is divalent copper, in temperature～50 ℃, with sodium hydroxide solution add lime milk solution neutralize copper ore concentrates, a small amount of arsenic co-precipitation under C, step are heated up in a steamer enters copper ore concentrates.

2, treatment method of high arsonium lead anode mud wet process as claimed in claim 1, when it is characterized in that carrying out 1A, process, the oxidation reduction potential control of said system is at 380～400mv, 15～20 ℃ of temperature, 4NHCl, solid: liquid=1: 4～6.

3, treatment method of high arsonium lead anode mud wet process as claimed in claim 1, when it is characterized in that carrying out 1B, process, add a small amount of K1 make pentavalent arsenic be reduced to arsenious reducing degree for～100% or＞70%.

4, treatment method of high arsonium lead anode mud wet process as claimed in claim 1, when it is characterized in that carrying out 1C, process, controlled temperature＜107 ℃.