CN1020755C

CN1020755C - Wet method for treating lead anode slurry

Info

Publication number: CN1020755C
Application number: CN89103853A
Authority: CN
Inventors: 胡绪铭; 赖友芳; 王友平
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: 1989-06-03
Filing date: 1989-06-03
Publication date: 1993-05-19
Anticipated expiration: 2004-06-03
Also published as: CN1047888A

Abstract

The present invention relates to a wet method for treating lead anode slurry. The method of the present is characterized in that materials are placed in a hydrochloric acid medium; chlorine is led at the temperature of 10 to 50 DEG C so that the oxidation-reduction potential of a system is controlled to be 400 to 450 mv to be selectively leached. According to the characteristics of the materials, after chloridizing leaching slag is processed by a sodium hydroxide solution, a silver product and a gold product can be obtained by the electrolytic refinement of a fire welding method; silver can also be extracted by a wet method or a pyrogenic method after gold is extracted by aqueous solution chlorination. The direct yield of the silver is from 96 to 97.5%, and the direct yield of the gold is 98%. Antimony is recovered by a hydrolysis method by chloridizing leaching liquid, arsenic is recovered by a reduction precipitation method, and copper, bismuth and antimony are separated by a complex method. The recovery rate of the antimony, the bismuth, the copper and the arsenic is respectively larger than and equal to 90%, larger than and equal to 93%, larger than and equal to 93%, and 90%.

Description

Wet method for treating lead anode slurry

A kind of method of lead anode slurry wet processing the invention relates to precious metal hydrometallurgy.

Lead anode slurry is one of main raw material that extracts precious metal silver and gold, and traditional treatment process is a pyrogenic process.Lead anode slurry gets precious metals containing lead, flue dust and shoddye through retailoring, and precious metals containing lead oxidation refining deleading divides slightly silver-coloredly silver-colored, 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 with copper, antimony, bismuth, arsenic, and flue dust and slag are difficult, the comprehensive difficulty that reclaims." extracting precious metal from the anode sludge " (application number 85106670 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, obtained power), proposed to extract from lead, antimony, nickel anode mud the method for precious metal with the CONTROLLED POTENTIAL method, system places 4～6NHCl and 1～1.4N NaCl medium with material, 75～85 ℃ of temperature, add NaClO and make the oxidation reduction potential control of system carry out the selectivity leaching at 400～460mV; Chloridizing with controlled voltage leaches gold once more.Provide one to be used for the precious metals metallurgy process and to extract, enrichment separates the effective ways of high and low metal.But this method chloridizing with controlled voltage must and have in the hydrochloric acid medium of NaCl 75～85 ℃ of temperature and carries out, and has aggravated the corrodibility of chloride media to equipment; Extraction to silver is not goed deep into; Copper, antimony, bismuth, plumbous comprehensive recovery are not related to.

The objective of the invention is to propose a lead anode slurry wet processing general flow, can separate high and low metal effectively, gold and silver rate of recovery height, copper, antimony, bismuth, lead also can comprehensively reclaim, and is little to equipment corrosion, free from environmental pollution.

Method provided by the present invention, be that said lead anode slurry material is placed 2.5～5N, preferably in the 3NHCl medium, solid (weight): liquid (volume)=1: 4～8, preferably under 1: 6 condition, 10～50 ℃ of temperature, best～20 ℃, make the oxidation reduction potential control of system carry out the selectivity leaching at 400～450mV by feeding chlorine, make copper, antimony, bismuth, arsenic change solution over to, gold and silver and lead are stayed in the slag.Potential value can be measured with the platinum electrode saturated calomel electrode, and the control of potential range is controlled by control chlorine feeding amount.Chlorine is the most frequently used, the most cheap chlorizating agent, owing to avoid adding salt chlorizating agent such as NaCl and process is carried out at normal temperature, greatly reduces the solution loss of silver.Chlorination process need not heat, and both save energy has alleviated the burden of equipment anticorrosion again, helps the selection of equipment material.Contain the low and silver-colored output of gold when big at material, the chlorination leached mud with 5～20% preferably 10% NaOH solution at 80～90 ℃, best 85 ℃ were leached 1～2 hour, make silver, lead change silver suboxide, plumbous oxide into, tellurium and plumbous part are deviate from, silver and further enrichment of gold make down to go on foot the improvement that matter has been arranged than traditional thermal process when getting silver-colored au-alloy plate with the soda melting, get silver-colored, golden product by electrorefining then.The thick silver of direct yield 〉=97.5%, thick gold 〉=98%.When material contained the higher and silver-colored output of gold and hangs down, leached mud can be carried gold by aqueous solution chlorination, reduce behind the proof gold, wet method or pyrogenic process desilver again.

Chloridizing with controlled voltage gained leach liquor be concentrated into original volume 1/8～1/10 with recovery part acid, add hot water hydrolytic precipitation antimony, logical again SO ₂After the arsenic precipitation, handle to PH3.5～4.5 with 100～200g/l, make the copper complexing, antimony, bismuth are precipitated fully, copper separates more complete with antimony, bismuth.The copper complex liquid destroys the copper network with NaClO or other oxygenant oxidations again and closes And neutralization precipitation copper.Direct yield: copper 〉=93%, antimony 〉=90%, bismuth 〉=93% waste liquid content: Cu1～3mg/l, Sb30～50mg/l, Bi1～5mg/l, Pb＜1mg/l, As＜0.5mg/l.

The immersion liquid of lead anode slurry alkali feeds Cl ₂Or SO ₂Behind the precipitation lead, contain NaClO or Na in the solution ₂SO ₃, can return the copper treatment process and use.

Advantage of the present invention is: (1) wet processing, and operation is few, and the cycle is short.(2) change according to silver, gold content in the chlorination leached mud, was connected with traditional firing method process again after both can alkali soaking extract silver-colored, golden; Also can use the subsequent extraction gold and silver of wet process.(3) agents useful for same is cheap and easy to get.(4) precious metal rate of recovery height, base metal also can comprehensively reclaim.(5) corrodibility is little, and equipment easily solves.(6) waste liquid reaches emission standard, and environmental pollution is little.(7) the 1A of the present invention method of separating high and low metal can also be used for the high and low metal separation of noble liquid cyanide zinc displacement gained gold mud, antimony electrolysis anode sludge, the anode mud of copper electroplating except that handling lead anode slurry.

Embodiment one, content are (weight %): Ag14, Au0.003, Cu8, Sb40, Bi6, Pb10, the low golden lead anode slurry of As1 is at 3NHCl, temperature～20 ℃, solid (weight): under liquid (volume)=1: 6 condition, feed the chlorine CONTROLLED POTENTIAL and leached 2 hours at 400～450mV; Chlorination leached mud 10%NaOH solution, 1 hour De Fuyin oxidation sludge is handled in temperature～85 ℃, and rich silver-colored oxidation sludge must contain the thick silver of Ag＞98%, silver-colored direct yield 〉=97.5% through the soda melting; After hydrochloric acid leachate is concentrated into 1/8 recovery part acid of original volume, dilute hydrolytic precipitation antimony, use the Na of 150g/l then ₂SO ₃Solution ℃ is handled to PH3.5～4.5 in temperature～30, and antimony, bismuth precipitate fully, separate with copper; The copper complex liquid adds the NaClO oxidation, is neutralized to PH8～9 again, and copper promptly precipitates fully, direct yield: antimony＞90%, bismuth＞94% bronze medal＞93%.

Embodiment two: content (weight %) is Au0.77, Ag7.76, and Cu4.96, Sb29.22, Bi11, Pb13.20, the high golden lead anode slurry of As16 is by example one condition CONTROLLED POTENTIAL chlorination; The rich silver of gained, golden slag leach gold with the aqueous solution known chlorination process, golden chlorated liquid with oxalic acid reduce the gold of purity 99.99%, direct yield 98%; Soak golden slag when silver yields poorly, with known ammonia soak-the hydrazine hydrate reduction method gets fine silver, silver-colored direct yield 96%, when silver-colored output is high, be smelted into thick silver but soak golden slag use-case one same procedure with soda, thick electrorefining of silver gets fine silver, and And reclaims remaining gold from silver electrolysis anode slime; The earlier logical SO of chloridizing with controlled voltage leach liquor ₂Arsenic precipitation is used then with example one same steps as and is handled recovery antimony, bismuth, copper, the rate of recovery: arsenic 〉=90%, antimony 〉=90%, bismuth 〉=93%, copper 〉=93%.

The present invention is not limited to the foregoing description.

Claims

1, a kind of method of lead anode slurry wet processing is characterized in that:

A, the lead anode slurry material is placed 2.5～5NHC1 medium, under the condition of solid-to-liquid ratio=1: 4～8,10～50 ℃ of temperature, make the oxidation reduction potential control of system carry out the selectivity leaching at 400～450mv (the saturated electrode of platinum-calomel) by feeding chlorine, the gained leached mud can extract gold and silver respectively with known wet processing;

B, A gained leached mud was leached 1～2 hour for 80～90 ℃ in temperature with the NaOH solution of 5～20% (weight), make silver and plumbous transition state, tellurium leaches, and plumbous part leaches, precious metal is enrichment again, and gained alkali soaks slag can obtain fine silver, proof gold with known pyrometallurgical smelting, electrolysis;

C, A gained leach liquor is concentrated recovery part hydrochloric acid, add hot water dilution precipitation antimony, logical SO ₂Arsenic precipitation is with 100～200g/1Na ₂SO ₃, 10～50 ℃ of temperature, complex copper also makes antimony, bismuth precipitation fully, and the copper complex liquid can use NaClO (or other oxygenants) oxidation to destroy copper complex and neutralization precipitation copper;

D, B gained leach liquor fed chlorine or feed sulfurous gas make plumbous precipitation, solution can return the C operation and use.

2, the method for lead anode slurry wet processing as claimed in claim 1, when it is characterized in that carrying out the 1A process, the oxidation reduction potential control of said system is at the saturated electrode of 400～450mv(platinum-calomel), about 20 ℃ of temperature, 3～4NHCl, solid-to-liquid ratio=1: 6.

3, NaOH solution lead anode slurry treatment process as claimed in claim 1, when it is characterized in that carrying out the 1B process, gained leached mud 10%(weight), about 85 ℃ of temperature was handled 1 hour.

4, lead anode slurry treatment process as claimed in claim 1 at the arsenic post precipitation, is used concentration 150g/lNa when it is characterized in that carrying out the 1C process ₂SO ₃Solution, about 30 ℃ of temperature is handled to PH3.5～4.5.