CN1199780A

CN1199780A - Ag and Au extracting and Sb, Bi, Cu and Pb recovering process from lead slime

Info

Publication number: CN1199780A
Application number: CN 97111023
Authority: CN
Inventors: 杨才; 周杨霁; 贺小昆
Original assignee: Kunming Institute of Precious Metals
Current assignee: Kunming Institute of Precious Metals
Priority date: 1997-05-15
Filing date: 1997-05-15
Publication date: 1998-11-25
Anticipated expiration: 2017-05-15
Also published as: CN1058299C

Abstract

The present invention includes the steps of lixiviation with mixed hydrochloric acid and sulfuric acid, hydrolysis deposition of Sb, hydrolysis deposition of Bi, neutralizing and substituting deposition of Cu, salt soaking to remove Pb, substitution of AgCl, deposition of Pb, electrolytic smelting Ag and electrolytic dissolving Au. It has the yield of Au not less than 99%, of Ag not less than 98%, of Sb and Bi greater than 90% and of Cu greater than 65%.

Description

Extract gold and silver and reclaim antimony, bismuth, copper, plumbous method from lead anode slurry

Extract gold and silver and reclaim antimony, bismuth, copper, plumbous method from lead anode slurry.The invention relates to precious metals metallurgy.

Lead anode slurry is to extract gold and silver, particularly one of Yin main raw material, the silver-colored output of China more than 1/2nd from lead anode slurry.Lead anode slurry main component mobility scale (%): Au0.002-0.8, Ag0.1-25, Cu0.5-10, Bi1-20, As0.5-27, Sb0.1-43, S0.1-2.13, Te0.1-0.74.The lead anode slurry traditional treatment method is a thermal process, reclaims gold through retailoring-oxidation blowing-electrum electrolysis De Yin-silver anode slime.The advantage of pyrogenic process is strong to material adaptability, and industrial scale is big, and equipment is simple.To be a part of gold and silver overstock at intermediate product shortcoming, so the gold and silver direct yield is low, and gold is nearly 93%, silver-colored 85-88%, and antimony, bismuth, copper, lead also disperse simultaneously, and the rate of recovery is low.It is (%): Au0.10 that one factory's lead anode slurry composition is arranged, Ag10.09, and Pb15.96, Sb32.69, Bi1.99, Cu8.85, As0.36, Fe0.16, Ca0.70, Mg0.034, SiO222.48 belongs to the low high silicon lead anode slurry of arsenic, and high and low metal ratio is about 1: 5.8.Originally adopt pyrogenic attack.

Purpose of the present invention is at above-mentioned factory lead anode slurry, and the plumbous anode mud of wet processing is explored in research, obtain rich silver-colored slag, gold and silver direct yield height (Au 99%, and Ag 98%), simultaneously can comprehensively reclaim antimony, bismuth, copper, lead, its rate of recovery antimony, bismuth＞80%, the method for copper＞65%.Method provided by the present invention, comprise that the hydrochloric acid+sulphuric acid nitration mixture leaches (or sodium-chlor+sulfuric acid medium leaches), antimony is sunk in hydrolysis, bismuth is sunk in hydrolysis, the heavy copper of neutralization displacement, salt soaks and takes off lead, the displacement silver chloride, heavy plumbous, the electrolysis of melting silver gets silver-colored, the golden several steps of aqua regia dissolution gold reduction, its method steps is: 1, with lead anode slurry at HCl2-4mol/L-+H2SO42mol/L (or NaCl3.5-4.5mol/L+H2SO42-4mol/L) medium, temperature 80-90 ℃, weight of material gram number is 1 with the ratio of liquid volume milliliter number: the 6-10 condition, agitation leach 2-4h, antimony, bismuth, copper changes solution over to, solid-liquid separation; 2 is normal temperature with 1 step gained leach liquor in temperature, stir to add tap water to volume dilution to 2 times, and adding a small amount of 10-20% (weight ratio) NaOH solution, to adjust the solution pH value is 1-1.5 condition hydrolysis antimony, finishes solid-liquid separation to the SbOCl precipitation; 3, with the heavy antimony mother liquor of 2 step gained, be normal temperature, under the agitation condition, add 10-20% (weight ratio) NaOH solution and adjust the solution pH value to 6.5-7.0 in temperature, complete to Ca (OH) 2 precipitations; Or be normal temperature in temperature, under the agitation condition, press Cu: Fe=1: 1-1.2 (weight ratio) adds iron replacement copper, reaction 1-2h, solid-liquid separation in solution; 5, with 1 step gained leached mud, at PH2-4, temperature is nearly 80 ℃, and slag weight in grams number is 1 with the ratio of liquor capacity milliliter number: the 13-18 condition is the NaCl solution of 150-200g/L with concentration, agitation leach 2h makes lead be converted into lead chloride fully and leaches solid-liquid separation; 6,5 step gained are soaked plumbous liquid,, under the agitation condition, add lead powder 2-4kg (or iron powder 4-6kg) displacement by every 1m3 solution and be dissolved in and soak silver chloride in the plumbous liquid, reaction 1-2h, solid-liquid separation at temperature 60-70 ℃; Be normal temperature then in temperature, under the agitation condition, with in the lime [Ca (OH) 2 or CaO] and displacement liquid to PH be 9-11, make lead and heavy metal ion and sulfate radical precipitation, solid-liquid separation, heavy plumbous mother liquor is adjusted back PH to 2-4 with hydrochloric acid, can return 5 step initial application; 7,5 step gained are soaked lead skim and 6 step gained and replace silver-colored slag merging, at temperature 1050-1100 ℃, add yellow soda ash and SODIUMNITRATE and carry out melting, slag: yellow soda ash: SODIUMNITRATE=1: 1.2-2.5: 0.05-0.1 (weight ratio), time 10-60min, melting obtains containing the thick silver ingot of gold, and thick silver obtains fine silver with traditional electrolytic refining process; 8, with the resultant electrorefining of silver anode sludge of 7 steps, add aqua regia dissolution, silver anode slime is 1 with the amount of chloroazotic acid than (weight ratio): 3-4.Gradation adds, and self-heating or later stage heating, stirring make the gold dissolving fully, silver stays in slag with the silver chloride form, filtering separation, filtrate catch up with nitre, catch up with acid after, at boiling temperature, add solid oxalic acid reduction gold, the amount that oxalic acid adds is than being H2C2O4: Au=1-3: 1, and time 4-6h, sponge bronze boil with 3mol/LHCl and wash, wash with water again to neutrality, obtain proof gold.

Advantage of the present invention is: 1. flow process is based on hydrometallurgy, the combination of pyrogenic process wet method, reasonable flowsheet structure; 2, gold and silver direct yield height: Au 〉=99%, Ag 〉=98%, antimony, bismuth, copper, plumbous comprehensive utilization degree good (rate of recovery Sb, Bi＞90%, Cu65%); 3, take off plumbous displacement and reclaim silver and mother liquor regeneration technology, take off plumbous efficient height (＞97%), silver loss little (displacement mother liquor argentiferous 0.011-0.0044g/l) can realize taking off the closed circuit operation of splicer's preface solution, helps environment protection; 4, method applicability is strong, and equipment is simple, easily realizes industrialization.

Embodiment 1, lead anode slurry 1578.35Kg, major ingredient (%), Au0.0085-0.0102, Ag22.416, Pb14.27, Bi0.046, Cu9.78, Sb30.11.Adopt HCl3mol/L+H2SO4 1mol/L medium, temperature 80-85 ℃, plumbous mud weight (Kg): liquid volume (L)=1: 10, agitation leach 2h, solid-liquid separation, leach liquor is by the heavy antimony of the listed hydrolysis antimony of 2 steps condition; Because the lead anode slurry bismuth-containing is very low will not to be reclaimed, heavy antimony mother liquor directly gets the blister copper powder with the heavy copper of waste iron filing displacement; Acid leaching residue is in 80 ℃, with 200g/LNaOH solution, press slag weight (Kg): liquid volume (L)=1: 15, plumbous 2h is soaked in stirring, solid-liquid separation, soak plumbous liquid under 60 ℃ of temperature, reclaim small amount of silver with the listed plumbous displacement chlorination silver bar spare of 6 steps, the displacement mother liquor is heavy plumbous through lime, return behind the technical hydrochloric acid readjustment PH and soak plumbous multiplexingly, soak lead skim by ratio of components: slag: Na2CO3: NaNO3=1: 1100 ℃ of 1.5: 0.1 (weight ratio), temperature, carry out melting and obtain dore bullion bar 389.08kg, grade: Au408-471g/t, Ag91.28-95.39%; The rate of recovery: Au＞99%, Ag99%; The byproduct grade of output, antimony slag Sb39.36-59.76%, blister copper powder Cu31.59%, lead skim Pb31.17-42.72%.

Embodiment 2 lead anode slurry 1000g, main component is (%): Au0.133, Ag10.946, Pb12.40, Bi5.78, Cu2.29, Sb42.38.Adopt the NaCl4.3mol/L+H2SO44mol/L medium, 80 ℃ of temperature, plumbous mud weight (g): liquid volume (ml)=1: 8, agitation leach 2h, solid-liquid separation, leach liquor is pressed 2 steps, 3 steps, the heavy antimony of the listed condition hydrolysis of 4 steps, heavy bismuth of hydrolysis and the heavy copper of iron replacement, leached mud NaCl200g/L solution, temperature 80-85 ℃, press slag weight (g): liquid volume (ml)=1: 15, stir and soak plumbous 2h, solid-liquid separation; Soak plumbous liquid under agitation condition, add the 2.2g lead powder by every 1L, under 65 ℃ of temperature, replacement(metathesis)reaction 2h, solid-liquid separation is soaked lead skim 236.5g, add yellow soda ash 425g, SODIUMNITRATE 12g is in 1100 ℃ of temperature melting 10min, obtain thick silver ingot 110g, grade Au1.214%, Ag97.29% adds silver content 0.58g among the silver-colored slag 18g of plumbous displacement, the rate of recovery: Au99.86%, Ag98.35%; Output byproduct antimony slag 805g contains Sb50.11%, the rate of recovery 95.28%, and bismuth slag 199g contains Bi59.50%, the rate of recovery 99%; Blister copper powder 19.5g contains Cu80.07%, the rate of recovery 68.16%, lead skim 122.9g, Pb grade 29.89%.

Claims

1, extracts gold and silver and reclaim antimony, bismuth, copper, plumbous method from lead anode slurry, comprise that hydrochloric acid+sulphuric acid nitration mixture (or sodium-chlor+sulfuric acid) leaches, antimony is sunk in hydrolysis, bismuth is sunk in hydrolysis, the heavy copper of neutralization displacement, salt soak take off lead, displacement silver chloride, heavy lead, melting, silver-colored electrolysis get silver-colored, aqua regia dissolution is golden, reduce golden several steps, it is characterized in that:

1.1 with lead anode slurry at HCl2-4mol/L (or NaCl3.5-4.5mol/L+H2SO42-4mol/L) medium, temperature 80-90 ℃, weight of material gram number is 1 with the ratio of liquid volume milliliter number: 6-10 condition, agitation leach 2h, antimony, bismuth, copper change solution over to, solid-liquid separation; 1.2 is normal temperature with 1.1 gained leach liquors in temperature, under the agitation condition, adds tap water with volume dilution to 2 times, and adding a small amount of 10-20%NaOH (weight ratio), to adjust the solution pH value be 1-1.5 condition hydrolysis antimony, finishes solid-liquid separation to the SbOCl precipitation;

1.3, be normal temperature in temperature with the heavy antimony mother liquor of 1.2 gained, under the agitation condition, add 10-20%NaOH (weight ratio) solution, adjust the solution pH value to 3.5-4.0 hydrolysis bismuth, complete to the BiOCl precipitation, solid-liquid separation;

1.4, be normal temperature in temperature with 1.3 gained mother liquor of precipitation of ammonium, under the agitation condition, add 10-20%NaCl (weight ratio) solution, adjust solution PH to 6.5-7.0, complete to Cu (OH) 2 precipitations; Or be normal temperature in temperature, under the agitation condition, press Cu: Fe=1: 1-1.2 (weight ratio) adds iron replacement copper in solution, reaction 1-2h, solid-liquid separation;

1.5 with 1.1 gained leached muds, at pH value=2-4, nearly 80 ℃ of temperature, slag weight in grams number is 1 with the ratio of liquid volume milliliter: the 13-18 condition, the NaCl solution stirring leaching 2h with 150-200g/L makes lead be converted into lead chloride fully and leaches solid-liquid separation;

1.6 1.5 gained are soaked plumbous liquid, at temperature 60-70 ℃, under the agitation condition, by every 1m ³Solution adds lead powder 2-4kg (or iron powder 4-6kg) displacement and is dissolved in the silver chloride that soaks in the plumbous liquid, reaction 1-2h, solid-liquid separation; Be normal temperature then, under the agitation condition, with lime [Ca (OH) in temperature ₂Or CaO] neutralization plumbous displacement liquid to PH be 9-11, make lead and heavy metal ion and sulfate radical the precipitation, solid-liquid separation; Heavy plumbous mother liquor to 2-4, can return 1.5 operation initial application with technical hydrochloric acid readjustment pH value;

1.7 1.5 gained are soaked lead skim and 1.6 gained replaces silver-colored slag and merges, at temperature 1050-1100 ℃, add yellow soda ash and SODIUMNITRATE and carry out melting, slag: yellow soda ash: SODIUMNITRATE=1: 1.2-2.5: 0.05-0.1 (weight ratio), time 10-60min, melting gets the thick silver ingot of alloy, and thick silver obtains fine silver with traditional electrolytic refining process;

1.8 with the 1.7 gained electrorefining of silver anode sludge, add aqua regia dissolution, silver anode slime is 1 with the amount of chloroazotic acid than (weight ratio): 3-4, gradation adds, and self-heating or later stage heating are stirred, make the gold dissolving fully, silver stays in slag filtering separation with the silver chloride form, filtrate catches up with nitre, catch up with acid after, at boiling temperature, add solid oxalic acid reduction gold, the amount that oxalic acid adds is H2C2O4: Au=1-3: 1, and time 4-6h, the sponge bronze boils with 3mol/LHCl and washes, wash with water again to neutrality, obtain proof gold.