CN108018431A - The recovery method of valuable metal in a kind of silver-zine slag - Google Patents

The recovery method of valuable metal in a kind of silver-zine slag Download PDF

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CN108018431A
CN108018431A CN201711350254.6A CN201711350254A CN108018431A CN 108018431 A CN108018431 A CN 108018431A CN 201711350254 A CN201711350254 A CN 201711350254A CN 108018431 A CN108018431 A CN 108018431A
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silver
zine
bismuth
zinc
recovery method
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CN108018431B (en
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粟明辉
陈兰
谢兆凤
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Chengzhou City Jingui Silver Co Ltd
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Chengzhou City Jingui Silver Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
    • C22B11/042—Recovery of noble metals from waste materials
    • C22B11/044—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00—Obtaining lead
    • C22B13/04—Obtaining lead by wet processes
    • C22B13/045—Recovery from waste materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/06—Obtaining bismuth
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • 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

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  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a kind of recovery method of valuable metal in silver-zine slag, by vacuum distillation, heavy lead is aoxidized, neutralizes heavy bismuth, neutralize heavy zinc, displacement puies forward bismuth this five step.The present invention Oxidation Leaching and neutralizes heavy zinc at normal temperatures, reduces the consumption of steam, improves operating efficiency, using vacuum distillation and wet method combined processing, compared with conventional method, processing procedure is simple and clear, and Process configuration is reasonable, metal separation is thorough, and the rate of recovery is higher, good in economic efficiency.

Description

The recovery method of valuable metal in a kind of silver-zine slag
Technical field
The invention belongs to smelting field of nonferrous metal, and in particular to the recovery method of valuable metal in a kind of silver-zine slag.
Background technology
The intermediate products of zincification desilver when silver-zinc crust is pyro-refining lead or bismuth, since zinc can be formed with metals such as gold, silver A series of infusible compounds, these compounds are almost not dissolved in bismuth liquid, and density is small compared with bismuth, therefore add metal into bismuth liquid Zinc, the copper in bismuth liquid and gold, silver form insoluble compound with zinc, float on bismuth liquid surface, i.e. silver-zine slag, are Comprehensive Recovery of Ag bismuths Raw material.Argentiferous bismuth is higher in silver-zine slag, general argentiferous 1-10%, and the content of bismuth is more than 50%, in addition containing some zinc, copper, Lead and a small amount of gold etc., have very high comprehensive utilization value.The processing method of silver-zine slag generally has：1st, directly return and work as dispensing Utilize；2nd, silver-zine slag pyrogenic attack；3rd, Whote-wet method extract technology.Pyrogenic attack shortcoming be complicated, metal recovery rate is low, After environmental pollution is serious and zinc brings silver converter into, the working of a furnace is degrading, increases the viscosity of shoddye, so as to increase the loss of silver.Entirely Wet method is usually that initial oxidation leaches separation of Bismuth and other base metals, and gold and silver are enriched in slag, then pass through wet-treating.This processing Mode has leaches silver-zine slag using nitric acid, the drawback is that acid consumption is big, severe operational environment and seriously pollution environment, bismuth nitrate into Entering electrolyte influences the quality of electrolytic silver.
Application number 201310609901.6 discloses a kind of method for recycling valuable metal in silver-zine slag, it is characterized in that using NaClO3- NaCl-HCl systems carry out silver-zine slag Oxidation Leaching, and silver-zine slag leaches using pre- leaching, leaches two sections of counterflow leachings Technique.The base metals such as bismuth, zinc enter in solution, obtain chlorine oxygen bismuth with hydrolytic precipitation, liquor zinci chloridi precipitates to obtain alkali with soda ash Formula zinc carbonate；And gold and silver are enriched in slag, further extract.The shortcomings that this method, is：Leaching is in environment is heated Carry out, and the valuable metal in silver-zine slag cannot be carried out to substep separation, silver metal carries out separation and be not thorough again after entering slag phase.
Application number 201110086563.3 disclose Zhou Song et al. disclose it is a kind of recycled from noble metal smelting slag it is valuable Silver-zinc crust is carried out vacuum distillation processing, obtains richness by the technique (invention patent mandate CN102703719B) of metal, the technique Kirsite containing noble metal, then carries out electrolysis to electrum and gold and silver is separately recovered through the electrum that blows to obtain again.This technique Silver-zinc crust is handled using traditional vacuum distillation method, then turns the valuable metals such as traditional pyrometallurgical smelting recycling gold, silver, zinc, exists The shortcomings of technological process is complicated, and production cost is high, metal recovery rate.
The content of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of recovery method of valuable metal in silver-zine slag.
The present invention provides a kind of recovery method of valuable metal in silver-zine slag, comprises the following steps：
A) it is evaporated in vacuo：By silver-zine slag under 10-20Pa vacuums, at a temperature of 910-940 DEG C, vacuum distillation obtains thick silver With zinc bismuth alloy；
B) heavy lead is aoxidized：Thick galactic longitude crosses processing and obtains silver products, and zinc bismuth alloy carries out oxygen with hydrochloric acid and dioxygen water mixed liquid Change and leach, filtrate 1 and filter residue 1 is obtained by filtration in normal-temperature reaction, and the processing of filter residue 1 obtains lead, the volume matter of mixed liquor and zinc bismuth alloy It is 4-6mL to measure ratio:1g；
C) heavy bismuth is neutralized：Filtrate 1 adjusts pH value 3-4 with lye, and after hydrolysis, filtrate 2 and filter residue 2 is obtained by filtration；
D) heavy zinc is neutralized：Into filtrate 2 plus lye adjusts pH value 7-8, and after hydrolysis, filtrate 3 and filter residue is obtained by filtration 3, lye is matched somebody with somebody in 3 reuse of filtrate, and the processing of filter residue 3 obtains zinc；
E) displacement carries bismuth：The hydrochloric acid solution that concentration is 20% of filter residue 2 dissolves, and then adds iron replacement and reacts to obtain sea The volume mass ratio of continuous bismuth, hydrochloric acid solution and filter residue 2 is 5mL:1g.
Preferably, silver-zine slag described in step a) includes the material of following weight percent content：Bi60-80%, Ag3- 6%, Zn10-20%, Pb1-5%.
Preferably, the time being evaporated in vacuo described in step a) is 1.5-2.5h.
Preferably, the hydrochloric acid solution and 30% hydrogen peroxide solution that mixed liquor described in step b) is 20% are with volume ratio 3： 1 mixes.
Preferably, the temperature of hydrolysis described in step c) is 60-70 DEG C.
Preferably, hydrolysis time described in step d) is 1-1.5h.
Preferably, lye is sodium hydroxide solution described in step c) and step d).
Preferably, step b), c) and d) described in be filtered into press filtration.
Preferably, the addition of iron powder described in step e) is 1-1.2 times of theoretical amount.
The beneficial effects of the invention are as follows：
1st, the purity of slag charge is high：Silver content 94-96% in silver-colored slag, bi content 97.5-98.4% in sponge bismuth, slag charge purity Height is conducive to improve metal recovery rate, and last metallic silver, bismuth, the rate of recovery of lead respectively reach 95%, 91%, more than 94%.
2nd, Oxidation Leaching at normal temperatures of the invention and the heavy zinc of neutralization, reduce the consumption of steam, improve operating efficiency.
3rd, the present invention uses vacuum distillation and wet method combined processing, and compared with conventional method, processing procedure is simple and clear, Process configuration is reasonable, and metal separation is thorough, and the rate of recovery is higher, good in economic efficiency, makees oxidant with hydrogen peroxide, reaction speed is fast And do not bring other impurity into, the bismuth purity obtained with iron replacement bismuth is preferable, and direct yield is high and production cost is low.
The main component of silver-zine slag of the present invention is bismuth, silver, zinc, lead, and the overwhelming majority exists for reduction-state.Vacuum distillation Metal and alloy it is basic according to being the different vapour pressure of each metal gas, the atom of each element when being coexisted due to each element, point The Interaction Force of son, influences the actual vapor of each element, and then influences the effect of separated.In temperature 910~940 DEG C when, in the case that vacuum is little, bismuth, zinc are easy to volatilize, and silver it is almost non-volatile, separated effect can be reached. To zinc bismuth alloy HCl+H2O2Mixed liquor dissolves to obtain zinc chloride and bismuth chloride solution, and metal chloride is because in hydrochloric acid solution In different solubility, the initial gross separation of metal can be realized by press filtration, and zinc bismuth alloy nubbin lead is with precipitation of lead chloride Form enter slag in.
BiCl in solution3、ZnCl2With the rise of pH value, then it can hydrolyze, reaction is as follows：
BiCl3+ 2NaOH=BiOCl ↓+2NaCl+2H2O
ZnCl2+ 2NaOH=Zn (OH)2↓+2NaCl
BiOCl passes through diluted hydrochloric acid dissolution, adds iron powder and displacement reaction then occurs, then react as follows：
BiOCl+2HCl=BiCl3+H2O
2BiCl3+ 3Fe=3FeCl2+2Bi↓
Brief description of the drawings
Fig. 1 is the process flow chart of the present invention.
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, below in conjunction with specific embodiment, and reference Technical scheme is clearly and completely described in attached drawing.
Embodiment 1
Process flow chart is as shown in Figure 1, comprise the following steps that：
A) it is evaporated in vacuo：The silver-zine slag of 1000Kg, wherein Bi71.3%, Ag3.8%, Zn11.8%, Pb1.7% are taken, is sent Distilled to vacuum drying oven, vacuum is maintained at 15Pa, 2h is kept the temperature at a temperature of 920 DEG C, obtains thick silver and zinc bismuth alloy, thick silver oxygen Casting Ag positive plate send silver-colored electrolysis after changing blowing.
B) heavy lead is aoxidized：Zinc bismuth alloy HCl and H2O2Mixed liquor carries out Oxidation Leaching, the body of mixed liquor and zinc bismuth alloy Product mass ratio is 4mL:1g；The mixed liquor of 4mL, normal-temperature reaction 1.5h are added i.e. in 1g silver-zine slags, press filtration obtains filtrate 1 and filter residue 1, filter residue 1 (predominantly lead chloride) returns to lead system extraction lead.
C) heavy bismuth is neutralized：Filtrate 1 adds sodium hydroxide solution and adjusts pH value 3, and 65 DEG C of temperature, reacts 1h, hydrolyze bismuth, presses Filter obtains filtrate 2 and filter residue 2 (predominantly chlorine oxygen bismuth).
D) heavy zinc is neutralized：Sodium hydroxide solution is added into filtrate 2, controls the pH=7 in solution, reaction 1.5h to be filtered Lye is matched somebody with somebody in slag 3 (predominantly zinc hydroxide precipitation) and filtrate 3,3 reuse of filtrate, and filter residue 3 carries out processing extraction zinc.
E) displacement carries bismuth：The hydrochloric acid solution that concentration is 20% of filter residue 2 dissolves, the volume mass of hydrochloric acid solution and filter residue 2 Than for 5mL:1g.Then the iron powder of 1 times of theoretical amount needed for displacement bismuth is added, reacts 2h, press filtration obtains sponge bismuth.
Embodiment 2
A) it is evaporated in vacuo：The silver-zine slag of 1000Kg, wherein Bi69.3%, Ag4.2%, Zn13.1%, Pb1.2% are taken, is sent Distilled to vacuum drying oven, vacuum is maintained at 20Pa, 2.5h is kept the temperature at a temperature of 940 DEG C, obtains thick silver and zinc bismuth alloy, thick silver Casting Ag positive plate send silver-colored electrolysis after oxidation blowing.
B) heavy lead is aoxidized：Zinc bismuth alloy HCl and H2O2Mixed liquor carries out Oxidation Leaching, the body of mixed liquor and zinc bismuth alloy Product mass ratio is 5mL:1g；The mixed liquor of 5mL, normal-temperature reaction 2h are added i.e. in 1g silver-zine slags, press filtration obtains filtrate 1 and filter residue 1, Filter residue 1 (predominantly lead chloride) returns to lead system extraction lead.
C) heavy bismuth is neutralized：Filtrate 1 adds sodium hydroxide solution and adjusts pH value 3.5, and temperature 70 C, reacts 1h, hydrolyze bismuth, Press filtration obtains filtrate 2 and filter residue 2 (predominantly chlorine oxygen bismuth).
D) heavy zinc is neutralized：Sodium hydroxide solution is added into filtrate 2, controls the pH=7.5 in solution, reaction 1h to be filtered Lye is matched somebody with somebody in slag 3 (predominantly zinc hydroxide precipitation) and filtrate 3,3 reuse of filtrate, and filter residue 3 carries out processing extraction zinc.
E) displacement carries bismuth：The hydrochloric acid solution that concentration is 20% of filter residue 2 dissolves, the volume mass of hydrochloric acid solution and filter residue 2 Than for 5mL:1g.Then the iron powder of 1.1 times of theoretical amounts needed for displacement bismuth is added, reacts 2.5h, press filtration obtains sponge bismuth.
Embodiment 3
A) it is evaporated in vacuo：The silver-zine slag of 1000Kg, wherein Bi76.8%, Ag4.0%, Zn14.8%, Pb3.2% are taken, is sent Distilled to vacuum drying oven, vacuum is maintained at 10Pa, 1.5h is kept the temperature at a temperature of 910 DEG C, obtains thick silver and zinc bismuth alloy, thick silver Casting Ag positive plate send silver-colored electrolysis after oxidation blowing.
B) heavy lead is aoxidized：Zinc bismuth alloy HCl and H2O2Mixed liquor carries out Oxidation Leaching, the body of mixed liquor and zinc bismuth alloy Product mass ratio is 6mL:1g；The mixed liquor of 6mL, normal-temperature reaction 1h are added i.e. in 1g silver-zine slags, press filtration obtains filtrate 1 and filter residue 1, Filter residue 1 (predominantly lead chloride) returns to lead system extraction lead.
C) heavy bismuth is neutralized：Filtrate 1 adds sodium hydroxide solution and adjusts pH value 4, and temperature 60 C, reacts 1.5h, hydrolyze bismuth, Press filtration obtains filtrate 2 and filter residue 2 (predominantly chlorine oxygen bismuth).
D) heavy zinc is neutralized：Ammonium hydroxide is added into filtrate 2, controls the pH=8 in solution, reaction 1h to obtain filter residue 3 (predominantly Zinc hydroxide precipitation) and filtrate 3,3 reuse of filtrate matches somebody with somebody lye, and filter residue 3 carries out processing extraction zinc.
E) displacement carries bismuth：The hydrochloric acid solution that concentration is 20% of filter residue 2 dissolves, the volume mass of hydrochloric acid solution and filter residue 2 Than for 5mL:1g.Then the iron powder of 1.2 times of theoretical amounts needed for displacement bismuth is added, reacts 1h, press filtration obtains sponge bismuth.
Comparative example 1
(1) silver-zine slag of 1000Kg, wherein Bi74.5%, Ag5.2%, Zn16.6%, Pb4.2% are taken, using NaClO3- NaCl-HCl systems are leached, and reaction temperature control is at 70 DEG C, liquid-solid ratio 4:1, NaClO3Dosage is 10g/L, NaCl dosages For 20g/L, HCl dosages are 80mL/L.After silver-zine slag reacts 4h, supernatant filtering, collects leachate and filter residue respectively.
(2) its pH value is adjusted with sodium hydroxide solution at the same time to after 2.5 stirring at normal temperature 1h in leaching liquid, place supernatant Filtering, obtains the chlorine oxygen bismuth filter residue and liquor zinci chloridi that bismuth-containing is 54.37%；Liquor zinci chloridi is adjusted into its pH value with soda ash again To 6, supernatant filters after stirring reaction 1h at a temperature of 40 DEG C, obtains basic zinc carbonate and waste liquid；
(3) filter residue in step (1) is further extracted into gold and silver；Waste liquid obtains Nacl by evaporative crystallization in step (2), Return again to leaching process, and mother liquid recycling.
Method using the present invention recycled from silver-zine slag each metal the rate of recovery and each regulus in tenor with The process ration used in comparative example 1 such as table 1 below.
In 1 silver-zine slag of table in each recovery rate of valuable metals and each regulus tenor comparison
Data can be seen that each metal in method recycling silver-zine slag using the present invention from upper table, and the purity of slag charge is high, Being conducive to improve metal recovery rate, the rate of recovery of each metal has all reached more than 90%, compared with comparative example, the recycling of silver and zinc Rate greatly improves.

Claims (9)

1. the recovery method of valuable metal in a kind of silver-zine slag, it is characterised in that comprise the following steps：
A) it is evaporated in vacuo：By silver-zine slag under 10-20Pa vacuums, at a temperature of 910-940 DEG C, vacuum distillation obtains thick silver and zinc Bismuth alloy；
B) heavy lead is aoxidized：Thick galactic longitude crosses processing and obtains silver products, and zinc bismuth alloy carries out oxidation leaching with hydrochloric acid and dioxygen water mixed liquid Go out, normal-temperature reaction, filtrate 1 and filter residue 1 is obtained by filtration, the processing of filter residue 1 obtains lead, the volume mass ratio of mixed liquor and zinc bismuth alloy For 4-6mL:1g；
C) heavy bismuth is neutralized：Filtrate 1 adjusts pH value 3-4 with lye, and after hydrolysis, filtrate 2 and filter residue 2 is obtained by filtration；
D) heavy zinc is neutralized：Into filtrate 2 plus lye adjusts pH value 7-8, and after hydrolysis, filtrate 3 and filter residue 3 is obtained by filtration, filters Lye is matched somebody with somebody in 3 reuse of liquid, and the processing of filter residue 3 obtains zinc；
E) displacement carries bismuth：The hydrochloric acid solution that concentration is 20% of filter residue 2 dissolves, and then adds iron replacement and reacts to obtain sponge The volume mass ratio of bismuth, hydrochloric acid solution and filter residue 2 is 5mL:1g.
2. the recovery method of valuable metal in silver-zine slag as claimed in claim 1, it is characterised in that silver-colored zinc described in step a) Cinder ladle includes the material of following weight percent content：Bi60-80%, Ag3-6%, Zn10-20%, Pb1-5%.
3. the recovery method of valuable metal in silver-zine slag as claimed in claim 1, it is characterised in that vacuum described in step a) The time of distillation is 1.5-2.5h.
4. the recovery method of valuable metal in silver-zine slag as claimed in claim 1, it is characterised in that mixed described in step b) The hydrochloric acid solution and 30% hydrogen peroxide solution that liquid is 20% are with volume ratio 3：1 mixes.
5. the recovery method of valuable metal in silver-zine slag as claimed in claim 1, it is characterised in that hydrolyzed described in step c) The temperature of reaction is 60-70 DEG C.
6. such as the recovery method of valuable metal in claim 1-5 any one of them silver-zine slags, it is characterised in that in step d) The hydrolysis time is 1-1.5h.
7. such as the recovery method of valuable metal in claim 1-5 any one of them silver-zine slags, it is characterised in that step c) and Lye described in step d) is sodium hydroxide solution.
8. such as the recovery method of valuable metal in claim 1-5 any one of them silver-zine slags, it is characterised in that step b), C) press filtration is filtered into described in and d).
9. such as the recovery method of valuable metal in claim 1-5 any one of them silver-zine slags, it is characterised in that in step e) The addition of the iron powder is 1-1.2 times of theoretical amount.
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