CN114350966A - Method for comprehensively recycling zinc anode mud by flotation silver concentrate matching treatment - Google Patents

Method for comprehensively recycling zinc anode mud by flotation silver concentrate matching treatment Download PDF

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CN114350966A
CN114350966A CN202210046721.0A CN202210046721A CN114350966A CN 114350966 A CN114350966 A CN 114350966A CN 202210046721 A CN202210046721 A CN 202210046721A CN 114350966 A CN114350966 A CN 114350966A
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zinc
liquid
zinc anode
phosphate
silver
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唐亦秋
陈敬阳
彭双义
王勇
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Zhuzhou Smelter Group Co Ltd
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Zhuzhou Smelter Group 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
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    • C01B25/00—Phosphorus; Compounds thereof
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    • C01B25/375—Phosphates of heavy metals of iron
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    • 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
    • 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
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • 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
    • C22B47/00—Obtaining manganese
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    • 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
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    • 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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Abstract

A method for comprehensively recovering zinc anode slime by matching flotation silver concentrate with treatment comprises the following steps: flotation silver concentrate, zinc anode slime and zinc electrolysis waste liquid are mixed and size-mixed, slurried silver concentrate pulp is added into a reaction kettle for high-temperature leaching, and leachate is neutralized, deacidified and filtered to obtain neutralized slag and neutralized liquid; slowly adding phosphate and an oxidant into the neutralized liquid to obtain iron phosphate precipitate, and returning the synthesized liquid to a zinc system to recover zinc; washing the iron phosphate slurry with water to obtain high-purity iron phosphate; carrying out reduction reaction on the leaching residue to obtain a manganese sulfate solution and silver-rich leaching residue; transferring the manganese sulfate solution into a purification tank, and filtering to obtain a purified liquid and purified slag after the reaction is finished; and synthesizing the obtained purified liquid, and drying to obtain a manganese product. The invention solves the technical problem that the zinc, iron, manganese, lead and silver can not be separated and enriched in the prior art so as to effectively recycle the zinc, iron, manganese, lead and silver respectively.

Description

Method for comprehensively recycling zinc anode mud by flotation silver concentrate matching treatment
Technical Field
The invention relates to the technical field of hydrometallurgy and chemical industry, in particular to a method for comprehensively recycling zinc anode mud by matching flotation silver concentrate.
Background
From the research direction and the industry level of the existing hydrometallurgy enterprises, more work is focused on the integral control of zinc contained in leaching slag of a leaching section and the washing of the silver concentrate after flotation. In a certain factory, an improved conventional leaching process is adopted, leached slag is subjected to flotation of silver after adjustment, tailing slag is treated in a rotary kiln, and silver concentrate is sold. The silver concentrate contains 18-20% zinc, its main phase is four kinds of zinc ferrite, zinc sulfate, zinc sulfide and zinc oxide, according to the phase analysis result (2-3% of zinc sulfide, 0.3% of zinc oxide, 2-3% of zinc sulfate and 10-12% of zinc ferrite), more than 50% of zinc content is zinc ferrite, and then zinc sulfate and zinc sulfide. The silver concentrate produced each year takes away several thousand tons of zinc loss, calculated as the concentrate yield is 7%.
At present, zinc smelters have two main disposal methods for zinc anode slime: firstly, zinc anode mud is directly returned to a zinc leaching procedure to be used as an oxidant; and secondly, directly putting the zinc anode slime into a lead system to recover lead and silver. However, the manganese content in the zinc system is easy to continuously rise, and the power consumption in the zinc electrodeposition process is increased. And because the quantity of the zinc anode slime is large and the manganese content is high, the lead and silver recovery cost is overhigh, and the manganese and the zinc in the zinc anode slime can not be effectively recycled.
Disclosure of Invention
The invention aims to provide a method for comprehensively recovering zinc anode slime by matching flotation silver concentrate with treatment. The invention solves the technical problem that the zinc, iron, manganese, lead and silver contained in the zinc hydrometallurgy acidic leaching residue flotation silver concentrate and zinc anode mud recovery method in the prior art can not be separated and enriched so as to effectively recover the zinc, iron, manganese, lead and silver respectively.
The technical scheme adopted for solving the technical problem is as follows:
a method for comprehensively recycling zinc anode mud in flotation silver concentrate matching treatment is characterized by comprising the following steps:
A. slurrying the silver concentrate: in the slurrying process, flotation silver concentrate, zinc anode mud and zinc electrolysis waste liquid are mixed and slurried, the sulfuric acid concentration of the zinc electrolysis waste liquid is 150-250 g/L, and the liquid-solid ratio of the flotation silver concentrate to the zinc electrolysis waste liquid is 1: 4-8, wherein the mass ratio of Zn in the flotation silver concentrate to Mn in the zinc anode mud is 2-5: 1.
B. high-temperature oxidation acid leaching: and adding the slurried silver concentrate ore pulp into a reaction kettle for high-temperature leaching, wherein the temperature in the reaction kettle is 80-100 ℃, the time is 5-10 hours, and filtering to obtain leaching slag and leaching liquid.
C. High-temperature pre-neutralization: and B, neutralizing the leachate obtained in the step B, filtering to obtain neutralized slag and neutralized liquid, wherein the pH of the neutralized liquid is = 0.5-1.5, the temperature is 80-100 ℃, and the time is 3-5 hours.
D. Synthesizing iron phosphate: and C, slowly adding phosphate and an oxidant into the neutralized liquid obtained in the step C, controlling the synthesis temperature to be 40-80 ℃, controlling the pH to be 3-5, and synthesizing for 3-6 hours to obtain iron phosphate precipitate, and returning the synthesized liquid to a zinc system to recover zinc.
E. Iron phosphate purification: and D, adding the iron phosphate obtained in the step D into phosphoric acid with the mass concentration of 30-40% for pulp washing, filtering to obtain pulp slag, and then washing with water to obtain the high-purity iron phosphate.
F. Reduction leaching: and D, adding the leaching residue obtained in the step B into sulfuric acid, adding oxalic acid, filtering after the reaction is finished to obtain a manganese sulfate solution and silver-rich leaching residue, and returning the silver-rich leaching residue to the rotary kiln to recover silver.
G. Purifying: transferring manganese sulfate solution into a purifying tank, adding ammonia water to pH 6.0-7.0, and adding (NH4)2S、NH4And F, filtering after the reaction is finished to obtain purified liquid and purified slag.
H. Synthesizing: and G, synthesizing the purified liquid obtained in the step G, and drying to obtain a manganese product.
Further, in the step A, the zinc anode mud contains 25-45% of Mn, and the granularity of 80% after drying and ball milling is more than 200 meshes; the flotation silver concentrate contains 15-25% of Zn and 15-35% of Fe.
Further, the end point acidity in the step B is controlled to be 5-40 g/L, wherein Mn2+As an oxidant, the leaching solution contains 55-80 g/L Zn and 20-40 g/L Fe.
Further, in the step C, the neutralizing agent is one of zinc calcine, zinc oxide, calcium carbonate and calcium hydroxide.
Further, in the step D, the oxidant is one or more of oxygen, air and hydrogen peroxide, and the molar ratio of O in the oxidant to Fe in the neutralized liquid is 0.5-1.5: 1; the phosphate is one or more of ammonium phosphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, normal salt of sodium phosphate and hydrogen salt of sodium phosphate; the mass ratio of P in the phosphate to Fe in the neutralized liquid is 1.05-1.2: 1.
further, in the step E, the slurry washing conditions are that the pH is = 1-2, the temperature is 80-100 ℃, and the ratio of the ferric phosphate to the phosphoric acid is 1: 6-10 hours for 1-3 hours; the washing conditions are that the pH = 3-5, the temperature is 20-60 ℃, and the ratio of the slurried slag to the phosphoric acid is 1: 1-3 hours for 1-3 hours.
Furthermore, in the step F, the using amount of the oxalic acid is 1.0 to 1.05 times of the theoretical consumption of completely reducing the manganese dioxide in the acid washing slag.
Further, in step G, (NH4)2The dosage of S is 1.0-1.05 times of the theoretical consumption of completely precipitating lead and zinc in the manganese sulfate solution, and NH4The dosage of F is 1 to 1.4 times of the theoretical consumption of completely precipitating calcium and magnesium in the manganese sulfate solution.
Compared with the conventional comprehensive recovery method, the method for comprehensively recovering the zinc anode slime by matching the flotation silver concentrate and the treatment method has the following beneficial effects:
the invention provides a method for comprehensively recycling zinc anode slime through matching flotation silver concentrate and processing, which can effectively recycle zinc, iron, manganese, lead and silver, achieves the aim of comprehensively recycling valuable metals of zinc, iron, manganese, lead and silver, dissolves zinc, iron and copper into leaching liquid through high-temperature oxidation acid leaching, enriches manganese, lead, gold, silver and sulfur into leaching residues, synthesizes iron phosphate through high-temperature pre-neutralization and neutralization liquid into the leaching liquid, purifies and recycles iron element from the iron phosphate, and returns the synthesized liquid to a zinc system to recycle zinc element. Furthermore, manganese is opened from a zinc system, the influence of overhigh zinc electro-deposited manganese on power consumption is reduced, the production cost in the zinc production process is reduced, and manganese series products can be prepared. The recovery rates of zinc, silver, iron, manganese and copper respectively exceed 95%, 99%, 90% and 90%, so that the recovery of zinc, iron, manganese and copper, lead, gold and silver in the flotation silver concentrate and the zinc anode slime in different names is realized, the recovery production cost is effectively reduced, and the economic and technical indexes of the comprehensive recovery of the flotation silver concentrate and the zinc anode slime are improved.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a method for comprehensively recovering zinc anode slime by matching flotation silver concentrate with treatment, and please refer to fig. 1.
The invention is further illustrated by the following specific examples.
Example 1
A. Slurrying the silver concentrate: mixing and pulping the flotation silver concentrate, the zinc anode mud and the zinc electrolysis waste liquid, wherein the sulfuric acid concentration of the zinc electrolysis waste liquid is 200g/L, and the liquid-solid ratio of the flotation silver concentrate to the zinc electrolysis waste liquid is 1: 7, the mass ratio of Zn in the flotation silver concentrate to Mn in the zinc anode mud is 3: 1.
B. high-temperature oxidation acid leaching: adding the slurried silver concentrate ore pulp into a reaction kettle for high-temperature leaching, wherein the temperature in the reaction kettle is 90 ℃, the time is 6 hours, and filtering to obtain leaching slag and leaching liquid; wherein the leaching is carried out at high temperatureThe terminal acidity of (1) is controlled to be 20g/L as Mn2+As an oxidant, the leaching solution contains 70g/L of Zn and 30g/L of Fe.
C. High-temperature pre-neutralization: and B, neutralizing the leachate obtained in the step B, filtering to obtain neutralized slag and neutralized liquid, wherein the pH =1 and the temperature is 90 ℃ and the time is 4 hours after neutralization.
D. And (3) synthesis of a neutralization solution: c, slowly adding phosphate and an oxidant into the neutralization solution obtained in the step C, controlling the synthesis temperature to be 60 ℃, controlling the pH to be 4.2, and synthesizing for 3 hours to obtain iron phosphate, and returning the synthesized solution to a zinc system to recover zinc; wherein the oxidant is one or more of oxygen, air and hydrogen peroxide, and the molar ratio of O in the oxidant to Fe in the neutralized liquid is 1: 1. the phosphate is one or more of ammonium phosphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, normal salt of sodium phosphate and hydrogen salt of sodium phosphate. The mass ratio of P in the phosphate to Fe in the neutralized liquid is 1.1: 1.
E. iron phosphate purification: d, adding the iron phosphate obtained in the step D into phosphoric acid with the mass concentration of 35% for pulp washing, filtering to obtain pulp slag, and then washing with water to obtain high-purity iron phosphate; wherein the slurry washing conditions are that the pH =1.5, the temperature is 90 ℃, and the ratio of ferric phosphate to phosphoric acid is 1: 8, the time is 2 hours; the washing conditions are that the pH =4 and the temperature is 40 ℃, the ratio of the slurried slag to the phosphoric acid is 1: 2, time 2 hours.
F. Reduction leaching: adding the leaching residue obtained in the step B into sulfuric acid, adding oxalic acid, filtering after the reaction is finished to obtain a manganese sulfate solution and silver-rich leaching residue, and returning the silver-rich leaching residue to the rotary kiln to recover silver; wherein the dosage of the oxalic acid is 1.0 time of the theoretical consumption of completely reducing the manganese dioxide in the acid washing slag.
G. Purifying: transferring the manganese sulfate solution into a purification tank, adding ammonia water at a pH value of 6.0, adding (NH4)2S, NH4F, and filtering after the reaction is finished to obtain a purified liquid and purified slag; wherein (NH)4) 2The dosage of S is 1.0 time of the theoretical consumption of completely precipitating lead and zinc in the manganese sulfate solution, and NH4The dosage of F is 1.2 times of the theoretical consumption of completely precipitating calcium and magnesium in the manganese sulfate solution.
H. Synthesizing: and G, synthesizing the purified liquid obtained in the step G, and drying to obtain a manganese product.
The zinc anode slime is comprehensively recovered by matching and processing the flotation silver concentrate, the recovery rates of zinc, silver, iron, manganese and copper are respectively more than 95%, 99.3%, 94%, 92% and 91%, and the recovery of zinc, iron, manganese and copper, lead, gold and silver in the flotation silver concentrate and the zinc anode slime in different names is realized.
Example 2
A. Slurrying the silver concentrate: mixing and pulping the flotation silver concentrate, the zinc anode mud and the zinc electrolysis waste liquid, wherein the sulfuric acid concentration of the zinc electrolysis waste liquid is 250g/L, and the liquid-solid ratio of the flotation silver concentrate to the zinc electrolysis waste liquid is 1: 8, the mass ratio of Zn in the flotation silver concentrate to Mn in the zinc anode mud is 4: 1.
B. high-temperature oxidation acid leaching: adding the slurried silver concentrate ore pulp into a reaction kettle for high-temperature leaching, wherein the temperature in the reaction kettle is 90 ℃, the time is 6 hours, and filtering to obtain leaching slag and leaching liquid; wherein the terminal acidity of the high-temperature leaching is controlled to be 40g/L by Mn2+As an oxidant, the leaching solution contains 75g/L of Zn and 35g/L of Fe.
C. High-temperature pre-neutralization: and B, neutralizing the leachate obtained in the step B, filtering to obtain neutralized slag and neutralized liquid, wherein the pH =1 and the temperature is 90 ℃ and the time is 4 hours after neutralization.
D. And (3) synthesis of a neutralization solution: c, slowly adding phosphate and an oxidant into the neutralization solution obtained in the step C, controlling the synthesis temperature to be 70 ℃, controlling the pH to be 4.5, and synthesizing for 4 hours to obtain iron phosphate, and returning the synthesized solution to a zinc system to recover zinc; wherein the oxidant is one or more of oxygen, air and hydrogen peroxide, and the molar ratio of O in the oxidant to Fe in the neutralized liquid is 1.05: 1. the phosphate is one or more of ammonium phosphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, normal salt of sodium phosphate and hydrogen salt of sodium phosphate. The mass ratio of P in the phosphate to Fe in the neutralized liquid is 1.12: 1.
E. iron phosphate purification: d, adding the iron phosphate obtained in the step D into phosphoric acid with the mass concentration of 40% for pulp washing, filtering to obtain pulp slag, and then washing with water to obtain high-purity iron phosphate; wherein the slurry washing conditions are that the pH =2, the temperature is 100 ℃, and the ratio of ferric phosphate to phosphoric acid is 1: 9, time 3 hours; the washing conditions are that the pH =5 and the temperature is 60 ℃, the ratio of the slurried slag to the phosphoric acid is 1: 3, time 3 hours.
F. Reduction leaching: adding the leaching residue obtained in the step B into sulfuric acid, adding oxalic acid, filtering after the reaction is finished to obtain a manganese sulfate solution and silver-rich leaching residue, and returning the silver-rich leaching residue to the rotary kiln to recover silver; wherein the dosage of the oxalic acid is 1.05 times of the theoretical consumption of completely reducing the manganese dioxide in the acid washing slag.
G. Purifying: transferring the manganese sulfate solution into a purification tank, adding ammonia water at a pH value of 6.0, adding (NH4)2S, NH4F, and filtering after the reaction is finished to obtain a purified liquid and purified slag; wherein (NH)4) 2The dosage of S is 1.05 times of the theoretical consumption of completely precipitating lead and zinc in the manganese sulfate solution, and NH4The dosage of F is 1.4 times of the theoretical consumption of completely precipitating calcium and magnesium in the manganese sulfate solution.
H. Synthesizing: and G, synthesizing the purified liquid obtained in the step G, and drying to obtain a manganese product.
The zinc anode slime is comprehensively recovered by matching and processing the flotation silver concentrate, the recovery rates of zinc, silver, iron, manganese and copper are respectively over 96.5%, 99.6%, 93%, 91% and 92%, and the recovery of zinc, iron, manganese and copper, lead, gold and silver in the flotation silver concentrate and the zinc anode slime in different names is realized.
Example 3
A. Slurrying the silver concentrate: mixing and pulping the flotation silver concentrate, the zinc anode mud and the zinc electrolysis waste liquid, wherein the sulfuric acid concentration of the zinc electrolysis waste liquid is 150g/L, and the liquid-solid ratio of the flotation silver concentrate to the zinc electrolysis waste liquid is 1: 6, the mass ratio of Zn in the flotation silver concentrate to Mn in the zinc anode mud is 5: 1.
B. high-temperature oxidation acid leaching: adding the slurried silver concentrate ore pulp into a reaction kettle for high-temperature leaching, wherein the temperature in the reaction kettle is 90 ℃, the time is 6 hours, and filtering to obtain leaching slag and leaching liquid; wherein the terminal acidity of the high-temperature leaching is controlled to be 10g/L by Mn2+As an oxidant, the leaching solution contains 60g/L of Zn and 25g/L of Fe.
C. High-temperature pre-neutralization: and B, neutralizing the leachate obtained in the step B, filtering to obtain neutralized slag and neutralized liquid, wherein the pH =1 and the temperature is 90 ℃ and the time is 4 hours after neutralization.
D. And (3) synthesis of a neutralization solution: c, slowly adding phosphate and an oxidant into the neutralization solution obtained in the step C, controlling the synthesis temperature to be 65 ℃, controlling the pH to be 4.1, and synthesizing for 4 hours to obtain iron phosphate, and returning the synthesized solution to a zinc system to recover zinc; wherein the oxidant is one or more of oxygen, air and hydrogen peroxide, and the molar ratio of O in the oxidant to Fe in the neutralized liquid is 0.5: 1. the phosphate is one or more of ammonium phosphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, normal salt of sodium phosphate and hydrogen salt of sodium phosphate. The mass ratio of P in the phosphate to Fe in the neutralized liquid is 1.2: 1.
E. iron phosphate purification: d, adding the iron phosphate obtained in the step D into phosphoric acid with the mass concentration of 30% for pulp washing, filtering to obtain pulp slag, and then washing with water to obtain high-purity iron phosphate; wherein the slurry washing conditions are that the pH =1, the temperature is 80 ℃, and the ratio of ferric phosphate to phosphoric acid is 1: 7, the time is 1 hour; the washing conditions were pH =3, temperature was 30 ℃, the ratio of slurried slag to phosphoric acid was 1: 1, for 1 hour.
F. Reduction leaching: adding the leaching residue obtained in the step B into sulfuric acid, adding oxalic acid, filtering after the reaction is finished to obtain a manganese sulfate solution and silver-rich leaching residue, and returning the silver-rich leaching residue to the rotary kiln to recover silver; wherein the dosage of the oxalic acid is 1.0 time of the theoretical consumption of completely reducing the manganese dioxide in the acid washing slag.
G. Purifying: transferring the manganese sulfate solution into a purification tank, adding ammonia water at a pH value of 6.0, adding (NH4)2S, NH4F, and filtering after the reaction is finished to obtain a purified liquid and purified slag; wherein (NH)4) 2The dosage of S is 1.0 time of the theoretical consumption of completely precipitating lead and zinc in the manganese sulfate solution, and NH4The dosage of F is 1 time of the theoretical consumption of completely precipitating calcium and magnesium in the manganese sulfate solution.
H. Synthesizing: and G, synthesizing the purified liquid obtained in the step G, and drying to obtain a manganese product.
The zinc anode slime is comprehensively recovered through the matching treatment of the flotation silver concentrate, the recovery rates of zinc, silver, iron, manganese and copper are respectively more than 94.5%, 98.6%, 92%, 90% and 91%, and the recovery of zinc, iron, manganese and copper, lead, gold and silver in the flotation silver concentrate and the zinc anode slime in different names is realized.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (8)

1. A method for comprehensively recycling zinc anode mud in flotation silver concentrate matching treatment is characterized by comprising the following steps:
A. slurrying the silver concentrate: in the slurrying process, flotation silver concentrate, zinc anode mud and zinc electrolysis waste liquid are mixed and slurried, the sulfuric acid concentration of the zinc electrolysis waste liquid is 150-250 g/L, and the liquid-solid ratio of the flotation silver concentrate to the zinc electrolysis waste liquid is 1: 4-8, wherein the mass ratio of Zn in the flotation silver concentrate to Mn in the zinc anode mud is 2-5: 1;
B. high-temperature oxidation acid leaching: adding the slurried silver concentrate ore pulp into a reaction kettle for high-temperature leaching, wherein the temperature in the reaction kettle is 80-100 ℃, the time is 5-10 hours, and filtering to obtain leaching slag and leaching liquid;
C. high-temperature pre-neutralization: neutralizing the leachate obtained in the step B, filtering to obtain neutralized slag and neutralized liquid, wherein the pH of the neutralized liquid is = 0.5-1.5, the temperature is 80-100 ℃, and the time is 3-5 hours;
D. synthesizing iron phosphate: c, slowly adding phosphate and an oxidant into the neutralized liquid obtained in the step C, controlling the synthesis temperature to be 40-80 ℃, controlling the pH to be 3-5, and synthesizing for 3-6 hours to obtain iron phosphate precipitate, and returning the synthesized liquid to a zinc system to recover zinc;
E. iron phosphate purification: d, adding the iron phosphate obtained in the step D into phosphoric acid with the mass concentration of 30-40% for pulp washing, filtering to obtain pulp slag, and then washing with water to obtain high-purity iron phosphate;
F. reduction leaching: adding the leaching residue obtained in the step B into sulfuric acid, adding oxalic acid, filtering after the reaction is finished to obtain a manganese sulfate solution and silver-rich leaching residue, and returning the silver-rich leaching residue to the rotary kiln to recover silver;
G. purifying: transferring manganese sulfate solution into a purifying tank, adding ammonia water to pH 6.0-7.0, and adding (NH)4) 2S、NH4F, filtering to obtain purified liquid and purified slag after the reaction is finished;
H. synthesizing: and G, synthesizing the purified liquid obtained in the step G, and drying to obtain a manganese product.
2. The method for the comprehensive recovery of the zinc anode slime from the flotation silver concentrate in combination with the processing of the zinc anode slime according to claim 1, which is characterized by comprising the following steps: in the step A, the zinc anode mud contains 25-45% of Mn, and the granularity of 80% after drying and ball milling is more than 200 meshes; the flotation silver concentrate contains 15-25% of Zn and 15-35% of Fe.
3. The method for the comprehensive recovery of the zinc anode slime from the flotation silver concentrate in combination with the processing of the zinc anode slime according to claim 1, which is characterized by comprising the following steps: in the step B, the terminal acidity is controlled to be 5-40 g/L, wherein Mn2+As the oxidant, the leaching solution contains 55-80 g/L Zn and 20-40 g/L Fe.
4. The method for the comprehensive recovery of the zinc anode slime from the flotation silver concentrate in combination with the processing of the zinc anode slime according to claim 1, which is characterized by comprising the following steps: in the step C, the neutralizing agent is one of zinc calcine, zinc oxide, calcium carbonate and calcium hydroxide.
5. The method for the comprehensive recovery of the zinc anode slime from the flotation silver concentrate in combination with the processing of the zinc anode slime according to claim 1, which is characterized by comprising the following steps: in the step D, the oxidant is one or more of oxygen, air and hydrogen peroxide, and the molar ratio of O in the oxidant to Fe in the neutralized liquid is 0.5-1.5: 1; the phosphate is one or more of ammonium phosphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, normal salt of sodium phosphate and hydrogen salt of sodium phosphate, and the mass ratio of P in the phosphate to Fe in the neutralized liquid is (1.05-1.2): 1.
6. the method for the comprehensive recovery of the zinc anode slime from the flotation silver concentrate in combination with the processing of the zinc anode slime according to claim 1, which is characterized by comprising the following steps: in the step E, the slurry washing conditions are that the pH is = 1-2, the temperature is 80-100 ℃, and the ratio of the ferric phosphate to the phosphoric acid is 1: 6-10 hours for 1-3 hours; the washing conditions are that the pH = 3-5, the temperature is 20-60 ℃, and the ratio of the slurried slag to the phosphoric acid is 1: 1-3 hours for 1-3 hours.
7. The method for the comprehensive recovery of the zinc anode slime from the flotation silver concentrate in combination with the processing of the zinc anode slime according to claim 1, which is characterized by comprising the following steps: in the step F, the consumption of the oxalic acid is 1.0 to 1.05 times of the theoretical consumption of completely reducing the manganese dioxide in the acid washing slag.
8. The method for the comprehensive recovery of the zinc anode slime from the flotation silver concentrate in combination with the processing of the zinc anode slime according to claim 1, which is characterized by comprising the following steps: in step G, (NH)4) 2The dosage of S is 1.0-1.05 times of the theoretical consumption of completely precipitating lead and zinc in the manganese sulfate solution, and NH4The dosage of F is 1 to 1.4 times of the theoretical consumption of completely precipitating calcium and magnesium in the manganese sulfate solution.
CN202210046721.0A 2022-01-17 2022-01-17 Method for comprehensively recycling zinc anode mud by flotation silver concentrate matching treatment Pending CN114350966A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0221760A2 (en) * 1985-11-01 1987-05-13 Montana Tech Foundation Method for recovering metal values from mixed-metal aqueous solutions by selective phosphate precipitation
CN1170044A (en) * 1996-07-05 1998-01-14 中南工业大学 Method for recovering zinc from dregs containing zinc ferrite
CN102586599A (en) * 2012-03-07 2012-07-18 株洲冶炼集团股份有限公司 Method for recovering valued metals from zinc anode sludge
CN103215435A (en) * 2013-04-27 2013-07-24 湖南水口山有色金属集团有限公司 Method for comprehensively recycling zinc, copper, lead, gold, silver and sulfur from floatation silver concentrate
CN112410555A (en) * 2020-11-10 2021-02-26 株洲冶炼集团股份有限公司 Comprehensive recovery method for flotation silver concentrate from zinc hydrometallurgy acidic leaching residue

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0221760A2 (en) * 1985-11-01 1987-05-13 Montana Tech Foundation Method for recovering metal values from mixed-metal aqueous solutions by selective phosphate precipitation
CN1170044A (en) * 1996-07-05 1998-01-14 中南工业大学 Method for recovering zinc from dregs containing zinc ferrite
CN102586599A (en) * 2012-03-07 2012-07-18 株洲冶炼集团股份有限公司 Method for recovering valued metals from zinc anode sludge
CN103215435A (en) * 2013-04-27 2013-07-24 湖南水口山有色金属集团有限公司 Method for comprehensively recycling zinc, copper, lead, gold, silver and sulfur from floatation silver concentrate
CN112410555A (en) * 2020-11-10 2021-02-26 株洲冶炼集团股份有限公司 Comprehensive recovery method for flotation silver concentrate from zinc hydrometallurgy acidic leaching residue

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