CN110295285A - A method of zinc is recycled from oxygen-enriched solid sulphur reduction melting clinker - Google Patents

A method of zinc is recycled from oxygen-enriched solid sulphur reduction melting clinker Download PDF

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CN110295285A
CN110295285A CN201910713362.8A CN201910713362A CN110295285A CN 110295285 A CN110295285 A CN 110295285A CN 201910713362 A CN201910713362 A CN 201910713362A CN 110295285 A CN110295285 A CN 110295285A
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zinc
leaching
oxygen
liquid
acid
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CN110295285B (en
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巫文嵩
陈巍
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Sichuan Zhengxiang Environmental Protection Technology Co Ltd
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Sichuan Zhengxiang Environmental Protection Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B17/00Obtaining cadmium
    • C22B17/04Obtaining cadmium by wet processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00Obtaining zinc or zinc oxide
    • C22B19/20Obtaining zinc otherwise than by distilling
    • C22B19/22Obtaining zinc otherwise than by distilling with leaching with acids
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00Obtaining zinc or zinc oxide
    • C22B19/20Obtaining zinc otherwise than by distilling
    • C22B19/26Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00Obtaining zinc or zinc oxide
    • C22B19/30Obtaining zinc or zinc oxide from metallic residues or scraps
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B41/00Obtaining germanium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B58/00Obtaining gallium or indium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/001Dry processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/04Working-up slag
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/16Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention discloses a kind of methods that zinc is recycled from oxygen-enriched solid sulphur reduction melting clinker, belong to solid dangerous waste processing technology field.The present invention uses pyrogenic process-wet process from leaded, zinc waste residue or the oxygen-enriched solid sulphur reduction melting clinker extracting zinc of lead plaster, the clinker that this method carries out after base block, oxygen-enriched solid sulphur reduction melting leaded, zinc waste residue or lead plaster is sufficiently recycled, it is both the further recycling to existing resource, in turn avoid pollution of the valuable metal to environment, safer environmental protection;Meanwhile this method principle is simple, process is reasonable, zinc recovery is high, low in cost.

Description

A method of zinc is recycled from oxygen-enriched solid sulphur reduction melting clinker
Technical field
The invention belongs to solid dangerous waste processing technology fields, and in particular to a kind of to return from oxygen-enriched solid sulphur reduction melting clinker The method for receiving zinc.
Background technique
Due to the development of present metallurgy industry, a large amount of leaded, zinc waste residue can be generated, and containing in these waste residues much has Valence metal, such as lead, zinc etc., but often by enterprises neglect.And if these valuable metals can be utilized by secondary recovery, both be avoided To the harm that environment generates, and resource is made to have obtained effective utilization and be unlikely to waste.
During lead-acid accumulator recycling disposal, sulfuric acid lead plaster, lead grid, modeling are broadly divided into after lead-acid accumulator dismantling Expect particle and spent acid etc., wherein sulfuric acid lead plaster had not only contained the valuable metals such as lead, zinc, tin and antimony, but also contained a large amount of harmful sulfuric acid Salt, sulfuric acid lead plaster are hazardous metals solid waste.Lead-acid accumulator is as the main consumer products in the whole world, therefore recycling contains Lead, zinc waste residue and the zinc in waste and old lead acid accumulator lead plaster are of great significance.
Sulfuric acid lead plaster and leaded, zinc waste residue are carried out base block, consolidate sulphur reduction melting smelt to be current many enterprises Applied method can generate multi-products under this approach, and wherein the content of zinc is prominent in slag product, but for furnace Slag proposes zinc operation often because the difference of technique and yield have biggish difference and at high price, and the valuable metal of low content is also Less than effective recycling.
Summary of the invention
In view of the above problems, the present invention provides a kind of side that zinc is recycled from oxygen-enriched solid sulphur reduction melting clinker Method, this method carry out the clinker after base block, solid sulphur reduction melting to leaded, zinc waste residue or lead plaster and carry out sufficiently circulation benefit With being both the further recycling to existing resource, in turn avoid pollution of the valuable metal to environment, safer environmental protection;Meanwhile it should Method And Principle is simple, process is reasonable, zinc recovery is high, low in cost.
The technical solution adopted by the present invention are as follows:
A method of zinc is recycled from oxygen-enriched solid sulphur reduction melting clinker, including the following steps:
S1. ingredient and base: lead-zinc residue or lead plaster, sulphur-fixing agent, flux mixing will be contained, obtain feed powder, the feed powder contains Water rate is 12%~15%;The feed powder is dried after briquetting base at 30~50MPa to moisture content is that 5%~6%, Pb contains Amount is 18%~28%, obtains briquet;
S2. consolidate sulphur reduction melting: 7.8m is added in the briquet and coke2Slag making is carried out in oxygen-enriched solid sulphur reducing and smelting furnace Reaction, obtains clinker;
S3. fuming furnace blowing: the clinker is mixed with the low-grade waste residue of leaded zinc, mixture is obtained, adds mixture into Fuming furnace blows, and at 1250 DEG C~1300 DEG C, obtains secondary zinc oxide flue dust;The secondary zinc oxide flue dust is sent into rotary kiln Interior roasting obtains secondary zinc oxide calcining;
S4. neutral to leach: the neutral of progress 7~8:1 of liquid-solid ratio in mixing acid pickle is added in secondary zinc oxide calcining and is leached, Oxidant is added when pH value reaches 5~5.2, is separated by solid-liquid separation, neutral leaching residue and neutral leachate are obtained;
S5. neutral leachate three-stage cleaning process, first segment: is added zinc into neutral leachate at 50 DEG C~55 DEG C Powder obtains after filter press filters containing copper-cadmium slag and filtrate 1;Second segment: by filtrate 1 with being steam heated to 80 DEG C~90 DEG C, add Antimonic salt, zinc powder removal of impurities, after filter press filters, obtain the slag of nickel containing cobalt and filtrate 2;Third section: by filtrate 2 be cooled to 70 DEG C with Under, zinc powder is added except Cd obtains dregs and filtrate 3 after filter press filters;The filtrate 3 and waste electrolyte by volume 1: It is added in Winning cell after 15~20 mixing and carries out electrodeposition, finished to electrodeposition, obtain cathode zinc and waste liquid, removed cathode zinc, must analyse Zinc metal sheet out;It is melted using line frequency furnace and zinc metal sheet is precipitated, clarifying agent is added, zinc liquid temperature maintains 470 DEG C~490 in furnace DEG C, cast zinc ingot metal;
S6. indium germanium enriching and recovering: preparing mixed acid liquid, and leaching tanks are added in mixed acid liquid, neutral leaching residue, leach complete it is laggard Row is separated by solid-liquid separation, and obtains acidic leaching residue and acid leaching solution, send acidic leaching residue to oxygen-enriched solid sulphur reducing and smelting furnace melting, acid Leachate enters in indium germanium enrichment slot;When acid leaching solution temperature is 75 DEG C~85 DEG C, Zn powder is that displacer is replaced, with After filter, obtain indium germanium enrichment slag, by the indium germanium be enriched with slag through Ore Leaching, separation, obtain acid leaching residue and pickle liquor;Pickle liquor is extracted After taking, rich indium organic phase and germanic raffinate are obtained, rich indium organic phase is stripped through hydrochloric acid, the zincification plate of liquid containing indium is replaced, and obtains sponge indium; The sponge indium is pressed into briquetting, the subsequent thick indium ingot of founding;Germanic raffinate obtains germanic richness through washing, concentration plus the heavy germanium of oxalic acid Collect object;
S7. reclaimer operation containing copper-cadmium slag are as follows: cadmium is recycled using sulfuric acid leaching, zinc dust precipitation, Spongy Cadmium rectification process.
Specifically, the low-grade waste residue main component of the leaded zinc are as follows: Pb20%~28%, Zn5%~8%.
Specifically, in the S4 mix acid pickle be lead-acid accumulator disintegrate battery recycling sulfuric acid, zinc electrolyte and The mixed liquor of wash water, mixing acid pickle beginning acid concentration are 70~120g/L, and oxidant is manganese dioxide, and additional amount is two in solution 1.2 times of valence iron;The wash water is the slag washing water of each process.
Further, the mass ratio described in the S1 containing lead-zinc residue or lead plaster, sulphur-fixing agent and flux are as follows: 100:5~ 8:5~10.
Further, briquet described in the S2 and coke quality ratio are 100:9~12.
Further, the solid sulphur reduction melting condition: burnt rate 9%~12%, 35~45m of blast intensity3/min·m2, 15~18kpa of wind pressure, slag type Fe/SiO2/ CaO:20~26:23~30:16~20, oxygen-rich concentration 23%~25%.
Further, described to propose fuming furnace blowing condition in zinc: mixture contains zinc 12%~18%, and the total blow rate required 19.5~ 23.6Km3/h;Total wind pressure: 55~58kPa, primary wind pressure: 45~51kPa;Secondary wind pressure: 55~58kPa;Tertiary air orifice is negative Pressure: -30~-80Pa.
Further, the acid concentration of mixed acid liquid described in the S6 is 150g/L;Leaching liquid-solid ratio is 5:1, extraction temperature 80 DEG C~90 DEG C, extraction time 8h, the residual acid of terminal is 15~20g/L.
Further, time swap described in the S6 is 4h, replaces endpoint pH 4.8~5.0.
Further, the concrete operations of the S7 are as follows:
The sulfuric acid leaching stage: leaching the waste liquid that bottom liquid is slag washing water and zinc electrolysis, containing copper-cadmium slag and leaches bottom liquid-liquid-solid ratio For 5:1, the acid 145g/L that begins is leached, extraction temperature is 70 DEG C~80 DEG C, and the oxidant of iron is manganese dioxide breeze, extraction time 4 ~5h is terminal when leaching into residual sour 3~5g/L, must leach copper ashes and leachate, will leach copper ashes return fuming furnace volatilization and mention Zinc process;
The leachate containing acid >=5g/L is put in iron removal trough and measures ferrous content, the throwing when ferrous iron does not have up to standard When entering hydrogen peroxide to pH value 5~5.2, investment removes Co except Co medicament, filters after the agent 1h that offers medicine, and filter residue is scum, returns to rotary kiln Harmless treatment is made in volatilization;Filtrate reaches 18kg/m containing Cd3When, flow into displacement slot;
With zinc dust precipitation Cd, replace 60 DEG C of temperature <, time swap is 1.5~2h, as the solution 50mg/L of < containing Cd into Row filters pressing, hot water washing, obtain Spongy Cadmium;Filtrate returns to secondary zinc oxide calcine neutral leaching step as replenisher;Spongy Cadmium essence It evaporates and continuous still purification is carried out using tower disc type electrothermal vacuum rectifying furnace, make rectifying cadmium content up to 99.995%, impurity summation < 0.005%, rectifying slag contains zinc 25%~30%, and rectifying slag is returned to fuming furnace volatilization and mentions zinc.
The beneficial effects of the present invention are: a kind of method that zinc is recycled from oxygen-enriched solid sulphur reduction melting clinker of the invention, Using pyrogenic process-wet process from the oxygen-enriched solid sulphur reduction melting clinker extracting zinc of leaded, zinc waste residue or lead plaster, this method to it is leaded, The clinker that zinc waste residue or lead plaster carry out after base block, solid sulphur reduction melting is sufficiently recycled, and is both to existing resource Further recycling, in turn avoids pollution of the valuable metal to environment, safer environmental protection;Meanwhile this method principle is simple, process is closed Reason, zinc recovery are high, low in cost.
Specific embodiment
Embodiment of the present invention can be replaced by the difference of specific range based on the above technical solution, Available numerous embodiment, therefore, several embodiments as described below are only merely the more excellent reality in numerous embodiment Example is applied, any technology replacement done in above-mentioned technical proposal all belongs to the scope of protection of the present invention.
Secondary zinc oxide calcine neutral leaches in embodiment:
ZnO·SiO2+H2SO4=ZnSO4+SiO2·H2O FeO·SiO2+H2SO4=FeSO4+SiO2·H2O
PbO·SiO2+H2SO4=PbSO4+SiO2·H2O ZnO+H2SO4=ZnSO4+H2O
PbO+H2SO4=PbSO4+H2O In2O3+3H2SO4=In2(SO4)3+3H2O
GeO2+H2SO4=GeSO4+H2O GaO+H2SO4=GaSO4+H2O
In2(SO4)3+ 3Zn=3ZnSO4+2In↓ Ge(SO4)2+ 2Zn=2ZnSO4+Ge↓
Three sections of secondary zinc oxide calcine neutral leachate purifications:
GaSO4+ Zn=ZnSO4+Ga↓ Zn+Cu2+=Zn2++Cu↓
Zn+Cd2+=Zn2++Cd↓ Zn+Co2+=Zn2++Co↓
8C2H5OCS2Na+2CuSO4+CoSO4=Cu2(C2H5OCS2)2↓+2Co(C2H5OCS2)3↓+NaSO4Cu+2Cl-+Cu2+ =Cu2Cl2
Embodiment 1
A method of zinc is recycled by fireworks furnace from oxygen-enriched solid sulphur reduction melting clinker, including the following steps:
S1. ingredient and base: take certain electrolytic zinc enterprise containing lead-zinc residue, be with mass ratio with sulphur-fixing agent, flux by it 100:5:5 mixing, obtains feed powder, and the moisture content of the feed powder is 12%;The feed powder is dried extremely after briquetting base at 30MPa Moisture content is that 5%, Pb content is 20%~25%, obtains briquet;
S2. 7.8m oxygen-enriched solid sulphur reduction melting: is added with mass ratio for 100:9 in the briquet and coke2Oxygen-enriched solid sulphur Slag making reaction is carried out in reducing and smelting furnace, Gu sulphur reduction melting condition: burnt rate 9%, blast intensity 35m3/min·m2, wind pressure 15kpa, slag type Fe/SiO2/ CaO is 20:23:16, and oxygen-rich concentration 23% obtains clinker;
S3. fuming furnace blowing: the clinker is mixed with the low-grade waste residue of leaded zinc, mixture is obtained, adds mixture into Fuming furnace blows, fuming furnace blowing condition: mixture contains zinc 15%~18%, total blow rate required 19.5Km3/h;Total wind pressure: 55kPa, primary wind pressure: 45kPa;Secondary wind pressure: 55kPa;Tertiary air orifice negative pressure: -30Pa;Weight at 1250 DEG C, in material Oxygen in metal gas and furnace gas generates metal oxide and enters in furnace gas, and waste heat cooling, bag collection recycles secondary zinc oxide Flue dust;It roasts, roasts by being sent into rotary kiln with furnace gas at adverse current after the secondary zinc oxide flue dust and the granulation of high indium secondary zinc oxide 1200 DEG C of temperature, obtain secondary zinc oxide calcining;
S4. neutral to leach: secondary zinc oxide calcining being added in the mixing acid pickle that beginning acid concentration is 90~100g/L and is carried out 1.2 times of manganese dioxide of solution divalent weight of iron is added, when pH value reaches 5~5.2 in 60 DEG C of neutral leachings, liquid-solid ratio 8:1 When, Fe (OH) in leachate3Hydrolyze and with foreign ion flocking settling, be separated by solid-liquid separation, obtain neutral leaching residue and neutral leaching Liquid out;
S5. neutral to leach purification: first segment: zinc powder is added in neutral leachate temperature when being 50 DEG C, zinc powder additional amount is 2g/ L is filtered through filter press after reacting 1h, is obtained containing copper-cadmium slag and filtrate 1;Second segment: by filtrate 1 with being steam heated to 80 DEG C, add antimony Salt, zinc powder removal of impurities, zinc powder additional amount are 3g/L, and the additional amount of antimonic salt is 0.6 times of cobalt quality in solution, through filters pressing after reaction 3h Machine filtering, obtains the slag of nickel containing cobalt and filtrate 2, the slag of nickel containing cobalt send cadmium recovery workshop;Third section: by filtrate 2 be cooled to 70 DEG C hereinafter, plus Enter zinc powder except Cd, zinc powder additional amount is 1g/L, is filtered after reacting 1h through filter press, and dregs and filtrate 3 are obtained, and dregs return to first segment Purification tank;1:15 is mixed in cooling tower outlet by volume for the filtrate 3 and waste electrolyte, is added to by chute and is closed with quaternary Golden plate (lead, silver, calcium, strontium) is anode, aluminium sheet is that electrodeposition is carried out in the Winning cell of cathode, electrodeposition condition are as follows: electrolyte mainly at It is divided into sulfuric acid 150g/L, Zn 50g/L, current density 180A/m2, the period for 24 hours, tank voltage 3.4V.It is finished to electrodeposition, obtains cathode Zinc and waste liquid remove cathode zinc, obtain precipitation zinc metal sheet;It is melted using line frequency furnace and zinc metal sheet is precipitated, addition clarifying agent (caustic soda, 30~40kg/t of additional amount zinc), zinc liquid temperature maintains 470 DEG C in furnace, casts zinc ingot metal;
S6. waste liquid, the concentrated sulfuric acid and wash water indium germanium enriching and recovering: are mixed to prepare mixed acid liquid, acid concentration 150g/L;It will mix Leaching tanks are added in acid solution, neutral leaching residue, and liquid-solid ratio 5:1,80 DEG C of extraction temperature, extraction time 8h, the residual acid of terminal is 20g/ L is then separated by solid-liquid separation, and acidic leaching residue and acid leaching solution are obtained, and send acidic leaching residue to oxygen-enriched solid sulphur reducing and smelting furnace Melting, acid leaching solution enter in indium germanium enrichment slot;When acid leaching solution temperature is 75 DEG C, Zn powder 50Kg/g indium is added, into Line replacement, time swap 4h replace endpoint pH 4.8~5.0, then filter, filtered fluid is as secondary zinc oxide calcine neutral Bottom liquid is leached, indium germanium enrichment slag is obtained;The indium germanium is enriched with slag through Ore Leaching, separation, obtains acid leaching residue and pickle liquor;By acid leaching residue Return to fuming furnace roasting;After pickle liquor is extracted, rich indium organic phase and germanic raffinate are obtained, rich indium organic phase is stripped through hydrochloric acid, The displacement of the zincification plate of liquid containing indium, obtains sponge indium;It is pressed into briquetting, in the thick indium ingot of 300 DEG C of foundings.Germanic raffinate through washing, concentration, plus Enter the oxalic acid that mass concentration is 7% and carry out heavy germanium, obtains Ge enriched material;
The pickle liquor extraction is 30%P with solvent204With 70% 260#Solvent naphtha with concentration is after 3 grades of extraction The H of 150g/L2SO4Wash 2 grades;The back extraction concentration of hydrochloric acid are as follows: 6mol/L is stripped 40 DEG C of temperature <, with dense after 3 grades of back extraction Degree is the H of 150g/L2SO42 grades are washed, liquid containing indium is obtained;Indium liquid feeding displacement case will be contained, extension zine plate carries out one week indium at room temperature and sets It changes, beginning acidity pH is 1.0, and solution contains In≤50mg/L after displacement;
S7. reclaimer operation containing copper-cadmium slag are as follows: cadmium is recycled using sulfuric acid leaching, zinc dust precipitation, Spongy Cadmium rectification process.Specifically Are as follows: the sulfuric acid leaching stage: leaching bottom liquid is waste liquid described in slag washing water and S5, is 5:1, leaching containing copper-cadmium slag and leaching bottom liquid-liquid-solid ratio Begin acid 145g/L out, and extraction temperature is 70 DEG C, 1.2 times of divalent iron of oxidant manganese dioxide breeze additional amount, extraction time 4h, It is terminal when leaching into residual sour 3~5g/L, copper ashes and leachate must be leached, copper ashes return fuming furnace volatilization will be leached and propose zinc work Sequence;
The leachate containing acid >=5g/L is put in iron removal trough and measures ferrous content, the throwing when ferrous iron does not have up to standard When entering hydrogen peroxide to pH value 5~5.2, the C of 1.2 times of cobalt quality of investment2H5OCS2Na removes Co, filters after the agent 1h that offers medicine, filter residue is iron Slag returns to rotary kiln evaporation and makees harmless treatment;Filtrate reaches 18kg/m containing Cd3When, flow into displacement slot;
With zinc dust precipitation Cd, 60 DEG C of temperature <, time swap 1.5h are replaced, is pressed as the solution 50mg/L of < containing Cd Filter, hot water washing, obtain Spongy Cadmium;Filtrate returns to secondary zinc oxide calcine neutral leaching step as replenisher;Spongy Cadmium rectifying is adopted Continuous still purification is carried out with tower disc type electrothermal vacuum rectifying furnace, makes rectifying cadmium content up to 99.995%, impurity summation < 0.005%, rectifying slag contains zinc 25%~27%, and rectifying slag is returned to fuming furnace volatilization and mentions zinc.
Embodiment 2
A method of zinc is recycled from oxygen-enriched solid sulphur reduction melting clinker, including the following steps:
S1. ingredient and base: take certain electrolytic zinc enterprise containing lead-zinc residue, be with mass ratio with sulphur-fixing agent, flux by it 100:7:8 mixing, obtains feed powder, and the moisture content of the feed powder is 14%;The feed powder is dried extremely after briquetting base at 40MPa Moisture content is that 5%, Pb content is 25%~28%, obtains briquet;
S2. 7.8m oxygen-enriched solid sulphur reduction melting: is added with mass ratio for 100:11 in the briquet and coke2Oxygen-enriched solid sulphur Slag making reaction, oxygen-enriched solid sulphur reduction melting condition: burnt rate 10%, blast intensity 39m are carried out in reducing and smelting furnace3/min·m2, wind Press 16kpa, slag type Fe/SiO2/ CaO is 24:27:18, and oxygen-rich concentration 24% obtains clinker;
S3. fuming furnace blowing: the clinker is mixed with the low-grade waste residue of leaded zinc, mixture is obtained, adds mixture into Fuming furnace blows, fuming furnace blowing condition: mixture contains zinc 17%~18%, total blow rate required 21.5Km3/h;Total wind pressure: 56kPa, primary wind pressure: 48kPa;Secondary wind pressure: 57kPa;Tertiary air orifice negative pressure: -50Pa;Weight at 1280 DEG C, in material Oxygen in metal gas and furnace gas generates metal oxide and enters in furnace gas, and waste heat cooling, bag collection recycles secondary zinc oxide Flue dust;It roasts, roasts by being sent into rotary kiln with furnace gas at adverse current after the secondary zinc oxide flue dust and the granulation of high indium secondary zinc oxide 1250 DEG C of temperature, obtain secondary zinc oxide calcining;
S4. neutral to leach: secondary zinc oxide calcining being added in the mixing acid pickle that beginning acid concentration is 100~120g/L and is carried out 1.2 times of manganese dioxide of solution divalent weight of iron is added, when pH value reaches 5~5.2 in 60 DEG C of neutral leachings, liquid-solid ratio 7:1 When, Fe (OH) in leachate3Hydrolyze and with foreign ion flocking settling, be separated by solid-liquid separation, obtain neutral leaching residue and neutral leaching Liquid out;
S5. neutral to leach purification: first segment: zinc powder is added in neutral leachate temperature when being 52 DEG C, zinc powder additional amount is 3g/ After L, reaction 1h after filter press filters, obtain containing copper-cadmium slag and filtrate 1;Second segment: by filtrate 1 with being steam heated to 85 DEG C, add Antimonic salt, zinc powder removal of impurities, zinc powder additional amount are 4.5g/L, and the additional amount of antimonic salt is 0.8 times of cobalt quality in solution, after reacting 3h, After filter press filters, the slag of nickel containing cobalt and filtrate 2 are obtained, the slag of nickel containing cobalt send cadmium recovery workshop;Third section: filtrate 2 is cooled to 70 DEG C hereinafter, be added zinc powder remove Cd, zinc powder additional amount be 1.5g/L, react 1h after after filter press filters, obtain dregs and filtrate 3, Dregs return to first segment purification tank;1:18 is mixed in cooling tower outlet by volume for the filtrate 3 and waste electrolyte, passes through chute Being added to using quaternary alloy plate (lead, silver, calcium, strontium) is anode, aluminium sheet to carry out electrodeposition, technical conditions electricity in the Winning cell of cathode Solve liquid main component sulfuric acid: 150g/L, Zn 50g/L, other element strict controls, current density 200A/m2, the period for 24 hours, slot Voltage 3.4V.It is finished to electrodeposition, obtains cathode zinc and waste liquid, removed cathode zinc, obtain precipitation zinc metal sheet;It is melted using line frequency furnace Zinc metal sheet is precipitated, is added clarifying agent (caustic soda, 30~40kg/t of additional amount zinc), zinc liquid temperature maintains 480 DEG C in furnace, casts zinc Ingot;
S6. waste liquid, the concentrated sulfuric acid and wash water indium germanium enriching and recovering: are mixed to prepare mixed acid liquid, acid concentration 150g/L;It will mix Leaching tanks are added in acid solution, neutral leaching residue, and liquid-solid ratio 5:1,80 DEG C of extraction temperature, extraction time 8h, the residual acid of terminal is 15g/ L is then separated by solid-liquid separation, and acidic leaching residue and acid leaching solution are obtained, and send acidic leaching residue to oxygen-enriched solid sulphur reducing and smelting furnace Melting, acid leaching solution enter in indium germanium enrichment slot;When acid leaching solution temperature is 75 DEG C, Zn powder additional amount 55Kg/g indium, It is replaced, time swap 4h, replaces endpoint pH 4.8~5.0, then filter, filtered fluid is as in secondary zinc oxide calcining Property leach bottom liquid, obtain indium germanium enrichment slag;The indium germanium is enriched with slag through Ore Leaching, separation, obtains acid leaching residue and pickle liquor;By acidleach Slag returns to fuming furnace roasting;After pickle liquor is extracted, rich indium organic phase and germanic raffinate are obtained, rich indium organic phase is anti-through hydrochloric acid Extraction, the zincification plate of liquid containing indium displacement, obtains sponge indium;It is pressed into briquetting, in the thick indium ingot of 400 DEG C of foundings.Germanic raffinate is washed, is dense The oxalic acid that contracting, addition mass concentration are 7% carries out heavy germanium, obtains Ge enriched material;
The pickle liquor extraction is 30%P with solvent204With 70% 260#Solvent naphtha with concentration is after 3 grades of extraction The H of 100g/L2SO4Wash 2 grades;The back extraction concentration of hydrochloric acid are as follows: 6mol/L is stripped 40 DEG C of temperature <, with dense after 3 grades of back extraction Degree is the H of 100g/L2SO42 grades are washed, liquid containing indium is obtained;Indium liquid feeding displacement case will be contained, extension zine plate carries out one week indium at room temperature and sets It changes, beginning acidity pH is 2.0, and solution contains In≤50mg/L after displacement;
S7. reclaimer operation containing copper-cadmium slag are as follows: cadmium is recycled using sulfuric acid leaching, zinc dust precipitation, Spongy Cadmium rectification process.Specifically Are as follows: the sulfuric acid leaching stage: leaching bottom liquid is waste liquid described in slag washing water and S5, is 5.5:1 containing copper-cadmium slag and leaching bottom liquid-liquid-solid ratio, The acid 155g/L that begins is leached, extraction temperature is 75 DEG C, 1.3 times of divalent iron of oxidant manganese dioxide breeze additional amount, extraction time 4.5h is terminal when leaching into residual sour 3~5g/L, must leach copper ashes and leachate, will leach copper ashes return fuming furnace volatilization and mention Zinc process;
The leachate containing acid >=5g/L is put in iron removal trough and measures ferrous content, the throwing when ferrous iron does not have up to standard When entering hydrogen peroxide to pH value 5~5.2, the C of 1.4 times of cobalt quality of investment2H5OCS2Na removes Co, filters after the agent 1h that offers medicine, filter residue is iron Slag returns to rotary kiln evaporation and makees harmless treatment;Filtrate reaches 18kg/m containing Cd3When, flow into displacement slot;
With zinc dust precipitation Cd, 60 DEG C of temperature <, time swap 1.8h are replaced, is pressed as the solution 50mg/L of < containing Cd Filter, hot water washing, obtain Spongy Cadmium;Filtrate returns to secondary zinc oxide calcine neutral leaching step as replenisher;Spongy Cadmium rectifying is adopted Continuous still purification is carried out with tower disc type electrothermal vacuum rectifying furnace, makes rectifying cadmium content up to 99.995%, impurity summation < 0.005%, rectifying slag contains zinc 26%~28%, and rectifying slag is returned to fuming furnace volatilization and mentions zinc.
Embodiment 3
A method of zinc is recycled from oxygen-enriched solid sulphur reduction melting clinker, including the following steps:
S1. ingredient and base: take certain electrolytic zinc enterprise containing lead-zinc residue, be with mass ratio with sulphur-fixing agent, flux by it 100:8:10 mixing, obtains feed powder, and the moisture content of the feed powder is 15%;The feed powder is dry after briquetting base at 50MPa Be 6%, Pb content to moisture content it is 18%~22%, obtains briquet;
S2. 7.8m oxygen-enriched solid sulphur reduction melting: is added with mass ratio for 100:12 in the briquet and coke2Oxygen-enriched solid sulphur Slag making reaction, oxygen-enriched solid sulphur reduction melting condition: burnt rate 12%, blast intensity 45m are carried out in reducing and smelting furnace3/min·m2, wind Press 18kpa, slag type Fe/SiO2/ CaO is 26:30:20, and oxygen-rich concentration 25% obtains clinker;
S3. fuming furnace blowing: the clinker is mixed with the low-grade waste residue of leaded zinc, mixture is obtained, adds mixture into Fuming furnace blows, fuming furnace blowing condition: mixture contains zinc 12%~15%, total blow rate required 23.6Km3/h;Total wind pressure: 58kPa, primary wind pressure: 51kPa;Secondary wind pressure: 58kPa;Tertiary air orifice negative pressure: -80Pa;Weight at 1300 DEG C, in material Oxygen in metal gas and furnace gas generates metal oxide and enters in furnace gas, and waste heat cooling, bag collection recycles secondary zinc oxide Flue dust;It roasts, roasts by being sent into rotary kiln with furnace gas at adverse current after the secondary zinc oxide flue dust and the granulation of high indium secondary zinc oxide 1300 DEG C of temperature, obtain secondary zinc oxide calcining;
S4. neutral to leach: secondary zinc oxide calcining being added in the mixing acid pickle that beginning acid concentration is 70~100g/L and is carried out 1.2 times of manganese dioxide of solution divalent weight of iron is added, when pH value reaches 5~5.2 in 60 DEG C of neutral leachings, liquid-solid ratio 8:1 When, Fe (OH) in leachate3Hydrolyze and with foreign ion flocking settling, be separated by solid-liquid separation, obtain neutral leaching residue and neutral leaching Liquid out;
S5. neutral to leach purification: first segment: zinc powder is added in neutral leachate temperature when being 55 DEG C, zinc powder additional amount is 4g/ After L, reaction 1h after filter press filters, obtain containing copper-cadmium slag and filtrate 1;Second segment: by filtrate 1 with being steam heated to 90 DEG C, add Antimonic salt, zinc powder removal of impurities, zinc powder additional amount are 6g/L, and the additional amount of antimonic salt is 1 times of cobalt quality in solution, after reacting 3h, through pressing After filter filtering, the slag of nickel containing cobalt and filtrate 2 are obtained, the slag of nickel containing cobalt send cadmium recovery workshop;Third section: by filtrate 2 be cooled to 70 DEG C with Under, be added zinc powder remove Cd, zinc powder additional amount be 2g/L, react 1h after after filter press filters, obtain dregs and filtrate 3, dregs return Return first segment purification tank;1:20 is mixed in cooling tower outlet by volume for the filtrate 3 and waste electrolyte, is added to by chute It is anode, aluminium sheet to carry out electrodeposition, technical conditions electrolyte master in the Winning cell of cathode using quaternary alloy plate (lead, silver, calcium, strontium) Want ingredient sulfuric acid: 150g/L, Zn 50g/L, other element strict controls, current density 160A/m2, the period for 24 hours, tank voltage 3.4V.It is finished to electrodeposition, obtains cathode zinc and waste liquid, removed cathode zinc, obtain precipitation zinc metal sheet;It is melted and is precipitated using line frequency furnace Zinc metal sheet is added clarifying agent (caustic soda, 30~40kg/t of additional amount zinc), and zinc liquid temperature maintains 490 DEG C in furnace, casts zinc ingot metal;
S6. waste liquid, the concentrated sulfuric acid and wash water indium germanium enriching and recovering: are mixed to prepare mixed acid liquid, acid concentration 150g/L;It will mix Leaching tanks are added in acid solution, neutral leaching residue, and liquid-solid ratio 5:1,80 DEG C of extraction temperature, extraction time 8h, the residual acid of terminal is 18g/ L is then separated by solid-liquid separation, and acidic leaching residue and acid leaching solution are obtained, and send acidic leaching residue to oxygen-enriched solid sulphur reducing and smelting furnace Melting, acid leaching solution enter in indium germanium enrichment slot;When acid leaching solution temperature is 75 DEG C, Zn powder additional amount 60Kg/g indium, It is replaced, time swap 4h, replaces endpoint pH 4.8~5.0, then filter, filtered fluid is as in secondary zinc oxide calcining Property leach bottom liquid, obtain indium germanium enrichment slag;The indium germanium is enriched with slag through Ore Leaching, separation, obtains acid leaching residue and pickle liquor;By acidleach Slag returns to fuming furnace roasting;After pickle liquor is extracted, rich indium organic phase and germanic raffinate are obtained, rich indium organic phase is anti-through hydrochloric acid Extraction, the zincification plate of liquid containing indium displacement, obtains sponge indium;Suppress it is agglomerating, in the thick indium ingot of 260 DEG C of foundings.Germanic raffinate is washed, is dense The oxalic acid that contracting, addition mass concentration are 7% carries out heavy germanium, obtains Ge enriched material;
The pickle liquor extraction is 30%P with solvent204With 70% 260#Solvent naphtha with concentration is after 3 grades of extraction The H of 120g/L2SO4Wash 2 grades;The back extraction concentration of hydrochloric acid are as follows: 6mol/L is stripped 40 DEG C of temperature <, with dense after 3 grades of back extraction Degree is the H of 120g/L2SO42 grades are washed, liquid containing indium is obtained;Indium liquid feeding displacement case will be contained, extension zine plate carries out one week indium at room temperature and sets It changes, beginning acidity pH is 1.5, and solution contains In≤50mg/L after displacement;
S7. reclaimer operation containing copper-cadmium slag are as follows: cadmium is recycled using sulfuric acid leaching, zinc dust precipitation, Spongy Cadmium rectification process.Specifically Are as follows: the sulfuric acid leaching stage: leaching bottom liquid is waste liquid described in slag washing water and S5, is 6:1, leaching containing copper-cadmium slag and leaching bottom liquid-liquid-solid ratio Begin acid 125g/L out, and extraction temperature is 80 DEG C, 1.2 times of divalent iron of oxidant manganese dioxide breeze additional amount, extraction time 5h, It is terminal when leaching into residual sour 3~5g/L, copper ashes and leachate must be leached, copper ashes return fuming furnace volatilization will be leached and propose zinc work Sequence;
The leachate containing acid >=5g/L is put in iron removal trough and measures ferrous content, the throwing when ferrous iron does not have up to standard When entering hydrogen peroxide to pH value 5~5.2, the C of 1.4 times of cobalt quality of investment2H5OCS2Na removes Co, filters after the agent 1h that offers medicine, filter residue is iron Slag returns to rotary kiln evaporation and makees harmless treatment;Filtrate reaches 18kg/m containing Cd3When, flow into displacement slot;
With zinc dust precipitation Cd, 60 DEG C of temperature <, time swap 2h are replaced, is pressed as the solution 50mg/L of < containing Cd Filter, hot water washing, obtain Spongy Cadmium;Filtrate returns to secondary zinc oxide calcine neutral leaching step as replenisher;Spongy Cadmium rectifying is adopted Continuous still purification is carried out with tower disc type electrothermal vacuum rectifying furnace, makes rectifying cadmium content up to 99.995%, impurity summation < 0.005%, rectifying slag contains zinc 27%~30%, and rectifying slag is returned to fuming furnace volatilization and mentions zinc.
The rate of recovery of metal obtained by Examples 1 to 3 is as shown in table 1 below.
1 metal recovery rate of table (%)
Valuable metal Zinc Indium Cadmium
Embodiment 1 96~97 92~94 95~96
Embodiment 2 96~98 92~95 95~96
Embodiment 3 96~98 93~95 95~96
The invention is not limited to specific embodiments above-mentioned.The present invention, which expands to, any in the present specification to be disclosed New feature or any new combination, and disclose any new method or process the step of or any new combination.

Claims (8)

1. a kind of method for recycling zinc from oxygen-enriched solid sulphur reduction melting clinker, characterized in that it comprises the following steps:
S1. ingredient and base: lead-zinc residue or lead plaster, sulphur-fixing agent, flux mixing will be contained, obtain feed powder, the moisture content of the feed powder It is 12%~15%;The feed powder is dried after briquetting base at 30~50MPa to moisture content is that 5%~6%, Pb content is 18%~28%, obtain briquet;
S2. 7.8m oxygen-enriched solid sulphur reduction melting: is added in the briquet and coke2Slag making is carried out in oxygen-enriched solid sulphur reducing and smelting furnace Reaction, obtains clinker;
S3. fuming furnace blowing: the clinker is mixed with the low-grade waste residue of leaded zinc, mixture is obtained, adds mixture into fuming Furnace blows, and at 1250 DEG C~1300 DEG C, obtains secondary zinc oxide flue dust;The secondary zinc oxide flue dust is sent into rotary kiln and is roasted It burns, obtains secondary zinc oxide calcining;
S4. neutral to leach: the neutral of progress 7~8:1 of liquid-solid ratio in mixing acid pickle is added in secondary zinc oxide calcining and is leached, is added Oxidant is separated by solid-liquid separation when pH value reaches 5~5.2, obtains neutral leaching residue and neutral leachate;
S5. neutral leachate three-stage cleaning process, first segment: being added zinc powder into neutral leachate at 50 DEG C~55 DEG C, warp After crossing filter press filtering, obtain containing copper-cadmium slag and filtrate 1;Second segment: by filtrate 1 with being steam heated to 80 DEG C~90 DEG C, add antimonic salt, Zinc powder removal of impurities, after filter press filters, obtains the slag of nickel containing cobalt and filtrate 2;Third section: filtrate 2 is cooled to 70 DEG C hereinafter, being added Zinc powder obtains dregs and filtrate 3 after filter press filters except Cd;1:15~20 are mixed by volume with waste electrolyte for the filtrate 3 It is added to after conjunction in Winning cell and carries out electrodeposition, finished to electrodeposition, obtain cathode zinc and waste liquid, removed cathode zinc, obtain precipitation zinc metal sheet;It adopts It is melted with line frequency furnace and zinc metal sheet is precipitated, clarifying agent is added, zinc liquid temperature maintains 470 DEG C~490 DEG C in furnace, casts zinc Ingot;
S6. indium germanium enriching and recovering: preparing mixed acid liquid, and leaching tanks are added in mixed acid liquid, neutral leaching residue, are consolidated after the completion of leaching Liquid separation, obtains acidic leaching residue and acid leaching solution, send acidic leaching residue to oxygen-enriched solid sulphur reducing and smelting furnace melting, acidic leaching Liquid enters in indium germanium enrichment slot;When acid leaching solution temperature is 75 DEG C~85 DEG C, Zn powder is that displacer is replaced, subsequent mistake Filter obtains indium germanium enrichment slag, and the indium germanium is enriched with slag through Ore Leaching, separation, obtains acid leaching residue and pickle liquor;Pickle liquor is extracted Afterwards, rich indium organic phase and germanic raffinate are obtained, rich indium organic phase is stripped through hydrochloric acid, the zincification plate of liquid containing indium is replaced, and obtains sponge indium;It will The sponge indium is pressed into briquetting, the subsequent thick indium ingot of founding;Germanic raffinate obtains germanic enrichment through washing, concentration plus the heavy germanium of oxalic acid Object;
S7. reclaimer operation containing copper-cadmium slag are as follows: cadmium is recycled using sulfuric acid leaching, zinc dust precipitation, Spongy Cadmium rectification process.
2. a kind of method for recycling zinc from oxygen-enriched solid sulphur reduction melting clinker as described in claim 1, which is characterized in that institute State the mass ratio described in S1 containing lead-zinc residue or lead plaster, sulphur-fixing agent and flux are as follows: 100:5~8:5~10.
3. a kind of method for recycling zinc from oxygen-enriched solid sulphur reduction melting clinker as described in claim 1, which is characterized in that institute It states briquet described in S2 and coke quality ratio is 100:9~12.
4. a kind of method for recycling zinc from oxygen-enriched solid sulphur reduction melting clinker as described in claim 1, which is characterized in that institute State solid sulphur reduction melting condition: burnt rate 9%~12%, 35~45m of blast intensity3/min·m2, 15~18kpa of wind pressure, slag type Fe/SiO2/ CaO:20~26:23~30:16~20, oxygen-rich concentration 23%~25%.
5. a kind of method for recycling zinc from leaded, zinc waste residue or lead plaster as described in claim 1, which is characterized in that described Propose fuming furnace blowing condition in zinc: mixture contains zinc 12%~18%, total 19.5~23.6Km of the blow rate required3/h;Total wind pressure: 55~ 58kPa, primary wind pressure: 45~51kPa;Secondary wind pressure: 55~58kPa;Tertiary air orifice negative pressure: -30~-80Pa.
6. a kind of method for recycling zinc from oxygen-enriched solid sulphur reduction melting clinker as described in claim 1, which is characterized in that institute The acid concentration for stating mixed acid liquid described in S6 is 150g/L;Leaching liquid-solid ratio be 5:1,80 DEG C~90 DEG C of extraction temperature, extraction time 8h, the residual acid of terminal is 15~20g/L.
7. a kind of method for recycling zinc from oxygen-enriched solid sulphur reduction melting clinker as described in claim 1, which is characterized in that institute Stating time swap described in S6 is 4h, replaces endpoint pH 4.8~5.0.
8. a kind of method for recycling zinc from oxygen-enriched solid sulphur reduction melting clinker as described in claim 1, which is characterized in that institute State the concrete operations of S7 are as follows:
The sulfuric acid leaching stage: leaching the waste liquid that bottom liquid is slag washing water and zinc electrolysis, is 5 containing copper-cadmium slag and leaching bottom liquid-liquid-solid ratio: 1, the acid 145g/L that begins is leached, extraction temperature is 70 DEG C~80 DEG C, and the oxidant of iron is manganese dioxide breeze, 4~5h of extraction time, It is terminal when leaching into residual sour 3~5g/L, copper ashes and leachate must be leached, copper ashes return fuming furnace volatilization will be leached and propose zinc work Sequence;
The leachate containing acid >=5g/L is put in iron removal trough and measures ferrous content, is put into when ferrous iron does not have up to standard double When oxygen water to pH value 5~5.2, investment removes Co except Co medicament, filters after the agent 1h that offers medicine, and filter residue is scum, returns to rotary kiln evaporation Make harmless treatment;Filtrate reaches 18kg/m containing Cd3When, flow into displacement slot;
With zinc dust precipitation Cd, 60 DEG C of temperature < are replaced, time swap is 1.5~2h, is pressed as the solution 50mg/L of < containing Cd Filter, hot water washing, obtain Spongy Cadmium;Filtrate returns to secondary zinc oxide calcine neutral leaching step as replenisher;Spongy Cadmium rectifying is adopted Continuous still purification is carried out with tower disc type electrothermal vacuum rectifying furnace, makes rectifying cadmium content up to 99.995%, impurity summation < 0.005%, rectifying slag contains zinc 25%~30%, and rectifying slag is returned to fuming furnace volatilization and mentions zinc.
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