CN110284005A - A method of the enriching and recovering lead from lead bullion - Google Patents

A method of the enriching and recovering lead from lead bullion Download PDF

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CN110284005A
CN110284005A CN201910713338.4A CN201910713338A CN110284005A CN 110284005 A CN110284005 A CN 110284005A CN 201910713338 A CN201910713338 A CN 201910713338A CN 110284005 A CN110284005 A CN 110284005A
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lead
bismuth
slag
bullion
tin
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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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    • 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
    • C22B13/02—Obtaining lead by 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
    • C22B25/00—Obtaining tin
    • C22B25/02—Obtaining tin by 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
    • C22B25/00—Obtaining tin
    • C22B25/06—Obtaining tin from scrap, especially tin scrap
    • 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
    • C22B25/00—Obtaining tin
    • C22B25/08—Refining
    • 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
    • C22B30/02—Obtaining antimony
    • 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
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
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Abstract

The method of the invention discloses a kind of from lead bullion enriching and recovering lead, belongs to solid dangerous waste processing technology field.Using the method that pyrogenic process and electrolysis combine, enriching and recovering lead, this method from lead bullion sufficiently recycle lead bullion to the present invention, are 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, lead recovery is high, low in cost.

Description

A method of the enriching and recovering lead from lead bullion
Technical field
The invention belongs to solid dangerous waste processing technology fields, and in particular to a method of the enriching and recovering lead from lead bullion.
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, tin and antimony, but also contained a large amount of harmful sulfate, Sulfuric acid lead plaster is hazardous metals solid waste.Lead-acid accumulator also becomes most main as the main consumer products in the whole world The lead regenerated resources wanted.The primary raw material of Chinese reviver has 80% or more to come from waste and old lead acid accumulator, therefore recycles waste and old Lead in lead-acid accumulator lead plaster is of great significance.
Sulfuric acid lead plaster and leaded, zinc waste residue carry out to base block, oxygen-enriched solid sulphur reduction melting smelt is many at present Method applied by enterprise can generate multi-products under this approach, and wherein the content of lead is the most prominent in lead bullion product, but That lead operation is proposed for lead bullion often because the difference of technique and yield have biggish difference and at high price, low content it is valuable Metal also cannot be recycled effectively.
Summary of the invention
In view of the above problems, the present invention provides a kind of method of enriching and recovering lead from lead bullion, this method pair Lead bullion is sufficiently recycled, and is both the further recycling to existing resource, is in turn avoided pollution of the valuable metal to environment, Safer environmental protection；Meanwhile this method principle is simple, process is reasonable, lead recovery is high, low in cost.
The technical solution adopted by the present invention are as follows:
A method of the enriching and recovering lead from lead bullion, including the following steps:
S1. pyrogenic process slightly refines: lead bullion progress pyrogenic process slightly being refined, after addition adopting electrolysis residual pole makes lead bullion liquid be down to 330 DEG C~340 DEG C Carry out liquate decopper(ing), the wooden chaff be added and carries out fishing copper dross slag processing, when lead liquid temperature is 700 DEG C~800 DEG C stirring 10~ Caustic soda is added in 15min, continues 3~5h of stirring, forms the miscellaneous slag of tin, then carries out the fishing miscellaneous Slag treatment of tin, obtains lead bullion liquid, will be thick Lead liquid is put into anode pot and qualified lead liquid is made to obtain；By qualified lead liquid injection anode formwork erection casting unit formwork erection, mold cooling water makes Chloride plate is made in the rapid cooling of lead liquid；
S2. electrolytic lead refining: using fluosilicic lead plumbate and free silica aqueous fluorine acid solution as electrolyte, chloride plate, lead electrode Piece presses interpolar away from being fitted into electrolytic cell, in 180~205A/m of current density2, under 0.4~0.6V of tank voltage, lead, tin are analysed in cathode Out, using cathode washing rod drawing machine group progress cathode, clean, pumping stick, gathering are in heaps, obtain precipitation lead flake；Contained current potential ratio in anode The negative valuable metal of lead is also from Anodic Stripping, and the current potential valuable metal more positive than lead is in forming the earth of positive pole on anode plate；It will be electrolysed residual Pole returns to the fusing of anode pot, double teeming chloride plate after scrubbing, filtering；
S3. two kinds of lead flake processing are precipitated: cathode pot are packed into after 1. scrubbing the precipitation lead flake, after lead flake is completely melt DM unit is pumped to using lead, lead volume is made, lead volume send cathode manufacture unit manufacture cathode together with conductive copper rod, obtains lead electrode Piece；2. sending the precipitation lead flake to finished product pot, it is completely melt to lead flake, when being warming up to 480 DEG C, carries out primary fishing dross；After It is continuous to be warming up to 510 DEG C~530 DEG C 1.5~2h of stirring, carry out secondary fishing dross；By fish out dross after lead liquid carry out ingot casting, stacking, Bundling, storage；
S4. the processing method of the miscellaneous slag of tin are as follows: stanniferous waste material is mixed with the miscellaneous slag of tin make 45 DEG C of Theil indices in mixture~ 55%, mixture, solvent, soda ash, reduction coal are sent into tin bottom convertor and carry out 1200 DEG C, reduction melting in 2~3 days obtains thick tin and closes Gold and smelting slag, the crude tin alloy are dumped into vacuum drying oven using alloy packet and carry out rectifying separation, output tin slab；
S5. precious metals containing lead furnace reduction melting: precious metals containing lead furnace is added after the earth of positive pole, char particle, iron filings, soda ash are mixed and is gone back Original obtains flue dust, precious metals containing lead and dregs；Flue dust, dregs return system ingredient are subjected to secondary use；Precious metals containing lead is added in reduction furnace 700 DEG C~850 DEG C are carried out, 2~3 days oxidation blown converter reaction removal antimony, stibium trioxide powder export trade then casts the precious metals containing lead for having removed antimony It is added after block and divides silver stove oxidation blowing, obtain lead dust, copper bismuth slag, electrum；Make anode with the electrum, titanium plate makees yin Pole, nitric acid and silver nitrate aqueous solution are electrolysed as electrolyte, and silver powder is precipitated on cathode；Lead dust send oxygen-enriched solid sulphur reduction molten The recycling of furnace ingredient；Copper bismuth slag uses wet process process separating valuable metals.
Further, caustic soda additional amount described in the S1 is 6%~7% of tin quality in lead liquid.
Further, the circulation of electrolyte described in the S2, purification style are as follows: use 2 electrolyte circulation systems, follow Ring mode is single-stage circulation, solution upper entering and lower leaving in electrolytic cell；The circulation rate of every slot electrolyte: 30~40L/min.
Further, mixture described in the S4, solvent, soda ash, reduction coal mass ratio are 100:5~8:5~6:10 ~15.
Further, the mass ratio of the earth of positive pole described in the S5, char particle, iron filings, soda ash are as follows: 90:12~15:3~5:5 ~6.
Further, the processing of copper bismuth slag described in the S5 are as follows: copper bismuth slag output bismuth mud, hydrogen-oxygen are made using wet process process Change copper, reduction furnace progress reduction melting is added in bismuth mud and obtains thick bismuth alloy, the thick bismuth alloy is subjected to pyrogenic process and is tentatively refined The isolated thick bismuth of vacuum drying oven progress rectifying, thick silver, bismuth slag is added after removing copper；Thick bismuth carries out bismuth refining procedure output bismuth ingot, Bismuth slag is returned into the reduction melting again of bismuth reduction furnace.
Specifically, vacuum drying oven is added after tentatively refining the copper index for removing copper less than 1% in the Guillaume metal.
Further, the wet process process output bismuth mud concrete operations are as follows: copper bismuth slag is dried, siccative is obtained, will be done Material makes copper bismuth slag particle degree less than 80 mesh after carrying out abrasive material, then adds it in immersion trough, and control beginning acid concentration is 50~100g/l, Solid-to-liquid ratio is 1:4, and sodium chloride is added, and filters pressing after 2h is stirred at 75 DEG C~85 DEG C, leached mud, leachate is obtained, leached mud is put Enter and carry out secondary filters pressing after stirring 1h in 30 DEG C~40 DEG C water, obtains bismuth mud.
Further, the additional amount of the sodium chloride is the 10%~15% of copper bismuth slag weight.
Further, the wet process process output Kocide SD concrete operations are as follows: the leachate is added in immersion trough, It is 6~7 that caustic soda is added after being warming up to 70 DEG C~80 DEG C and adjusts solution ph, stirs 0.5h, subsequent filters pressing obtains Kocide SD and filter Liquid, filtrate, which flows into, neutralizes reservoir, is subsequently sent to waste water station processing.
Specifically, the lead bullion the preparation method comprises the following steps:
1) ingredient and base: by sulfuric acid lead plaster, sulphur-fixing agent, flux with mass ratio are as follows: 100:5~8:5~10 is mixed, and must be expected Powder, the moisture content of the feed powder are 12%~15%；The feed powder is dried after briquetting base to moisture content at 30~50MPa For 5%~6%, Pb18%~25%, briquet is obtained；
2) 7.8m oxygen-enriched solid sulphur reduction melting: is added with mass ratio for 100:9~12 in the briquet and coke2It is oxygen-enriched solid It is dehydrated, decomposed in sulphur reducing and smelting furnace, being melted, sulphur reduction and slag making reaction admittedly, obtaining clinker 1, matte, lead bullion, flue dust；Gu 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 is 20~26:23~30:16~20, oxygen-rich concentration 25%.
The beneficial effects of the present invention are: the present invention provides a kind of method of enriching and recovering lead from lead bullion, this method pair Lead bullion is sufficiently recycled, and is both the further recycling to existing resource, is in turn avoided pollution of the valuable metal to environment, Safer environmental protection；Meanwhile this method principle is simple, process is reasonable, lead recovery is 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.
Electrolytic lead refining reaction equation in embodiment are as follows:
2Pb+2S=2PbS PbS+2Cu=Pb+Cu2S
PbS (FeS)+2Cu=Cu2S+Pb(Fe) 4PbS+4Na2CO3=4Pb+3Na2S+Na2SO4+4CO2
2Pb+O2=2PbO PbO+Sn=Pb+SnO
2Sn+O2=2SnO Sn+2PbO=2Pb+SnO2
3PbO+2SnO2=3PbO2SnO2 5Sn+6NaOH+4NaNO3=5Na2SnO3+2N2+3H2O
Pb2++ 2e=Pb 2H++ 2e=H2
Pb-2e=Pb2+ 2OH-- 2e=H2O+1/2O2
SiF6 2-- 2e=SiF6 SiF6+ H2O=H2SiF6+1/2O2
Embodiment 1
A method of the enriching and recovering lead from lead bullion, including the following steps:
S1. pyrogenic process slightly refines: lead bullion progress pyrogenic process slightly being refined, addition adopting electrolysis residual pole is melted after so that lead bullion liquid is down to 330 DEG C Decopper(ing) is analysed, the wooden chaff is added and carries out fishing copper dross slag processing, 10min is stirred when lead liquid temperature is 700 DEG C, tin quality in lead liquid is added 6% caustic soda continues to stir 3h, forms the miscellaneous slag of tin, then carries out the fishing miscellaneous Slag treatment of tin, obtains lead bullion liquid, lead bullion liquid is put into Anode pot obtains qualified lead liquid；By qualified lead liquid injection anode formwork erection casting unit formwork erection, mold cooling water is quickly cooled down lead liquid Chloride plate is made；
S2. electrolytic lead refining: using fluosilicic lead plumbate and free silica aqueous fluorine acid solution as electrolyte, chloride plate, lead electrode Piece presses interpolar away from being fitted into electrolytic cell, in 180~190A/m of current density2, under 0.4~0.5V of tank voltage, lead, tin are analysed in cathode Out, using cathode washing rod drawing machine group progress cathode, clean, pumping stick, gathering are in heaps, obtain precipitation lead flake；Contained current potential ratio in anode The negative valuable metal of lead is also from Anodic Stripping, and the current potential valuable metal more positive than lead is in forming the earth of positive pole on anode plate；It will be electrolysed residual Pole returns to the fusing of anode pot, double teeming chloride plate after scrubbing, filtering；The circulation of the electrolyte, purification style are as follows: use 2 Electrolyte circulation system, endless form are single-stage circulation, solution upper entering and lower leaving in electrolytic cell；The circulation rate of every slot electrolyte: 30L/min；
S3. two kinds of lead flake processing are precipitated: cathode pot are packed into after 1. scrubbing the precipitation lead flake, after lead flake is completely melt DM unit is pumped to using lead, lead volume is made, lead volume send cathode manufacture unit manufacture cathode together with conductive copper rod, obtains lead electrode Piece；2. sending the precipitation lead flake to finished product pot, it is completely melt to lead flake, when being warming up to 480 DEG C, carries out primary fishing dross；After It is continuous to be warming up to 510 DEG C of stirring 1.5h, carry out secondary fishing dross；Lead liquid after fishing dross is subjected to ingot casting, stacking, bundling, storage；
S4. the processing method of the miscellaneous slag of tin are as follows: mixing stanniferous waste material with the miscellaneous slag of tin makes Theil indices 45% in mixture, will Mixture, solvent, soda ash, reduction coal are that tin bottom convertor progress 1200 is sent into 100:5:5:10 mixing by mass ratio of mass ratio DEG C, reduction melting in 2 days obtains crude tin alloy and smelting slag, and the crude tin alloy is dumped into vacuum drying oven using alloy packet and carries out essence Fraction is from output tin slab；
S5. precious metals containing lead furnace reduction melting: the earth of positive pole, char particle, iron filings, soda ash are mixed with mass ratio for 90:12:3:5 Precious metals containing lead furnace is added afterwards to be restored, flue dust, precious metals containing lead and dregs are obtained；Flue dust, dregs return system ingredient are subjected to secondary use；It will Precious metals containing lead, which is added in reduction furnace, carries out 700 DEG C, and 2 days oxidation blown converter reaction removal antimony, stibium trioxide powder export trade will then remove antimony Precious metals containing lead ingot bar after be added divide silver stove oxidation blowing, obtain lead dust, copper bismuth slag, electrum；Make anode, titanium with the electrum Plate makees cathode, and nitric acid and silver nitrate aqueous solution are electrolysed as electrolyte, and silver powder is precipitated on cathode；Lead dust send oxygen-enriched solid sulphur The recycling of reducing and smelting furnace ingredient；Copper bismuth slag uses wet process process separating valuable metals.
The processing of the copper bismuth slag are as follows: copper bismuth slag output bismuth mud, Kocide SD are made using wet process process, specifically: by copper Bismuth slag is dried, and siccative is obtained, and makes copper bismuth slag particle degree less than 80 mesh after siccative is carried out abrasive material, then add it in immersion trough, Control beginning acid concentration is 50~60g/l, solid-to-liquid ratio 1:4, the sodium chloride that quality is copper bismuth slag weight 10% is added, at 75 DEG C Filters pressing after stirring 2h, obtains leached mud, leachate, leached mud is put into after stirring 1h in 30 DEG C of water and carries out secondary filters pressing, obtains bismuth mud； The leachate is added in immersion trough, it is 6~6.5 that caustic soda is added after being warming up to 70 DEG C and adjusts solution ph, 0.5h is stirred, with Filters pressing afterwards obtains Kocide SD and filtrate, and filtrate, which flows into, neutralizes reservoir, is subsequently sent to waste water station processing.Bismuth mud is added and is restored Furnace carries out reduction melting and obtains thick bismuth alloy, and the thick bismuth alloy is carried out pyrogenic process and tentatively refines removing copper (content is less than 1%) Vacuum drying oven is added afterwards and carries out the isolated thick bismuth of rectifying, thick silver, bismuth slag；Thick bismuth carries out bismuth refining procedure output bismuth ingot, by bismuth slag Return to the reduction melting again of bismuth reduction furnace.
The preparation of the lead bullion: taking the lead-acid accumulator sulfuric acid lead plaster of certain enterprise, by it with sulphur-fixing agent, flux with quality Than mixing for 100:5:5, feed powder is obtained, the moisture content of the feed powder is 12%；The feed powder is done after briquetting base at 30MPa It is dry to moisture content be 5%, Pb18%~20%, obtain briquet；7.8m is added with mass ratio for 100:9 in the briquet and coke2 It is dehydrated in oxygen-enriched solid sulphur reducing and smelting furnace, decomposes, melts, sulphur reduction and slag making reaction admittedly, Gu sulphur reduction melting condition: it is burnt Rate 9%, blast intensity 35m3/min·m2, wind pressure 15kpa, slag type Fe/SiO2/ CaO is 20:23:16, and oxygen-rich concentration 25% obtains Clinker, matte, lead bullion, flue dust.
Embodiment 2
A method of the enriching and recovering lead from lead bullion, including the following steps:
S1. pyrogenic process slightly refines: lead bullion progress pyrogenic process slightly being refined, addition adopting electrolysis residual pole is melted after so that lead bullion liquid is down to 335 DEG C Decopper(ing) is analysed, the wooden chaff is added and carries out fishing copper dross slag processing, 12min is stirred when lead liquid temperature is 750 DEG C, tin quality in lead liquid is added 6.5% caustic soda continues to stir 4h, forms the miscellaneous slag of tin, then carries out the fishing miscellaneous Slag treatment of tin, obtains lead bullion liquid, lead bullion liquid is put Enter anode pot, obtains qualified lead liquid；By qualified lead liquid injection anode formwork erection casting unit formwork erection, mold cooling water makes the fast quickly cooling of lead liquid But chloride plate is made；
S2. electrolytic lead refining: using fluosilicic lead plumbate and free silica aqueous fluorine acid solution as electrolyte, chloride plate, lead electrode Piece presses interpolar away from being fitted into electrolytic cell, in 190~198A/m of current density2, under 0.5~0.55V of tank voltage, lead, tin are in cathode Precipitation, using cathode washing rod drawing machine group progress cathode, clean, pumping stick, gathering are in heaps, obtain precipitation lead flake；Contained current potential in anode The valuable metal born than lead is also from Anodic Stripping, and the current potential valuable metal more positive than lead is in forming the earth of positive pole on anode plate；It will electrolysis Anode scrap returns to the fusing of anode pot, double teeming chloride plate after scrubbing, filtering；The circulation of the electrolyte, purification style are as follows: use 2 A electrolyte circulation system, endless form are single-stage circulation, solution upper entering and lower leaving in electrolytic cell；The circulation speed of every slot electrolyte Degree: 35L/min；
S3. two kinds of lead flake processing are precipitated: cathode pot are packed into after 1. scrubbing the precipitation lead flake, after lead flake is completely melt DM unit is pumped to using lead, lead volume is made, lead volume send cathode manufacture unit manufacture cathode together with conductive copper rod, obtains lead electrode Piece；2. sending the precipitation lead flake to finished product pot, it is completely melt to lead flake, when being warming up to 480 DEG C, carries out primary fishing dross；After It is continuous to be warming up to 520 DEG C of stirring 1.8h, carry out secondary fishing dross；Lead liquid after fishing dross is subjected to ingot casting, stacking, bundling, storage；
S4. the processing method of the miscellaneous slag of tin are as follows: mixing stanniferous waste material with the miscellaneous slag of tin makes Theil indices 50% in mixture, will Mixture, solvent, soda ash, reduction coal are that 1200 DEG C, 2.5 days of tin bottom convertor progress is sent into 100:6:5.5:13 mixing with mass ratio Reduction melting obtains crude tin alloy and smelting slag, and the crude tin alloy is dumped into vacuum drying oven using alloy packet and carries out rectifying separation, Output tin slab；
S5. precious metals containing lead furnace reduction melting: the earth of positive pole, char particle, iron filings, soda ash are mixed with mass ratio for 90:13:4:5.5 Precious metals containing lead furnace is added after conjunction to be restored, flue dust, precious metals containing lead and dregs are obtained；Flue dust, dregs return system ingredient are subjected to secondary use； Precious metals containing lead is added in reduction furnace and carries out 800 DEG C, 2.5 days oxidation blown converter reaction removal antimony, stibium trioxide powder export trade will then be gone Divide silver stove oxidation blowing except being added after the precious metals containing lead ingot bar of antimony, obtains lead dust, copper bismuth slag, electrum；Make sun with the electrum Pole, titanium plate make cathode, and nitric acid and silver nitrate aqueous solution are electrolysed as electrolyte, and silver powder is precipitated on cathode；Lead dust send richness Oxygen consolidates the recycling of sulphur reducing and smelting furnace ingredient；Copper bismuth slag uses wet process process separating valuable metals.
The processing of the copper bismuth slag are as follows: copper bismuth slag output bismuth mud, Kocide SD are made using wet process process, specifically: by copper Bismuth slag is dried, and siccative is obtained, and makes copper bismuth slag particle degree less than 80 mesh after siccative is carried out abrasive material, then add it in immersion trough, Control beginning acid concentration is 60~80g/l, solid-to-liquid ratio 1:4, the sodium chloride that quality is copper bismuth slag weight 13% is added, at 80 DEG C Filters pressing after stirring 2h, obtains leached mud, leachate, leached mud is put into after stirring 1h in 35 DEG C of water and carries out secondary filters pressing, obtains bismuth mud； The leachate is added in immersion trough, it is 6.5~6.8 that caustic soda is added after being warming up to 75 DEG C and adjusts solution ph, 0.5h is stirred, Subsequent filters pressing obtains Kocide SD and filtrate, and filtrate, which flows into, neutralizes reservoir, is subsequently sent to waste water station processing；Bismuth mud is added also Former furnace carries out reduction melting and obtains thick bismuth alloy, and the thick bismuth alloy progress pyrogenic process is tentatively refined removing copper, and (content is less than 1%) vacuum drying oven is added afterwards and carries out the isolated thick bismuth of rectifying, thick silver, bismuth slag；Thick bismuth carries out bismuth refining procedure output bismuth ingot, will Bismuth slag returns to the reduction melting again of bismuth reduction furnace.
The preparation method of the lead bullion: taking leaded, the zinc waste residue of certain enterprise, is 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 5.5%, Pb20%~22%, obtains briquet；7.8m is added with mass ratio for 100:11 in the briquet and coke2It is rich Oxygen, which is consolidated in sulphur reducing and smelting furnace, to be dehydrated, decomposes, melts, consolidating sulphur reduction and slag making reaction, Gu sulphur reduction melting condition: burnt rate 10%, blast intensity 39m3/min·m2, wind pressure 16kpa, slag type Fe/SiO2/ CaO is 24:27:18, and oxygen-rich concentration 25% obtains Clinker, matte, lead bullion, flue dust.
Embodiment 3
A method of the enriching and recovering lead from lead bullion, including the following steps:
S1. pyrogenic process slightly refines: lead bullion progress pyrogenic process slightly being refined, addition adopting electrolysis residual pole is melted after so that lead bullion liquid is down to 340 DEG C Decopper(ing) is analysed, the wooden chaff is added and carries out fishing copper dross slag processing, 15min is stirred when lead liquid temperature is 800 DEG C, tin quality in lead liquid is added 7% caustic soda continues to stir 5h, forms the miscellaneous slag of tin, then carries out the fishing miscellaneous Slag treatment of tin, obtains lead bullion liquid, lead bullion liquid is put into Anode pot obtains qualified lead liquid；By qualified lead liquid injection anode formwork erection casting unit formwork erection, mold cooling water is quickly cooled down lead liquid Chloride plate is made；
S2. electrolytic lead refining: using fluosilicic lead plumbate and free silica aqueous fluorine acid solution as electrolyte, chloride plate, lead electrode Piece presses interpolar away from being fitted into electrolytic cell, in 198~205A/m of current density2, under 0.55~0.6V of tank voltage, lead, tin are in cathode Precipitation, using cathode washing rod drawing machine group progress cathode, clean, pumping stick, gathering are in heaps, obtain precipitation lead flake；Contained current potential in anode The valuable metal born than lead is also from Anodic Stripping, and the current potential valuable metal more positive than lead is in forming the earth of positive pole on anode plate；It will electrolysis Anode scrap returns to the fusing of anode pot, double teeming chloride plate after scrubbing, filtering；The circulation of the electrolyte, purification style are as follows: use 2 A electrolyte circulation system, endless form are single-stage circulation, solution upper entering and lower leaving in electrolytic cell；The circulation speed of every slot electrolyte Degree: 40L/min.
S3. two kinds of lead flake processing are precipitated: cathode pot are packed into after 1. scrubbing the precipitation lead flake, after lead flake is completely melt DM unit is pumped to using lead, lead volume is made, lead volume send cathode manufacture unit manufacture cathode together with conductive copper rod, obtains lead electrode Piece；2. sending the precipitation lead flake to finished product pot, it is completely melt to lead flake, when being warming up to 480 DEG C, carries out primary fishing dross；After It is continuous to be warming up to 530 DEG C of stirring 2h, carry out secondary fishing dross；Lead liquid after fishing dross is subjected to ingot casting, stacking, bundling, storage；
S4. the processing method of the miscellaneous slag of tin are as follows: mixing stanniferous waste material with the miscellaneous slag of tin makes Theil indices 55% in mixture, will Mixture, solvent, soda ash, reduction coal are that 1200 DEG C of tin bottom convertor progress is sent into 100:8:6:15 mixing with mass ratio, are restored within 3 days Melting, obtains crude tin alloy and smelting slag, and the crude tin alloy is dumped into vacuum drying oven using alloy packet and carries out rectifying separation, output Tin slab；
S5. precious metals containing lead furnace reduction melting: the earth of positive pole, char particle, iron filings, soda ash are mixed with mass ratio for 90:15:5:6 Precious metals containing lead furnace is added afterwards to be restored, flue dust, precious metals containing lead and dregs are obtained；Flue dust, dregs return system ingredient are subjected to secondary use；It will Precious metals containing lead, which is added in reduction furnace, carries out 850 DEG C, and 3 days oxidation blown converter reaction removal antimony, stibium trioxide powder export trade will then remove antimony Precious metals containing lead ingot bar after be added divide silver stove oxidation blowing, obtain lead dust, copper bismuth slag, electrum；Make anode, titanium with the electrum Plate makees cathode, and nitric acid and silver nitrate aqueous solution are electrolysed as electrolyte, and silver powder is precipitated on cathode；Lead dust send oxygen-enriched solid sulphur The recycling of reducing and smelting furnace ingredient；Copper bismuth slag uses wet process process separating valuable metals.
The processing of the copper bismuth slag are as follows: copper bismuth slag output bismuth mud, Kocide SD are made using wet process process, specifically: by copper Bismuth slag is dried, and siccative is obtained, and makes copper bismuth slag particle degree less than 80 mesh after siccative is carried out abrasive material, then add it in immersion trough, Control beginning acid concentration is 80~100g/l, solid-to-liquid ratio 1:4, the sodium chloride that quality is copper bismuth slag weight 15% is added, at 85 DEG C Filters pressing after lower stirring 2h, obtains leached mud, leachate, leached mud is put into after stirring 1h in 40 DEG C of water and carries out secondary filters pressing, obtains bismuth Mud；The leachate is added in immersion trough, it is 6.8~7 that caustic soda is added after being warming up to 80 DEG C and adjusts solution ph, stirring 0.5h, subsequent filters pressing obtain Kocide SD and filtrate, and filtrate, which flows into, neutralizes reservoir, are subsequently sent to waste water station processing；Bismuth mud is added Enter reduction furnace progress reduction melting and obtain thick bismuth alloy, the thick bismuth alloy progress pyrogenic process is tentatively refined removing copper, and (content is small The isolated thick bismuth of rectifying, thick silver, bismuth slag are carried out in vacuum drying oven 1%) is added afterwards；Thick bismuth carries out bismuth refining procedure output bismuth ingot, Bismuth slag is returned into the reduction melting again of bismuth reduction furnace.
The preparation of the lead bullion: taking the lead-acid accumulator sulfuric acid lead plaster of certain enterprise, by it with sulphur-fixing agent, flux with quality Than mixing for 100:8:10, feed powder is obtained, the moisture content of the feed powder is 15%；By the feed powder at 50MPa after briquetting base Drying to moisture content is 6%, Pb22%~25%, obtains briquet；It with mass ratio is that 100:12 is added by the briquet and coke 7.8m2It is dehydrated in oxygen-enriched solid sulphur reducing and smelting furnace, decomposes, melts, sulphur reduction and slag making reaction admittedly, Gu sulphur reduction melting item Part: burnt rate 12%, blast intensity 45m3/min·m2, wind pressure 18kpa, slag type Fe/SiO2/ CaO is 26:30:20, oxygen-rich concentration 25%, obtain clinker, matte, lead bullion, flue dust.
For the embodiment of the present invention, to guarantee quality of cathode silver in S5, when in electrolyte content of copper ion be more than 50~ When 60g/L, extraction section electrolyte is needed to be handled and supplemented corresponding new liquid, silver electrolyte purification is using " salt precipitating- Neutralizing hydrolysis method ", i.e., sodium chloride solution, which is added, into silver electrolyte makes silver ion be precipitated as AgCl, and AgCl is washed, after pulp, In acid condition, black silver powder is generated by iron replacement, return divides silver stove oxidation blowing；Waste liquid after displacement, which is added, to be neutralized Slot, in hot addition soda, it is 7~8 that stirring, which is neutralized to pH value, makes antimony, bismuth, copper ion neutralization precipitation, and neutralization purification slag, which is sent, to be contained Leady raw materials workshop ingredient.
Electrolyte composition range used in Examples 1 to 3 is as shown in table 1:
1 electrolytic lead refining electrolyte composition range table of table
The yield that metal is returned obtained by Examples 1 to 3 is as shown in table 2 below.
2 metal recovery rate of table (%)
Valuable metal Lead Tin Bismuth Antimony Silver
Embodiment 1 96~97 92~95 89~91 92~95 95~96
Embodiment 2 97~98 92~95 89~92 92~95 95~96
Embodiment 3 97~98 93~95 89~92 92~95 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 (9)

1. a kind of method of the enriching and recovering lead from lead bullion, characterized in that it comprises the following steps:
S1. pyrogenic process slightly refines: lead bullion progress pyrogenic process slightly being refined, addition adopting electrolysis residual pole carries out after so that lead bullion liquid is down to 330 DEG C~340 DEG C Liquate decopper(ing) is added the wooden chaff and carries out fishing copper dross slag processing, 10~15min is stirred when lead liquid temperature is 700 DEG C~800 DEG C, is added Enter caustic soda, continue 3~5h of stirring, form the miscellaneous slag of tin, then carries out the fishing miscellaneous Slag treatment of tin, obtain lead bullion liquid, lead bullion liquid is put into Qualified lead liquid is made in anode pot；By qualified lead liquid injection anode formwork erection casting unit formwork erection, mold cooling water makes the fast quickly cooling of lead liquid But chloride plate is made；
S2. electrolytic lead refining: using fluosilicic lead plumbate and free silica aqueous fluorine acid solution as electrolyte, chloride plate, lead electrode piece are pressed Interpolar is away from being fitted into electrolytic cell, in 180~205A/m of current density2, under 0.4~0.6V of tank voltage, lead, tin are precipitated in cathode, Using cathode washing rod drawing machine group progress cathode, clean, pumping stick, gathering are in heaps, obtain precipitation lead flake；Contained current potential compares lead in anode Negative valuable metal is also from Anodic Stripping, and the current potential valuable metal more positive than lead is in forming the earth of positive pole on anode plate；By adopting electrolysis residual pole The fusing of anode pot, double teeming chloride plate are returned after scrubbing, filtering；
S3. two kinds of lead flake processing are precipitated: being packed into cathode pot after 1. scrubbing the precipitation lead flake, is used after lead flake is completely melt Lead is pumped to DM unit and lead volume is made, and lead volume send cathode manufacture unit manufacture cathode together with conductive copper rod, obtains lead electrode piece；② The precipitation lead flake is sent to finished product pot, is completely melt to lead flake, when being warming up to 480 DEG C, carries out primary fishing dross；Continue to heat up To 510 DEG C~530 DEG C 1.5~2h of stirring, secondary fishing dross is carried out；Lead liquid after fishing dross is subjected to ingot casting, stacking, bundling, Storage；
S4. the processing method of the miscellaneous slag of tin are as follows: mixing stanniferous waste material with the miscellaneous slag of tin makes Theil indices 45%~55% in mixture, Mixture, solvent, soda ash, reduction coal are sent into tin bottom convertor and carry out 1200 DEG C, reduction melting in 2~3 days obtains crude tin alloy and melts Slag is refined, the crude tin alloy is dumped into vacuum drying oven using alloy packet and carries out rectifying separation, output tin slab；
S5. precious metals containing lead furnace reduction melting: precious metals containing lead furnace is added after the earth of positive pole, char particle, iron filings, soda ash are mixed and restores, obtains Flue dust, precious metals containing lead and dregs；Flue dust, dregs return system ingredient are subjected to secondary use；Precious metals containing lead is added in reduction furnace and is carried out 700 DEG C~850 DEG C, 2~3 days oxidation blown converter reaction removal antimony, stibium trioxide powder export trade then will be after the precious metals containing lead ingot bar that remove antimony Addition divides silver stove oxidation blowing, obtains lead dust, copper bismuth slag, electrum；Make anode with the electrum, titanium plate makees cathode, nitre Acid and silver nitrate aqueous solution are electrolysed as electrolyte, and silver powder is precipitated on cathode；Lead dust send oxygen-enriched solid sulphur reducing and smelting furnace Ingredient recycling；Copper bismuth slag uses wet process process separating valuable metals.
2. a kind of method of the enriching and recovering lead from lead bullion as described in claim 1, which is characterized in that severe described in the S1 Property sodium additional amount be lead liquid in tin quality 6%~7%.
3. a kind of method of the enriching and recovering lead from lead bullion as described in claim 1, which is characterized in that electricity described in the S2 Solve circulation, the purification style of liquid are as follows: use 2 electrolyte circulation systems, endless form is single-stage circulation, in electrolytic cell on solution Into it is lower go out；The circulation rate of every slot electrolyte: 30~40L/min.
4. a kind of method of the enriching and recovering lead from lead bullion as described in claim 1, which is characterized in that mixed described in the S4 Closing material, solvent, soda ash, reduction coal mass ratio is 100:5~8:5~6:10~15.
5. a kind of method of the enriching and recovering lead from lead bullion as described in claim 1, which is characterized in that sun described in the S5 Pole mud, char particle, iron filings, soda ash mass ratio are as follows: 90:12~15:3~5:5~6.
6. a kind of method of the enriching and recovering lead from lead bullion as described in claim 1, which is characterized in that copper described in the S5 The processing of bismuth slag are as follows: copper bismuth slag output bismuth mud, Kocide SD are made using wet process process, it is molten that bismuth mud addition reduction furnace is carried out reduction Refining obtains thick bismuth alloy, the thick bismuth alloy is carried out vacuum drying oven progress rectifying point is added after pyrogenic process tentatively refines removing copper, tellurium From obtaining thick bismuth, thick silver, bismuth slag；
Thick bismuth carries out bismuth refining procedure output bismuth ingot, and bismuth slag is returned to the reduction melting again of bismuth reduction furnace.
7. a kind of method of the enriching and recovering lead from lead bullion as claimed in claim 6, which is characterized in that the wet process process produces Bismuth mud concrete operations out are as follows: copper bismuth slag is dried, siccative is obtained, makes copper bismuth slag particle degree less than 80 after siccative is carried out abrasive material Mesh, then add it in immersion trough, control beginning acid concentration is 50~100g/l, solid-to-liquid ratio 1:4, sodium chloride is added, at 75 DEG C Filters pressing after stirring 2h, obtains leached mud, leachate at~85 DEG C, leached mud is put into after stirring 1h in 30 DEG C~40 DEG C water and carries out two Secondary filters pressing obtains bismuth mud.
8. a kind of method of the enriching and recovering lead from lead bullion as claimed in claim 7, which is characterized in that the sodium chloride adds Enter 10%~15% that amount is copper bismuth slag weight.
9. a kind of method of the enriching and recovering lead from lead bullion as claimed in claim 6, which is characterized in that the wet process process produces Kocide SD concrete operations out are as follows: the leachate is added in immersion trough, caustic soda is added after being warming up to 70 DEG C~80 DEG C and adjusts Solution ph is 6~7, stirs 0.5h, and subsequent filters pressing obtains Kocide SD and filtrate, and filtrate, which flows into, neutralizes reservoir, is subsequently sent to Waste water station processing.
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CN111172409A (en) * 2020-01-19 2020-05-19 河南豫光金铅股份有限公司 Recovery smelting process of tin-containing material
CN112359206A (en) * 2020-10-10 2021-02-12 福达合金材料股份有限公司 Method for electrolytic impurity removal and recycling of silver tin oxide scraps
CN117144425A (en) * 2023-10-26 2023-12-01 内蒙古兴安银铅冶炼有限公司 Lead bismuth alloy electrolysis process

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CN111172409A (en) * 2020-01-19 2020-05-19 河南豫光金铅股份有限公司 Recovery smelting process of tin-containing material
CN112359206A (en) * 2020-10-10 2021-02-12 福达合金材料股份有限公司 Method for electrolytic impurity removal and recycling of silver tin oxide scraps
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