CN108588420A - A kind of method of lead-acid accumulator hydrometallurgic recovery lead - Google Patents
A kind of method of lead-acid accumulator hydrometallurgic recovery lead Download PDFInfo
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- CN108588420A CN108588420A CN201711433182.1A CN201711433182A CN108588420A CN 108588420 A CN108588420 A CN 108588420A CN 201711433182 A CN201711433182 A CN 201711433182A CN 108588420 A CN108588420 A CN 108588420A
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- lead
- brown
- acid
- ammonium
- acid accumulator
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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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
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- 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
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- 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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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Electrolytic Production Of Metals (AREA)
Abstract
The present invention provides a kind of method of lead-acid accumulator hydrometallurgic recovery lead, will be mainly crushed after lead-acid accumulator acid, sorting, obtains lead plaster；Lead plaster is added ammonium carbonate and carries out reduction conversion with lead sulfate, obtains lead oxide, brown lead oxide, ceruse precipitation, while recycling ammonium sulfate saturated solution；Fluosilicic acid solution, electrolysis liquid leaching of the sediment using 20%, obtain electric effusion, brown lead oxide, fluosilicic lead plumbate, water and carbon dioxide；It is separated by solid-liquid separation, filters out solid brown lead oxide, remaining liq supplements silicofluoric acid, additive is added, and enters in electrolytic cell after stirring and is electrolysed, brown lead oxide is precipitated, and obtain pure lead.Wherein, each link is combined closely, and is recycled using generated liquid, gas in recovery process, substantially reduces the use of raw material, effectively control production cost.
Description
Technical field
It is related that the present invention relates to nonferrous metallurgies, more particularly with lead-acid accumulator reclaiming non-ferrous metal metallurgy work
Skill technical field is related, refers in particular to a kind of method of lead-acid accumulator hydrometallurgic recovery lead.
Background technology
Since reform and opening-up, waste water, the exhaust gas of many industrial discharges such as plating, mining, process hides have been continuously increased in environment
Lead contamination load has exceeded the self-purification capacity of environment, and lead is a kind of heavy metal toxic to human body, and the discharge of lead containing sludge destroys
The ecological balance influences people’s lives.Currently, the raw material of reviver further includes lead-acid accumulator, cable in addition to leaded virgin material
The waste garrulous material etc. that sheath, lead pipe, stereotype and leadwork generate in process, and lead-acid accumulator is wherein more difficult time
One kind of receipts.
Hydrometallurgic recovery is one of main way of recycling of lead-acid accumulator, various wet-treating decopper(ing)s, zinc, arsenic it is leaded
Along screen, lead mud and other lead-containing materials, they are with sulfuric acid for slag, lead bismuth slag or various lead mud, vulcanized lead filter cake, accumulator
Lead, lead oxide, lead peroxide, vulcanized lead or metallic lead state exist, therefore, in traditional recovery process, there are each point breakthrough,
Heavy metal progress for required recycling is individually operated, wastes lot of materials and process can be only achieved purpose, and not only consumptive material is big,
And efficiency is low.
Invention content
It is an object of the invention to be directed to the existing state of the art, a kind of side of lead-acid accumulator hydrometallurgic recovery lead is provided
Method, each link are combined, and are recycled to lead metal with efficient process, efficient, low cost.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
The present invention is a kind of method of lead-acid accumulator hydrometallurgic recovery lead, it is characterised in that steps are as follows：
（1）It will be crushed after lead-acid accumulator acid, sorting, obtain lead plaster；
（2）Lead plaster is added ammonium carbonate and carries out reduction conversion with lead sulfate, obtains lead oxide, brown lead oxide, ceruse precipitation, simultaneously
Recycle ammonium sulfate saturated solution；
（3）Sediment using 20% fluosilicic acid solution, electrolysis liquid leaching, obtain electric effusion, brown lead oxide, fluosilicic lead plumbate, water and
Carbon dioxide；
（4）It is separated by solid-liquid separation, filters out solid brown lead oxide, remaining liq supplements silicofluoric acid, additive is added, and electrolysis is entered after stirring
Electrodeposition, the pure lead of cathode output are carried out in slot, a small amount of brown lead oxide is precipitated in anode；
（5）In step（3）In carbon dioxide reacted with ammonium hydroxide, generate ammonium hydrogen carbonate, ammonium hydrogen carbonate further with hydrogen-oxygen
Change ammonium and reacts to obtain ammonium carbonate；
（6）Step（4）The electrolyte of middle generation is used for step（3）In leaching operation.
Above-mentioned steps（4）Middle additive be added is jelly powder 0.3g/L and B- naphthols 0.01g/L.
Above-mentioned steps（4）The tank voltage of middle electrolytic cell is 2.3V, current density control is in 180-210A/m2。
Above-mentioned steps（4）Middle filtered out brown lead oxide merges processing red lead with the brown lead oxide that electrolysis is precipitated.
Above-mentioned steps（2）In the concentrated crystallization of ammonium sulfate saturated solution agrochemical ammonium sulfate is made.
Above-mentioned steps（5）In ammonium carbonate be used for step（2）In conversion procedure.
In said program, the plumbum ion concentration in electric effusion is 110-130g/L, a concentration of 170-190g/L of total acid, dissociates
A concentration of 93-99g/L of silicofluoric acid.
Beneficial effects of the present invention are：The technique of the present invention carries out desulfurization conversion using ammonium sulfate to lead sulfate, generation
Electric effusion is made with the leaching of ceruse precipitation fluosilicic acid solution in lead oxide, and ammonia, hydrogen is added using leaching gained carbon dioxide
It is anticaustic in the use of lead sulfate desulfurization conversion, the insoluble matter brown lead oxide filtered out and the two of electrodeposition precipitation that amine-oxides produce ammonium carbonate
Red lead is processed into lead oxide merging, and the ammonium sulfate saturated solution after conversion carries out condensing crystallizing and agrochemical ammonium sulfate is made.Gained
Lead powder purity is more than 99.98%.
Description of the drawings：
Attached drawing 1 is the process flow chart of the present invention.
Specific implementation mode：
Shown in attached drawing 1, below the present invention will be further described：
The present invention is a kind of method of lead-acid accumulator hydrometallurgic recovery lead, it is characterised in that steps are as follows：
（1）It will be crushed after lead-acid accumulator acid, sorting, obtain lead plaster；
（2）Lead plaster is added ammonium carbonate and carries out reduction conversion with lead sulfate, obtains lead oxide, brown lead oxide, ceruse precipitation, simultaneously
Recycle ammonium sulfate saturated solution；Lead plaster main material is by lead sulfate（PbSO4）, brown lead oxide (PbO2) composition, ammonium carbonate is added and turns
Change lead sulfate, obtains the ceruse of not sulfur-bearing, chemical equation is；PbSO4+(NH4)2CO3=PbCO3+(NH4)2SO4, dioxy
Change lead because being acidic oxide, not reacting with ammonium carbonate.Suspension after conversion obtains filter cake ceruse and dioxy after filtering
Change the mixture of lead, filtrate is mainly ammonium sulfate saturated solution, which goes condensing crystallizing process to obtain ammonium sulfate and pay product.
（3）Sediment using 20% fluosilicic acid solution, electrolysis liquid leaching, obtain electric effusion, brown lead oxide, fluosilicic lead plumbate,
Water and carbon dioxide；Sediment is leached using 20% fluosilicic acid solution, chemical equation；PbCO3+H2SiF6=PbSiF6+H2O
+CO2,
（4）It is separated by solid-liquid separation, filters out solid brown lead oxide, remaining liq supplements silicofluoric acid, additive is added, and electrolysis is entered after stirring
Electrodeposition, the pure lead of cathode output are carried out in slot, a small amount of brown lead oxide is precipitated in anode；
（5）In step（3）In carbon dioxide reacted with ammonium hydroxide, generate ammonium hydrogen carbonate, ammonium hydrogen carbonate further with hydrogen-oxygen
Change ammonium and reacts to obtain ammonium carbonate；Carbon dioxide recovery in above-mentioned reaction product, carbon dioxide and the aqua ammonia of recycling prepare carbonic acid
Hydrogen ammonium.It prepares ammonium hydrogen carbonate and prepares ammonium carbonate with aqua ammonia again, the chemical reaction for preparing ammonium carbonate is；NH4OH+CO2=
NH4HCO3、NH4HCO3+NH4OH=(NH4)2CO3+H2O, with the ammonium carbonate { (NH prepared4)2CO3Remove conversion lead sulfate
(PbSO4) it is ceruse (PbCO3)。
（6）Step（4）The electrolyte of middle generation is used for step（3）In leaching operation.The not ceruse of sulfur-bearing after conversion
PbSiF is obtained after fluosilicic Acid leaching6, the electric effusion for being suitble to lead electrodeposition is adjusted after filtering, which enters electrodeposition system,
The 99.99 pure lead of output on cathode only has seldom brown lead oxide precipitate, electric effusion to recycle on anode.In filter cake
PbO2It cannot be reacted with silicofluoric acid, after ceruse is reacted with silicofluoric acid, the filter cake brown lead oxide through being obtained by filtration goes reduction work
Sequence produces red lead (Pb3O4) or yellow lead (PbO).
In said program, step（4）Middle additive be added is jelly powder 0.3g/L and B- naphthols 0.01g/L, effect
It is：Can obtain better cathode crystalline quality, improve current efficiency, improve electrodeposition condition to allow to improve current density and
Strengthening digestion.Step（5）In ammonium carbonate be used for step（2）In conversion restore process, reduce CO2 emission and material
Cost；Step（4）The tank voltage of middle electrolytic cell is 2.3V, current density control is in 180-210A/m2, wherein current efficiency is
96%。
Above-mentioned steps（4）Middle filtered out brown lead oxide merges processing red lead with the brown lead oxide that electrolysis is precipitated；And step
（2）In the concentrated crystallization of ammonium sulfate saturated solution agrochemical ammonium sulfate is made.
Certainly, illustrated above is only better embodiment of the present invention, and the use scope of the present invention is not limited with this, therefore,
It is every made in the principle of the invention it is equivalent change should be included within the scope of the present invention.
Claims (6)
1. a kind of method of lead-acid accumulator hydrometallurgic recovery lead, it is characterised in that technique is as follows：
（1）It will be crushed after lead-acid accumulator acid, sorting, obtain lead plaster；
（2）Lead plaster is added ammonium carbonate and carries out reduction conversion with lead sulfate, obtains lead oxide, brown lead oxide, ceruse precipitation, simultaneously
Recycle ammonium sulfate saturated solution；
（3）Sediment using 20% fluosilicic acid solution, electrolysis liquid leaching, obtain electric effusion, brown lead oxide, fluosilicic lead plumbate, water and
Carbon dioxide；
（4）It is separated by solid-liquid separation, filters out solid brown lead oxide, remaining liq supplements silicofluoric acid, additive is added, and electrolysis is entered after stirring
Electrodeposition, the pure lead of cathode output are carried out in slot, a small amount of brown lead oxide is precipitated in anode；
（5）In step（3）In carbon dioxide reacted with ammonium hydroxide, generate ammonium hydrogen carbonate, ammonium hydrogen carbonate further with hydrogen-oxygen
Change ammonium and reacts to obtain ammonium carbonate；
（6）Step（4）The electrolyte of middle generation is used for step（3）In leaching operation.
2. a kind of method of lead-acid accumulator hydrometallurgic recovery lead according to claim 1, it is characterised in that：The step
（4）Middle additive be added is jelly powder 0.3g/L and B- naphthols 0.01g/L.
3. a kind of method of lead-acid accumulator hydrometallurgic recovery lead according to claim 1 or 2, it is characterised in that：It is described
Step（4）The tank voltage of middle electrolytic cell is 2.3V, current density control is in 180-210A/m2。
4. a kind of method of lead-acid accumulator hydrometallurgic recovery lead according to claim 1 or 2, it is characterised in that：It is described
Step（4）Middle filtered out brown lead oxide merges processing red lead with the brown lead oxide that electrolysis is precipitated.
5. a kind of method of lead-acid accumulator hydrometallurgic recovery lead according to claim 1, it is characterised in that：The step
（2）In the concentrated crystallization of ammonium sulfate saturated solution agrochemical ammonium sulfate is made.
6. a kind of method of lead-acid accumulator hydrometallurgic recovery lead according to claim 1, it is characterised in that：The step
（5）In ammonium carbonate be used for step（2）In conversion procedure.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711433182.1A CN108588420A (en) | 2017-12-26 | 2017-12-26 | A kind of method of lead-acid accumulator hydrometallurgic recovery lead |
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| CN201711433182.1A CN108588420A (en) | 2017-12-26 | 2017-12-26 | A kind of method of lead-acid accumulator hydrometallurgic recovery lead |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109735870A (en) * | 2018-12-28 | 2019-05-10 | 祥云高鑫循环科技有限责任公司 | The electrolyte electrochemical purification method of waste lead acid battery lead cream Solid phase electrolysis hydrometallurgic recovery lead |
| CN111170351A (en) * | 2018-11-13 | 2020-05-19 | 湖南省金翼有色金属综合回收有限公司 | Lead sulfate waste material desulfurization device and process thereof |
| CN111270267A (en) * | 2020-02-11 | 2020-06-12 | 云南驰宏资源综合利用有限公司 | Method for supplementing lead ions of lead electrolyte by using lead plaster of waste lead-acid storage battery |
| CN112054253A (en) * | 2020-07-30 | 2020-12-08 | 济南大学 | Preparation method and application of activated compatibilizer for repairing failed lead-acid storage battery |
| CN112111654A (en) * | 2020-10-09 | 2020-12-22 | 昆明理工大学 | Method for separating lead and manganese from electrolytic manganese anode slime |
| CN113363426A (en) * | 2021-06-04 | 2021-09-07 | 河北大学 | Preparation method of sodium ion battery based on metal Pb negative electrode and metal Pb recovery method |
| CN114606538A (en) * | 2022-01-24 | 2022-06-10 | 湘潭大学 | Waste lead paste recovery treatment method |
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| CN101205080A (en) * | 2006-12-18 | 2008-06-25 | 湖南大学 | Method for preparing high-quality red lead by lead slime of lead-acid batteries |
| CN103045853A (en) * | 2013-01-15 | 2013-04-17 | 浙江汇同电源有限公司 | Process for recovering lead from lead-acid battery paste |
| CN103509949A (en) * | 2012-06-15 | 2014-01-15 | 杨春晓 | Methods and equipment for recovering waste diachylon by wet method and manufacturing electrode active material of high performance lead acid battery by wet method |
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2017
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Patent Citations (3)
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| CN101205080A (en) * | 2006-12-18 | 2008-06-25 | 湖南大学 | Method for preparing high-quality red lead by lead slime of lead-acid batteries |
| CN103509949A (en) * | 2012-06-15 | 2014-01-15 | 杨春晓 | Methods and equipment for recovering waste diachylon by wet method and manufacturing electrode active material of high performance lead acid battery by wet method |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170351A (en) * | 2018-11-13 | 2020-05-19 | 湖南省金翼有色金属综合回收有限公司 | Lead sulfate waste material desulfurization device and process thereof |
| CN109735870A (en) * | 2018-12-28 | 2019-05-10 | 祥云高鑫循环科技有限责任公司 | The electrolyte electrochemical purification method of waste lead acid battery lead cream Solid phase electrolysis hydrometallurgic recovery lead |
| CN111270267A (en) * | 2020-02-11 | 2020-06-12 | 云南驰宏资源综合利用有限公司 | Method for supplementing lead ions of lead electrolyte by using lead plaster of waste lead-acid storage battery |
| CN112054253A (en) * | 2020-07-30 | 2020-12-08 | 济南大学 | Preparation method and application of activated compatibilizer for repairing failed lead-acid storage battery |
| CN112054253B (en) * | 2020-07-30 | 2021-09-10 | 济南大学 | Preparation method and application of activated compatibilizer for repairing failed lead-acid storage battery |
| CN112111654A (en) * | 2020-10-09 | 2020-12-22 | 昆明理工大学 | Method for separating lead and manganese from electrolytic manganese anode slime |
| CN112111654B (en) * | 2020-10-09 | 2021-10-22 | 昆明理工大学 | Method for separating lead and manganese from electrolytic manganese anode slime |
| CN113363426A (en) * | 2021-06-04 | 2021-09-07 | 河北大学 | Preparation method of sodium ion battery based on metal Pb negative electrode and metal Pb recovery method |
| CN114606538A (en) * | 2022-01-24 | 2022-06-10 | 湘潭大学 | Waste lead paste recovery treatment method |
| CN114606538B (en) * | 2022-01-24 | 2023-10-03 | 湘潭大学 | Waste lead plaster recycling method |
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