CN105895983A - Method for preparing high-purity PbO by cycle wet method - Google Patents
Method for preparing high-purity PbO by cycle wet method Download PDFInfo
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- CN105895983A CN105895983A CN201410756642.4A CN201410756642A CN105895983A CN 105895983 A CN105895983 A CN 105895983A CN 201410756642 A CN201410756642 A CN 201410756642A CN 105895983 A CN105895983 A CN 105895983A
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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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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention relates to a method for preparing high-purity PbO by a cycle wet method, and provides a method for recycling a waste lead-acid battery to directly produce high-purity PbO and recycling a chemical raw material. The preparation method for the high-purity PbO comprises the following steps of smashing a waste battery, separating positive/negative lead paste, and allowing lead in the lead paste to be completely converted to a lead raw material composed of PbO and PbSO4 through oxidation and reduction reaction of the positive/negative lead pate; immersing the lead raw material with a mixed solution of an organic acid and an organic acid salt to remove impurity, and carrying out lead deposition and desulfuration on the solution, generating a byproduct sodium sulfate to obtain a lead precipitate; purifying the lead precipitate with an alkaline solution by dissolving the precipitation process to obtain high-purity lead hydroxide; and carrying out low-temperature sintering on the lead hydroxide to obtain a high-purity PbO product, wherein an organic acid salt mother liquid can be used for next circulation. By the method, the defects of long process period of a PbO synthesis process, high energy consumption and a large amount of chemical raw materials required to be consumed are overcome, the cost is reduced, and the method is a new technology which has the advantages of high technological additional value, energy saving and environment friendliness, and is suitable for industrial production at a large scale.
Description
Technical field
The present invention relates to a kind of method that circulation type wet method prepares high-purity PbO, belong to and waste lead acid battery and lead-containing material are reclaimed
The technical field of reviver.
Background technology
Modern American-European and large enterprise of China continues to use traditional pyrometallurgical smelting of lead technique or the pre-sulfur removal technology of sodium carbonate, then pyrogenic process always
The lead bullion smelted becomes product by electrolysis lead bullion again.Owing to pyrometallurgical smelting needs the high temperature of more than 1200 degree, in pyrolytic semlting
Journey produces substantial amounts of lead steam and lead powder dirt, easily causes secondary lead and pollute, and the most frequently used carbonate sulfur method mother liquor is difficult to
Cycling and reutilization.Lead refining has been used up Betts fluosilicic acid purifying method in 1902, and consuming electric power is high, and produces and the most corrosive have
Poison fluoro-gas.Through the lead bullion that complex process obtains, it it is not the lead oxide raw material needed for lead-acid battery.Battery enterprise needs
Buying lead bullion, obtain lead oxide powder again by fusing, cast ball and the oxidation of Shimadzu ball milling, this process consumes again the substantial amounts of energy,
And produce leaded dust.Therefore, waste lead acid battery recycle during environmental pollution and energy-saving and emission-reduction the most all
It it is the bottleneck of restriction industry development.
Wet method refining lead technology is considered the recovery lead technology of cleaning, and currently mainly can be divided into two kinds: one is electricity of wet process deposition technique；
One is wet chemical technology.Electricity of wet process deposition technique, with the graphite cake through specially treated as inert anode, makees negative electrode with pure lead,
Desulfurization material is joined in leaching reactive tank, with HBF4/H2SiF6The lean electrolyte reaction produced with lead electrolytic deposition, obtains rich lead
Electrolyte is electrochemically reacted the hydrometallurgical technology separating out lead.This technology has material strong adaptability, process cleans, product
Quality is high, lead recovery is high, without advantages such as lead dust, lead steam, lead skim generations.Its shortcoming is that energy consumption is higher, produce corrosion
The poisonous fluorine-containing waste liquid of property and waste gas.Solid phase electro-deposition techniques is to make cathode-anode plate with stainless steel, is uniformly filled out by the lead plaster after desulfurization
Fill in the cathode frame with special construction, then yin, yang pole plate is put into equipped with the alkaline solution with NaOH as main medium
Electrolytic cell in, be passed through direct current carry out electrolysis produce pure lead hydrometallurgical technology.This techniqueflow is simple, take up an area less, throw
The advantages such as money province, lead recovery height, process cleans.Its shortcoming is need to be with the alkali of higher concentration, and alkaline consumption is high.People open again in the recent period
Begin to explore the new wet chemical lead recovery technology being directly prepared as superfine lead powder, lead oxide or lead orthoplumbate, basic lead sulphate.
Pan Jun is clear etc. reports two kinds of methods directly being prepared lead oxide by lead plaster, and a kind of is by scrap lead cream and the strong base solution containing catalyst
Reaction obtains containing NaHPbO2Mixed solution, mixed solution cooling and filter, directly obtain PbO crystal (CN
103014347A)；Another kind of method is to sink lead desulfurization and the method (CN of molten lead crystallisation by cooling based on atom economy variable concentrations alkali lye
103146923A).This process equally exists the problem that alkaline consumption is high, and alkali lye sweetening process is difficult to control to.R.V.Kumar etc. carry
Go out to utilize the new technology (Hydrometallurgy, 2009,95:53-60) of citric acid wet-treating waste lead acid battery lead cream, the method
The superfine powder Pb/PbO mixture for lead-acid battery can be directly obtained.The method has been got through and has been directly obtained plumbic acid electricity by scrap lead cream
The new way of the Pb/PbO required for pond, has been greatly shortened the flow process of existing lead recycling.If reducing sintering further
In energy consumption, and improve lead refining process, improve product purity, be expected to generally be received by following lead-acid battery enterprise.Base
In this citric acid method, studies in China person improved, and has applied for direct preparation Pb3O4(CN 103022593A), employing citric acid
Zymotic fluid (CN102560122A), prepare the multinomial patent of invention of four basic lead sulphates (CN103022594A) etc., but the most unresolved
The intrinsic problem that the method exists.
In the environment of current automobile and electric motor car are flourish, waste lead accumulator lead recovery technology need to constantly realize prior art liter
Level, reduces treatment technology construction and operating cost, improves waste lead accumulator lead removal process security and secondary pollution controls level,
Foundation a new generation cleaning is reliable, the lead recovery technology of energy-conserving and environment-protective, solves the cycle length of lead resource cyclic process, energy consumption height and two
Secondary pollution problem, it is achieved the sustainable development of lead resource, improves waste lead accumulator secure processing capability.
Summary of the invention
The present invention is directed to existing wet chemical reviver technology and have that technical process difficulty control, step be many, cycle length, consumption of raw materials etc.
Problem, propose and devise lead molten-liquid phase sinks lead desulfurization-alkali liquid washing-low sintering approach to produce high-purity superfine powder
The new technology of PbO, the product produced can be directly used for lead-acid battery electrode to be prepared.
The present invention is achieved in that a kind of method preparing high-purity mangesium oxide lead from waste lead acid battery/scrap lead, and the method walks
Below Zhou:
(1) waste lead acid battery is used lead plaster, stereotype grid, plastics and dilute sulfuric acid that conventional broken apart technique respectively obtains
Solution；
(2) the positive and negative electrode lead plaster powder after pulverizing carries out solid phase mixing, and then in air, heating carries out redox reaction and obtains
Containing lead oxide, lead sulfate, and PbO2Powder and the solid mixture of impurity；Reaction temperature, between 100～300 DEG C, is reacted
Time is 30～300 minutes.
(3) in the product that (2) process obtains, add reducing agent and make PbO2Powder is fully converted into PbO；Reducing agent is dioxygen
Water, sodium sulfite, sodium dithionate, sodium tetrathionate and ammonium sulfite, ammonium dithionate, tetrathionic acid ammonium, hydrazine hydrate or
HAS, the consumption of reducing agent is 0.2～0.5 times of lead plaster weight, and reaction temperature is 10～40 DEG C, the reaction time 10～120
Minute.
(4) solid mixture that (3) process obtains is dissolved in acylate and organic acid or the mixing of more than one acylates
In solution, obtain the mixed solution containing lead ion and undissolved impurity, and carry out filtering separation；Organic acid includes: acetic acid and
Tartaric acid, pyrovinic acid；Acylate is organic acid sodium salt, organic acid potassium salt, ammonium salt organic acid, organic acid lithium salts；Organic
Acid is 0.1～0.9 with the volume ratio of acylate or organic acid sodium and other acylates, and pH value is 4～7, and organic acid is with a kind of
The consumption of above acylate mixed solution is lead plaster weight 10～20 times；Solution temperature is 15～80 DEG C, and the stirring and dissolving time is
5～180 minutes.
(5) in the mixed solution that (4) process obtains, add the heavy lead agent desulfurization that cation is identical with acylate, obtain lead and sink
Lead thing and filtrate；Heavy lead agent includes: sodium citrate, ammonium citrate, sodium carbonate, ammonium carbonate, sodium oxalate, ammonium oxalate, fourth two
Oxime, tussol, ortho-aminobenzoic acid, thiocarbamide, quina pyridine acid, consumption is lead plaster weight 0.5～5 times of heavy lead agent, instead
Answering temperature is 10～40 DEG C, reaction time 10～120 minutes.
(6) the desulfurization lead sediment that (5) process obtains is dissolved in high alkali liquid, then obtains high-purity by dilution adjustment pH value precipitation
Lead hydroxide sediment, this sediment low-temperature sintering in atmosphere obtains high-purity PbO product；Alkali used be KOH,
NaOH and ammonium hydroxide, the concentration of alkali lye is 5～15mol/L；The consumption of alkali lye is lead plaster weight 5～20 times；Solution temperature is
15～80 DEG C, the stirring and dissolving time is 5～180 minutes；Dilution adjusts the pH value range of solution between 7～13；Lead hydroxide
Precipitation sintering is carried out in atmosphere, and reaction temperature is between 100～350 DEG C, and the time of heating was at 1～10 hour
(7) filtrate that (5) process obtains is carried out sub-cooled crystallization and obtains sodium sulfate byproduct, or add organic acid precipitated barium
Obtaining barium sulfate accessory substance, isolated acylate solution is re-used for the lead salt course of dissolution of (4).
Beneficial effects of the present invention: the method process flow steps is few, simple to operate, product purity is high, lead organic efficiency high,
Chemical raw material reusable edible used, has energy-saving and environmental protection, the efficient and feature of low cost.
Accompanying drawing explanation
Fig. 1 circulation type wet method prepares the method process chart of high-purity PbO
Detailed description of the invention
Embodiment 1
(1) use the method that machinery is disassembled by waste lead acid battery separating/selecting, obtain lead plaster, grid, Waste Sulfuric Acid, dividing plate and shell.
Carrying out the positive/negative lead plaster of isolated pulverizing and sieve with the stainless steel mesh of 100 mesh, bigger lead plaster particle continues to turn
Enter pulverizer to pulverize, until all lead plasters can pass through screen cloth.The positive/negative lead plaster pulverized, sieve is carried out sufficiently solid
Mix mutually.
(2) take 1kg lead plaster powder mixture, be to slowly warm up to 280 DEG C at ambient pressure, and keep 3 hours making brown lead oxide therein
Carry out redox reaction with lead in a heated condition and be converted into lead oxide, generate lead oxide and lead sulfate is main solid mixture；
The hydrazine hydrate solution being subsequently added 3mL content 80% reacts 10 minutes at 20 DEG C so that it is in unreacted PbO2Solidification
Compound is fully converted to PbO.
(3) PbO above-mentioned reaction obtained and lead sulfate solid mixture put into reactor, add 10kg by the second of 0.5kg
Acid sodium, the ammonium acetate of 3.5kg and the solution that pH is 5.6 of 6kg aqueous solvent configuration, and at room temperature with 150 revs/min stir
Mixing speed sustained response makes the lead in solid-phase mixture be fully converted to lead acetate and dissolve for 60 minutes, is filtered to remove battery and is producing
During the impurity such as the additive that is mingled with of shattering process and clay, obtain lead acetate and sulfate be main clear solution.
(4) in clear solution obtained above, add sodium carbonate 1kg, react 30 minutes at 20 DEG C, make lead Precipitation desulfurization,
Being filtrated to get the mixed solution of acetate and sulfate, this filtrate crystallisation by cooling obtains Na2SO4Byproduct, based on acetate
Disposing mother liquor is used further to PbO/PbSO4The dissolving of solid mixture.
(5) lead sediment is put into reactor, add the 8M NaOH aqueous solution, keep 60-150 rev/min of mixing speed and room
The condition of temperature, makes lead sediment be completely dissolved, and being diluted with water solution ph is 9.8, obtains high-purity lead hydroxide sediment.Should
Sediment is placed in air, rises to 160 DEG C of constant temperature 2 hours with the programming rate of 5 DEG C/min, and the PbO preparing high pure and ultra-fine produces
Product, lead recovery is 96%, and product purity is 99.98%.
Embodiment 2
(1) use the method that machinery is disassembled by waste lead acid battery separating/selecting, obtain lead plaster, grid, Waste Sulfuric Acid, dividing plate and shell.
Carrying out the positive/negative lead plaster of isolated pulverizing and sieve with the stainless steel mesh of 100 mesh, bigger lead plaster particle continues to turn
Enter pulverizer to pulverize, until all lead plasters can pass through screen cloth.The positive/negative lead plaster pulverized, sieve is carried out sufficiently solid
Mix mutually.
(2) take 2kg lead plaster powder mixture, be to slowly warm up to 320 DEG C at ambient pressure, and keep 4 hours making brown lead oxide therein
Carry out redox reaction with lead in a heated condition and be converted into lead oxide, generate lead oxide and lead sulfate is main solid mixture；
Be subsequently added the hydrazine hydrate solution that 6mL concentration is 80% to react 20 minutes at 25 DEG C so that it is in unreacted PbO2Solid
Compound is fully converted to PbO.
(3) PbO above-mentioned reaction obtained and lead sulfate solid mixture put into reactor, add 20kg by the wine of 2.5kg
Stone acid potassium, the ammonium tartrate of 4.5kg and 13kg aqueous solvent configuration the solution that pH is 5.2, and at room temperature with 100 turns/
The mixing speed sustained response divided makes lead in solid-phase mixture be fully converted to lead tartrate and dissolve for 30 minutes, is filtered to remove battery
The impurity such as shattering process is mingled with in process of production additive and clay, obtain lead tartrate and sulfate is main clear solution.
(4) in clear solution obtained above, add NaOH 2kg, react 15 minutes at 25 DEG C, make lead Precipitation take off
Sulphur, is filtrated to get the mixed solution of tartrate and sulfate, and this filtrate crystallisation by cooling obtains Na2SO4Byproduct, with tartaric acid
The disposing mother liquor that salt is main is used further to PbO/PbSO4The dissolving of solid mixture.
(5) lead sediment is put into reactor, add the 10M NaOH aqueous solution, keep 60-150 rev/min of mixing speed and room
The condition of temperature, makes lead sediment be completely dissolved, and being diluted with water solution ph is 10.3, obtains high-purity lead hydroxide sediment.
This sediment is placed in air, rises to 150 DEG C of constant temperature 1 hour with the programming rate of 5 DEG C/min, prepares the PbO of high pure and ultra-fine
Product, lead recovery is 98%, and product purity is 99.992%.
The effect of above example: the PbO high purity more than 99.98% of above-mentioned preparation, can meet lead-acid battery to high-purity
The requirement of PbO, thus mix with high-purity lead powder with the weight ratio of 10～40% as additive, directly apply to lead-acid battery
The manufacture of pole plate, improves active material utilization and the electrochemistry capacitance of negative plate, it is not necessary to again through the high energy work consuming of melted-oxidation
Skill process.Compared with pyrometallurgical smelting, while saving volume energy consumption, the organic efficiency of lead is greatly improved.
Claims (1)
1. the method that a circulation type wet method prepares high-purity PbO, it is characterised in that below the method step:
(1) waste lead acid battery is used lead plaster, stereotype grid, plastics and dilute sulfuric acid that conventional broken apart technique respectively obtains
Solution；
(2) the positive and negative electrode lead plaster powder after pulverizing carries out solid phase mixing, and then in air, heating carries out redox reaction and obtains
Containing lead oxide, lead sulfate, and PbO2Powder and the solid mixture of impurity；Reaction temperature, between 100～300 DEG C, is reacted
Time is 30～300 minutes.
(3) in the product that (2) process obtains, add reducing agent and make PbO2Powder is fully converted into PbO；Reducing agent is dioxygen
Water, sodium sulfite, sodium dithionate, sodium tetrathionate and ammonium sulfite, ammonium dithionate, tetrathionic acid ammonium, hydrazine hydrate or
HAS, the consumption of reducing agent is 0.2～0.5 times of lead plaster weight, and reaction temperature is 10～40 DEG C, the reaction time 10～120
Minute.
(4) solid mixture that (3) process obtains is dissolved in acylate and organic acid or the mixing of more than one acylates
In solution, obtain the mixed solution containing lead ion and undissolved impurity, and carry out filtering separation；Organic acid includes: acetic acid and
Tartaric acid, pyrovinic acid；Acylate is organic acid sodium salt, organic acid potassium salt, ammonium salt organic acid, organic acid lithium salts；Organic
Acid is 0.1～0.9 with the volume ratio of acylate or organic acid sodium and other acylates, and pH value is 4～7, and organic acid is with a kind of
The consumption of above acylate mixed solution is lead plaster weight 10～20 times；Solution temperature is 15～80 DEG C, and the stirring and dissolving time is
5～180 minutes.
(5) in the mixed solution that (4) process obtains, add the heavy lead agent desulfurization that cation is identical with acylate, obtain lead and sink
Lead thing and filtrate；Heavy lead agent includes: sodium citrate, ammonium citrate, sodium carbonate, ammonium carbonate, sodium oxalate, ammonium oxalate, fourth two
Oxime, tussol, ortho-aminobenzoic acid, thiocarbamide, quina pyridine acid, consumption is lead plaster weight 0.5～5 times of heavy lead agent, instead
Answering temperature is 10～40 DEG C, reaction time 10～120 minutes.
(6) the desulfurization lead sediment that (5) process obtains is dissolved in high alkali liquid, then obtains high-purity by dilution adjustment pH value precipitation
Lead hydroxide sediment, this sediment low-temperature sintering in atmosphere obtains high-purity PbO product；Alkali used be KOH,
NaOH and ammonium hydroxide, the concentration of alkali lye is 5～15mol/L；The consumption of alkali lye is lead plaster weight 5～20 times；Solution temperature is
15～80 DEG C, the stirring and dissolving time is 5～180 minutes；Dilution adjusts the pH value range of solution between 7～13；Lead hydroxide
Precipitation sintering is carried out in atmosphere, and reaction temperature is between 100～350 DEG C, and the time of heating was at 1～10 hour
(7) filtrate that (5) process obtains is carried out sub-cooled crystallization and obtains sodium sulfate byproduct, or add organic acid precipitated barium
Obtaining barium sulfate accessory substance, isolated acylate solution is re-used for the lead salt course of dissolution of (4).
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| CN108118155A (en) * | 2017-12-26 | 2018-06-05 | 广东工业大学 | A kind of method of discarded ickel-cadmium cell recycling |
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| CN108417866A (en) * | 2018-01-31 | 2018-08-17 | 浩发环保科技（深圳）有限公司 | A kind of reducing/regenerating method of pyrovinic acid lead electrolytic solution reducing/regenerating agent and pyrovinic acid lead electrolytic solution |
| CN108425019A (en) * | 2018-03-19 | 2018-08-21 | 贵州宏达环保科技有限公司 | A kind of method of the sulfuric acid lead skim recycling lead zinc-silver of alkaline leaching zinc abstraction |
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| CN113677812A (en) * | 2019-01-21 | 2021-11-19 | 奥勒留环保有限公司 | Recovery of lead-containing waste |
| CN110016570A (en) * | 2019-05-08 | 2019-07-16 | 北京科技大学 | A method of oxidation lead skim Central Plains position autoreduction, which is soaked, from ammonia efficiently mentions lead |
| CN110453077A (en) * | 2019-08-26 | 2019-11-15 | 湘潭大学 | A kind of method that scrap lead cream recycles |
| CN113088684A (en) * | 2021-03-18 | 2021-07-09 | 华中科技大学 | Method for preparing lead powder by wet recovery of waste lead paste with acid leaching circulation |
| CN113136492A (en) * | 2021-03-30 | 2021-07-20 | 广西大学 | Method for recovering lead from waste lead paste |
| CN113136492B (en) * | 2021-03-30 | 2023-03-10 | 广西大学 | Method for recovering lead from waste lead paste |
| CN113979470A (en) * | 2021-12-09 | 2022-01-28 | 安徽徽能化工科技有限公司 | Energy-conserving wet process yellow lead preparation equipment |
| CN113979470B (en) * | 2021-12-09 | 2024-03-05 | 安徽骏马新材料科技股份有限公司 | Energy-saving wet-process yellow lead preparation equipment |
| CN114990327A (en) * | 2022-05-18 | 2022-09-02 | 济源豫光有色冶金设计研究院有限公司 | Method for resource utilization of waste lead storage battery electrolyte |
| CN118028903A (en) * | 2024-04-11 | 2024-05-14 | 矿冶科技集团有限公司 | Method for preparing lead particles by two-stage suspension electrolysis of waste lead plaster |
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Application publication date: 20160824 |