CN105950870B - A kind of method of waste lead acid battery lead cream hydro-thermal deep conversion desulfurization - Google Patents

A kind of method of waste lead acid battery lead cream hydro-thermal deep conversion desulfurization Download PDF

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CN105950870B
CN105950870B CN201610501218.4A CN201610501218A CN105950870B CN 105950870 B CN105950870 B CN 105950870B CN 201610501218 A CN201610501218 A CN 201610501218A CN 105950870 B CN105950870 B CN 105950870B
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lead
desulfurization
cream
conversion
scrap
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CN105950870A (en
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刘伟锋
邓循博
傅新欣
朱鹏春
饶帅
杨天足
张杜超
陈霖
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Central South University
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Central South University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006Wet processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00Obtaining lead
    • C22B13/04Obtaining lead by wet processes
    • C22B13/045Recovery from waste materials
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

A kind of method of waste lead acid battery lead cream hydro-thermal deep conversion desulfurization, scrap lead cream is added in autoclave after being mixed with aqueous slkali, reacted in the case where requiring temperature and nitrogen partial pressure, lead sulfate is set to react removing sulfate radical completely with alkali, reach separation of solid and liquid after the reaction time, desulfurization conversion liquid reclaims sodium sulphate, and desulfurization conversion slag further extracts lead.The present invention enhances scrap lead cream alkalescence conversion sweetening process using hydro-thermal mode, realize the complete removing of sulfate radical in scrap lead cream, the consumption of alkali is only 1.0~1.05 times of theoretical amount, and desulfurization degree reaches more than 99.0%, and advantage is created for conversion slag subsequent extracted lead.

Description

A kind of method of waste lead acid battery lead cream hydro-thermal deep conversion desulfurization
Technical field
The present invention relates to hydrometallurgy process in nonferrous metallurgy field, particularly waste lead acid battery lead cream hydro-thermal depth to turn Change the Wet-process metallurgy method of desulfurization.
Background technology
Lead is silvery white heavy non-ferrous metal, is primarily used to manufacture alloy based on its special physicochemical properties, wherein Lead-acid accumulator is most important consumer field, and it accounts for more than the 80.0% of global total lead consumption.Although lead-acid accumulator weight Energy ratio is less than MH-Ni batteries and Li-ion batteries, but because its is cost-effective, technology maturation and the advantages that have a safety feature, Be widely used in the every field of national economy, lead-acid accumulator usage amount account for the 70.0% of the global secondary cell market share with On.The fast development of Domestic Automotive Industry in recent years have stimulated the rapid development of lead-acid accumulator industry, and China has become generation Maximum lead-acid accumulator manufacturing nation, country of consumption and exported country in boundary, a large amount of uses of lead-acid accumulator will certainly produce quite The lead-acid accumulator of quantity so that waste and old lead acid accumulator has changed into most important lead regenerated resources(The scrap lead such as Dai Shaozhen Acid accumulator recovery technology present situation [J] World Nonferrous Metals, 2015,9,15-17.).Had according to State Statistics Bureau and China Non-ferrous metal TIA data, Chinese refined lead yield in 2014 reach 421.8 ten thousand tons, and wherein reviver yield is 160.0 ten thousand Ton, accounts for the 37.9% of annual lead yield, and has further increased trend.
The recycling process of lead-acid accumulator is separately recovered again after typically first disassembling(Height is pretty to wait waste and old lead acids to store Battery crushing separation system research and discussion [J] batteries, 2013,50 (1), 3-7), disassembling product has four kinds, when Waste electrolyte, composition are sulfuric acid solution, generally send wastewater treatment;Second, grid, main component is lead-antimony alloy, is generally melted again Cast alloy;Third, plastics, generally return to plastics producer and re-use;Fourth, scrap lead cream, main component is lead sulfate and lead oxygen Compound, it is generally used for refining leady raw materialses, the weight of these four products accounts for 10-20%, 20-30%, 10- of battery gross weight respectively 15% and 35-50%.The composition of scrap lead cream is because cell production companies are different and scrap degree difference, each component content ripple It is dynamic, respectively PbSO4(40-60%)、PbO2(25-35%), PbO (5-10%) and Pb (1-5%) and a small amount of Sb (0.5%).
Due to containing substantial amounts of lead sulfate and a variety of oxides of lead in scrap lead cream, intractability is big, becomes useless The bottleneck that lead-acid accumulator recycles.The processing of scrap lead cream is divided into thermal process and wet processing, and both techniques are generally all Using cathode lead as target product, cut both ways, wherein thermal process is applied widely.
Thermal process is that scrap lead cream obtains lead bullion by reduction melting, then electrorefining output cathode lead, is had individually molten Refining and the class of mixed smelting two.Independent method of smelting includes directly or indirectly two ways(Before the lead-acid accumulators such as Li Weifeng again The raw state of the art and progress [J] China YouSes are metallurgical, and 2011, (6): 53-57.), directly individually smelting process refers to scrap lead cream The directly reduction melting in the smelting furnaces such as reverberatory furnace, blast furnace, rotary furnace, bottom convertor and side-blown converter, after melting flue gas is scrubbed Discharge, there is the advantages of flow is short and obtain extensive use, but melting high energy consumption, high-temperature lead dust harzard and smoke pollution be present The shortcomings of difficulty of governance is big, it is due in scrap lead cream caused by the presence of lead sulfate to generally believe this.In order to overcome this shortcoming, grind Study carefully personnel and propose independent method of smelting indirectly([J] batteries are studied in the comparative analysis of the scrap lead cream smelting processes such as Wu Guanglong, 2015,152(5): 209-211.), i.e. scrap lead cream is single again using preprocess method removing sulfate radical, intermediate product before melting Only reduction melting output lead bullion, the shortcomings that this method seems to overcome direct independent method of smelting, but preprocessing process is often The halfway problem of desulfurization be present.Mixed smelting method is by melting after scrap lead cream and lead concentrate collocation, utilizes the change of lead concentrate Reaction heat is learned, makes both synchronous melting output lead bullion.This method is applied widely in primary lead smeltery, is solved on surface Requirement of the scrap lead cream fusion process to temperature and treating tail gas, but the low high-grade lead plaster of impurity content mixed with lead concentrate Melting is closed, the lead bullion of output is of poor quality, adds the difficulty of purification, in addition, the supplying of lead plaster causes primary lead smelting system stove Condition deteriorates and the increase of waste acid yield.
The shortcomings that in order to overcome thermal process to handle, researcher develop the wet processing process of scrap lead cream, i.e. scrap lead Cream by electrodeposition output cathode lead after Solid phase electrolysis or wet dissolution, mainly include Solid phase electrolysis technique, leaching-electrodeposition process and Conversion-the class of leaching-electrodeposition process three(Progress [J] modernizations of the waste lead acid battery lead plaster recovery technologies such as Yang Jiakuan Work, 2009,29 (3): 32-37.).Solid phase electrolysis technique is scrap lead cream to be coated on minus plate and in alkaline system barrier film It is electrolysed output cathode lead.Leaching-electrodeposition process is that scrap lead cream is leached into simultaneously electrodeposition output cathode lead, the direct leaching process of scrap lead cream Usually using reagents such as acetic acid, sodium hydroxide, ammonium salt, chloride and the alkaline organics that complex can be formed with lead.Conversion-leaching Go out-electrodeposition process be then scrap lead cream conversion desulfurization after again through leaching and electrodeposition output cathode lead, the technique focus on scrap lead cream in Extraction efficiency and solution regeneration of lead etc., so leaching with electrodeposition generally in HBF4Or H2SiF6System is carried out, but different works Skill is slightly different to conversion sweetening process.Classical RSR techniques are then with the sulfate radical in ammonium carbonate strip scrap lead cream and make it Ceruse is converted into, then with the brown lead oxide in sodium sulfite and sulphur dioxide reduction lead plaster, conversion slag HBF4Or H2SiF6 Leach, containing the last electrodeposition output cathode lead of lead solution.It is and the CX- as reducing agent using lead powder that USBM techniques are slightly distinguishing EW techniques then use sodium carbonate as desulfurizing agent and hydrogen peroxide as reducing agent.EX-EWS techniques are then with bacterium by the lead in lead plaster Compound is converted into PbS, and PbS fluoboric acid high iron solution Oxidation Leachings, leachate is in cathode chamber electrodeposition cathode lead, anode chamber's reality The regeneration of existing fluoboric acid high iron solution.Wet processing solves the problems, such as that thermal process is present well, but there are still examination Agent consumes the shortcomings that big and high energy consumption, especially electrolytic deposition process and is difficult to suppress anode PbO2Precipitation so that lead recovery is low.
The difficult point that detailed comparisons' scrap lead cream handling process can be seen that thermal process how is treated in fusion process PbSO4Resolution problem, the difficult point of wet processing is then how to make PbSO4Conversion desulfurization completely, the solution of the two problems are all By the preprocessing process for converting desulfurization.The purpose of scrap lead cream conversion sweetening process is removing scrap lead cream PbSO4Sulfate radical and make It is converted into ceruse or lead hydroxide, and the transforming agent that desulfurization conversion process uses mainly has Na2CO3、K2CO3、(NH4)2CO3、 NH4HCO3, NaOH and KOH etc., the removal efficiency of sulfate radical only 85-95% in usual practical operation, desulfurization is not thorough and reduction efficiency The low application effect for having had a strong impact on this method, researcher, which proposes to strengthen using means such as hypergravity, ball milling and ultrasonic waves, to be turned Change sweetening process(Current situation [J] the Beijing University of Chemical Technology journal of the such as Pan Junqing lead-acid accumulators recovery lead technology, 2014, 41(3): 1-14.), but still not reaching intended effect, main cause is probably lead-acid accumulator in discharge process grid The non-conductive sulfuric acid leading crystal of upper precipitation, it is difficult and reagent reacting in routine transformation sweetening process.So using which kind of method energy It is then the key of scrap lead cream processing to realize conversion desulfurization completely.
Country had put into effect more in succession for the recovery system and treatment technology of further specification lead-acid accumulator in recent years For individual file to ensure the normal development of lead-acid accumulator recovery, especially Ministry of Industry and Information in 2012 combines what is formulated with Chinese Ministry of Environmental Protection《Again Bullion lead industry access condition》, production scale, technique and equipment etc. are proposed and are distinctly claimed, " lead plaster sub-elected must be entered Row desulfurization pretreatment send concentrate of lead sulfide ore smeltery merging treatment, and desulphurization mother solution must be handled and reclaim by-product Product ..., reviver enterprise must not direct smelting zone shell waste lead accumulator, crucible melting reviver must not be utilized, should be used close Advanced technologies and the equipment such as melting, low temperature continuous smelting, novel energy-saving environment-friendly smelting furnace are closed, and is produced under condition of negative pressure, is prevented Only waste gas escapes." these files formulation, effectively advance reviver industry standard health development, improve the utilization of resources Rate and energy-conserving and environment-protective are horizontal.
The content of the invention
In order to overcome the shortcomings of traditional scrap lead cream conversion sulfur method, the present invention provides a kind of deep using hydro-thermal schedule of reinforcement Sulfate radical in degree conversion removing scrap lead cream, and alkali consumption is low and the small Wet-process metallurgy method of environmental pollution.
It is to reach above-mentioned purpose the technical solution adopted by the present invention:It is anti-that scrap lead cream is added to high pressure after being mixed with aqueous slkali Answer in kettle, reacted in the case where requiring temperature and nitrogen partial pressure, lead sulfate is reacted removing sulfate radical completely with alkali, reach reaction Separation of solid and liquid after time, desulfurization conversion liquid recovery sodium sulphate, desulfurization conversion slag further extract lead.The essence of the technical program is Scrap lead cream alkalescence conversion sweetening process is enhanced using hydro-thermal mode, the complete removing of sulfate radical in scrap lead cream is realized, for conversion Slag subsequent extracted lead creates advantage.
Specific technical process and parameter are as follows:
Scrap lead cream presses liquid-solid ratio(The ratio between liquid volume and solid weight, L/Kg)Add water slurry at 1~3: 1, while adds useless Solid base of the lead plaster weight than 0.15~0.40 times, mixed serum is added in stainless steel autoclave, starts stirring simultaneously It is 100~200r/min to control rotating speed, is passed through nitrogen into reactor, 0.2~0.5MPa of control nitrogen partial pressure ventilations 1~ 5min, temperature is then raised to 100~200 DEG C, 0.5~1.0MPa of control nitrogen partial pressure reacts 1~5h, and cooling drop is completed in reaction When low temperature is to 60~80 DEG C, solid-liquor separation, desulfurization conversion liquid recovery sodium sulphate, desulfurization conversion are realized using vacuum filtration mode Slag further extracts lead.The main chemical reactions that hydro-thermal deep conversion sweetening process occurs are as follows:
(1)
(2)
The alkali that the present invention uses is one or both of sodium carbonate and sodium hydroxide.
The present invention disassembles the scrap lead cream product suitable for processing lead-acid accumulator, and its main component is with percentage by weight It is calculated as(%):Pb50.0~75.0%, S4.0~6.5%, Sb0.1~0.5% and H2O5.0~10.0%.It also is adapted for handling sulfur acid The solid material of lead.
It is of the invention compared with traditional scrap lead cream conversion desulfuration processing method, have the advantage that:1st, the present invention uses hydro-thermal Mode enhances scrap lead cream alkalescence conversion sweetening process, realizes the complete removing of sulfate radical in scrap lead cream, desulfurization degree reaches 99.0% More than;2nd, the present invention uses hydro-thermal schedule of reinforcement, not only increases desulfurization degree, and reduces the consumption of alkali, the consumption of alkali Only 1.0~1.05 times of theoretical amount;3rd, the present invention has technical process simple to operate, technical indicator stabilization, labor intensity The small advantage such as low with production cost.
Brief description of the drawings
Fig. 1:Present invention process schematic flow sheet.
Embodiment
Embodiment 1:
Lead-acid accumulator disassembles the scrap lead cream in product, and its main component is by weight percentage(%): Pb73.80%, S5.25% and Sb0.15%, sodium carbonate are AR.2000g scrap lead cream and 356g sodium carbonate are added simultaneously The pulp into 4000ml water, then mixed serum be added in stainless steel autoclave, mixing speed is maintained at 120r/ Min, control nitrogen partial pressure 0.3MPa ventilation 2min, then raises temperature to 160 DEG C, control nitrogen partial pressure 0.8MPa reaction 3h, When reaction completes cooling and reduces temperature to 65 DEG C, solid-liquor separation is realized using vacuum filtration mode, sulfur content in desulfurization conversion slag 0.02% is reduced to, desulfurization degree reaches 99.40%.
Embodiment 2:
Lead-acid accumulator disassembles the scrap lead cream in product, and its main component scope is by weight percentage(%): Pb73.80%, S5.25% and Sb0.15%, sodium hydroxide are AR.By 2000g scrap lead cream and 268g sodium hydroxides simultaneously Pulp in 4000ml water is added to, then mixed serum is added in stainless steel autoclave, is maintained at mixing speed 120r/min, control nitrogen partial pressure 0.3MPa ventilation 2min, then raises temperature to 180 DEG C, control nitrogen partial pressure 0.8MPa is anti- Answer 3h, when reaction completes cooling and reduces temperature to 70 DEG C, solid-liquor separation is realized using vacuum filtration mode, sulphur in desulfurization conversion slag Content is reduced to 0.01%, and desulfurization degree reaches 99.38%.

Claims (3)

  1. A kind of 1. method of waste lead acid battery lead cream hydro-thermal deep conversion desulfurization, it is characterised in that:Scrap lead cream adds water slurry, presses Water volume L and scrap lead cream weight kg liquid-solid ratio is 1~3: 1, while adds solid of the scrap lead cream weight than 0.15~0.40 times Alkali, mixed serum is added in autoclave, it is 100~200r/min to start stirring and control rotating speed, into reactor Nitrogen is passed through, control nitrogen partial pressure 0.2~0.5MPa, 1~5min of ventilation, temperature is then raised to 150~200 DEG C, controls nitrogen 0.5~1.0MPa of partial pressure reacts 1~5h, and cooling is completed in reaction reduces temperature to 60~80 DEG C, then real using vacuum filtration mode Existing solid-liquor separation, desulfurization conversion liquid recovery sodium sulphate, desulfurization conversion slag further extract lead.
  2. 2. the method for waste lead acid battery lead cream hydro-thermal deep conversion desulfurization as claimed in claim 1, it is characterised in that described Solid base be one or both of sodium carbonate and sodium hydroxide.
  3. 3. the method for waste lead acid battery lead cream hydro-thermal deep conversion desulfurization as claimed in claim 1, it is characterised in that:It is described The main component of scrap lead cream be by weight percentage:The and of Pb50.0~75.0%, S4.0~6.5%, Sb0.1~0.5% H2O5.0~10.0%.
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CN106498167B (en) * 2016-10-31 2018-08-03 湘潭大学 A kind of intensified by ultrasonic wave ammonium hydrogen carbonate is the diachylon desulphurization method of desulfurizing agent
CN106676270B (en) * 2017-01-05 2018-07-31 中南大学 A method of Whote-wet method extracts lead from lead plaster and concentrate of lead sulfide ore
GB2582248A (en) * 2019-01-21 2020-09-23 Aurelius Env Ltd Recycling of lead-containing waste

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US3689253A (en) * 1970-08-27 1972-09-05 Minerals Technology Corp Reclaiming lead from storage batteries
US3883348A (en) * 1973-09-06 1975-05-13 R S R Corp Process for the removal of sulfur from battery wrecker material using ammonium carbonate solution
US4269810A (en) * 1978-10-10 1981-05-26 Nl Industries, Inc. Method for desulfation of battery mud
CN101956214B (en) * 2010-09-30 2012-05-09 北京化工大学 Method for recycling secondary lead by electrolyzing alkaline leaded solution
US8715615B2 (en) * 2011-07-06 2014-05-06 Retriev Technologies Incorporated Recovery of high purity lead oxide from lead acid battery paste
CN102367577B (en) * 2011-09-30 2014-08-06 北京化工大学 Method for preparing Na2[Pb(OH)4] solution and method for recycling lead from lead-containing waste
CN103146923B (en) * 2013-03-15 2015-02-04 北京化工大学 Method for producing lead oxide by recovering waste lead-acid batteries based on atom economy way

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