CN105755290B - A kind of restoring method of waste lead acid battery lead cream - Google Patents
A kind of restoring method of waste lead acid battery lead cream Download PDFInfo
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- CN105755290B CN105755290B CN201610319271.2A CN201610319271A CN105755290B CN 105755290 B CN105755290 B CN 105755290B CN 201610319271 A CN201610319271 A CN 201610319271A CN 105755290 B CN105755290 B CN 105755290B
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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
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
- H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The present invention relates to a kind of restoring method of waste lead acid battery lead cream, including：By Na2S2O3、H2C2O4Or FeSO4The conversion fluid of a concentration of 0.2~1mol/l is configured to as reducing agent；After conversion fluid is heated to 20 DEG C~80 DEG C, adds in waste lead acid battery lead cream and react 30~90min, reaction liquid-solid ratio is 10~30ml/g；It treats to cool down after completion of the reaction, vacuum filter, rinse, you can.The present invention is by controlling the factors such as reaction time, reaction temperature, reductant concentration, liquid-solid ratio, it is determined that best technological parameter, the PbO in lead plaster2Can the overwhelming majority be reduced conversion, simple process and low cost has a good application prospect.
Description
Technical field
The invention belongs to lead-acid accumulator recycling field, more particularly to a kind of reduction of waste lead acid battery lead cream
Method.
Background technology
In recent years, climbing up and up with lead-acid accumulator consumption figure, learies also accordingly increase.China's plumbic acid at present
The consumption lead amount of accumulator occupies 70% of total value or so, but recycling waste lead batteries rate is less than 90%, and developed country is general
Ensure 100%；Lead recovery during China's secondary lead smelting is generally 80% or so, and Foreign Advanced Lerel is reachable
More than 98%.Therefore there are about 30,000 tons or so of waste lead accumulators in annual China to fail to be recycled utilization, simultaneously because the rate of recovery
The low lead and lead compound for leading to China every year there are about 4.5 ten thousand tons or so is flowed into air, soil and water body, is caused serious
The wasting of resources and environmental pollution.Therefore the research for carrying out pollution-free or light pollution lead regenerative process is directly related to China's plumbing
Development.
Simultaneously according to the literature, according to the reserve-production ratio for having verified lead ore resource at present, the enough exploitations of lead ore 25~30 years.
With the increasingly depleted of lead ore resource, the recycling and reuse of lead metal become realize plumbing sustainable development must be by
Road.Lead metal is mainly consumed in the production of accumulator at present, therefore the regenerative process of lead is mainly to lead-acid accumulator
In lead plaster slag mud carry out reduction conversion to obtain the process of lead and metal.The difficult point of the process is the smelting of lead plaster,
Method can be divided into pyrogenic process, wet method and dry and wet combination method at present.Pyrometallurgical smelting is low there is metal recovery rate, and high energy consumption and pollution are tight
Weight three major issues.Dry and wet combination method generally takes wet desulphurization, pyrometallurgical smelting, i.e., carries out cracking and sorting, comprehensive to waste lead accumulator
It closes recycling, lead plaster desulfurization conversion and then carries out melting with rotary kiln or reverberatory furnace.This purer pyrometallurgical smelting of method,
Significantly reduce SO2Discharge capacity, but later stage melting still employs high-temperature service, therefore lead dust can be caused dirty with can not avoiding
Dye.The wet-treating of waste lead accumulator can be divided into three classes：(1) lead plaster desulfurization conversion --- leaching --- electrodeposition method；(2) lead plaster is straight
Connect leaching --- electrodeposition method；(3) lead plaster direct electrowinning method.
The lead plaster that lead-acid accumulator obtains after cracking and sorting is the hybrid solid of lead-containing compounds, and main component is big
Cause be：PbSO425%~30%, PbO215%~20%, Pb 2%~3%.The desulfurization conversion of lead plaster is will be therein
PbSO4It is converted into the process for the other compound forms for being easier to reduction treatment.The technique mainly uses soluble carbonate salt at present
As desulfurizing agent, such as Na2CO3、NH4HCO3Deng.And desulfurizing agent mainly consumes the PbSO in lead plaster4Conversion on, in lead plaster
PbO2It is not involved in reacting with Pb.
During wet reclamation lead, PbO, Pb, PbSO in lead plaster4PbCO can be converted into3, H is used later2SiF4
Or HBF4Electrolyte is made in solution leaching, and PbO and Pb can also be leached directly.And the main component PbO in lead plaster2It cannot be direct
Conversion is leached, it is necessary to which being reduced into PbO or Pb could carry out, therefore PbO in lead plaster2Reduction process be wet reclamation lead
The important link of technique.
Invention content
The technical problems to be solved by the invention are to provide a kind of restoring method of waste lead acid battery lead cream, and this method is led to
Cross the factors such as control reaction time, reaction temperature, reductant concentration, liquid-solid ratio, it is determined that best technological parameter, in lead plaster
PbO2Can the overwhelming majority be reduced conversion, simple process and low cost has a good application prospect..
A kind of restoring method of waste lead acid battery lead cream of the present invention, including：
By Na2S2O3、H2C2O4Or FeSO4The conversion fluid of a concentration of 0.2~1mol/l is configured to as reducing agent；It will conversion
After liquid is heated to 20 DEG C~80 DEG C, adds in waste lead acid battery lead cream and react 30~90min, reaction liquid-solid ratio is 10~30ml/
g；It treats to cool down after completion of the reaction, vacuum filter, rinse, you can.
Preferably, the Na2S2O3As reducing agent, reaction condition is：Reaction liquid-solid ratio 30ml/g, 70 DEG C of reaction temperature,
Conversion fluid concentration 1mol/L, reaction time 90min.
Preferably, the H2C2O4As reducing agent, reaction condition is：Reaction liquid-solid ratio 30ml/g, 70 DEG C of reaction temperature,
Conversion fluid concentration 1mol/L, reaction time 90min.
Preferably, the FeSO4As reducing agent, reaction condition is：Reaction liquid-solid ratio 20ml/g, 50 DEG C of reaction temperature,
Conversion fluid concentration 0.6mol/L, reaction time 90min.
The FeSO4As reducing agent, addition and FeSO in conversion fluid4Molar ratio is 5:1 H2SO4。
The grain size of the waste lead acid battery lead cream is 125~180 μm, is decomposed by the spare DZM-10 types lead-acid accumulators of 6-
Pretreatment obtains afterwards.
The present invention is with Na2S2O3、H2C2O4、FeSO4Restore PbO in lead plaster2Reaction mechanism difference it is as follows：
PbO2+2Na2S2O3+H2O→PbO+Na2S2O3+2NaOH+2S；
3PbO2+H2C2O4→3PbO+H2O+2CO2↑+O2↑；
PbO2+2Fe2++SO4 2-+4H+→PbSO4+2Fe3++2H2O。
The analytical reagents Na of use2S2O3、H2C2O4、FeSO4、H2SO4Etc. originating from, Shanghai Chinese medicines group chemical reagent is limited
Company.
Advantageous effect
The present invention is by controlling the factors such as reaction time, reaction temperature, reductant concentration, liquid-solid ratio, it is determined that best
Technological parameter, the PbO in lead plaster2Can the overwhelming majority be reduced conversion, simple process and low cost, before there is good application
Scape.
Description of the drawings
Fig. 1 is influence of the reaction temperature of the present invention to lead plaster reduction efficiency；
Fig. 2 is influence of the reaction time of the invention to lead plaster reduction efficiency；
Fig. 3 is influence of the reductant concentration of the present invention to lead plaster reduction efficiency；
Fig. 4 is the influence that reaction solution of the present invention compares lead plaster reduction efficiency admittedly；
Fig. 5 is lead plaster of the present invention reduction conversion index sign trend.
Specific embodiment
With reference to specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
By Na2S2O3、H2C2O4Or FeSO4Conversion fluid (the FeSO of a concentration of 0.2~1mol/l is configured to as reducing agent4Turn
Change in liquid and contain H2SO4(fixed molar ratio n H2SO4：n FeSO4=5：1))；Conversion fluid is heated to 20 DEG C with water bath with thermostatic control bed
After~80 DEG C, add in waste lead acid battery lead cream and react 30~90min, reaction liquid-solid ratio is 10~30ml/g；Treat that reaction finishes
Postcooling, with ceramic crucible vacuum filter, and it is multiple to rinse with distilled water filter residue repeatedly.It takes filter residue and drying, grinding and uniformly
Sample is dissolved in the mixed liquor of sodium acetate and acetic acid.KI solution is added in later to there is the generation of free state iodine, using starch as indicator,
Na2S2O3Solution titrates, and measures after reduction PbO in lead plaster sample2Content, computational methods are as follows：
n(PbO2)=0.5*c (S2O3 2-)*V(S2O3 2-)
In formula：c(S2O3 2-) it is Na2S2O3Solution concentration, V (S2O3 2-) to titrate consumed Na2S2O3Liquor capacity.It is logical
Cross PbO before and after detection lead plaster restores2Changes of contents, being converted into reduction rate H, H expression formula is：
H=[1- (w2/w1)] * 100%
In formula：w1、w2Wherein PbO before and after lead plaster reduction converts is corresponded to respectively2Content of material, %.
Embodiment 2
Lead plaster restores experiment of single factor result and analysis
Respectively with Na2S2O3、H2C2O4、FeSO4As reducing agent, control condition changes for single-factor, each changed factor
5 kinds of levels are taken, 2 experiments are done under each level, are averaged interpretation of result.
1. influence of the temperature to reduction efficiency
Condition control is reaction time 60min, reductant concentration 0.6mol/L, liquid-solid ratio 20ml/g, studies different temperatures
Influence to lead plaster reduction efficiency.Experimental result is as shown in Figure 1.
As seen from Figure 1, for three kinds of reducing agents, the variation of caused reduction efficiency value is to differ due to temperature change
It causes.For Na2S2O3, the increase and the promotion of reduction efficiency value of temperature are substantially in a linear relationship, during by 20 DEG C
43.05% is gradually promoted to 77.63% at 80 DEG C；For H2C2O4, when temperature is below 50 DEG C, reduction efficiency is from 20 DEG C
When 55.72% it is rapid when being promoted to 50 DEG C 79.57%, when temperature surpasses 50 DEG C, reduction efficiency only rises to 80 from 79.57%
DEG C when 86.91%, variation it is no longer notable；For FeSO4, excessively high temperature can reduce PbO in lead plaster instead2Reduction efficiency,
When temperature is below 50 DEG C, reduction efficiency from 20 DEG C when 48.01% be promoted to 50 DEG C when maximum value 77.12%, Zhi Housui
The raising of temperature, reduction efficiency from 77.12% drop to 80 DEG C when 46.58%, reason may be because of reaction product
PbSO4Viscosity at relatively high temperatures is larger, thus increases inside diffusional resistance, leads to the agglomerating and viscous wall of solid occur in experiment
Phenomenon, reduction reaction are obstructed, and efficiency declines.Therefore under this experiment condition, the corresponding reaction temperature of three kinds of reducing agent reduction lead plasters
It is controllable to：Na2S2O3 80℃、H2C2O4And FeSO4 50℃。
2. influence of the reaction time to reduction efficiency
Condition control is 50 DEG C, reductant concentration 0.6mol/L, liquid-solid ratio 20ml/g of reaction temperature, studies the reaction time pair
The influence of lead plaster reduction efficiency.The results are shown in Figure 2.
From Figure 2 it can be seen that with the increase in reaction time, three kinds of reducing agents are to PbO in lead plaster2Reduction efficiency can be on
It rises.For Na2S2O3, reduction efficiency from 30min when 42.78% be gradually promoted to 90min when maximum value 72.87%；For
H2C2O4And FeSO4, when reacted between in below 60min, reduction efficiency respectively from 30min when it is 57.44%, 46.25% fast
Speed is promoted to 79.57%, 77.12%, if the time is more than 60min, reduction efficiency only increases to 90min from 79.57%, 77.12%
When 88.65%, 74.98%, impact effect is no longer notable.Therefore in lead plaster reduction process, the corresponding reaction of three kinds of reducing agents
Time is controllable to：Na2S2O3 90min、H2C2O4And FeSO4 60min。
Influence of 3 reductant concentrations to reduction efficiency
Condition control is 50 DEG C, reaction time 60min, liquid-solid ratio 20ml/g of reaction temperature, and research reductant concentration is to lead
The influence of cream reduction efficiency.The results are shown in Figure 3.
As seen from Figure 3, for three kinds of reducing agents, due to changing for reduction efficiency value caused by the variation of reductant concentration
It is also inconsistent to become.For Na2S2O3, the increase and the promotion of reduction efficiency value of reductant concentration are substantially in a linear relationship,
42.42% during by 0.2mol/L is gradually promoted to 75.93% during 1mol/L；For H2C2O4, when reductant concentration exists
During below 0.6mol/L, reduction efficiency from 0.2mol/L when 54.58% it is rapid be promoted to 0.6mol/L when 79.57%, when
Reductant concentration surpasses 0.6mol/L, and 87.89% when reduction efficiency only rises to 1mol/L from 79.57%, no significant changes；It is right
In FeSO4, excessively high reductant concentration can reduce PbO in lead plaster instead2Reduction efficiency, concentration in below 0.6mol/L, also
Former efficiency from 0.2mol/L when 51.01% be promoted to 0.6mol/L when maximum value 77.12%, later with the liter of temperature
Height, reduction efficiency from 77.12% drop to 1mol/L when 59.09%, reason may be the FeSO because of high concentration4In solution
In easily occur electrochemical reaction generation colloidal solid shape substance, cause react solid occur agglomerating and wall sticking phenomenon, increase in
Diffusional resistance hinders the progress of reduction reaction, reduces reduction efficiency.Therefore in lead plaster reduction process, three kinds of reducing agents are dense
Degree is controllable to：Na2S2O3 1mol/L、H2C2O4And FeSO4 0.6mol/L。
4. reaction solution compares the influence of reduction efficiency admittedly
Condition control is 50 DEG C, reaction time 60min, reductant concentration 0.6mol/L of reaction temperature, and research reaction solution is consolidated
Compare the influence of lead plaster reduction efficiency.Experimental result is as shown in Figure 4.
From fig. 4, it can be seen that with the increase of reaction liquid-solid ratio, three kinds of reducing agents are to PbO in lead plaster2The influence of reduction efficiency has
Institute's difference.For Na2S2O3, reduction efficiency from 10ml/g when 36.44% be gradually promoted to 30ml/g when maximum value
75.34%；For H2C2O4And FeSO4, when react liquid-solid ratio in below 20ml/g when, reduction efficiency respectively from 10ml/g when
55.26%th, 44.22% 79.57%, 77.12% is promoted to rapidly, if liquid-solid ratio is more than 20ml/g, H2C2O4And FeSO4Also
Former efficiency respectively can it is slowly varying to 30ml/g when 81.36%, 63.16%, impact effect is not notable.Therefore lead plaster reduction
In the process, the corresponding reaction liquid-solid ratio of three kinds of reducing agents is controllable to：Na2S2O3 30ml/g、H2C2O4And FeSO4 20ml/g。
Lead plaster restores Orthogonal experiment results and analysis
1. Orthogonal Experiment and Design
Na is used respectively2S2O3、H2C2O4、FeSO4As reducing agent, using orthogonal experiment method research reaction temperature, reaction
Time, reductant concentration, reaction 4 factors of liquid-solid ratio are to PbO in lead plaster2The influence of reduction efficiency.Orthogonal experiment factor level
Table is shown in Table 1, according to four factors, three water-glass L9(34) tested.
The orthogonal experiment factor and level of 1 lead plaster of table reduction
②Na2S2O3Method restores lead plaster experimental study
With Na2S2O3As reducing agent to lead plaster carry out reduction conversion experimental result and each factor in different level item
Mean reduction efficiency and very poor calculated value under part are shown in Table 2.
Table 2Na2S2O3The experimental result of method reduction lead plaster and analysis
According to very poor size, it is known that with Na2S2O3Restore the PbO in lead plaster2, each governing factor is on reduction efficiency influence journey
The reduction of degree be ranked sequentially for：React liquid-solid ratio>Reaction temperature>Reductant concentration>Reaction time.
According to the height of factor average horizontal value each in experimental result, as can be seen from the table, reciprocation is not being considered
In the case of, with Na2S2O3The PbO in lead plaster is restored as reducing agent2, the preferred embodiment under this experiment condition should be：Reaction solution is consolidated
Than 30ml/g, 70 DEG C, reductant concentration 1mol/L, reaction time 90min of reaction temperature.It is carried out according to this preferred embodiment condition real
It tests, the desulfurization conversion rate for obtaining lead plaster is 76.87%, higher than the best desulfurization results 68.74% of orthogonal test.
③H2C2O4Method restores lead plaster experimental study
With H2C2O4As reducing agent to lead plaster carry out reduction conversion experimental result and each factor in different level condition
Under mean reduction efficiency and very poor calculated value be shown in Table 3：
Table 3H2C2O4The experimental result of method reduction lead plaster and analysis
According to very poor size, it is known that with H2C2O4Restore the PbO in lead plaster2, each governing factor is to reduction efficiency influence degree
Reduction be ranked sequentially for：Reaction temperature>Reductant concentration>Reaction time>React liquid-solid ratio.In the reaction process, have big
The water generation of amount, therefore liquid-solid ratio can constantly change during the reaction, but the progress of reaction is had no effect on, so liquid-solid ratio
Influence to reduction efficiency is little.
According to the height of factor average horizontal value each in experimental result, as can be seen from the table, reciprocation is not being considered
In the case of, with H2C2O4The PbO in lead plaster is restored as reducing agent2, the preferred embodiment under this experiment condition should be：Reaction temperature
70 DEG C, reductant concentration 1mol/L, reaction time 90min, reaction liquid-solid ratio 30ml/g.It is carried out according to this preferred embodiment condition real
It tests, the desulfurization conversion rate for obtaining lead plaster is 94.46%, higher than the best desulfurization results 92.81% of orthogonal test.
④FeSO4Method restores lead plaster experimental study
With FeSO4As reducing agent to lead plaster carry out reduction conversion experimental result and each factor in different level condition
Under mean reduction efficiency and very poor calculated value be shown in Table 4：
Table 4FeSO4The experimental result of method reduction lead plaster and analysis
According to very poor size, it is known that with FeSO4Restore the PbO in lead plaster2, each governing factor is to reduction efficiency influence degree
Reduction be ranked sequentially for：React liquid-solid ratio>Reaction time>Reductant concentration>Reaction temperature.
According to the height of factor average horizontal value each in experimental result, as can be seen from the table, reciprocation is not being considered
In the case of, with FeSO4The PbO in lead plaster is restored as reducing agent2, the preferred embodiment under this experiment condition should be：React liquid-solid ratio
20ml/g, reaction time 90min, reductant concentration 0.6mol/L, 50 DEG C of reaction temperature.It is carried out according to this preferred embodiment condition real
It tests, the desulfurization conversion rate for obtaining lead plaster is 86.73%, higher than the best desulfurization results 75.22% of orthogonal test.
5. lead plaster reduction conversion index trend comparative analysis figure
The average value of lead plaster reduction efficiency as ordinate is drawn using each reducing agent under the conditions of respective governing factor respectively and is rolled over
It is as shown in Figure 5 to restore index sign trend for line chart.
As seen from Figure 5, Na2S2O3、H2C2O4、FeSO4When corresponding to 70 DEG C, 70 DEG C, 50 DEG C of reaction temperature respectively, to lead plaster also
Former rate reaches maximum value, because of Na after 50 DEG C2S2O3Reduction efficiency promotes unobvious, therefore with Na2S2O3When making reducing agent
Reaction temperature is kept for 50 DEG C.Similarly, the concentration of three kinds of reducing agents should be 0.6mol/L, 1.0mol/L, 0.6mol/L.When anti-
When being 90min between seasonable, the reduction efficiency of three kinds of reducing agents reaches maximum value simultaneously.Na2S2O3With FeSO4Liquid-solid ratio difference
30ml/g, 20ml/g are should be, for H2C2O4For, because having H during reduction lead plaster2O is continuously generated, the shadow of liquid-solid ratio
Sound is not notable, and initial value takes 10ml/g.
Conclusion：
(1) with Na2S2O3The preferred embodiment control condition for carrying out reduction conversion to lead plaster as reducing agent should be：Reaction solution
Gu than 30ml/g, 70 DEG C, reductant concentration 1mol/L, reaction time 90min of reaction temperature.Under the conditions of this scheme, in lead plaster
PbO2Reduction efficiency up to 76.87%.
(2) with H2C2O4The preferred embodiment control condition for carrying out reduction conversion to lead plaster as reducing agent should be：Reaction temperature
70 DEG C, reductant concentration 1mol/L, reaction time 90min, reaction liquid-solid ratio 30ml/g.Under the conditions of this scheme, PbO in lead plaster2
Reduction efficiency 92.81%.
(3) with FeSO4The preferred embodiment control condition for carrying out reduction conversion to lead plaster as reducing agent should be：Reaction solution is consolidated
Than 20ml/g, reaction time 90min, reductant concentration 0.6mol/L, 50 DEG C of reaction temperature.Under the conditions of this scheme, in lead plaster
PbO2Reduction efficiency 86.73%.
(4) among tendency chart can be seen that three kinds of reducing agents, H2C2O4To PbO in lead plaster2Reducing power generally
It is better than FeSO4And Na2S2O3, by reducing power power be arranged in order for：H2C2O4﹥ FeSO4﹥ Na2S2O3。
Claims (2)
1. a kind of restoring method of waste lead acid battery lead cream, including：
By Na2S2O3The conversion fluid of a concentration of 1mol/l is configured to as reducing agent；After conversion fluid is heated to 70 DEG C, add in useless
Lead-acid accumulator lead plaster reacts 90min, and reaction liquid-solid ratio is 30ml/g；It treats to cool down after completion of the reaction, vacuum filter, rinse, i.e.,
It can.
2. a kind of restoring method of waste lead acid battery lead cream according to claim 1, it is characterised in that：The scrap lead acid
The grain size of accumulator lead plaster is 125~180 μm.
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| CN1105784A (en) * | 1994-01-22 | 1995-07-26 | 湖南大学 | Reducing and conversion method for waste lead accumulator dregs |
| CN101514395B (en) * | 2009-03-31 | 2010-11-10 | 大连物华天宝科技发展有限公司 | Method for recovering lead oxide by waste lead-acid storage battery |
| CN101608264A (en) * | 2009-06-30 | 2009-12-23 | 张天任 | A kind of waste lead recovering method for lead-acid storage batteries |
| CN101899576A (en) * | 2010-04-30 | 2010-12-01 | 浙江汇同电源有限公司 | Method for recycling lead from lead-acid battery paste |
| JP2012036498A (en) * | 2010-07-14 | 2012-02-23 | Jx Nippon Mining & Metals Corp | Method for manufacturing iridium |
| CN102206750A (en) * | 2011-05-04 | 2011-10-05 | 中南大学 | Method for recovering lead from lead-containing material by matching leaching-electrowinning method |
| CN103374657A (en) * | 2012-04-24 | 2013-10-30 | 湖北金洋冶金股份有限公司 | Ultrafine lead oxide prepared by using waste lead plaster and preparation method thereof |
| CN103045853B (en) * | 2013-01-15 | 2014-08-13 | 浙江汇同电源有限公司 | Process for recovering lead from lead-acid battery paste |
| CN104141045B (en) * | 2014-08-20 | 2017-04-12 | 北京化工大学 | Method for recovering lead oxide from waste lead plaster |
| CN104393364B (en) * | 2014-11-13 | 2017-07-14 | 张家港智电芳华蓄电研究所有限公司 | A kind of method for preparing PbO from the direct wet method of waste lead acid battery |
| CN105177297B (en) * | 2015-10-16 | 2017-08-01 | 沈阳有色金属研究院 | The method that lead-acid accumulator cream mud is leached using raw material redox characteristic |
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2016
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