CN102306856A - Method for recycling waste lead storage battery - Google Patents

Method for recycling waste lead storage battery Download PDF

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Publication number
CN102306856A
CN102306856A CN201110241191A CN201110241191A CN102306856A CN 102306856 A CN102306856 A CN 102306856A CN 201110241191 A CN201110241191 A CN 201110241191A CN 201110241191 A CN201110241191 A CN 201110241191A CN 102306856 A CN102306856 A CN 102306856A
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lead
waste
plaster
solution
filtrating
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刘悉承
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TONGLIANG INTEGRITY ELECTRODE PLATES PLANT
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TONGLIANG INTEGRITY ELECTRODE PLATES PLANT
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Priority to CN201110241191A priority Critical patent/CN102306856A/en
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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
    • 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 invention discloses a method for recycling a waste lead storage battery. The method comprises the following steps of: cutting, crushing and separating the waste lead storage battery to separate waste electrolyte, plastics, lead nails, lead pigs and lead plaster; precipitating and filtering the waste electrolyte to obtain a concentrated sulfuric acid; melting the lead nails and the lead pigs at low temperature, adding antimony, tin and selenium into melt to obtain a lead-based alloy; and preparing yellow lead or red lead directly from the lead plaster at low temperature, and preparing plastic grains from the plastics.

Description

The recoverying and utilizing method of waste and old lead accumulator
Technical field
The present invention relates to a kind of recoverying and utilizing method of waste and old lead accumulator.
Background technology
China's reviver industry is under the condition of paying attention to environmental protection and comprehensive utilization of resources policy requirements, progressively to grow up.Along with developing rapidly of China's automobile, communication and chemical industry, the requirement of lead is improved constantly, the reviver industry has become and has realized the indispensable important component part of lead metal industrial sustainable development strategy.
Lead is again the metal that is harmful to environment and health simultaneously, and various scrap leads all can become the pollutant sources of environment if do not reclaim.Especially scrap battery has only abundant recycling, just can avoid wherein lead plaster and sulfate pollution environment.It is thus clear that, be the protection environment, the sustainable development of the plumbous row industry of assurance must develop the reviver industry, makes lead metal get into the optimum consumption of producing---consumption---regeneration, and this is a long-range strategic issue.
The reviver raw material is mainly from waste and old lead acid accumulator.Lead accumulator can not be replaced by other batteries in a short time on a large scale.Along with technological progresses such as advanced lead acid accumulator and superbatteries, the application in new-energy automobile fields such as plumbic acid hybrid power has more tangible cost advantage.
(data that information centre of the Ministry of Public Security announces) according to statistics: by the end of the end of the year 2010; China's vehicle guaranteeding organic quantity has reached 1.99 hundred million at present; Wherein automobile is more than 8,500 ten thousand, and more than 2,000 ten thousand on annual newly-increased motor vehicle is wherein increasing with 8,000,000 speed in automobile every year.1.2 hundred million of the present electric bicycle recoverable amounts of China. and annual scale with 2,000 ten thousand is increasing.It is two to three years that automobile uses lead acid accumulator normal useful life, and the useful life of electric bicycle lead accumulator is shorter.Rough calculation is got off, and China is annual approximately to produce 670,000 tons automobile with the waste and old lead accumulator of electric vehicle of used and scrapped battery and 900,000 tons.If consider the quantity of scrapping of industries such as motorcycle, agricultural vehicle, communication, boats and ships, ups power, total amount can be more in the storage battery of scrapping in year.Relevant statistics shows that at present, the total lead of the lead acid accumulator that China scraps in year is above 1,500,000 tons.
2010,1,300,000 tons of the reviver output of China accounted for 32% of plumbous total output.The prosperity of car industry and electric motor car industry maybe will cause the large quantities of replacings from lead acid accumulator in 2012; The deputy secretary-general Cao Guoqing of China Battery Industry Association expects 2015; Lead acid accumulator will reach 24,000 ten thousand kVAh., balanced growth 16.7%, and consumption of lead will reach 420 ten thousand-470 ten thousand tons.
Go up both at home and abroad at present reclaim plumbous technology be elder generation with the lead accumulator cracking and sorting, isolate plastics, lead plaster, lead nail and lead, the main component of lead plaster is PbSO 4, PbO, PbO 2,, make the PbSO in the lead plaster through the conversion process of lead plaster 4Be converted into PbCO 3PbCO 3Theoretical decomposition temperature is 315 ℃, catabolite PbO.Become metal Pb with in smelting furnace, adding carbon reduction after lead plaster after transforming and the mixing of lead nail lead, the lead that obtains with reduction is produced other products again.The mass content of lead sulfate reaches 40%-80% in the lead plaster.At present with the PbSO in the lead plaster 4The technology that is converted into ceruse does; Carbonate or acid carbonate are converted into ceruse with PbSO4; When transforming; In carbonate or acid carbonate, add various additives; But its conversion ratio still has only 85%-90%; This just causes in reduction, still has little amounts of Pb SO owing to transform in the lead plaster of back 4Exist,, on the one hand, still need add a large amount of metal iron filings in the reduction production process and could reduce PbSO so temperature still can not be lower than 1000 ℃ in the general stove 4The PbS that generates after the thermal decomposition; On the other hand, because the most of material that transforms in the lead plaster of back is PbCO 3, PbO, PbO 2This part material is in the time of 800 ℃; It has been molten condition; And temperature is more than 1000 ℃ in the tower; This must cause the big situation of big, the plumbous volatile quantity of melting energy consumption, and this part volatile quantity is no less than 5% of total amount of metal, melting, reinforced, stir, and the process of blowing in the lead that volatilizees all be scattered in the reviver enterprise ambient air with gaseous form; Existing bell-type cloth bag dust collect plant is difficult to collect, thereby causes serious lead contamination.Cause serious injury to environment and workman healthy.Therefore this technology can be described as complex procedures, and energy consumption is high, and pollutes heavy.
The current recovery method to electrolyte is a neutralisation treatment in the present domestic reviver enterprise, sulfur waste acid get into disintegrating machine together with sorting water together neutralize, press filtration gets into the cracking and sorting system once more after purification of waste water.Reviver enterprise in when the waste acid water because two alkaline process are generally taked in the restriction of cost, i.e. lime mixings NaOH is handled, and the sulfate in the waste water had both contained calcium sulfate, sodium sulphate, lead sulfate in addition simultaneously.This just causes the composition complicacy of sulfate finally big in the waste water treatment difficulty, and cost is high.
Based on the above defective of existing technology, seek the recoverying and utilizing method of a kind of unleaded steam contamination, waste and old lead accumulator that energy consumption is low, become the new problem of research in the present industry.
Summary of the invention
The object of the invention just is to provide the recoverying and utilizing method of a kind of environmental protection, waste and old lead accumulator that energy consumption is low.
For achieving the above object, technical scheme of the present invention is: a kind of recoverying and utilizing method of waste and old lead accumulator: it is characterized in that: accomplish according to following steps:
(1), waste and old lead accumulator is through machine cuts, cracking and sorting, tells waste electrolyte, plastics, lead nail lead and lead plaster;
(2), waste electrolyte is through sedimentation and filtration, filter residue mixes with lead plaster, filtrating is adopted the non-volatile solution concentration method of vapor-liquid separation type to handle and is obtained the concentrated sulfuric acid;
(3), the lead nail lead after 300-400 ℃ of thawing, remove floating impurity on the liquation, detect the content of antimony in the liquation and tin then, in liquation, add antimony, tin and selenium more as required and make lead-containing alloy;
(4), the lead plaster of separating being crushed to particle diameter is the 160-200 order; Lead plaster after pulverizing is added saturated NH 4HCO 3In the solution, stirring reaction 1-2h makes that the lead sulfate in the lead plaster is converted into ceruse, stops reaction; Suction filtration, filter cake cleans to neutral with distilled water, obtains wet article, then the article of wetting is put into baking oven, under 150 ℃ of conditions, dries, and obtains sample; Add NH in the filtrating 4HCO 3Be used for the processing of next group lead plaster after extremely saturated; Sample is heated to 250-320 ℃, and insulation 1-1.5h makes brown lead oxide be decomposed into lead oxide fully, and then sample is heated to 320-450 ℃, and insulation 3-4h is decomposed into lead oxide fully with wherein ceruse, promptly obtains yellow lead;
Adopt technique scheme; At first; The present invention need not add any additive in carbonate or acid carbonate; Through control to the lead plaster particle diameter; The control in ammonium bicarbonate soln concentration and reaction time makes conversion ratio can reach 99.49%-99.6%, and the lead sulfate in the lead plaster is converted into ceruse fully.Secondly; The present invention is with lead nail lead separate processes; Do not adopt the method for smelting reducing to reclaim plumbous; But directly under cryogenic conditions, lead plaster is prepared into yellow lead; The molecular formula of yellow lead is PbO, can be used as pigment, metallurgical cosolvent, paint drier, thiofide, pesticide and lead accumulator etc.Because the temperature of reaction is low, in course of reaction, almost there is not lead steam to pollute, energy consumption is low, in whole process of preparation, does not also have the discharging of waste residue, waste water and gas, and is very friendly to environment.Once more; The present invention is melted the lead nail lead under cryogenic conditions; Remove impurity, add antimony, tin and selenium then and process lead-containing alloy, directly be used for the production of lead accumulator; Processing step is simple; The course of processing time spent is short, and energy consumption is low, and using rate of metal is high; And, therefore almost there is not the pollution of lead steam owing to be fusing under cryogenic conditions yet.At last, the present invention reclaims electrolyte and processes concentrated sulfuric acid utilization, and cost recovery is low, has improved resource utilization, and makes with acid content in the sorting water seldom, deals with also than being easier to, to environment ten minutes close friend.
Waste lead accumulator is broken again through machine cuts, can also effectively avoid impurity to get into lead plaster, finally improves product purity.
The equation of above-mentioned each step of reaction is:
PbSO 4+2NH 4HCO 3=PbCO 3+(NH 4) 2SO 4+CO 2+H 2O
2PbO 2=?2PbO?+O 2
PbCO 3=?PbO+CO 2
In technique scheme, the yellow lead that makes is heated to 450-500 ℃ of oxidation obtains red lead.Red lead has another name called red lead, plumbous red, molecular formula Pb 30 4, be the crystalline powder of reddish orange, red lead is as rust inhibitor, and with the lacquer that it is made into, adhesive force is very strong, and suitable stability is arranged in atmosphere.So the bridge of iron and steel, ship, machine pipeline all are coated with red lead primer.Also be used for storage battery, glass, system mirror etc.Do not have waste residue, waste water, exhaust gas discharging in same this process yet, do not have the pollution of lead steam.
The equation of above-mentioned reaction is:
6PbO+O 2=?2Pb 3O 4?
In technique scheme, said waste or used plastics is processed plastic pellet through fragmentation.
In technique scheme, after recycling through 4 times, the filtrating in the said step (4) is used for preparation (NH 4) 2SO 4, its preparation technology is:
(a), in said filtrating, add activated carbon, at 100 ℃ of decolouring 30min down, simultaneously can be with minor N H in the filtrating 4HCO 3Remove, filter;
(b), filtrating 100 ℃, distill under stirring, up to obtaining (NH 4) 2SO 4Supersaturated solution, mixing speed are 300-400rpm;
(c), stop heating, turn down mixing speed, film just do not occur to liquid level of solution and be advisable, after treating to begin in the solution crystallization to occur, the control mixing speed is at 50-80 rpm, after solution was cooled to room temperature, growing the grain 2h filtered, drying obtains (NH 4) 2SO 4Reacted Ammonium bicarbonate food grade solution recovery is used to prepare ammonium sulfate product, and ammonium sulfate can be used for making fertilizer etc., has both made material be fully utilized, and has reduced the pollution to environment again.
In technique scheme, the washing fluid power that washing leaching cake is used in the step (4) is recycled 5 times, adds carbonic hydroammonium then therein and is made into the carbonic hydroammonium saturated solution, is used for lead plaster lead sulfate is converted into ceruse; Filtrate cycle in the said step (4) is used until the conversion ratio that detects lead sulfate less than 99%.Cleaning solution is recycled 5 times, not only can not influenced the content of sulfate in the filter cake, also washings are used to prepare the carbonic hydroammonium saturated solution at last, reduce the discharging of waste water.Conversion fluid (unsaturated carbonate hydrogen ammonium salt solution) is recycling in addition, do not make that the content of ammonium hydrogen sulfate increases in the conversion fluid, thereby energy consumption is low in the process of reclaim sulfuric acid hydrogen ammonium.
The invention has the beneficial effects as follows:
(1) conversion process of lead plaster of the present invention is simple, and conversion ratio is high.
(2) the present invention is with lead plaster and lead nail lead separate processes; Do not adopt the mode of pyrolytic semlting; Directly the lead nail lead is converted into lead-containing alloy at low temperatures; Lead plaster is converted into yellow lead or red lead; Technology is simple; Energy consumption is low, and whole process all carries out at a lower temperature, does not therefore almost have the pollution of lead steam.
(3) the present invention makes full use of conversion fluid and cleaning solution; Reduce discharge of wastewater; The present invention recycles conversion fluid; Making does not almost have waste residue, waste water, exhaust gas discharging in the whole production process of the present invention; Very friendly to environment; And the ammonium sulfate that makes can directly be used as chemical fertilizer, also can be used for making composite fertilizer, potassium sulfate, ammonium chloride, ammonium persulfate etc., in food, weaving, leather, pharmaceuticals industry certain purposes is arranged also.
(4), the present invention reclaims electrolyte, avoided its pollution to environment on the one hand, makes also that on the other hand resource is fully utilized.
Embodiment
Embodiment 1
(1) gets waste and old lead accumulator (100 kg) through machine cuts, cracking and sorting, tell waste electrolyte, plastics, lead nail lead and lead plaster; Above-mentioned steps is collected waste electrolyte 12kg altogether; Plastics 7kg; Lead nail lead 34.2kg; Wherein the lead nail lead is mainly from battery grid, pole and the connecting plate of lead accumulator; Waste and old lead plaster 46.8kg; Its main component is lead sulfate, lead oxide and brown lead oxide, and wherein the mass content of lead sulfate is 77%.
(2) waste electrolyte obtains filter residue 0.12kg through sedimentation and filtration, and this filter residue is mixed with lead plaster, and it is 98% concentrated sulfuric acid 6.08kg that filtrating adopts the non-volatile solution concentration method of vapor-liquid separation type to handle to obtain concentration; The concrete processing step of its preparation is: the dilute sulfuric acid that will give up is squeezed into the circulation concentration tower by storage tank with acid-proof pump and is concentrated into water content less than 2%; After the heat exchanger heating, getting into mist device and diffuser then forces atomizing and further forces vaporization; Gas after the separation gets into gas purifier after the height demist, purify the back discharging.Acid solution after the separation is got back to the circulation concentration tower once again, after circulation repeatedly concentrates distillation, reaches concentration requirement, squeezes into concentrated sulfuric acid storage tank with pump.The concentrated sulfuric acid can be used as the storage battery factory and utilizes.
(3), the lead nail lead is after 340-400 ℃ of thawing; Remove floating impurity on the liquation; Detect wherein that the content of antimony, tin is respectively 1.7% and 0.13%, under this temperature, do not contained selenium: in liquation, add selenium 0.01kg, tin 0.006kg, antimony 0.06kg then and make lead-containing alloy 33.77kg.
(4), the lead plaster of separating being crushed to particle diameter is the 160-200 order; Lead plaster after pulverizing is added by 19.57kg NH 4HCO 3In the saturated solution that (carbonic hydroammonium excessive 4%) is made into, stirring reaction 1h makes that the lead sulfate in the lead plaster is converted into ceruse, is 99.6% through detecting the conversion ratio of finding lead sulfate, and reaction equation is:
PbSO 4+?2NH 4HCO 3? →?PbCO 3＋（NH 4） 2SO 4＋CO 2↑＋H 2O
Stop reaction; Suction filtration, filter cake cleans to neutral with 113.8kg distilled water, obtains wet article, then the article of wetting is put into baking oven, and baking is 2 hours under 150 ℃ of conditions, obtains sample; Add NH in the filtrating 4HCO 3After saturated, obtain secondary carbonic hydroammonium saturated solution; Secondary carbonic hydroammonium saturated solution is used for the processing of next group lead plaster; Cleaning solution collects and obtains secondary washing liquid; Washing leaching cake when being used for the processing of next group lead plaster; This batch cleaning solution can be used for cleaning filter cake altogether 5 times; And can not influence the content of sulfate in the filter cake, be used to dispose unsaturated carbonate hydrogen ammonium salt solution then;
Sample after the oven dry is heated to 250 ℃, insulation 1h, the brown lead oxide in the lead plaster is decomposed into lead oxide fully at this moment, and reaction equation is:
2PbO 2=?2PbO?+O 2
And then sample is heated to 320 ℃, the ceruse among the insulation 3h, this moment lead plaster is decomposed into lead oxide fully, then sample is crushed to 200 orders, promptly obtains yellow lead; Reaction equation is:
PbCO 3=?PbO+CO 2
Through two sections intensification roastings, the lead plaster main component is PbCO 3, PbO 2All be decomposed into PbO, and PbO has neither part nor lot in reaction, thereby obtain high-purity yellow lead product 36.76kg.
Yellow lead 36.76kg is heated to 450 ℃ again, kept 4 hours, PbO is oxidized to Pb 3O 4, its reaction equation is:
6PbO+O 2=?2Pb 3O 4
Sample is crushed to 200 orders, promptly gets red lead 37.6kg.
Through the intensification roasting, the further oxidation of yellow lead generates lightweight, porous, high-intensity red lead product.
(5), waste or used plastics, process plastic pellet through fragmentation.
(6) be used for preparation (NH after the filtrating in the step (4) is recycled through 4 times 4) 2SO 4, its preparation technology is:
(a), in above-mentioned filtrating, add the 5kg activated carbon, at 100 ℃ of decolouring 30min down, simultaneously can be with minor N H in the filtrating 4HCO 3Remove, filter; If the amount of filtrating surpasses 0.5 times of desulfurization lead plaster not, i.e. 23.4kg then will filtrate once more through adding thermal crystalline, be not 0.5 times of desulfurization lead plaster, i.e. 23.4kg until the amount of filtrating
(b), filtrating 100 ℃, distill under stirring, up to obtaining (NH 4) 2SO 4Supersaturated solution, have small amount of solid state material in the solution this moment, and mixing speed is 300-400rpm;
(c), stop heating, turn down mixing speed, film just do not occur to liquid level of solution and be advisable, after treating to begin in the solution crystallization to occur, the control mixing speed is at 50-80 rpm, after solution was cooled to room temperature, growing the grain 2h filtered, drying obtains (NH 4) 2SO 416.3kg.
Embodiment 2
(1) gets waste and old lead accumulator (100 kg) through machine cuts, cracking and sorting, tell waste electrolyte, plastics, lead nail lead and lead plaster; Above-mentioned steps is collected waste electrolyte 13.8kg altogether; Plastics 6.5kg; Lead nail lead 33.5kg; Wherein the lead nail lead is mainly from battery grid, pole and the connecting plate of lead accumulator; Waste and old lead plaster 46.2kg; Its main component is lead sulfate, lead oxide and brown lead oxide, and wherein the mass content of lead sulfate is 77%.
(2) waste electrolyte obtains filter residue 0.2kg through sedimentation and filtration, and this filter residue is mixed with lead plaster, and it is 98% concentrated sulfuric acid 6.2kg that filtrating adopts the non-volatile solution concentration method of vapor-liquid separation type to handle to obtain concentration; The concrete processing step of its preparation is: the dilute sulfuric acid that will give up is squeezed into the circulation concentration tower by storage tank with acid-proof pump and is concentrated into water content less than 2%; After the heat exchanger heating, getting into mist device and diffuser then forces atomizing and further forces vaporization; Gas after the separation gets into gas purifier after the height demist, purify the back discharging.Acid solution after the separation is got back to the circulation concentration tower once again, after circulation repeatedly concentrates distillation, reaches concentration requirement, squeezes into concentrated sulfuric acid storage tank with pump.The concentrated sulfuric acid can be used as the storage battery factory and utilizes.
(3), the lead nail lead is after 340-400 ℃ of thawing; Remove floating impurity on the liquation; Detect wherein that the content of antimony, tin is respectively 1.56% and 0.126%, under this kind temperature, do not contained selenium: in liquation, add selenium 0.01kg, tin 0.0078kg, antimony 0.11kg then and make lead-containing alloy 32.5kg.
(4), the lead plaster of separating being crushed to particle diameter is the 160-200 order; Lead plaster after pulverizing is added in the secondary carbonic hydroammonium saturated solution that obtains among the embodiment 1, and stirring reaction 1.5h makes that the lead sulfate in the lead plaster is converted into ceruse, is 99.58% through the conversion ratio that detects lead sulfate, and reaction equation is:
PbSO 4+?2NH 4HCO 3? →?PbCO 3＋（NH 4） 2SO 4＋CO 2↑＋H 2O
Stop reaction; Suction filtration, filter cake cleans to neutral with the secondary washing liquid among the embodiment 1, obtains wet article, does not increase through the content that detects sulfate in the wet article.Then the article of wetting are put into baking oven, baking is 2.5 hours under 150 ℃ of conditions, obtains sample; Continue to add carbonic hydroammonium in the filtrating to the saturated processing that obtains three times the carbonic hydroammonium saturated solution is used for the next group lead plaster, cleaning solution collects and obtains cleaning solution three times, washing leaching cake when continuing on for next lead plaster and handling.
Sample after the oven dry is heated to 320 ℃, insulation 1.5h, the brown lead oxide in the lead plaster is decomposed into lead oxide fully at this moment, and reaction equation is:
2PbO 2=?2PbO?+O 2
And then sample is heated to 450 ℃, the ceruse among the insulation 4h, this moment lead plaster is decomposed into lead oxide fully, then sample is crushed to 200 orders, promptly obtains yellow lead; Reaction equation is:
PbCO 3=?PbO+CO 2
Through two sections intensification roastings, the lead plaster main component is PbCO 3, PbO 2All be decomposed into PbO, and PbO has neither part nor lot in reaction, thereby obtain high-purity yellow lead product 36kg.
Yellow lead 36kg is heated to 500 ℃ again, kept 4 hours, PbO is oxidized to Pb 3O 4, its reaction equation is:
6PbO+O 2=?2Pb 3O 4
Sample is crushed to 200 orders, promptly gets red lead 36.8kg.
Through the intensification roasting, the further oxidation of yellow lead generates lightweight, porous, high-intensity red lead product.
(5), waste or used plastics, process plastic pellet through fragmentation.
(6) be used for preparation (NH after the filtrating in the step (4) is recycled through 4 times 4) 2SO 4, its preparation technology is:
(a), in above-mentioned filtrating, add the 5kg activated carbon, at 100 ℃ of decolouring 30min down, simultaneously can be with minor N H in the filtrating 4HCO 3Remove, filter; If the amount of filtrating surpasses 0.5 times of desulfurization lead plaster not, i.e. 23.1kg then will filtrate once more through adding thermal crystalline, be not 0.5 times of desulfurization lead plaster, i.e. 23.1kg until the amount of filtrating.
(b), filtrating 100 ℃, distill under stirring, up to obtaining (NH 4) 2SO 4Supersaturated solution, have small amount of solid state material in the solution this moment, and mixing speed is 300-400rpm;
(c), stop heating, turn down mixing speed, film just do not occur to liquid level of solution and be advisable, after treating to begin in the solution crystallization to occur, the control mixing speed is at 50-80 rpm, after solution was cooled to room temperature, growing the grain 2h filtered, drying obtains (NH 4) 2SO 416 kg.
Embodiment 3
1, get waste and old lead accumulator (100 kg) through machine cuts, cracking and sorting, obtain lead plaster 46.8kg, its main component is lead sulfate, lead oxide and brown lead oxide, and wherein the mass content of lead sulfate is 77%.
2, the lead plaster of separating being crushed to particle diameter is the 160-200 order; Lead plaster after pulverizing is added by 19.57kg NH 4HCO 3In the saturated solution that (carbonic hydroammonium excessive 4%) is made into, stirring reaction 1h makes that the lead sulfate in the lead plaster is converted into ceruse, is 99.6% through detecting the conversion ratio of finding lead sulfate, and reaction equation is:
PbSO 4+?2NH 4HCO 3? →?PbCO 3＋（NH 4） 2SO 4＋CO 2↑＋H 2O
Stop reaction; Suction filtration, filter cake cleans to neutral with 113.8kg distilled water, obtains wet article, then the article of wetting is put into baking oven, and baking is 2 hours under 150 ℃ of conditions, obtains sample; Add NH in the filtrating 4HCO 3After saturated, obtain secondary carbonic hydroammonium saturated solution; Secondary carbonic hydroammonium saturated solution is used for the processing of next group lead plaster; Cleaning solution collects and obtains secondary washing liquid; Washing leaching cake when being used for the processing of next group lead plaster; This batch cleaning solution can be used for cleaning filter cake altogether 5 times; And can not influence the content of sulfate in the filter cake, be used to dispose unsaturated carbonate hydrogen ammonium salt solution then;
Sample after the oven dry is heated to 290 ℃, insulation 1h, the brown lead oxide in the lead plaster is decomposed into lead oxide fully at this moment, and reaction equation is:
2PbO 2=?2PbO?+O 2
Sample after will decomposing for the first time then is heated to 380 ℃, insulation 3h, and the ceruse in the lead plaster is decomposed into lead oxide fully at this moment, then sample is crushed to 200 orders, promptly obtains yellow lead; Reaction equation is:
PbCO 3=?PbO+CO 2
Through two sections intensification roastings, the lead plaster main component is PbCO 3, PbO 2All be decomposed into PbO, and PbO has neither part nor lot in reaction, thereby obtain high-purity yellow lead product 36.76kg.
Yellow lead 36.76kg is heated to 480 ℃ again, kept 4 hours, PbO is oxidized to Pb 3O 4, its reaction equation is:
6PbO+O 2=?2Pb 3O 4
Sample is crushed to 200 orders, promptly gets red lead 37.6kg.
Through the intensification roasting, the further oxidation of yellow lead generates lightweight, porous, high-intensity red lead product.
3, be used for preparation (NH after the filtrating in the step 2 is recycled through 4 times 4) 2SO 4, its preparation technology is:
(a), in above-mentioned filtrating, add the 5kg activated carbon, at 100 ℃ of decolouring 30min down, simultaneously can be with minor N H in the filtrating 4HCO 3Remove, filter; If the amount of filtrating surpasses 0.5 times of desulfurization lead plaster not, i.e. 23.4kg then will filtrate once more through adding thermal crystalline, be not 0.5 times of desulfurization lead plaster, i.e. 23.4kg until the amount of filtrating
(b), filtrating 100 ℃, distill under stirring, up to obtaining (NH 4) 2SO 4Supersaturated solution, have small amount of solid state material in the solution this moment, and mixing speed is 300-400rpm;
(c), stop heating, turn down mixing speed, film just do not occur to liquid level of solution and be advisable, after treating to begin in the solution crystallization to occur, the control mixing speed is at 50-80 rpm, after solution was cooled to room temperature, growing the grain 2h filtered, drying obtains (NH 4) 2SO 416.3kg.
Embodiment 4
Other steps are identical with enforcement 2, and just three the carbonic hydroammonium saturated solutions of conversion fluid for obtaining at embodiment 2 in the step (4) transform after the conversion ratio of detection lead sulfate is 99.56%.Cleaning solution in the step 4 is three cleaning solutions collecting among the embodiment 2, and washing is after detect the content of sulfate in the wet article and do not increase.Obtain high-purity yellow lead product 35.8kg at last.. same, continue in the filtrating to add carbonic hydroammonium to the saturated carbonic hydroammonium saturated solution that obtains four times, continue on for the processing of next group lead plaster.Cleaning solution still collects and obtains cleaning solution four times, when being used for handling lead plaster next time as cleaning solution.
Embodiment 5
Other steps with implement 2 identically, four the carbonic hydroammonium saturated solutions of conversion fluid in embodiment 3, obtaining in the step (4) just transform after to detect its conversion ratio be 99.54%.Cleaning solution in the step 4 is four cleaning solutions collecting among the embodiment 3, and washing is after detect the content of sulfate in the wet article and do not increase.Obtain high-purity yellow lead product 35.65kg at last.Continue to add carbonic hydroammonium to the saturated carbonic hydroammonium saturated solution that makes five times in the filtrating.Cleaning solution still collects and obtains cleaning solution five times, when being used for handling lead plaster next time as cleaning solution.
Embodiment 6
Other steps with implement 2 identically, five the carbonic hydroammonium saturated solutions of conversion fluid in embodiment 4, obtaining in the step (4) just transform after to detect its conversion ratio be 99.49%.Cleaning solution in the step 4 is the cleaning solution of collecting among the embodiment 4, and washing is after detect the content of sulfate in the wet article and do not increase.Obtain high-purity yellow lead product 35.58kg at last.The cleaning solution collection is used to prepare unsaturated carbonate hydrogen ammonium salt solution.Continue to add carbonic hydroammonium to the saturated carbonic hydroammonium saturated solution that obtains six times in the filtrating.
Embodiment 7
Other steps with implement 1 identically, just the conversion fluid in the step (4) is to use the unsaturated carbonate hydrogen ammonium salt solution that is mixed with through the cleaning solution after 5 washings, transforms after detect, the conversion ratio of lead sulfate is 99.58%.Obtain high-purity yellow lead product 36.69kg at last.
Embodiment 8
Other steps with implement 5 identically, six the carbonic hydroammonium saturated solutions of conversion fluid in embodiment 5, obtaining in the step (4) just transform after to detect its conversion ratio be 92.8%.Cleaning solution in the step 4 is through the cleaning solution after 5 washings, finds that after testing the content of sulfate increases in the filter cake.Therefore six carbonic hydroammonium saturated solutions can not be used for the conversion of lead plaster, and the cleaning solution after 5 washings also no longer is suitable for washing leaching cake.
The present invention is not limited to embodiment, and is different according to the content of lead sulfate in the lead plaster, and the recycling number of times of filtrating is different.Content like lead sulfate in the lead plaster of secondary unsaturated carbonate hydrogen ammonium processing only has 40%, and this batch conversion fluid (unsaturated carbonate hydrogen ammonium salt solution) can will increase by recycling number of times so.As long as the conversion ratio that detects lead sulfate less than 99%, does not just re-use this batch conversion fluid.

Claims (6)

1. the recoverying and utilizing method of a waste and old lead accumulator is characterized in that, accomplishes according to following steps:
(1), waste and old lead accumulator is through machine cuts, cracking and sorting, tells waste electrolyte, plastics, lead nail lead and lead plaster;
(2), waste electrolyte is through sedimentation and filtration, filter residue mixes with lead plaster, filtrating is adopted the non-volatile solution of vapor-liquid separation type Concentration methodHandle and obtain the concentrated sulfuric acid;
(3), the lead nail lead after 300-400 ℃ of fusing, remove floating impurity on the liquation, detect the content of antimony in the liquation and tin then, in liquation, add antimony, tin and selenium more as required and make lead-containing alloy;
(4), the lead plaster of separating further being crushed to particle diameter is the 160-200 order; Lead plaster after pulverizing is added saturated NH 4HCO 3In the solution, stirring reaction 1-2h makes that the lead sulfate in the lead plaster is converted into ceruse, stops reaction; Suction filtration, filter cake cleans to neutral with distilled water, obtains wet article, under 150 ℃ of conditions, dries then, obtains sample; Add NH in the filtrating 4HCO 3Be used for the processing of next group lead plaster after extremely saturated; Sample is heated to 250-320 ℃, and insulation 1-1.5h makes brown lead oxide be decomposed into lead oxide fully, and then sample is heated to 320-450 ℃, and insulation 3-4h is decomposed into lead oxide fully with wherein ceruse, promptly obtains yellow lead.
2. according to the recoverying and utilizing method of the said waste and old lead accumulator of claim 1, it is characterized in that: the yellow lead that makes in the step (4) is heated to 450-500 ℃, and insulation 4-5h obtains red lead with the yellow lead complete oxidation.
3. according to the recoverying and utilizing method of the said waste and old lead accumulator of claim 1, it is characterized in that: said waste or used plastics is processed plastic pellet through fragmentation.
4. according to the recoverying and utilizing method of the said waste and old lead accumulator of claim 1, it is characterized in that: be used for preparation (NH after the filtrating in the said step (4) is recycled through 4 times 4) 2SO 4, its preparation technology is:
(a), in said filtrating, add activated carbon, at 100 ℃ of decolouring 30min down, simultaneously can be with minor N H in the filtrating 4HCO 3Remove, filter;
(b), filtrating 100 ℃, distill under stirring, up to obtaining (NH 4) 2SO 4Supersaturated solution, mixing speed are 300-400rpm;
(c), stop heating, turn down mixing speed, film do not occur to liquid level of solution and be advisable, after treating to begin in the solution crystallization to occur, the control mixing speed is at 50-80 rpm, after solution was cooled to room temperature, growing the grain 2h filtered, drying obtains (NH 4) 2SO 4
5. according to the recoverying and utilizing method of the said waste and old lead accumulator of claim 1; It is characterized in that: the washing fluid power that washing leaching cake is used in the said step (4) is recycled 5 times; Add carbonic hydroammonium then therein and be made into the carbonic hydroammonium saturated solution, be used for lead plaster lead sulfate is converted into ceruse.
6. according to the recoverying and utilizing method of the said waste and old lead accumulator of claim 1, it is characterized in that: the filtrate cycle in the said step (4) is used until the conversion ratio that detects lead sulfate less than 99%.
CN201110241191A 2011-08-22 2011-08-22 Method for recycling waste lead storage battery Pending CN102306856A (en)

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Application publication date: 20120104