CN102306855A - Method for recycling lead plaster from waste lead storage battery - Google Patents

Method for recycling lead plaster from waste lead storage battery Download PDF

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Publication number
CN102306855A
CN102306855A CN201110241182A CN201110241182A CN102306855A CN 102306855 A CN102306855 A CN 102306855A CN 201110241182 A CN201110241182 A CN 201110241182A CN 201110241182 A CN201110241182 A CN 201110241182A CN 102306855 A CN102306855 A CN 102306855A
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lead
plaster
solution
lead plaster
waste
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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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    • 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

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Abstract

The invention discloses a method for recycling lead plaster from a waste lead storage battery. The method is implemented by the following steps of: (1) crushing the lead plaster separated from the waste lead storage battery into particle sizes of 160 to 220 meshes; (2) adding the crushed lead plaster into saturated solution of NH4HCO3, reacting the lead plaster with the solution of NH4HCO3 under stirring to convert lead sulfate in the lead plaster into lead carbonate, and stopping reaction; (3) performing suction filtration, washing a filter cake to be neutral by using distilled water to obtain a wet product, placing the wet product into a drying oven for drying under the condition of 150 DEG C to obtain a sample, and adding NH4HCO3 into filtrate until the mixed solution is saturated for the treatment of lead plaster of the next batch; and (4) heating the sample obtained by the step (3) to 250 to 350 DEG C, preserving heat for 1 to 1.5h to completely dissolve lead dioxide into lead oxide, heating the sample to 350 to 450 DEG C, and preserving the heat for 3 to 4h to completely dissolve the lead carbonate to obtain yellow lead.

Description

The recoverying and utilizing method of lead plaster in the waste and old lead accumulator
Technical field
The present invention relates to a kind of recovery method of waste and old lead accumulator, the special recoverying and utilizing method that relates to lead plaster in a kind of waste and old lead accumulator fully.
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.
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.Lead plaster after transforming and lead nail and lead mixed then in smelting furnace, add carbon reduction and become metal Pb.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; Lead plaster and 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 PbCO3, PbO, PbO 2This part material is in the time of 800 ℃; It has been molten condition; This must cause the big situation of big, the plumbous volatile quantity of melting energy consumption; 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 gaseous form in the reviver enterprise ambient air, 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.
Summary of the invention
The object of the invention just is to provide the recoverying and utilizing method of lead plaster in the low waste and old lead accumulator of a kind of environmental protection, energy consumption.
For achieving the above object, technical scheme of the present invention is: the recoverying and utilizing method of lead plaster in a kind of waste and old lead accumulator: accomplish as follows:
(1), to be crushed to particle diameter be the 160-200 order to the lead plaster that will from waste and old lead accumulator, separate;
(2), the lead plaster after will pulverizing adds 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;
(3), 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;
(4), the sample that obtains in the step (3) be heated to 250-320 ℃ make brown lead oxide be decomposed into lead oxide, and then sample is heated to 320-450 ℃ ceruse wherein is decomposed into lead oxide, promptly obtain 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; It is plumbous that the present invention does not adopt the method for smelting reducing to reclaim; But directly under cryogenic conditions, lead plaster being 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.
The equation of above-mentioned 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 304, 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, after recycling through 4 times, the filtrating in the said step (3) is used for preparation (NH 4) 2SO 4, its preparation technology is:
(a), in said filtrating, add activated carbon, at 100 ℃ of 30min that decolour down, minor N H in will filtrating simultaneously 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 4Reacted Ammonium bicarbonate food grade solution recovery is used to prepare ammonium sulfate, and ammonium sulfate can be used for making fertilizer etc., has both made material be fully utilized, and reduces the pollution to environment again.
In technique scheme, the washing fluid power that washing leaching cake is used in the said step (3) 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.Cleaning solution is recycling, not only can not influence the content of sulfate in the filter cake, also washings is used to prepare the carbonic hydroammonium saturated solution at last, reduces the discharging of waste water.
Filtrate cycle in the said step (3) is used until the conversion ratio that detects lead sulfate less than 99%.Conversion fluid (unsaturated carbonate hydrogen ammonium salt solution) is recycling in addition, not only can not influence the conversion ratio of lead sulfate, make that on the contrary 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 adopts the lead plaster after not smelting mode is handled conversion, and technology is simple, energy consumption is low, and 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; And conversion fluid is recycled; 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., certain purposes is also arranged in food, weaving, leather, pharmaceuticals industry.
Embodiment
Embodiment 1
1, get waste and old lead accumulator (100 kg) through cutting, 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 in the saturated solution that is made into by 19.57kg NH4HCO3 (carbonic hydroammonium excessive 4%), and 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.
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 2
1, get waste and old lead accumulator (100 kg) through cutting, cracking and sorting, obtain 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, 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.
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. 23.1kg 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 cutting, 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 in the saturated solution that is made into by 19.57kg NH4HCO3 (carbonic hydroammonium excessive 4%), and 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
And then sample is heated to 380 ℃, 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 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 2 transform after the conversion ratio of detection lead sulfate is 99.56%.Cleaning solution in the step 2 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 2 just transform after to detect its conversion ratio be 99.54%.Cleaning solution in the step 2 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 2 just transform after to detect its conversion ratio be 99.49%.Cleaning solution in the step 2 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 2 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 2 just transform after to detect its conversion ratio be 92.8%.Cleaning solution in the step 2 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 such as 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 (5)

1. the recoverying and utilizing method of lead plaster in the waste and old lead accumulator is characterized in that: accomplish as follows:
(1), to be crushed to particle diameter be the 160-200 order to the lead plaster that will from waste and old lead accumulator, separate;
(2), the lead plaster after will pulverizing adds 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;
(3), 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;
(4), the sample that obtains in the step (3) is heated to 250-320 ℃, insulation 1-1.5h makes brown lead oxide be decomposed into lead oxide fully; And then sample is heated to 320-450 ℃; 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 lead plaster in the said waste and old lead accumulator of claim 1: it is characterized in that: the yellow lead that makes 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 lead plaster in 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 (3) is recycled through 4 times 4) 2SO 4, its preparation technology is:
(a), in said filtrating, add activated carbon, at 100 ℃ of 30min that decolour down, minor N H in will filtrating simultaneously 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
4. according to the recoverying and utilizing method of the said waste and old lead accumulator of claim 1; It is characterized in that: the cleaning solution that washing leaching cake is used in the said step (3) 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.
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 filtrate cycle in the said step (3) is used until the conversion ratio that detects lead sulfate less than 99%.
CN201110241182A 2011-08-22 2011-08-22 Method for recycling lead plaster from waste lead storage battery Pending CN102306855A (en)

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CN103523820A (en) * 2013-09-23 2014-01-22 襄阳远锐资源工程技术有限公司 Lead oxide taking lead paste in waste battery as main raw material and preparation method thereof
CN104789776A (en) * 2014-01-16 2015-07-22 北京化工大学 Method for recovering lead oxide from waste containing lead oxide
CN105197988A (en) * 2015-11-02 2015-12-30 扬州大学 Ammonia process separation and refinement method of lead sulfate
CN105206800A (en) * 2015-08-20 2015-12-30 东南大学 Lead-acid cell positive electrode with lead sulfate as active material and method for preparing lead-acid cell through positive electrode
CN105280976A (en) * 2014-10-27 2016-01-27 李洪亮 Environmental-friendly and high-efficiency processing method of waste lead-acid storage battery
CN105925807A (en) * 2016-05-26 2016-09-07 广东新生环保科技股份有限公司 Recycling process of waste battery lead
US9533273B2 (en) 2014-06-20 2017-01-03 Johnson Controls Technology Company Systems and methods for isolating a particulate product when recycling lead from spent lead-acid batteries
US9670565B2 (en) 2014-06-20 2017-06-06 Johnson Controls Technology Company Systems and methods for the hydrometallurgical recovery of lead from spent lead-acid batteries and the preparation of lead oxide for use in new lead-acid batteries
US10062933B2 (en) 2015-12-14 2018-08-28 Johnson Controls Technology Company Hydrometallurgical electrowinning of lead from spent lead-acid batteries
CN109713392A (en) * 2018-12-21 2019-05-03 重庆煌达环保科技有限公司 Lead-acid accumulator chemical disposal method
CN109811140A (en) * 2019-02-20 2019-05-28 湘潭大学 A kind of lead plaster ammonium sulfur method of product purity height guarantee
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CN112280992A (en) * 2020-10-28 2021-01-29 超威电源集团有限公司 Recovery method of acid leaching lead mud
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CN103374658A (en) * 2012-04-24 2013-10-30 湖北金洋冶金股份有限公司 Ultrafine lead oxide prepared from desulfurated lead plaster by means of three-stage process and method thereof
CN103523820A (en) * 2013-09-23 2014-01-22 襄阳远锐资源工程技术有限公司 Lead oxide taking lead paste in waste battery as main raw material and preparation method thereof
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US11923518B2 (en) 2014-06-20 2024-03-05 Clarios Advanced Germany Gmbh & Co. KG Systems and methods for closed-loop recycling of a liquid component of a leaching mixture when recycling lead from spent lead-acid batteries
US9533273B2 (en) 2014-06-20 2017-01-03 Johnson Controls Technology Company Systems and methods for isolating a particulate product when recycling lead from spent lead-acid batteries
US9555386B2 (en) 2014-06-20 2017-01-31 Johnson Controls Technology Company Systems and methods for closed-loop recycling of a liquid component of a leaching mixture when recycling lead from spent lead-acid batteries
US9670565B2 (en) 2014-06-20 2017-06-06 Johnson Controls Technology Company Systems and methods for the hydrometallurgical recovery of lead from spent lead-acid batteries and the preparation of lead oxide for use in new lead-acid batteries
US11005129B2 (en) 2014-06-20 2021-05-11 Clarios Germany Gmbh & Co. Kgaa Systems and methods for closed-loop recycling of a liquid component of a leaching mixture when recycling lead from spent lead-acid batteries
US9757702B2 (en) 2014-06-20 2017-09-12 Johnson Controls Technology Company Systems and methods for purifying and recycling lead from spent lead-acid batteries
US10403940B2 (en) 2014-06-20 2019-09-03 Cps Technology Holdings Llc Systems and methods for closed-loop recycling of a liquid component of a leaching mixture when recycling lead from spent lead-acid batteries
US10122052B2 (en) 2014-06-20 2018-11-06 Johnson Controls Technology Company Systems and methods for purifying and recycling lead from spent lead-acid batteries
CN105280976A (en) * 2014-10-27 2016-01-27 李洪亮 Environmental-friendly and high-efficiency processing method of waste lead-acid storage battery
CN105206800B (en) * 2015-08-20 2018-08-21 东南大学 A method of lead-acid battery is prepared as the lead-acid battery of active material anode and using the anode using lead sulfate
CN105206800A (en) * 2015-08-20 2015-12-30 东南大学 Lead-acid cell positive electrode with lead sulfate as active material and method for preparing lead-acid cell through positive electrode
CN105197988A (en) * 2015-11-02 2015-12-30 扬州大学 Ammonia process separation and refinement method of lead sulfate
US10062933B2 (en) 2015-12-14 2018-08-28 Johnson Controls Technology Company Hydrometallurgical electrowinning of lead from spent lead-acid batteries
CN105925807B (en) * 2016-05-26 2018-07-20 广东新生环保科技股份有限公司 A kind of recovery process of waste battery lead
CN105925807A (en) * 2016-05-26 2016-09-07 广东新生环保科技股份有限公司 Recycling process of waste battery lead
CN109713392B (en) * 2018-12-21 2020-12-01 重庆煌达环保科技有限公司 Chemical treatment method for waste lead-acid storage battery
CN109713392A (en) * 2018-12-21 2019-05-03 重庆煌达环保科技有限公司 Lead-acid accumulator chemical disposal method
CN109811140A (en) * 2019-02-20 2019-05-28 湘潭大学 A kind of lead plaster ammonium sulfur method of product purity height guarantee
CN111575498A (en) * 2020-06-19 2020-08-25 刘洪强 Chemical treatment method for lead-containing waste
CN112582606A (en) * 2020-09-03 2021-03-30 蚌埠睿德新能源科技有限公司 Preparation method and device of lead-acid storage battery positive electrode material
WO2022048042A1 (en) * 2020-09-03 2022-03-10 杭州铅锂智行科技有限公司 Method for preparing cathode material of lead-acid battery
CN112582606B (en) * 2020-09-03 2022-06-24 浙江铅锂智行科技有限公司 Preparation method and device of lead-acid storage battery positive electrode material
CN112280992A (en) * 2020-10-28 2021-01-29 超威电源集团有限公司 Recovery method of acid leaching lead mud

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