CN103060569A - Process of recovering lead from pasty fluid of waste lead-acid storage battery - Google Patents
Process of recovering lead from pasty fluid of waste lead-acid storage battery Download PDFInfo
- Publication number
- CN103060569A CN103060569A CN2013100133136A CN201310013313A CN103060569A CN 103060569 A CN103060569 A CN 103060569A CN 2013100133136 A CN2013100133136 A CN 2013100133136A CN 201310013313 A CN201310013313 A CN 201310013313A CN 103060569 A CN103060569 A CN 103060569A
- Authority
- CN
- China
- Prior art keywords
- lotion
- desulfurization
- waste
- filter cake
- desulfuration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Abstract
The invention relates to a process for recovering lead, and mainly relates to a process of recovering lead from a pasty fluid of a waste lead-acid storage battery, which belongs to the technical field of environmental protection. The process sequentially comprises the following steps of: pre-desulfuration by a ball-mill; secondary desulfuration; leaching filter cakes; and electrolytic deposition. The pre-desulfuration by the ball-mill comprises the following step of: feeding separated pasty fluid of the waste lead-acid storage battery and a Na2CO3 aqueous liquid to the ball-mill according to a mass ratio of 2:1 for pre-desulfuration by the ball-mill to obtain a pre-desulfuration pasty fluid by the ball-mill; secondary desulfuration comprises the following step of: introducing Na2CO3 aqueous liquor with mass concentration of 19-21% to the pre-desulfuration pasty fluid by the ball-mill. The invention aims to overcome deficiencies in the prior art and provides the process of recovering lead from the pasty fluid of the waste lead-acid storage battery. The process is low in desulfuration cost, high in desulfuration efficiency, high in lead recovery yield and simple and easy in operation of the desulfuration process, so that the process is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of recovery technique of lead, mainly relate to from the waste and old lead acid accumulator lotion, reclaim plumbous technique.
Background technology
In recent years, along with the increase of lead acid cell consumption, corresponding learies is also increasing.At present, China's lead acid cell consumption accounts for 70% of total value, but the waste lead storage battery rate of recovery just about 80%, and well below developed country's level, therefore a large amount of lead can not get waste that efficient recovery not only can cause resource and also can produce environment and pollute.At present, China's technology comparatively ripe to be that pyrogenic process reclaims plumbous, but the method is very large to the pollution of environment, be not suitable for the long term growth of reclaiming plumbous industry, also there are some researchists to begin to adopt hydrometallurgic recovery plumbous, but hydrometallurgic recovery splicer skill is perfect not enough at present, exist the rate of recovery low, the high in cost of production shortcoming, be CN101636512A(2010-01-27 such as publication number) Chinese patent, by in lead sulfate solution, directly adding yellow soda ash or salt of wormwood or volatile salt to generate the identical cationic soluble sulphate of insoluble lead carbonate and/or oxycarbonate and the carbonate that is added, but the method desulfurization Chengdu is low, and is larger to the consumption of sweetening agent.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, provide and reclaim plumbous technique from waste and old lead acid accumulator, this technique desulphurization cost is low, desulfuration efficiency is high, lead recovery is high, sweetening process is simple to operation, is fit to suitability for industrialized production.
The objective of the invention is to be achieved by the following technical programs: reclaim plumbous technique from the waste and old lead acid accumulator lotion, it may further comprise the steps successively: the pre-desulfurization of ball milling, secondary desulfuration, filter cake leach and electrolytic deposition;
The pre-desulfurization of described ball milling is: with waste and old lead acid accumulator lotion and the Na that separates
2CO
3The aqueous solution in mass ratio 2:1 is sent into and is carried out the pre-desulfurization of ball milling in the ball mill and obtain the pre-desulfurization lotion of ball milling; The granularity of lotion is the 60-80 micron after the pre-desulfurization of described ball milling; Pass into water in the pre-sweetening process of described ball milling;
Described secondary desulfuration is: pass into the Na that mass concentration is 19-21% in the lotion after the pre-desulfurization of ball milling
2CO
3The aqueous solution, wherein, the lotion PbSO after the pre-desulfurization of ball milling
4With Na
2CO
3Mass ratio be 2:1, temperature of reaction is controlled at 40-45 ℃.React as follows:
PbSO
4+Na
2CO
3=PbCO
3+Na
2SO
4。
The present invention adopts pre-desulfurization to combine with secondary desulfuration the lead sulfate in the waste and old lead acid accumulator is carried out desulfurization, in sweetening process, pre-desulfurization and secondary desulfuration are respectively according to the different concns preparation, and these concentration parameter proportionings all are that the contriver obtains through long-term practice; Pre-desulfurization stage waste and old lead acid accumulator lotion and Na
2CO
3The mass ratio 2:1 of the aqueous solution participates in reaction process with abundant assurance sweetening agent, to reduce the loss of sweetening agent in the vitriol byproduct removal process; PbSO in the secondary desulfuration
4With Na
2CO
3Mass ratio be 2:1 since lotion in incessantly contain PbSO
4Therefore should the concentration of sweetening agent be higher than pre-desulfurization stage in the stage, and can remove to greatest extent sulphur remaining in the lotion, high-concentration desulfurized dose that contains in the solution behind the secondary desulfuration will be returned to the fs, continue recycle, also can be used as and continue the secondary desulfuration use; Dimension the present invention combines pre-desulfurization with secondary desulfuration technique has greatly lowered desulphurization cost and has also improved desulfuration efficiency, and whole sweetening process is simple to operation; The present invention also passes into the effect that water plays wet-milling in pre-sweetening process, it is lubricated that wet-milling not only can play channel, can also prevent the generation of plumbous micronic dust.
In addition, the principal element that affects the lead plaster sweetening effectiveness is the surface-area that contacts with doctor solution of temperature, lead plaster particle, the concentration of sweetening agent; Follow simultaneously ball milling in the pre-sweetening process of the present invention, in mechanical milling process, can fully contact with sweetening agent by lotion, the continuous minimizing of granularity has also improved the contact range with sweetening agent, improved desulfuration efficiency, the granularity of the pre-desulfurization lotion of ball milling is the 60-80 micron among the present invention, this granularity is to get through contriver's long-term practice institute, because can't increase sweetening effectiveness after granularity is too small, on the contrary can the loss machine, increase desulfurization time, reduce desulfuration efficiency, the granularity of lotion is excessive to be unfavorable for again and fully the contacting of sweetening agent; Usually, the higher sweetening effectiveness of the concentration of sweetening agent is better, but also corresponding raising of cost, and the present invention is by twice desulfurization and rationally adjust the concentration of middle yellow soda ash of twice desulfurization so that desulfuration efficiency has reduced the waste of sweetening agent when improving; In addition, although the high desulphurization reaction temperature that is conducive to of temperature increases rear also corresponding increase of cost, desulfuration efficiency was best when the temperature of reaction of contriver's long-term practice research discovery secondary desulfuration was controlled at 40-45 ℃, and cost is also minimum.
The granularity of the pre-desulfurization lotion of ball milling is the 60-80 micron after the pre-desulfurization of the present invention's process ball milling, this granularity can make not only that lotion is fully contacted with sweetening agent in the pre-sweetening process, lotion is fully contacted with sweetening agent in the time of can also making secondary desulfuration, improves desulfuration efficiency; In addition, desulfurization degree improves in the lotion through making behind the pre-desulfurization of ball milling of the present invention and the secondary desulfuration, and plumbous granularity greatly reduces, and the solution that makes follow-up filter cake leach high lead tolerance is more prone to, thereby satisfy the needs of concentration of electrolyte configuration in the last electrolytic deposition, lead recovery is improved greatly.
The present invention adopts the lead in the full hydrometallurgic recovery waste lead storage battery, and not only organic efficiency is high, and environmentally safe, the interaction that closely cooperates of each step of whole technique, so that technological operation of the present invention is simple, cost is low, and organic efficiency is high.
As preferably, Ball-milling Time is 60-80min in the pre-desulfurization of described ball milling.
As preferably, churning time is 2-3 hour during described secondary desulfuration, and stir speed (S.S.) is 400-500r/min.
As preferably, the pH value is 6-8 in the described secondary desulfuration.When the pH value was 6-8, the desulfurization transformation efficiency was best.
As preferably, it is first the lotion behind the secondary desulfuration to be carried out press filtration to obtain filter cake that described filter cake leaches, and more described filter cake is placed reaction vessel and successively adds oxalic acid again and silicofluoric acid obtains the filter cake leach liquor.React as follows:
As preferably, described filter cake and described H
2C
2O
4Mass ratio be 1:5; Temperature was 45-55 ℃ when described filter cake leached.Because the solubleness of yellow soda ash is maximum at 40-45 ℃.
As preferably, lead amount is 170-190g/L in the described filter cake leach liquor.
As preferably, electrolytic solution is to be formed by filter cake leach liquor, plumbous liquid, gelatin and phosphoric acid configuration through after the electrolysis in the described electrolytic deposition; Lead content is 120-130g/L in the described electrolytic solution.Reduce through containing lead concentration in the plumbous liquid after the electrolysis, can carry out mixed preparing with high lead content solution in the filter cake leach liquor and obtain the electrolytic solution that lead content is 120-130g/L, the recycle of plumbous liquid, not only greatly reduce cost, residual lead in the plumbous liquid after the electrolysis can also be continued electrolysis, improve the plumbous rate of recovery.
As preferably, described electrolytic solution gelatin is 0.8～1.5Kg/t, and phosphoric acid is 2～5Kg/t.
As preferably, described electrolytic deposition middle-jiao yang, function of the spleen and stomach very is coated with the graphite cake of lead dioxide plating coat; Current density is 180～250A/m in the described electrolytic deposition
2, temperature is 36～42 ℃.Because plumbic oxide has high catalytic activity, high overpotential for oxygen evolution and unreactiveness as anode, can when galvanic deposit is plumbous, not bring other impurity into plumbic oxide as anode simultaneously.
The invention has the beneficial effects as follows:
1, the present invention adopts pre-desulfurization to combine with secondary desulfuration the lead sulfate in the waste and old lead acid accumulator is carried out desulfurization, pre-desulfurization and secondary desulfuration are prepared according to different concns respectively, high-concentration desulfurized dose that contains in the solution behind the secondary desulfuration will be returned to the fs, continue recycle, also can be used as and continue the secondary desulfuration use, greatly lowered desulphurization cost and also improved desulfuration efficiency, whole sweetening process is simple to operation.
2, follow simultaneously ball milling in the pre-sweetening process of the present invention, lotion can fully contact with sweetening agent in mechanical milling process, and the continuous minimizing of granularity has also improved the contact range with sweetening agent, has improved desulfuration efficiency.
3, the granularity of the pre-desulfurization lotion of ball milling is the 60-80 micron after the pre-desulfurization of the present invention's process ball milling, this granularity can make not only that lotion is fully contacted with sweetening agent in the pre-sweetening process, lotion is fully contacted with sweetening agent in the time of can also making secondary desulfuration, improves desulfuration efficiency.
4, the present invention adopts the lead in the full hydrometallurgic recovery waste lead storage battery, and not only organic efficiency is high, and environmentally safe, the interaction that closely cooperates of each step of whole technique, so that technological operation of the present invention is simple, cost is low, and organic efficiency is high.
Embodiment
This specific embodiment only is explanation of the invention; it is not limitation of the present invention; those skilled in the art can make the modification that does not have creative contribution to the present embodiment as required after reading this specification sheets, but as long as all are subject to the protection of patent law in claim scope of the present invention.
Embodiment 1
Reclaiming plumbous technique from the waste and old lead acid accumulator lotion, carry out first the pre-desulfurization of ball milling, is 16% Na with the waste and old lead acid accumulator lotion separated and mass concentration
2CO
3The aqueous solution in mass ratio 2:1 is sent into and is carried out the pre-desulfurization of ball milling in the ball mill and obtain the pre-desulfurization lotion of ball milling, the pre-desulfurization time of ball milling is 60min, the granularity of lotion is 60 microns after the pre-desulfurization of ball milling, passes into water to reduce dust and to play the wet-milling effect in the pre-sweetening process of ball milling; Material after the pre-desulfurization of ball milling is sent into the desulfurization storage tank after with the filter pressing pump press filtration, and it is 19% Na to improve desulfuration efficiency, to contain mass concentration in the desulfurization storage tank that the solid material is carried out secondary desulfuration
2CO
3The aqueous solution, PbSO in the described desulfurization storage tank
4Quality and described Na
2CO
3Aqueous solution mass ratio is 2:1, and temperature of reaction is 40 ℃, and material carries out press filtration again behind the secondary desulfuration, and the solid materials after the press filtration is put into washing bath with the Na of flush away filter residue
2SO
4And Na
2CO
3Deng impurity, stir during secondary desulfuration, churning time is 3 hours, and stir speed (S.S.) is 400r/min, and the pH value is 6 in the secondary desulfuration; Lotion after then will washing carries out press filtration and obtains filter cake, and filter cake is placed reaction vessel and successively add oxalic acid again and silicofluoric acid obtains the filter cake leach liquor, wherein, filter cake and described H
2C
2O
4Mass ratio be 1:5, temperature was 45 ℃ when filter cake leached, filter cake obtains the filter cake leach liquor that lead content is 170-190g/L after leaching; Carry out at last electrolytic deposition, electrolytic deposition middle-jiao yang, function of the spleen and stomach very is coated with the graphite cake of lead dioxide plating coat, and current density is 180A/m in the electrolytic deposition
2, temperature is 36 ℃, electrolytic solution is by the filter cake leach liquor, be set to the solution that lead content is 120g/L through plumbous liquid, gelatin and phosphorylated ligand after the electrolysis.
Embodiment 2
Reclaiming plumbous technique from the waste and old lead acid accumulator lotion, carry out first the pre-desulfurization of ball milling, is 18% Na with the waste and old lead acid accumulator lotion separated and mass concentration
2CO
3The aqueous solution in mass ratio 2:1 is sent into and is carried out the pre-desulfurization of ball milling in the ball mill and obtain the pre-desulfurization lotion of ball milling, the pre-desulfurization time of ball milling is 70min, the granularity of lotion is 70 microns after the pre-desulfurization of ball milling, passes into water to reduce dust and to play the wet-milling effect in the pre-sweetening process of ball milling; Material after the pre-desulfurization of ball milling is sent into the desulfurization storage tank with filter pressing pump after by press filtration, and it is 20% Na to improve desulfuration efficiency, to contain mass concentration in the desulfurization storage tank that the solid material is carried out secondary desulfuration
2CO
3The aqueous solution, PbSO in the described desulfurization storage tank
4Quality and described Na
2CO
3Aqueous solution mass ratio is 2:1, and temperature of reaction is 42 ℃, and material carries out press filtration again behind the secondary desulfuration, and the solid materials after the press filtration is put into washing bath with the Na of flush away filter residue
2SO
4And Na
2CO
3Deng impurity, stir during secondary desulfuration, churning time is 2 hours, and stir speed (S.S.) is 450r/min, and the pH value is 7 in the secondary desulfuration; Lotion after then will washing carries out press filtration and obtains filter cake, and filter cake is placed reaction vessel and successively add oxalic acid again and silicofluoric acid obtains the filter cake leach liquor, wherein, filter cake and described H
2C
2O
4Mass ratio be 1:5, temperature was 47 ℃ when filter cake leached, filter cake obtains the filter cake leach liquor that lead content is 170-190g/L after leaching; Carry out at last electrolytic deposition, electrolytic deposition middle-jiao yang, function of the spleen and stomach very is coated with the graphite cake of lead dioxide plating coat, and current density is 210A/m in the electrolytic deposition
2, temperature is 39 ℃, electrolytic solution is by the filter cake leach liquor, be set to the solution that lead content is 125g/L through plumbous liquid, gelatin and phosphorylated ligand after the electrolysis.
Embodiment 3
Reclaiming plumbous technique from the waste and old lead acid accumulator lotion, carry out first the pre-desulfurization of ball milling, is 17% Na with the waste and old lead acid accumulator lotion separated and mass concentration
2CO
3The aqueous solution in mass ratio 2:1 is sent into and is carried out the pre-desulfurization of ball milling in the ball mill and obtain the pre-desulfurization lotion of ball milling, the pre-desulfurization time of ball milling is 80min, the granularity of lotion is 80 microns after the pre-desulfurization of ball milling, passes into water to reduce dust and to play the wet-milling effect in the pre-sweetening process of ball milling; Material after the pre-desulfurization of ball milling is sent into the desulfurization storage tank after with the filter pressing pump press filtration, and it is 21% Na to improve desulfuration efficiency, to contain mass concentration in the desulfurization storage tank that the solid material is carried out secondary desulfuration
2CO
3The aqueous solution, PbSO in the described desulfurization storage tank
4Quality and described Na
2CO
3Aqueous solution mass ratio is 2:1, and temperature of reaction is 45 ℃, and material carries out press filtration again behind the secondary desulfuration, and the solid materials after the press filtration is put into washing bath with the Na of flush away filter residue
2SO
4And Na
2CO
3Deng impurity, stir during secondary desulfuration, churning time is 3 hours, and stir speed (S.S.) is 500r/min, and the pH value is 8 in the secondary desulfuration; Lotion after then will washing carries out press filtration and obtains filter cake, and filter cake is placed reaction vessel and successively add oxalic acid again and silicofluoric acid obtains the filter cake leach liquor, wherein, filter cake and described H
2C
2O
4Mass ratio be 1:5, temperature was 55 ℃ when filter cake leached, filter cake obtains the filter cake leach liquor that lead content is 170-190g/L after leaching; Carry out at last electrolytic deposition, electrolytic deposition middle-jiao yang, function of the spleen and stomach very is coated with the graphite cake of lead dioxide plating coat, and current density is 250A/m in the electrolytic deposition
2, temperature is 42 ℃, electrolytic solution is by the filter cake leach liquor, be set to the solution that lead content is 130g/L through plumbous liquid, gelatin and phosphorylated ligand after the electrolysis.
Comparative Examples 1
From the waste and old lead acid accumulator lotion, reclaim plumbous technique, carry out first ball milling, the waste and old lead acid accumulator lotion of separating sent into carry out ball milling in the ball mill and obtain the ball milling lotion, Ball-milling Time is 80min, the granularity of lotion is 80 microns behind the ball milling, passes into water to reduce dust and to play the wet-milling effect in mechanical milling process; Material behind the ball milling is sent into the desulfurization storage tank, contain mass concentration in the desulfurization storage tank and be 21% Na
2CO
3The aqueous solution, PbSO in the described desulfurization storage tank
4Quality and described Na
2CO
3Aqueous solution mass ratio is 2:1, and temperature of reaction is 45 ℃, delivers to pressure filter with the material of filter pressing pump after with desulfurization and carries out press filtration, and the solid materials after the press filtration is put into washing bath with the Na of flush away filter residue
2SO
4And Na
2CO
3Deng impurity, stir during desulfurization, churning time is 3 hours, and stir speed (S.S.) is 500r/min, and the pH value is 8 in the desulfurization; Lotion after then will washing carries out press filtration and obtains filter cake, and filter cake is placed reaction vessel and successively add oxalic acid again and silicofluoric acid obtains the filter cake leach liquor, wherein, filter cake and described H
2C
2O
4Mass ratio be 1:5, temperature was 55 ℃ when filter cake leached, filter cake obtains the filter cake leach liquor that lead content is 170-190g/L after leaching; Carry out at last electrolytic deposition, electrolytic deposition middle-jiao yang, function of the spleen and stomach very is coated with the graphite cake of lead dioxide plating coat, and current density is 250A/m in the electrolytic deposition
2, temperature is 42 ℃, electrolytic solution is by the filter cake leach liquor, be set to the solution that lead content is 130g/L through plumbous liquid, gelatin and phosphorylated ligand after the electrolysis.
Comparative Examples 2
Reclaiming plumbous technique from the waste and old lead acid accumulator lotion, carry out first the pre-desulfurization of ball milling, is 16% Na with the waste and old lead acid accumulator lotion separated and mass concentration
2CO
3The aqueous solution in mass ratio 2:1 is sent into and is carried out the pre-desulfurization of ball milling in the ball mill and obtain the pre-desulfurization lotion of ball milling, the pre-desulfurization time of ball milling is 80min, the granularity of lotion is 80 microns after the pre-desulfurization of ball milling, passes into water to reduce dust and to play the wet-milling effect in the pre-sweetening process of ball milling; Then the lotion after the pre-desulfurization is carried out press filtration obtains filter cake, and filter cake is placed reaction vessel and successively add oxalic acid again and silicofluoric acid obtains the filter cake leach liquor, wherein, filter cake and described H
2C
2O
4Mass ratio be 1:5, temperature was 55 ℃ when filter cake leached, filter cake obtains the filter cake leach liquor that lead content is 170-190g/L after leaching; Carry out at last electrolytic deposition, electrolytic deposition middle-jiao yang, function of the spleen and stomach very is coated with the graphite cake of lead dioxide plating coat, and current density is 250A/m in the electrolytic deposition
2, temperature is 42 ℃, electrolytic solution is by the filter cake leach liquor, be set to the solution that lead content is 130g/L through plumbous liquid, gelatin and phosphorylated ligand after the electrolysis.
Testing scheme:
(1) desulfurization transformation efficiency test: the lead plaster particle after the lead plaster particle after the embodiment of the invention desulfurization conversion and the Comparative Examples desulfurization conversion is filtered pressure, filter is dried, grinds after pressing, measure the wherein massfraction of S with high frequency-infrared carbon sulphur instrument, represent with percentage composition.
(2) lead recovery: claim to get the ratio of plumbous weight and original lotion weight behind the embodiment of the invention and the Comparative Examples electrolytic deposition, represent with percentage composition.
The result is as shown in table 1:
Table 1 embodiment of the invention and comparative example's test result
Test result analysis: as shown in Table 1, desulfurization degree is higher than the desulfurization degree of Comparative Examples once desulfurization technique far away in the embodiment of the invention secondary desulfuration technique; In addition, the lead recovery of the embodiment of the invention also is higher than the lead recovery of Comparative Examples, illustrates that technique of the present invention has not only improved the lotion desulfurization degree, has also promoted follow-up technique, and then has improved lead recovery.
Claims (10)
1. reclaim plumbous technique from the waste and old lead acid accumulator lotion, it is characterized in that it may further comprise the steps successively: the pre-desulfurization of ball milling, secondary desulfuration, filter cake leach and electrolytic deposition;
The pre-desulfurization of described ball milling is: with waste and old lead acid accumulator lotion and the Na that separates
2CO
3The aqueous solution in mass ratio 2:1 is sent into and is carried out the pre-desulfurization of ball milling in the ball mill and obtain the pre-desulfurization lotion of ball milling; The granularity of lotion is the 60-80 micron after the pre-desulfurization of described ball milling; Pass into water in the pre-sweetening process of described ball milling;
Described secondary desulfuration is: pass into the Na that mass concentration is 19-21% in the lotion after the pre-desulfurization of ball milling
2CO
3The aqueous solution, wherein, the lotion PbSO after the pre-desulfurization of ball milling
4With Na
2CO
3Mass ratio be 2:1, temperature of reaction is controlled at 40-45 ℃.
2. reclaim plumbous technique from the waste and old lead acid accumulator lotion, it is characterized in that: Ball-milling Time is 60-80min in the pre-desulfurization of described ball milling.
3. reclaim as claimed in claim 2 plumbous technique from the waste and old lead acid accumulator lotion, it is characterized in that: churning time is 2-3 hour during described secondary desulfuration, and stir speed (S.S.) is 400-500r/min.
4. reclaim as claimed in claim 3 plumbous technique from the waste and old lead acid accumulator lotion, it is characterized in that: the pH value is 6-8 in the described secondary desulfuration.
5. from the waste and old lead acid accumulator lotion, reclaim as claimed in claim 4 plumbous technique, it is characterized in that: it is first the lotion behind the secondary desulfuration to be carried out press filtration to obtain filter cake that described filter cake leaches, and more described filter cake is placed reaction vessel and successively adds oxalic acid again and silicofluoric acid obtains the filter cake leach liquor.
6. from the waste and old lead acid accumulator lotion, reclaim as claimed in claim 5 plumbous technique, it is characterized in that: described filter cake and described H
2C
2O
4Mass ratio be 1:5; Temperature was 45-55 ℃ when described filter cake leached.
7. reclaim as claimed in claim 6 plumbous technique from the waste and old lead acid accumulator lotion, it is characterized in that: lead amount is 170-190g/L in the described filter cake leach liquor.
8. reclaim as claimed in claim 7 plumbous technique from the waste and old lead acid accumulator lotion, it is characterized in that: electrolytic solution is to be formed by the plumbous liquid after filter cake leach liquor, the process electrolysis, gelatin and phosphoric acid configuration in the described electrolytic deposition; Lead content is 120-130g/L in the described electrolytic solution.
9. reclaim as claimed in claim 8 plumbous technique from the waste and old lead acid accumulator lotion, it is characterized in that: described electrolytic solution gelatin is 0.8～1.5Kg/t, and phosphoric acid is 2～5Kg/t.
10. reclaim as claimed in claim 9 plumbous technique from the waste and old lead acid accumulator lotion, it is characterized in that: described electrolytic deposition middle-jiao yang, function of the spleen and stomach very is coated with the graphite cake of lead dioxide plating coat; Current density is 180～250A/m in the described electrolytic deposition
2, temperature is 36～42 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100133136A CN103060569A (en) | 2013-01-15 | 2013-01-15 | Process of recovering lead from pasty fluid of waste lead-acid storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100133136A CN103060569A (en) | 2013-01-15 | 2013-01-15 | Process of recovering lead from pasty fluid of waste lead-acid storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103060569A true CN103060569A (en) | 2013-04-24 |
Family
ID=48103458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100133136A Pending CN103060569A (en) | 2013-01-15 | 2013-01-15 | Process of recovering lead from pasty fluid of waste lead-acid storage battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103060569A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106834734A (en) * | 2017-03-18 | 2017-06-13 | 江西理工大学 | A kind of agitating ball mill high-efficiency desulfurization method |
| CN108754129A (en) * | 2018-06-01 | 2018-11-06 | 骆驼集团蓄电池研究院有限公司 | A kind of method of waste diachylon segmented desulfurization |
| CN113621812A (en) * | 2021-08-17 | 2021-11-09 | 太和县大华能源科技有限公司 | Lead oxide preparation process based on waste lead-acid storage battery lead plaster |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1664132A (en) * | 2004-03-02 | 2005-09-07 | 沈阳环境科学研究院 | Environmental protection method for extracting lead in waste storage battery |
| US20060018819A1 (en) * | 2004-07-20 | 2006-01-26 | Engitech S.R.I. | Desulfurization process of pastel and grids of lead accumulators |
| 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 |
-
2013
- 2013-01-15 CN CN2013100133136A patent/CN103060569A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1664132A (en) * | 2004-03-02 | 2005-09-07 | 沈阳环境科学研究院 | Environmental protection method for extracting lead in waste storage battery |
| US20060018819A1 (en) * | 2004-07-20 | 2006-01-26 | Engitech S.R.I. | Desulfurization process of pastel and grids of lead accumulators |
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| 刘建斌等: "废铅酸蓄电池渣泥湿法脱硫和还原新工艺研究", 《无机盐工业》 * |
| 孙佩极等: "废蓄电池渣泥二段脱硫工艺研究", 《有色金属（冶炼部分）》 * |
| 王岳: "从蓄电池糊膏回收铅的RSR法", 《中国有色冶金》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106834734A (en) * | 2017-03-18 | 2017-06-13 | 江西理工大学 | A kind of agitating ball mill high-efficiency desulfurization method |
| CN108754129A (en) * | 2018-06-01 | 2018-11-06 | 骆驼集团蓄电池研究院有限公司 | A kind of method of waste diachylon segmented desulfurization |
| CN113621812A (en) * | 2021-08-17 | 2021-11-09 | 太和县大华能源科技有限公司 | Lead oxide preparation process based on waste lead-acid storage battery lead plaster |
| CN113621812B (en) * | 2021-08-17 | 2022-11-08 | 太和县大华能源科技有限公司 | Lead oxide preparation process based on waste lead-acid storage battery lead plaster |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109763143B (en) | Resource recycling method for waste lead-acid batteries | |
| CN102618884B (en) | Lead regeneration method for recovering lead paste from waste lead acid storage battery by wet method | |
| CN101831668B (en) | Clean wet-method solid-liquid two-phase electroreduction lead recovery method | |
| CN101956214B (en) | Method for recycling secondary lead by electrolyzing alkaline leaded solution | |
| CN101899576A (en) | Method for recycling lead from lead-acid battery paste | |
| CN102560535B (en) | Method for recovering lead in waste lead-acid storage battery filler by using wet process | |
| CN101760757B (en) | Method for producing lead by executing electrolysis and alkaline leaching on lead sulfate material | |
| CN111411366B (en) | Method for recovering metal ions in lithium iron phosphate waste through solid-phase electrolysis | |
| CN103074642B (en) | Process for recycling lead from waste lead-acid battery paste | |
| CN106282567A (en) | A kind of method reclaiming metal from useless acidic etching liquid | |
| CN102367578B (en) | Combined method for electrolyzing and recovering lead | |
| CN103014354B (en) | Process for recycling lead from lead-acid battery paste | |
| CN113862479A (en) | Resource recovery processing method for lead plaster in waste lead storage battery | |
| CN106803588B (en) | A kind of recycling and reusing method of sodium sulfate waste liquid | |
| CN103060569A (en) | Process of recovering lead from pasty fluid of waste lead-acid storage battery | |
| CN107268028A (en) | A kind of method that lead bullion is prepared from waste lead acid battery lead plaster | |
| CN108163873B (en) | A method of extracting lithium hydroxide from phosphoric acid lithium waste residue | |
| CN1808761A (en) | Clean recovery method of lead from waste storage cells by acidic electrolyzing and in-situ deoxidation in solid phase through wet process | |
| CN101525752A (en) | Clean production method for high-purity cobaltosic oxide powder | |
| CN108754126A (en) | A kind of copper indium gallium selenide recovery method | |
| CN110219020B (en) | Method for improving conductivity of lead electrolyte | |
| CN103045853B (en) | Process for recovering lead from lead-acid battery paste | |
| CN106086414A (en) | A kind of method reclaiming lead from waste lead acid battery lead cream | |
| CN113277550B (en) | Lead-containing solid waste treatment method, and preparation method and application of lead dioxide powder | |
| CN103484679A (en) | Method for recycling tin and copper from waste tinned copper needles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130424 |