CN103014354A - Process for recycling lead from lead-acid battery paste - Google Patents
Process for recycling lead from lead-acid battery paste Download PDFInfo
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- CN103014354A CN103014354A CN2013100133155A CN201310013315A CN103014354A CN 103014354 A CN103014354 A CN 103014354A CN 2013100133155 A CN2013100133155 A CN 2013100133155A CN 201310013315 A CN201310013315 A CN 201310013315A CN 103014354 A CN103014354 A CN 103014354A
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- China
- Prior art keywords
- lead
- lotion
- desulfurization
- filter cake
- solution
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- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000002253 acid Substances 0.000 title claims abstract description 43
- 238000004064 recycling Methods 0.000 title abstract 6
- 239000012065 filter cake Substances 0.000 claims abstract description 64
- 238000000498 ball milling Methods 0.000 claims abstract description 61
- 230000008021 deposition Effects 0.000 claims abstract description 26
- 239000002699 waste material Substances 0.000 claims abstract description 21
- 238000006477 desulfuration reaction Methods 0.000 claims description 132
- 230000023556 desulfurization Effects 0.000 claims description 82
- 239000006210 lotion Substances 0.000 claims description 59
- 239000000243 solution Substances 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 19
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008151 electrolyte solution Substances 0.000 claims description 11
- 108010010803 Gelatin Proteins 0.000 claims description 9
- 239000008273 gelatin Substances 0.000 claims description 9
- 229920000159 gelatin Polymers 0.000 claims description 9
- 235000019322 gelatine Nutrition 0.000 claims description 9
- 235000011852 gelatine desserts Nutrition 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 7
- 210000000952 spleen Anatomy 0.000 claims description 7
- 210000002784 stomach Anatomy 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000002386 leaching Methods 0.000 abstract description 6
- 238000003825 pressing Methods 0.000 abstract description 5
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 abstract 1
- 229910001626 barium chloride Inorganic materials 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 235000003599 food sweetener Nutrition 0.000 description 19
- 239000003765 sweetening agent Substances 0.000 description 19
- 238000011084 recovery Methods 0.000 description 16
- 238000003860 storage Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001238 wet grinding Methods 0.000 description 7
- 239000000428 dust Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 238000010129 solution processing Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000011505 plaster Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000003701 mechanical milling Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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
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- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention relates to a lead recycling process, and mainly relates to a process for recycling lead from lead-acid battery paste. The process for recycling the lead from the lead-acid battery paste is characterized by comprising the following steps in sequence: ball milling for preliminary desulphurization, secondary desulphurization, treatment of desulphurized solution, leaching of filter cake and electrolytic deposition, wherein the treatment of the desulphurized solution comprises the following steps: performing filter pressing on the paste after the secondary desulphurization to obtain the desulphurized solution, adding Ba2CO3 and BaCl2 into the desulphurized solution to treat the desulphurized solution, controlling the temperature of the desulphurized solution at 35-40 DEG C and the pH value to be 13-14 when treating the desulphurized solution, and controlling the treatment time to be 30-50 minutes. The invention aims at overcoming defects of the prior art and providing the process for recycling the lead from waste lead-acid batteries; and the process has the advantages of low desulphurization cost, high desulphurization efficiency and high lead recycling rate, and is suitable for industrial production.
Description
The present invention relates to a kind of recovery technique of lead, mainly relate to from the lead acid cell 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, as still 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, use first acetic acid, nitric acid, the acid such as silicofluoric acid and fluoroboric acid is the insoluble sulfur lead plumbate with leaded Substance Transformation, with yellow soda ash or salt of wormwood or volatile salt the desulfurization of insoluble sulfur lead plumbate is changed into carbonate again, not only the complicated cost recovery of removal process is high, and also do not take appropriate measures aspect the recovery of the product after sweetening agent uses, cost is high.
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, 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 lead acid cell lotion, it is characterized in that it may further comprise the steps processing successively: the pre-desulfurization of ball milling, secondary desulfuration, doctor solution are processed, filter cake leaches 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 is again with PbSO
4Join wherein and stir, wherein, PbSO
4With Na
2CO
3Mass ratio be 2:1, temperature of reaction is controlled at 40-45 ℃, pH value in reaction is 6-8.Concrete reaction is as follows:
Described doctor solution is processed: the lotion behind the secondary desulfuration is carried out obtaining doctor solution after the press filtration, add Ba in described doctor solution
2CO
3And BaCl
2Carry out doctor solution and process, temperature was 35-40 ℃ when the control doctor solution was processed, and the pH value is 13-14, and the time is 30-50 minute.Concrete reaction is as follows:
Doctor solution of the present invention adopts Ba in processing
2CO
3And BaCl
2Carry out doctor solution and process, generate product Na
2CO
3And BaSO
4, wherein, product Na
2CO
3Can be used as sweetening agent continues to use product B aSO
4Be widely used in paint, printing ink, electronics, store battery, glass, medicine and other fields, greatly reduce desulphurization cost; In addition, temperature was 35-40 ℃ when doctor solution was processed, and this temperature does not need extra heating, and the waste heat that produces in the time of only need utilizing secondary desulfuration just can react, and has also saved desulphurization cost.
The present invention by pre-desulfurization ball milling and secondary desulfuration technique after, can greatly increase desulfuration efficiency and then high Na is produced in reaction
2SO
4The doctor solution of content, the higher Na of concentration
2SO
4Doctor solution is conducive to the carrying out that follow-up doctor solution is processed, because Ba
2CO
3With BaSO
4Be similarly precipitation, but Ba
2CO
3With respect to BaSO
4Processable is higher, and reaction is carried out, and adds simultaneously high Na
2SO
4Content can make and react carry out faster, in addition, adds among the present invention by adding Ba
2CO
3And BaCl
2Two kinds of doctor solution treatment agents, controlling the pH value is that 13-14 and temperature are 35-40 ℃ again, can make the desulfurization treatment solution treatment time shorten to 30-50 minute.
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, increase rear also corresponding increase of cost although the temperature height is conducive to the desulphurization reaction temperature, 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, interactions that closely cooperate of each step of whole technique, so that technological operation of the present invention is simple, cost is low, the organic efficiency height.
As preferably, stir during described doctor solution processing, stir speed (S.S.) is 500-700r/min.Under the agitation condition, the doctor solution processing efficiency is higher.
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, 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.
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.
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, doctor solution of the present invention adopts Ba in processing
2CO
3And BaCl
2Carry out doctor solution and process, generate product Na
2CO
3And BaSO
4, wherein, product Na
2CO
3Can be used as sweetening agent continues to use product B aSO
4Be widely used in paint, printing ink, electronics, store battery, glass, medicine and other fields, greatly reduce desulphurization cost.
2, the present invention in desulfurization product reclaims by passing into CO
2Absorb the NH in the above-mentioned chemical equilibrium
3To generate Na
2CO
3, the Na of generation
2CO
3Can continue to use as sweetening agent, greatly reduce desulphurization cost, improve desulfurization degree.
3, follow simultaneously ball milling in the pre-sweetening process of the present invention, can fully contact with sweetening agent by lotion in mechanical milling process, the continuous minimizing of granularity has also improved the contact range with sweetening agent, has improved desulfuration efficiency; 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, interactions that closely cooperate of each step of whole technique, so that technological operation of the present invention is simple, cost is low, the organic efficiency height.
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 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 waste and old lead acid accumulator, 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 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; The filter cake of material after the pre-desulfurization of ball milling after by press filtration sent into the desulfurization storage tank carry out secondary desulfuration, contain mass concentration in the desulfurization storage tank and be 19% 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 40 ℃, and material carries out press filtration again behind the secondary desulfuration, stirs during secondary desulfuration, and churning time is 3 hours, and stir speed (S.S.) is 400r/min, and the pH value is 6 in the secondary desulfuration; Filter filter cake and stay doctor solution, in described doctor solution, add Ba
2CO
3And BaCl
2Carry out doctor solution and process Ba
2CO
3And BaCl
2The adding quality be the 4/1-2/1 of doctor solution quality; Carry out stir process in the doctor solution treating processes, stir speed (S.S.) is 500-700r/min, and temperature is 35-40 ℃ when controlling in addition the doctor solution processing, and the pH value is 13-14, and the time is 30-50 minute, and supernatant liquor was Na after doctor solution was processed
2CO
3The aqueous solution, throw out are Ba
2SO
4Filter cake behind the secondary desulfuration is put into washing bath with the Na of flush away filter residue
2SO
4And Na
2CO
3Deng impurity, the filter cake after will washing again places reaction vessel and priority adds oxalic acid and silicofluoric acid obtains the filter cake leach liquor, wherein, and 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 waste and old lead acid accumulator, 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 filter cake into the desulfurization storage tank after by the filter pressing pump press filtration carry out secondary desulfuration, contain mass concentration in the desulfurization storage tank and be 19% 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 40 ℃, stirs during secondary desulfuration, and churning time is 3 hours, and stir speed (S.S.) is 400r/min, and the pH value is 6 in the secondary desulfuration; Material carries out press filtration again behind the secondary desulfuration, and the filter cake after the press filtration is put into washing bath with the Na of flush away filter residue
2SO
4And Na
2CO
3Deng impurity, stay doctor solution behind the filtration filter cake, in described doctor solution, add Ba
2CO
3And BaCl
2Carry out doctor solution and process Ba
2CO
3And BaCl
2The adding quality be the 4/1-2/1 of doctor solution quality; Carry out stir process in the doctor solution treating processes, stir speed (S.S.) is 500-700r/min, and temperature is 35-40 ℃ when controlling in addition the doctor solution processing, and the pH value is 13-14, and the time is 30-50 minute, and supernatant liquor was Na after doctor solution was processed
2CO
3The aqueous solution, throw out are Ba
2SO
4Filter cake after the secondary desulfuration washing places reaction vessel also successively to add oxalic acid again and silicofluoric acid obtains the filter cake leach liquor, wherein, and 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 3
Reclaiming plumbous technique from waste and old lead acid accumulator, 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 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, contain mass concentration in the desulfurization storage tank and be 19% Na
2CO
3The aqueous solution, PbSO in the described desulfurization storage tank
4Quality and described Na
2CO
3Aqueous solution mass ratio is 2:1, temperature of reaction is 40 ℃, deliver to pressure filter with the material of filter pressing pump after with pre-desulfurization and carry out press filtration, filter cake after the press filtration carries out secondary desulfuration to improve desulfuration efficiency, 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; Then the lotion behind the secondary desulfuration is carried out press filtration obtains filter cake, filters filter cake and stays doctor solution, adds Ba in described doctor solution
2CO
3And BaCl
2Carry out doctor solution and process Ba
2CO
3And BaCl
2The adding quality be the 4/1-2/1 of doctor solution quality; Carry out stir process in the doctor solution treating processes, stir speed (S.S.) is 500-700r/min, and temperature is 35-40 ℃ when controlling in addition the doctor solution processing, and the pH value is 13-14, and the time is 30-50 minute, and supernatant liquor was Na after doctor solution was processed
2CO
3The aqueous solution, throw out are Ba
2SO
4Filter cake after secondary desulfuration and the washing places reaction vessel also successively to add oxalic acid again and silicofluoric acid obtains the filter cake leach liquor, wherein, and 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.
Comparative Examples 1
From waste and old lead acid accumulator, 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 after with the filter pressing pump press filtration carry out desulfurization, 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 ℃, carries out press filtration after the desulfurization 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 desulfurization and the washing 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 waste and old lead acid accumulator, 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 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 far away in the embodiment of the invention technique, in addition, the lead recovery of the embodiment of the invention also is higher than the lead recovery of Comparative Examples, illustrate that technique of the present invention has not only improved the lotion desulfurization degree, also promote follow-up technique, and then improved lead recovery.
Claims (10)
1. reclaim plumbous technique from the lead acid cell lotion, it is characterized in that it may further comprise the steps processing successively: the pre-desulfurization of ball milling, secondary desulfuration, doctor solution are processed, filter cake leaches 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 is again with PbSO
4Join wherein and stir, wherein, PbSO
4With Na
2CO
3Mass ratio be 2:1, temperature of reaction is controlled at 40-45 ℃, pH value in reaction is 6-8;
Described doctor solution is processed: the lotion behind the secondary desulfuration is carried out obtaining doctor solution after the press filtration, add Ba in described doctor solution
2CO
3And BaCl
2Carry out doctor solution and process, temperature was 35-40 ℃ when the control doctor solution was processed, and the pH value is 13-14, and the time is 30-50 minute.
2. reclaim as claimed in claim 1 plumbous technique from the lead acid cell lotion, it is characterized in that: described doctor solution stirs when processing, and stir speed (S.S.) is 500-700r/min.
3. reclaim as claimed in claim 2 plumbous technique from the lead acid cell lotion, it is characterized in that: Ball-milling Time is 60-80min in the pre-desulfurization of described ball milling.
4. reclaim as claimed in claim 3 plumbous technique from the lead acid cell 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.
5. from the lead acid cell 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 lead acid cell 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 lead acid cell 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 lead acid cell 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 lead acid cell 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 lead acid cell 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 ℃.
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