CN103014354B - 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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- CN103014354B CN103014354B CN201310013315.5A CN201310013315A CN103014354B CN 103014354 B CN103014354 B CN 103014354B CN 201310013315 A CN201310013315 A CN 201310013315A CN 103014354 B CN103014354 B CN 103014354B
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- lead
- lotion
- desulfurization
- filter cake
- ball milling
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- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000002253 acid Substances 0.000 title claims abstract description 40
- 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 56
- 239000000243 solution Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 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
- 238000010129 solution processing 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 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
- 238000002386 leaching Methods 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 37
- 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
- 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
- 229910052708 sodium Inorganic materials 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
- 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
- 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
- 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
Landscapes
- 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 process of lead, mainly relate to reclaim plumbous technique from lead acid cell lotion.
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 just 80% left and right of the waste lead storage battery rate of recovery, and well below developed country's level, therefore a large amount of lead can not get efficient recovery and not only can cause the waste of resource also can environment be produced and be polluted.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 start to adopt hydrometallurgic recovery lead, as still hydrometallurgic recovery splicer skill is perfect not enough at present, exist the rate of recovery low, high in cost of production shortcoming, if publication number is CN101636512A(2010-01-27) Chinese patent, first use acetic acid, nitric acid, the acid such as silicofluoric acid and fluoroboric acid is insoluble sulfur lead plumbate by leaded Substance Transformation, with sodium carbonate 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 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 from waste and old lead acid accumulator, reclaim plumbous technique, this technique desulphurization cost is low, desulfuration efficiency is high, lead recovery is high, is applicable to suitability for industrialized production.
The object of the invention is to be achieved by the following technical programs: from lead acid cell lotion, reclaim plumbous technique, it is characterized in that it comprises the following steps processing successively: the pre-desulfurization of ball milling, secondary desulfuration, doctor solution processing, filter cake leach and electrolytic deposition;
The pre-desulfurization of described ball milling is: by the waste and old lead acid accumulator lotion and the Na that separate
2cO
3the aqueous solution in mass ratio 2:1 is sent into and in ball mill, is carried out the pre-desulfurization of ball milling and obtain the pre-desulfurization lotion of ball milling; After the pre-desulfurization of described ball milling, the granularity of lotion is 60-80 micron; In the pre-sweetening process of described ball milling, pass into water;
Described secondary desulfuration is: in the lotion after the pre-desulfurization of ball milling, pass into the Na that mass concentration is 19-21%
2cO
3the aqueous solution, then by PbSO
4join wherein and stir, wherein, PbSO
4with Na
2cO
3mass ratio be 2:1, temperature of reaction is controlled at 40-45 DEG C, pH value in reaction is 6-8.Concrete reaction is as follows:
Described doctor solution processing is: the lotion after secondary desulfuration is carried out obtaining doctor solution after press filtration, in described doctor solution, add Ba
2cO
3and BaCl
2carry out doctor solution processing, while controlling doctor solution processing, temperature is 35-40 DEG C, and 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 processing, generate product Na
2cO
3and BaSO
4, wherein, product Na
2cO
3can be used as sweetening agent and continue to use, product B aSO
4be widely used in paint, ink, electronics, store battery, glass, medicine and other fields, greatly reduce desulphurization cost; In addition, when doctor solution is processed, temperature is 35-40 DEG C, and this temperature does not need extra heating, and the waste heat producing only need utilize secondary desulfuration time 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 so that reaction produce high Na
2sO
4the doctor solution of content, the higher Na of concentration
2sO
4doctor solution is conducive to the carrying out of follow-up doctor solution processing, because Ba
2cO
3with BaSO
4be similarly precipitation, but Ba
2cO
3with respect to BaSO
4processable is higher, therefore can make reaction carry out, and adds high Na simultaneously
2sO
4content can make to react carry out faster, in addition, adds in the present invention by adding Ba
2cO
3and BaCl
2two kinds of doctor solution treatment agents, then control pH value for 13-14 and temperature are 35-40 DEG C, can make the desulfurization treatment solution treatment time shorten to 30-50 minute.
The present invention adopts pre-desulfurization to combine the lead sulfate in waste and old lead acid accumulator is carried out to desulfurization with secondary desulfuration, in sweetening process, pre-desulfurization and secondary desulfuration are respectively according to different concns preparation, and these concentration parameter proportionings are all that 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, fully to ensure that sweetening agent participates in reaction process, to reduce the loss of sweetening agent in vitriol byproduct removal process; PbSO in secondary desulfuration
4with Na
2cO
3mass ratio be 2:1, owing to incessantly containing PbSO in lotion
4therefore in this stage, the concentration of sweetening agent, higher than pre-desulfurization stage, can remove sulphur remaining in lotion to greatest extent, and high-concentration desulfurized dose that after secondary desulfuration, in solution, contains will be returned to the first stage, continue recycle, also can be used as and continue secondary desulfuration use; Dimension the present invention combines pre-desulfurization technique with secondary desulfuration 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 water and plays the effect of wet-milling in pre-sweetening process, and 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 lead plaster sweetening effectiveness is the surface-area that contacts with doctor solution of temperature, lead plaster particle, the concentration of sweetening agent; In the pre-sweetening process of the present invention, follow ball milling simultaneously, 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, improve desulfuration efficiency, in the present invention, the granularity of the pre-desulfurization lotion of ball milling is 60-80 micron, this granularity is to obtain through contriver's long-term practice institute, because can't increase sweetening effectiveness after granularity is too small, on the contrary can 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; Conventionally, the higher sweetening effectiveness of the concentration of sweetening agent is better, but also corresponding raising of cost, and the present invention has reduced the waste of sweetening agent when desulfuration efficiency being improved by twice desulfurization and the concentration of rationally adjusting the middle sodium carbonate of twice desulfurization; In addition, although the high desulphurization reaction temperature that is conducive to of temperature increases rear also corresponding increase of cost, when the temperature of reaction of contriver's long-term practice research discovery secondary desulfuration is controlled at 40-45 DEG C, desulfuration efficiency is best, and cost is also minimum.
The granularity of the present invention's pre-desulfurization lotion of ball milling after the pre-desulfurization of ball milling is 60-80 micron, this granularity not only can make lotion in pre-sweetening process fully be contacted with sweetening agent, can also make secondary desulfuration time, lotion is fully contacted with sweetening agent, improves desulfuration efficiency; In addition, after the pre-desulfurization of ball milling of the present invention and secondary desulfuration, make desulfurization degree in lotion improve, plumbous granularity greatly reduces, and the solution that makes follow-up filter cake leach high lead tolerance is more prone to, thereby the needs that meet concentration of electrolyte configuration in last electrolytic deposition, improve lead recovery greatly.
The present invention adopts the lead in full hydrometallurgic recovery waste lead storage battery, and not only organic efficiency is high, and environmentally safe, and the interaction that closely cooperates of each step of whole technique, makes technological operation of the present invention simple, and cost is low, and organic efficiency is high.
As preferably, when described doctor solution processing, stir, stir speed (S.S.) is 500-700r/min.Under agitation condition, doctor solution processing efficiency is higher.
As preferably, in the pre-desulfurization of described ball milling, Ball-milling Time is 60-80min.
As preferably, when described secondary desulfuration, churning time is 2-3 hour, and stir speed (S.S.) is 400-500r/min.
As preferably, it is first the lotion after secondary desulfuration to be carried out to press filtration to obtain filter cake that described filter cake leaches, more described filter cake is placed in to reaction vessel and successively adds oxalic acid and silicofluoric acid to obtain filter cake leach liquor again.React as follows:
As preferably, described filter cake and described H
2c
2o
4mass ratio be 1:5; When described filter cake leaches, temperature is 45-55 DEG C.
As preferably, content plumbous in described filter cake leach liquor is 170-190g/L.
As preferably, in described electrolytic deposition, electrolytic solution is to be formed by filter cake leach liquor, plumbous liquid, gelatin and phosphoric acid configuration after electrolysis; In described electrolytic solution, lead content is 120-130g/L.
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 is very coated with the graphite cake of lead dioxide plating coat; In described electrolytic deposition, current density is 180～250A/m
2, temperature is 36～42 DEG C.Because plumbic oxide has high catalytic activity, high overpotential for oxygen evolution and unreactiveness as anode, can in the time that galvanic deposit is plumbous, not bring other impurity using plumbic oxide into 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 processing, generate product Na
2cO
3and BaSO
4, wherein, product Na
2cO
3can be used as sweetening agent and continue to use, product B aSO
4be widely used in paint, ink, electronics, store battery, glass, medicine and other fields, greatly reduce desulphurization cost.
2, the present invention desulfurization product reclaim in by passing into CO
2absorb the NH in 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, in the pre-sweetening process of the present invention, follow ball milling simultaneously, 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, has improved desulfuration efficiency; The granularity of the present invention's pre-desulfurization lotion of ball milling after the pre-desulfurization of ball milling is 60-80 micron, this granularity not only can make lotion in pre-sweetening process fully be contacted with sweetening agent, can also make secondary desulfuration time, lotion is fully contacted with sweetening agent, improves desulfuration efficiency.
4, the present invention adopts the lead in full hydrometallurgic recovery waste lead storage battery, and not only organic efficiency is high, and environmentally safe, and the interaction that closely cooperates of each step of whole technique, makes technological operation of the present invention simple, and cost is low, and organic efficiency is high.
Embodiment
This specific embodiment is only explanation of the invention; it is not limitation of the present invention; those skilled in the art are reading after this specification sheets and can make to the present embodiment the amendment that there is no creative contribution as required, but as long as within the scope of claim of the present invention, are all subject to the protection of patent law.
Embodiment 1
From waste and old lead acid accumulator, reclaim plumbous technique, first carry out the pre-desulfurization of ball milling, the Na that is 18% by the waste and old lead acid accumulator lotion of separating and mass concentration
2cO
3the aqueous solution in mass ratio 2:1 is sent into and in ball mill, is carried out the pre-desulfurization of ball milling and obtain the pre-desulfurization lotion of ball milling, the pre-desulfurization time of ball milling is 60min, after the pre-desulfurization of ball milling, the granularity of lotion is 60 microns, passes into water to reduce dust and to play wet-milling effect in the pre-sweetening process of ball milling; Filter cake by the material after pre-ball milling desulfurization after by press filtration is sent into desulfurization storage tank and is carried out secondary desulfuration, contains mass concentration and be 19% Na in desulfurization storage tank
2cO
3the aqueous solution, PbSO in described desulfurization storage tank
4quality and described Na
2cO
3aqueous solution mass ratio is 2:1, and temperature of reaction is 40 DEG C, and after secondary desulfuration, material carries out press filtration again, when secondary desulfuration, stirs, and churning time is 3 hours, and stir speed (S.S.) is 400r/min, and in secondary desulfuration, pH value is 6; Filter filter cake and leave doctor solution, in described doctor solution, add Ba
2cO
3and BaCl
2carry out doctor solution processing, Ba
2cO
3and BaCl
2the quality that adds be the 4/1-2/1 of doctor solution quality; In doctor solution treating processes, carry out stir process, stir speed (S.S.) is 500-700r/min, and while controlling in addition doctor solution processing, temperature is 35-40 DEG C, and pH value is 13-14, and the time is 30-50 minute, and doctor solution is processed rear supernatant liquor and is Na
2cO
3the aqueous solution, throw out is Ba
2sO
4; Filter cake after secondary desulfuration is put into washing bath to wash away the Na of filter residue
2sO
4and Na
2cO
3deng impurity, then the filter cake after washing is placed in to reaction vessel and successively adds oxalic acid and silicofluoric acid to obtain filter cake leach liquor, wherein, filter cake and described H
2c
2o
4mass ratio be 1:5, filter cake leach time temperature be 45 DEG C, filter cake leach after obtain the filter cake leach liquor that lead content is 170-190g/L; Finally carry out electrolytic deposition, electrolytic deposition middle-jiao yang, function of the spleen and stomach is very coated with the graphite cake of lead dioxide plating coat, and in electrolytic deposition, current density is 180A/m
2, temperature is 36 DEG C, electrolytic solution is set to by filter cake leach liquor, plumbous liquid, gelatin and phosphorylated ligand after electrolysis the solution that lead content is 120g/L.
Embodiment 2
From waste and old lead acid accumulator, reclaim plumbous technique, first carry out the pre-desulfurization of ball milling, the Na that is 16% by the waste and old lead acid accumulator lotion of separating and mass concentration
2cO
3the aqueous solution in mass ratio 2:1 is sent into and in ball mill, is carried out the pre-desulfurization of ball milling and obtain the pre-desulfurization lotion of ball milling, the pre-desulfurization time of ball milling is 60min, after the pre-desulfurization of ball milling, the granularity of lotion is 60 microns, passes into water to reduce dust and to play wet-milling effect in the pre-sweetening process of ball milling; Material after pre-ball milling desulfurization is sent filter cake into desulfurization storage tank after by filter pressing pump press filtration and carry out secondary desulfuration, in desulfurization storage tank, contain mass concentration and be 19% Na
2cO
3the aqueous solution, PbSO in described desulfurization storage tank
4quality and described Na
2cO
3aqueous solution mass ratio is 2:1, and temperature of reaction is 40 DEG C, when secondary desulfuration, stirs, and churning time is 3 hours, and stir speed (S.S.) is 400r/min, and in secondary desulfuration, pH value is 6; After secondary desulfuration, material carries out press filtration again, and the filter cake after press filtration is put into washing bath to wash away the Na of filter residue
2sO
4and Na
2cO
3deng impurity, after filtration filter cake, leave doctor solution, in described doctor solution, add Ba
2cO
3and BaCl
2carry out doctor solution processing, Ba
2cO
3and BaCl
2the quality that adds be the 4/1-2/1 of doctor solution quality; In doctor solution treating processes, carry out stir process, stir speed (S.S.) is 500-700r/min, and while controlling in addition doctor solution processing, temperature is 35-40 DEG C, and pH value is 13-14, and the time is 30-50 minute, and doctor solution is processed rear supernatant liquor and is Na
2cO
3the aqueous solution, throw out is Ba
2sO
4; Filter cake after secondary desulfuration washing is placed in reaction vessel and successively adds oxalic acid and silicofluoric acid to obtain filter cake leach liquor again, wherein, and filter cake and described H
2c
2o
4mass ratio be 1:5, filter cake leach time temperature be 45 DEG C, filter cake leach after obtain the filter cake leach liquor that lead content is 170-190g/L; Finally carry out electrolytic deposition, electrolytic deposition middle-jiao yang, function of the spleen and stomach is very coated with the graphite cake of lead dioxide plating coat, and in electrolytic deposition, current density is 180A/m
2, temperature is 36 DEG C, electrolytic solution is set to by filter cake leach liquor, plumbous liquid, gelatin and phosphorylated ligand after electrolysis the solution that lead content is 120g/L.
Embodiment 3
From waste and old lead acid accumulator, reclaim plumbous technique, first carry out the pre-desulfurization of ball milling, the Na that is 17% by the waste and old lead acid accumulator lotion of separating and mass concentration
2cO
3the aqueous solution in mass ratio 2:1 is sent into and in ball mill, is carried out the pre-desulfurization of ball milling and obtain the pre-desulfurization lotion of ball milling, the pre-desulfurization time of ball milling is 60min, after the pre-desulfurization of ball milling, the granularity of lotion is 60 microns, passes into water to reduce dust and to play wet-milling effect in the pre-sweetening process of ball milling; Material after pre-ball milling desulfurization is sent into desulfurization storage tank, in desulfurization storage tank, contain mass concentration and be 19% Na
2cO
3the aqueous solution, PbSO in described desulfurization storage tank
4quality and described Na
2cO
3aqueous solution mass ratio is 2:1, temperature of reaction is 40 DEG C, with filter pressing pump, the material after pre-desulfurization is delivered to pressure filter and carry out press filtration, filter cake after press filtration carries out secondary desulfuration to improve desulfuration efficiency, after secondary desulfuration, material carries out press filtration again, and the solid materials after press filtration is put into washing bath to wash away the Na of filter residue
2sO
4and Na
2cO
3deng impurity, when secondary desulfuration, stir, churning time is 3 hours, and stir speed (S.S.) is 400r/min, and in secondary desulfuration, pH value is 6; Then the lotion after secondary desulfuration is carried out to press filtration obtains filter cake, filters filter cake and leaves doctor solution, in described doctor solution, adds Ba
2cO
3and BaCl
2carry out doctor solution processing, Ba
2cO
3and BaCl
2the quality that adds be the 4/1-2/1 of doctor solution quality; In doctor solution treating processes, carry out stir process, stir speed (S.S.) is 500-700r/min, and while controlling in addition doctor solution processing, temperature is 35-40 DEG C, and pH value is 13-14, and the time is 30-50 minute, and doctor solution is processed rear supernatant liquor and is Na
2cO
3the aqueous solution, throw out is Ba
2sO
4; Filter cake after secondary desulfuration washing is placed in reaction vessel and successively adds oxalic acid and silicofluoric acid to obtain filter cake leach liquor again, wherein, and filter cake and described H
2c
2o
4mass ratio be 1:5, filter cake leach time temperature be 45 DEG C, filter cake leach after obtain the filter cake leach liquor that lead content is 170-190g/L; Finally carry out electrolytic deposition, electrolytic deposition middle-jiao yang, function of the spleen and stomach is very coated with the graphite cake of lead dioxide plating coat, and in electrolytic deposition, current density is 180A/m
2, temperature is 36 DEG C, electrolytic solution is set to by filter cake leach liquor, plumbous liquid, gelatin and phosphorylated ligand after electrolysis the solution that lead content is 120g/L.
Comparative example 1
From waste and old lead acid accumulator, reclaim plumbous technique, first carry out ball milling, the waste and old lead acid accumulator lotion of separating is sent into and in ball mill, carried out ball milling and obtain ball milling lotion, Ball-milling Time is 80min, after ball milling, the granularity of lotion is 80 microns, passes into water to reduce dust and to play wet-milling effect in mechanical milling process; Material after ball milling is carried out to desulfurization with sending into desulfurization storage tank after filter pressing pump press filtration, in desulfurization storage tank, contain mass concentration and be 21% Na
2cO
3the aqueous solution, PbSO in described desulfurization storage tank
4quality and described Na
2cO
3aqueous solution mass ratio is 2:1, and temperature of reaction is 45 DEG C, carries out press filtration and the solid materials after press filtration is put into washing bath to wash away the Na of filter residue after desulfurization
2sO
4and Na
2cO
3deng impurity, when desulfurization, stir, churning time is 3 hours, and stir speed (S.S.) is 500r/min, and in desulfurization, pH value is 8; Lotion after desulfurization washing is placed in to reaction vessel and successively adds oxalic acid and silicofluoric acid to obtain filter cake leach liquor again, wherein, filter cake and described H
2c
2o
4mass ratio be 1:5, filter cake leach time temperature be 55 DEG C, filter cake leach after obtain the filter cake leach liquor that lead content is 170-190g/L; Finally carry out electrolytic deposition, electrolytic deposition middle-jiao yang, function of the spleen and stomach is very coated with the graphite cake of lead dioxide plating coat, and in electrolytic deposition, current density is 250A/m
2, temperature is 42 DEG C, electrolytic solution is set to by filter cake leach liquor, plumbous liquid, gelatin and phosphorylated ligand after electrolysis the solution that lead content is 130g/L.
Comparative example 2
From waste and old lead acid accumulator, reclaim plumbous technique, first carry out the pre-desulfurization of ball milling, the Na that is 18% by the waste and old lead acid accumulator lotion of separating and mass concentration
2cO
3the aqueous solution in mass ratio 2:1 is sent into and in ball mill, is carried out the pre-desulfurization of ball milling and obtain the pre-desulfurization lotion of ball milling, the pre-desulfurization time of ball milling is 80min, after the pre-desulfurization of ball milling, the granularity of lotion is 80 microns, passes into water to reduce dust and to play wet-milling effect in the pre-sweetening process of ball milling; Then the lotion after pre-desulfurization is carried out to press filtration obtains filter cake, and filter cake is placed in to reaction vessel and successively adds oxalic acid and silicofluoric acid to obtain filter cake leach liquor again, wherein, filter cake and described H
2c
2o
4mass ratio be 1:5, filter cake leach time temperature be 55 DEG C, filter cake leach after obtain the filter cake leach liquor that lead content is 170-190g/L; Finally carry out electrolytic deposition, electrolytic deposition middle-jiao yang, function of the spleen and stomach is very coated with the graphite cake of lead dioxide plating coat, and in electrolytic deposition, current density is 250A/m
2, temperature is 42 DEG C, electrolytic solution is set to by filter cake leach liquor, plumbous liquid, gelatin and phosphorylated ligand after electrolysis the solution that lead content is 130g/L.
Testing scheme:
(1) desulfurization transformation efficiency test: the lead plaster particle after the lead plaster particle after embodiment of the present invention desulfurization is transformed and comparative example desulfurization transform 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 obtain plumbous weight and the ratio of original lotion weight after the embodiment of the present invention and comparative example electrolytic deposition, represent with percentage composition.
Result is as shown in table 1:
Table 1 embodiment of the present invention and comparative example's test result
Test result analysis: as shown in Table 1, in embodiment of the present invention technique, desulfurization degree is far away higher than the desulfurization degree of comparative example, in addition, the lead recovery of the embodiment of the present invention is also higher than the lead recovery of comparative example, illustrate that technique of the present invention has not only improved lotion desulfurization degree, also promote follow-up technique, and then improved lead recovery.
Claims (7)
1. from lead acid cell lotion, reclaim plumbous technique, it is characterized in that it comprises the following steps processing successively: the pre-desulfurization of ball milling, secondary desulfuration, doctor solution processing, filter cake leach and electrolytic deposition;
The pre-desulfurization of described ball milling is: by the waste and old lead acid accumulator lotion and the Na that separate
2cO
3the aqueous solution in mass ratio 2:1 is sent into and in ball mill, is carried out the pre-desulfurization of ball milling and obtain the pre-desulfurization lotion of ball milling; After the pre-desulfurization of described ball milling, the granularity of lotion is 60-80 micron; In the pre-sweetening process of described ball milling, pass into water;
Described secondary desulfuration is: in the lotion after the pre-desulfurization of ball milling, pass into the Na that mass concentration is 19-21%
2cO
3the aqueous solution, then by PbSO
4join wherein and stir, wherein, PbSO
4with Na
2cO
3mass ratio be 2:1, temperature of reaction is controlled at 40-45 DEG C, pH value in reaction is 6-8;
Described doctor solution processing is: the lotion after secondary desulfuration is carried out obtaining doctor solution after press filtration, in described doctor solution, add Ba
2cO
3and BaCl
2carry out doctor solution processing, while controlling doctor solution processing, temperature is 35-40 DEG C, and pH value is 13-14, and the time is 30-50 minute;
In described electrolytic deposition, electrolytic solution is to be formed by filter cake leach liquor, plumbous liquid after electrolysis, gelatin and phosphoric acid configuration; In described electrolytic solution, lead content is 120-130g/L;
Described electrolytic deposition middle-jiao yang, function of the spleen and stomach is very coated with the graphite cake of lead dioxide plating coat; In described electrolytic deposition, current density is 180～250A/m
2, temperature is 36～42 DEG C;
It is first the lotion after secondary desulfuration to be carried out to press filtration to obtain filter cake that described filter cake leaches, more described filter cake is placed in to reaction vessel and successively adds oxalic acid and silicofluoric acid to obtain filter cake leach liquor again.
2. from lead acid cell lotion, reclaim as claimed in claim 1 plumbous technique, it is characterized in that: described doctor solution stirs while processing, and stir speed (S.S.) is 500-700r/min.
3. from lead acid cell lotion, reclaim as claimed in claim 2 plumbous technique, it is characterized in that: in the pre-desulfurization of described ball milling, Ball-milling Time is 60-80min.
4. from lead acid cell lotion, reclaim as claimed in claim 3 plumbous technique, it is characterized in that: when described secondary desulfuration, churning time is 2-3 hour, stir speed (S.S.) is 400-500r/min.
5. from lead acid cell lotion, reclaim as claimed in claim 4 plumbous technique, it is characterized in that: described filter cake and described H
2c
2o
4mass ratio be 1:5; When described filter cake leaches, temperature is 45-55 DEG C.
6. from lead acid cell lotion, reclaim as claimed in claim 5 plumbous technique, it is characterized in that: content plumbous in described filter cake leach liquor is 170-190g/L.
7. from lead acid cell lotion, reclaim as claimed in claim 6 plumbous technique, it is characterized in that:
Described electrolytic solution gelatin is 0.8～1.5Kg/t, and phosphoric acid is 2～5Kg/t.
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| CN103833070B (en) * | 2013-12-20 | 2015-11-11 | 柳州百韧特先进材料有限公司 | A kind of method reducing lead content in tin protochloride |
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| ITMI20041456A1 (en) * | 2004-07-20 | 2004-10-20 | Engitec S R L | PASTEL DESULFORATION PROCESS AND LEAD STORAGE GRIDS + |
| CN100569967C (en) * | 2007-06-22 | 2009-12-16 | 上海飞轮有色冶炼厂 | A kind of desulfurization and transformation method of waste lead accumulator regenerative lead |
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