CN102351217A - Method of removing lead in by-product sodium sulfate of recovery and processing of waste lead storage batteries - Google Patents
Method of removing lead in by-product sodium sulfate of recovery and processing of waste lead storage batteries Download PDFInfo
- Publication number
- CN102351217A CN102351217A CN2011101671334A CN201110167133A CN102351217A CN 102351217 A CN102351217 A CN 102351217A CN 2011101671334 A CN2011101671334 A CN 2011101671334A CN 201110167133 A CN201110167133 A CN 201110167133A CN 102351217 A CN102351217 A CN 102351217A
- Authority
- CN
- China
- Prior art keywords
- lead
- sodium sulfate
- carbonate
- sodium
- mother liquor
- 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.)
- Granted
Links
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 16
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 15
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000002699 waste material Substances 0.000 title claims abstract description 11
- 239000006227 byproduct Substances 0.000 title claims abstract description 6
- 238000011084 recovery Methods 0.000 title abstract description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 9
- 229910000004 White lead Inorganic materials 0.000 claims abstract description 8
- 239000012452 mother liquor Substances 0.000 claims abstract description 7
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000004821 distillation Methods 0.000 claims abstract description 3
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 claims description 8
- 235000017550 sodium carbonate Nutrition 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 238000006477 desulfuration reaction Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 230000023556 desulfurization Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000000706 filtrate Substances 0.000 abstract 2
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 abstract 2
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 5
- 239000010413 mother solution Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910000003 Lead carbonate Inorganic materials 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
Provided is a method of removing lead in the by-product sodium sulfate of recovery and processing of waste lead storage batteries. According to the invention, mother liquor for desulphurization by using crude lead mud and sodium carbonate are fully stirred, and a sodium hydroxide solution is added until the pH value of the mother liquor is 10; a sodium carbonate solution is added drop by drop under the condition of complete stirring until the pH value of the mother liquor is 10.5; lead sulfate is converted into basic lead carbonate which is precipitated; basic lead carbonate precipitate is removed by filtering and is recovered; obtained filtrate is condensed through distillation, and condensed filtrate is cooled to obtain crystals of sodium sulfate decahydrate, wherein, lead content in the crystals of sodium sulfate decahydrate meets quality requirements for industrial products of sodium sulfate. The method provided in the invention is simple and feasible.
Description
Technical field
The present invention relates to waste and old lead storage battery and recycle, specifically, is that waste and old lead storage battery reclaims the method for taking off lead in the processing in the sodium sulfate byproduct.
Background technology
Along with the automotive industry great development; The recovery processing of waste and old lead storage battery is important all the more; The plumbous mud that obtains in the recovery processing of waste and old lead storage battery; Adopt the preparatory sulfur removal technology of yellow soda ash; The lead sulfate that is about in the plumbous mud transfers lead carbonate to; Desulfuration efficiency reaches more than 96% in advance; Greatly reduce the sulphur content in the raw materials for metallurgy; Reduced the sulphur emissions amount in the flue gas in the fusion process; Be converted into low-melting lead carbonate because of high-melting-point lead sulfate in the raw material simultaneously; Reduce the smelting reducing temperature, reduced fuel consumption.Fig. 1 is seen in its technical process.
Mainly contain sodium sulfate, yellow soda ash in the desulphurization mother solution in advance, and unconverted lead sulfate (lead content about 0.2% in the sodium sulfate) etc., directly condensing crystal is inevitable leaded in the gained sodium sulfate.
Summary of the invention
The present invention adopts the chemical precipitation technology that preparatory desulphurization mother solution is taken off plumbous the processing, and its technical scheme is following:
A kind of waste and old lead storage battery reclaims the method for removing lead of by-product sodium sulfate in the processing, and as shown in Figure 2, it comprises the steps:
Step 1. adds lead bullion mud mother liquor hydro-oxidation sodium solution under fully stirring of yellow soda ash desulfurization, to its pH value=10,
Step 2. drips sodium carbonate solution with step 1 gained solution under fully stirring, to its pH=10.5, make lead sulfate be converted into white lead carbonate (Pb
2(OH)
2CO
3), deposition,
Step 3. removes by filter step 2 gained deposition white lead carbonate, reclaims,
Step 4. concentrates the filtrating distillation of step 3 gained, and cooling obtains the sal glauberi crystallization, and its lead tolerance reaches the industrial goods specification of quality of sodium sulfate.
Method simple possible of the present invention, the lead of the plumbiferous sodium sulfate mother liquor that waste and old lead storage battery is reclaimed produce in the plumbous sweetening process is produced white lead carbonate and is reclaimed, and the mother liquor behind the deleading concentrates the sal glauberi that obtains meeting sodium sulfate industrial goods specification of quality.
Description of drawings
Fig. 1 is waste and old lead storage battery roughing flow diagram;
Fig. 2 takes off splicer's process flow skeleton diagram for plumbous mud desulphurization mother solution of the present invention.
Embodiment
Embodiment
Get the preparatory desulphurization mother solution of 100ml, its sodium sulphate content is 15.3%, and lead content is 500mg/L.Under agitation drip 15% sodium hydroxide solution to pH=10, change into and drip 15% sodium carbonate solution, to pH=10.5, continue to stir 20min, generate a large amount of white cotton-shaped white lead carbonate depositions, filter, lead concentration is 0.4 mg/L in the filtrating.
Filtrating is concentrated into 50ml, and crystallisation by cooling is separated out colourless sal glauberi crystal 12.6g.Get the 5g sal glauberi and use water dissolution again, survey its lead content, obtaining the sal glauberi lead content is 0.022%, satisfies the specification of quality of industrial goods sodium sulfate.
Claims (1)
1. the method for removing lead of by-product sodium sulfate is characterized in that it comprises the steps: during a waste and old lead storage battery reclaimed and processes
Step 1. adds lead bullion mud mother liquor hydro-oxidation sodium solution under fully stirring of yellow soda ash desulfurization, to its pH value=10,
Step 2. at abundant agitation and dropping sodium carbonate solution, to its pH=10.5, makes lead sulfate be converted into white lead carbonate step 1 gained solution, deposition,
Step 3. removes by filter step 2 gained deposition white lead carbonate, reclaims,
Step 4. concentrates the filtrating distillation of step 3 gained, and cooling obtains the sal glauberi crystallization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110167133.4A CN102351217B (en) | 2011-06-21 | 2011-06-21 | Method of removing lead in by-product sodium sulfate of recovery and processing of waste lead storage batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110167133.4A CN102351217B (en) | 2011-06-21 | 2011-06-21 | Method of removing lead in by-product sodium sulfate of recovery and processing of waste lead storage batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102351217A true CN102351217A (en) | 2012-02-15 |
| CN102351217B CN102351217B (en) | 2013-07-31 |
Family
ID=45574900
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110167133.4A Expired - Fee Related CN102351217B (en) | 2011-06-21 | 2011-06-21 | Method of removing lead in by-product sodium sulfate of recovery and processing of waste lead storage batteries |
Country Status (1)
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|---|---|
| CN (1) | CN102351217B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9533273B2 (en) | 2014-06-20 | 2017-01-03 | Johnson Controls Technology Company | Systems and methods for isolating a particulate product when recycling lead from spent lead-acid batteries |
| CN106337112A (en) * | 2016-08-25 | 2017-01-18 | 安徽华铂再生资源科技有限公司 | Wet low-liquid-solid-ratio desulfurization process for waste lead-acid storage battery lead plaster |
| US9670565B2 (en) | 2014-06-20 | 2017-06-06 | Johnson Controls Technology Company | Systems and methods for the hydrometallurgical recovery of lead from spent lead-acid batteries and the preparation of lead oxide for use in new lead-acid batteries |
| CN107640778A (en) * | 2017-09-04 | 2018-01-30 | 超威电源有限公司 | A kind of method of the low cost recovery sodium sulphate from leaded desulfurization waste liquor |
| US10062933B2 (en) | 2015-12-14 | 2018-08-28 | Johnson Controls Technology Company | Hydrometallurgical electrowinning of lead from spent lead-acid batteries |
| CN113846223A (en) * | 2021-10-16 | 2021-12-28 | 安徽省华鑫铅业集团有限公司 | Method for desulfurizing, processing and recycling lead slime of waste battery |
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| US20060018819A1 (en) * | 2004-07-20 | 2006-01-26 | Engitech S.R.I. | Desulfurization process of pastel and grids of lead accumulators |
| CN101244831B (en) * | 2008-03-18 | 2010-06-30 | 华中科技大学 | Method and device for recycling anhydrous sodium sulfate from desulfurization lead plaster filter liquor |
-
2011
- 2011-06-21 CN CN201110167133.4A patent/CN102351217B/en not_active Expired - Fee Related
Patent Citations (2)
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| US20060018819A1 (en) * | 2004-07-20 | 2006-01-26 | Engitech S.R.I. | Desulfurization process of pastel and grids of lead accumulators |
| CN101244831B (en) * | 2008-03-18 | 2010-06-30 | 华中科技大学 | Method and device for recycling anhydrous sodium sulfate from desulfurization lead plaster filter liquor |
Non-Patent Citations (1)
| Title |
|---|
| 胡辉等: "铅膏脱硫及其滤液中硫酸钠回收利用的影响因素实验研究", 《中国环境科学学会学术年会论文集》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10403940B2 (en) | 2014-06-20 | 2019-09-03 | Cps Technology Holdings Llc | Systems and methods for closed-loop recycling of a liquid component of a leaching mixture when recycling lead from spent lead-acid batteries |
| US10122052B2 (en) | 2014-06-20 | 2018-11-06 | Johnson Controls Technology Company | Systems and methods for purifying and recycling lead from spent lead-acid batteries |
| US9555386B2 (en) | 2014-06-20 | 2017-01-31 | Johnson Controls Technology Company | Systems and methods for closed-loop recycling of a liquid component of a leaching mixture when recycling lead from spent lead-acid batteries |
| US9670565B2 (en) | 2014-06-20 | 2017-06-06 | Johnson Controls Technology Company | Systems and methods for the hydrometallurgical recovery of lead from spent lead-acid batteries and the preparation of lead oxide for use in new lead-acid batteries |
| US9751067B2 (en) | 2014-06-20 | 2017-09-05 | Johnson Controls Technology Company | Methods for purifying and recycling lead from spent lead-acid batteries |
| US9757702B2 (en) | 2014-06-20 | 2017-09-12 | Johnson Controls Technology Company | Systems and methods for purifying and recycling lead from spent lead-acid batteries |
| US11923518B2 (en) | 2014-06-20 | 2024-03-05 | Clarios Advanced Germany Gmbh & Co. KG | Systems and methods for closed-loop recycling of a liquid component of a leaching mixture when recycling lead from spent lead-acid batteries |
| US11791505B2 (en) | 2014-06-20 | 2023-10-17 | Cps Technology Holdings Llc | Methods for purifying and recycling lead from spent lead-acid batteries |
| US11005129B2 (en) | 2014-06-20 | 2021-05-11 | Clarios Germany Gmbh & Co. Kgaa | Systems and methods for closed-loop recycling of a liquid component of a leaching mixture when recycling lead from spent lead-acid batteries |
| US9533273B2 (en) | 2014-06-20 | 2017-01-03 | Johnson Controls Technology Company | Systems and methods for isolating a particulate product when recycling lead from spent lead-acid batteries |
| US10777858B2 (en) | 2014-06-20 | 2020-09-15 | Cps Technology Holdings Llc | Methods for purifying and recycling lead from spent lead-acid batteries |
| US10062933B2 (en) | 2015-12-14 | 2018-08-28 | Johnson Controls Technology Company | Hydrometallurgical electrowinning of lead from spent lead-acid batteries |
| CN106337112A (en) * | 2016-08-25 | 2017-01-18 | 安徽华铂再生资源科技有限公司 | Wet low-liquid-solid-ratio desulfurization process for waste lead-acid storage battery lead plaster |
| CN107640778A (en) * | 2017-09-04 | 2018-01-30 | 超威电源有限公司 | A kind of method of the low cost recovery sodium sulphate from leaded desulfurization waste liquor |
| CN113846223A (en) * | 2021-10-16 | 2021-12-28 | 安徽省华鑫铅业集团有限公司 | Method for desulfurizing, processing and recycling lead slime of waste battery |
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| Publication number | Publication date |
|---|---|
| CN102351217B (en) | 2013-07-31 |
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