CN101885510B - A method for preparing lead chloride and calcium sulfate by wet method of waste lead storage battery lead paste - Google Patents
A method for preparing lead chloride and calcium sulfate by wet method of waste lead storage battery lead paste Download PDFInfo
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- CN101885510B CN101885510B CN201010211871XA CN201010211871A CN101885510B CN 101885510 B CN101885510 B CN 101885510B CN 201010211871X A CN201010211871X A CN 201010211871XA CN 201010211871 A CN201010211871 A CN 201010211871A CN 101885510 B CN101885510 B CN 101885510B
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- CN
- China
- Prior art keywords
- lead
- chloride
- filtrate
- calcium sulfate
- leaching
- 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.)
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 35
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 title claims abstract description 28
- 239000002699 waste material Substances 0.000 title claims abstract description 19
- 239000011505 plaster Substances 0.000 claims abstract description 38
- 238000002386 leaching Methods 0.000 claims abstract description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001110 calcium chloride Substances 0.000 claims abstract description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000011780 sodium chloride Substances 0.000 claims abstract description 4
- 239000000706 filtrate Substances 0.000 claims abstract 13
- 239000011593 sulfur Substances 0.000 claims abstract 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract 3
- 239000002244 precipitate Substances 0.000 claims abstract 2
- 239000012065 filter cake Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 230000004087 circulation Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 19
- 229910052602 gypsum Inorganic materials 0.000 abstract description 2
- 239000010440 gypsum Substances 0.000 abstract description 2
- 235000011132 calcium sulphate Nutrition 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 4
- 239000001175 calcium sulphate Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Processing Of Solid Wastes (AREA)
Abstract
A method for preparing lead chloride and calcium sulfate from waste lead storage battery lead plaster by a wet method takes the waste lead storage battery lead plaster as a raw material, comprises the steps of leaching the lead plaster in an HCl-NaCl system, performing cold separation and crystallization on leaching solution, separating, washing and drying, and is characterized in that: recovering sulfur resources from the cold separation filtrate and realizing closed cycle of the cold separation filtrate, namely adding calcium chloride into the cold separation filtrate to generate calcium sulfate precipitate, separating, washing and drying to obtain a calcium sulfate product, and returning the filtrate to the leaching process by being matched with saturated NaCl solution. The method not only obtains lead chloride, but also obtains industrial gypsum with the purity of more than 97 percent, so that sulfur resources are recycled, cold separation filtrate is recycled, the lead recovery rate is more than 96 percent after four cycles, and the problems of lead resource waste and lead pollution are avoided.
Description
One, technical field
The present invention relates to the technical field of recycling, recycling and the inorganic salt preparation of waste lead accumulator; Be particularly related to a kind of recovery and treatment method of waste lead accumulator lead plaster, relate in particular to the method for preparing lead chloride and calcium sulfate by waste lead accumulator lead plaster wet method.
Two, background technology
Plumbous purposes is very extensive, and its YO is only second to aluminium, copper, zinc and occupies the 4th in non-ferrous metal.Along with the development of society, human demand to lead is still in continuous increase.Because the lead resource of occurring in nature is exhausted day by day, the recovery and the recycling that therefore contain scrap lead have obtained paying close attention to widely.
According to incompletely statistics, in the lead of whole world consumption, nearly 80%～85% is used for lead storage battery, so waste lead accumulator is the current topmost plumbous raw material that reclaims.Different based on the recovery method of waste lead accumulator, plumbous recovery technology is broadly divided into pyrogenic process, do three kinds of wet combination method and full wet methods.At present, domestic secondary lead factory extensively adopts pyrogenic process to reclaim waste lead accumulator.This technical maturity, equipment is simple, the little income of cost is big, but problem such as the ubiquity lead recovery is lower, environmental pollution is more serious.Adopt of modern secondary lead factory done wet integrated process, i.e. wet desulphurization conversion-fire reduction smelting technique more.Full hydrometallurgic recovery technology does not produce pollution basically, and lead recovery is high, energy consumption is low, is a kind of eco-friendly recycling waste lead batteries method, also is the main direction of studying of current secondary lead recovery method.
The method of utilizing the lead plaster wet method to prepare lead chloride at present mainly is the villaumite method, promptly under the HCl-NaCl system, the lead in the lead plaster is leached out with the form of lead chloride, behind cold crystallization, makes the lead chloride product.The villaumite legal system is equipped with lead chloride and has characteristics such as technological process is simple, energy expenditure is low, good product quality.But cold crystallization can not make lead chloride separate out fully in this method, causes lead recovery low.In addition, to the sulfate ion removal yet not yet in effect in the cold analysis filtrating, cause cold analysis filtrating can not carry out recycle, the waste resource is not said, and is prone to cause Lead contamination etc.
Three, summary of the invention
The present invention is directed to above-mentioned existing in prior technology weak point, aim to provide and a kind ofly improvedly prepare the method for lead chloride and calcium sulfate by waste lead accumulator lead plaster wet method, technical problem to be solved is to improve lead recovery, reclaims the sulphur resource simultaneously.
The method for preparing lead chloride and calcium sulfate by waste lead accumulator lead plaster wet method provided by the invention; With the waste lead accumulator lead plaster is raw material; Comprise that lead plaster leaches in the HCl-NaCl system, leaching liquid cold crystallization and separation, washing and drying, difference with the prior art is in cold analysis filtrating, to reclaim the sulphur resource and realize the closed cycle of cold analysis filtrating.Here it is adds calcium chloride in cold analysis filtrating, generate calcium sulfate precipitation, after separation, washing, drying, obtains the calcium sulfate product, and filtrating is used for joining saturated NaCl solution and returns the leaching operation.
The major constituent content of used lead plaster is as shown in table 1:
Table 1 lead plaster major constituent content
The concrete operations step is following:
Described lead plaster leaching is in the lead plaster of granularity less than 100 μ m; By lead plaster and saturated nacl aqueous solution weight ratio is 1: 13～15 adding saturated nacl aqueous solutions; And by lead plaster with it weight ratio be that 1: 2～2.5 to add weight percent concentration be 37% hydrochloric acid; React 150～180min down at 70-100 ℃, filtered while hot got filter cake and filtrating after reaction finished;
Described leaching liquid cold crystallization is that said lead plaster leaching filtrating is reduced to room temperature, and at room temperature leaves standstill more than the 3h, and lead chloride crystallisation by cooling is wherein separated out, and filters; Filter cake is through washing, be drying to obtain lead chloride; Contain undecomposed lead chloride and sodium sulfate byproduct in the filtrating;
The described sulphur resource that in cold analysis filtrating, reclaims is in cold analysis filtrating, to add calcium chloride, and wherein sulfate ion generates calcium sulfate precipitation, filters; Filter cake is through washing, be drying to obtain the calcium sulfate product; Sulfate ion content has obtained effective reduction in the filtrating, can prepare saturated NaCl solution return the leaching operation recycle the little amounts of Pb Cl that it is contained
2Also be able to reclaim once more.
Each step reaction equation of the inventive method is:
A, lead plaster leaching
PbSO
4+2NaCl→PbCl
2+Na
2SO
4
Pb+2HCl→PbCl
2+H
2↑
PbO+2HCl→PbCl
2+H
2O
PbO
2+4HCl→PbCl
2+2H
2O+Cl
2↑
Pb+PbO
2+4HCl→2PbCl
2+2H
2O
B, cold analysis filtrating sulfate radical ion
Na
2SO
4+CaCl
2→CaSO
4↓+2NaCl
Compared with present technology, beneficial effect of the present invention is embodied in:
1, the inventive method can make the sulfate ion in the cold analysis filtrating effectively removed; Realized recycling of cold analysis filtrating, effectively improved the plumbous recovery, cold analysis filtrating is through four circulations; Lead recovery reaches more than 96%, and more traditional 85% has improved more than 11%.Plumbous waste and the Lead contamination problem of bringing have thus been avoided;
2, the inventive method has also been produced byproduct calcium sulfate when the sulfate ion in the cold analysis filtrating is effectively removed, and purity reaches more than 97%, can be used as industrial gypsum and directly uses, and makes the sulphur resource obtain effective recycling.
Four, embodiment
Embodiment 1: present embodiment carries out as follows:
1, be in the lead plaster of 74 μ m in granularity; By lead plaster and saturated nacl aqueous solution weight ratio is 1: 13 adding saturated nacl aqueous solution; And by lead plaster with it weight ratio be that to add weight percent concentration at 1: 2.5 be 37% hydrochloric acid; React 170min down at 75 ℃, filtered while hot got filter cake and filtrating after reaction finished, and plumbous leaching yield is 99.2%.
2, above-mentioned lead plaster leaching filtrating is reduced to room temperature, and at room temperature leave standstill 3.5h, lead chloride crystallisation by cooling is wherein separated out, filter; Filter cake promptly got the lead chloride product in 1.5 hours through washing, 105 ℃ of dryings.Lead chloride content is 99.6% in this product, has reached the requirement of quality standard.
3, in above-mentioned cold analysis filtrating by lead plaster with it weight ratio be to add industrial calcium chloride at 1: 0.25, wherein sulfate ion generates calcium sulfate precipitation, filters; Filter cake promptly got the calcium sulfate product in 2 hours through washing, 110 ℃ of dryings, and calcium sulphate content is 97.5% in this product, has reached the requirement of quality standard.Filtrating is joined and is returned the leaching operation behind the saturated nacl aqueous solution and recycle.The cold analysis not circulation time of filtrating, the plumbous recovery is 85.6%; When cold analysis filtrating was handled back circulation 4 times, the plumbous recovery was 96.8%.
Embodiment 2: present embodiment carries out as follows:
1, be in the lead plaster of 74 μ m in granularity; By lead plaster and saturated nacl aqueous solution weight ratio is 1: 14 adding saturated nacl aqueous solution; And by lead plaster with it weight ratio be that to add weight percent concentration at 1: 2.2 be 37% hydrochloric acid; React 150min down at 95 ℃, filtered while hot got filter cake and filtrating after reaction finished, and plumbous leaching yield is 99.5%.
2, above-mentioned lead plaster leaching filtrating is reduced to room temperature, and at room temperature leave standstill 4h, lead chloride crystallisation by cooling is wherein separated out, filter; Filter cake promptly got the lead chloride product in 2 hours through washing, 101 ℃ of dryings.Lead chloride content is 99.4% in this product, has reached the requirement of quality standard.
3, in above-mentioned cold analysis filtrating by lead plaster with it weight ratio be to add industrial calcium chloride at 1: 0.22, wherein sulfate ion generates calcium sulfate precipitation, filters; Filter cake promptly got the calcium sulfate product in 2.5 hours through washing, 106 ℃ of dryings, and calcium sulphate content is 97.4% in this product, has reached the requirement of quality standard.Filtrating is joined and is returned the leaching operation behind the saturated nacl aqueous solution and recycle.The cold analysis not circulation time of filtrating, the plumbous recovery is 85.4%; When cold analysis filtrating was handled back circulation 4 times, the plumbous recovery was 96.5%.
Embodiment 3: present embodiment carries out as follows:
1, be in the lead plaster of 74 μ m in granularity; By lead plaster and saturated nacl aqueous solution weight ratio is 1: 15 adding saturated nacl aqueous solution; And by lead plaster with it weight ratio be that to add weight percent concentration at 1: 2 be 37% hydrochloric acid; React 160min down at 85 ℃, filtered while hot got filter cake and filtrating after reaction finished, and plumbous leaching yield is 99.7%.
2, above-mentioned lead plaster leaching filtrating is reduced to room temperature, and at room temperature leave standstill 4.5h, lead chloride crystallisation by cooling is wherein separated out, filter; Filter cake promptly got the lead chloride product in 1 hour through washing, 108 ℃ of dryings.Lead chloride content is 99.2% in this product, has reached the requirement of quality standard.
3, in above-mentioned cold analysis filtrating by lead plaster with it weight ratio be to add industrial calcium chloride at 1: 0.25, wherein sulfate ion generates calcium sulfate precipitation, filters; Filter cake promptly got the calcium sulfate product in 3 hours through washing, 102 ℃ of dryings, and calcium sulphate content is 97.2% in this product, has reached the requirement of quality standard.Filtrating is joined and is returned the leaching operation behind the saturated nacl aqueous solution and recycle.The cold analysis not circulation time of filtrating, the plumbous recovery is 85.0%; When cold analysis filtrating was handled back circulation 4 times, the plumbous recovery was 96.1%.
Claims (1)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010211871XA CN101885510B (en) | 2010-06-25 | 2010-06-25 | A method for preparing lead chloride and calcium sulfate by wet method of waste lead storage battery lead paste |
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|---|---|---|---|
| CN201010211871XA CN101885510B (en) | 2010-06-25 | 2010-06-25 | A method for preparing lead chloride and calcium sulfate by wet method of waste lead storage battery lead paste |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730748B (en) * | 2012-04-01 | 2015-04-29 | 东北大学 | Method for preparing lead chloride and zinc sulfate by using mid low grade zinc oxide ores and zinc oxide-lead oxide paragenetic ores |
| CN103667735B (en) * | 2013-12-06 | 2016-01-13 | 云南祥云飞龙再生科技股份有限公司 | A method for recycling lead from waste lead storage batteries |
| CN104891704A (en) * | 2015-05-05 | 2015-09-09 | 岳嵩 | High-salt content waste water treatment method |
| CN105063368A (en) * | 2015-09-29 | 2015-11-18 | 卢润湖 | Method for preparing lead chloride |
| CN107385227A (en) * | 2017-07-25 | 2017-11-24 | 上海第二工业大学 | The mechanochemistry recovery method of lead in a kind of flint glass |
| CN110791661A (en) * | 2019-09-18 | 2020-02-14 | 超威电源集团有限公司 | Waste lead paste recovery treatment method |
| CN110923467A (en) * | 2019-11-28 | 2020-03-27 | 三明学院 | A method for recycling lead from waste lead-acid battery |
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| US4229271A (en) * | 1979-05-24 | 1980-10-21 | Rsr Corporation | Method of recovering lead values from battery sludge |
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