CN113151864A - Process for treating waste lead storage battery by rotating cathode four-row anode continuous solid-phase electrolysis, ion electrolysis, anodic oxidation and mechanical separation - Google Patents
Process for treating waste lead storage battery by rotating cathode four-row anode continuous solid-phase electrolysis, ion electrolysis, anodic oxidation and mechanical separation Download PDFInfo
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- CN113151864A CN113151864A CN202110331238.2A CN202110331238A CN113151864A CN 113151864 A CN113151864 A CN 113151864A CN 202110331238 A CN202110331238 A CN 202110331238A CN 113151864 A CN113151864 A CN 113151864A
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- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000007790 solid phase Substances 0.000 title claims abstract description 21
- 239000002699 waste material Substances 0.000 title claims abstract description 21
- 238000003860 storage Methods 0.000 title claims abstract description 18
- 230000003647 oxidation Effects 0.000 title claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 11
- 238000000926 separation method Methods 0.000 title claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 4
- 239000010935 stainless steel Substances 0.000 claims abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 4
- 239000010959 steel Substances 0.000 claims abstract description 4
- 239000011505 plaster Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 229910000978 Pb alloy Inorganic materials 0.000 abstract description 4
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 3
- 229910052924 anglesite Inorganic materials 0.000 abstract description 2
- 150000002611 lead compounds Chemical class 0.000 abstract description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005096 rolling process Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 2
- 238000004064 recycling Methods 0.000 abstract 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 7
- 238000003723 Smelting Methods 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000005272 metallurgy Methods 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 208000008127 lead poisoning Diseases 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a process for treating waste lead storage batteries by rotating cathodes, four rows of anodes, continuous solid-phase electrolysis, ionic electrolysis, anodic oxidation and mechanical separation. The electrolysis is carried out in an electrolytic bath made of steel, NaOH electrolyte. The rotating anode is formed by rolling an inner layer steel plate and an outer layer stainless steel plate. The inner layer is drilled with holes and is distributed with spiral belts. The desulfurized and converted polar plate is mechanically separated from the grid in the rotating cathode. Lead plaster components: pb 0、PbO、PbO2、PbSO4Uniformly and freely suspended in electrolyte as dispersed solid phase, and lead in lead compound is reduced into lead by solid phase electrolysisThe electric lead is deposited on the surface of the rotating cathode; a part of Pb 0Reducing the lead into electric lead through ion electrolysis, and depositing the electric lead on the surface of the rotating cathode. Another part Pb 0Is oxidized into P by the oxygen atoms separated out at the anodebAnd O, depositing on the anode plate. The grid after de-pasting is discharged out of the groove from the rotary cathode. Increase the yield of P in the anodebO, less electric lead is produced. Electric lead production PbThe O process is complex and pollutes the environment. Electric lead, lead alloy and PbAnd O is used as a storage battery. The resource recycling is green and environment-friendly, and no carbon is discharged.
Description
Technical Field
The invention belongs to the field of lead-containing waste solid-phase electrolysis, ion electrolysis, anodic oxidation and mechanical separation metallurgy. Method for treating waste lead storage battery by wet metallurgy to recover lead, lead alloy and PbO。
Background
Lead is recovered from waste lead accumulators by the traditional method of pyrometallurgical smelting. The method is operated at high temperature, and a large amount of sulfur dioxide and lead steam are discharged during smelting, thereby seriously polluting the environment and causing lead poisoning of operators. Low metal recovery rate and high energy consumption.
In order to solve the problems of pyrometallurgical extraction, the technological research of extracting lead metal by wet smelting is widely carried out. The research method has long process and higher production cost than the fire method.
The American Ministry of mining services roller research center breaks and separates the waste lead storage battery by M.A, so that a plate grid of a polar plate is separated from lead plaster, and the lead plaster is desulfurized, converted, dissolved and electrolyzed to obtain the electric lead. And melting and casting the grid into an anode plate, and carrying out electrolytic refining to obtain the electrolytic lead. Industrial experiments were performed.
Engitec, Italy, semi-industrial experiments. CX crushing and separating waste lead accumulator, Na for lead paste2CO3Desulfurization conversion with HBF4Leaching to form Pb(BF4)2And (3) solution. Electrolyzing to obtain the electrolytic lead.
The solid-phase electrolysis process for treating waste lead storage batteries from lead materials contained in chemical metallurgy in Chinese academy of sciences. The waste lead storage battery is crushed and separated by M.A to obtain lead paste and a grid, the grid is melted to obtain lead alloy, and the slag yield is 20 percent and is used as a return material. And (4) carrying out desulfurization and conversion on the lead plaster to prepare a cathode plate, and carrying out alkaline solution and solid-phase electrolysis to obtain the electric lead. Realizes industrial production, the electrolysis period is 20 hours, and the intermittent production is realized.
The three processes all adopt CX or M.A crushing and separating systems. The lead plaster is desulfurized, converted and dissolved in acid or electrolyzed in solid phase to obtain the electrolytic lead. The process is complicated. A set of small CX crushing and separating device can process 50 tons of waste lead storage batteries per hour, and the weight of the equipment is 50 tons.
A process for treating waste lead accumulator by continuous solid-phase electrolysis of the rotary cathode of a vest. The invention patent No. 201110173817.5, the electrode plate after desulfurization and conversion is not broken and separated by CX or M.A, and is added into a rotary cathode to carry out solid phase electrolysis in alkaline solution. And (4) obtaining electric lead on the surface of the rotating cathode, obtaining a grid in the electric lead, and automatically discharging the electric lead out of the groove. Lead and the grid are completely separated, so that industrial production is realized, and the production is continuously carried out. The invention does not disclose P in the lead pasteb 0Removing, generating P on the anodebThe reaction mechanism of O.
Disclosure of Invention
To disclose the lead paste P in the 201110173817.5 invention patentb 0Removing, generating P on the anodebThe invention relates to a reaction mechanism of O and an additional anode, and particularly discloses a process for treating waste lead storage batteries by rotating a cathode, four rows of anodes, continuous solid-phase electrolysis, ion electrolysis, anodic oxidation and mechanical separation. Adding anode to make the anode generate more PbO, reducing the yield of cathode electrolytic lead, and producing P from the electrolytic leadbThe process flow is as follows:
process for preparing lead monoxide
Metallic lead → melting → granulation → grinding → oxidizing roasting → PbO
Long process flow and environmental pollution.
Production of P by the inventionbO is simple, pollution-free, carbon emission-free and has obvious advantages.
The technological process of the invention is shown as the following:in the figure, 1, a feed inlet, 2 polar plates, 3 electrolytic tanks, 4 electrolytic solutions, 5 anodes, 6 rotating cathodes, 7 electric leads, 8 conductive rods, 9 spiral belts, 10 grid collecting hoppers, 11 discharge ports, 12 rotating shafts, 13 conductive rings, 14 grids and 15Pb 0、 16PbO。
The process is described in detail as follows:
the electrode plate (2) after desulfurization conversion is added into a rotating cathode (6), and the electrode plate (6) is formed by rolling an inner layer steel plate and an outer layer stainless steel plate, wherein holes are drilled in the inner layer, and spiral belts (9) are distributed on the inner layer, so that the electrode plate (2) moves from a feeding port (1) to a discharging port (11). The lead plaster in the polar plate (2) is mechanically separated from the grid (14). Lead plaster components: pb 0、PbO、PbO2、PbSO4Uniformly and freely suspended in the electrolyte (4) as a dispersed solid phase, lead in the lead compound is reduced into electric lead (7) through solid phase electrolysis, and the electric lead is deposited on the surface of the rotating cathode (6), and part of Pb 0(15) The electrolytic reduction of ions into electric lead (7) is deposited on the surface of the rotating cathode (6). Another part Pb 0(15) Is oxidized by oxygen atoms precipitated at the anode to form Pb0(16) is deposited on the anode (5) with the chemical formula Pb 0+o→ PbAnd O, discharging the grid (14) after de-pasting out of the groove from the inside of the rotary cathode (6). Obtaining the electrolytic lead (7) grid (14) and PbO (16) three products.
The following are the process conditions of the rotary cathode continuous solid phase electrolysis, the ion electrolysis, the anodic oxidation and the mechanical separation treatment of the waste lead storage battery.
The waste lead accumulator is not broken and separated by CX or M.A, the pole plate after desulfurization and conversion is directly added into a rotary cathode for electrolysis, and the technological conditions are as follows: the concentration of NaOH is 150g/L, the temperature of the electrolyte is 40-50 ℃, the cell voltage is 2.5-3V, and the cathode current density is 200A/m2The distance between the poles is 60 mm.
Compared with the pyrometallurgical smelting, the process of the invention has the advantages of simple process, no environmental pollution, no carbon emission and high metal recovery rate, and is a green and environment-friendly good process.
Of particular mention are: the key equipment of the invention is a rotating cathode which replaces a CX or M.A crushing and separating system,replacing the process and equipment of pyrometallurgical smelting to obtain two products of electrolytic lead and lead alloy, and obtaining P at the anodebO product instead of lead for producing PbO process and apparatus. No pollution, no carbon emission, green and environmental protection.
Description of the drawings:
FIG. 1 is a schematic plan view of a device for treating waste lead storage batteries by rotating cathodes and four rows of anodes, continuously performing solid-phase electrolysis, ion electrolysis, anodic oxidation and mechanical separation, and feeding and producing the waste lead storage batteries.
Detailed Description
The device for treating the waste lead storage battery by rotating the cathode and four rows of anodes through continuous solid-phase electrolysis, ionic electrolysis, anodic oxidation and mechanical separation is shown in figure 1: FIG. 1 is a material feeding process, 2 polar plates, 3 electrolytic tanks, 4 electrolyte, 5 anodes, 6 rotating cathodes, 7 electric leads, 8 conductive rods, 9 spiral belts, 10 grid collecting hoppers, 11 discharge ports, 12 rotating shafts, 13 conductive rings, 14 grids, 15Pb 0、16PbAnd O. The polar plate 2 is mechanically separated into diachylon and 15P in the rotating cathode 6b 0And 14 grids, lead paste and a part of 15Pb 0After solid-phase electrolysis and ion electrolysis, 7 electric lead and the other part of 15Pb are obtained on the surface of the rotating cathode 60Oxidized to 16P by the oxygen atoms evolved at the anodebO, to obtain P on the anode 5bO16, and discharging the grid 14 after de-pasting from the inside of the rotary cathode 6 to the outside of the groove to obtain the grid 14. Three products were used as lead storage batteries. And the cyclic utilization of resources is realized. No pollution, environmental protection, no carbon emission and continuous production.
Claims (3)
1. The process for treating the waste lead storage battery by rotating the cathode and four rows of anodes through continuous solid-phase electrolysis, ionic electrolysis, anodic oxidation and mechanical separation comprises an electrolytic cell, NaoH electrolyte, the rotating cathode and four rows of anodes, and is characterized in that: the rotating cathode is made of an inner layer steel plate and an outer layer stainless steel coil, and the inner layer is drilled with holes and is distributed with spiral belts.
2. The process for treating the waste lead storage battery by the continuous solid-phase electrolysis, the ionic electrolysis, the anodic oxidation and the mechanical separation of the four rows of the rotating cathodes as claimed in claim 1 is characterized in that: the spiral belt has an outer diameter phi of 1200mm, an inner diameter phi of 800mm, a belt length of 82m, and is welded with a conductive rod.
3. The process for treating the waste lead storage battery by rotating the anode and four rows of anodes, continuously performing solid-phase electrolysis, ionic electrolysis, anodic oxidation and mechanical separation according to claim 1, is characterized in that: four rows of anodes are arranged at two sides of the rotary cathode, two rows are arranged at each side, and the anodes are stainless steel plates.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110331238.2A CN113151864A (en) | 2021-03-26 | 2021-03-26 | Process for treating waste lead storage battery by rotating cathode four-row anode continuous solid-phase electrolysis, ion electrolysis, anodic oxidation and mechanical separation |
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| CN202110331238.2A CN113151864A (en) | 2021-03-26 | 2021-03-26 | Process for treating waste lead storage battery by rotating cathode four-row anode continuous solid-phase electrolysis, ion electrolysis, anodic oxidation and mechanical separation |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115094484A (en) * | 2022-06-12 | 2022-09-23 | 马光甲 | Process for treating waste lead storage battery by rotating cathode and four rows of anodes in sulfuric acid solution through continuous solid phase, ionic electrolysis, oxidation and mechanical separation |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102296325A (en) * | 2011-06-15 | 2011-12-28 | 马光甲 | Process for treating waste lead accumulator through continuous solid phase electrolysis of rotating cathode |
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- 2021-03-26 CN CN202110331238.2A patent/CN113151864A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102296325A (en) * | 2011-06-15 | 2011-12-28 | 马光甲 | Process for treating waste lead accumulator through continuous solid phase electrolysis of rotating cathode |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115094484A (en) * | 2022-06-12 | 2022-09-23 | 马光甲 | Process for treating waste lead storage battery by rotating cathode and four rows of anodes in sulfuric acid solution through continuous solid phase, ionic electrolysis, oxidation and mechanical separation |
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