CN113113689A - Acid liquor recovery method for waste lead-acid storage battery - Google Patents
Acid liquor recovery method for waste lead-acid storage battery Download PDFInfo
- Publication number
- CN113113689A CN113113689A CN202110245161.7A CN202110245161A CN113113689A CN 113113689 A CN113113689 A CN 113113689A CN 202110245161 A CN202110245161 A CN 202110245161A CN 113113689 A CN113113689 A CN 113113689A
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- China
- Prior art keywords
- acid
- lead
- plate
- waste lead
- acid storage
- 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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- 239000002253 acid Substances 0.000 title claims abstract description 50
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- 238000003860 storage Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000011084 recovery Methods 0.000 title claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000005192 partition Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 229910000464 lead oxide Inorganic materials 0.000 claims description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 description 22
- 239000011505 plaster Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 9
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 8
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 230000003009 desulfurizing effect Effects 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to an acid liquor recovery method of a waste lead-acid storage battery, which is characterized by comprising the following steps: step 1: disassembling the waste lead-acid storage battery, and taking out the partition plate; and 2, extruding the partition plate to obtain sulfuric acid. The acid liquor recovery method of the waste lead-acid storage battery is low in cost and high in efficiency.
Description
Technical Field
The invention relates to the field of lead-acid storage battery recovery.
Background
At present, two methods for recovering waste lead-acid storage batteries are mainly used, the first method is to add one or more desulfurizing agents (ammonium carbonate, ammonium bicarbonate, sodium carbonate and sodium hydroxide) into waste lead plaster for lead plaster desulfurization, and simultaneously smelt lead carbonate to obtain lead. And secondly, the waste lead plaster and the smelting auxiliary agent are smelted together in a smelting furnace in an oxygen-enriched high-temperature mode, generated sulfur dioxide flue gas is converted into sulfur trioxide and then absorbed by ionic liquid to prepare sulfuric acid, on one hand, the method needs new substances to increase the production cost, meanwhile, the generated byproducts are very complex to treat, on the other hand, the products can only obtain lead, and meanwhile, a large amount of waste gas can be generated. In addition, the acid solution cannot be recovered.
Disclosure of Invention
In order to solve the technical problem, the invention provides an acid liquor recovery method of a waste lead-acid storage battery, which is characterized by comprising the following steps of: step 1: disassembling the waste lead-acid storage battery, and taking out the partition plate; and 2, extruding the partition plate to obtain sulfuric acid.
Further, the method also comprises a step 3 of filtering the sulfuric acid obtained by extrusion through an ionic membrane to obtain sulfuric acid for paste mixing.
Further, step 4, the sulfuric acid obtained by filtering is conveyed to a paste mixer.
Further, the step 1 includes taking out a positive plate and a negative plate, placing one end of the positive plate into a conductive liquid, connecting the other end of the positive plate with a positive electrode of a power supply, placing one end of the negative plate into the conductive liquid, connecting the other end of the negative plate with a negative electrode of the power supply, electrifying, and conveying the electrified conductive liquid to the paste mixer.
Further, the product obtained by processing lead oxide obtained after the positive plate is electrified in the step 1 or the product obtained by processing lead obtained after the negative plate is electrified is conveyed to the paste mixer.
The acid liquor recovery method of the waste lead-acid storage battery is low in cost and high in efficiency.
Drawings
FIG. 1 is a schematic diagram of a lead plaster desulfurization device for waste lead-acid storage batteries according to the present invention.
Detailed Description
The invention is further described below with reference to the specific drawings.
As shown in fig. 1, the lead plaster desulfurization device for waste lead-acid storage batteries of the invention comprises a waste lead-acid storage battery dismantling device 1, a polar plate conveying device 2, a polar plate sorting device 3, a lead plaster electrolysis device 4, a lead dioxide treatment device 5, a lead treatment device 6, a partition plate extrusion device 7, an acid liquid storage device 8, and a plaster mixer 9, which can also be used as a part of the lead plaster desulfurization device for waste lead-acid storage batteries of the invention.
The method for desulfurizing the diachylon of the waste lead-acid storage battery comprises the following steps: disassembling the waste lead-acid storage battery by using a waste lead-acid storage battery disassembling device 1, and taking out the positive plate and the negative plate; the disassembled positive plate and negative plate are sent to a plate conveying device 2 and classified by a plate sorting device 3, such as a color sorter, namely collecting the positive plates together and the negative plates together, then placing the positive plates in parallel into the positive position of a lead plaster electrolysis device 4, and the negative plate can be put in parallel at the negative position in the diachylon electrolysis device 4, namely one end of the positive plate is put in the conductive liquid, the other end is connected with the anode of an external power supply, one end of the negative plate is put into the conductive liquid, the other end is connected with the cathode of the external power supply, electrifying, treating the lead dioxide obtained after the positive electrode is desulfurized by a lead dioxide treatment device 5 to obtain a treated product, such as red lead or beta lead oxide, treating the treated product and sending the treated product to a paste mixer 9, and smelting the lead obtained after the negative electrode is desulfurized by a lead treatment device 6 at a low temperature to obtain refined lead, wherein the treated product can also be sent to the paste mixer 9. According to the acid liquor recovery method for the waste lead-acid storage batteries, when the waste lead-acid storage battery disassembling device 1 is disassembled, the partition plates are also taken out, the partition plates are separated by the separation device 3 and then sent to the partition plate extrusion device 7 to be extruded to obtain sulfuric acid, the sulfuric acid obtained by extrusion is filtered by an ionic membrane to obtain sulfuric acid for paste mixing, and the sulfuric acid for paste mixing is sent to the paste mixing machine 9 or directly sent to the paste mixing machine 9 through the acid liquor storage device 8 after being treated by the sulfuric acid for paste mixing. According to the method for desulfurizing the lead plaster of the waste lead-acid storage battery, the conductive liquid of the lead plaster electrolysis device 4 can be dilute sulfuric acid with the density of 1.01-1.10 g/ml, the density of the acid liquid is increased after the electrification and electrolysis are finished, part of the conductive liquid after the electrification and electrolysis is added with pure water to be prepared to 1.01-1.10 g/ml and then is continuously used for electrochemically desulfurizing the waste polar plate, and the rest part of the conductive liquid is used as paste combination or formed acid for standby after impurity removal through an ionic membrane. After treatment, it may be fed to the mixer 9.
The diachylon electrolysis device 4 in the diachylon desulphurization device of the waste lead-acid storage battery can only carry out positive electrode electrolysis according to the needs, for example, one end of a positive plate or a negative plate is put into a conductive liquid, the other end of the positive plate or the negative plate is connected with the positive electrode of an external power supply, the negative electrode of the external power supply is connected with one end of a negative electrode, and the other end of the negative electrode is put into the conductive liquid and electrified; it is also possible to perform only negative electrode electrolysis, such as placing one end of a positive or negative electrode plate in a conductive liquid, connecting the other end to the negative electrode of an external power supply, connecting the positive electrode of the external power supply to one end of a positive electrode, placing the other end of the positive electrode in a conductive liquid, and conducting electricity; the positive electrode and the negative electrode can be electrolyzed simultaneously; the electrolysis may be performed on both the positive electrode of the lead paste electrolysis device 4 and the negative electrode of the lead paste electrolysis device 4 after the positive and negative electrode plates of the waste battery are connected in parallel, or the electrolysis may be performed on both the positive electrode plate and the negative electrode plate of the lead paste electrolysis device 4. The lead paste desulfurization of the lead-acid storage battery is carried out on the positive electrode only when lead dioxide is obtained, and is carried out on the negative electrode only when lead is obtained, or the positive electrode and the negative electrode are simultaneously electrolyzed according to the requirement of the raw material demand of the paste, or the negative electrode electrolysis and the positive electrode electrolysis can be alternately carried out. The positive electrode and the negative electrode simultaneously carry out electrolytic desulfurization on the positive electrode plate and the negative electrode plate, so that electric energy can be saved. The lead plaster electrolysis device 4 provides different electrolysis modes, can realize flexible control in the production process, better realizes raw material preparation, and improves the production efficiency.
In the lead plaster desulfurization device for the waste lead-acid storage batteries, the positive and negative electrode plates of the waste lead-acid storage batteries are directly electrolyzed by the lead plaster electrolysis device 4, so that the working procedure of stripping lead plaster from the electrode plates can be omitted, particularly, in the negative electrode electrolysis process, the waste electrode plates can be directly smelted at low temperature after the negative electrode is electrolyzed, the efficiency is improved, and the cost is reduced.
In addition, in the diachylon desulphurization device for the waste lead-acid storage batteries, the electrolysis desulphurization product, the waste acid liquid and even the electrolysis conductive liquid are conveyed to the diachylon mixing machine for recycling, so that the cost reduction and the efficiency improvement of the recycling of the waste batteries can be realized, a complete waste recycling system is formed, in addition, the desulphurization recycling product is used as a raw material for battery production, the recycling and the production can be unified and coordinated, and the cost and the safety problem of long-distance transportation are avoided.
The invention can also disassemble the waste lead-acid storage battery, separate the lead plaster on the positive plate and the negative plate after being taken out, and respectively electrolyze the positive lead plaster and the negative lead plaster as the positive electrode and the negative electrode, or electrolyze the positive lead plaster and the negative lead plaster after being mixed as the positive electrode or the negative electrode, thereby realizing the aim of the invention.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (5)
1. An acid liquor recovery method for waste lead-acid storage batteries is characterized by comprising the following steps: step 1: disassembling the waste lead-acid storage battery, and taking out the partition plate; and 2, extruding the partition plate to obtain sulfuric acid.
2. The acid liquor recovery method for waste lead-acid storage batteries according to claim 1, further comprising a step 3 of filtering the sulfuric acid obtained by extrusion through an ionic membrane to obtain sulfuric acid for paste mixing.
3. The acid liquor recovery method for waste lead-acid storage batteries according to claim 2, further comprising a step 4 of conveying the filtered sulfuric acid to a paste mixer.
4. The acid liquor recovery method of waste lead-acid storage batteries according to claim 3, characterized in that the step 1 further comprises taking out a positive plate and a negative plate, putting one end of the positive plate into a conductive liquid, connecting the other end of the positive plate with a positive electrode of a power supply, putting one end of the negative plate into the conductive liquid, connecting the other end of the negative plate with a negative electrode of the power supply, electrifying, and conveying the electrified conductive liquid to the paste mixer.
5. The acid liquor recovery method for waste lead-acid storage batteries according to claim 4, characterized in that the product obtained after the positive plate is electrified in the step 1 is treated to obtain lead oxide, or the product obtained after the negative plate is electrified is conveyed to the paste mixer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110245161.7A CN113113689A (en) | 2021-03-05 | 2021-03-05 | Acid liquor recovery method for waste lead-acid storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110245161.7A CN113113689A (en) | 2021-03-05 | 2021-03-05 | Acid liquor recovery method for waste lead-acid storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113113689A true CN113113689A (en) | 2021-07-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110245161.7A Pending CN113113689A (en) | 2021-03-05 | 2021-03-05 | Acid liquor recovery method for waste lead-acid storage battery |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4557908A (en) * | 1983-04-25 | 1985-12-10 | Minemet Recherche | Process for the treatment of a purge solution particularly intended for a process for the extraction of zinc by electrolysis |
| CN101488597A (en) * | 2009-02-23 | 2009-07-22 | 东南大学 | Method for waste lead-acid cell resourcization and lead-acid cell cyclic production |
| CN206858679U (en) * | 2017-06-22 | 2018-01-09 | 四会市宏创工业机械设备有限公司 | A kind of new sulfuric acid oxidation electrolyte recycling device |
| CN207024771U (en) * | 2016-12-14 | 2018-02-23 | 张净 | The recycle and reuse system of lead-acid accumulator waste liquid |
| WO2019087682A1 (en) * | 2017-10-31 | 2019-05-09 | 株式会社Ｇｓユアサ | Lead storage battery |
| CN110967277A (en) * | 2019-12-25 | 2020-04-07 | 天能电池(芜湖)有限公司 | Method for measuring content and proportion of sulfuric acid in polar plate and partition plate of valve-controlled lead-acid storage battery |
-
2021
- 2021-03-05 CN CN202110245161.7A patent/CN113113689A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4557908A (en) * | 1983-04-25 | 1985-12-10 | Minemet Recherche | Process for the treatment of a purge solution particularly intended for a process for the extraction of zinc by electrolysis |
| CN101488597A (en) * | 2009-02-23 | 2009-07-22 | 东南大学 | Method for waste lead-acid cell resourcization and lead-acid cell cyclic production |
| CN207024771U (en) * | 2016-12-14 | 2018-02-23 | 张净 | The recycle and reuse system of lead-acid accumulator waste liquid |
| CN206858679U (en) * | 2017-06-22 | 2018-01-09 | 四会市宏创工业机械设备有限公司 | A kind of new sulfuric acid oxidation electrolyte recycling device |
| WO2019087682A1 (en) * | 2017-10-31 | 2019-05-09 | 株式会社Ｇｓユアサ | Lead storage battery |
| CN110967277A (en) * | 2019-12-25 | 2020-04-07 | 天能电池(芜湖)有限公司 | Method for measuring content and proportion of sulfuric acid in polar plate and partition plate of valve-controlled lead-acid storage battery |
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| PB01 | Publication | ||
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| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20211129 Address after: 311100 room 1120, 3rd floor, building 1, 187 Yunxi Road, Tangqi Town, Yuhang District, Hangzhou City, Zhejiang Province Applicant after: Hangzhou lead lithium Zhixing Technology Co.,Ltd. Address before: 233000 No.31, building 25, District 9, Guangcai market, bengshan District, Bengbu City, Anhui Province Applicant before: Bengbu Ruide New Energy Technology Co.,Ltd. |
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| RJ01 | Rejection of invention patent application after publication | ||
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Application publication date: 20210713 |