CN110386700A - A kind of combination treatment method of old and useless battery electric discharge and sulfur-containing waste water desulfurization - Google Patents
A kind of combination treatment method of old and useless battery electric discharge and sulfur-containing waste water desulfurization Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 77
- 239000011593 sulfur Substances 0.000 title claims abstract description 73
- 239000002351 wastewater Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 18
- 230000023556 desulfurization Effects 0.000 title claims abstract description 18
- 238000011284 combination treatment Methods 0.000 title 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 39
- 239000002699 waste material Substances 0.000 claims abstract description 34
- 239000010926 waste battery Substances 0.000 claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 13
- 238000007599 discharging Methods 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims description 15
- 238000004064 recycling Methods 0.000 claims description 11
- 239000003463 adsorbent Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004020 conductor Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 241000209140 Triticum Species 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 235000013312 flour Nutrition 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims 1
- 229920000128 polypyrrole Polymers 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 208000028659 discharge Diseases 0.000 description 64
- 230000000694 effects Effects 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000011084 recovery Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- -1 Nickel-Cobalt-Manganate Lithium Oxide Chemical compound 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/4608—Treatment of water, waste water, or sewage by electrochemical methods using electrical discharges
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- 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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Abstract
本发明涉及废水以及废旧电池联合处理领域，具体公开了一种废旧电池放电及含硫废水脱硫的联合处理方法，将废旧锂离子电池的电池组或者经拆解得到的电池单体置于含硫废水中放电；分离得到放电后的电池组或电池单体，以及脱硫处理后的出水；所述的含硫废水中含有H2S、HS‑、S2‑中的至少一种。该方法实现了废旧锂电池中余能的充分利用，高效清洁，克服了传统处理工业废水中硫化氢方法的劣势、简单实用、经济可行，适合工业化生产。The invention relates to the field of joint treatment of waste water and waste batteries, and specifically discloses a joint treatment method for waste battery discharge and sulfur-containing waste water desulfurization. Discharging in wastewater; separating and obtaining discharged battery packs or battery cells, and desulfurized effluent; the sulfur-containing wastewater contains at least one of H 2 S, HS ‑ , and S 2‑ . The method realizes the full utilization of residual energy in waste lithium batteries, is highly efficient and clean, overcomes the disadvantages of traditional methods for treating hydrogen sulfide in industrial wastewater, is simple, practical, economically feasible, and is suitable for industrial production.
Description
技术领域technical field
本发明属于废旧锂离子电池回收领域，特别涉及到一种废旧锂电池中余能梯次利用处理废水中硫化氢的方法。The invention belongs to the field of waste lithium ion battery recycling, and in particular relates to a method for treating hydrogen sulfide in waste water by cascade utilization of residual energy in waste lithium batteries.
背景技术Background technique
随着现代化科技的高速发展，社会能源与环境生态污染问题日益突出，各种废弃电池对环境及生态的污染问题已经成了社会关注的焦点。而镍钴锰酸锂离子电池由于容量高、循环性能稳定、工作平台电压高等特点被广泛应用于动力电池和储能电池，而动力和储能电池对电池材料的需求通常大于常规的小型电池。因此，在未来3-5年内，将有大量的废旧锂离子电池报废，对其进行回收具有很高的社会价值。With the rapid development of modern science and technology, the problem of social energy and environmental ecological pollution has become increasingly prominent, and the environmental and ecological pollution of various waste batteries has become the focus of social attention. Nickel-cobalt manganese oxide lithium-ion batteries are widely used in power batteries and energy storage batteries due to their high capacity, stable cycle performance, and high working platform voltage. Power and energy storage batteries usually require more battery materials than conventional small batteries. Therefore, in the next 3-5 years, a large number of used lithium-ion batteries will be scrapped, and their recycling has high social value.
然而，废旧锂离子电池仍残留相当部分的电压，为了确保人员和设备安全必须进行放电操作使残留电压降至安全范围以内。目前废旧锂离子电池的回收关注点主要集中在后段产品回收上，对前段放电处理关注度较少，普遍采用5-10％的NaCl溶液进行放电操作。如中国专利CN 106558739 A公布的“基于废旧手机中锂离子电池高效回收分离工艺”中提及在电池破碎拆解前要进行放电操作，利用10％的NaCl盐溶液浸泡48h至电池残留电压达到安全拆解的要求。采用5-10％的NaCl盐溶液进行电池放电操作可使废旧电池残留电压达到安全拆解的要求，但放电速率较慢，一般要浸泡24h以上使残留电压将至1V以下，且会引入难以去除的氯离子进入到浸出液中对后续的除杂净化和产品回收阶段带来影响。又如中国专利CN 104538695 A公布的“废镍钴锰酸锂电池中回收金属并制备镍钴锰酸锂的方法”，在电池破碎拆解前利用0.1-1mol/L的NaOH溶液在室温下对电池进行1-3h的放电操作，OH-在水溶液中比Cl-更难放电，采用NaOH溶液势必会降低电池的放电速率以及放电效果，且在处理软包电池时NaOH会对铝壳造成腐蚀导致电解液的泄露污染水质。However, a considerable part of the voltage remains in the used lithium-ion battery. In order to ensure the safety of personnel and equipment, a discharge operation must be performed to reduce the residual voltage to a safe range. At present, the focus of recycling waste lithium-ion batteries is mainly on the recycling of the back-end products, and less attention is paid to the front-end discharge treatment. 5-10% NaCl solution is generally used for discharge operation. For example, the Chinese patent CN 106558739 A published "Based on the high-efficiency recovery and separation process of lithium-ion batteries in waste mobile phones" mentioned that before the battery is broken and disassembled, a discharge operation should be performed, and the battery should be soaked in 10% NaCl salt solution for 48 hours until the residual voltage of the battery reaches a safe level. Dismantling requirements. Using 5-10% NaCl salt solution to discharge the battery can make the residual voltage of the used battery meet the requirements of safe disassembly, but the discharge rate is slow. Generally, it needs to be soaked for more than 24 hours to reduce the residual voltage to below 1V, and it will introduce difficult to remove. Chloride ions entering the leachate will affect the subsequent stages of impurity removal and product recovery. Another example is the "Method for Recycling Metal from Waste Nickel-Cobalt-Lithium Manganate Batteries and Preparation of Nickel-Cobalt-Manganate Lithium Oxide" announced by Chinese patent CN 104538695 A. The battery is discharged for 1-3 hours. OH - is more difficult to discharge than Cl - in aqueous solution. The use of NaOH solution will inevitably reduce the discharge rate and discharge effect of the battery, and NaOH will cause corrosion to the aluminum shell when handling soft pack batteries. Leakage of electrolyte pollutes water quality.
综上，现有锂离子回收放电过程中，还普遍存在放电时间长(通常需要24h以上)，且放电效果不理想，仅能放电至0.7V左右，且处理过程中，容易腐蚀电池组，导致剧毒的电解液泄露至放电体系中，对人员以及环境安全极为不利。To sum up, in the existing lithium ion recovery and discharge process, it is common to have a long discharge time (usually more than 24 hours), and the discharge effect is not ideal, and can only be discharged to about 0.7V, and the battery pack is easily corroded during the process, resulting The highly toxic electrolyte leaks into the discharge system, which is extremely harmful to the safety of personnel and the environment.
另外，现有废水中含有较多负二价硫，例如，硫化氢属剧毒物质，工业废水中特别是造纸工业产生的废水含有较高的浓度的硫化氢，若不进行处理会对生态环境和人类健康带来重大危害。废水中硫化氢的处理方法一般有密闭收集处置法，物理吸附法，氧化法和生物法等，这些方法都存在着操作复杂或者回收效率低等问题，且易造成二次污染。In addition, the existing wastewater contains more negative divalent sulfur. For example, hydrogen sulfide is a highly toxic substance. Industrial wastewater, especially the wastewater produced by the paper industry, contains a relatively high concentration of hydrogen sulfide. If it is not treated, it will damage the ecological environment. serious harm to human health. The treatment methods of hydrogen sulfide in wastewater generally include closed collection and disposal method, physical adsorption method, oxidation method and biological method, etc. These methods all have problems such as complicated operation or low recovery efficiency, and are easy to cause secondary pollution.
发明内容Contents of the invention
为解决现有锂离子电池回收的放电方法存在的放电时间长、放电效果不理想，以及工业废水含硫污染等技术问题，本发明创新性地提出了一种全新的联合处理思路，达到在充分放电的前提下，又脱除工业废水中的低价硫。In order to solve technical problems such as long discharge time, unsatisfactory discharge effect and sulfur pollution in industrial waste water existing in the discharge method of lithium-ion battery recovery, the present invention innovatively proposes a brand-new combined treatment idea to achieve full Under the premise of discharge, low-priced sulfur in industrial wastewater is removed.
一种废旧电池放电及含硫废水脱硫的联合处理方法，将废旧锂离子电池的电池组或者经拆解得到的电池单体置于含硫废水中放电；分离得到放电后的电池组或电池单体，以及脱硫处理后的出水；A combined treatment method for the discharge of waste batteries and the desulfurization of sulfur-containing wastewater, in which the battery packs or disassembled battery cells of waste lithium-ion batteries are placed in sulfur-containing wastewater for discharge; the discharged battery packs or battery cells are separated to obtain Body, and effluent after desulfurization treatment;
所述的含硫废水中含有H2S、HS-、S2-中的至少一种。The sulfur-containing wastewater contains at least one of H 2 S, HS − , and S 2 −.
本发明通过研究发现，在本发明所述的含硫废水中进行放电，通过氧化还原方法，实现废旧锂离子电池残留电量的放电。通过本发明方法，可实现高效放电，研究发现，本发明方法不仅放电时间明显缩短，还有助于达到彻底放电(放电至0V)，相比于现有方法仅能达到0.7V的放电效果，具有明显优势。本发明方法还不会腐蚀电池组(或电池单体)器件，放电过程中不会使剧毒的电解液(例如羧酸甲酯类)泄露，不会对人员以及环境造成不利影响，本发明方法真正实现了高效、清洁地使废旧锂离子电池的放电，利于工业实际应用。此外，本发明方法为一种全新的含硫废水的脱除思路，通过利用废旧电池的残存电量，脱除废水中的有害硫成分。本发明方法首次实现了废水和废旧电池的联合处理。The present invention finds through research that discharging in the sulfur-containing waste water described in the present invention realizes the discharge of the residual power of the waste lithium-ion battery through the oxidation-reduction method. Through the method of the present invention, high-efficiency discharge can be realized. Research has found that the method of the present invention not only significantly shortens the discharge time, but also helps to achieve a complete discharge (discharge to 0V), compared with the existing method that can only achieve a discharge effect of 0.7V. has obvious advantages. The method of the present invention will not corrode the battery pack (or battery cell) devices, will not leak highly toxic electrolytes (such as methyl carboxylate) during the discharge process, and will not cause adverse effects on personnel and the environment. The method truly realizes the efficient and clean discharge of the waste lithium ion battery, which is beneficial to industrial practical application. In addition, the method of the present invention is a brand-new idea for removing sulfur-containing wastewater, and removes harmful sulfur components in wastewater by using the residual power of waste batteries. The method of the invention realizes the combined treatment of waste water and waste batteries for the first time.
作为优选，所述的含硫废水在用于放电前，预先进行以下预处理：As a preference, the sulfur-containing wastewater is pre-treated as follows before being used for discharging:
将待处理的含硫废水经第一固液分离得到第一滤液；向第一滤液中添加吸附剂，吸附后进行第二固液分离，得第二滤液，将第二滤液作为所述的含硫废水用作放电的介质。The sulfur-containing wastewater to be treated is subjected to first solid-liquid separation to obtain a first filtrate; adding an adsorbent to the first filtrate, and performing second solid-liquid separation after adsorption to obtain a second filtrate, which is used as the Sulfur wastewater is used as the medium for the discharge.
作为优选，吸附剂是活性炭，聚丙烯酰胺，小麦胚粉，碳分子筛中的一种或几种。Preferably, the adsorbent is one or more of activated carbon, polyacrylamide, wheat germ flour, and carbon molecular sieve.
研究还发现，控制在合适的溶液的低价硫(负二价硫)的浓度，有助于进一步提升放电效率，进一步改善放电效果。The study also found that controlling the concentration of low-valent sulfur (negative divalent sulfur) in a suitable solution helps to further increase the discharge efficiency and further improve the discharge effect.
作为优选，含硫废水中，负二价总硫量的浓度不低于5wt％；优选为5～20wt％。在该优选的浓度下，可放电至0V，且放电至0V的时间更短。此外，可实现该高浓度的含硫废水的处理。Preferably, in the sulfur-containing wastewater, the concentration of negative divalent total sulfur is not lower than 5 wt%, preferably 5-20 wt%. At this preferred concentration, it can be discharged to 0V, and the time to discharge to 0V is shorter. In addition, the treatment of this high-concentration sulfur-containing wastewater can be realized.
本发明人研究还发现，对放电过程中，控制放电过程的pH、放电过程的温度以及在含硫废水中添加导电材料等操作，可进一步改善放电效果，缩短放电时间，改善放电效果。The inventor also found that during the discharge process, controlling the pH and temperature of the discharge process and adding conductive materials to the sulfur-containing wastewater can further improve the discharge effect, shorten the discharge time, and improve the discharge effect.
作为优选，所述的硫废水的pH为1-10.5。Preferably, the pH of the sulfur wastewater is 1-10.5.
进一步优选，所述的硫废水的pH为1-6。所述的含硫废水为酸性，体系中的负二价硫主要以H2S的形态存在，通过本发明的联合处理方法，脱除其中的H2S，此外，还实现了废旧电池的充分放电。Further preferably, the pH of the sulfur wastewater is 1-6. The sulfur-containing wastewater is acidic, and the negative divalent sulfur in the system mainly exists in the form of H2S. Through the combined treatment method of the present invention, the H2S is removed, and in addition, the full discharge of the waste battery is realized.
作为优选，所述的含硫废水中，含有H2S，进行放电后，还收集得到H2和硫。Preferably, the sulfur-containing wastewater contains H2S, and H2 and sulfur are also collected after discharging.
进一步优选，所述的硫废水的pH为8-10.5。所述的含硫废水为碱性，体系中的负二价硫主要以HS-、S2-的形态存在。研究发现，在该碱性条件下放电效果以及废水脱硫效果均更优，处理过程的放电更彻底，且处理过程不会产生H2S。Further preferably, the pH of the sulfur wastewater is 8-10.5. The sulfur-containing wastewater is alkaline, and the negative divalent sulfur in the system mainly exists in the form of HS - and S 2- . The study found that the discharge effect and wastewater desulfurization effect are better under this alkaline condition, the discharge is more thorough during the treatment process, and H2S will not be generated during the treatment process.
作为优选，所述的含硫废水中，含有HS-、S2-中，进行放电后，还收集得到硫。Preferably, the sulfur-containing wastewater contains HS - and S 2- , and sulfur is also collected after discharge.
作为优选，放电过程中，控制含硫废水的温度为25-35℃；优选为25-30℃。所述的含硫废水的温度也即是放电过程的温度。控制在该优选的放电温度下，可进一步提升放电效率，进一步改善放电效果，还有助于改善脱硫效果。Preferably, during the discharge process, the temperature of the sulfur-containing wastewater is controlled to be 25-35°C; preferably 25-30°C. The temperature of the sulfur-containing wastewater is also the temperature of the discharge process. Controlling at the preferred discharge temperature can further increase the discharge efficiency, further improve the discharge effect, and also help to improve the desulfurization effect.
通过在放电过程的含硫废水中添加导电材料，可进一步改善放电效果，提升放电效率。By adding conductive materials to the sulfur-containing wastewater in the discharge process, the discharge effect can be further improved and the discharge efficiency can be improved.
作为优选，所述的导电材料为石墨、氧化石墨、导电聚苯胺中的至少一种。Preferably, the conductive material is at least one of graphite, graphite oxide, and conductive polyaniline.
作为优选，所述的含硫废水中，所述的导电材料的体积分数为5-20％。Preferably, in the sulfur-containing wastewater, the volume fraction of the conductive material is 5-20%.
作为优选，所述的废旧锂离子电池为废旧三元动力电池，钴酸锂电池，锰酸锂电池，磷酸铁锂电池中的一种或几种。Preferably, the waste lithium ion battery is one or more of waste ternary power battery, lithium cobalt oxide battery, lithium manganese oxide battery, and lithium iron phosphate battery.
优选地，所述的电池组、电池单体的残留电压不低于1V，优选为3.8V～3.85V。Preferably, the residual voltage of the battery pack and battery cells is not lower than 1V, preferably 3.8V-3.85V.
本发明的放电时间可根据实际废水的含硫量进行控制，当废旧电池的放电量达到0V时，可以更换新的待处理的废旧电池，当废水中的硫含量达到排放标准时，排放处理后的出水，并更换新的待处理的含硫废水。The discharge time of the present invention can be controlled according to the sulfur content of the actual wastewater. When the discharge capacity of the waste battery reaches 0V, a new waste battery to be treated can be replaced. When the sulfur content in the waste water reaches the discharge standard, the treated waste battery can be discharged. The water is discharged and replaced with new sulfur-containing wastewater to be treated.
一种优选的联合处理方法(废旧锂电池中余能梯次利用处理废水中硫化氢的方法)，包括以下步骤：A preferred combined treatment method (the method for the step-by-step utilization of residual energy in waste lithium batteries to treat hydrogen sulfide in waste water) comprises the following steps:
1)对工业含硫化氢废水进行初级过滤除去粒径大于0.5mm的大颗粒悬浮物，得到初级滤液；1) Perform primary filtration on industrial hydrogen sulfide-containing wastewater to remove large suspended solids with a particle size greater than 0.5 mm to obtain a primary filtrate;
2)向初级滤液中添加吸附剂，搅拌后固液分离，得到次级滤液；2) adding an adsorbent to the primary filtrate, and separating the solid and liquid after stirring to obtain the secondary filtrate;
3)将次级滤液倒入装有废旧锂电池的装置中，进行放电反应，随后经二次过滤可分别得到放完电的废旧锂电池和单质硫，3) Pour the secondary filtrate into a device equipped with a waste lithium battery, carry out a discharge reaction, and then obtain a fully discharged waste lithium battery and elemental sulfur through secondary filtration.
所述的装有废旧锂电池的装置为带有集气装置的密闭容器，所述的装置还带有用于检测水中H2S浓度的硫化氢浓度探测仪；The device containing the waste lithium battery is a closed container with a gas collecting device, and the device is also equipped with a hydrogen sulfide concentration detector for detecting the concentration of H2S in water;
放电过程中，在集气装置中得到氢气，其中废旧锂电池送电池回收工序；During the discharge process, hydrogen is obtained in the gas collection device, and the waste lithium battery is sent to the battery recycling process;
4)对处理前后废水中硫化氢浓度进行测量，经充分时间反应后废水(脱硫处理后的出水)中硫化氢浓度可达到工业废水排放对硫化氢浓度的要求；没有达到排放标准的处理后的出水循环套用至步骤1)中循环处理。4) Measure the concentration of hydrogen sulfide in the wastewater before and after treatment. After a sufficient time of reaction, the concentration of hydrogen sulfide in the wastewater (effluent after desulfurization treatment) can meet the requirements for the concentration of hydrogen sulfide in industrial wastewater discharge; The effluent circulation is applied to the circulation treatment in step 1).
步骤1中所述的大颗粒悬浮物是指粒径在0.5mm的以上的颗粒。The large particle suspension mentioned in step 1 refers to particles with a particle size above 0.5mm.
步骤2所述的吸附剂是活性炭，聚丙烯酰胺，小麦胚粉，碳分子筛中的一种或几种。The adsorbent described in step 2 is one or more of activated carbon, polyacrylamide, wheat germ flour, and carbon molecular sieves.
步骤3中所述的装置是配备有集气装置的封闭体系，所述气体纯度采用气体纯度分析仪分析所得。The device described in step 3 is a closed system equipped with a gas collection device, and the gas purity is analyzed by a gas purity analyzer.
步骤4中所述的处理前后硫化氢的浓度均采用硫化氢浓度探测仪进行测定，充分反应时间是指时间应大于12h。The concentration of hydrogen sulfide before and after the treatment described in step 4 is measured by a hydrogen sulfide concentration detector, and the sufficient reaction time means that the time should be greater than 12h.
本发明优选的方法，利用简单的化学和电化学方法实现废水中硫化氢的制氢固硫，同时实现废旧锂电池余能的梯次利用，相较于其它处理废水中硫化氢的方法成本大幅降低且无二次污染。The preferred method of the present invention uses simple chemical and electrochemical methods to realize hydrogen production and sulfur fixation of hydrogen sulfide in wastewater, and at the same time realizes cascaded utilization of residual energy of waste lithium batteries, which greatly reduces the cost compared with other methods for treating hydrogen sulfide in wastewater And no secondary pollution.
本发明的有益效果是：The beneficial effects of the present invention are:
本发明利用废旧锂电池中余能应用于处理工业废水中的负二价硫(例如，硫化氢)，实现固硫，所述的硫化氢还可实现制氢，生成的硫和制备的氢气可回收再利用，为废弃物再生提供了一种环保低成本的可靠路径。The present invention utilizes the residual energy in waste lithium batteries to apply negative divalent sulfur (for example, hydrogen sulfide) in industrial waste water to achieve sulfur fixation. Recycling provides an environmentally friendly and low-cost reliable path for waste regeneration.
反应完后的废旧锂电池的放电效果彻底，放电时间短；处理后送电池回收工序，拆解前无需再进行放电操作，处理过的工业废水中硫化氢的浓度满足排放标准可重新作为工业用水，资源循环利用大大降低了处理成本。After the reaction, the waste lithium battery has a thorough discharge effect and a short discharge time; after treatment, it is sent to the battery recycling process, and no discharge operation is required before disassembly. The concentration of hydrogen sulfide in the treated industrial wastewater meets the discharge standard and can be reused as industrial water , Resource recycling greatly reduces processing costs.
附图说明Description of drawings
图1是本发明的工艺流程示意图。Fig. 1 is a process flow diagram of the present invention.
具体实施案例Specific implementation cases
为了便于本领域技术人员更加简单的理解本发明，现结合具体实施案例对本发明作进一步说明，但应理解本发明不限于这些实施例。In order to make it easier for those skilled in the art to understand the present invention, the present invention will be further described in conjunction with specific examples of implementation, but it should be understood that the present invention is not limited to these examples.
废旧电池为523型废旧锂离子电池Waste batteries are 523 type waste lithium-ion batteries
实施例1Example 1
如图1所示，本发明是一种电池中余能梯次利用处理废水中硫化氢的方法，工业废水(废水中，硫的存在形式为S2-以及HS-，硫的总质量分数在9.6wt.％)经初级过滤预先出去粒径大于0.5mm的悬浮物；随后进行次级过滤，次级过滤时加入吸附剂离心过滤除去粒径小于0.5mm的悬浮物得到次级滤液。次级滤液的PH值在7.3左右(7.3±0.1)，次级滤液送入装有废旧锂电池的反应装置中(将废旧锂电池浸泡在次级滤液中)进行放电处理，放电反应过程中对生成的气体进行收集得到高纯的氢气，经充分时间反应后过滤得到含固态硫的悬浮液，对悬浮液采用离心过滤得到单质硫，反应完全后的废旧锂电池送回收工序。具体操作步骤如下：As shown in Figure 1, the present invention is a method for cascade utilization of residual energy in batteries to treat hydrogen sulfide in waste water. In industrial waste water (in waste water, sulfur exists in the form of S 2 - and HS - , and the total mass fraction of sulfur is 9.6 wt.%) through primary filtration to remove suspended matter with a particle size greater than 0.5mm in advance; followed by secondary filtration, adding an adsorbent during secondary filtration and centrifugal filtration to remove suspended matter with a particle size less than 0.5mm to obtain a secondary filtrate. The pH value of the secondary filtrate is about 7.3 (7.3 ± 0.1), and the secondary filtrate is sent to the reaction device equipped with waste lithium batteries (soaking the waste lithium batteries in the secondary filtrate) for discharge treatment. The generated gas is collected to obtain high-purity hydrogen, and after sufficient time to react, it is filtered to obtain a suspension containing solid sulfur. The suspension is centrifugally filtered to obtain elemental sulfur. After the reaction is complete, the waste lithium battery is sent to the recycling process. The specific operation steps are as follows:
1)对工业含硫化氢废水进行初级过滤除去粒径大于0.5mm的大颗粒悬浮物和一部分有害物质得到初级滤液；1) Perform primary filtration on industrial hydrogen sulfide-containing wastewater to remove large suspended solids and some harmful substances with a particle size greater than 0.5mm to obtain primary filtrate;
2)向初级滤液中添加吸附剂活性碳经机械搅拌一定时间，后进行次级离心过滤除去粒径小于0.5mm的悬浮物得到次级滤液；2) adding adsorbent activated carbon to the primary filtrate, mechanically stirring for a certain period of time, and then performing secondary centrifugal filtration to remove suspended matter with a particle size less than 0.5mm to obtain a secondary filtrate;
3)将次级滤液倒入装有废旧锂电池的装置(配备有集气装置)中经放电反应，反应时间应大于12h，后经过滤可分别得到放完电的废旧锂电池和含硫单质的悬浮液，对所得悬浮液进行离心过滤得到高纯单质硫，集气装置中得到高纯的氢气，其中废旧锂电池送电池回收工序；3) Pour the secondary filtrate into a device equipped with waste lithium batteries (equipped with a gas collection device) for discharge reaction. The reaction time should be greater than 12 hours. After filtration, the discharged waste lithium batteries and sulfur-containing elemental substances can be obtained respectively. The suspension is centrifugally filtered to obtain high-purity elemental sulfur, and high-purity hydrogen is obtained in the gas collection device, and the waste lithium battery is sent to the battery recovery process;
4)对处理前后废水中硫化氢浓度进行测量，经充分时间反应后废水中硫化氢浓度可达到工业废水排放对硫化氢浓度的要求。放电后的废旧电池平均残压降至0.3V以下，综合余能利用率在90％以上，处理后的出水的H2S的含量均可降至0.5wt.％以下，H2S的综合回收利用率在85％以上。4) Measure the concentration of hydrogen sulfide in the wastewater before and after treatment. After a sufficient time of reaction, the concentration of hydrogen sulfide in the wastewater can meet the requirements for the concentration of hydrogen sulfide in industrial wastewater discharge. After discharge, the average residual voltage of the used battery drops below 0.3V, the comprehensive residual energy utilization rate is above 90%, the H 2 S content of the treated effluent can be reduced to below 0.5wt.%, and the comprehensive recovery of H 2 S The utilization rate is above 85%.
实施例2Example 2
取10L工业废水，经初级过滤和次级吸附过滤之后得到无悬浮物的次级滤液对其硫含量进行测定为9.6wt.％。然后将次级滤液倒入装有废旧电池的密闭装置中，废旧电池的初始电压为3.8～3.85V，加硫酸调节滤液PH值至1左右，此时溶液中硫以H2S，HS-的形式存在。放电24h之后对其中硫含量进行测定为0.73wt.％，废旧电池平均残压在0.5V左右，对集气装置中的气体成份进行分析氢气体积分数为73％，硫化氢体积分数为25％。可见在酸性环境下有硫化氢气体析出释放。Take 10L of industrial waste water, and after primary filtration and secondary adsorption filtration, the sulfur content of the secondary filtrate without suspended solids is determined to be 9.6wt.%. Then pour the secondary filtrate into a closed device with waste batteries. The initial voltage of the waste batteries is 3.8-3.85V. Add sulfuric acid to adjust the pH value of the filtrate to about 1. At this time, the sulfur in the solution is in the form of H 2 S, HS- form exists. After 24 hours of discharge, the sulfur content was determined to be 0.73wt.%, the average residual voltage of the waste battery was around 0.5V, and the gas composition in the gas collection device was analyzed to find that the hydrogen gas fraction was 73%, and the hydrogen sulfide volume fraction was 25%. It can be seen that hydrogen sulfide gas is released in acidic environment.
实施例3Example 3
取10L工业废水，经初级过滤和次级吸附过滤之后得到无悬浮物的次级滤液对其硫含量进行测定为9.6wt.％。然后将次级滤液倒入装有废旧电池的密闭装置中，废旧电池的初始电压为3.8～3.85V。加氢氧化钠调节滤液PH值至10左右(10±0.1)，此时溶液中硫以S2-的形式存在。放电24h之后对其中硫含量进行测定为0.13wt.％，废旧电池平均残压在0V左右，对集气装置中的气体成份进行分析氢气体积分数为98％，未检测到硫化氢气体。可见在碱性环境下无硫化氢气体析出释放。Take 10L of industrial waste water, and after primary filtration and secondary adsorption filtration, the sulfur content of the secondary filtrate without suspended solids is determined to be 9.6wt.%. Then pour the secondary filtrate into a closed device containing waste batteries, the initial voltage of which is 3.8-3.85V. Add sodium hydroxide to adjust the pH value of the filtrate to about 10 (10±0.1), and at this time, sulfur exists in the form of S2- in the solution. After 24 hours of discharge, the sulfur content was determined to be 0.13wt.%, the average residual voltage of the waste battery was around 0V, the gas composition in the gas collection device was analyzed and the hydrogen gas fraction was 98%, and no hydrogen sulfide gas was detected. It can be seen that no hydrogen sulfide gas is released under alkaline environment.
对比例1Comparative example 1
取10L工业废水，经初级过滤和次级吸附过滤之后得到无悬浮物的次级滤液对其硫含量进行测定为9.6wt.％。加氢氧化钠调节才几级滤液的PH值至10左右，然后加过量的水溶性硫酸锌搅拌静止24h后过滤得到不含S2-的滤液，然后将不含S2-的滤液倒入装有废旧电池的放电装置中，废旧电池的初始电压为3.8～3.85V。放电24h之后废旧电池平均残压在3.0V左右，对集气装置中的气体成份进行分析氢气体积分数为98％，未检测到硫化氢气体。Take 10L of industrial waste water, and after primary filtration and secondary adsorption filtration, the sulfur content of the secondary filtrate without suspended solids is determined to be 9.6wt.%. Add sodium hydroxide to adjust the pH value of the first-stage filtrate to about 10, then add excess water - soluble zinc sulfate and stir for 24 hours, then filter to obtain the filtrate without S2-, then pour the filtrate without S2- into the container In the discharge device with waste batteries, the initial voltage of the waste batteries is 3.8-3.85V. After 24 hours of discharge, the average residual voltage of the waste battery is about 3.0V, and the gas composition in the gas collection device is analyzed for the hydrogen gas fraction is 98%, and no hydrogen sulfide gas is detected.
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| CN117046517A (en) * | 2023-08-15 | 2023-11-14 | 苏州清然环保科技有限公司 | Desulfurization catalyst and application thereof in sulfur-containing wastewater treatment |
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| CN110386700B (en) | 2020-07-31 |
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