CN114703371A - Device and method for recovering copper from waste battery discharge co-processing copper-containing waste liquid - Google Patents
Device and method for recovering copper from waste battery discharge co-processing copper-containing waste liquid Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 99
- 239000010949 copper Substances 0.000 title claims abstract description 99
- 239000002699 waste material Substances 0.000 title claims abstract description 53
- 239000010926 waste battery Substances 0.000 title claims abstract description 50
- 239000007788 liquid Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000012545 processing Methods 0.000 title claims description 26
- 239000002351 wastewater Substances 0.000 claims description 31
- 238000004064 recycling Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- 238000003723 Smelting Methods 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004043 dyeing Methods 0.000 claims description 3
- 238000009713 electroplating Methods 0.000 claims description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 3
- 238000005065 mining Methods 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- 239000012776 electronic material Substances 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000011084 recovery Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
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- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明公开了一种废旧电池放电协同处理含铜废液回收铜的装置与方法，主要为将含铜废液倒入放电容器中，废旧电池放置在传送带上，通过传送到达放电容器中的含铜废液，并被含铜废液浸没进行放电；本方法不仅能对废旧电池进行放电预处理使电池达到安全拆解电压，还能协同处理回收废液中的铜，充分利用了废旧电池中残余电量，节约了传统处理废旧电池所需的放电溶液及放电完之后需要处理的废液。
The invention discloses a device and a method for cooperating discharge of waste batteries to process copper-containing waste liquid to recover copper. The copper waste liquid is immersed in the copper-containing waste liquid for discharge; this method can not only discharge and pre-treat the waste battery to make the battery reach a safe disassembly voltage, but also synergistically treat and recover the copper in the waste liquid, making full use of the waste battery. The residual power saves the discharge solution required for the traditional treatment of used batteries and the waste liquid that needs to be treated after discharge.
Description
技术领域technical field
本发明属于废旧电池再利用技术领域，具体涉及一种废旧电池放电协同处理含铜废液回收铜的装置与方法。The invention belongs to the technical field of waste battery recycling, and in particular relates to a device and method for recovering copper from waste battery discharge co-processing copper-containing waste liquid.
背景技术Background technique
随着新能源汽车的发展，电池成为目前炙手可热的行业，占据了大部分的电池行业。相比于其他类型电池，电池具有能量密度大，没有记忆效应，自放电小以及平均输出电压高等优点，也被称为绿色电池，其种类主要包括钴酸锂电池、锰酸锂电池、磷酸铁锂电池以及三元动力电池。With the development of new energy vehicles, batteries have become a hot industry, occupying most of the battery industry. Compared with other types of batteries, the battery has the advantages of high energy density, no memory effect, low self-discharge and high average output voltage. It is also called green battery, and its types mainly include lithium cobalt oxide battery, lithium manganate battery, iron phosphate. Lithium battery and ternary power battery.
近些年由于锂电行业的快速发展，造成全球范围内的钴，锂，锰以及镍等金属资源短缺，这势必会影响锂电行业的进一步发展。同时电池在报废之后的无害化处理也是大家关注的重点，因而废旧电池回收资源化成为必然趋势。因为废旧电池在回收后都带有一定的残余电量，所以在回收废旧电池后需要对其进行放电预处理才能继续进行下一步处理，避免直接对废旧电池拆解破碎时发生爆炸等危险。In recent years, due to the rapid development of the lithium battery industry, there has been a global shortage of metal resources such as cobalt, lithium, manganese and nickel, which will inevitably affect the further development of the lithium battery industry. At the same time, the harmless treatment of batteries after they are scrapped is also the focus of everyone's attention, so the recycling of used batteries has become an inevitable trend. Because waste batteries have a certain residual power after recycling, they need to be discharged and pretreated after recycling, so as to avoid the danger of explosion when directly dismantling and breaking the waste batteries.
目前工业上有许多含铜的废水需要处理回收废液中的金属。在铜冶炼、电镀加工、印染、矿山开采、印刷电路板制造以及化工等行业会产出大量的含铜废水，含铜废水是一种典型的重金属污染水。未经处理的工业含铜废水直接排放会对生态系统带来了一系列严重的负面影响，比如污染土壤和水资源，造成农作物生长发育缓慢和减产，被鱼类生物吸收后会导致发育异常。除此之外，铜化合物进入生物链后会不断在生态系统中传播，严重危害人与自然。同时，含铜废水未经处理直接排放到环境中，铜资源不能回收再利用，是对资源的严重浪费，如果能对含铜废水中的铜进行资源回收利用不但可以减少环境污染，还能促进资源的可持续发展。At present, there are many copper-containing wastewaters in the industry that need to be treated to recover the metals in the wastewater. In copper smelting, electroplating processing, printing and dyeing, mining, printed circuit board manufacturing and chemical industries, a large amount of copper-containing wastewater will be produced. Copper-containing wastewater is a typical heavy metal polluted water. The direct discharge of untreated industrial copper-containing wastewater will bring a series of serious negative impacts on the ecosystem, such as pollution of soil and water resources, resulting in slow growth and production of crops, and abnormal development after being absorbed by fish organisms. In addition, copper compounds will continue to spread in the ecosystem after entering the biological chain, seriously endangering people and nature. At the same time, copper-containing wastewater is directly discharged into the environment without treatment, and copper resources cannot be recycled and reused, which is a serious waste of resources. Recycling copper in copper-containing wastewater can not only reduce environmental pollution, but also promote sustainable development of resources.
目前，大家对废旧电池的放电预处理方法主要有物理放电和化学放电，分别采用盐溶液和导电介质粉末对废旧电池进行化学放电和物理放电，但此举不仅需要额外的准备化学溶液和导电介质粉末对电池进行放电预处理，还需要处理放电后产生的废液，且完全没能利用废旧电池中残余的能量。同时，工业上对含铜废水的处理方法主要是物理法、化学法和生物法，这几种方法都需要额外的工艺成本去处理含铜废水。At present, the discharge pretreatment methods for waste batteries mainly include physical discharge and chemical discharge. Salt solution and conductive medium powder are used to perform chemical discharge and physical discharge on waste batteries, but this not only requires additional preparation of chemical solutions and conductive media. The powder pre-discharges the battery, and also needs to deal with the waste liquid generated after discharge, and completely fails to utilize the residual energy in the spent battery. At the same time, the industrial treatment methods for copper-containing wastewater are mainly physical, chemical and biological methods, all of which require additional process costs to treat copper-containing wastewater.
因此，我们使用废旧电池放电协同处理含铜废液回收铜，以废治废，变废为宝，协同处理工艺减少了传统废旧电池放电工艺和含铜废液处置工艺的成本，帮助企业实现绿色可持续发展。Therefore, we use waste battery discharge to co-process copper-containing waste liquid to recover copper, treat waste from waste and turn waste into treasure. The co-processing process reduces the cost of traditional waste battery discharge process and copper-containing waste liquid disposal process, helping enterprises to achieve green sustainable development.
发明内容SUMMARY OF THE INVENTION
为解决现有的废旧电池放电预处理、残余电量再利用以及处理回收工业含铜废液中的铜等技术问题，本发明创新性的提出了一种废旧电池放电协同处理含铜废液回收废液中铜的装置与方法，不仅对废旧电池进行了放电预处理，还利用其残余电量，回收处理了工业上含铜废液中的铜，避免了废水的排放；In order to solve the technical problems of the existing waste battery discharge pretreatment, residual power reuse and treatment and recovery of copper in industrial copper-containing waste liquid, the present invention innovatively proposes a waste battery discharge co-processing copper-containing waste liquid recycling waste. The device and method for copper in liquid not only discharge pretreatment of waste batteries, but also use their residual power to recycle copper in industrial copper-containing waste liquids, thereby avoiding the discharge of waste water;
为了达到上述技术目的，本发明是通过以下技术方案实现的：一种废旧电池放电协同处理含铜废液回收铜的方法，包括以下步骤：In order to achieve the above-mentioned technical purpose, the present invention is achieved through the following technical solutions: a method for recycling copper from waste battery discharge co-processing copper-containing waste liquid, comprising the following steps:
将废旧电池放置于传送带上，通过传送到达放电容器中被含铜废水浸没进行放电；The waste batteries are placed on the conveyor belt, and they are immersed in copper-containing wastewater for discharge by conveying them to the discharge vessel;
优选的，所述含铜废水淹没过废旧电池，废液与废旧电池的体积比为2:1～5:1；Preferably, the copper-containing wastewater has flooded the waste battery, and the volume ratio of the waste liquid to the waste battery is 2:1 to 5:1;
优选的，所述含铜废水温度为20～45℃；Preferably, the temperature of the copper-containing wastewater is 20-45°C;
优选的，所述废旧电池包括钴酸锂电池、锰酸锂电池、磷酸铁锂电池以及三元动力电池；Preferably, the used batteries include lithium cobalt oxide batteries, lithium manganate batteries, lithium iron phosphate batteries and ternary power batteries;
优选的，所述废旧电池剩余电压不低于0.5V；Preferably, the residual voltage of the used battery is not lower than 0.5V;
优选的，所述含铜废水来源于铜冶炼、电镀、电池、印染、矿山开采、电子材料加工、化工等行业的废水，其中离子态铜的含量为1g/L～200g/L；Preferably, the copper-containing wastewater is derived from wastewater from copper smelting, electroplating, batteries, printing and dyeing, mining, electronic material processing, chemical industry and other industries, wherein the content of ionic copper is 1g/L～200g/L;
优选的，所述放电时间为1～10h；优选为4～6h；Preferably, the discharge time is 1-10h; preferably 4-6h;
本发明的另一目的在于提供一种废旧电池放电协同处理含铜废液回收铜的装置，包括：放电容器、传送带、抽气机、吸气扇；所述放电容器内盛装有含铜废水，传送带中部置于放电容器的含铜废水内，传送带两边延伸出放电容器；放电容器上方设置有抽气机，抽气机上方连接排气管道，排气管道上设置有吸气扇；Another object of the present invention is to provide a device for recovering copper from waste battery discharge and co-processing copper-containing waste liquid, comprising: a discharge vessel, a conveyor belt, an air extractor, and a suction fan; the discharge vessel is filled with copper-containing waste water, The middle of the conveyor belt is placed in the copper-containing waste water of the discharge vessel, and the discharge vessel extends from both sides of the conveyor belt; an air extractor is arranged above the discharge vessel, an exhaust pipe is connected above the air extractor, and a suction fan is arranged on the exhaust pipe;
优选的，所述传送带上设置有铆钉；Preferably, the conveyor belt is provided with rivets;
优选的，所述放电容器底部设置有漏网。Preferably, the bottom of the discharge vessel is provided with a drain.
本发明的有益效果是：The beneficial effects of the present invention are:
1)本发明有效利用了废旧电池中的残余电量，也对废旧电池进行了放电预处理。1) The present invention effectively utilizes the residual power in the waste battery, and also performs discharge pretreatment on the waste battery.
2)本发明有效回收了含铜废液中的铜，实现了同资源的回收利用，节约了工业含铜废液的处理成本。2) The present invention effectively recovers the copper in the copper-containing waste liquid, realizes the recycling and utilization of the same resource, and saves the processing cost of the industrial copper-containing waste liquid.
3)本发明将废旧电池余能利用、放电预处理和工业含铜的废液回收处理结合，简化了工艺流程，以废治废，降低了电池预处理和工业含铜废水处理成本。实现了能源、资源协同利用。3) The invention combines the utilization of waste battery residual energy, discharge pretreatment and industrial copper-containing waste liquid recovery and treatment, which simplifies the process flow, treats waste with waste, and reduces battery pre-treatment and industrial copper-containing wastewater treatment costs. The coordinated utilization of energy and resources has been realized.
附图说明Description of drawings
图1是本发明的废旧电池放电协同处理含铜废液的步骤图；Fig. 1 is the step diagram of the waste battery discharge co-processing copper-containing waste liquid of the present invention;
图2是本发明的废旧电池放电协同处理含铜废液的装置图；Fig. 2 is the device diagram of the waste battery discharge co-processing copper-containing waste liquid of the present invention;
附图中，各标号所代表的结构名称为：In the accompanying drawings, the structure names represented by each label are:
1-放电容器，2-传送带，3-漏网，4-铆钉，5-抽气机，6-吸气扇。1- Discharge vessel, 2- Conveyor belt, 3- Sleeve net, 4- Rivet, 5- Air extractor, 6- Suction fan.
具体实施方式Detailed ways
为了对本发明的技术方案及效果做出清楚完整的描述，通过以下实施例进行详细说明。In order to clearly and completely describe the technical solutions and effects of the present invention, the following embodiments are used for detailed description.
实施例1Example 1
一种废旧电池放电协同处理含铜废液的装置与方法，包括以下步骤：A device and method for co-processing copper-containing waste liquid with waste battery discharge, comprising the following steps:
1)取2L含铜量为20g/L的废水，倒入放电容器中；1) Take 2L of wastewater with a copper content of 20g/L and pour it into the discharge vessel;
2)在传送带上放置1kg待处理的废旧电池，电池电压为3.7V；将废旧电池传送到放电容器中进行放电；2) Place 1kg of waste batteries to be processed on the conveyor belt, and the battery voltage is 3.7V; transfer the waste batteries to the discharge vessel for discharge;
3)放电5h后，通过漏网过滤废液，得到电解还原的金属铜；3) After discharging for 5h, filter the waste liquid through a leak screen to obtain electrolytically reduced metal copper;
4)对放电过程中产生的气体被抽气机抽离集中处理；4) The gas generated during the discharge process is evacuated by the air extractor for centralized treatment;
5)处理后废旧电池的电压降为0.1V；5) The voltage drop of the used battery after treatment is 0.1V;
6)处理后的废液中的铜含量由20g/L下降至0.01g/L。6) The copper content in the treated waste liquid is reduced from 20g/L to 0.01g/L.
实施例2Example 2
一种废旧电池放电协同处理含铜废液的装置与方法，包括以下步骤：A device and method for co-processing copper-containing waste liquid with waste battery discharge, comprising the following steps:
1)取2L含铜量为40g/L的废水，倒入放电容器中；1) Take 2L of wastewater with a copper content of 40g/L and pour it into the discharge vessel;
2)在传送带上放置1kg待处理的废旧电池，电池电压为3.7V；将废旧电池传送到放电容器中进行放电；2) Place 1kg of waste batteries to be treated on the conveyor belt, the battery voltage is 3.7V; transfer the waste batteries to the discharge vessel for discharge;
3)放电5h后，通过漏网过滤废液，得到电解还原的金属铜；3) After discharging for 5h, filter the waste liquid through a leak screen to obtain electrolytically reduced metal copper;
4)对放电过程中产生的气体被抽气机抽离集中处理；4) The gas generated during the discharge process is evacuated by the air extractor for centralized treatment;
5)处理后废旧电池的电压降为0.1V；5) The voltage drop of the used battery after treatment is 0.1V;
6)处理后的废液中的铜含量由40g/L下降至19.8g/L。6) The copper content in the treated waste liquid is reduced from 40g/L to 19.8g/L.
实施例3Example 3
一种废旧电池放电协同处理含铜废液的装置与方法，包括以下步骤：A device and method for co-processing copper-containing waste liquid with waste battery discharge, comprising the following steps:
1)取2L含铜量为20g/L的废水，倒入放电容器中；1) Take 2L of wastewater with a copper content of 20g/L and pour it into the discharge vessel;
2)在传送带上放置2kg待处理的废旧电池，电池电压为3.7V；将废旧电池传送到放电容器中进行放电；2) Place 2kg of waste batteries to be treated on the conveyor belt, the battery voltage is 3.7V; transfer the waste batteries to the discharge vessel for discharge;
3)放电5h后，通过漏网过滤废液，得到电解还原的金属铜；3) After discharging for 5h, filter the waste liquid through a leak screen to obtain electrolytically reduced metal copper;
4)对放电过程中产生的气体被抽气机抽离集中处理；4) The gas generated during the discharge process is evacuated by the air extractor for centralized treatment;
5)处理后废旧电池的电压降为1V；5) The voltage drop of the used battery after treatment is 1V;
6)处理后的废液中的铜含量由20g/L下降至0.01g/L。6) The copper content in the treated waste liquid is reduced from 20g/L to 0.01g/L.
由实施例3对比实施例1表明含铜废水中的铜含量与废旧电池的比例会影响最终放电效果；From Example 3 to Example 1, it is shown that the ratio of the copper content in the copper-containing wastewater to the waste battery can affect the final discharge effect;
实施例4Example 4
一种废旧电池放电协同处理含铜废液的装置与方法，包括以下步骤：A device and method for co-processing copper-containing waste liquid with waste battery discharge, comprising the following steps:
1)取2L含铜量为40g/L的废水，倒入放电容器中；1) Take 2L of wastewater with a copper content of 40g/L and pour it into the discharge vessel;
2)在传送带上放置2kg待处理的废旧电池，电池电压为3.7V；将废旧电池传送到放电容器中进行放电；2) Place 2kg of waste batteries to be treated on the conveyor belt, the battery voltage is 3.7V; transfer the waste batteries to the discharge vessel for discharge;
3)放电5h后，通过漏网过滤废液，得到电解还原的金属铜；3) After discharging for 5h, filter the waste liquid through a leak screen to obtain electrolytically reduced metal copper;
4)对放电过程中产生的气体被抽气机抽离集中处理；4) The gas generated during the discharge process is evacuated by the air extractor for centralized treatment;
5)处理后废旧电池的电压降为0.1V；5) The voltage drop of the used battery after treatment is 0.1V;
6)处理后的废液中的铜含量由40g/L下降至0.01g/L。6) The copper content in the treated waste liquid is reduced from 40g/L to 0.01g/L.
实施例4对比实施例2表明含铜废水中的铜含量与废旧电池的比例会影响最终含铜废水中铜的回收量。Example 4 and Example 2 show that the ratio of copper content in copper-containing wastewater to spent batteries will affect the recovery of copper in the final copper-containing wastewater.
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| CN106229571A (en) * | 2016-08-12 | 2016-12-14 | 上海交通大学 | Batch reclaims the semi-enclosed electric discharge device of waste and old lithium ion battery |
| CN110386700A (en) * | 2018-04-23 | 2019-10-29 | 中南大学 | A kind of combination treatment method of old and useless battery electric discharge and sulfur-containing waste water desulfurization |
| CN113716790A (en) * | 2021-09-17 | 2021-11-30 | 格林美股份有限公司 | Combined treatment method for discharging waste batteries and removing heavy metal ions in wastewater |
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| CN106229571A (en) * | 2016-08-12 | 2016-12-14 | 上海交通大学 | Batch reclaims the semi-enclosed electric discharge device of waste and old lithium ion battery |
| CN110386700A (en) * | 2018-04-23 | 2019-10-29 | 中南大学 | A kind of combination treatment method of old and useless battery electric discharge and sulfur-containing waste water desulfurization |
| CN113716790A (en) * | 2021-09-17 | 2021-11-30 | 格林美股份有限公司 | Combined treatment method for discharging waste batteries and removing heavy metal ions in wastewater |
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