CN101673829A - Recycling method of waste zinc-manganese battery - Google Patents
Recycling method of waste zinc-manganese battery Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 73
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002699 waste material Substances 0.000 title claims abstract description 29
- 238000004064 recycling Methods 0.000 title claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 48
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 29
- 239000011701 zinc Substances 0.000 claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 238000011084 recovery Methods 0.000 claims abstract description 21
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 10
- 238000004090 dissolution Methods 0.000 claims abstract description 9
- 239000010926 waste battery Substances 0.000 claims abstract description 7
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 238000005868 electrolysis reaction Methods 0.000 claims description 21
- 239000003792 electrolyte Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 15
- 239000011162 core material Substances 0.000 claims description 13
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 11
- 150000002697 manganese compounds Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000012785 packaging film Substances 0.000 claims description 7
- 229920006280 packaging film Polymers 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 239000007772 electrode material Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000007885 magnetic separation Methods 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 1
- 229910000368 zinc sulfate Inorganic materials 0.000 claims 1
- 239000011686 zinc sulphate Substances 0.000 claims 1
- 235000009529 zinc sulphate Nutrition 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- 239000011572 manganese Substances 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 230000008901 benefit Effects 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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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
本发明是一种废旧锌锰电池的回收处理方法。包括有如下步骤：1)电池破碎和回收电解液；2)从水洗破碎物中分离铁和有机物组份；3)酸溶解分离剩余物；4)从滤液中回收锌。本发明可回收处理包括锌锰干电池和碱性锌锰电池，不但可解决这些废旧电池可能引起的环保问题，同时也能实现对废旧电池中所含有价物的再资源化。该工艺方法可具有很高的经济和社会价值；本发明给出的工艺流程中，所使用的设备简单，有价物质的分离效果好，回收过程中的二次污染物生成量很小且可以做到无害化治理，在工艺技术上具有先进性；本发明给出工艺方法很容易被应用于规模化生产中。本发明是一种简单易行，经济实用，可规模化回收处理废旧锌锰电池的回收处理方法。
The invention relates to a recovery and treatment method for waste zinc-manganese batteries. The method comprises the following steps: 1) crushing the battery and recovering the electrolytic solution; 2) separating iron and organic components from the water-washed broken product; 3) separating the residue by acid dissolution; 4) recovering zinc from the filtrate. The recyclable treatment of the invention includes zinc-manganese dry batteries and alkaline zinc-manganese batteries, which can not only solve the environmental protection problems that these waste batteries may cause, but also realize the recycling of valuables contained in the waste batteries. The process method can have high economic and social value; in the process flow provided by the present invention, the equipment used is simple, the separation effect of valuable substances is good, and the amount of secondary pollutants generated in the recovery process is very small and can be recovered. Harmless treatment is advanced in process technology; the process method provided by the invention can be easily applied to large-scale production. The invention is a simple, easy, economical and practical recovery and treatment method for large-scale recovery and treatment of waste zinc-manganese batteries.
Description
技术领域 technical field
本发明属于固体废弃物的资源化回收处理技术领域，特别涉及锌锰干电池和碱性锌锰电池等废旧锌锰电池的回收处理方法，属于回收处理废旧锌锰电池的创新技术。The invention belongs to the technical field of resource recovery and treatment of solid waste, in particular to a recovery and treatment method for waste zinc-manganese batteries such as zinc-manganese dry batteries and alkaline zinc-manganese batteries, and belongs to an innovative technology for recycling and treatment of waste zinc-manganese batteries.
背景技术 Background technique
电池已在现代社会的诸多领域得到普遍应用。特别是通过电池行业近年来的产品结构调整，中国已成为世界电池生产和出口大国。2008年电池行业的销售收入超过2000亿元，化学电池的产量超过320亿只，出口量超过250亿只。锌锰电池(包括锌锰干电池和碱性锌锰电池)的生产量占到产量约三分之二。据推算，每生产10亿只碱性锌锰电池将消耗金属锌0.52万t，二氧化锰1.1万t，铜906t，冷轧钢0.45万t，氢氧化钾0.16万t。由于生产电池所使用的各活性物质在电池寿命终结后依然存在电池中，因此，对废旧电池进行回收处理，不但可使电池中所含有的锌和锰等物质实现再资源化，缓解日益严峻的全球资源压力，而且也可解决废电池对环境造成的潜在污染问题。Batteries have been widely used in many fields of modern society. Especially through the product structure adjustment of the battery industry in recent years, China has become the world's largest battery producer and exporter. In 2008, the sales revenue of the battery industry exceeded 200 billion yuan, the output of chemical batteries exceeded 32 billion, and the export volume exceeded 25 billion. The production of zinc-manganese batteries (including zinc-manganese dry batteries and alkaline zinc-manganese batteries) accounts for about two-thirds of the output. It is estimated that the production of 1 billion alkaline zinc-manganese batteries will consume 5,200 tons of zinc metal, 11,000 tons of manganese dioxide, 906 tons of copper, 4,500 tons of cold-rolled steel, and 1,600 tons of potassium hydroxide. Since the active substances used in the production of batteries still exist in the battery after the battery life ends, recycling waste batteries can not only recycle the zinc and manganese contained in the battery, but also alleviate the increasingly severe Global resource pressure, but also can solve the potential pollution problem caused by waste batteries to the environment.
在过去几十年中，人们在研究锌锰电池的回收处理技术时，主要基于火法或湿法冶金工艺流程来对废旧锌锰电池中的有价物质进行处理。这些方法一般都是先对电池进行破碎，然后依次分离回收其中的汞、锌、锰、铜和电解液等。其中，火法冶金流程是根据电池中的不同物质在高温条件下挥发性的差别而依次分离，这种方法的优点是工艺流程较短，回收效率高，缺点是能耗量大且设备投入多；湿法冶金方法则通过把电池废料先溶解再分离，工艺流程较复杂，易于实现对电池中不同物种的分别回收，但该流程往往会带来二次污染。随着技术进步，近年来普通锌锰干电池的使用正逐步被淘汰，取而代之的是无汞碱性锌锰电池的大量生产和使用。据报道，一些发达国家的碱性化率已接近90％，而中国也已达到了50％，并且这个数字还正在不断高速增长。可以预见，在不久的将来所面临的废锌锰电池主要为无汞碱性锌锰电池。In the past few decades, when people were studying the recycling technology of zinc-manganese batteries, they mainly processed the valuable substances in waste zinc-manganese batteries based on pyrometallurgical or hydrometallurgical processes. These methods generally firstly crush the battery, and then separate and recover the mercury, zinc, manganese, copper and electrolyte in sequence. Among them, the pyrometallurgical process is sequentially separated according to the volatility difference of different substances in the battery under high temperature conditions. The advantage of this method is that the process flow is short and the recovery efficiency is high. The disadvantage is that the energy consumption is large and the investment in equipment is large. ; The hydrometallurgical method dissolves the battery waste first and then separates it. The process is more complicated, and it is easy to realize the separate recovery of different species in the battery, but this process often brings secondary pollution. With the advancement of technology, the use of ordinary zinc-manganese dry batteries is gradually being eliminated in recent years, replaced by the mass production and use of mercury-free alkaline zinc-manganese batteries. According to reports, the alkalization rate in some developed countries is close to 90%, while in China it has reached 50%, and this figure is still growing rapidly. It can be foreseen that the waste zinc-manganese batteries faced in the near future are mainly mercury-free alkaline zinc-manganese batteries.
发明内容 Contents of the invention
本发明的目的在于考虑上述问题而提供一种简单易行，经济实用，可规模化回收处理的废旧锌锰电池的回收处理方法。本发明可无害化处理包括锌锰干电池和碱性锌锰电池在内的废锌锰电池，回收过程中得到的铁物质、电解液、锰化合物、金属锌等都可运用于其它行业，实现对电池中有价值物质的回收，从而使废锌锰电池得到最大程度的资源化。The purpose of the present invention is to consider the above problems and provide a simple, economical and practical method for the recovery and treatment of waste zinc-manganese batteries that can be recovered on a large scale. The invention can harmlessly treat waste zinc-manganese batteries including zinc-manganese dry batteries and alkaline zinc-manganese batteries, and the iron substances, electrolytes, manganese compounds, and metal zinc obtained in the recycling process can be used in other industries to realize The recovery of valuable substances in the battery can maximize the resource utilization of waste zinc-manganese batteries.
本发明的技术方案是：本发明废旧锌锰电池的回收处理方法，其包括有如下步骤：The technical scheme of the present invention is: the recovery processing method of waste zinc-manganese battery of the present invention, it comprises the following steps:
1)电池破碎和回收电解液；1) The battery is broken and the electrolyte is recovered;
2)从水洗破碎物中分离铁和有机物组份；2) Separating iron and organic components from the water-washed crushed product;
3)酸溶解分离剩余物；3) acid dissolves and separates the residue;
4)从滤液中回收锌。4) Zinc is recovered from the filtrate.
上述步骤1)中是把废旧电池的外壳打开，然后用水洗的方法分离出其中的电解液。In the above step 1), the shell of the used battery is opened, and then the electrolyte is separated by washing with water.
上述步骤1)中电池的外壳首先经破碎打开，并在随后的球磨过程中使极芯物质能从外壳上脱落下来，通过在破碎物中加入水分浸泡后，用过滤的方法回收电解液。In the above step 1), the shell of the battery is first broken and opened, and the pole core material can fall off from the shell in the subsequent ball milling process, and the electrolyte is recovered by filtering after adding water to the broken material for soaking.
上述步骤2)中是使用包括球磨、筛分和磁选的方法，从水洗破碎物中分离出来其中的铁质外壳和导电棒，以及隔膜、外包装膜和密封圈有机物组份。In the above step 2), the method including ball milling, sieving and magnetic separation is used to separate the iron shell and conductive rod, as well as the organic components of the diaphragm, outer packaging film and sealing ring from the water-washed broken product.
上述步骤2)中用球磨机对水洗破碎物进行球磨，使电池极芯物质从电池壳上脱落，然后用筛分的方法把电池壳、电池极芯导电棒和有机物组份分离出来，再借助磁选最终分离出隔膜、外包装膜和密封圈。In the above step 2), use a ball mill to grind the water-washed crushed matter to make the battery pole core material fall off from the battery case, and then separate the battery case, battery pole core conductive rod and organic components by sieving, and then use magnetic Finally, separate the diaphragm, outer packaging film and sealing ring.
上述步骤3)中是使用硫酸溶解已分离出铁和有机物组份的剩余物，然后过滤溶解物，分别得到含锌离子的滤液和含锰化合物的滤渣。In the above-mentioned step 3), sulfuric acid is used to dissolve the residue from which the iron and organic components have been separated, and then the dissolved matter is filtered to obtain the filtrate containing zinc ions and the filter residue containing manganese compounds respectively.
上述步骤3)中使用浓度为0.5-6mol/L的硫酸溶解已分离出铁和有机物组份的剩余物，然后用过滤的方法分别得到含锌离子的滤液和含锰化合物的滤渣。In the above step 3), sulfuric acid with a concentration of 0.5-6 mol/L is used to dissolve the residue of the separated iron and organic components, and then the filtrate containing zinc ions and the filter residue containing manganese compounds are respectively obtained by filtering.
上述步骤4)中是用电解沉积的方法回收滤液中的锌。Above-mentioned step 4) is to reclaim the zinc in the filtrate with the method for electrolytic deposition.
上述步骤4)中电解使用铅板或钛板作为电解池的电极材料，用直流电解的方法在阴极上得到金属锌。In the above-mentioned step 4), the electrolysis uses a lead plate or a titanium plate as the electrode material of the electrolytic cell, and obtains metal zinc on the cathode with a direct current electrolysis method.
上述电解过程中电解液中ZnSO4的含量控制在160-50g/L；电解后的溶液可以重复使用，用于步骤2)中的溶解过程。During the electrolysis process, the ZnSO content in the electrolyte is controlled at 160-50g/L; the solution after electrolysis can be reused for the dissolution process in step 2).
目前，废旧锌锰电池中的锌锰干电池主要以锌为外壳，碱性锌锰则以铁为电池外壳，收集到的废旧锌锰电池通常是这两种电池的混合物。很多锌锰电池还以铁作为电池电极的集流体。总体来看，铁在整个废旧锌锰电池中的使用量很大，而铁的存在对回收高价值的锌具有很大的影响。因此，对铁的分离方法直接影响到回收处理工艺流程的制定以及工艺的经济效益。在本发明中，采用把电池破碎开，然后在洗去电解液后用筛分方法分离出破碎物中的铁质组份，不但可简化工艺流程，而且也可降低工艺对设备和化学药品的需求。此外，用水洗涤破碎物回收电解液，然后对水洗物进行球磨处理，可使极芯物质以小颗粒形式从电池壳体和导电棒上脱落下来，满足随后的筛分分离操作需求，实现从破碎物中分离出铁质外壳、导电棒、有机组份等的目的。在筛分过程中得到的筛下物主要为锌、锌化合物和锰化合物。另外，本发明利用锌及其化合能溶解于硫酸中，而二氧化锰不溶于稀硫酸的性质特点，可以实现用一定浓度的硫酸来溶解筛下物中的锌，然后用过滤的方法与锰分离的目标。过滤所得到的滤渣为锰化合物，可以直接烘干后作为原料出售。滤液中的离子主要为锌离子，但由于二氧化锰放电后的产物也可以部分被溶解为二价锰离子进入溶液，因此滤液中也含有少量锰离子。与有机物萃取和化学沉淀等方法相比，本发明采用电解的方法将是分离含有二价锌离子和锰离子溶液中锌和锰的较好方法。特别是该方法可以直接得到高纯度的电解锌。在电解锌的过程中，由于采用室温环境条件，从而可使锰离子留在电解液中。电解时电解液中ZnSO4的含量控制在160-50g/L，这样可以提高整个电解过程的电流效率。电解后的溶液酸度会得到提高，该溶液可以重复使用于前面的酸溶解步骤中。当电解剩余溶液中锰含量累积过高时，则用碱沉淀、焙烧再硫酸溶解的方法，使锰以二氧化锰的形式得到分离。整个回收处理结束后，可以得到电解液、铁质的外壳和导电棒、锌和锰化合物，以及隔膜、密封圈和外包装膜等。特别是本方法中因没有高温焙烧工序，故可以免除废气二次污染物的生成。而在锌锰分离过程中尽管使用了硫酸，但结合随后的电解分离过程，酸表现出可重复使用的特点，消耗物实际上是水，故因酸可能造成二次污染的可能性也很小。在处理高锰含量电解液时，则可以使用回收得到的电解液来进行酸中和以及沉淀处理。工艺流程的这些特点，不但可使整个回收过程中产生的二次污染物很少且可得到无害化处理，而且也能提高整个流程的经济效益。本发明与现有技术相比，具有如下的优点或效果：At present, zinc-manganese dry batteries in waste zinc-manganese batteries mainly use zinc as the shell, while alkaline zinc-manganese batteries use iron as the battery shell. The collected waste zinc-manganese batteries are usually a mixture of these two batteries. Many zinc-manganese batteries also use iron as the current collector of the battery electrodes. Overall, the use of iron in the whole waste zinc-manganese battery is very large, and the presence of iron has a great impact on the recovery of high-value zinc. Therefore, the iron separation method directly affects the formulation of the recycling process and the economic benefits of the process. In the present invention, the battery is crushed, and then the iron components in the crushed product are separated by sieving after washing away the electrolyte, which not only simplifies the process flow, but also reduces the cost of the process to equipment and chemicals. need. In addition, washing the broken material with water to recover the electrolyte, and then ball milling the washed material can make the pole core material fall off the battery case and conductive rod in the form of small particles, which can meet the requirements of subsequent screening and separation operations, and realize the recovery from crushing. The purpose of separating iron shells, conductive rods, organic components, etc. from objects. The undersize obtained during the sieving process is mainly zinc, zinc compounds and manganese compounds. In addition, the present invention utilizes the property that zinc and its compound can be dissolved in sulfuric acid, while manganese dioxide is insoluble in dilute sulfuric acid, so that sulfuric acid with a certain concentration can be used to dissolve the zinc in the sieve, and then use the method of filtration to combine with manganese. separate goals. The filter residue obtained by filtration is a manganese compound, which can be directly dried and sold as a raw material. The ions in the filtrate are mainly zinc ions, but since the discharged manganese dioxide products can also be partially dissolved as divalent manganese ions and enter the solution, the filtrate also contains a small amount of manganese ions. Compared with methods such as organic matter extraction and chemical precipitation, the method using electrolysis in the present invention will be a better method for separating zinc and manganese in a solution containing divalent zinc ions and manganese ions. In particular, the method can directly obtain high-purity electrolytic zinc. In the process of electrolyzing zinc, manganese ions can be left in the electrolyte due to the use of room temperature environment conditions. During electrolysis, the content of ZnSO 4 in the electrolyte is controlled at 160-50g/L, which can improve the current efficiency of the entire electrolysis process. The acidity of the solution after electrolysis will be improved, and the solution can be reused in the previous acid dissolution step. When the manganese content in the electrolytic residual solution is too high, the manganese is separated in the form of manganese dioxide by alkali precipitation, roasting and sulfuric acid dissolution. After the whole recycling process, you can get electrolyte, iron shell and conductive rod, zinc and manganese compounds, as well as diaphragm, sealing ring and outer packaging film. In particular, because there is no high-temperature roasting process in the method, the generation of waste gas secondary pollutants can be avoided. In the zinc-manganese separation process, although sulfuric acid is used, combined with the subsequent electrolytic separation process, the acid shows the characteristics of reusability, and the consumable is actually water, so the possibility of secondary pollution caused by the acid is also very small. . When dealing with high manganese content electrolyte, the recovered electrolyte can be used for acid neutralization and precipitation treatment. These characteristics of the technological process can not only make the secondary pollutants produced in the whole recycling process very small and can be treated harmlessly, but also can improve the economic benefits of the whole process. Compared with the prior art, the present invention has the following advantages or effects:
1)包括锌锰干电池和碱性锌锰电池是现在使用最为广泛的一次性电池，采用本方法回收处理这些电池，不但可解决这些废旧电池可能引起的环保问题，同时也能实现对废旧电池中所含有价物的再资源化。该工艺方法可具有很高的经济和社会价值；1) Zinc-manganese dry batteries and alkaline zinc-manganese batteries are the most widely used disposable batteries at present. Using this method to recycle these batteries can not only solve the environmental problems that these waste batteries may cause, but also realize the recovery of waste batteries. Recycling of contained valuables. The process can have high economic and social value;
2)本发明给出的工艺流程中，所使用的设备简单，有价物质的分离效果好，回收过程中的二次污染物生成量很小且可以做到无害化治理，在工艺技术上具有先进性；2) In the technical process provided by the present invention, the equipment used is simple, the separation effect of valuable substances is good, and the amount of secondary pollutants generated in the recovery process is very small and can be treated harmlessly. advanced;
3)本发明给出工艺方法很容易被应用于规模化生产中。3) The process method provided by the present invention is easy to be applied in large-scale production.
本发明是一种方便实用的废旧锌锰电池的回收处理方法。The invention is a convenient and practical recycling method for waste zinc-manganese batteries.
附图说明 Description of drawings
图1为本发明的流程图。Fig. 1 is a flowchart of the present invention.
具体实施方式 Detailed ways
实施例：Example:
本发明的流程图如图1所示，本发明废旧锌锰电池的回收处理方法，其包括有如下步骤：Flow chart of the present invention is as shown in Figure 1, and the recovery processing method of waste zinc-manganese battery of the present invention, it comprises the following steps:
1)电池破碎和回收电解液；1) The battery is broken and the electrolyte is recovered;
2)从水洗破碎物中分离铁和有机物组份；2) Separating iron and organic components from the water-washed crushed product;
3)酸溶解分离剩余物；3) acid dissolves and separates the residue;
4)从滤液中回收锌。4) Zinc is recovered from the filtrate.
上述步骤1)中是把废旧电池的外壳打开，然后用水洗的方法分离出其中的电解液。In the above step 1), the shell of the used battery is opened, and then the electrolyte is separated by washing with water.
上述步骤1)中电池的外壳首先经破碎打开，并在随后的球磨过程中使极芯物质能从外壳上脱落下来，通过在破碎物中加入水分浸泡后，用过滤的方法回收电解液。In the above step 1), the shell of the battery is first broken and opened, and the pole core material can fall off from the shell in the subsequent ball milling process, and the electrolyte is recovered by filtering after adding water to the broken material for soaking.
上述步骤2)中是使用包括球磨、筛分和磁选的方法，从水洗破碎物中分离出来其中的铁质外壳和导电棒，以及隔膜、外包装膜和密封圈有机物组份。In the above step 2), the method including ball milling, sieving and magnetic separation is used to separate the iron shell and conductive rod, as well as the organic components of the diaphragm, outer packaging film and sealing ring from the water-washed broken product.
上述步骤2)中用球磨机对水洗破碎物进行球磨，使电池极芯物质从电池壳上脱落，然后用筛分的方法把电池壳、电池极芯导电棒和有机物组份分离出来，再借助磁选最终分离出锌壳、隔膜、外包装膜和密封圈。In the above step 2), use a ball mill to grind the water-washed crushed matter to make the battery pole core material fall off from the battery case, and then separate the battery case, battery pole core conductive rod and organic components by sieving, and then use magnetic Finally, the zinc shell, diaphragm, outer packaging film and sealing ring are separated.
上述步骤3)中是使用硫酸溶解已分离出铁和有机物组份的剩余物，然后过滤溶解物，分别得到含锌离子的滤液和含锰化合物的滤渣。In the above-mentioned step 3), sulfuric acid is used to dissolve the residue from which the iron and organic components have been separated, and then the dissolved matter is filtered to obtain the filtrate containing zinc ions and the filter residue containing manganese compounds respectively.
上述步骤3)中使用浓度为0.5-6mol/L的硫酸溶解已分离出铁和有机物组份的剩余物，然后用过滤的方法分别得到含锌离子的滤液和含锰化合物的滤渣。In the above step 3), sulfuric acid with a concentration of 0.5-6 mol/L is used to dissolve the residue of the separated iron and organic components, and then the filtrate containing zinc ions and the filter residue containing manganese compounds are respectively obtained by filtering.
上述步骤4)中是用电解沉积的方法回收滤液中的锌。Above-mentioned step 4) is to reclaim the zinc in the filtrate with the method for electrolytic deposition.
上述步骤4)中电解使用铅板或钛板作为电解池的电极材料，用直流电解的方法在阴极上得到金属锌。In the above-mentioned step 4), the electrolysis uses a lead plate or a titanium plate as the electrode material of the electrolytic cell, and obtains metal zinc on the cathode with a direct current electrolysis method.
上述电解过程中电解液中ZnSO4的含量控制在160-50g/L；电解后的溶液可以重复使用，用于步骤3)中的溶解过程。The content of ZnSO in the electrolytic solution is controlled at 160-50g/L during the above electrolysis process; the solution after electrolysis can be reused for the dissolution process in step 3).
本实施例中，所处理的废旧锌锰电池为从市场上收集得到的锌锰干电池和碱性锌锰电池混合物，二者的比例约各占50％，具体操作如下：In the present embodiment, the waste zinc-manganese battery to be processed is a mixture of zinc-manganese dry battery and alkaline zinc-manganese battery collected from the market, and the ratio of the two accounts for about 50% respectively. The specific operations are as follows:
1)使用电池破碎机(中国发明专利ZL 200410051922.1)把电池破碎。把破碎物放入有机械搅拌装置且耐酸碱的塑料容器中，并加入去离子水至全部浸没破碎物。机械搅拌10分钟后过滤。然后再重复水洗操作1次。第二次水洗过滤液用于后续破碎物的第一次水洗，以最大限度地增加水洗效果并节约用水。从水洗液中回收电池电解液。1) Use a battery crusher (Chinese invention patent ZL 200410051922.1) to crush the battery. Put the broken material into an acid and alkali resistant plastic container with a mechanical stirring device, and add deionized water until the broken material is completely submerged. After mechanical stirring for 10 minutes, it was filtered. Then repeat the washing operation once more. The second wash filtrate is used for the first wash of the subsequent broken material to maximize the washing effect and save water. Recover battery electrolyte from water wash.
2)用球磨机对水洗破碎物进行球磨30分钟，使电池极芯物质从电池壳中脱落出来，然后用网孔大小为2毫米的筛子进行分离。得到的筛上物中有电池壳、电池极芯导电棒和有机物组份，筛下物主要为电池极芯物质。用磁铁把具有铁磁性的物质吸附在磁铁表面上，从筛上物中分离出铁物质。磁选剩余物用3mol/L的硫酸溶解后过滤，得到含锌离子的过滤液，以及隔膜、外包装膜和密封圈等滤渣。含锌离子的过滤液加入到后续酸溶解步骤得到的滤液中，一并作为电解锌工序中的电解液。2) Use a ball mill to mill the water-washed broken material for 30 minutes, so that the battery pole core material falls off from the battery case, and then separate it with a sieve with a mesh size of 2 mm. The obtained oversize includes battery case, battery pole core conductive rod and organic components, and the undersize is mainly battery pole core material. Use a magnet to adsorb ferromagnetic substances on the surface of the magnet, and separate iron substances from the sieve. The magnetic separation residue is dissolved with 3mol/L sulfuric acid and then filtered to obtain the filtrate containing zinc ions, and filter residues such as diaphragm, outer packaging film and sealing ring. The filtrate containing zinc ions is added to the filtrate obtained in the subsequent acid dissolution step, and used together as the electrolyte in the electrolytic zinc process.
3)使用浓度为3mol/L的硫酸溶解已分离出铁和有机物组份的剩余物。其中，金属锌和锌化合物可全部被溶解为锌离子而进入溶液，然后用过滤的方法分别得到滤液和含锰化合物的滤渣。3) Use sulfuric acid with a concentration of 3 mol/L to dissolve the residue from which the iron and organic components have been separated. Among them, metal zinc and zinc compounds can all be dissolved into zinc ions and enter the solution, and then the filtrate and the filter residue containing manganese compounds can be obtained respectively by filtering.
4)从溶液中电沉积分离锌时，使用铅板作为电解池的电极材料，用直流电解的方法在阴极上得到金属锌。采用溶液浓缩的方法把浸出液中ZnSO4的含量事先调整到约160g/L，电解时ZnSO4的含量最低控制50g/L，低于该浓度则换用新鲜溶液。电解剩余溶液重复使用于前面的酸溶解步骤中。当溶解液中锰含量累计到影响锌的沉积时，则用回收到的电解液沉淀锰，并依次经焙烧和硫酸溶解使锰以二氧化锰的形式得到分离。4) When zinc is separated by electrodeposition from the solution, the lead plate is used as the electrode material of the electrolytic cell, and metal zinc is obtained on the cathode by direct current electrolysis. Use the solution concentration method to adjust the ZnSO 4 content in the leaching solution to about 160g/L in advance. During electrolysis, the ZnSO 4 content should be controlled at a minimum of 50g/L. If it is lower than this concentration, use a fresh solution. The remaining solution from electrolysis was reused in the previous acid dissolution step. When the manganese content in the solution accumulates enough to affect the deposition of zinc, the recovered electrolyte is used to precipitate the manganese, and the manganese is separated in the form of manganese dioxide through roasting and sulfuric acid dissolution.
实施例2Example 2
本实施例与实施例1的回收方法相同，不同之处在于回收处理的电池为废旧锌锰干电池，在步骤1)中使用切割机把电池破开，步骤3)中溶解电池破碎物的硫酸浓度为6mol/L，在步骤4)中，电解使用钛板作为电解池的电极材料。The recycling method of this embodiment is the same as that of Embodiment 1, the difference is that the battery to be recycled is a waste zinc-manganese dry battery, and in step 1) a cutting machine is used to break the battery, and in step 3) the sulfuric acid concentration of the broken battery is dissolved 6mol/L, in step 4), the electrolysis uses a titanium plate as the electrode material of the electrolytic cell.
实施例3Example 3
本实施例与实施例1的回收方法相同，不同之处在于回收处理的电池全部为碱性锌锰电池，步骤3)中溶解电池破碎物的硫酸浓度为0.5mol/L，在步骤4)中，电解使用钛板作为电解池的电极材料。The recovery method of this embodiment is the same as that of Example 1, the difference is that the batteries recovered are all alkaline zinc-manganese batteries, and the concentration of sulfuric acid for dissolving the broken battery in step 3) is 0.5mol/L, and in step 4) , Electrolysis uses titanium plates as the electrode material of the electrolytic cell.
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| CN108123144A (en) * | 2017-12-22 | 2018-06-05 | 横琴国际知识产权交易中心有限公司 | Urban energy-saving environment-friendly type community intelligent waste dry battery recycling device and method |
| CN109825708A (en) * | 2019-01-25 | 2019-05-31 | 中南大学 | A kind of recovery method of positive and negative electrode material in waste alkaline zinc-manganese battery |
| CN110752384A (en) * | 2019-09-16 | 2020-02-04 | 东南大学 | A kind of recycling method of waste zinc-manganese battery |
| CN113299937A (en) * | 2021-05-17 | 2021-08-24 | 成都工业学院 | A method for recycling waste zinc-manganese dry batteries and directly using them in rechargeable zinc-manganese batteries |
| CN113299937B (en) * | 2021-05-17 | 2022-07-12 | 成都工业学院 | Method for recycling waste zinc-manganese dry batteries and directly using waste zinc-manganese dry batteries in rechargeable zinc-manganese batteries |
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