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Atık çinko-karbon ve alkalin pil karışımının hidrometalurjik geri kazanım prosesinin oluşturulması

Development of a hydrometallurgical process for the recycling of spent zinc-carbon and alkaline batteries mixture

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  1. Tez No: 710872
  2. Yazar: BAYRAM ANDAK
  3. Danışmanlar: DOÇ. DR. FATMA ELİF GENCELİ GÜNER
  4. Tez Türü: Doktora
  5. Konular: Kimya Mühendisliği, Chemical Engineering
  6. Anahtar Kelimeler: Belirtilmemiş.
  7. Yıl: 2021
  8. Dil: Türkçe
  9. Üniversite: İstanbul Teknik Üniversitesi
  10. Enstitü: Lisansüstü Eğitim Enstitüsü
  11. Ana Bilim Dalı: Kimya Mühendisliği Ana Bilim Dalı
  12. Bilim Dalı: Kimya Mühendisliği Bilim Dalı
  13. Sayfa Sayısı: 170

Özet

Çinko-karbon ve alkalin piller, kullanılan en yaygın enerji depolama aygıtlarındandır. Metal içerikleri sebebiyle bu piller tehlikeli atık olarak nitelendirilmektedir. Ayrıca, tekrar kullanılamamaları doğal kaynakların geri dönüşsüz olarak tükenmesine neden olmaktadır. Bu durum atık pillerin geri kazanımının önemini ortaya koymaktadır. Bu çalışmada amaç, taşınabilir enerji depolama sistemleri içerisinde en yaygın kullanım alanına sahip pil grubunu oluşturan çinko-karbon ve alkalin pillerin geri kazanılması için hidrometalurjik bir proses oluşturulmasıdır. Bu kapsamda, atık çinko-karbon ve alkalin pil karışımı bir dizi fiziksel ve kimyasal işlemlerden geçirilmiştir. Çalışmanın ilk aşamasında farklı marka ve boyuttaki pillerin fiziksel ve kimyasal karakterizasyonu yapılmıştır. Deneysel çalışmalarda kullanılacak olan pil tozu, gerçek durumu daha iyi temsil etmesi için kırma, eleme, manyetik ayırma, havalı ayırma ve öğütme gibi bir dizi endüstriyel ölçekli mekanik işlemler yardımıyla elde edilmiştir. Bu mekanik işlemler sonucunda, atık pil miktarının %71,9'u pil tozu şeklinde elde edilirken %4,4'ü çinko hurda, %12,4'ü demir hurda, %6,1'i demir tozu ve %5,2'si kağıt-plastik olarak geri kazanılmıştır. Atık çinko-karbon ve alkalin pil karışımının mekanik işlemlerden geçirilmesi sonucu elde edilen pil tozu içerisinde %26,20 Mn, %21,93 Zn, %2,60 K, %1,93 Fe, %0,55 Ni, %0,37 Ca, %0,24 Cu, %0,16 Na, %0,05 Cd, %0,04 Co, %0,03 Pb ve %14,30 karbon tespit edilmiştir. Pil tozu içerisinde bulunan alkali metallerin ayrılması için farklı sıvı/katı oranı, pH değeri ve farklı sayıda kademede nötral çözme deneyleri yapılmıştır. Sıvı/katı oranı 10, sıcaklık 25 °C, kademe sayısı 3 olan çalışmada, potasyumun %99,2'si çözelti fazına alınmış, bununla birlikte çözelti içerisindeki Zn, Mn ve Fe 1 ppm'in altında tutulmuştur. Yapılan asidik ve bazik çözme çalışmalarındaki hedef, pil tozu içerisindeki çinko ve/veya manganın çözelti içerisine alınırken diğer safsızlıkların katı fazda bırakılmasıdır. Bu amaçla, farklı sıcaklık (40 °C ve 80 °C), NaOH konsantrasyonu (ağırlıkça %20, %25 ve %30) ve sıvı/katı oranlarında (5 ve 10) bazik çözme çalışmalar gerçekleştirilmiştir. Bu çalışmalar sonucunda çinkonun %65'inin çözelti fazına alınırken, mangan ve demirin çözünme miktarının ise ihmal edilebilir düzeyde (

Özet (Çeviri)

Zinc-carbon and alkaline batteries are the most common portable storage devices which are being used. These batteries are classified as dangerous waste due to their potential danger to the environment and human health. In addition, their single-use causes the irreversible depletion of natural resources. This situation reveals the importance of recycling of waste batteries. The aim of this study is to develop a hydrometallurgical process for the separation of zinc sulfate and manganese sulfate from the leach liquors of the spent zinc-carbon/alkaline batteries. Within this scope, a series of physical and chemical processes were performed to the spent battery mixture. In the first stage of this study, the physical characterization and chemical characterization of batteries from different brands and sizes were made. Battery powder (black mass) to be used in the experimental studies was obtained by a series of industrial-scale mechanical processes such as crushing, sieving, magnetic separation, air separation and grinding to represent the real case. As a result of these mechanical processes, 12.4%, 6.1%, 4.4%, 5.2% and 71.9% of the spent battery were obtained as iron scrap, iron powder, zinc scrap, plastics/paper and black mass, respectively. The elemental analysis results of the black mass showed that it contains 26.20% Mn, 21.93% Zn, 2.60% K, 1.93% Fe, 0.55% Ni, 0.37% Ca, 0.24% Cu, 0.16% Na, 0.05% Cd, 0.04% Co, 0.03% Pb and 14,30% carbon by weight. In order to separate the alkali metals in the black mass, a series of neutral leaching experiments at different levels of liquid/solid ratio and pH values were performed. As a result of neutral leaching experiments, 99.2% of potassium removal from black mass was achieved by three-stage washing at liquid/solid ratios of 10 at 25 °C. The amount of impurities in the filtrate such as Zn, Mn and Fe was found to be less than 1 ppm. The aim of the acidic and caustic leaching studies was to take the zinc or/and manganese in the black mass into the solution while leaving the other impurities in the solid phase. For this purpose, caustic leaching studies were carried out at different temperatures (40 °C and 80 °C), different NaOH concentrations (20%, 25% and 30% by weight) and with different liquid/solid ratios (5 and 10). It was observed that 65% of the zinc can be taken into the solution phase, while the dissolution amount of manganese and iron was lower than 10 ppm in the solution. In the next stage, acidic leaching studies were carried out at different temperatures (50 °C and 80 °C), liquid/solid ratios (5, 7 and 10) and stoichiometric acid ratios (100%, 150% and 200%), since the desired recovery percentage of zinc could not be reached with caustic leaching. In the acidic leaching experiments, desired zinc recovery percentages (between 96.9% and 99.6%) were achieved, but this time iron impurity in the solution was found to be high. In order to achieve lower iron impurity, pH-controlled selective acidic leaching experiments at different temperatures (40 and 60 °C), pH values (1.5, 2, 2.5, 3 and 3.5) and liquid/solid ratios (5 and 10) were performed. In the light of experimental results, pH 2, liquid/solid ratio of 10 and 60°C were found to be the optimum conditions to achieve the desired zinc (99,24%), manganese (36,78%) and iron (4,01%) extraction yields. The iron impurity in the solution was detected as 87.4 ppm after the experiment in the stated condition. In order to remove the iron remaining in the solution, different amounts (0.5 g, 1 g and 2 g) of washed black mass were added to the solution after the pH-controlled selective acidic leaching. At the end of this, iron impurity was reduced to 2 ppm. In the next step, in order to remove the impurities such as Cd, Co, Cu, and Ni, a series of cementation experiments at 80 °C were carried out by adding different amounts of zinc powder (1 g/L, 2 g/L, and 3 g/L), Sb2O3 (50% and 100% stoichiometric equivalent of Co) and CuSO4.5H2O (100% stoichiometric equivalent of Co) into the solution. Cd, Co, Cu and Ni removals were found to be 97.9%, 74.7%, 84.0% and 75.9%, respectively, after the experiment at 80 °C, with the addition of 3 g/L zinc powder, Sb (100% stoic. eq. of Co) and Cu (100% stoic. eq. of Co). Thus, impurities were removed without accumulation in the process cycle. Based on the dissolution rates obtained from pH-controlled selective acidic leaching experiments and the MnSO4-ZnSO4-H2O phase equilibrium diagrams at 15 °C and 40 °C, a crystallization process was formed. According to the proposed crystallization process, the main solution leaving the cementation step was subjected to an evaporation process where MnSO4.H2O salt was formed at 40 °C. Then, the solution leaving the evaporation process was sent to the cooling crystallization process in order to form ZnSO4.7H2O salt at 15 °C. In the last stage, the salts obtained from the crystallization processes were dried. In the light of the results of all the physical and chemical experiments performed; a hydrometallurgical process for the recovery of the waste zinc-carbon and alkaline battery mixture has been proposed. 28.1% of the spent battery mixture (4.4% zinc scraps, 12.4% iron scraps, 6.1% iron powder and 5.2% paper-plastic) was recovered as a by-product with the help of only mechanical processes. Zinc and manganese in the remaining part, which is named as black mass, was exposed to the chemical processes to obtain MnSO4.H2O and ZnSO4.7H2O salts. For this purpose, the black mass was subjected to neutral leaching (washing) in order to separate the alkali metals (K, Na, etc.) it contains. Then, the washed black was sent to pH-controlled selective acidic leaching process where zinc and manganese were taken into the liquid phase. In the next step, the leachate was exposed to cementation process in order to eliminate the impurities in it. The leachate, which is almost free of impurities, was processed in the evaporative crystallizer and cooling crystallizer, respectively. MnSO4.H2O salt was obtained in the evaporative crystallizer, while ZnSO4.7H2O salt was formed in the cooling crystallizer. Moreover, it is thought that the cake leaving the pH-controlled selective acidic leaching step can be used in the iron-steel or ceramic industry due to its low zinc, rich manganese, and high carbon contents. In order to determine the capacity of the proposed process, the import amounts and battery collection rates determined by the regulation were used. According to these, the capacity of the facility has been selected as 4,000 tons/year of spent zinc-carbon and alkaline batteries' mixture. In the first stage of the economic analysis, the mass and energy balances of the process were established. Then, the basic dimensions of the equipment's were calculated with the help of the mass and energy balances. Also, the consumption of utilities (electricity, natural gas, etc.) for each equipment was determined. Quotations were received for all equipment's to determine the total equipment purchase cost. Other costs such as installation, piping, instrumentation etc., were calculated on the basis of the total equipment purchase cost. As a result of the economic analysis, the payback time of the facility was found to be 2.8 years, and the return on investment was found to be 25.1%. These values also reveal that the proposed project is economical to implement.

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