İKİ KADEMELİ LİÇ İŞLEMİ İLE ATIK ALKALİ PİL TOZUNDAN ÇİNKO VE MANGAN KAZANILMASI
Bu çalışmada, atık alkali pil tozlarındaki çinko ve manganın seçimli çözünürlüğü iki kademeli liç
yönteminin uygulanmasıyla incelenmiştir. Birinci liç kademesinde, pil tozundaki çinko sodyum
hidroksit çözeltileri kullanılarak çözündürülmüştür. Mangan içeren katı kalıntı filtrasyonla çözeltiden
ayrıldıktan sonra ikinci liç kademesinde kullanılmıştır. İkinci liç işleminde melas içeren sülfürik asit
çözeltileri liç ajanı olarak kullanılmıştır. Her bir liç basamağında çözelti derişimi, sıcaklık, karıştırma
hızı ve katı/sıvı oranının çinko ve mangan çözünmesine olan etkileri araştırılmıştır. Elde edilen bulgular
deney parametrelerinin çinko ve mangan çözünmesi üzerinde önemli bir etkiye sahip olduğunu
göstermiştir. Her iki metal için de çözünme veriminin çözücü derişimi, sıcaklık ve karıştırma hızının
artmasıyla, katı/sıvı oranının ise azalmasıyla arttığı gözlenmiştir. Sodyum hidroksit derişiminin
1.5 mol/L, reaksiyon sıcaklığının 40 °C, katı/sıvı oranının 2/500 g/mL, karıştırma hızının 500 dev/
dk ve reaksiyon süresinin 120 dk olduğu deney şartlarında atık pil tozundaki çinkonun %77’sinin
çözündüğü belirlenmiştir. Sülfürik asit derişimi, reaksiyon sıcaklığı, katı/sıvı oranı, karıştırma hızı ve
reaksiyon süresi sırasıyla 1 mol/L, 50 °C, 2/500 g/mL, 500 dev/dk ve 120 dk iken liç kalıntısındaki
manganın %85’inin çözündüğü bulunmuştur.
RECOVERY OF ZINC AND MANGANESE FROM WASTE ALKALINE BATTERY POWDER BY TWO-STAGE LEACHING PROCESS
In this work, the selective dissolution of zinc and manganese in the waste alkaline battery
powders was investigated by applying two-stage leaching method. In the first-stage of leaching,
zinc in the battery powder was dissolved using NaOH solutions. The solid residue containing
manganese was separated from the solution by filtration and used in the second leaching step.
Sulfuric acid solutions containing molasses was used as leaching agent in the second-stage
leaching treatment. In each leaching step, the effects of solution concentration, temperature,
stirring speed and solid to liquid ratio on the dissolution of zinc and manganese were examined.
The findings obtained showed that the experimental parameters had a significant effect on the
dissolution of zinc and manganese. It was observed that the dissolution efficiency for both metal
increased with an increase in the solution concentration, temperature and stirring speed, and
with a decrease in the solid to liquid ratio. At the experimental conditions of a sodium hydroxide
concentration of 1.5 mol/L, a reaction temperature of 40 °C, a solid to liquid ratio of 2/500 g/mL,
a stirring speed of 500 rpm, and a reaction time of 120 min., it was determined that 77% of zinc
in waste battery powder was dissolved. While concentration of sulfuric acid, temperature, solid
to liquid ratio, stirring speed, and reaction time were 1.5 mol/L, 50 °C, 2/500 g/mL, 500 rpm, and
120 min. respectively, it was found that 85% of manganese in the leach residue was dissolved.
___
- Bernardes, A.M., Espinosa, D.C.R., Tenorio,
J.A.S., 2004. Recyling of Batteries: A Review of
Current Processes and Technologies. Journal of
Power Sources, 130, 291-298.
- Buzatu M., Saceanu S., Petrescu M.I., Ghica
G.V., Buzatu T., 2014. Recovery of Zinc and
Manganese from Spent Batteries by Reductive
Leaching in Acidic Media. Journal of Power
Sources, 247, 612-617.
- Demirkıran, N., Turhan Özdemir, G.D., 2019.
A Kinetic Model for Dissolution of Zinc Oxide
Powder Obtained from Waste Alkaline Batteries
in Sodium Hydroxide Solutions. Metallurgical and
Materials Transactions B, 50B, 491-501.
- De Souza, C.C.B.M., De Oliveria, D.C., Tenorio,
J.A.S., 2001. Characterization of Used Alkaline
Batteries Powder and Analysis of Zinc Recovery
by Acid Leaching. Journal of Power Sources,
103, 120-126.
- El Hazek, M.N., Lasheen T.A., Helal A.S., 2006.
Reductive Leaching of Manganese from Low
Grade Sinai Ore in HCl Using H2
O2
as Reductant.
Hydrometallurgy, 84, 187-191.
- El Nadi, Y.A., Daoud, J.A., Aly, H.F., 2007.
Leaching and Separation of Zinc from the Black
Paste of Spent MnO2
-Zn Dry Cell Batteries.
Journal of Hazardous Materials, 143, 328-334.
- Gega, J., Walkowiak, W., 2011. Leaching of Zinc
and Manganese from Used up Zinc-Carbon
Batteries Using Aqueous Sulfuric Acid Solution.
Physicochemical Problems of Mineral Processing,
46, 155-162.
- Gupta, C.K., Murkherjee, T.K., 1990.
Hydrometallurgy in Extraction Processes, CRC
Press, USA.
- Gülensoy, H., 1984. Kompleksometrinin Esasları
ve Kompleksometrik Titrasyonlar. Fatih Yayınevi,
İstanbul.
- Jha, M.K., Kumar, V., Singh, R.J., 2001. Review
of Hydrometallurgical Recovery of Zinc from
Industrial Wastes, Resources. Conservation and
Recycling, 33, 1-22.
- Lashenn, T.A., El-Hazek, M.N., Helal, A.S., ElNagar, W., 2009. Recovery of Manganese Using
- Molasses as Reductant in Nitric Acid Solution.
International Journal of Mineral Processing, 92,
109-114.
- Nayl, A.A., Ismail, I.M., Aly, H.F., 2011. Recovery
of Pure MnSO4
.H2
O by Reductive Leaching of
Manganese from Pyrolusite Ore by Sulfuric Acid
and Hydrogen Peroxide. International Journal of
Mineral Processing, 100, 116-123.
- Rabah, M.A, El-Sayed, A.S., 1995. Recovery of
Zinc and Some of Its Valuable Salts from Secondary
Resources and Wastes. Hydrometallurgy, 37, 23-32.
- Rosenqvist, T., 2004. Principles of Extractive
Metallurgy. Tapir Academic Press, USA.
- Sadeghi, S.M., Vanpeteghem, G., Neto, I.F.F.,
Soares, H.M.V.M., 2017. Selective Leaching
of Zn from Spent Alkaline Batteries Using
Environmentally Friendly Approaches. Waste
Management, 60, 696-705.
- Sayılgan, E., Kükrer, T., Ferella, F., Akcıl, A.,
Veglio, F., Kitis, M., 2009. Reductive Leaching
of Manganese and Zinc from Spent Alkaline
and Zinc-Carbon Batteries in Acidic Media.
Hydrometallurgy, 97, 73-79.
- Sayılgan, E., Kükrer, T., Yiğit N.O., Civelekoğlu, G.,
Kitis, M., 2010. Acidic Leaching and Precipitation
of Zinc and Manganese from Spent Battery
Powders using Various Reductants. Journal of
Hazardous Materials, 173, 137-143.
- Senanayake, G., Shin, S.M., Senaputra, A.,
Winn, A., Pugaev, D., Avraamides, J., Sohn J.S.,
Kim, D.J., 2010. Comparative Leaching of Spent
Zinc-Manganese-Carbon Batteries Using Sulphur
Dioxide in Ammoniacal and Sulfuric Acid Solution.
Hydrometallurgy, 105, 36-41.
- Seyed Ghasemi, S.M., Azizi, A., 2017.
Investigation of Leaching Kinetics of Zinc from
a Low-Grade Ore in Organic and Inorganic
Acids. Journal of Mining and Environment, 8,
579-591.
- Shalchian, H., Rafsanjani-Abbasi, A., VahdatiKhaki, J., Babakhani, A., 2015. Selective Acidic
Leaching of Spent Zinc-Carbon Batteries
Followed by Zinc Electrowinning. Metallurgical
and Materials Transactions B, 46B, 38-47.
- Shin, S.M., Senanayake, G., Sohn, J., Kang,
J., Yang D, Kim, T., 2009. Separation of
Zinc from Spent Zinc-Carbon Batteries by
Selective Leaching with Sodium Hydroxide.
Hydrometallurgy, 96, 349-353.
- Veloso, L.R.S., Rodrigues, L.E.O.C., Ferreira,
D.A, Magalhaes F.S., Mansur, M.B., 2005.
Development of a Hydrometallurgical Route for
the Recovery of Zinc and Manganese from Spent
Alkaline Batteries. Journal of Power Sources,
152, 295-302.
- Venkatachalam, S., 1998. Hydrometallurgy
Narosa Publishing House, India.
- Xionga, S., Lia, X., Liua, P., Haoa, S., Haoa, F.,
Hydrometallurgy. Yinb, Z., Liua, J., 2018. Recovery
of Manganese from Low Grade Pyrolusite Ore by
Reductively Acid Leaching Process Using Lignin
as a Low Cost Reductant. Minerals Engineering,
125, 126-132.
- Xu, W., Liang, L., Zhu, M. 2015. Determination
of Sugars in Molasses by HPLC Following SolidPhase Extraction. International Journal of Food
Properties, 18, 547-557.
- Yamaguchi, T., Nagano, H., Murai, R., Sugimori,
H., Sekiguchi, C., Sumi, I., 2018. Development
of Mn Recovery Process from Waste Dry Cell
Batteries. Journal of Material Cycles Waste
Management, 20, 1909-1917.