本研究探討在批式系統中利用鋅片作為犧牲金屬來金屬置換水溶液中的銅、鎳離子，探討各項操作變因對於反應的影響。在單一金屬與同時金屬置換中探討包含犧牲金屬面積(30-120cm2)、溶液pH值(pH 2.0-5.0)和溶液溫度(25.0-85.0 ℃)對反應的影響，並在共同金屬置換中探討兩金屬離子銅鎳質量比例(1:1-4:1)。對於反應的影響。透過XRD與SEM等分析對金屬置換後的沉積物進行定性以及半定量分析。
研究結果顯示，不論在單一或共同金屬置換時，以鋅板金屬置換銅、鎳離子時其擬一階反應速率會微微受溶液pH值所影響，較低的溶液初始pH有助於銅離子的置換但不利於鎳離子的去除，犧牲金屬的消耗量也會隨著pH的降低而上升。銅離子單一金屬置換時的反應速率符合擬一階的模型，而鎳離子在單一金屬置換時由於鎳沉積物的影響導致擬一皆反應速率分為兩階段。並且在單一金屬系統中利用不同溶液溫度金屬置換銅、鎳離子，透過阿瑞尼斯方程式所得到的反應活化能分別為17.89 及20.64 kJ/mol，其活化能表明反應為擴散控制。在共同金屬置換時提高銅離子的比例時，鎳離子的反應速率與去除率有明顯提升。從共同置換沉積物的XRD分析中觀察到銅鎳合金、氧化亞銅和氧化鋅等，XPS分析再次確認了銅鎳合金的存在。

In the present study, zinc plates were used as sacrificial metal to replace copper and nickel ions in a batch system. The effects of various operating variables on the reaction were discussed. The effects of surface area of sacrificial metal (30-120cm2), solution pH (pH 2.0-5.0), and solution temperature (25.0-85.0 ℃) on the reaction were investigated in both single and simultaneous cementation system. The effect of mass ratio of metal ions (Cu to Ni was 1:1-4:1) on the reaction were investigated in simultaneous cementation. Qualitative and semi-quantitative analyses of the deposits were carried out by XRD and SEM analyses. The reaction rate of copper cementation in single cementation system conforms to the pseudo-first-order model, while the pseudo-first-order reaction rate of nickel cementation in single cementation system were divided into two stage due to the influence of the morphology deposits.
Regardless of single or simultaneous cementation, the pseudo-first-order reaction rate of copper and nickel ions replaced by zinc plate would slightly affected by the pH of solution. A lower initial pH of the solution was helpful for the cementation of copper ions but not conducive to the cementation of nickel ions. The consumption of sacrificial metals also increases with decreasing value of solution pH. The activation energies of the reactions obtained by single metal cementation for copper and nickel ions are 17.89 and 20.64 kJ/mol respectively, and their activation energies indicate that the reaction is diffusion-controlled. When the mass ratio of copper ions was increased during simultaneous cementation, the reaction rate and removal rate of nickel ions are significantly improved. Cu-Ni alloy, cuprous oxide and zinc oxide, etc. were observed from the XRD analysis and the existence of the Cu-Ni alloy was confirmed by XPS analysis.

Aboody, H. Najafabadi, A. T. and Saidi, M.,”Production of High Purity Magnetic Nickel Powder from Spent DRI Catalyst via Cementation Method”, J Ind Eng Chem, Vol. 110, pp. 382-394 (2022)
Ahmed, I. M., El-Nadi, Y. A. and Daoud, J. A., “Cementation of Copper from Spent Copper-Pickle Sulfate Solution by Zinc Ash,” Hydrometallurgy, Vol. 110, pp. 62-66 (2011)
Angelidis, T., Fytianos, K, and Vasilikiotis, “Lead Recovery from Aqueous Solution and Wastewater by Cementation Utilizing an Iron Rotating Disc,” Resour. Conserv. Recy., Vol. 2, pp. 131-138 (1989)
Annamalai, V. and Murr, L. E., “Effects of the Source of chloride Ion and Surface Corrosion Patterns on the Kinetics of the Copper-Aluminum Cementation System,” Hydrometallurgy, Vol. 3, pp. 249-263 (1978)
Annamalai, V., Hiskey, J. B. and Murr, L. E., “The Effects of Kinetic Variables on the Structure of Copper Deposits Cemented on Pure Aluminum Discs: a Scanning Electron Microscopic Study,” Hydrometallurgy, Vol. 3, pp. 163-180 (1978)
Annamalai, V. and Murr, L. E., “Influence of Deposit Morphology on the Kinetics of Copper Cementation on Pure Iron,” Hydrometallurgy, Vol. 4, pp. 57-82 (1979)
Arbeláez, O., Reina, T. R., Ivanova, S., Bustamante, F., Villa, A. L., Centeno, M. A., and Odriozola, J. A.,” Mono and Bimetallic Cu-Ni Structured Catalysts for the Water Gas Shift Reaction.” Applied Catalysis A: General, Vol. 497, pp. 1-9 (2015)
Bard, A. J., Stratmann, M., Gileadi, E., Urbakh, K. (2000). Thermodynamics and Electrified Interfaces. Location: Wiley-VCH.
Chen, Y., Schneider, P., and Erbe, A.,” Investigation of Native Oxide Growth on Zinc in Different Atmospheres by Spectroscopic Ellipsometry”, PHYS STATUS SOLIDI A,Vol. 209 (5), pp.846-853 (2012)
Did, A., Makhloui, L.,” Mass Transfer Correlation of Removal of Nickel by Cementation onto Rotating Zinc Disc in Industrial Zinc Sulfate Solutions”, Miner. Eng., Vol. 20 (2), pp. 146-151 (2006)
Demirkiran, N., Ekmekyapar, A., Kunkul, A. and Baysar, A., “A Kinetic Study of Copper Cementation with Zinc in Aqueous Solutions,” Int. J. Miner. Process., Vol. 82, pp. 80-85 (2007)
Demirkiran, N. and Kunkul, A., “Recovering of Copper with Metallic Aluminum,” Trans. Nonferrous Met. Soc. China, Vol. 21, pp. 2778-2782 (2011)
Demirkıran, N.,”Copper Cementation with Zinc Recovered from Spent Zinc-Carbon Batteries and Dissolution of Cement Copper in Hydrochloric Acid Solutions”, Ind. Eng. Chem. Res., Vol. 52, pp. 8157-8166 (2013)
Gordon, R. B., Graedel, T. E., Bertram, M., Fuse, K., Lifset, R., Rechberger, H. and Spatari, S.,” The Characterization of Technological Zinc Cycles.” Resources. Conser. Recycl. Vol. 39 (2), pp. 107–135. (2003)
Guan, W., Yu, H. Y., Jin, Y., and Sun, D. B.,“Effect of Pickling on Plating Porosity and Related Electrochemical Test”, Surf. Eng., Vol. 28(6), pp. 430-434 (2012)
Ghassa, S., Farzanegan, A., Gharabaghi, M. and Abdollahi, H.,” Iron Scrap, a Sustainable Reducing Agent for Waste Lithium Ions Batteries Leaching: An Environmetally Friendly Method to Treating Wastte With Waste”, Resources. Conser. Recycl, Vol. 166, 105348, (2021)
Ghassa, S., Farzanegan, A., Gharabaghi, M., and Abdollahi, H.,” The Reductive Leaching of Waste Lithium Ion Batteries in Presence of Iron Ions: Process Optimization and Kinetics Modelling.” J. Clean. Prod., Vol. 262, 121312 (2020)
Ji, H., Li, H., Zhang, Y., Ding, H., Gao, Y., and Xing, Y.,”Distribution and Risk Assessment of Heavy Metals in Overlying Water, Porewater, and Sediments of Yongding River in A Coal Mine Brownfield.” J. Soils Sediments, Vol. 18 (2), pp. 624-639. (2017)
Ku, Y. and Chen, C. H., “Kinetic Study of Copper Deposition on Iron by Cementation Reaction,” Sep. Sci. Technol., Vol. 27(10), pp. 1259-1275 (1992)
Ku, Y., Wu, M. H. and Shen, Y. S., “A Study on the Cadmium Removal from Aqueous Solution by Zinc Cementation,” Sep. Sci. Technol., Vol. 37(3), pp. 571-590 (2002)
Karavasteva, M., “Kinetics and Deposit Morphology of Copper Cementation onto Zinc, Iron and Aluminum,” Hydrometallurgy, Vol. 76, pp. 149-152 (2005)
Ku, Y. and Lee, C. S., “Kinetic Study on the Removal of Lead from Wastewaters by Iron Cementation,” J. Chin. Inst. Eng., Vol. 20(3), pp. 295-301 (1997)
Lu, J., Dreisinger, D., Ree, K.,”Simultaneous Removal of Co, Cu, Cd and Ni from Zinc Sulfate Solution by Zinc Dust Cementation”, Hydrometallurgy, 105479
Mashhadikhan, S., Amooghin, A. E., Sanaeepur, H., Shirazi, M. M. A.,” A Critial Review on Cadmium Recovery from Wastewater Towards Environmental Sustainability,” Desalination, Vol. 535, 115815 (2022)
Makhloufi, L., Saidani, B. and Hammache, H., “Removal of Lead Ions from Acidic Aqueous Solution by Cementation on Iron,” Water Res., Vol. 34(9), pp. 2517-2524 (2000)
Mahon, M. J.” Dynamic process simulation of zinc electrowinning (T)”, University of British Columbia. (2016)
https://open.library.ubc.ca/collections/ubctheses/24/items/1.0223280
Muir, D. M.,”Basic Principles of Chloride Hydrometallurgy,” In: Peek, E.M., van Weert, G. (Eds.), Chloride Metallurgy 2002, Montreal (2002), pp. 759-791
Nguyen, B. T., Do, D. D., Nguyen, T. X., Nguyen, V. N., Phuc Nguyen, D. T., Nguyen, M. H., Troung, H. T. T., Dong, H. P., Le, A. H., Bach, Q.-V.,”Seasonal, Spatial Variation, and Pollution Sources of Heavy Metals in the Sediment of the Saigon River, Vietnam.” Environ. Pollut., pp. 113412. (2019)
Palansooriya, K. N., Shaheen, S. M., Chen, S. S., Tsang, D. C. W., Hashimoto, Y., Hou, D., Bolan, N. S., Rinklebe, J., Ok, Y. S.,”Soil Amendments for Immobilization of Potentially Toxic Elements in Contaminated Soils: A Critical Review,” Environ Int, Vol. 134, pp. 105046 (2020)
Porvali, A., Aaltonen, M., Ojanen, S., Velazquez-Martinez, O., Eronen, E., Liu, F., Wilson, B.P., Serna-Guerrero, R., Lundstrom, M., Mechanical and Hydrometallurgical Processes in HCl Media for the Recycling of Valuable Metals from Li-ion Battery Waste.” Resour. Conserv. Recycl,” Vol 142, pp. 257–266 (2019)
Rao, M. D., Meshram, a., Verma, H. R., Singh, K. K. and Mankhand, T. R., “Study to Enhance Cementation of Impurities from Zinc Leach Liquor by Modifying the Shape and Size of Zinc Dust,” Hydrometallurgy, Vol. 195, pp. 105352 (2020)
Shayesteh, K., Abbasi, P., Vahid Fard, V., and Shahedi Asl, M. “Simultaneous Removal of Nickel and Cadmium During the Cold Purification of Zinc Sulfate Solution”, Arab. J. Sci. Eng., Vol. 45 (2), pp. 587–598 (2020)
Shayesteh, K., Abbasi, P., Vahid Fard, V., and Shahedi Asl, M. “Simultaneous Removal of Nickel and Cadmium During the Cold Purification of Zinc Sulfate Solution”, Arab. J. Sci. Eng., Vol. 45 (2), pp. 587–598 (2020)
Seisko, S., Aromaa, J. and Lundström,”Effect of Redox Potential and OCP in Ferric and Cupric Chlorid Leaching of Gold”, HydrometallurgyI, Vol 195, pp.105374 (2020)
Taiwan Environmental Protection Administration, Survey of Heavy Metals in the Soil Samples. (1985)
Wang, Q., kuang, Q., Wang, K., Wang, X., and Xie, Z.,”A Surfactant Free Synthesis and Formation Mechanism of Hollow Cu2O Nano Cubes Using Cl− Ions as the Morphology Regulator,” RSC Advances, Vol. 5 (75), pp. 61421-61425. (2015)
Wang, Y.-L., Tsou, M.-C., Liao, H.-T., Hseu, Z.-Y., Dang, W., Hsi, H.-C., and Chien, L.-C.,” Influence of Soil Properties on the Bioaccessibility of Cr and Ni in Geologic Serpentine and Anthropogenically Contaminated Non-Serpentine Soils in Taiwan.,” Sci. Total. Environ., Vol. 714, pp. 136761 (2020)
Wu, N. M. and Chen, W. C.,”Application of Cementation Technology in Chemical Recycle Plant Treating Waste Copper-Bearing Solution from Micro-Etching Process”, J. Environ. Treat. Tech., Vol 7, pp. 289-294 (2019)
Wu, Q., Duchstein, L. D. L., Chiarello, G. L., Christensen, J. M., Damsgaard, C. D., Elkjaer, C. F., Wnager, J. B., Temel, B., Grunwaldt, J. D., and TemelJensen, A. D.,”In Situ Observation of Cu-Ni Alloy Nanoparticle Formation by X-Ray Diffraction, X-Ray Absorption Spectroscopy, and Transmission Electron Microscopy: Influence of Cu/Ni Ratio. Chem. Cat. Chem., Vol. 6 (1), pp, 301–310 (2013)
Wu, H. T.,“Simultaneous Cementation of Copper, Cadmium and Lead Ions in Aqueous Solution with Zinc Plate.” Unpublished doctoral dissertation, National Taiwan University of Science and Technology, Taiwan.
Xiao, H., Shahab, A., Xi, B., Chang, Q., You, S., Li, J., Sun, X., Huang, H., Li, X., Siddique, J.”Heavy Metal Pollution, Ecological Risk, Spatial Distribution, and Source Identification in Sediments of the Lijiang River, China. Environ. Pollut., pp. 116189. (2020)
Younesi, S. R., Alimadadi, H., Alamdari, E. K. and Marashi, S. P. H., “Kinetic Mechanisms of Cementation of Cadmium Ions by Zinc Powder from Sulphate Solutions,” Hydrometallurgy, Vol. 84, pp. 155-164 (2006)