Clean Technology (청정기술)

The Korean Society of Clean Technology (한국청정기술학회)
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Recovery of Nickel from Waste Iron-Nickel Alloy Etchant and Fabrication of Nickel Powder

에칭 폐액으로부터 용매추출과 가수분해를 이용한 니켈분말제조에 관한 연구

  • Received : 2018.10.08
  • Accepted : 2018.12.12
  • Published : 2019.03.30
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Abstract

In general after the etching process, waste etching solution contains metals. (ex. Nickel (Ni), Chromium (Cr), Zinc (Zn), etc.) In this work, we proposed a recycling process for waste etching solution and refining from waste liquid contained nickel to make nickel metal nano powder. At first, the neutralization agent was experimentally selected through the hydrolysis of impurities such as iron by adjusting the pH. We selected sodium hydroxide solution as a neutralizing agent, and removed impurities such as iron by pH = 4. And then, metal ions (ex. Manganese (Mn) and Zinc (Zn), etc.) remain as impurities were refined by D2EHPA (Di-(2-ethylhexyl) phosphoric acid). The nickel powders were synthesized by liquid phase reduction method with hydrazine ($N_2H_4$) and sodium hydroxide (NaOH). The resulting nickel chloride solution and nickel metal powder has high purity ( > 99%). The purity of nickel chloride solution and nickel nano powders were measured by EDTA (ethylenediaminetetraacetic) titration method with ICP-OES (inductively coupled plasma optical emission spectrometer). FE-SEM (field emission scanning electron microscopy) was used to investigate the morphology, particle size and crystal structure of the nickel metal nano powder. The structural properties of the nickel nano powder were characterized by XRD (X-ray diffraction) and TEM (transmission electron microscopy).

여러 금속 부품을 가공하기 위하여 사용된 염화제이철 에칭 폐액은 유가금속인 니켈 등을 함유하고 있다. 본 연구에서는 식각공정을 완료한 에칭폐액을 재생하고 부산물로 나온 니켈 함유 폐액으로부터 정제하여 니켈 금속분말로 제조하는 공정을 개발하였다. 부산물인 니켈함유용액을 철 등의 불순물을 침전 제거하기 위하여 수산화나트륨 수용액을 실험을 통하여 가수분해 중화제로서 선정하였고, 이를 통하여 철 등의 불순물을 pH = 4 조건하에 침전 제거하였다. 그 후, 불순물로 잔류하는 망간 및 아연과 같은 금속이온들을 D2EHPA (Di-(2-ethylhexyl) phosphoric acid)를 사용하여 용매추출 하였다. 정제된 염화니켈은 99% 이상의 순도를 가지고 있으며, 그 후 환원제로 하이드라진을 이용하여 99% 이상의 순도와 약 150 nm의 크기를 가지는 니켈 금속분말로 제조하였다. 염화니켈 및 니켈 금속분말의 성분은 EDTA 적정법과 유도결합 플라즈마 방출분광법(inductively coupled plasma optical emission spectrometer, ICP-OES)을 이용하여 확인하였으며, 전계방사 주사전자현미경(field emission scanning electron microscope, FE-SEM), X-선 회절분석기(X-ray diffraction, XRD) 및 투과전자현미경(transmission electron microscopy, TEM)을 통하여 금속분말의 형태, 입자 크기 및 결정성과 같은 물리적 특성을 확인하였다.

Keywords

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Figure 1. Process flow diagram of fabrication Ni nano powder from waste iron-nickel alloy etchant.

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Figure 2. The change of metal concentrations through each processes hydroxide precipitation by (a) NaOH solution and (b) NH3 solution.

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Figure 3. Simplified Pourbaix diagram for Fe/Ni.

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Figure 4. (a) SEM image (b) XRD pattern and TEM images (insets) of the fabricated nickel nano powder layer.

Table 1. The metal composition of waste solution

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Table 2. The metal composition through each process

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Table 3. The composition of manufactured nickel nano powder in this experiment

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References

  1. Lee, H. M., Park, M., Park, G. H., and Park, C., "Wet Etching of Stainless Steel Foil by Aqueous Ferric Chloride Solution," Korean Chem. Eng. Res., 50(2), 211-216 (2012). https://doi.org/10.9713/kcer.2012.50.2.211
  2. Allen, D. M., and Heather, J. A. A., "Characterisation of Aqueous Ferric Chloride Etchants used in Industrial Photochemical Machining," J. Mater Process Technol., 149(1-3), 238-245 (2004). https://doi.org/10.1016/j.jmatprotec.2004.02.044
  3. Lee, H. Y., Ahn, E., Park, C., and Tak, Y., "Regeneration of Waste Ferric Chloride Etchant Using HCl and $H_2O_2$," Appl. Chem. Eng., 24(1), 67-71 (2013).
  4. Kim, D. W., Park, I., Kim, G. H., Lee, S. W., and Choi, H. L., "A Study on the Oxidation for Regeneration of Ferric Chloride Etching Solution," J. Korean Inst. Resour. Recycl., 26(2), 18-24 (2017). https://doi.org/10.7844/KIRR.2017.26.2.18
  5. Kim, D. W., Park, I., Kim, G. H., Chae, B. M., Lee, S. W., Choi, H. L., and Jung, H. C., "Oxidation Process for the Etching Solution Regeneration of Ferric Chloride Using Liquid and Solid Oxidizing Agent," Clean Technol., 23(2), 158-162 (2017). https://doi.org/10.7464/KSCT.2017.23.2.158
  6. Park, I. J., Kim D. W., Kim, G. H., Chae, B. M., Lee, S. W., and Jung, H. C., "The Optimization of Solvent Extraction Process of Iron Chloride Etching Waste Solution," Clean Technol., 23(3), 279-285 (2017). https://doi.org/10.7464/ksct.2017.23.3.279
  7. Chae, B. M., Hwang, S. O., Lee, S. H., Kim D. H., Lee, S. W., Kim, D. W., and Choi, H. L., "A Study on the Preparation of High Purity Nickel Carbonate Powders in Solvent Extraction Processing Solution from Waste Iron-Nickel Alloy Etchant," J. Korean Crystal Growth and Crystal Technol., 27(6), 303-308 (2017). https://doi.org/10.6111/JKCGCT.2017.27.6.303
  8. Chae, B. M., Kim, D. W., Hwang, S. O., Lee, S. H., and Kim, D. H., "Recovery of Iron-Nickel Alloy Etching Waste Solution in Pilot Scale," Clean Technol., 23(4), 393-400 (2017). https://doi.org/10.7464/KSCT.2017.23.4.393
  9. Yun, D. S., Lee, G. S., and Park, J. H., "Studies on the Ferric Chloride Etching of Shadow Masks," Korean Chem. Eng. Res., 38(3), 393-393 (2000).
  10. Lee, M. S., and Kim, M. S., "Recovery of Nickel Metal from the Spent $FeCl_3$ Etching Solution by Solvent Extraction and Chemical Reduction," J. Korean Inst. Resour. Recycl., 14(3), 48-54 (2005).
  11. Park, J. W., Chae, E. H., Kim, S. H., Lee, J. H., Kim, J. W., Yoon, S. M., and Choi, J. Y., "Preparation of Fine Ni Powders from Nickel Hydrazine Complex," Mater Chem. Phys., 97(2-3), 371-378 (2006). https://doi.org/10.1016/j.matchemphys.2005.08.028
  12. Hwang, S. O., Chae, B. M., Kim D. H., Park, K. S., Go, A. R., and Lee, S. W., "Recovery of Nickel from Waste Lithium Ion Secondary Battery and Fabrication of Nickel Nanopowder," Key Eng. Mater, 733, 22-26 (2017). https://doi.org/10.4028/www.scientific.net/KEM.733.22