Abstract
The elution mechanism of rare earth elements in cation exchange resin which was substituted with $NH_4^+,\;Zn^{2+}\;or\;Al^{3+}$ as a retaining ion had been investigated. Rare earths or rare earths-EDTA complex solution was loaded on the top of resin bed and eluted with 0.0269M EDTA solution. When the rare earth-EDTA complex was adsorbed on the $Zn^{2+}\;or\;Al^{3+}$ resin form, retaining ion was complexed with EDTA and liberated rare earths was adsorbed in the resin again. Adsorbed rare earths in resin phase could be eluted by the complexation reaction with EDTA eluent. On $NH_4^+$ resin form, the rare earth-EDTA complex which had negative charge could not adsorbed on the cation exchange resin because the complexation reaction between $NH_4^+$ and EDTA was impossible. So the elution time was much shorter than in $Zn^{2+}\;or\;Al^{3+}$ resin form. When the rare earths solution was loaded on the $Zn^{2+},\;Al^{3+}$ resin form bed, rare earths was adsorbed in the resin and the retaining ion was liberated. Adsorbed rare earths in resin bed was exchanged by EDTA eluent forming rare earths-EDTA complex, and eluted through these processes. On $NH_4^+$ resin form, rare earths loaded was adsorbed by exchange reaction with $NH_4^+$. As the EDTA eluent was added, rare earths was liberated from resin forming negatively charged rare earth-EDTA complex and eluted without any exchange reaction. So the elution time was greatly shortened and there was no metallic ion except rare earths in effluent. When the $Zn^{2+}\;and\;Al^{3+}$ was used as retaining ion, the pH of efflent was decreased seriousely because the $H^+$ liberated from EDTA molecule.
$NH_4^+,\;Zn^{2+}$ 및 $Al^{3+}$ 를 retining이온으로 치환시킨 양이온 교환수지관에 희토류를 직접 흡착시키거나 EDTA와 착물을 만들어 흡착시킨 후 0.0269M EDTA로 용리하여 각 분액에 포함된 화학종을 분석하여 이온교환 mechanism을 규명하였다. $Zn^{2+}$나 $Al^{3+}$으로 치환된 수지층에 희토류-EDTA 착물을 흡착시키면 retaining 이온과 EDTA가 착물을 형성하고 유리된 희토류가 수지에 흡착된 후 용리액인 EDTA 용액을 가하면 수지에 흡착되었던 희토류가 EDTA와 착물을 이루어 교환반응을 통해 용리된다. $NH_4^+$형 수지관에 희토류-EDTA 착물을 가하면 retaining 이온인 $NH_4^+$가 EDTA와 착물을 형성하지 못하므로 음의 전하를 띤 희토류-EDTA 화학종이 수지에 흡착되지 못하고 40ml이내에서 유출되었다. $Zn^{2+}$과 $Al^{3+}$형 수지관에 희토류 이온을 흡착시키면 희토류는 수지에 흡착되고 $Zn^{2+}$과 $Al^{3+}$이 유리된다.수지에 흡착된 희토류는 용리액인 EDTA용액과 반응하여 희토류-EDTA 착물을 이루어 교환반응을 하며 용리된다. $NH_4^+$형 수지관에 희토류 이온을 흡착시키면 희토류가 $NH_4^+$와 치환되어 흡착되어 EDTA를 가하면 희토류-EDTA 착물이 형성되어 교환반응 없이 그대로 유출되어 희토류가 빨리 용출된다. 이때에는 희토류 이외의 금속이 용출되지 않기 때문에 희토류의 분리에 대단히 유리하다. $Zn^{2+}$과 $Al^{3+}$으로 치환시킨 수지에서는 각 용출액의 pH는 용리액의 pH에 비해 대단히 감소하였다. 그 이유는 금속이온이 EDTA와 착물을 이룰때 EDTA에서 수소이온이 유리되기 때문이었다.