M4ft 15or03100421 PDF Download

Significant progress in understanding the role of alkaline conditioning of polyethylene-fiber adsorbent, developed at the Oak Ridge National Laboratory (ORNL), is demonstrated in this report, which is essentially a manuscript prepared for publication in the journal Industrial & Engineering Chemistry Research of the American Chemical Society. The manuscript describes the influence of various parameters involved in adsorbent alkaline conditioning, including base concentration and duration and temperature of conditioning, on the uranium uptake history by the adsorbent. Various solutions have been used to determine the influence of conditioning parameters including (i) a screening solution containing uranyl nitrate at approximately 8 ppm and sodium bicarbonate and sodium chloride at concentrations similar to those found in seawater, (ii) seawater spiked with approximately 75 ppb uranium, and (iii) natural seawater. In addition to concentration measurements by inductively coupled plasma (ICP) spectroscopy to determine the uranium uptake capacity and kinetics, spectroscopic methods such as Fourier transformed infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy were employed to investigate the effect of base treatment on the various chemical bonds of the adsorbent. Scanning electron microscopy (SEM) has also been employed to determine structural effects of the alkali on the adsorbent. The results are summarized as follows: 1. Alkali conditioning is necessary to prepare the adsorbent for uranium uptake. ICP analysis showed that without alkali conditioning, no appreciable uranium adsorption occurs. 2. FTIR showed that the base converts amidoxime to carboxylate groups. 3. FTIR showed that formation of carboxylate groups is irreversible and reduces the selectivity of the adsorbent toward uranium. 4. NMR showed that alkali conditioning leads also to the formation of cyclic imidedioxime, which is suspected to bind uranium, vanadium, iron, copper, and other metals. 5. Uptake of V, Fe, and Cu follows the same trend as that of uranium. Uptake of Ca, Mg, and Zn ions increases with increasing KOH conditioning time due to formation of carboxylate groups. 6. SEM showed that long conditioning times may also lead to adsorbent degradation. 7. The optimal conditioning parameters are: 0.44 M KOH, 70 C, for 1 hour. The results of this study are useful in the selection of optimal values of the parameters involved in preparing amidoxime-based adsorbent for uranium uptake from seawater. Additional work is still ongoing to provide a complete understanding of the chemistry of base conditioning and its role on the functioning of the adsorbent.