Selective adsorption of Pd(II) over Ag(I) in nitric acid solutions using nitrogen-donor-type adsorbents

Suzuki, Tomoya*; Otsubo, Ukyo*; Ogata, Takeshi*; Shiwaku, Hideaki; Kobayashi, Toru; Yaita, Tsuyoshi; Matsuoka, Mitsuaki*; Murayama, Norihiro*; Narita, Hirokazu*

Separation and Purification Technology, 308, p.122943_1 - 122943_7, 2023/03

https://doi.org/10.1016/j.seppur.2022.122943

HNO leaching is used in recycling Pd metal from spent products that primarily contain Ag, and most Pd residues are separated from solutions containing Ag(I). However, a small amount of Pd(II) often remains in these Ag(I) solutions. Therefore, the separation of Pd(II) and Ag(I) in HNO solutions is essential to promote efficient Pd recycling. In this study, the separation of Pd(II) and Ag(I) in HNO solutions was investigated using four N-donor-type adsorbents functionalized with amine (R-Amine), iminodiacetic acid (R-IDA), pyridine (R-Py), or bis-picolylamine (R-BPA). R-Amine, R-IDA, and R-Py selectively adsorbed Pd(II) over Ag(I), Cu(II), Ni(II), and Fe(III) from HNO solutions (0.3-7 M), but R-Amine exhibited a lower Pd adsorption efficiency. In contrast, 90% of Pd(II), Ag(I), and Cu(II) were adsorbed by R-BPA over the entire range of HNO concentrations. Structural analyses of the adsorbed metal ions using Fourier transform infrared spectroscopy and extended X-ray absorption fine structure spectroscopy revealed the separation mechanisms of the N-donor-type adsorbents. Pd(II) adsorption on R-IDA, R-Py, and R-BPA occurred via Pd(II) coordination of the functional groups (iminodiacetic acid, pyridine, and bis-picolylamine, respectively), whereas that on R-Amine occurred via anion exchange of NO with [Pd(NO)]. The coordinative adsorption mechanisms resulted in the higher Pd(II) adsorption behaviors of R-IDA, R-Py, and R-BPA. HCl (5.0 M) and thiourea (0.1 M) eluents desorbed 83% of Pd(II) from R-IDA and 95% from R-Py, respectively. R-Py was the most effective Pd(II) adsorbent based on adsorption selectivity and desorption efficiency.

New design of a sample cell for neutron reflectometry in liquid-liquid systems and its application for studying structures at air-liquid and liquid-liquid interfaces

Akutsu-Suyama, Kazuhiro*; Yamada, Norifumi*; Ueda, Yuki; Motokawa, Ryuhei; Narita, Hirokazu*

Applied Sciences (Internet), 12(3), p.1215_1 - 1215_10, 2022/02

https://doi.org/10.3390/app12031215

no abstracts in English

Precious metal separations

Narita, Hirokazu*; Kasuya, Ryo*; Suzuki, Tomoya*; Motokawa, Ryuhei; Tanaka, Mikiya*

Encyclopedia of Inorganic and Bioinorganic Chemistry (Internet), 28 Pages, 2020/12

https://doi.org/10.1002/9781119951438.eibc2756

Proton chelating ligands drive improved chemical separations for rhodium

Narita, Hirokazu*; Nicolson, R. M.*; Motokawa, Ryuhei; Ito, Fumiyuki*; Morisaku, Kazuko*; Goto, Midori*; Tanaka, Mikiya*; Heller, W. T.*; Shiwaku, Hideaki; Yaita, Tsuyoshi; et al.

Inorganic Chemistry, 58(13), p.8720 - 8734, 2019/07

https://doi.org/10.1021/acs.inorgchem.9b01136

Speciation of ruthenium(III) chloro complexes in hydrochloric acid solutions and their extraction characteristics with an amide-containing amine compound

Suzuki, Tomoya*; Ogata, Takeshi*; Tanaka, Mikiya*; Kobayashi, Toru; Shiwaku, Hideaki; Yaita, Tsuyoshi; Narita, Hirokazu*

Metals, 8(7), p.558_1 - 558_10, 2018/07

AA2018-0670.pdf:2.11MB

https://doi.org/10.3390/met8070558

The refining of platinum group metals is based mainly on solvent extraction methods, whereas Ru is selectively recovered by distillation as RuO. Replacement of distillation byextraction is expected to simplify the purification process. To develop an effective extraction system for Ru, we analyzed the Ru species in HCl with UV-Vis and EXAFS spectroscopies, and we examined the properties of Ru extracted with N-2-ethylhexyl-bis(N-di-2-ethylhexyl-ethylamide) amine (EHBAA). EXAFS and UV-Vis spectra of Ru in HCl solutions revealed that the predominant Ru species in 0.5-10 M HCl solutions changed from [RuCl(HO)] to [RuCl] with the HCl concentration. The extraction percentages of Ru in the EHBAA system increased with increasing HCl concentration, reached 80% at [HCl] = 5 M, and decreased athigher HCl concentrations. EXAFS analysis of the extracted complex indicated that the Ru had 5 Cl and 1 HO in its inner coordination sphere. The similarity of the dependence on HCl concentrations of the extraction in the EHBAA system and the distribution profile of [RuCl(HO)] on [RuCl(HO)] suggested that the EHBAA extracted the pentachlorido species.

Recent research in solvent extraction of platinum group metals

Narita, Hirokazu*; Suzuki, Tomoya*; Motokawa, Ryuhei

Nihon Kinzoku Gakkai-Shi, 81(4), p.157 - 167, 2017/04

https://doi.org/10.2320/jinstmet.JE201604

Small-angle neutron scattering study of specific interaction and coordination structure formed by mono-acetyl-substituted dibenzo-20-crown-6-ether and cesium ions

Motokawa, Ryuhei; Kobayashi, Toru; Endo, Hitoshi*; Ikeda, Takashi; Yaita, Tsuyoshi; Suzuki, Shinichi; Narita, Hirokazu*; Akutsu, Kazuhiro*; Heller, W. T.*

Journal of Nuclear Science and Technology, 53(8), p.1205 - 1211, 2016/08

https://doi.org/10.1080/00223131.2015.1102100

Extraction of Am(III) and Lanthanide(III) ions from HNO solutions using -dimethyl--diphenylpyridine-2,6-dicarboxyamide

Shimada, Asako; Yaita, Tsuyoshi; Narita, Hirokazu; Tachimori, Shoichi; Kimura, Takaumi; Okuno, Kenji*; *

Solvent Extraction Research and Development, Japan, 11, p.1 - 10, 2004/04

The distribution ratio () of Am(III) and lighter Ln(III) in the extraction with -dimethyl--diphenylpyridine-2,6-dicarboxyamide(DMDPhPDA) from HNO solutions were determined. The D's increased with an increase of HNO concentration. Additionally, separation of Am(III) from Ln(III) were confirmed for all the HNO concentration range (S.F.=(D/D)). From 4 M HNO solution with 0.5 M DMDPhPDA CHCl solution, the 's of Am(III), Eu(III) and Nd(III) were 1.3, 0.25 and 0.24, respectively. This result suggests that Am(III) can be separated from Eu and Nd in the higher HNO concentration region than that has been reported so far. These 's value and the S.F. were reproduced in the extraction from the metal concentration range from 10 M order to 10 M.

Local structure of molten LaCl by K-absorption edge XAFS

Okamoto, Yoshihiro; Shiwaku, Hideaki; Yaita, Tsuyoshi; Narita, Hirokazu; Tanida, Hajime*

Journal of Molecular Structure, 641(1), p.71 - 76, 2002/10

https://doi.org/10.1016/S0022-2860(02)00329-0

The local structure of molten LaCl was investigated by X-ray absorption fine structure(XAFS) of the La K-edge. The nearest La-Cl distance andcoordination number were 2.89 and 7.4 from the curve fitting of the 1st peak in the fourier transform magnitude . The coordination number larger than 6 suggests that the local structure of molten LaCl is not a simple octahedral coordination (LaCl), but 7-fold (LaCl) and/or 8-fold (LaCl) complexes. The 1st La-La distance, of which correlation was observed as a weak 2nd peak in the , was evaluated to be 4.9. It suggests that the distorted corner-sharing connection of the complex species is predominant in the melt, inontrast with molten YCl in which the edge-sharing connection of the 6-fold (YCl) mainly exists.

Structural study on lanthanide complexes with tridentate ligands in solution

Narita, Hirokazu; Yaita, Tsuyoshi; Okamoto, Yoshihiro; Takai, Konomi; Shiwaku, Hideaki; Shimada, Asako*; Yamamoto, Takeshi*; Tanida, Hajime*

Spring-8 Experiment Report, Vol.6, P. 9, 2001/00

no abstracts in English