BUNSEKI KAGAKU
Print ISSN : 0525-1931
Volume 66 , Issue 11
Showing 1-10 articles out of 10 articles from the selected issue
Accounts
  • Kyoichi SAITO, Shiho ASAI
    Type: Accounts
    2017 Volume 66 Issue 11 Pages 771-782
    Published: November 05, 2017
    Released: December 05, 2017
    JOURNALS FREE ACCESS
    Polymeric adsorbents capable of capturing and purifying rare metal ions were prepared using radiation-induced graft polymerization. Polymeric chain was appended onto porous polyethylene membrane or sheet, and nylon-6 fiber, followed by the introduction of chelate-forming groups and the impregnation of extractants. First, adenine, one of four nucleic acids, was immobilized to the polymer chains grafted onto porous polyethylene hollow-fiber membrane or 6-nylon fiber to specifically bind palladium or ruthenium ionic species. The density of adenine immobilized was 0.85 mmol g−1, which was comparable to the ion-exchange group density of conventional ion-exchange beads. HDEHP, bis(2-ethylhexyl) phosphate, representative of acidic extractants was impregnated onto the polymer chains grafted onto porous polyethylene sheet or 6-nylon fiber. During the permeation of yttrium solution through the HDEHP-impregnated porous sheet with a density of HDEHP impregnated of 3.4 mmol g−1, the amount of yttrium ions adsorbed was constant irrespective of flow rate because of negligible diffusional mass-transfer resistance in the pores. Neodymium and dysprosium ions loaded onto the HDEHP-impregnated fiber-packed bed were purified by elution chromatography at a high loading and a high flow rate, compared with HDEHP-impregnated bead-packed bed. Neodymium and dysprosium ions loaded onto the HDEHP-impregnated fiber-packed bed were purified by elution chromatography at high loading and high flow rate, compared with HDEHP-impregnated bead-packed bed. Third, hybrid fibers coexisting of dodecane-thiol group with dioctyl sulfide specifically collected palladium ions in concentrated HCl medium.
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  • Yuiko TASAKI-HANDA, Kenta OOI, Hirokazu NARITA, Mikiya TANAKA, Akihiro ...
    Type: Accounts
    2017 Volume 66 Issue 11 Pages 783-796
    Published: November 05, 2017
    Released: December 05, 2017
    JOURNALS FREE ACCESS
    Ion-exchange and fractional precipitation using phosphorster coordination polymers have been studied to develop an environmental friendly lanthanide separation method, where only water is used as a solvent. In an ion-exchange system, high selectivity has been found in the lanthanide series. In addition, the selectivity changes depending on the ion exchange rate, which is likely to be caused by the contributions of both "electrostatic interaction between metal ions and phosphorester ligands" and "size matching of the ingoing ion to the framework of the coordination polymer". Such a mechanism may be feasible because the framework is formed by a lanthanide-selective phophoester and it is moderately rigid, which is not observed either in solvent extraction and conventional ion exchange systems. Furthermore, fabrication of phosphorester coordination polymers has been demonstrated: grain powders of phosphorester coordination polymer can be transformed to a monolithic structure through organogel formation and lypholization. As a consequence, the distribution coefficients and kinetic constant of ion exchange have been improved. Finally, successful fractional precipitation of Nd3+ and Dy3+ in an aqueous solution has been demonstrated.
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  • Hirochika NAGANAWA
    Type: Accounts
    2017 Volume 66 Issue 11 Pages 797-808
    Published: November 05, 2017
    Released: December 05, 2017
    JOURNALS FREE ACCESS
    A new liquid-liquid extraction method, called the "emulsion-flow" method, has recently been developed at Japan Atomic Energy Agency (JAEA). The emulsion-flow method, where low cost, simplicity, high efficiency, compactness, safety, and eco-friendly go together, has attracted attention, and has been expected to bring innovation to liquid-liquid extraction technologies. An apparatus based on the emulsion-flow method can actualize very efficient liquid-liquid extraction with its high two-phase mixing ability to an emulsion by spraying micrometer-sized oil droplets into a counter-current aqueous solution by only solution sending. Meanwhile, at the same time, the emulsion produced in the apparatus disappears rapidly and perfectly by drastically changing the cross-section where liquid droplets pass through in its vessel structure. Such a rapid and perfect phase separation can realize a high processing speed with a small-sized apparatus. Compared with conventional industrial apparatuses, an emulsion-flow apparatus successfully combines the lowest cost superior to a spray column and the highest performance (the highest efficiency and the highest processing speed) comparable to a centrifugal extractor. Furthermore, the emulsion-flow method can also be used for collecting particulate components by utilizing their aggregation onto a liquid-liquid interface and for purifying water polluted by oil with its remarkable phase-separating ability.
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Research Papers
  • Nobuo UEHARA, Hiroaki TAIRAKO, Toyoji YAMAGUCHI, Kazutoshi HANADA, Kyo ...
    Type: Research Papers
    2017 Volume 66 Issue 11 Pages 809-815
    Published: November 05, 2017
    Released: December 05, 2017
    JOURNALS FREE ACCESS
    Fabrication of novel adsorbents which adsorbed cesium(I) were investigated based on modification of steel-making slags. Treatment of the steel-making slags with a sodium hydroxide solution containing sodium metasilicate developed adsorption ability of cesium(I) to the slags. Effects of treatment conditions such as concentrations of sodium metasilicate and sodium hydroxide on the adsorption abilities of the resulting adsorbents were investigated. Characterization of the adsorbents was also performed with XRD, XRF and SEM observation. Adsorption of cesium(I) was caused by deposited layers resulting from reaction of metasilicate with the slags.
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  • Shigeo UMETANI, Yukari SASAKI, Yoshiki SOHRIN, Hiroshi MUKAI, Shoko YA ...
    Type: Research Papers
    2017 Volume 66 Issue 11 Pages 817-824
    Published: November 05, 2017
    Released: December 05, 2017
    JOURNALS FREE ACCESS
    The solvent extraction of Group-13 metals (Al, Ga and In) and Zn with trifluorocycloalkanones and some β-Diketones has been examined. The distances between the donating oxygen atoms (bite size) in the ligand were calculated based on the density functional theory. It was found that the solvent extraction of group-13 metals was under a significant influence of the bite size and inter-ligand contact. Indium was not extracted with trifluoroacetylcyclohexanone, trifluoroacetylcycloheptanone, phenylacetylacetone and phenylbenzoylacetone, which have a small bite size owing to the 6 and 7-membered ring structure and the α-phenyl group. The effect of the inter-ligand contact was seen in the extraction of Al. Zn was extracted with trifluorocycloalkanones in a far higher pH region than group-13 metals, and it is very easy to separate group-13 metals from Zn.
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  • Haruyuki KOMINAMI, Yoshinari SUZUKI
    Type: Research Papers
    2017 Volume 66 Issue 11 Pages 825-837
    Published: November 05, 2017
    Released: December 05, 2017
    JOURNALS FREE ACCESS
    Comprehensive analyses of 67 elements including noble metal elements (NME: Ru, Rh, Pd, Os, Ir, Pt, Au) were performed by using tandem quadrupole inductively coupled plasma mass spectrometry (ICP-MS/MS). Any spectral interference on NME from a coexisting matrix could be removed under the optimized condition of usage NH3 gas as a collision/reaction gas. The validation of the analytical procedure was confirmed by analyzing a river water reference material (SLRS-5) and showed good agreements with the certified value, reported value, and estimated value including NME. The quantitative analysis of ng L−1 or less level could be performed without any separation/purification procedures by using ICP-MS/MS. The optimized analysis conditions were applied to the spring and river water in the eastern part of Shimane prefecture, and comprehensive analyses of 67 elements were performed. The results of statistical element classification by cluster analysis did not completely reflect the chemical properties. For example, Rh was classified into clusters containing Na, Mg, and so on. Next, from the geochemical point of view, the abundance of 67 elements was chemically classified by comparing to concentration in tap water. It could classify river samples into four basic patterns and combinations thereof; the geographical distribution of the element pattern shows good agreement with the geological distribution. On the other hand, the geographical distribution of Rh, which was difficult to be explained from the geochemical properties, shows a good agreement with the geographical distribution of the road density, suggesting a link with the catalytic converter to purify exhaust gas.
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  • Masaaki TABATA, Shinya UEDA
    Type: Research Papers
    2017 Volume 66 Issue 11 Pages 839-846
    Published: November 05, 2017
    Released: December 05, 2017
    JOURNALS FREE ACCESS
    Mietsu Naval Facility Site in Saga was approved as a World Heritage by UNESCO in July, 2015, because it is the first dry-dock constructed with a wooden frame in Japan. The dock location was used during 1858-1871. From the facility site many porcelain objects have been excavated. We analyzed rare metals of Rb, Sr, Y, Zr and Nb involved in the body clay of the porcelains of the Mietsu Naval Facility Site and ones found at old porcelain production areas, Toshikitani (Arita), Hirosemukai (Arita), Shida Higashiyama (Shiota, Ureshio) and Hasami, in Hizen at the end of the Edo period by synchrotron X-ray fluorescence analysis. Their fluorescence intensities were compared with each other. We focused on the difference in the solubility of Rb(I), Zr(IV) and Nb(V) compounds in water to estimate the production area of the porcelains of the Mietsu Naval Facility Site, because Rb(I) is very soluble in water, and is removed during the clay mud production process using water; however, Zr(IV) and Nb(V) are hardly soluble in water, and remain in the clay. A plot of the Intensity ratio (Rb/Nb) vs. Intensity ratio (Zr/Nb) gave three different groups, which are a group of Toshikitani and Hirosemukai, a group of Shida Higashiyama and a group of Hasami. The plot for small bowls found at the Mietsu Naval Facility Site was also separated into three groups. That is, bowls on which the letters of "YAKU", "UMI" and "OFUNAKA" were separated in the plot. Interestingly, the plot of the Hasami group was scattered compared to other groups, and depended on the production kiln in Hasami. Other plots of the Intensity ratio (Fe/Rb) vs. Intensity ratio (Sr/Rb) and log{Intensity ratio (Rb/Sr)} vs. log{Intensity ratio (Zr/Sr)} also depended on the production area of the porcelains. From the difference in the group we proposed the production area of the three types of bowls of Mietsu Naval Facility Site.
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Technical Papers
  • Naoya MATSUURA, Kanako IMAI, Tadashi YAMADA, Yutaka HAYASHIBE, Shinich ...
    Type: Technical Papers
    2017 Volume 66 Issue 11 Pages 847-852
    Published: November 05, 2017
    Released: December 05, 2017
    JOURNALS FREE ACCESS
    We have developed an automatic As analyzer (Flow Injection Analyzer (FIA)) in the smelting process drainage. An As molybdate complex was formed by reacting As and ammonium molybdate in the equipment route, and by using an UV–VIS Detector, an analytical system selective to As was constructed. An extensive smelting process In order to be compatible with the As concentration range in drainage, incorporates two kinds with different sampling amounts in the sampling valve. It also incorporates two liquid cells with different optical path lengths in a subsequent UV–VIS Detector. Quantitative measurements have been made possible even for a smelting process drainage with an As concentration of up to 3000 times different. A 10 mg L−1 standard solution was measured without maintenance for 1 month; the relative standard deviation (% RSD) of all measurements was 1.1 %, and the long-term stability of the developed device was confirmed. When applied to the smelting process drainage at our smelting site, it was confirmed that the drainage concentration of As could be measured in the range of 0.01 to 30 mg L−1. This equipment is already in operation at the actual smelting site, it is possible to operate with low running cost and long-term maintenance free.
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Notes
  • Rina HAYAKAWA, Shoko NARUKE, Kunio FUJIWARA, Takanobu SUGO, Takashi KO ...
    Type: Notes
    2017 Volume 66 Issue 11 Pages 853-856
    Published: November 05, 2017
    Released: December 05, 2017
    JOURNALS FREE ACCESS
    Hydrous cerium oxide was impregnated onto a sufonic-acid-group-containing fiber (SS fiber) prepared by radiation-induced graft polymerization and subsequent chemical modifications. Cerium ions (Ce3+) were adsorbed onto SS fiber before the formation of hydrous cerium oxide (H-CeO) via precipitation by a reaction with a sodium hydroxide (NaOH) solution at various NaOH concentrations in the range from 0.001 to 0.1 mol L−1. The maximum percentage impregnation of H-CeO was 12 %. In the batch mode, neither SS fiber nor anion-exchange fiber removed any antimony ions, whereas H-CeO fiber captured antimony ions at a high rate.
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Analytical Reports
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