化学的抽出法による金属分離に基づいた廃棄物の再利用技術の開発

13301甲第4418号博士(工学)金沢大学博士論文本文Full 以下に掲載：Chemical Engineering Journal 277 pp.219-228 2015. Elsevier. 共著者：Hikaru Sawai, Ismail M. M. Rahman, Yoshinori Tsukagoshi, Tomoya Wakabayashi, Teruya Maki, Satoshi Mizutani, Hiroshi Hasegaw

Structural effects of phosphate groups on apatite formation in a copolymer modified with Ca2+ in a simulated body fluid

Organic–inorganic composites are novel bone substitutes that can ameliorate the mismatch of Young\u27s moduli between natural bone and implanted ceramics. Phosphate groups contribute to the formation of apatite in a simulated body fluid (SBF) and the adhesion of osteoblast-like cells. Therefore, modification of a polymer with these functional groups is expected to enhance the ability of the organic–inorganic composite to bond with bone. Two phosphate groups have been used, phosphonic acid (–C–PO3H2) and phosphoric acid (–O–PO3H2). However, the effects of structural differences between these phosphate groups have not been clarified. In this study, the apatite formation of copolymers modified with Ca2+ and either –C–PO3H2 or –O–PO3H2 was examined. The mechanism of apatite formation is discussed based on analytical and computational approaches. The copolymers containing –O–PO3H2, but not those containing –C–PO3H2, formed apatite in the SBF, although both released similar amounts of Ca2+ into the SBF. Adsorption of HPO42− from –O–PO3H2 in the SBF following Ca2+ adsorption was confirmed by zeta-potential measurement and X-ray photoelectron spectroscopy. The measurement of the complex formation constant revealed that the –O–PO32−⋯Ca2+ complex was thermodynamically unstable enough to convert into CaHPO4, which was not the case with –C–PO32−⋯Ca2+. The formation of CaHPO4-based clusters was found to be a key factor for apatite nucleation. In conclusion, this study revealed that modification with –O–PO3H2 was more effective for enhancing apatite formation compared with –C–PO3H2

Chemical-induced washing remediation of metal-contaminated soils (Book Chapter)

The immobilization or removal of toxic components using aqueous extractants, with or without additives, is one of the commonly practiced techniques for the treatment of metal-contaminated soils. However, rather than the use of water alone, the solution with chemical-additives is preferred due to the less time requirement and better separation effectiveness. There is a long-favored list of additives that have been used for the chemical-induced washing remediation of soils, which include acids, bases, chelants, surfactants, and so forth. The objective of this chapter is to provide a brief overview of the chemical-assisted soil washing approaches. © Springer Japan 2016. All rights are reserved.[Book Chapter

Decontamination of spent iron-oxide coated sand from filters used in arsenic removal

Sand filters devised with iron-rich adsorbents are extensively promoted and deployed in the arsenic-prone south and south-east Asian countries (e.g., Bangladesh). The approach offers superior performance in removing arsenic while the spent sludge from the sand filters is an issue of concern due to the possibility of toxic releases after being discarded. In this work, a new technique is proposed for the treatment of spent iron-oxide coated sand (IOCS) from filters used in arsenic removal. Chelant-washing of the arsenic-loaded IOCS is combined with the solid phase extraction treatment to accomplish the objective. The unique point of the proposed process is the cost-effective scheme, which includes the option of recycling of the washing solvent beside the decontamination of the spent arsenic-rich sludge. © 2013 Elsevier Ltd

Stability constants of Fe(III) and Cr(III) complexes with dl-2-(2-carboxymethyl)nitrilotriacetic acid (GLDA) and 3-hydroxy-2,2\u27- iminodisuccinic acid (HIDS) in aqueous solution

The complex formation equilibria of Cr3+ and Fe3+ ions in aqueous solution with two biodegradable aminopolycarboxylate chelants (dl-2-(2-carboxymethyl)nitrilotriacetic acid (GLDA) and 3-hydroxy-2,2\u27- iminodisuccinic acid (HIDS)) were investigated. The potentiometric data obtained at the constant ionic strengths (I) of (0.1 and 1.0) mol·dm-3 KCl and at (25 ± 0.1) °C was processed with the aid of the computer program HYPERQUAD 2008. The formation constants of the proton-chelant and metal-chelant (log KML) species (M = Fe3+ or Cr 3+; L = GLDA or HIDS) were determined, and the concentration distributions of complex species in solution were evaluated for both metal ions. In various pH conditions, the interaction between the chelants (L = GLDA or HIDS) and the metal ions (M = Fe3+ or Cr3+) leads to the formation of different complexes formulated as MH2L+, MHL, ML-, M(OH)L2-, and M(OH)2L3-. The log KML values at I = 0.1 mol·dm-3 KCl (T = (25 ± 0.1) °C) were 15.27 (log KFe-GLDA), 14.96 (log K Fe-HIDS), 13.77 (log KCr-GLDA), 12.67 (log K Cr-HIDS), and at I = 1.0 mol·dm-3 KCl (T = (25 ± 0.1) °C) were 14.79 (log KFe-GLDA), 14.34 (log K Fe-HIDS), 12.90 (log KCr-GLDA), 12.09 (log K Cr-HIDS). The conditional stability constants (log K\u27ML) of the ML complexes were calculated in terms of pH in the range of 2 to 12 and compared with the same for EDTA and other biodegradable chelants (NTA and EDDS). © 2012 American Chemical Society

Effect of Extraction Variables on the Biodegradable Chelant-Assisted Removal of Toxic Metals from Artificially Contaminated European Reference Soils

Development of aminopolycarboxylate chelants (APCs) having enhanced biodegradability is gaining increasing focus to replace the EDTA and its homologs with those used widely for the ex situ treatment of contaminated soils and are potential eco-threats. The paper reports the chelant-assisted extraction of the toxic metals (Cd, Cu, Pb, and Zn) from the metal-spiked European reference soils (Eurosoil 1 and Eurosoil 4) using biodegradable APCs, namely EDDS, GLDA, and HIDS. The effects of chelant-to-metal molar ratio, solution pH, and metal/chelant stability constants were evaluated, and compared with that of EDTA. The selectivity aptitude of the biodegradable chelants towards the toxic metals was assumed from the speciation calculations, and a proportionate correlation was observed at neutral pH. Pre- and post-extractive solid phase distributions of the target metals were defined using the sequential extraction procedure and dissolution of metals from the theoretically immobilized fraction was witnessed. The effect of competing species (Al, Ca, Fe, Mg, and Mn) concentrations was proven to be minimized with an excess of chelant in solution. The highlight of the outcomes is the superior decontamination ability of GLDA, a biodegradable APC, at minimum chelant concentration in solution and applicability at a wide range of pH environments. © 2012 Springer Science+Business Media Dordrecht

Remediation of toxic metal contaminated soil by washing with biodegradable aminopolycarboxylate chelants

Ex situ soil washing with synthetic extractants such as, aminopolycarboxylate chelants (APCs) is a viable treatment alternative for metal-contaminated site remediation. EDTA and its homologs are widely used among the APCs in the ex situ soil washing processes. These APCs are merely biodegradable and highly persistent in the aquatic environments leading to the post-use toxic effects. Therefore, an increasing interest is focused on the development and use of the eco-friendly APCs having better biodegradability and less environmental toxicity. The paper deals with the results from the lab-scale washing treatments of a real sample of metal-contaminated soil for the removal of the ecotoxic metal ions (Cd, Cu, Ni, Pb, and Zn) using five biodegradable APCs, namely [S,S]-ethylenediaminedisuccinic acid, imminodisuccinic acid, methylglycinediacetic acid, DL-2-(2-carboxymethyl) nitrilotriacetic acid (GLDA), and 3-hydroxy-2,2\u27-iminodisuccinic acid. The performance of those biodegradable APCs was evaluated for their interaction with the soil mineral constituents in terms of the solution pH and metal-chelant stability constants, and compared with that of EDTA. Speciation calculations were performed to identify the optimal conditions for the washing process in terms of the metal-chelant interactions as well as to understand the selectivity in the separation ability of the biodegradable chelants towards the metal ions. A linear relationship between the metal extraction capacity of the individual chelants towards each of the metal ions from the soil matrix and metal-chelant conditional stability constants for a solution pH greater than 6 was observed. Additional considerations were derived from the behavior of the major potentially interfering cations (Al, Ca, Fe, Mg, and Mn), and it was hypothesized that use of an excess of chelant may minimize the possible competition effects during the single-step washing treatments. Sequential extraction procedure was used to determine the metal distribution in the soil before and after the extractive decontamination using biodegradable APCs, and the capability of the APCs in removing the metal ions even from the theoretically immobilized fraction of the contaminated soil was observed. GLDA appeared to possess the greatest potential to decontaminate the soil through ex situ washing treatment compared to the other biodegradable chelants used in the study. © 2012 Elsevier Ltd

Selective recovery of indium from lead-smelting dust

Non-ferrous smelting dust, especially lead-smelting dust (LSD), contains percent levels of indium and thus constitutes a novel indium resource. The main difficulty in recovering indium from LSD is the coexisting presence of lead and zinc. In this study, a unique indium separation process was designed, combining techniques that involve washing with a chelant, leaching with acid and precipitation as hydroxide. The majority of the Pb in the LSD was selectively separated during chelant-assisted washing with ethylenediaminedisuccinate (EDDS), while the residual Pb was diminished through an acid leaching treatment with a mixed solution of sulfuric acid and hydrochloric acid. The chelant washing step also ensures a decrease in the raw LSD weight at a ratio of approximately 82% due to the removal of lead and counterions such as sulfate, and the washing step also minimizes the consumption of corrosive acids in the subsequent step. Selective indium separation from LSD is further complicated by the similarity of the behavior of zinc during the acid leaching step. Therefore, hydroxide precipitation at pH 5 has been introduced as the final step, ensuring the maintenance of zinc as a soluble species in the supernatant and the selective separation of indium (~88%) as a hydroxide precipitate. © 2015 Elsevier B.V.Embargo Period 48mouth

Selective recovery of indium from the etching waste solution of the flat-panel display fabrication process

The waste byproducts from the indium-consuming fabrication processes are considered as the viable resource for indium due to the unique preference to the element in designing optoelectronic devices. The present work introduces a new technique for the selective recovery of indium from the etching waste, which produced during the patterning of indium tin oxide (ITO) layer on the flat-panel displays. The process includes the application of a solid phase extraction (SPE) assembly, known as molecular recognition technology (MRT) gel, consisting of a metal-selective ligand immobilized to silica gel or polymer substrates. The samples were the real solution of etching waste from the liquid-crystal display fabrication process, and the simulated waste solution prepared using the commercially available etching solution composition containing ethanedioic acid. The retention and the corresponding indium recovery rate (%) were the key characteristics for the appraisal of MRT-SPE types: AnaLig TE 02 (TE 02), AnaLig TE 03, AnaLig TE 07, AnaLig TE 13 and AnaLig PM 02. The other conclusive factors were the influence of ion intensity in solution and the interfering effects from tin, the co-content element in the ITO-formulation. The TE 02 MRT-SPE came across all the requisite aspects for the selective recovery of indium from the etching effluent. The indium retention or recovery with TE 02 MRT-SPE from the real etching waste solution was in the range of 97 to 99% with the relative standard deviation of <4.4%. The separation of the ITO co-element tin from the waste mixture was successively selective, and thereby minimizes the possibility of interference. A three-step elution with 0.3molL-1 HNO3, 6molL-1 HCl and 1molL-1 HCl/10mmolL-1 EDTA was required to accomplish the sequential selectivity in the process. The indium retention capacity of the TE 02 MRT-SPE was 0.147mmolg-1. © 2013 Elsevier B.V

Chelant-induced reclamation of indium from the spent liquid crystal display panels with the aid of microwave irradiation

Indium is a rare metal that is mostly consumed as indium tin oxide (ITO) in the fabrication process of liquid crystal display (LCD) panels. The spent LCD panels, termed as LCD-waste hereafter, is an increasing contributor of electronic waste burden worldwide and can be an impending secondary source of indium. The present work reports a new technique for the reclamation of indium from the unground LCD-waste using aminopolycarboxylate chelants (APCs) as the solvent in a hyperbaric environment and at a high-temperature. Microwave irradiation was used to create the desired system conditions, and a substantial abstraction of indium (≥80%) from the LCD-waste with the APCs (EDTA or NTA) was attained in the acidic pH region (up to pH 5) at the temperature of ≥120. °C and the pressure of ~50. bar. The unique point of the reported process is the almost quantitative recovery of indium from the LCD-waste that ensured via the combination of the reaction facilitatory effect of microwave exposure and the metal extraction capability of APCs. A method for the selective isolation of indium from the extractant solution and recycle of the chelant in solution is also described. © 2013 Elsevier B.V