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Synthesis and characterisation of aurothiosulfate-selective magnetic ion exchange resins

机译:硫代硫酸盐选择性磁性离子交换树脂的合成与表征

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摘要

A series of novel ion-exchange resins was prepared based upon the commercial Magnetic Ion Exchange (MIEXTm) substrate produced by Orica Watercare for the selective adsorption and removal of aurothiosulfate from ammoniacal thiosulfate leach liquors. Gold adsorption by these resins was ascertained using bottle-roll tests both from water and from a synthetic thiosulfate leach solution. Elution of aurothiosulfate from these resins was examined using a variety of eluents and used to narrow the set of prospective resins.udA common synthetic method was utilised, based upon amination using primary, secondary and tertiary amines of the terminal epoxide group present on the MIEXTM substrate using an aqueous solvent. The weak-base resins formed were then dried and solvated in dimethylformamide, followed by alkylation employing a variety of alkyl halides to form quaternary ammonium moieties. Several structurally-related derivatives of imidazole, piperidine, piperazine and diethylamine were prepared with ion-exchange capacities ranging between 0.5 and 1.5mmol/g, dependent on the steric nature of the amine.udThe strong-base functionalised resins formed by initial amination and alkylation of weak-base groups were then characterised by ion-exchange capacity determination, elemental analysis and attenuated-total-reflectance infrared spectroscopy with results from each of the techniques being comparable. The resin substrate was also characterised using BETudsurface area analysis and scanning electron microscopy, with surface areas ranging between 40-47m2/g.udThe performance of the resins was compared using a synthetic thiosulfate leach solution (pH-10.5) containing gold (20ppm), copper (200ppm), ammonia (1.3M) and thiosulfate (0.1M), with resin gold loadings of aurothiosulfate ranging between 14 and 124g/kg.udElution studies were performed using acidic thiourea, basic thiocyanate and concentrated nitrate solutions, with all resins showing efficient elution of aurothiosulfate utilising one or more of the elution regimes, with typical efficiencies in the range of 30 to 75% elution.udThe performance of a subset of resins was assessed by the sequential addition of small amounts of trithionate to assess the selective nature of the resins against a significant competitor ion. The best performing resins retained over 75% of the previously adsorbed aurothiosulfate when exposed to 10mM trithionate. Resins were also assessed for their permanent binding of the aurothiosulfate complex by repeated uptake/elution/regeneration studies utilising basic thiocyanate elution, followed by regeneration with ferric nitrate. The optimal resins tested eluted 63-78% aurothiosulfate over 5 cycles. Resins completing this testing were then destructively analysed for aurothiosulfate retained between elution cycles, with optimum resins retaining less than lmg Au over 5 cycles.udThe following alkylamine functionalised ion-exchange resins were determined to be viable industrial candidates, including N-methyl-piperidine, N,N-dimethyl-piperazine, methyl-diethylamine and piperidine-ethanol-based resins. Of these, N-methyl-piperidine showed the most selective uptake of aurothiosulfate from leach solution, coupled with the most efficient elution using the regime tested and is the most likely candidate for further study.
机译:基于Orica Watercare生产的商品化磁性离子交换(MIEXTm)底物,制备了一系列新型离子交换树脂,用于选择性吸附和去除氨硫代硫酸盐浸出液中的硫代硫代硫酸盐。这些树脂在水和合成硫代硫酸盐浸出液中的瓶辊测试确定了金的吸附。使用多种洗脱液检查了从这些树脂中洗脱出的硫代硫代硫酸盐,并用于缩小潜在树脂的范围。底物使用水性溶剂。然后将形成的弱碱树脂干燥并在二甲基甲酰胺中溶剂化,然后使用各种烷基卤化物进行烷基化以形成季铵部分。制备了几种咪唑,哌啶,哌嗪和二乙胺的结构相关衍生物,其离子交换容量在0.5至1.5mmol / g之间,具体取决于胺的空间性质。然后通过离子交换容量测定,元素分析和衰减全反射红外光谱对弱碱基团的烷基化进行表征,每种技术的结果均具有可比性。还使用BET ud表面积分析和扫描电子显微镜对树脂基材进行了表征,表面积在40-47m2 / g之间。 ud使用合成的含金的硫代硫酸盐浸出溶液(pH-10.5)比较了树脂的性能20ppm),铜(200ppm),氨(1.3M)和硫代硫酸盐(0.1M),金硫代硫酸盐的树脂载金量为14至124g / kg。 ud使用酸性硫脲,碱性硫氰酸盐和浓硝酸盐溶液进行了洗脱研究,通过使用一种或多种洗脱方案,所有树脂均显示出对硫代硫代硫酸盐的有效洗脱,典型效率在30%到75%的洗脱范围内。 ud通过依次添加少量三硫代硫酸盐来评估部分树脂的性能。评估树脂对明显竞争者的选择性。当暴露于10mM三硫代硫酸盐时,性能最好的树脂保留了先前吸附的硫代硫代硫酸盐的75%以上。还通过使用碱性硫氰酸盐洗脱进行反复摄取/洗脱/再生研究,然后用硝酸铁进行再生,评估了树脂与硫代硫酸盐络合物的永久结合。在5个循环中,测试的最佳树脂洗脱出63-78%的硫代硫代硫酸盐。然后对完成此测试的树脂进行破坏性分析,以分析洗脱循环之间保留的金硫代硫酸盐,最佳树脂在5个循环中保留的金含量低于1mg。 ud以下烷基胺官能化的离子交换树脂被确定为可行的工业候选物,包括N-甲基-哌啶,N,N-二甲基-哌嗪,甲基二乙胺和哌啶-乙醇基树脂。其中,N-甲基-哌啶显示出从浸出溶液中选择最多的硫代硫酸盐,并使用测试的方案进行了最有效的洗脱,是最有可能进行进一步研究的对象。

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    Marshall Elijah Michael;

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  • 年度 2010
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