Estudo da especiação do cromo no processo de adsorção por carvão ativado usando a espectroscopia de emissão de raios X Kβ

• Ano de defesa: 2011
• Autor(a) principal: Camera, Adriana Simane
• Orientador(a): Quiñones, Fernando Rodolfo Espinoza
• Banca de defesa: Vilar, Vitor Jorge Pais , Palácio, Soraya Moreno
• Tipo de documento: Dissertação
• Tipo de acesso: Acesso aberto
• Idioma: por
• Instituição de defesa: Universidade Estadual do Oeste do Parana
• Programa de Pós-Graduação: Programa de Pós-Graduação Stricto Sensu em Engenharia Química
• Departamento: Desenvolvimento de Processos
• País: BR
• Palavras-chave em Português: Redução de Cr(VI); Remoção de íons metálicos; Fluorescência de raios X; Alta resolução; Carvão ativado - Adsorção; Cromo; Redução (Química)
• Palavras-chave em Inglês: Cr (VI) reduction; Removal of metal ions; X-ray fluorescence; High resolution
• Área do conhecimento CNPq: CNPQ::ENGENHARIAS::ENGENHARIA MECANICA::ENGENHARIA TERMICA::CONTROLE AMBIENTAL
• Link de acesso: http://tede.unioeste.br:8080/tede/handle/tede/1896

This work aims to study the reduction of hexavalent chromium to trivalent form through the adsorption process as assessed by the Kβ X-ray emission spectrometry. As adsorbent material activated carbon samples were used, while the resin Amberlite IR 120 was used as an indicator of the presence of Cr(III) in all solutions containing Cr(VI). Preliminar speciation tests were performed previously in solutions containing Cr(VI) in order to analyze the possible reduction to Cr(III) due to the effect of solution pH. A EDTA-based colorimetric speciation method of Cr(III) was applied. Preliminary kinetic Cr adsorption tests were performed at controlled temperature and agitation, achieving the equilibrium at 24 h for activated carbon. Batch single equilibrium Cr adsorption experiments using activated carbon and cation exchange resin materials as adsorbents and 8 mequiv.L-1 of Cr (III) and Cr(VI) ions as adsorvates were performed at pH 3.5 and under controlled temperature and agitation. Adsorbent and Cr reference material samples were pressed in pellets for spectrometric analysis. By using a high-resolution spectrometer of Johann type and a 6.1 keV monochromatic X-ray beam, Kβ X-ray emission spectra of Cr-treated adsorbent and reference material samples were registered by a Si detector, scanning the scattering X-ray by a spherycal bent analyzer around the Kβ1,3 spectral line of metallic chromium. The sample, spherical bent analyzer and detector system was positioned on the Rowland circle in order to scan in high resolution condition, focus the maximum back-scattered X-ray beam on the main detector and built Kβ X-ray emission spectra. As the incident monochromatic X-ray beam is a time-depending function, X-ray intensity that was registrated by detector was monitored and it was normalized to monitor-detector intensity. By setting measurement time of 2-4 h for Cr-treated adsorbent samples and 10-30 min for Cr reference material ones, a complete full scan of Kβ X-ray emission region was performed with enough statistic to observe the sattelite lines of chromium, which suffer a strong influence due to the oxidation state of metal ion and the chemical environment. The Cr-Kβ emission spectra were plotted on the basis of recorded X-ray intensity (y-axis) and spherical bent analyzer (SBA) position (x-axis), performing both the monitor-to-normalized intensity and the converted-to-energy SBA position. Besides this, scattered X-rays on matrix bulk and chromium absorption edge effect were systematically subtracted from Cr-Kβ emission spectra, applying pseudo-physical procedures and consequentely allowing enhancing the weaker sattellites lines of chromium. Main physical characteristic such as energy and intensity of main (Cr-Kβ1,3) and satellite lines (Cr-Kβ2,5 and Cr-Kβ ) for Cr-Kβ emission spectra of Cr treated-adsorbent samples were extracted by gaussian type peak fits and then compared with those of Cr reference materials, allowing to assign the oxidation state of chromium ions adsorbed on activated carbon surface and removed by an ion exchange process on cationic resin surface. In addition, no Cr(VI) reduction in acidic solutions was observed according to the EDTA-based colorimetric speciation result as well as with no presence of Cr(III)-Kβ spectral line pattern in Cr(VI) treated cationic resin samples. Based on Cr-Kβ spectral line analysis, the activated carbon samples treated with Cr(III) and Cr(VI) ions have shown the same spectral line pattern corresponding to the Cr(III) one. Thus, the reduction of Cr(VI) to Cr(III) has occurred by the adsorption process