A fast, simple and reliable method for Hg determination in green coke and oily sludge samples by atomic fluorescence spectrometry is described. Microwave digestion and extraction procedures were evaluated for highly complex samples of coke and oily sludge. The concentrations of SnCl2 and HCl to promote Hg vapor, were optimized, as well as the concentration of KMnO4, to stabilize the Hg2+ before the atomic vapor formation. Accuracy of the method was evaluated through certified reference material, for green coke, and comparison with cold vapor atomic absorption spectrometry (CV AAS), for oily sludge. Recovery tests were also performed. Limits of detection and quantification were 0.8 and 2.6 µg kg−1, respectively. Ten green coke and nine sludge samples were analysed and Hg concentrations in coke are very low, between 0.005 and 0.065 mg kg−1, but oily sludge samples have high concentrations, ranging from 42.5 to 376.6 mg kg−1, requiring careful management.

A determinação de elementos terras raras (REE) em catalisadores gastos provenientes da indústria de petróleo é proposta. Foram testados três procedimentos de tratamento de amostra, um sem adição de HF e outros dois usando diferentes quantidades de HF e ácido bórico, além de uma etapa de evaporação assistida por radiação micro-ondas para dissolução dos fluoretos de REE. O meio contendo 1,0 mL de HF e 8,0 mL de ácido bórico foi eficiente para promover a completa digestão da amostra. Estudos foram realizados usando uma célula de reação para redução de interferências por íons poliatômicos para quatro elementos por espectrometria de massas com plasma acoplado indutivamente (ICP-MS). Material de referência certificado, TDB-1, foi utilizado para avaliar a exatidão do método aplicado a dez amostras de catalisadores. O procedimento proposto é rápido, eficiente e apresentou exatidão e precisão adequadas para 14 dos 16 analitos determinados. Testes de adição e recuperação apresentaram valores entre 87% e 101%.

The determination of rare earth elements (REE) in spent catalyst samples from oil refinery is proposed. Three sample treatment procedures were tested, one without HF and two using different amounts of HF and boric acid. A microwave evaporation step to promote the dissolution of the REE fluorides was carried out. The medium containing 1.0 mL of HF and 8.0 mL of boric acid promoted the complete digestion. Studies were carried out using a reaction cell to overcome polyatomic interferences on four elements by inductively coupled plasma mass spectrometry (ICP-MS). Certified reference material, TDB-1, was used to evaluate the method accuracy applied to ten spent catalysts. The sample treatment is fast and promotes the complete digestion of the samples and the developed procedure led to proper accuracy for 14 of the 16 determined analytes. Recovery tests presented values between 87% and 101%.