Automatized Separation of Fractions from Petroleum Based on Spectrophotometric Signal Derivative Using Open-Source Hardware for the Determination of Ni and V Linked to Porphyrins

An automated method based on open-source hardware was created for the separation of porphyrins fractions from crude oil, an essential step for the quantification of V and Ni as metalloporphyrins. Preparative liquid chromatography was implemented with a reverse phase gradient from MeOH to toluene. The system allows three solvents and fractions changes by using quaternary valves connected to an Arduino microcontroller, programmed on the basis of the absorbance signal measured and its first derivative. Additionally, the method was applied to crude oils (Venezuelan National Institute of Standards and Technology (NIST) 8505 and from a marine reservoir). V and Ni were determined by inductively coupled plasma mass spectrometry (ICP-MS) and the V-porphyrin profile was determined by high performance liquid chromatography (HPLC)-ICP-MS. The concentrations of the metals grow in the last eluting toluene fractions, associated with asphaltenes. On the other hand, V-porphyrins in the first eluting MeOH fractions showed profiles of labile compounds, with a higher percentage in the Brazilian crude oil (4.9 mg L-1, corresponding to 18% of total V), in comparison to the one from the biodegraded NIST 8505 (59 mg L-1, corresponding to 7% of total V). The overall methodology has a good reproducibility and provides information on elements concentrations associated with porphyrin class compounds.