4.7 Article

Non-catalytic vanadium removal from vanadyl etioporphyrin (VO-EP) using a mixed solvent of supercritical water and toluene: A kinetic study

Journal

FUEL
Volume 92, Issue 1, Pages 288-294

Publisher

ELSEVIER SCI LTD
DOI: 10.1016/j.fuel.2011.07.002

Keywords

Vanadyl etioporphyrin; Batch reactor; Demetallation; Reaction kinetics; Arrhenius parameters

Funding

  1. Global COE program on Global Initiative Center for Pulsed Power Engineering
  2. Japan Petroleum Energy Center (JPEC)
  3. Ministry of Economy, Trade and Industry, Japan

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Reaction kinetics and mechanisms of the decomposition of vanadyl etioporphyrin (VO-EP), the most common metal compounds present in heavy crude, were studied in a mixed solvent of supercritical water (SCW) and toluene without the addition of any catalyst, H-2 or H2S to remove vanadium. The aim of this study was to remove vanadium an environmentally benign way from VO-EP at a high extent and in a short reaction time. The experiments were conducted in an 8.8 mL batch reactor fabricated from Hastelloy C-276. The capability of SCW to remove vanadium from VO-EP was discovered at temperatures of 410-490 degrees C and a water partial pressure (WPP) of 25 MPa. Experimental results revealed that the overall VO-EP conversion was 90.51% at a temperature of 490 degrees C, WPP of 25 MPa and reaction time of 180 min. Under the same reaction conditions, approximately 80.26% vanadium was removed by reaction with SCW. The global reaction followed first order kinetics, with Arrhenius parameters of activation energy 8.93 kcal/mol and a pre-exponential factor 5.66 s (1). A kinetic model of demetallation that well-fit the experimental results, was proposed. The reaction kinetics may be critically explained in terms of free radical mechanism. The obtained results suggest that SCW is capable of removing vanadium from VO-EP. (C) 2011 Elsevier Ltd. All rights reserved.

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