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Upgrading renewables, secondary, and waste streams through innovative hydroprocessing catalysts and reaction pathways

Problem statement

Hydroprocessing is a well-implemented and versatile refinery conversion strategy, comprising a wide array of reaction routes such as: (i) hydrotreating, aiming for the hydrogenation of unsaturated hydrocarbons and the removal (hydrogenolysis) of heteroatoms such as sulfur or nitrogen; (ii) hydrocracking, for promoting C–C bond scission and the partial saturation of aromatics; or (iii) hydrodeoxygenation, for the specific removal of oxygen moieties. In this project, we investigate the conversion of highly polyaromatic feedstock like heavy fuel oil (HFO), pyrolysis fuel oil (PFO), or bio-oils from different biomass sources (i.e., agricultural waste, algae) for quality improvement and obtaining products with higher added value.

We seek new (thermo-) catalytic strategies and improved heterogeneous catalysts with increased activity and stability. We put advanced analytical characterization techniques (i.e., nuclear magnetic resonance, high-res mass spectrometry) to work and combine their results with modeling and statistical tools.

Goals

  • Develop a quantitative analytical workflow to analyze and interpret these complex reacting environments
  • Explore novel renewable and waste resources to obtain chemicals and fuels
  • Deploy ad-hoc catalysts and process conditions to incorporate these wastes in the refinery (bio- and waste-refinery)
  • Analyze process dynamics and kinetics
HPC

Related People

Related Publications

Kinetic Modeling of the Hydrotreating and Hydrocracking Stages for Upgrading Scrap Tires Pyrolysis Oil (STPO) towards High Quality Fuels

by Hita, Aguayo, Olazar, Azkoiti, Bilbao, Arandes, Castaño
Energy & Fuels Year: 2015

Abstract

The upgrading of scrap tires pyrolysis oil (STPO) has been studied in order to produce high-quality alternative fuels, conceived as the second and third stage of an industrially orientated valorization pathway for tires: pyrolysis, hydrotreating, and hydrocracking. The experiments have been carried out in a fixed-bed reactor under the following experimental conditions: (i) for hydrotreating: NiMo/Al2O3 catalyst; time on stream (TOS), 0–8 h; 300–375 °C; 65 bar; H2:oil ratio, 1000 (v/v); space time, 0–0.5 gcat h gfeed–1; and (ii) for hydrocracking: PtPd/SiO2–Al2O3 catalyst; TOS, 0–6 h; 440–500 °C; 65 bar; space time, 0–0.28 gcat h gfeed–1; H2:oil ratio, 1000 (v/v). From the results, lump-based kinetic models have been established for both stages, considering the reactions of (i) hydrodesulfurization (HDS), (ii) hydrocracking (HC), and (iii) hydrodearomatization (HDA) in each one of them. Catalyst deactivation is insignificant in the hydrotreating stage but important for the hydrocracking stage. Therefore, deactivation has been considered in the corresponding kinetic equations. The computed deactivation constants have allowed for quantifying the contribution of each lump/composition fraction to coke formation.

Keywords

HPC MKM W2C