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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

Gontzal Lezcano
Idoia Hita

Related Publications

Role of the Ru and Support in Sulfided RuNiMo Catalysts in Simultaneous Hydrodearomatization (HDA), Hydrodesulfurization (HDS), and Hydrodenitrogenation (HDN) Reactions

by Pawelec, Navarro, Castaño, Alvarez-Galvan, Fierro
Energy & Fuels Year: 2009

Abstract

Simultaneous hydrodesulfurization (HDS), hydrodearomatization (HDA), and hydrodenitrogenation (HDN) reactions have been studied over sulfided RuNiMo/Al2O3 catalysts. The effects of Ru promotion and alumina support modification with HY zeolite and P on catalyst performance have been studied using a synthetic feed containing dibenzothiophene, toluene, naphthalene, and pyridine. Activity tests were carried out in a semi-automatic microplant equipped with a continuous flow reactor, working under conditions similar to industrial practice (P = 5 MPa, T = 285−360 °C, and liquid hourly space velocity (LHSV) = 3 and 4.5 h−1). The catalysts were characterized by SBET, X-ray diffraction (XRD), temperature-programmed reduction (TPR), temperature-programmed desorption of ammonia (TPD−NH3), and X-ray photoelectron spectroscopy (XPS) techniques. Activity tests revealed that optimal Ru loading is 1 wt % (nominal). Under fixed experimental conditions (300 °C, 5 MPa, and LHSV = 3 h−1), ultra-low sulfur diesel (S < 20 ppm S) was obtained over a Ru(1%)Ni(5%)Mo(14%)/γ-Al2O3 catalyst from a feed containing 18361 ppm S. However, this catalyst showed similar capability toward aromatics and pyridine removal as a commercial NiMo/Al2O3 catalyst. At a reaction temperature of 345 °C, the 5% HY−Al2O3 substrate led to a small increase in the hydrogenation capability of this catalyst but without enhancement of its HDS/HDN capability. On the contrary, the P-modified substrate resulted in a lower activity. The properties of the supported catalysts are discussed in terms of the support effect and Ru promotion.

Keywords

HCE HPC