Devising Strategies to Evaluate Ni/Zeolite Beta Catalysts for Upgrading Palm Oil and Acetone to Biofuel and Hydrogen

  • Sara Alkhoori

Student thesis: Doctoral Thesis

Abstract

This PhD dissertation is focused on the design and optimization of catalysts for upgrading of bio-oil and its derivatives to renewable fuels adopting two different pathways: deoxygenation and steam reforming. By utilizing zeolite Beta-supported Ni catalysts throughout this work, the main objective is to alter various functional sites including active metallic sites and acid/base sites by integrating different promoters and changing the Si/Al ratios of the zeolite support to selectively manipulate mechanistic pathways and product distribution. In the first contribution, the role of alkaline-earth metal promoters (Mg2+, Ca2+, Sr2+, Ba2+) on monometallic zeolite Beta-supported Ni catalysts are studied for the deoxygenation of palm oil to produce biofuels. The goal is to understand how periodicity of elements re-balances different functional sites and hence bridge it to the catalytic performance. Given the complex nature of palm oil, oleic acid which is one of the most abundant compounds in palm oil is considered for the second contribution of this PhD. In particular, the role of transition metals promoters (Mn, Fe, Co, Cu) on zeolite Beta-supported Ni to form bimetallic catalysts is studied for the deoxygenation of oleic acid. The goal is to explore the effect of bimetallic character and acid sites nature on the production of diesel-range hydrocarbons. The third contribution of this PhD gives deeper insights into the role of acidity in zeolite Beta-supported Ni catalysts on Acetone steam reforming reaction. In this study, the acidic character of the catalysts is tailored based on two routes: (i) synthesis of zeolite Beta support with different Si/Al ratios (i.e., 14, 29, 44), and (ii) incorporation of La2O3 as a basic promoter. While the acidity is critical for understanding deactivation behaviors, post-reaction investigations are carried out to further elaborate on the catalyst’s stability and coke formation. In each contribution, different analytical techniques are used to evaluate the material properties including X-Ray Diffraction (XRD), High-Resolution Transmission Electron Microscopy (HR-TEM), N2-physisorption, H2 Temperature Programmed Reduction (H2-TPR), CO2, NH3 and H2 Temperature Programmed Desorption (CO2-, NH3-, H2-TPD), CO/NH3-DRIFTS, and Temperature-Programmed Oxidation (O2-TPO). The surfaces chemistry is analyzed using X-Ray Photoelectron Spectroscopy (XPS), synchrotron X-ray Absorption Spectroscopy (XAS) and solid-state Nuclear Magnetic Resonance (MAS NMR). Out of this work, different valuable conclusions can be drawn. First, the incorporation of Sr as a promoter result in the highest conversion of palm oil (44%) at 400 °C due to its low acidity (NH3-TPD/DRIFTS), higher dispersion (H2TPD) and high amount of accessible Ni sites at the reaction temperature (H2-TPR, XANES). Moreover, different periodic trends are established with respect to the catalyst’s acidity, reducibility, dispersion, and average metal nanoparticle size. Second, the bimetallic Ni/M-Beta (M: Mn, Fe, Co, Cu) catalysts result in full conversion of oleic acid at 350 and 400 °C, mainly yielding hydrocarbons in the gasoline-range (C8-C14). In regards to deoxygenation pathway selectivity, the addition of Mn leads to a fine structure with good dispersion (XRD, H2-TPD) and enhances Lewis acid sites (NH3-DRIFTS), promoting C-C cleavage through DCO/DCO2 pathways. Conversely, the addition of Cu induces structural distortion indicative of the formation of Ni-Cu alloys (XRD, HRTEM), meanwhile increases Brønsted sites that facilitates the dehydration of oxygen groups and C18 production, thus promoting the HDO pathway. Finally, the Ni/La-Beta catalyst having Si/Al ratio equivalent to 29 enhances the low-temperature (400 °C) conversion of acetone by twofold (~80%) compared to the other catalysts (< 40%), and achieves full conversion at 450 °C and above, maintaining high selectivity to H2 with minimal CO production.
Date of Award22 Jul 2024
Original languageAmerican English
SupervisorKyriaki Polychronopoulou (Supervisor)

Keywords

  • Biofuel
  • Hydrogen,
  • Deoxygenation
  • Steam reforming
  • Heterogeneous catalysts
  • Metal Oxides
  • Zeolite support
  • DRIFTS
  • Synchrotron XAS
  • NMR
  • HRTEM

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