Mechanistic reaction micro-kinetics-based structure–activity relationships for palmitic acid hydrodeoxygenation over NiMoS$_x$/Al$_2$O$_3$ catalysts

Žula, Matej (author), Grilc, Miha (author), Likozar, Blaž (author)

The kinetics of palmitic acid hydro-deoxygenation over sulfided NiMo/γ-Al$_2$O$_3$ have been described, including the gas–liquid–solid mass transport/surface chemistry in a magnetically-stirred batch reactor via temperature (225–275 °C), hydrogen pressure (30–70 bar) and catalyst loading (0.1–0.4 g) variation. Intermediates, the hexadecanol and palmityl palmitate, have been probed for a deeper physical understanding of mechanisms. Rates were used to show the impact of the continuum H$_2$ thermodynamic phenomena, availability and coverages on the selectivity among the direct hydrogenation, hydrogenolysis and decarbonylation reactions through the role of H$^•$ formation dependent and independent changes. The system was reduced to 11 catalytic transformation steps, including 8 different molecular species, present in medium. Sequence is simulated to happen on the calculated functional number of active site structures, the activity of which was averaged, while the activation of H$_2$ was supposed to initiate independently. The results of model integrate parameters, such as energies, constants and performance. Process was highly temperature-related, while H$_2$ presence expressed linearly. Phases were characterized with temperature-programmed desorption analysis, coupled with mass spectrometry (TPD–MS) technique, transmission- (TEM), scanning electron microscopy (SEM), X-ray powder diffraction (XRD).

• Language: English
• Keywords: kinetics, hydrodeoxygenation, fatty acids, mechanisms of hydrodeoxygenation
• Work type: Article
• Typology: 1.01 - Original Scientific Article
• Organization: FKKT - Faculty of Chemistry and Chemical Technology
• Publication status: Published
• Publication version: Version of Record
• Year: 2023
• Number of pages: 15 str.
• Numbering: Vol. 467, art. 143425
• PID: 20.500.12556/RUL-148283
• UDC: 544.3/.4
• ISSN on article: 1873-3212
• DOI: 10.1016/j.cej.2023.143425
• COBISS.SI-ID: 156074243
• Publication date in RUL: 09.08.2023

Record is a part of a journal

• Title: Chemical engineering journal
• Publisher: Elsevier
• ISSN: 1873-3212
• COBISS.SI-ID: 23123973

Licences

• License: CC BY-NC-ND 4.0, Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International
• Link: http://creativecommons.org/licenses/by-nc-nd/4.0/
• Description: The most restrictive Creative Commons license. This only allows people to download and share the work for no commercial gain and for no other purposes.

Secondary language

• Language: Slovenian
• Keywords: kataliza, katalizatorji, palmitinska kislina, elektronska mikroskopija