Refractory Character of 4,6‐Dialkyldibenzothiophenes: Structural and Electronic Instabilities Reign Deep Hydrodesulfurization

Abstract

We studied the most commonly S‐containing compounds present in crude oils, the so‐called 4,6‐dialkyldibenzothiophenes. The alkyl derivatives in this study were methyl, ethyl and isopropyl. Computationally rotating the alkyl substituents, we found differences in their stability. The most stable compound (isopropyl) was transformed into the most instable by changes in its structure. Aromaticity revealed the changes taking place upon structural modifications. The most refractory compound (isopropyl derivative) reduced much more its aromatic character than the methyl derivative. The interaction of these molecules with MoS2 confirmed their instable character upon adsorption. The stability of the refractory molecules and their destabilization prior to be transformed shed light into the key step that reign deep HDS.

Evaluating the Benefits of Data Fusion and PARAFAC for the Chemometric Analysis of FT-ICR MS Data Sets from Gas Oil Samples

“…The application of PARAFAC on fused data is then very efficient to highlight atypical samples and condense the most significant contributions from all samples. The loadings from the sample mode are presented in Figure 6B is then correlated to a very strong contribution of the DBT and carbazoles family that mainly remain in the sample as they are known to be refractory 2,25 . It should be noted that these observations are the same as the ones obtained throughout the single analysis of the ESI(-) and APPI(+) datasets hence proving the sensitivity and relevance of such data fusion approach to put forward significant information.…”

“…The efficiency of the HDT process is reliant on the molecular composition because the kinetic of the hydrodesulfurization (HDS) reactions depends strongly on the structure of the sulfur compounds in the gas oil cuts 2 . The efficiency of hydrodesulfurization is also dependent on nitrogen compounds.…”

“…Molecular-based kinetic modeling approaches are increasingly used 7 to predict the reactivity of the different gas oil cuts and to optimize the operating conditions of the HDT process. There is then a real need for molecular characterization of these different gas oils 2 . The detailed characterization of sulfur compounds in gas oils can be achieved through atmospheric pressure photo-ionization (APPI) coupled to ultra-high resolution mass spectrometry (Fourier Transform Ion Cyclotron Resonance Mass Spectrometry known as FT-ICR MS) analysis [8][9][10][11] while nitrogen compounds are described using the electrospray ionization (ESI) source in two different polarities (negative polarity for neutral nitrogen compounds and positive polarity for basic nitrogen compounds) 12,13 .…”

Hierarchical Porous Nitrogen‐Doped Carbon Modified with Nickel Nanoparticles for Selective Ultradeep Desulfurization

“…[4] Researchers across the globe have reported various techniques adapted to reduce sulfur contents in fuels, which include conventional hydrodesulfurization, ionic liquids desulfurization, bio-desulfurization, oxidative desulfurization and adsorptive desulfurization. [5][6][7][8][9] Amidst these technologies, adsorption of sulfur in fuel via electrostatic interaction or pi-complexation is favorable due to low cost as it avoids high operational conditions of temperature and pressure with no consumption of hydrogen. [10] Thus, it could be a complimentary approach of sulfur removal to expensive industrially employed HDS approach for ultra-deep desulfurization.…”

Reactivity of Atomically Functionalized C-Doped Boron Nitride Nanoribbons and Their Interaction with Organosulfur Compounds

“…The remaining undesirable molecules present in oil fuels, such as gasoline, highway diesel and jet fuel include the organosulfur compounds [20]. A direct environmental impact occurs when lower sulfur levels are achieved, due to the increasing operational costs of traditional hydrodesulfurization processes [21,22]. In this way, alternative techniques, e.g., by using adsorbent materials [23,24,25,26], have been tested to selectively eliminate residual organosulfur compounds.…”