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In the present work, the liquid‐solid interaction of liquid N‐heteroaromatic compounds, commonly present in the petroleum feedstocks of the refineries, with Y zeolites used as hydrocracking catalysts was followed using IR‐ATR spectroscopy. The inhibition of the zeolitic acid sites by strongly basic pyridine and weakly basic indole was highlighted using a continuous flow IR‐ATR cell. Results were assessed by Density Functional Theory calculations to compute the vibrational frequencies of pyridine and indole according to the nature of the interaction sites: silanol groups or acidic OH groups. The study points out that IR‐ATR spectroscopy opens the way for investigating the interaction modes of low vapor pressure molecules (e. g. indole) that present an inherent difficulty to be operated in the gas phase. Moreover, the IR‐ATR makes possible the analysis of the little‐explored low wavenumber zone (<800 cm−1), that presents informative vibrational modes on the adsorption mode of N‐molecules. Hence, this work points out that for pyridine, the bands at 686 and 727 cm−1 are characteristic of pyridinium species formed over zeolitic OH groups, meanwhile, the signals at 703 and 750 cm−1, are associated to pyridine in interaction with silanol groups. The IR‐ATR study reveals that indole, a weakly basic compound, can be protonated on acidic Y zeolites as unambiguously evidenced by the formation of the bands at 1617, 1608, 1543 and 705 cm−1. Findings here exposed are crucial for studying inhibitory effects exerted by weak nitrogenated compounds on acidic materials during hydrocracking processes. [ABSTRACT FROM AUTHOR]

Abstract: CoMo catalysts supported on a commercial γ-Al2O3 modified with B, Na or K were prepared in order to analyze the effect of acid–base characteristics on the FCC naphtha hydrotreatment. Catalysts were characterized by NH3 TPD, IR of pre-adsorbed pyridine and CO2, XPS, Raman, and XRD. In general, with either boron or alkaline metal modification the HDS/HYDO selectivity did not significantly improve. However, it is remarkable that when the alumina was modified to be either more acidic (B) or more basic (K, Na), improvements in the ratio between the HDS and the conversion of the internal branched olefin as well as in the ratio double-bond isomerization to HYD of linear olefins were observed. For both modifications, this fact was related to the promotion of the double-bond isomerization reaction from external to internal positions. For alkaline-doped catalysts, it was found that the double-bond isomerization was related to the existence of basic sites. For the boron, there is a range of boria content (2–3wt.%) where the double-bond isomerization was promoted selectively over the cracking and alkylation reactions because only weak Brönsted acid sites are present. Additionally, both modifications (Boron or alkaline metals) of alumina led to a decrease in the HDS activity, which was found to be related to changes in the distribution of Co and Mo species in the oxide state. Alkaline metal introduction led to the formation of alkaline metal molybdates, whereas boron introduction increased the proportion of octahedral polymeric Mo species, consequently, decreasing the dispersion of the Mo phase. [ABSTRACT FROM AUTHOR]

CoMo catalysts supported on γ-Al2O3 modified with potassium (K, 1, 3 and 5 wt%) were prepared and evaluated in simultaneous hydrodesulfurization (HDS) of 2-methyltiophene and hydrogenation of olefins (trimethyl-1-pentene to trimethyl-2-pentene ratio) reactions. The acid-base properties of the catalysts were measured by ammonia temperature-programmed desorption (TPD) and by the decomposition reaction of 2-propanol. Results showed that the BET surface area and the acidity of catalysts modified with potassium decreased when the potassium concentration increased as long as hydrodesulfurization/ hidrogenation (HDS/HYD of internal olefins increased. However, the activity of the modified catalysts decreased for all reactions. Comparison with literature information allowed establishing that modifications in the structure and dispersion of the active phase caused by the introduction of potassium are not the responsible for the activity decrease. [ABSTRACT FROM AUTHOR]