Catalysts to produce the important petrochemicals like benzene, toluene, and xylene (BTX) from refinery feedstocks, like light cycle oil (LCO) are reviewed here by covering published papers using model mixtures and real feeds. Model compounds experiments like tetralin and naphthalene derivatives provided a 53–55% total BTX yield. Higher yields were never attained due to the inevitable gas formation and other C9+-alkylbenzenes formed. For tetralin, the best catalysts are those conformed by Ni, CoMo, NiMo, or NiSn over zeolite H-Beta. For naphthalene derivatives, the best catalysts were those conformed by W and NiW over zeolite H-Beta silylated. Real feeds produced a total BTX yield of up to 35% at the best experimental conditions. Higher yields were never reached due to the presence of other types of hydrocarbons in the feed which can compete for the catalytic sites. The best catalysts were those conformed by Mo, CoMo, or NiMo over zeolite H-Beta. Some improvements were obtained by adding ZSM-5 to the support or in mixtures with other catalysts.

The study of the best experimental conditions and catalyst for the hydrogenation (HYD) of light cycle oil (LCO) for upgrading purposes was carried out. The objective was to examine the ability of two commercial hydrotreatment (HDT) catalysts for selective aromatic saturation. The effect of the hydrotreatment operation parameters (temperature, pressure, liquid hourly space velocity, H2/HC ratio) on the sulfur and nitrogen contents and in the saturation of aromatic hydrocarbons was also investigated. The goal was to obtain the highest conversion to mono-aromatic hydrocarbons from this di-aromatic (naphthalene derivatives) type feedstock, and at the same time to get reasonable hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) performance to avoid contaminant hydrocarbons for the next step (usually hydrocracking, HCK). An appropriate hydrotreated product with the highest concentration of mono-aromatic derivatives, a minimum reduction on the total aromatic content, and suitable decrements of sulfur and nitrogen compounds, was achieved using a cobalt-molybdenum supported on alumina catalyst, at 330 °C, 5.5 MPa, and a liquid hourly space velocity of 1.1 h−1. Additionally, the kinetics of the HDA was studied, assuming a lump characterization into tri-, di- and mono-aromatic and aliphatic hydrocarbons, pseudo-first-order reaction rates between these conversions, and thermal losses and diffusional resistances to be undetectable.

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The effect of the chemical composition of the hydrotreated light cycle oil (HDT LCO) on the benzene, toluene, ethylbenzene, and xylene (BTEX) production by a hydrocracking (HCK) procedure, is presented. Six different types of HDT LCOs were obtained by submitting two types of LCOs to hydrotreating (HDT) with different catalysts and experimental conditions. The products were analyzed as mono-, di- and tri-aromatic compounds using the supercritical fluid chromatography (SFC) method (ASTM D5186). The HDT LCOs were subjected to HCK with a 50/50 in weight mixture of nickel-molybdenum on alumina (NiMo/Al2O3) and H-ZSM5 (NiMo/H-ZSM5, 50/50) at 375 °C, 7.5 MPa, 1.2 h−1, and 750 m3/m3 H2/Oil. The HCK products were analyzed by gas chromatography with a flame ionization detector (GC-FID) and divided into five groups: gas, light hydrocarbons (LHCs), BTEX, middle hydrocarbons (MHCs), and heavy hydrocarbons (HHCs).The results showed that the BTEX formation ranged from 27.0 to 29.8 wt.% and it did not show a significant dependence on the mono-aromatic (59.9 and 75.6 wt.%), total aromatic (61.1–84.2 wt.%) contents or MHCs conversion (58.3–64.3 wt.%) from the departing HDT LCO feedstock. This result implies that, contrary to previous expectations, the BTEX formation does not directly depend on the amounts of total or mono-aromatic compounds when departing from real feedstocks. A GC-PIONA (paraffin, isoparaffin, olefin, naphthene, aromatic) characterization method (ASTM D6623) for mechanism understanding purpose was also carried out.

The effect of the experimental conditions on the hydrocracking (HCK) of a hydrotreated light cycle oil (HDT LCO) was studied in this work. The catalyst tested was a 50/50 weight mixture of nickel-molybdenum-phosphorous on alumina (NiMo/Al2O3) and a commercial ZSM5 zeolite (HCK 50/50). The experimental conditions tested were 340, 350, 360, and 370 °C; 7.5 MPa; 0.9, 1.2, 1.5, and 1.8 h−1 LHSV, and H2/HC of 752 m3/m3. Two phases: gas and liquid, were obtained as HDK products. The gas phase consisted mostly of C1–C5 paraffins, iso-paraffins, and olefins. The liquid phase was characterized by GC-PIONA and was distributed in lumps as follows: NAPA by C11 to C13-naphthalenes; TET by C11 to C13-tetralins; IND by C9 to C13-indanes and indenes; AKB by C9 to C13-alkylbenzenes; BTEX by benzene, toluene, ethylbenzene, and xylenes; NAPE by C9 to C13-naphthenes; and PIP by C3 to C14 paraffin, iso-paraffin, and olefin type hydrocarbons. Using this classification, the results showed that increments in temperature and decrements in LHSV produced increments in the formation of gases, PIP, BTEX, and NAPE. At the same conditions, AKB, TET, NAPA, and IND decreased sharply. TET and NAPA derivatives were no longer present at high temperatures (360–370 °C). It seemed to be a limit of the BTEX formation directly related to the TET and IND presence, and it did not seem to depend on the transalkylation process of AKB hydrocarbons. Instead, AKB hydrocarbons were directly correlated to NAPE hydrocarbon formation by hydrogenation. A kinetic model was prepared. The model presented correlation coefficients higher than 98 %. The kinetic model that was made predicted that neither increasing the temperature nor lowering the LHSV would improve the BTEX formation when departing from this feedstock.