Phonolite Material as Catalyst Support for the Hydrotreatment of Gas Oil and Vegetable Oil Type Feedstocks

Phonolite material has shown to be promising catalyst support for the deoxygenation of triglycerides. In this work, we continue with our previous research by synthesising and testing three acid-treated phonolite-supported Co-Mo, Ni-Mo and Ni-W catalysts for the hydrotreating of atmospheric gas oil and co-processing with rapeseed oil at industrial operating conditions (350–370 °C, WHSV 1–2 h−1, 5.5 MPa) in the continuous regime for more than 270 h. The phonolite-supported catalysts showed hydrotreating activity comparable with commercial catalysts, together with a complete conversion of triglycerides into n-alkanes. During co-processing, the Ni-promoted catalyst showed strong stability, with similar activity previous to the rapeseed oil addition. Our results enable us to evaluate the suitability of phonolite as catalyst support for the development of plausible alternatives to conventional hydrotreating catalysts for the co-processing of middle distillates with vegetable oils.

Biofuels for Maritime Transportation: A Spatial, Techno-Economic, and Logistic Analysis in Brazil, Europe, South Africa, and the USA

Low or zero carbon fuels are crucial for maritime transportation decarbonization goals. This paper assesses potential localities for maritime biofuels (biobunkers) production in Brazil, Europe, South Africa, and United States considering geographical, logistic, and economic aspects. This assessment combines georeferenced and techno-economic analyses to identify suitable fuel production hotspots based on not only plant performance and costs but also on logistic integration and biomass seasonality. Five technology pathways were considered: Straight vegetable Oils (SVO), Hydrotreated Vegetable Oils (HVO), Fischer–Tropsch Biomass-to-liquids (FT-BTL), Alcohol oligomerization to middle distillates (ATD), and Hydrotreated Pyrolysis Oil (HDPO). Findings reveal that biomass concentration in Brazil makes it the region with highest biobunker potential, which are mostly close to coastal areas and surpasses regional demand. Although other regions registered more limited potentials, hotspots proximity to ports would enable fossil fuel replacements in these areas. For all cases, biobunker costs (USD 21–104/GJ) are higher than conventional marine fuels prices (USD 11–17/GJ). Only 15% of the hotspots’ carbon prices that would allow its competitiveness are lower than USD 100/tCO2. Alternatives to incentivize biobunker production would be, first, to establish mandatory fuel blends and second, to join forces with other sectors that would be benefited from the co-production of advanced biofuels.

The Effect of the Reaction Conditions on the Properties of Products from Co-hydrotreating of Rapeseed Oil and Petroleum Middle Distillates

This study compares the hydrotreating of the mixture of petroleum middle distillates and the same mixture containing 20 wt % of rapeseed oil. We also study the effect of the temperature and the weight hourly space velocity (WHSV) on the co-hydrotreating of gas oil and rapeseed oil mixture. The hydrotreating is performed over a commercial hydrotreating Ni-Mo/Al2O3 catalyst at temperatures of ca. 320, 330, 340, and 350 °C with a WHSV of 0.5, 1.0, 1.5, and 2.0 h−1 under a pressure of 4 MPa and at a constant hydrogen flow of 28 dm3·h−1. The total conversion of the rapeseed oil is achieved under all the tested reaction conditions. The content of the aromatic hydrocarbons in the products reached a minimum at the lowest reaction temperature and WHSV. The content of sulphur in the products did not exceed 10 mg∙kg−1 at the reaction temperature of 350 °C and a WHSV of 1.0 h−1 and WHSV of 0.5 h−1 regardless of the reaction temperature. Our results show that in the hydrotreating of the feedstock containing rapeseed oil, a large amount of hydrogen is consumed for the dearomatisation of the fossil part and the saturation of the double bonds in the rapeseed oil and its hydrodeoxygenation.

Towards cost-competitive middle distillate fuels from ethanol within a market-flexible biorefinery concept

Ethanol to middle distillates (ETMD) is a promising pathway to produce sustainable liquid fuels to decarbonize the hard-to-electrify transportation sectors due to (1) the abundant sugar/starch and lignocellulosic biomass, (2)...

Nitrogen compounds removal from oil-derived middle distillates by MIL-101(Cr) and its impact on ULSD production by hydrotreating

Oil-derived middle distillates (straight-run gas oil and mixture with light cycle oil and coker gas oil) for Ultra-Low Sulfur Diesel (ULSD) production by HyDroTreating (HDT) were pretreated by selective Nitrogen Organic Compounds (NOC) adsorption. Highly crystalline Metal-Organic Framework (MOF) MIL-101(Cr) prepared with propylene oxide (proton scavenger) as textural improver was used to that end. MOF was characterized by N2 physisorption, X-ray diffraction, thermal analysis, infrared, Raman and UV-vis spectroscopies, and electron microscopy (SEM and HR-TEM). NOC removal was carried out at room temperature and atmospheric pressure, the adsorbent being easily regenerable under mild conditions. Extruded MOF efficiently removed NOC from real feedstocks to concentrations ~ 80 ppm which allowed ULSD production at much milder conditions to those used during pristine feedstocks HDT. Operating temperature could be significantly diminished (from 350 to 330 °C, at 56 kg cm−2 (5.77 MPa), LHSV = 1.5 h−1, H2/oil = 2500 ft3 bbl−1 (445 m3 m−3)) which could notably prolong cycle life of NiMo/Al2O3 formulation used.

Conversion of heavy gasoil into ultra-low sulfur and aromatic diesel over NiWRu/TiO2–γAl2O3 catalysts: Role of titanium and ruthenium on improving catalytic activity

This contribution deals with about selective conversion of heavy gas oils into middle distillates fuels that meet ultra-low sulfur and aromatic compound quality standards by using a novel NiWRu/TiO2–γAl2O3 catalyst under typical hydrotreatment conditions. A diesel fuel fraction having sulfur, nitrogen and aromatics compound content of about 50 ppm, 10 ppm and 15 v%, respectively, was obtained when the reactor was operated at T = 370 °C, P = 12.4 MPa, LHSV = 0.5 h−1 and H2/hydrocarbon ratio = 800 Nm3/m3. Titanium and ruthenium additives used in the preparation of the NiWRu/TiO2–γAl2O3 catalyst, remarkably improved the catalytic activities for the hydrogenolysis, hydrogenation and hydrocracking reactions compared to the reference NiW/γAl2O3 catalyst. The coprecipitation of titanium and aluminum hydroxides produced a catalyst support having greater surface area, pore volume and surface acidity. An improvement in mechanical properties of the support extrudates was also observed. Characterization analysis by XPS, AUGER and XRD techniques of the TiO2–γAl2O3 support suggested the formation of an aluminum-titanate mixed phase (AlxTiyOz) having a non-well-defined stoichiometry. The NiW/TiO2–γAl2O3 and NiWRu/TiO2–γAl2O3 exhibited a greater surface dispersion of the supported nickel and tungsten species compared to the NiW/γAl2O3 catalyst. The promoter effect of ruthenium on the NiW bimetallic system caused a strong increase in both hydrogenolysis and hydrogenation reactions. Hydrodenitrogenation and hydrocracking reactions were also favored by the increase in the hydrogenation capacity and in the surface acidity of the catalyst. The highest conversion levels for all investigated reactions were obtained when the NiWRu/TiO2–γAl2O3 catalyst was prepared by co-impregnation of Ni and Ru in a second step. This catalyst showed sulfur tolerance properties when the reaction was conducted in the presence of different H2S partial pressures. The catalytic behavior of the NiWRu/TiO2–γAl2O3 catalyst was explained by the existence of a promoting effect between separated Ni and Ru sulfides species and the NiWS phase (dual mechanism).

Assessment of the Oxidative Desulfurization of Middle Distillate Surrogate Fuels with Spectroscopic Techniques

The oxidative desulfurization of five (5) model sulfur compounds and eleven (11) surrogate blends was investigated using the hydrogen peroxide (H2O2)-acetic acid (CH3COOH) system. Consequently, extractive desulfurization was carried out using conventional solvents. The model sulfur compounds, as well as the solvent, are present in petroleum middle distillates. The selection of the compounds was made so that they represent various kinds of sulfur compounds. The goal of this study was the implementation of a simple and economical oxidative and extractive system for the desulfurization of surrogate mixtures with an intermediate sulfur concentration 1% w/w, at the mild temperature of 70°C, and without the use of supplementary and assisting methods such as heterogeneous catalysis or ultrasound irradiation. The sulfur content was estimated using X-ray fluorescence. The progress of the oxidation reaction was monitored using liquid FT-IR. The solid sediments of the oxidation procedure were identified with solid-state FT-IR and 1H NMR spectroscopy.