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The feasibility of producing distillate fuels (gasoline, diesel and aviation fuels) from coal syncrude was determined. A syncrude from direct liquefaction of subbituminous coal was first deasphalted by ultrasonic disaggregation in n-hexane, to reduce the heteroatom content. The oil was then catalytically hydrogenated in a continuous hydroprocessing unit at 450°C and 10 MPa hydrogen pressure. The...
Chemical structure changes in Condor shale oil during catalytic hydrotreatment were studied based on elemental analysis, 1 H-NMR analysis, TLC/FID and GCD. Catalytic activities of red-mud/sulfur and Ni-Mo catalysts were discussed as to the hydrogenation and hydrogenolysis of structure units in addition to the removal of heteroatoms.
Novel catalysts were developed for the hydrodesulfurization, hydrodenitrogenation and hydrocracking of Israeli shale oil. They were designed to operate on feedstock containing a high level of sulfur and nitrogen. Two hydrotreating stages and one hydrocracking stage were performed in a batch reactor. High-activity catalysts with large macropores yielded 97 and 79% conversion of sulfur and nitrogen...
Atmospheric residual oil hydroprocessing over a dispersed catalyst of cobalt and molybdenum was conducted in continuous mode under 6.9MPa of H 2 using an expanded-bed reactor which was loaded with an appropriate amount of activated carbon granules. As dispersed catalyst precursors, oil-soluble cobalt naphthenate and molybdenum naphthenate were used. Throughout this work, the optimum catalyst...
This study focuses on the synthesis of NiMo-based catalysts in both bulk and coated forms, using ion-exchangeable silica-doped hydrous titanium oxide (HTO:Si) supports. These catalysts were evaluated and compared against commercial NiMo-based catalysts (Amocat 1C and Shell 324) with respect to the hydrogenation of pyrene and the hydrodesulfurization/hydrodenitrogenation of coal-derived liquids. ...
Catalytic activities of high-silica zeolites of ZSM type and also bi-zeolite catalysts HY-ZSM and LaY-ZSM in the hydrotreatment of a wide fraction of liquefaction products from brown coal (328-698 K boiling range) were determined. All the zeolites were modified by Mo and also Pd, Co and Ni loading. It was shown that ZSM use provides an opportunity to hydrogenate nitrogen compounds selectively in...
The hydrotreatment of PR Spring bitumen-derived heavy oils was achieved in a fixed-bed reactor over presulfided commercial NiMo/alumina hydrodenitrogenation catalysts. The extends of heteroatom and metal removal and of Conradson carbon residue (CCR) and residuum (> 811 K) conversion were determined as a function of process operating variables: temperature (625-685 K) and liquid hourly space velocity...
A new procedure is proposed for the effective conversion of biomass flash pyrolysis liquids (BFPLs) to transportation fuels. First, the hydrotreatment of a BFPL was studied, both in a thermal and in a catalytic mode. The thermal hydrogenation of BFPLs, a modification of the VEBA Combi Cracking process, is a low cost and low severity hydrogenation process without any operational problems. It has been...
Oil shale from the Kimmeridge Clay, of Jurassic age from the UK was pyrolysed in a 5kg fixed bed reactor at 525 o C in a nitrogen atmosphere. The derived shale oil was then hydrotreated at 15.0Mpa pressure and 400 o C in a stirred reactor with a nickel-molybdenum (Ni-Mo) catalyst and residence times from 8 to 56h. The shale oils were analysed for polycyclic aromatic hydrocarbons (PAH)...
Effect of reaction temperature on hydrotreatment of a recycle solvent in the NEDOL coal liquefaction process was studied from the data obtained by the operation of a 150t/d pilot plant. Hydrotreatment of the recycle solvent was carried out under a hydrogen pressure of 100kg/cm2G over Ni–Mo/Al2O3 catalyst in a fixed bed reactor. As the reaction temperature increased from 290 to 330°C, the hydrogen...
Pyrolysis oil derived from oil shale was hydrotreated in a stirred reactor at 400 o C for a hydrotreatment time of 12h. The influence of hydrogen pressure at 7, 9, 11 and 15MPa and the role of catalyst type in the form of nickel-molybdenum and cobalt-molybdenum types was investigated in relation to the yield and composition of the products. The results showed that nitrogen and sulphur contents...
The distribution of basic and non-basic nitrogen compounds along the distillation curves of the middle distillates atmospheric gas oil (AGO) and light cycle oil (LCO), used as feedstocks for diesel fuel production, is presented in this paper. For this purpose, the total and basic nitrogen content of true boiling point distillation fractions of AGO and LCO were obtained, followed by nitrogen compounds...
Pyrolysis gasoline upgrading by hydrogenation and ring opening was investigated over highly loaded Ni catalysts supported on amorphous silica–alumina and incorporating promoters as Pd, seeking a higher aromatic reduction of this feedstock in order to meet stringent fuel regulations. The effect of Ni loading and Pd component on the activity of those systems was evaluated in a fixed bed reactor under...
The effects of H 2 purity, pressure, gas/oil ratio, temperature, and LHSV on hydrotreating activities were investigated in a micro-trickle bed reactor using a commercial NiMo/γ-Al 2 O 3 catalyst. Heavy gas oil (HGO) from Athabasca bitumen was used as feed. Due to their significant effects on H 2 partial pressure, H 2 purity, pressure, and gas/oil ratio were...
An approach to model the hydrodesulfurization (HDS) and hydrodemetallization (HDNi and HDV) of a heavy crude oil (21°API and 3.51wt% sulfur) was developed. By using data obtained from an experimental bench-scale reactor at different reaction conditions of LHSV (0.33–1.5h −1 ), temperature (380–420°C) and pressure (6.9MPa) keeping constant the hydrogen-to-oil ratio at 5000stdft 3 /bbl...
The present work is focused on attempt to understand the importance of aromaticity in the elimination of N, O and S atoms from five-membered heterocycles and catalyst poisoning by basic nitrogen six-membered heterocyclic compounds in the hydrotreatment (HDT) process. Pyrrole, furan, thiophene and pyridine, and their fused benzene ring derivatives have been studied by means of density functional theory...
Bio-oil cannot be directly used as biofuel mainly due to its abundant oxygen-containing functional groups. Therefore, bio-oil must be upgraded to produce high quality biofuels. As the first part of this series, this paper reports the transformation of GC-detectable light components during the hydrotreatment of bio-oil using noble-metal catalyst Pd/C over a wide range of reaction temperature (150–300°C)...
This study has investigated the hydrotreatment of bio-oil (derived from the fast pyrolysis of mallee woody biomass) in a batch reactor under 10MPa pressure with Pd/C catalyst at temperatures between 150°C and 300°C. Our results indicate that the chemical fractions, coking tendency as well as the aromatic structures are highly influenced by the hydrotreating conditions such as temperature and time...
Hydrothermal liquefaction (HTL) oil and hydrotreated product from pine tree farm waste (forest product residual, FPR) have been analyzed by direct infusion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) in both positive- and negative-ionization modes and high-resolution two-dimensional heteronuclear 1H–13C NMR spectroscopy. FT-ICR MS resolves thousands...
Modeling the catalyst deactivation due to hydrodeasphaltenization (HDAsph), hydrodemetallization (HDM) and hydrodesulfurization (HDS) reactions with time-on-stream (TOS) was carried out by using a model that considers three deactivation stages: start-of-run (SOR), middle-of-run (MOR) and end-of-run (EOR). Experimental data of kinetics, intra-particle mass transfer and conversion affected by deactivation...
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