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International audience; Recent advances in instrumentation for high-field Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) have enabled access to ∼70 »000 unique molecular formulas in broadband mass spectral characterization of unfractionated/whole asphaltenes. The results accumulated over a decade highlight the need for an asphaltene molecular model that acknowledges the coexistence of (1) monofunctional and polyfunctional species; (2) island and archipelago structural motifs; and (3) heteroatom-depleted/highly aromatic compounds, as well as atypical species with low aromaticity but increased heteroatom content. Collectively, results from FT-ICR MS, preparatory-scale separations (extrography/interfacial material), gel permeation chromatography, precipitation behavior in heptane:toluene, thermal decomposition, and aggregate microstructure by atomic force microscopy (among other techniques), suggest that the strong aggregation of asphaltenes results from the synergy between several intermolecular forces: π-stacking, hydrogen bonding, London forces, and acid/base interactions. This review presents general features of asphaltene molecular composition reported over the past five decades. We focus on mass spectrometry characterization and expose the reasons why early results supported the dominance of single-core motifs. Then, the discussion shifts to recent advances in instrumentation for high-field FT-ICR MS, which have enabled the detection of thousands of species in asphaltene samples, whose molecular composition and fragmentation behavior in ultrahigh vacuum agree with the coexistence of single-core and multicore structural motifs. Furthermore, evidence that highlights the limitations of commercially available/custom-built ion sources and selective ionization effects is presented. Consequently, the limitations require separations (e.g., chromatography, extrography) to gain more-comprehensive molecular-level insights into the composition of these complex organic mixtures. The final sections present evidence for the role of aggregation in selective ionization and suggest that advanced characterization by both thermal desorption/decomposition and liquid chromatography with online FT-ICR MS detection can be employed to mitigate the effects of aggregation and provide unique insights in molecular composition/structure.

To satisfy the global demand, more and more high quality fuels pure or converted from heavy oil cuts, such as vacuum gas oil (VGO), into highly refined fuels, are demanded1. To meet this increasing...

International audience; Solid circulation in chemical looping combustion (CLC) is very important and affects the mass and heat balance and autothermal operation of a CLC system. A key task in developing CLC technology is to control the solid circulation. In this work, the solid circulation characteristic of a 1.5 MWth CLC cold flow model is reported. The solid circulation between the fuel reactor and the simplified air reactor riser is controlled by the overflow method. Three kinds of quartz sands are selected as fluidized particles, and their median particle diameters are 392, 249, and 122 μm, respectively. A reasonable pressure profile is obtained in the 1.5 MWth CLC cold flow model. The effects of operational parameters, including the fuel reactor gas velocity, loop seal gas velocity, simplified riser gas velocity, particle size, and static bed height, on the solid circulation and hydrodynamic characteristics are measured and analyzed. The maximum solid circulation rate can approach 130 kg/(m2·s), and this value satisfies the requirements of mass and heat balance in the CLC system. The static bed height in the fuel reactor should be higher than the overflow port to prevent it from becoming a constraint factor on the solid circulation rate. An overflow model is developed to predict the solid circulation rate, and the relative errors between the predicted result and the experimental data are within 25%.

International audience; Asphaltenes are among the most challenging components in petroleum processing because they contain high amounts of heteroatoms (i.e., S, N, O, V, and Ni) thought to be responsible for strong aggregation tendencies, precipitation, and fouling problems. The role of vanadium- and nickel-containing petroleum compounds (i.e., petroporphyrins) in aggregation and fouling is not completely understood because asphaltene composition and structure is still a subject of debate in the petroleum chemistry community. Characterization of asphaltenes, namely, molecular analysis that employs no chromatographic separation, often fails to reveal their comprehensive composition. The work herein presents asphaltene fractionation by (1) solid/liquid extraction, which allows for separation of single-core (“island”) and multicore (“archipelago”) structural motifs and by (2) high-performance thin layer chromatography (HPTLC) with cellulose as the stationary phase and DCM/MeOH as the eluent, which facilitates access to petroporphyrins. Characterization is performed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and matrix-assisted laser desorption ionization Fourier transform ion cyclotron resonance mass spectrometry (MALDI FT-ICR MS). The results demonstrate that even with multiple separation steps, a large quantity of vanadyl porphyrins remains inaccessible for molecular analysis by MALDI FT-ICR MS, which raises the question of what portion of a complex sample of asphaltene can be revealed by ultrahigh resolution mass spectrometry. Furthermore, the results show that easily accessible porphyrins migrate with the solvent front in HPTLC. Thus, HPTLC can be used to isolate and identify “free” porphyrins not locked into asphaltene aggregates; however, further development of separation methods is required to access the most difficult and problematic asphaltene fractions, which do not migrate and impose analytical challenges due to their stronger aggregation tendency.

International audience; The numerical simulations on the large-scale fluidized beds still remain challenging due to the computational limitation and experimental validation. In the present work, a CFD study of a large-scale fluidized bed is investigated using the NEPTUNE_CFD code based on an Eulerian n-fluid modeling approach. A SubGrid Scale (SGS) drag model based on the filtered approach is used to take into account the effect of very small solid structures unresolved with the coarse mesh. The numerical results are compared with the experimental data carried out in a pilot-scale fluidized bed unit and provided by Particulate Solid Research Inc (PSRI). By applying the SGS drag model without any specific or empirical tuning, mesh-independent numerical results are obtained. The flow regimes inside the fluidized bed are well predicted for all the superficial gas velocities studied here. The bed density profiles and the solid entrainment fluxes are also in good agreement with the experimental measurement.  The large-scale fluidized bed simulations are validated against PSRI experiments for different flow regimes from turbulent to fast fluidization.  A SGS drag model based on the filtered approach is using without any specific or empirical tuning which shows certain universality.  The gas-solid flows inside the fluidized bed with different gas velocities are characterized.  The validation in this study is a critical step toward industrial-scale fluidized bed simulations. Gas-solid fluidized bed simulations using the filtered approach: Validation against pilot-scale experiments Abstract The numerical simulations on the large-scale fluidized beds still remain challenging due to the computational limitation and experimental validation. In the present work, a CFD study of a large-scale fluidized bed is investigated using the NEPTUNE CFD code based on an Eulerian n-fluid modeling approach. A SubGrid Scale (SGS) drag model based on the filtered approach is used to take into account the effect of very small solid structures unresolved with the coarse mesh. The numerical results are compared with the experimental data carried out in a pilot-scale fluidized bed unit and provided by Particulate Solid Research Inc (PSRI). By applying the SGS drag model without any specific or empirical tuning, mesh-independent numerical results are obtained. The flow regimes inside the fluidized bed are well predicted for all the superficial gas velocities studied here. The bed density profiles and the solid entrainment fluxes are also in good agreement with the experimental measurement.

International audience; A detailed distributed lumped kinetic model for slurry phase Vacuum Residue hydroconversion process (boiling range 525 + °C) has been constructed. Simulated distillation and Gel Permeation Chromatography analysis results were combined to estimate feedstock and product compositions over the whole boiling range. The model uses 21 distributed lumps to represent the hydrocarbons, takes hydrogen consumption into account and calculates reaction rates using molar concentrations. Vapour liquid mass transfer resistances and vapour-liquid equilibrium are also accounted for. The resulting model represents the evolution of the reaction mixture physical properties well and provides a good fit with the experimental data. From estimated parameters, it is deduced that thermally activated and catalytic reactions in cascade occur simultaneously and also that material boiling above 750 °C is converted in a different manner to lighter material.

International audience; In this work, Arabian light atmospheric residue and Safaniya vacuum residue were hydroconverted in a slurry phase semi-batch stirred tank reactor at 15 MPa for a wide range of temperatures (420–440 °C) and reaction times up to 4 h. Experimental data was used to develop a semi-batch reactor model including vapor-liquid equilibrium, gas-liquid mass transfer and gas phase hydrodynamics. Mass transfer and kinetic parameters were estimated by minimizing not only the total masses of products but also the outlet gas flow dynamics. Mass transfer and hydrogen consumption were compared against former studies using a batch reactor, a continuous stirred tank reactor and work by other authors, reported in the literature. Higher hydrogen consumption was achieved with the semi-batch reactor and no hydrogen mass transfer limitation was observed. Therefore, it was concluded that this setup is more suited and reliable for studying the chemical kinetics of slurry-phase hydroconversion of petroleum residues and permits improved representation of the role of hydrogen compared with current models.

International audience; Petroleum and its fractions are some of the most complex mixtures found in analytical chemistry. Mass spectrometry currently plays an increasing role in the characterization of these matrices. Since the last review on this topic in 2011, several new approaches have been introduced, and these approaches increasingly use sample fractionation by extraction and/or liquid chromatographic techniques. This review considers molecular mass spectrometry (with special emphasis on the use of ion mobility) and inorganic mass spectrometry. The combination of both techniques paves the way to "petrointeractomic" approaches, which are introduced as a novel, important part of "petroleomic" approaches.

International audience; The size distributions of sulfur (S), vanadium (V), and nickel (Ni) compounds in four crude oils, two residues, and their saturate, aromatic, resin, and asphaltene (SARA) fractions were determined using gel permeation chromatography (GPC) coupled to inductively coupled plasma high-resolution mass spectrometry (ICP HR MS). The results show trimodal distributions of V, Ni, and S compounds in the crude oils and residues. V and Ni compounds are present in both resins and asphaltenes. Trimodal distributions are clearly apparent in the resins but not apparent in the asphaltenes. In the latter, the predominant compounds have a high molecular weight (HMW), even when the solution of asphaltenes is diluted by 40000-fold. In the resins, compounds with a medium molecular weight (MMW) were expected; however, HMW compounds were observed, indicating that nanoaggregates or large molecules exist in both the asphaltenes and resins. Low-molecular-weight (LMW) compounds are predominantly present in the resins and do not represent more than 22% of V and Ni present in crude oil. These compounds appear to have molecular weights similar to simple metalloporphyrins.

International audience; The heat capacities at constant pressure of FAMEs were measured within the temperature range of 250-390 K. The measurements were performed on 7 pure saturated fatty acid methyl esters and 5 unsaturated fatty acid methyl esters. These data were then employed to calculate heat capacities of four different biodiesels (rapeseed and soybean origins) through an ideal mixing rule. The calculated and the experimental heat capacity of these biodiesels were then compared and an absolute average deviation of 0.9% was observed.

International audience; The melting temperature of fatty acid methyl esters (FAMEs) have been measured both at atmospheric pressure by using a μDSC calorimeter and at high pressure (up to 80 MPa) thanks to a dedicated microscope. The values obtained at atmospheric pressure have been compared with literature data. The influence of the chain structure on the melting temperatures has been discussed, as well as the slopes of the liquid-solid transition curves in the (T, P) diagram. The experimental results have efficiently allowed predicting the solid molar volume and consequently, the difference between the volume in liquid and solid phases has been evaluated

International audience; A circulating turbulent fluidized bed connected with a riser and an annular carbon stripper (CS) is proposed to be used as a fuel reactor (FR) in chemical looping combustion. The bottom section of the FR is operated under a turbulent fluidization regime, which can achieve enough solid residence time and enhance the mixing of the oxygen carrier with solid fuel. A 1.5 MWth cold model of the FR was designed, constructed, and tested to investigate the hydrodynamics of solid particles with different sizes. Three kinds of quartz sands with different particle sizes (d50 = 122, 249, and 392 μm) were used as bed materials to simulate the oxygen carrier. Continuous operation with a reasonable pressure balance was achieved in the cold model. The effects of important variables, including gas velocity, static bed height, and particle size, on the gas–solid hydrodynamics of the FR were measured and discussed. It was found that the transition velocities from bubbling to turbulent fluidization for different particles of d50 = 122, 249, and 392 μm were measured to be 0.78, 0.95, and 1.06 m/s, respectively, indicating that the transition velocity increased with increasing the particle size. The solid fraction profile along the reactor height and solid circulation rate were affected by gas velocity and static bed height. A modified correlation was proposed to predict the solid fraction of the annular CS dilute phase, and the predicted results agree well with the experimental data under a wide range of operational conditions.