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Thermochemical conversion of larger biomass particles (thermally thick regime) toward high-end products still suffers from an unrevealed quantitative relationship between process and product parameters. The main issue relates to the influence of heating rate within the particle, critical conversion-wise but difficult to assess experimentally. Computational fluid dynamics (CFD) modelling may help, but first the model must prove its reliability to prevent error transfer to the results. This study aimed to provide an unbiased, state-of-the-art model constructed in a stepwise mode to investigate the heating rate's distribution. Several datasets with broadly varying parameters from the literature were used for the development and validation since the reproduction of datasets would not bring novelty to solving the problem. Instead of the model's calibration to fit to the data, the parameters for each step-model were meticulously selected to match the experimental conditions. The stepwise development showed the best accuracy when the anisotropy and the heat sink drying sub-model were implemented. Moreover, using the Ranzi-Anca-Couce (RAC) scheme led to more accurate results than the Ranzi scheme. The comprehensive model was positively validated against a broad range of production parameters (pyrolysis temperature: 500 degrees C - 840 degrees C, diameter of particles: 10 mm - 20 mm, shapes: cylinders and spheres). Investigation showed a pattern in volatiles release profiles and homogeneous heating rate distribution when particle size is below 4 mm. Despite basing the models on the literature's data, the study includes novel and valuable insights for biomass conversion and constitutes a solid foundation for future development.

Turning raw biogas into biomethane as energy carrier requires the selective removal of CO2 in a biogas upgrading process or a total conversion of CO2 to CH4 which is generally energy intensive. During membrane electrolysis, electrical energy can be used to simultaneously remove CO2 (and H2S) and produce H2 as side product. Biogas is thus scrubbed with catholyte and the captured HCO3− and HS− migrate towards the anode. Simultaneously, cathodic H2 mixes with residual biogas in a ratio that can be fine-tuned. We obtained in one step an ideal 4:1 H2:CO2 ratio in the reactor off gas. Subsequently the gas could be further upgraded via chemoautotrophic microbial conversion of CO2 to CH4. Biomethanation delivered biomethane with 98.9 ± 0.9% purity. The electrochemically-assisted scrubbing and stripping of CO2 and H2S resulted in high CO2 removal efficiencies (up to 100%), without addition of chemicals. The system was flexible depending on temporarily available power. Electrochemical biogas upgrading (EBU) can be envisaged as a scalable and decentralized storage of excess or off-peak renewable power, making better use of the power input used to drive a biological CO2 conversion.

Droplet-based microfluidic extraction is a promising way for effective lanthanides extraction due to its outstanding mass transfer performance. The separation process can be greatly enhanced with the droplet-based microfluidic extraction technique. However, the interactions between mass transfer, microfluidic dynamics and extraction kinetics are still unclear, which has hindered further manipulation on microfluidic extraction to boost extraction performance. In this study, the mechanisms of microfluidic droplet-based extraction and separation intensification of lanthanides are for the first time unveiled by using a numerical simulation model. The limiting factors for the performance of droplet-based microfluidic extraction are identified through a model-based parametric analysis. The numerical analyses provide a comprehensive understanding of droplet-based microfluidic extraction systems and offer operation and optimization guidelines for future research in this area.

The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) was performed in perfluoroalkoxy alkane capillary microreactors packed with a carbon-supported ruthenium (Ru/C) catalyst with an average particle diameter of 0.3 or 0.45 mm. The reaction was executed under an upstream gas–liquid slug flow with 1,4-dioxane as the solvent and H2 as the hydrogen donor in the gas phase. Operating conditions (i.e., flow rate and gas to liquid flow ratio, pressure, temperature and catalyst particle size) were varied in the microreactor to determine the influence of mass transfer and kinetic characteristics on the reaction performance. At 130 °C, 12 bar H2 and a weight hourly space velocity of the liquid feed (WHSV) of 3.0 gfeed/(gcat·h), 100% LA conversion and 84% GVL yield were obtained. Under the conditions tested (70–130 °C and 9–15 bar) the reaction rate was affected by mass transfer, given the notable effect of the mixture flow rate and catalyst particle size on the LA conversion and GVL yield at a certain WHSV. A microreactor model was developed by considering gas–liquid–solid mass transfer therein and the reaction kinetics estimated from the literature correlations and data. This model well describes the measured LA conversion for varying operating conditions, provided that the internal diffusion and kinetic rates were not considered rate limiting. Liquid–solid mass transfer of hydrogen towards the external catalyst surface was thus found dominant in most experiments. The developed model can aid in the further optimization of the Ru/C catalyzed levulinic acid hydrogenation in packed bed microreactors.

A catalyst preparation method, consisting of slurry washcoating with γ-Al2O3 followed by impregnating platinum on the microreactor walls, has been investigated. The effect of various factors in the preparation procedures on the adhesion of the washcoated γ-Al2O3 was studied, including the slurry property (i.e., the binder type, concentration and molecular weight, γ-Al2O3 concentration and particle size, pH), and the (micro)reactor substrate and channel shape. The results show that the adhesion of γ-Al2O3 washcoat strongly depended on the slurry rheological characteristics. A good adhesion on FeCrAlloy substrates was obtained using the slurry with polyvinyl alcohol as the binder (typical concentration at 3–5 wt% and molecular weight of 57,000–186,000), 20 wt% γ-Al2O3 (particle size being around 3 µm) and pH = 3.5. FeCrAlloy as the substrate exhibited an excellent coating adhesion in rectangular or round channels, primarily due to the formation of alumina film over the surface during thermal pretreatment. The aluminum-free stainless steel as the substrate only showed a good adhesion in a round channel. Well-adhered Pt/γ-Al2O3 catalysts were then applied in a microreactor comprising parallelized microchannels made of FeCrAlloy under the optimized coating procedures, and investigated in terms of its performance in the catalytic methane combustion. It is shown that the reaction temperature has a greater influence on the methane conversion than the flow rate, and a favorable coverage of methane and oxygen on the catalyst surface is essential to obtain a good catalytic performance. These reaction results are in line with the temperature behavior measured along the microreactor.

Mass transfer was studied at the external electrode of a cylindrical electrochemical reactor with decaying swirling flow using a single phase electrolyte and also a dispersion of a gas phase in the solution. The local mass-transfer coefficients were measured with a segmented cathode using the reduction of ferricyanide as test reaction. Two strategies were used to introduce the gas phase. In the first case the gas was fed by three holes symmetrically drilled at the bottom of the central anode tube and in the second one by means of a tee fitting at the reactor inlet. The best performance was obtained with the single phase electrolyte giving 0.78 as the exponent of the Reynolds number and the mass-transfer distribution along the reactor length is more uniform than that reported for a parallel plate electrochemical reactor under laminar flow conditions. The mass-transfer enhancement factor related to an annular duct with axial developing flow ranges from 8 to 11. This high value is the consequence of two factors: (i) the intensive forced convection produced by the swirling flow at the outer electrode and (ii) the sudden expansion of the flow at the entrance due to the small tangential inlet. The fed of a gas phase in the reactor has scarce influence on the mass-transfer performance. A comparison of mass-transfer results with previous studies is made. Fil: Contigiani, Camila Cecilia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentina Fil: Gonzalez Perez, Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentina Fil: Bisang, Jose Maria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentina

International audience; A simple dynamic absorption procedure to assess the mass-transfer performances of a solvent toward a selected gaseous solute is presented. Absorption was operated semi-continuously at transient state until the equilibrium was reached without solvent recirculation. Four volatile organic compounds (VOC) more or less hydrophobic (toluene, acetone, dichloromethane, isopropanol) were absorbed in water and two heavy organic solvents (Bis(2-ethylhexyl) adipate DEHA and polydimethylsiloxane PDMS). A numerical resolution procedure was developed to simulate the gas-liquid mass-transfer and to deduce the VOC partition coefficients, expressed as the Henry’s law constants, as well as the overall liquid-phase mass-transfer coefficients. The overall liquid-phase mass-transfer coefficients were correlated to the diffusion coefficients using the Higbie penetration theory. The results confirm the high selectivity of water whereas the two organic solvents, especially DEHA, exhibit rather good affinity with all VOC even if the Henry’s law constants of the most soluble and the less soluble compounds for those solvents differ by 1 or 2 orders of magnitude. The liquid-film mass-transfer coefficients in the two organic solvents, even being more viscous, are larger than in water which confirms their good potential for hydrophobic VOC treatment.

A continuous-flow adsorption/desorption process for the recovery of phenolic compounds (PCs) from olive mill wastewaters (OMWs) was developed in a 0.53 m packed column, using a previously selected resin (Amberlite XAD16) and an actual OMW. The main goals of the study were (i) to evaluate the PC adsorption/desorption performances of XAD16 by means of adsorption isotherms and adsorption/desorption breakthrough tests, and (ii) to develop a reliable model of the process. A combination of centrifugation and microfiltration resulted necessary to attain a high suspended solid removal (98.5%) and thus avoid clogging of the packed bed. The quality of two packing procedures was evaluated by means of frontal analysis tests. XAD16 performed well in terms of both adsorption yield at 20% breakthrough (87–88%) and PC/COD selectivity (PC/COD adsorption constant = 7–9). The desorption solvent (acidified ethanol) was effectively regenerated by vacuum distillation. The adsorption breakthrough curves were successfully simulated with a 1-D convection/dispersion model with mass-transfer (R2 = 0.95–0.99; kLa = 0.8–2.5 · 10−3 1/s), whereas an equilibrium adsorption model with dispersion failed to predict the experimental data. In the perspective of a process scale-up, the simulation of the best-performing operational condition was used to evaluate the process performances for different column lengths (0.5–10 m). A precise and automated HPLC method for total PC measurement was developed and compared to the traditional Folin–Ciocalteu methodology. Further research is needed to optimize the desorption step, to scale up the process and to evaluate the long-term resin performances.

Falling film reactors represent the actual technology to run sulfonation reaction at pilot and industrial scale. The reaction is characterized by high thermal tenor, thus realizing a liquid reactive film flowing directly downwards on the internal reactor wall, it benefits of high heat exchange to the external jacket. The scale-up of such reactors is straightforward as it consists mainly on increasing the pipe numbers, with heat exchanger shell/pipe architecture. The main problem of this reactor solution is its modelling. The fluid-dynamics is complex to be fully described and the few models proposed in the literature lacks in rigorousness. The aim of the present work is the realization of a detailed reactor model able to describe sulfonation reaction in a falling film reactor. The simulations were compared with data collected on a pilot-plant.

Reactive chromatography is a special topic in chemical reaction engineering, consisting of the combination of chemical reaction and chromatographic separation. The main idea is to avoid a further separation unit, by performing reaction and separation in one unique equipment, allowing process intensification. This technology is usually applied in hydrolysis (or esterification) reactions, that undergoes through the reaching of chemical equilibrium. The chromatographic reactor application would lead to complete conversion, by separating reactants and products as the reaction proceeds. Modelling is certainly a delicate issue for chromatographic reactor to optimize the operation conditions, thus different approaches were published. The aim of the present work is to show a novel chromatographic reactor model, were all the physical and chemical phenomena involved and described by a rigorous approach. The fluid-dynamics was treated by axial dispersion approach, and the Peclet number values were obtained from dedicated experiments. The external fluid-solid mass transfer was calculated from existing correlations, demonstrating to be negligible for the modelled chromatographic reactor. The intraparticle mass diffusion was assumed to be the sum of two parallel contributions, i.e. porous and surface diffusivity. The model was tested on literature data for methyl acetate hydrolysis experiments with satisfactory results, obtaining reliable values of the surface diffusivity. A sensitivity analysis was conducted highlighting that the model can predict complete ester conversion and product separation.