Catalytic transformation of biomass derivatives to value-added chemicals and fuels in microreactors

Biomass is an abundantly available renewable carbon source with potential to (partially) replace fossil feedstocks for the production of chemicals and fuels. Although chemical and catalytic aspects of biomass transformations have been extensively reported up to this date, dedicated reactor engineering concepts are not widely examined yet. Continuous flow microreactors have received much research attention as a process intensification tool and may offer advantages for the catalytic conversion of biomass derivatives to value-added chemicals and fuels. In this thesis, the potential of microreactor technology for biomass transformations was assessed by investigating several case studies in different multiphase reaction systems. These case studies include the gas-liquid oxidation of benzyl alcohol to benzaldehyde and benzoic acid using a homogeneous Co/Mn/Br catalyst (Chapter 2), as well as the oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran, 5-formylfurancarboxylic acid and 2,5-furandicarboxylic acid using the same catalytic system (Chapter 3). In Chapter 4, the gas-liquid-solid hydrogenation of levulinic acid to γ-valerolactone was performed in a packed bed microreactor with a heterogeneous Ru/C catalyst. Finally, in Chapter 5, the esterification of oleic acid and 1-butanol to biodiesel was executed in a biphasic system using a free Rhizomucor Miehei lipase as the enzymatic catalyst that is active on the liquid-liquid interface

Aerobic oxidation of benzyl alcohol in a slug flow microreactor:Influence of liquid film wetting on mass transfer

Homogeneous Co/Mn/Br catalyzed aerobic oxidation of benzyl alcohol in acetic acid to benzaldehyde was performed in polytetrafluoroethylene microreactors operated under slug flow at temperatures up to 150°C and pressures up to 5 bar. Depending on the bubble velocity and length, a wetted or dewetted slug flow was observed, characterized typically by a complete or partially wetting liquid film around the bubble body. The latter flow suffered from a limited interfacial area for mass transfer. Experiments at temperatures up to ca. 90°C were under kinetic control given no product yield difference under wetted and dewetted slug flows and were used to establish a simplified kinetic expression (first order in benzyl alcohol and zero order in oxygen). This allows to develop a mass transfer model combined with an instantaneous reaction regime that well described the experimental results at higher temperatures where mass transfer was limiting in the dewetted slug flow

Physicochemical Phenomena in the Roasting of Cocoa (Theobroma cacao L.)

The quality of cocoa depends on both the origin of the cacao and the processing stages. The roasting process is critical because it develops the aroma and flavor, changing the beans’ chemical composition significantly by chemical reactions induced by thermal energy. Aspects have been identified as the main differences between bulk cocoa and fine cocoa, the effect of time and temperature on the formation of the flavor and aroma, and the differences between conductive heating in an oven, convective with airflow, and steam flow. Thermal energy initially causes drying, then non-enzymatic browning chemical reactions (Maillard reaction, Strecker degradation, oxidation of lipids, and polyphenols), which produce volatile and non-volatile chemical compounds related to the flavor and aroma of cocoa roasted. This review identified that the effect of the heating rate on the physicochemical conversion of cocoa is still unknown, and the process has not been evaluated in inert atmospheres, which could drastically influence the avoidance of oxidation reactions. The effect of particle size on the performance of product quality is still unknown. A more in-depth explanation of energy, mass, and chemical kinetic transfer phenomena in roasting is needed to allow a deep understanding of the effect of process parameters. In order to achieve the above challenges, experimentation and modeling under kinetic control (small-scale) are proposed to allow the evaluation of the effects of the process parameters and the development of new roasting technologies in favor of product quality. Therefore, this work seeks to encourage scientists to work under a non-traditional scheme and generate new knowledge

Experimental and modeling studies on the Ru/C catalyzed levulinic acid hydrogenation to γ–valerolactone in packed bed microreactors

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

Mass Transfer and Reaction Characteristics of Homogeneously Catalyzed Aerobic Oxidation of 5-Hydroxymethylfurfural in Slug Flow Microreactors

Oxidation of 5-hydroxymethylfurfural (HMF) using air or pure oxygen was performed in polytetrafluoroethylene capillary microreactors under gas–liquid slug flow, with Co/Mn/Br as the homogeneous catalyst in the acetic acid solvent. The temperature was varied from 90 to 165 °C at a pressure of 1 or 5 bar. At atmospheric pressure conditions (and 90 °C), acetaldehyde was further added as a co-oxidant to accelerate the reaction. At 150 °C, 5 bar oxygen and a residence time of 2.73 min, an HMF conversion of 99.2% was obtained, with the yields of 2,5-diformylfuran (DFF), 5-formylfurancarboxylic acid (FFCA) and 2,5-furandicarboxylic acid (FDCA) being 22.9%, 46.7%, and 23.8%, respectively. By operation under wetted slug flows and elevated partial oxygen pressures, mass transfer limitations and oxygen depletion in the microreactor could be eliminated. This allowed to run the microreactor under kinetically controlled conditions, where both the HMF consumption and DFF formation were found zero order in partial oxygen pressure and roughly first order in HMF. The total selectivity towards DFF/FFCA/FDCA was ca. 40% at low partial oxygen pressures due to the dominant occurrence of side reactions. By using pure oxygen at 5 bar the total selectivity was improved to 60–94%. The space time yields of DFF and FFCA in the microreactor exceeded those obtained in conventional (semi-)batch reactors at slightly elevated temperatures and pressures, due to the superior mass transfer and higher initial HMF concentrations in the microreactor. For highly efficient FDCA synthesis, more dedicated microreactor operations are needed to tackle its precipitation

Efficient depolymerization of lignin to biobased chemicals using a two-step approach involving ozonation in a continuous flow microreactor followed by catalytic hydrotreatment

Lignin is a promising feedstock for the replacement of conventional carbon sources for the production of chemicals and fuels. In this paper, results are reported for the depolymerization of various residual lignins in the absence of a catalyst by utilizing ozone. Reactions were performed in a microreactor setup ensuring high gas-liquid mass transfer rates, a low inventory of ozone, and straightforward scale-up possibilities. The ozonation is demonstrated using a representative model compound (vanillin) and various lignins (pyrolytic and organosolv) dissolved in methanol (2.5 wt %). Experiments were performed under ambient conditions, at gas-liquid flow ratios ranging from 30 to 90 and short residence times on the order of 12-24 s. Analyses of the products after methanol removal revealed the presence of (di)carboxylic acids, methyl esters, and acetals. Extensive depolymerization was achieved (i.e., up to 30% for pyrolytic lignin and 70% for organosolv lignins). Furthermore, a two-step approach in which the ozonated lignin is further hydrotreated (350-400 degrees C, 100 bar H-2, 4 h, Pd/C as catalyst) showed a substantial increase in depolymerization efficiency, yielding a 2.5-fold increased monomer yield in the product oil compared to a hydrotreatment step only

Process Intensification of Enzymatic Fatty Acid Butyl Ester Synthesis Using a Continuous Centrifugal Contactor Separator

Fatty acid butyl esters were synthesized from sunflower oil with 1-butanol using a homogeneous Rhizomucor miehei lipase in a biphasic organic (triglyceride, 1-butanol, hexane)– water (with enzyme) system in a continuous setup consisting of a cascade of a stirred tank reactor and a continuous centrifugal contactor separator (CCCS), the latter being used for integrated reaction and liquid–liquid separation. A fatty acid butyl ester yield up to 93% was obtained in the cascade when operated in a once-through mode. The cascade was run for 8 h without operational issues. Enzyme recycling was studied by reintroduction of the water phase from the CCCS outlet to the stirred tank reactor. Product yield decreased over time to an average of 50% of the initial value, likely due to accumulation of 1-butanol in water phase, loss of enzyme due to agglomeration, and the formation of a separate enzyme layer

Intensification and mass transfer characteristics of HMF oxidation using a Co/Mn/Br catalyst under mild conditions in a continuous flow micro-reactor

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