Biodiesel, which was earlier used only as an alternative fuel, is now an indispensable component of commercial diesel. Conventional production processes are unable to cope with the increasing demand for biodiesel, and therefore more and more work is being done to intensify the existing processes. The intensification of the biodiesel production process, taking into account the environmental and economic factors, is based on increasing productivity. One way to achieve that is by reducing the volume of production units. The application of the enzymatic reaction path, while reducing the volume of process equipment to the micro-level, has significantly magnified the productivity of the biodiesel production process, which is primarily due to better mass transfer in microsystems. Additional breakthrough is the use of deep eutectic solvents (DES) instead of buffers for enzyme stabilization. In this study, a lipase from Thermomyces lanuginosus (TlL) (both commercial and produced by solid-state fermentation) was used as a catalyst for biodiesel production. Edible and waste sunflower oil, as well as methanol, were used as substrates. The reaction mediums were buffer and DES. The transesterification reaction was carried out in a batch reactor and the emphasis was made on different microreactor configurations. The highest yield of 32% for residence time of only τ = 30 min was obtained in the microreactor system with an emulsion of waste oil and a commercial enzyme suspended in a buffer. This indicates that enzymatic transesterification could be a valuable reaction path for dealing with waste oils. Furthermore, biodiesel synthesis in DES showed somewhat lower yields, but by increasing the water content in the system, the reaction could prove much better results. In the end, the effects of reaction conditions on the volumetric productivity of the process were analyzed.
A simple and efficient protocol is utilized for the transformation studies of a thiophene analog of E-resveratrol by photocatalytic oxygenation using an anionic and a cationic free-base porphyrin, as well as their manganese(III) complexes. The starting substrate was chosen as a representative of heterostilbenes with proven good antioxidant activity. The experiments were carried out in two photoreactor types (batch and microflow reactor) to investigate the impact of the reactor type and design on conversion and photoproduct composition. NMR spectroscopy and UHPLC/MS analyses were applied for the identification and quantification of four photoproducts (Z-1, 2, 3, and 4), results of isomerization, dimerization, cyclization, and oxygenation. Different yields of photoproducts were obtained in a batch reactor and microflow reactor. In the experiments performed in a microflow reactor, Z-1 was most dominant because it was constantly removed from the reaction mixture. Therefore, the formation of other products (2, 3, 4, and undefined) whose precursor is Z-1 was avoided. This was not the case in the experiments performed in a batch reactor. Additionally, all the reactions tested were significantly accelerated in a microflow reactor, making it the preferred reactor type and design for the photocatalytic transformation of resveratrol derivative.
In this research, optimization of the integrated biodiesel production process composed of transesterification of edible sunflower oil, catalyzed by commercial lipase, with simultaneous extraction of glycerol from the reaction mixture was performed. Deep eutectic solvents (DESs) were used in this integrated process as the reaction and extraction media. For two systems, choline chloride:glycerol (ChCl:Gly) and choline chloride:ethylene glycol (ChCl:EG), respectively, the optimal water content, mass ratio of the phase containing the mixture of reactants (oil and methanol) with an enzyme and a DES phase (mass ratio of phases), and the molar ratio of deep eutectic solvent constituents were determined using response surface methodology (RSM). Experiments performed with ChCl:Gly resulted in a higher biodiesel yield and higher glycerol extraction efficiency, namely, a mass ratio of phases of 1:1, a mass fraction of water of 6.6%, and a molar ratio of the ChCl:Gly of 1:3.5 were determined to be the optimal process conditions. When the reaction was performed in a batch reactor under the optimal conditions, the process resulted in a 43.54 ± 0.2% yield and 99.54 ± 0.19% glycerol extraction efficiency (t = 2 h). Unfortunately, the free glycerol content was higher than the one defined by international standards (wG > 0.02%); therefore, the process was performed in a microsystem to enhance the mass transfer. Gaining the same yield and free glycerol content below the standards (wG = 0.0019 ± 0.003%), the microsystem proved to be a good direction for future process optimization.
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