Search Results (10)

Microreactor technology is seen as a promising approach to achieve green and sustainable synthesis in chemical fields because of the significant process intensification and fine control over reaction parameters caused by the miniaturization of reactor scale. The incorporation of solid catalysts as a packed bed in microreactors opens numerous opportunities for the efficient heterogeneous catalysis that plays a pivotal role in many industrially relevant chemical processes. In this review, the recent development in the use of packed bed microreactors as a versatile research tool and intensified production unit will be highlighted in the application areas including the synthesis of valuable chemicals and fuels, high-throughput catalyst screening, and kinetic/chemistry investigation. Selected reaction examples involving different reactant phases and catalyst categories will be particularly discussed, with an emphasis on the reactor performance in relation to the fundamental chemistry and engineering principles under microflow. In the end, future challenges and the outlook of packed bed microreactors for sustainable chemistry and process development will be provided. Full article

The application of ultrasonic waves in the processing of hydrocarbons is a new promising technology that has developed rapidly in recent years. However, the acoustic-induced cavitation erosion phenomenon is poorly studied. In this paper, a comparison study of cavitation erosion was carried out in water and oils with different viscosities produced from Ashal’cha and North Komsomol using an ultrasonic reactor operating at an industrial frequency of 20 kHz. The acoustic spectra obtained from hydrophones during the ultrasonic treatment of fluids can be characterized by using subharmonics of the main frequency and a continuous white noise level. Moreover, the cavitation erosion of aluminum foil under various ultrasound irradiation times and power levels was thoroughly investigated. It has been found that the process of ultrasonic cavitation has a less erosive impact on metal foil in oil due to its high viscosity. In addition, the formation of microflows in the oil phase, which also intensify the erosion process, is hindered. Cavitation erosion in the Ashal’cha oil sample exhibited a higher intensity compared to that in the North Komsomol oil sample. It was found that upon increasing ultrasound intensity in the case of the viscous (Ashal’cha) oil sample, cavitation stability was disrupted. In turn, this led to a reduction in the collapse energy of the cavitation bubbles. The results we obtained enable the assessment of cavitation erosion in crude oil and could be used to improve methodologies for monitoring and optimizing cavitation processes in crude oil. Full article

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. Full article

Heterogeneous catalysis plays a central role in the chemical and energy fields, owing to the high and tunable activities of solid catalysts that are essential to achieve the favorable reaction process efficiency, and their ease of recycle and reuse. Numerous research efforts have been focused on the synthesis of solid catalysts towards obtaining the desired structure, property and catalytic performance. The emergence and development of microfluidic reactor technology provide a new and attractive platform for the controllable synthesis of solid catalysts, primarily because of its superior mixing performance and high heat/mass transfer efficiency. In this review, the recent research progress on the synthesis of solid catalysts based on microfluidic reactor technology is summarized. The first section deals with the synthesis strategies for solid catalysts, including conventional methods in batch reactors and microfluidic alternatives (based on single- and two-phase flow processing). Then, different kinds of solid catalysts synthesized in microflow are discussed, especially with regard to the catalyst type, synthetic process, structure and property, and catalytic performance. Finally, challenges in the microreactor operation and scale-up, as well as future perspectives in terms of the synthesis of more types of catalysts, catalyst performance improvement, and the combination of catalyst synthesis process and catalytic reaction in microreactors, are provided. Full article

The hydrogenation of polyaromatic compounds (PACs) present in mineral oils is of great importance when it comes to the desired product properties and the minimization of health hazards; however, the presence of organonitrogen inhibits the conversion of these compounds. In this study, the inhibition effects of different types of organonitrogen compounds (acridine (ACR) and carbazole (CBZ)-basic and nonbasic organonitrogen) on the hydrodearomatization (HDA) of phenanthrene over a sulfided commercial NiMo/Al₂O₃ catalyst were investigated in a microflow trickle-bed reactor at a temperature range of 280 to 320 °C and at a total pressure of 120 barg. Analysis of the experimental results shows that the hydrogenation of phenanthrene is significantly decreased in the presence of organonitrogen, with acridine showing stronger inhibiting effects. The extent of hydrodenitrogenation (HDN) is shown to correlate with the inhibition degree with a higher extent of HDN being achieved for carbazole than for acridine. Results from co-feeding different nitrogen types (acridine and carbazole) indicate that basic nitrogen is the dominating type of organonitrogen inhibitor. Recovery of catalyst activity in the absence of organonitrogen indicates fully reversible deactivation suggesting that inhibition relates to competitive adsorption and slower reaction rate of HDN compared to HDA. Full article

On the basis of earlier results with furan and thiophene derivatives of benzobicyclo[3.2.1]octadiene, photocatalytic oxygenation of novel furo- and thieno heterostilbenes with water-soluble manganese(III) porphyrins offered suitable possibilities to study their reactivities and reaction pathways depending on the heteroatom and the catalyst charge. The experiments were carried out in two reactors types (batch and microflow) to investigate the geometric effects. NMR spectroscopy, GC, and UPLC/MS analyses were applied for identification and quantification of the products. As our results indicated, the 2-thienyl and the common p-tolyl groups in the starting compounds remained intact due to their stronger aromaticity. Hence, the thieno derivative underwent oxygenation only at the open-chain part of the molecule, and the rates of its reactions were much lower than those of the furyl analogue. The less stable furan ring was easily oxygenated, its products with highest ratios were 2-furanon derivatives. Epoxide formation occurred at the open-chain parts of both substrates preferably by the anionic catalyst. Nevertheless, the conversion rates of the substrates were higher with the cationic porphyrin, according to electrophilic attacks by photogenerated Mn(V)=O species. Additionally, the reactions were significantly faster in microflow reactors due to the more favorable circumstances of mass transfer, diffusion, and light penetration. Full article

Photochemistry involves processes in which light, the principal reagent, and photocatalysts open pathways to diversifying photochemical products. Promising results are obtained in reactions where porphyrin complexes coordinated with certain metals are used as catalysts. The most common porphyrin complexes used in various organic reactions were manganese porphyrins. Nowadays, batch reactors used for photochemical reactions are commonly replaced with flow reactors. Microflow reactors are one of the reactor types, whose main characteristic is the micro-dimension of channels (max. diameter of 500 μm). Flow chemistry performed on a microscale brings improvements in many aspects of photochemical reactions, such as efficient and fast phase mixing and heat transfer, precise retention time control, homogeneous use of light irradiation throughout the reaction mixture, process safety, and potentially simple scale-up. In this research, anionic/cationic manganese(III) porphyrins were used as photocatalysts. The reactions were first performed in a batch reactor, where complete conversion of the substrate was observed after 2 h for furostilbene and 16 h for thienostilbene substrate. As a result, the formation of formyl, epoxy, carbonyl, or hydroxy derivatives was observed. A step forward in process development was made by replacing batch with microflow reactors. A total of four different tubular microflow reactors were studied and compared with results obtained in a batch reactor based on substrate conversion and reaction time. Reactions were significantly accelerated in the microflow reactors, where the complete substrate conversion for furostilbene substrate was observed in a residence time of 0.7 min and for thienostilbene substrate in 3.5 min. Full article

Developments that result in high-yielding, low-cost, safe, scalable, and less-wasteful processes are the most important goals in synthetic organic chemistry. Continuous-flow reactions have garnered much attention due to many advantages over conventional batch reactions that include precise control of short reaction times and temperatures, low risk in handling dangerous compounds, and ease in scaling up synthesis. Combinations of continuous-flow reactions with homogeneous, metal-free catalysts further enhances advantages that include low-cost and ready availability, low toxicity, higher stability in air and water, and increased synthetic efficiency due to the avoidance of the time-consuming removal of toxic metal traces. This review summarizes recently reported continuous-flow reactions using metal-free homogeneous catalysts and classifies them either as acidic catalysts, basic catalysts, or miscellaneous catalysts. In addition, we compare the results between continuous-flow conditions and conventional batch conditions to reveal the advantages of using flow reactions with metal-free homogeneous catalysts. Full article

In this work, the kinetics of Meerwein–Ponndorf–Verley chemoselective reduction of carbonyl compounds was studied in monolithic continuous-flow microreactors. To the best of our knowledge, this is the first report on the MPV reaction kinetics performed in a flow process. The microreactors are a very attractive alternative to the batch reactors conventionally used in this process. The proposed micro-flow system for synthesis of unsaturated secondary alcohols proved to be very efficient and easily controlled. The microreactors had reactive cores made of zirconium-functionalized silica monoliths of excellent catalytic properties and flow characteristics. The catalytic experiments were carried out with the use of 2-butanol as a hydrogen donor. Herein, we present the kinetic parameters of cyclohexanone reduction in a flow reactor and data on the reaction rate for several important ketones and aldehydes. The lack of diffusion constraints in the microreactors was demonstrated. Our results were compared with those from other authors and demonstrate the great potential of microreactor applications in fine chemical and complex intermediate manufacturing. Full article

Although studies about the origin of life are a frontier in science and a number of effective approaches have been developed, drawbacks still exist. Examples include: (1) simulation of chemical evolution experiments (which were demonstrated for the first time by Stanley Miller); (2) approaches tracing back the most primitive life-like systems (on the basis of investigations of present organisms); and (3) constructive approaches for making life-like systems (on the basis of molecular biology), such as in vitro construction of the RNA world. Naturally, simulation experiments of chemical evolution under plausible ancient Earth environments have been recognized as a potentially fruitful approach. Nevertheless, simulation experiments seem not to be sufficient for identifying the scenario from molecules to life. This is because primitive Earth environments are still not clearly defined and a number of possibilities should be taken into account. In addition, such environments frequently comprise extreme conditions when compared to the environments of present organisms. Therefore, we need to realize the importance of accurate and convenient experimental approaches that use practical research tools, which are resistant to high temperature and pressure, to facilitate chemical evolution studies. This review summarizes improvements made in such experimental approaches over the last two decades, focusing primarily on our hydrothermal microflow reactor technology. Microflow reactor systems are a powerful tool for performing simulation experiments in diverse simulated hydrothermal Earth conditions in order to measure the kinetics of formation and degradation and the interactions of biopolymers. Full article