Copper-Catalyzed Continuous-Flow Transfer Hydrogenation of Nitroarenes to Anilines: A Scalable and Reliable Protocol.

A robust supported catalyst that is made up of copper nanoparticles on Celite has been successfully prepared for the selective transfer hydrogenation of aromatic nitrobenzenes to anilines under continuous flow. The method is efficient and environmentally benign thanks to the absence of hydrogen gas and precious metals. Long-term stability studies show that the catalytic system is able to achieve very high nitrobenzene conversion (>99%) when working for up to 145 h. The versatility of the transfer hydrogenation system has been tested using representative examples of nitroarenes, with moderate-to-excellent yields being obtained. The packed bed reactor (PBR) permits the use of a setup that can provide products via simple isolation by SPE without the need for further purification. The recovery and reuse of either EG or the ion-exchange resin leads to consistent waste reduction; therefore, E-factor distribution analysis has highlighted the environmental efficiency of this synthetic protocol.

The interplay between nucleation and patterning during shear-induced crystallization from solution in a parallel plate geometry.

Cooling crystallization of small organic molecules from solution is an important operation for the separation and purification of drug products. In this research, shear-induced nucleation from a supersaturated solution is studied in a parallel plate geometry. Under conditions of shear and small gap sizes, narrow mesoscale circular bands of small crystals appeared spontaneously and reproducibly on the plate's surface. We have investigated the connection between nucleation and the emergence of these circular patterns. Our results show that nucleation occurs preferably in zones with high local shear rate (located at the outer edges of the plates), compared to zones with low local shear rate (at the center of the plates). The time before nucleation occurs decreases significantly for increasing mean shear rate and time. The circular crystalline patterns appear at the plate's surface, where heterogeneous nucleation first occurs. Multiple hypotheses are explored to understand the pattern formation in crystallization. Since no satisfactory explanation is found, a new mechanism is proposed. This hypothesis involves crystals initially forming on the surface of the plates and undergoing stick-slip motion, which influences the local nucleation kinetics. This results in an interplay between (secondary) nucleation and stick-slip motion at the start of the crystallization process. By modifying the surface of the plates, their ability to act as a heterogeneous nucleation site can be altered, allowing control over the formation of patterns.

An immersive virtual reality learning environment with CFD simulations: Unveiling the Virtual Garage concept.

Virtual reality has become a significant asset to diversify the existing toolkit supporting engineering education and training. The cognitive and behavioral advantages of virtual reality (VR) can help lecturers reduce entry barriers to concepts that students struggle with. Computational fluid dynamics (CFD) simulations are imperative tools intensively utilized in the design and analysis of chemical engineering problems. Although CFD simulation tools can be directly applied in engineering education, they bring several challenges in the implementation and operation for both students and lecturers. In this study, we develop the "Virtual Garage" as a task-centered educational VR application with CFD simulations to tackle these challenges. The Virtual Garage is composed of a holistic immersive virtual reality experience to educate students with a real-life engineering problem solved by CFD simulation data. The prototype is tested by graduate students (n = 24) assessing usability, user experience, task load and simulator sickness via standardized questionnaires together with self-reported metrics and a semi-structured interview. Results show that the Virtual Garage is well-received by participants. We identify features that can further leverage the quality of the VR experience with CFD simulations. Implications are incorporated throughout the study to provide practical guidance for developers and practitioners.

Understanding the ultrasound field of high viscosity mixtures: Experimental and numerical investigation of a lab scale batch reactor.

In this work, mixtures of increasing viscosity (from 0.9 to ≈720 mPas) are sonicated directly using an ultrasonic horn at 30 kHz to investigate the effect of viscosity on the ultrasound field both from an experimental and numerical point of view. The viscosity of the mixtures is modified by preparing water-polyethylene glycol solutions. The impact of the higher viscosity on the acoustic pressure distribution is studied qualitatively and semi-quantitatively using sonochemiluminescence. The velocity of light scattering particles added in the mixtures is also explored to quantify acoustic streaming effects using Particle Image Velocimetry (PIV). A numerical model is developed that is able to predict cavitationally active zones accounting for both thermoviscous and cavitation based attenuation. The results show that two cavitation zones exist: one directly under the horn tip and one around the part of the horn body that is immersed in the liquid. The erosion patterns on aluminum foil confirm the existence of both zones. The intensity of the cavitationally active zones decreases considerably with increasing viscosity of the solutions. A similar reduction trend is observed for the velocity of the particles contained in the jet directly under the tip of the horn. Less erratic flow patterns relate to the high viscosity mixtures tested. Finally, two numerical models were made combining different boundary conditions related to the ultrasonic horn. Only the model that includes the radial horn movements is able to qualitatively predict well the location of the cavitation zones and the decrease of the zones intensity, for the highest viscosities studied. The current findings should be taken into consideration in the design and modelling phase of horn based sonochemical reactors.

Insight Into Solventless Production of Hydrophobically Modified Ethoxylated Urethanes (HEURs): The Role of Moisture Concentration, Reaction Temperature, and Mixing Efficiency.

In this work, we report for the first time on the influence of the quality of reactants and reaction conditions on the production of hydrophobically modified ethoxylated urethanes (HEURs) and selected prepolymers without the use of solvents. We show that the polyol water concentration is detrimental to the progress of the main urethane forming reaction, confirming the necessity of carefully drying the reactants below 1000 ppm to suppress the consumption of diisocyanate toward urea during HEUR synthesis. Increasing the mixing speed (≈30 to 750 rpm), reaction temperature (80-110 °C), and catalyst concentration (0.035-2.1 wt % bismuth carboxylate) can significantly increase the rate of molecular weight buildup, but their effect decreases with time as the bulk viscosity increases and mixing limitations eventually take over, leading to the Weissenberg effect and chain growth termination. Consequently, for the selected formulation, the maximum product molecular weight attained lies in the range of ≈20 000-22 000 g/mol, irrespective of the specific process conditions applied.

Droplet size distribution, atomization mechanism and dynamics of dental aerosols.

Since the outbreak of COVID-19 pandemic, maintaining safety in dental operations has challenged health care providers and policy makers. Studies on dental aerosols often focus on bacterial viability or particle size measurements inside dental offices during and after dental procedures, which limits their conclusions to specific cases. Fundamental understanding on atomization mechanism and dynamics of dental aerosols are needed while assessing the risks. Most dental instruments feature a build-in atomizer. Dental aerosols that are produced by ultrasonic or rotary atomization are considered to pose the highest risks. In this work, we aimed to characterize dental aerosols produced by both methods, namely by Mectron PIEZOSURGERY® and KaVo EXPERTtorque™. Droplet size distributions and velocities were measured with a high-speed camera and a rail system. By fitting the data to probability density distributions and using empirical equations to predict droplet sizes, we were able to postulate the main factors that determine droplet sizes. Both dental instruments had wide size distributions including small droplets. Droplet size distribution changed based on operational parameters such as liquid flow rate or air pressure. With a larger fraction of small droplets, rotary atomization poses a higher risk. With the measured velocities reaching up to 5 m s-1, droplets can easily reach the dentist in a few seconds. Small droplets can evaporate completely before reaching the ground and can be suspended in the air for a long time. We suggest that relative humidity in dental offices are adjusted to 50% to prevent fast evaporation while maintaining comfort in the office. This can reduce the risk of disease transmission among patients. We recommend that dentists wear a face shield and N95/FFP2/KN95 masks instead of surgical masks. We believe that this work gives health-care professionals, policy makers and engineers who design dental instruments insights into a safer dental practice.

Continuous Counter-Current Ionic Liquid Metathesis in Mixer-Settlers: Efficiency Analysis and Comparison with Batch Operation.

Following the initial cation formation, the synthesis of ionic liquids (ILs) often involves an anion-exchange or metathesis reaction. For hydrophobic ILs, this is generally performed through several cross-current contacts of the IL with a fresh salt solution of the desired anion. However, if a large number of contacts is required to attain an adequate conversion, this procedure is not economical because of the large excess of the reagent that is consumed. In this study, the metathesis of an IL, Aliquat 336 or [A336][Cl], to ILs with other anions ([A336][X] with X = HSO4 -, Br-, NO3 -, I-, and SCN-) was studied in a continuous counter-current mixer-settler setup. McCabe-Thiele diagrams were constructed to estimate the required number of stages for quantitative conversion. Significantly higher IL conversions were achieved, combined with reduced reagent consumption and waste production. This improvement in efficiency was most pronounced for anions placed low in the Hofmeister series, for example, HSO4 -, Br-, and NO3 -, which are difficult to exchange. The performance of the counter-current experiments was compared with the conventional multistep cross-current batch process by calculating the reaction mass efficiency (RME) and the environmental factor (E-factor). The RMEs of the cross-current experiments were notably smaller, that is, 38-78% of the values observed for the counter-current experiments. The E-factors of the counter-current experiments were a factor of 2.0-6.8 smaller than those of the cross-current experiments. These sustainability metrics indicate a highly efficient reagent use and a considerable, simultaneous decrease in waste production for the counter-current IL metathesis reactions.

Determination of Chlorides in Ionic Liquids by Wavelength Dispersive X-ray Fluorescence Spectrometry.

The synthesis of ionic liquids (ILs) usually involves two steps: (i) quaternization of a precursor followed by (ii) a salt metathesis reaction to introduce the desired anion. A consequence of the second step is that most ILs still contain some amount of the initial anion, often chloride. In this work, wavelength dispersive X-ray fluorescence (WDXRF) spectrometry is presented for the direct measurement of chlorides in ILs. The WDXRF settings were optimized, and the system was calibrated for the detection of chloride in several analogues of the commercially available IL Aliquat 336, [A336][X] (with X = I-, Br-, NO3 -, or SCN-). The Cl Kα intensity showed excellent linearity for samples with a conversion >0.80 (approximately Cl < 8000 ppm). Synthetic quality control samples showed that the instrumental error and deviations induced by the calibration procedure were small with maximum values of 1 and 5%, respectively. Detection and quantification limits depended strongly on the matrix (i.e., anion system and dilution) but were relatively low: 42-191 and 127-578 ppm Cl, respectively. Compared with other analytical techniques used for this purpose, the strengths of WDXRF include its ease of use, rapid measurements, the near absence of sample preparation steps, and versatility in terms of anion systems and chloride concentration range.

Dawn of a new era in industrial photochemistry: the scale-up of micro- and mesostructured photoreactors.

Photochemical activation routes are gaining the attention of the scientific community since they can offer an alternative to the traditional chemical industry that mainly utilizes thermochemical activation of molecules. Photoreactions are fast and selective, which would potentially reduce the downstream costs significantly if the process is optimized properly. With the transition towards green chemistry, the traditional batch photoreactor operation is becoming abundant in this field. Process intensification efforts led to micro- and mesostructured flow photoreactors. In this work, we are reviewing structured photoreactors by elaborating on the bottleneck of this field: the development of an efficient scale-up strategy. In line with this, micro- and mesostructured bench-scale photoreactors were evaluated based on a new benchmark called photochemical space time yield (mol·day-1·kW-1), which takes into account the energy efficiency of the photoreactors. It was manifested that along with the selection of the photoreactor dimensions and an appropriate light source, optimization of the process conditions, such as the residence time and the concentration of the photoactive molecule is also crucial for an efficient photoreactor operation. In this paper, we are aiming to give a comprehensive understanding for scale-up strategies by benchmarking selected photoreactors and by discussing transport phenomena in several other photoreactors.

SANS study of mixed cholesteric cellulose nanocrystal - gold nanorod suspensions.

Self-assembly of cellulose nanocrystals (CNCs) doped with anisotropic gold nanorods (AuNRs) was studied by small-angle neutron scattering. Correlation distances and structured domains were analysed to determine the influence of CNC and AuNR concentration on structuring. The transfer of the nematic structure of CNCs to AuNRs is explained in terms of an entropy-driven evolution from an isotropic to a cholesteric phase, with small nematic domains already present in the "isotropic" phase in equilibrium with the chiral nematic phase.

Effect of ultrasound on leaching of lead from landfilled metallurgical residues.

The potential of ultrasound as a process intensification technique in the extraction of lead from a landfilled metallurgical residues is explored. The silent or non-sonicated process makes use of acidic sodium chloride as the leachate with lead leaching in the range of 45% if a three-stage process is followed. The mixture was sonicated in a batch setup manufactured in-house. The yield obtained in silent conditions at the end of 240 min was already obtained within 30 min with ultrasound, which by itself was an improvement of 8 times. The yield of the process as a whole was improved by 19-26%. The reason for this improvement was investigated with respect to the reaction kinetics. The physical effect of ultrasound on the particle size was also studied by laser diffraction analysis. Finally, the improvement when using ultrasound in a multi-stage process was studied and it was shown that yields being obtained at the end of the 3rd stage in silent conditions is already obtained in the second stage when using ultrasound with 20% more selectivity.

Effects of ultrasonic irradiation on crystallization kinetics, morphological and structural properties of zeolite FAU.

In this work, NaX zeolite was synthesized and the effect of ultrasound irradiation on reaction kinetics, morphological and structural properties was investigated. Ultrasound was applied, by using a plate transducer (91.8 kHz), for the first time during the crystallization of zeolite NaX, at high temperature, varying the irradiation moment and its duration. Furthermore, ultrasound was applied after the crystallization by a horn-type transducer (20-24 kHz) at low temperature. The effects of irradiated volume (100-300 mL), sonication time (2-10 min) and ultrasound power (10-200 W) were studied with a power intensity up to 100 W/cm2. It was found that the application of ultrasound during the first hour of crystallization resulted in 20% reduction of reaction time compared to a standard crystallization. Ultrasound can also reduce the agglomeration degree of the final powder by combining high power and long sonication time. After 5 min sonication time at 0.3 W/mL, the tapped density of the powder was increased by 10%, from 0.37 to 0.41 g/mL. Finally, by scanning electron microscopy (SEM) it was demonstrated that ultrasound can disrupt the agglomerates without affecting the morphology of individual crystals.

Dataset of lithium phosphate recovery from a low concentrated lithium-containing solution.

The lithium-containing solution is also rich in lithium after preparation of lithium carbonate. With the depletion of primary lithium resource, it is necessary to recovery lithium from a low concentrated lithium-containing solution which can solve the shortage of lithium resources and avoid the waste of lithium. In this article, the lithium phosphate is recovered from lithium-containing solution with a concentration of 2 g/L after preparation of lithium carbonate. The results show that by the application of ultrasound, the lithium recovery rate can be increased. The concentration of lithium is less than 0.3 g/L after preparation of lithium phosphate. For lithium carbonate recovery by ultrasound, please refer to the full length article entitled "Lithium carbonate recovery from lithium-containing solution by ultrasound assisted precipitation", https://doi.org/10.1016/j.ultsonch.2018.12.025 (Chunlong Zhao et al., 2019) [1].

Lithium carbonate recovery from lithium-containing solution by ultrasound assisted precipitation.

Lithium carbonate (Li2CO3), one of the most important lithium compounds, is usually prepared from lithium-containing solution. The lithium recovery rate and the purity of Li2CO3 are highly dependent on the lithium concentration. In order to get a high lithium recovery rate, high concentrated lithium-containing solution is required, while the purity of Li2CO3 can be low remaining a significant amount of impurities. Usually, it is not possible to obtain high purity Li2CO3 by single-step precipitation with a relatively high lithium recovery rate especially from a low concentrated lithium-containing solution. In this research, ultrasound is introduced to increase lithium recovery rate and prepare industrial grade Li2CO3. The research found that ultrasound can significantly reduce the polymerization of Li2CO3 crystal particles and promote dissociation of impurity ions. At the same time, ultrasound accelerates the nucleation process of Li2CO3 and boosts lithium recovery rate because of cavitation. The different parameters during the Li2CO3 precipitation process were systematically discussed. Under the optimized conditions, the lithium recovery rate can be increased by 12% with a global lithium recovery rate of 97.4%. Li2CO3 with a purity higher than industrial grade can be obtained by one-step precipitation. It demonstrates a potential pathway for effective lithium recovery from low concentrated lithium-containing solution and preparation of industrial grade Li2CO3.

Microbubbles as Heterogeneous Nucleation Sites for Crystallization in Continuous Microfluidic Devices.

Injecting a stream of microbubbles and thereby introducing a heterogeneous interface is proposed for enhancing nucleation and controlling particle formation in continuous microfluidic devices. Different gas and liquid flow rates were investigated to establish the two-phase flow regime map and to identify the optimum characteristics for microbubble flow. Subsequently, the effect of microbubbles was studied for the cooling crystallization of paracetamol. An enhanced nucleation rate compared to that in the operation without bubbles was observed and the presence of microbubbles results in the formation of more crystals, which indicates that nucleation is faster than that in operation without bubbles, i.e., the metastable zone width is reduced. Determining the crystal yield confirmed that a larger mass of crystals is obtained in a two-phase flow with microbubbles. Furthermore, results showed that the presence of microbubbles allows crystallizing continuously without clogging of the microreactor.

Ultrasound-assisted emerging technologies for chemical processes.

The chemical industry has witnessed many important developments during past decades largely enabled by process intensification techniques. Some of them are already proven at commercial scale (e.g. reactive distillation) while others (e.g. ultrasound-assisted extraction/crystallization/reaction) are on their way to becoming the next-generation technologies. This article focuses on the advances of ultrasound (US)-assisted technologies that could lead in the near future to significant improvements in commercial activities. The aim is to provide an authoritative discussion on US-assisted technologies that are currently emerging from the research environment into the chemical industry, as well as give an overview of the current state-of-the-art applications of US in chemical processing (e.g. enzymatic reactive distillation, crystallization of API). Sufficient information is included to allow the assessment of US-assisted technologies and the challenges for implementation, as well as their potential for commercial applications. © 2017 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

An accessible visible-light actinometer for the determination of photon flux and optical pathlength in flow photo microreactors.

Coupling photochemistry with flow microreactors enables novel synthesis strategies with higher efficiencies compared to batch systems. Improving the reproducibility and understanding of the photochemical reaction mechanisms requires quantitative tools such as chemical actinometry. However, the choice of actinometric systems which can be applied in microreactors is limited, due to their short optical pathlength in combination with a large received photon flux. Furthermore, actinometers for the characterization of reactions driven by visible light between 500 and 600 nm (e.g. photosensitized oxidations) are largely missing. In this paper, we propose a new visible-light actinometer which can be applied in flow microreactors between 480 and 620 nm. This actinometric system is based on the photoisomerization reaction of a diarylethene derivative from its closed to the open form. The experimental protocol for actinometric measurements is facile and characterized by excellent reproducibility and we also present an analytical estimation to calculate the photon flux. Furthermore, we propose an experimental methodology to determine the average pathlength in microreactors using actinometric measurements. In the context of a growing research interest on using flow microreactors for photochemical reactions, the proposed visible-light actinometer facilitates the determination of the received photon flux and average pathlength in confined geometries.

Applications of ultrasound to chiral crystallization, resolution and deracemization.

Industrial synthesis of enantiopure compounds is nowadays heavily based on the separation of racemates through crystallization processes. Although the application of ultrasound in solution crystallization processes (sonocrystallization) has become a promising emerging technology, offering several benefits (e.g. reduction of the induction time and narrowing of the metastable zone width, control over the product size, shape and polymorphic modification), little attention has been paid so far to the effects of ultrasound on chiral crystallization processes. Several recent studies have reported on the application of acoustic energy to crystallization processes that separate enantiomers, ranging from classical (diastereomeric) resolution and preferential crystallization to new and emerging processes such as attrition-enhanced deracemization (Viedma ripening). A variety of interesting effects have been observed, which include among others, enhanced crystallization yield with higher enantiomeric purity crystals, spontaneous mirror symmetry breaking crystallization, formation of metastable conglomerate crystals and enhanced deracemization rates. The objective of this review is to provide an overview of the effects of ultrasound on chiral crystallization and outline several aspects of interest in this emerging field.

Effect of fluid properties on ultrasound assisted liquid-liquid extraction in a microchannel.

When immiscible liquids are subjected to an ultrasonic field, they form emulsions. This principle has been used to improve the mass transfer characteristics of a liquid-liquid extraction process in microreactor systems. The formation of emulsion and its characteristics are prominently dependent on the properties of the liquids used and this also holds true for emulsion brought about by ultrasound. This paper focuses on the properties of fluids that are reported to have an influence on the cavitation behaviour, namely viscosity, interfacial tension and vapour pressure. These properties were examined by changing the solvent of the organic phase in the hydrolysis of p-nitrophenyl acetate. The study is performed by comparing pairs of solvents that are different in one property but similar in the other two. The pairs selected are toluene - chlorobenzene for viscosity, toluene - methyl Isobutyl ketone for interfacial tension and methyl isobutyl ketone - 2-Methyl tetrahydrofuran for vapour pressure effects. A qualitative study was performed with a high-speed camera in flow to understand the emulsification initiation mechanisms and behaviours. These findings were further explored by performing the sonicated emulsion in a batch-sonicated reactor. The quantitative analysis of the fluid properties was evaluated and compared based on the relative percentage increase in yield upon sonication with respect to their individual silent conditions. The quantitative results were further supported by the quantification of the emulsion performed with an FBRM probe. The results indicate a two times improvement in yield with solvent of lower viscosity as 2 times more droplets were formed in the emulsion. Both the solvent systems with higher interfacial tension and vapour pressure had an improved yield of 1.4 times owing to larger number of droplets formed.

Non-innocent probes in direct sonication: Metal assistance in oxidative radical CH functionalization.

Direct sonication by means of ultrasound horns constitutes a widely used technique in chemical process technology. However, the direct contact between the metal probe and the reaction mixture does not always leave the chemical system unaffected. In this report, we study the tert-butyl hydroperoxide-mediated trifluoromethylation of heterocyclic structures, and the influence of sonication thereon. Metal leaching is observed during the process and further examined, showing that several metals can interfere significantly with the chemical reaction under study. Notably, vanadium metal was found to increase the reaction rate exceptionally well, rendering it a useful additive for this type of reactions. Ultimately, some mechanistic considerations are offered, to provide more insight into the nature of the catalytic effect of leached metals.