Flow Reactor Research Articles

Fine-tuning N-doped species of C catalysts for 98% current efficiency of electrocatalytic decarboxylation into hindered ether

Regulating the interaction between the substrate and electrode is crucial for maximizing catalytic performance. In this study, we developed a method for controlling the sintering temperature and introducing H2O2 post-treatment to modulate the N-doping of C catalysts, enhancing the interaction between the substrate and electrode to cause a radical reaction, thereby promoting electrocatalytic decarboxylation. When 10 g of feedstock was used, the electrocatalytic system exhibited 9.4- and 4.2-fold increases in productivity and current efficiency, respectively, compared with the conventional method. A systematic investigation combining experiments and theoretical calculations revealed that pyridine N-oxide units not only promote bridging adsorption of the substrate and the formation of a substrate-enriched electric layer but also the transfer of mass and electrons, generating more reactive carboxyl radicals. The electrocatalytic system delivers a current efficiency of 98%, which is exceptional compared to previously reported electrocatalysts. The system is in line with the development trend of the green chemical industry, combining flow reactors and photovoltaic technology. This study offers valuable insights and guidance for advancing electrocatalytic organic synthesis for future industrial applications.

Estimating errors in vehicle secondary aerosol production factors due to oxidation flow reactor response time

Abstract. Oxidation flow reactors used in secondary aerosol research do not immediately respond to changes in the inlet concentration of precursor gases because of their broad transfer functions. This is an issue when measuring the vehicular secondary aerosol formation in transient driving cycles because the secondary aerosol measured at the oxidation flow reactor outlet does not correspond to the rapid changes in the exhaust flow rate. Since the secondary aerosol production factor is determined by multiplying the secondary aerosol mass by the exhaust flow rate, the misalignment between the two leads to incorrect production factors. This study evaluates the extent of the error in production factors due to oxidation flow reactor transfer functions using synthetic and semi-synthetic exhaust emission data. It was found that the transfer-function-related error could be eliminated when only the total production factor of the full cycle was measured using constant-volume sampling. For shorter segments within a driving cycle, a narrower transfer function led to a smaller error. Even with a narrow transfer function, the oxidation flow reactor could report production factors that were more than 10 times higher than the reference production factors if the segment duration was too short.

Electrochemical Nitrate Reduction to Ammonia on CuCo Nanowires at Practical Level

AbstractElectrochemical reduction of nitrate (NO3RR) holds great promise for environmentally friendly ammonia production. Tandem catalysis is a promising strategy for boosting the NO3RR and inhibiting side effects, but it is still challenged by lacking well‐designed catalysts to drive this catalytic process. Herein, the study develops the CuCo branched nanowires (CuCo NW) catalyst, which efficiently converts NO3 − to NH3 on Co (111) and Cu (111) crystal facets through a tandem catalysis mechanism. The in situ grown CuCo NW on Cu foam demonstrates a remarkable Faraday efficiency of 90.3% at 1.0 A cm−2 and maintains stable operation for 200 h at 100 and 200 mA cm−2 in a flow reactor. Density functional theory calculations suggest that the initial absorption and subsequent deoxygenation of *NO3 on Co (111) leading to the formation of *NO2, followed by its transfer to Cu (111) and further conversion to *NH3, establish an optimal pathway by managing rate‐determining steps on individual surfaces for NO3RR. To showcase the practical application of the catalyst, the study further develops a scaling‐up prototype reactor for continuous ammonia production, realizing the gram‐level yield rate of 1474.09 mg h−1 and Faraday efficiency of 91.26% at practical‐level 20.0 A.

Ultrasonic reactor set-ups and applications: A review

Sonochemistry contributes to green science as it uses less hazardous solvents and methods to carry out a reaction. In this review, different reactor designs are discussed in detail providing the necessary knowledge for implementing various processes. The main characteristics of ultrasonic batch systems are their low cost and enhanced mixing; however, they still have immense drawbacks such as their scalability. Continuous flow reactors offer enhanced production yields as the limited cognition which governs the design of these sonoreactors, renders them unusable in industry. In addition, microstructured sonoreactors show improved heat and mass transfer phenomena due to their small size but suffer though from clogging. The optimisation of various conditions of regulations, such as temperature, frequency of ultrasound, intensity of irradiation, sonication time, pressure amplitude and reactor design, it is also discussed to maximise the production rates and yields of reactions taking place in sonoreactors. The optimisation of operating parameters and the selection of the reactor system must be considered to each application’s requirements. A plethora of different applications that ultrasound waves can be implemented are in the biochemical and petrochemical engineering, the chemical synthesis of materials, the crystallisation of organic and inorganic substances, the wastewater treatment, the extraction processes and in medicine. Sonochemistry must overcome challenges that consider the scalability of processes and its embodiment into commercial applications, through extensive studies for understanding the designs and the development of computational tools to implement timesaving and efficient theoretical studies.

Promoter Effect of Pt on Zr Catalysts to Increase the Conversion of Furfural to γ-Valerolactone Using Batch and Continuous Flow Reactors: Influence of the Way of the Incorporation of the Pt Sites.

The valorization of biomass and its transformation into fuels are highly interesting due to the abundance of biomass and its almost neutral carbon emissions. In this article, we show the production of γ-valerolactone (GVL), a valuable product, from furfural (FF), a compound that can be easily obtained from biomass. This FF to GVL transformation involves a catalytic cascade reaction with two hydrogenation steps. Pt and/or Zr supported on sepiolite catalysts have been prepared and tested in the FF transformation reaction. A physical mixture of a Zr-based and a Pt-based catalyst has reached a yield to GVL of ca. 50% after 16 h at 180 °C. This performance largely exceeds that obtained by each of the single Pt or single Zr metal catalysts independently, showing a strong synergistic effect. These data suggest that each metal (Pt and Zr) plays an important and complementary role in different reaction steps. Furthermore, the physical mixture appears to be much more efficient than bimetallic Pt/Zr catalysts synthesized with the same amount of metals. The role of the type of acidity and the oxidation state of the surface platinum species on the catalytic performance has been discussed. Moreover, this reaction has been carried out in batch and continuous flow reactors, and a comparative study between the two operation modes has been undertaken. A certain correlation between the catalytic results obtained by both operation modes has been found.

Influence of Heat Treatment on Microstructure Evolution and Yield Surfaces of Ni/PU Hybrid Foams

Metal foams are characterized by low weight, high resource efficiency, high relative stiffness, and exceptional energy absorption capacity under compressive load. Nickel/polyurethane (Ni/PU) hybrid foams consist of an open‐cell polyurethane foam coated with a layer of nickel produced by electrochemical deposition. The coating of the PU foams takes place in a flow reactor, in which the electrolyte is pumped through the foam at a defined flow velocity. The macromechanical properties of foam‐like structures depend on the structure of the skeleton, the inherent material properties and, in the case of Ni/PU hybrid foams, the properties of the electrochemically generated nickel layer. To influence their mechanical properties, the Ni/PU hybrid foams are subjected to heat treatment. In the given experimental setup, the parameters flow velocity, temperature, and duration of the heat treatment are each investigated at two different levels. Thus, interactions between the initial microstructure and the type of heat treatment are evaluated by means of X‐ray diffraction (XRD) and electron backscatter diffraction (EBSD) measurements. Interactions between initial mechanical properties and heat treatment are investigated by uniaxial compression tests and superimposed compression‐torsion tests. The knowledge gained is used to control the macromechanical properties of the hybrid foam.

Effect of internal structure of a batch-processing wet-etch reactor on fluid flow and heat transfer

Batch-processing wet-etch reactors are the key equipment widely used in chip fabrication, and their performance is largely affected by the internal structure. This work develops a three-dimensional computational fluid dynamics (CFD) model considering heat generation of wet-etching reactions to investigate the fluid flow and heat transfer in the wet-etch reactor. The backflow is observed below and above the wafer region, as the flow resistance in this region is high. The temperature on the upper part of a wafer is higher due to the accumulation of reaction heat, and the average temperature of the side wafer is highest as its convective heat transfer is weakest. Narrowing the gap between wafer and reactor wall can force the etchant to flow in the wafer region and then facilitate the convective heat transfer, leading to better within-wafer and wafer-to-wafer etch uniformities. An inlet angle of 60° balances fluid by-pass and mechanical energy loss, and it yields the best temperature and etch uniformities. The batch with 25 wafers has much wider flow channels and much lower flow resistance compared with that with 50 wafers, and thus it shows better temperature and etch uniformities. These results and the CFD model should serve to guide the optimal design of batch-processing wet-etch reactors.

Direct Measurements of Covalently Bonded Sulfuric Anhydrides from Gas-Phase Reactions of SO3 with Acids under Ambient Conditions.

Sulfur trioxide (SO3) is an important oxide of sulfur and a key intermediate in the formation of sulfuric acid (H2SO4, SA) in the Earth's atmosphere. This conversion to SA occurs rapidly due to the reaction of SO3 with a water dimer. However, gas-phase SO3 has been measured directly at concentrations that are comparable to that of SA under polluted mega-city conditions, indicating gaps in our current understanding of the sources and fates of SO3. Its reaction with atmospheric acids could be one such fate that can have significant implications for atmospheric chemistry. In the present investigation, laboratory experiments were conducted in a flow reactor to generate a range of previously uncharacterized condensable sulfur-containing reaction products by reacting SO3 with a set of atmospherically relevant inorganic and organic acids at room temperature and atmospheric pressure. Specifically, key inorganic acids known to be responsible for most ambient new particle formation events, iodic acid (HIO3, IA) and SA, are observed to react promptly with SO3 to form iodic sulfuric anhydride (IO3SO3H, ISA) and disulfuric acid (H2S2O7, DSA). Carboxylic sulfuric anhydrides (CSAs) were observed to form by the reaction of SO3 with C2 and C3 monocarboxylic (acetic and propanoic acid) and dicarboxylic (oxalic and malonic acid)-carboxylic acids. The formed products were detected by a nitrate-ion-based chemical ionization atmospheric pressure interface time-of-flight mass spectrometer (NO3--CI-APi-TOF; NO3--CIMS). Quantum chemical methods were used to compute the relevant SO3 reaction rate coefficients, probe the reaction mechanisms, and model the ionization chemistry inherent in the detection of the products by NO3--CIMS. Additionally, we use NO3--CIMS ambient data to report that significant concentrations of SO3 and its acid anhydride reaction products are present under polluted, marine and polar, and volcanic plume conditions. Considering that these regions are rich in the acid precursors studied here, the reported reactions need to be accounted for in the modeling of atmospheric new particle formation.

Degradation of Di (2-ethylhexyl) phthalic acid plasticizer in baijiu by a foam titanium flow reactor attached with hairpin-like structured peptide enzyme mimics

Because of the significant environmental and health hazards imposed by di(2-ethylhexyl) phthalate (DEHP), a common plasticizer, developing safe and green techniques to degrade DEHP plasticizer is of huge scientific significance. It has been observed that environmental contamination of DEHP may also induce serious food safety problems because crops raised in plasticizers contaminated soils would transfer the plasticizer into foods, such as Baijiu. Additionally, when plastic packaging or vessels are used during Baijiu fermentation and processing, plasticizer compounds frequently migrate and contaminate the product. In this study, hairpin-like structured peptides with catalytically active sites containing serine, histidine and aspartic acid were found to degrade DEHP. Furthermore, after incorporating caffeic acid molecules at the N-terminus, the peptides could be attached onto foam titanium (Ti) surfaces via enediol-metal interactions to create an enzyme-mimicking flow reactor for the degradation of DEHP in Baijiu. The structure and catalytic activity of peptides, their interaction with DEHP substrate and the hydrolysis mechanism of DEHP were discussed in this work. The stability and reusability of the peptide-modified foam Ti flow reactor were also investigated. This approach provides an effective technique for the degradation of plasticizer compounds.

Preparation of inorganic salt particles by reactive crystallization in an annular swirling flow reactor

This study investigates the performance of an annular conical swirling flow reactor in liquid–liquid reactions for the preparation of inorganic salt particles. Utilizing Particle Image Velocimetry (PIV) measurements and Computational Fluid Dynamics (CFD) simulations, it was observed that the conical design effectively inhibited the attenuation of swirling flow intensity along the axial direction, with the primary mass transfer region close to the central conical wall. In comparison to a stirred reactor, calcium carbonate particles synthesized in the swirling flow reactor exhibited more uniform morphology, smoother and defect-free surface. Notably, the average particle size remained consistently within 5–6 μm (excluding the 0.3 M feedstock), whereas stirring led to particles with an average size ranging from 8-11 μm. Analysis of the residence time distribution curve revealed minimal back mixing in the swirling flow reactor, ensuring nearly equal growth time for salt particles, thus yielding particles with a uniform size distribution. As a result, the swirling flow reactor presents compelling prospects for applications in reactive crystallization.

Decarboxylative Ketonization of Aliphatic Carboxylic Acids in a Continuous Flow Reactor Catalysed by Manganese Oxide on Silica.

The sustainable synthesis of long carbon chain molecules from carbon dioxide, water and electricity relies on the development of waste-free, highly selective C-C bond forming reactions. An example for such a power-to-chemicals process is the industrial-scale fermentation for the production of hexanoic acid. Herein, we describe how this product is transformed into 6-undecanone via decarboxylative ketonization using a heterogeneous manganese oxide/silica catalyst. The reaction reaches full conversion with near-complete selectivity when carried out in a continuous flow reactor, requires no solvent or carrier gas, and releases carbon dioxide and water as the only by-products. The reactor was operated for several weeks with no loss of reactivity, producing 7 kg of 6-undecanone from 10 g of catalyst and achieving a productivity of 1.135 kg per litre of reactor volume per hour. 6-Undecanone and other long-chain ketones accessible this way can be hydrogenated to industrially meaningful alkanes, or converted into valuable fatty acids via a hydrogenation/elimination/isomerizing hydrocarboxylation sequence.

Structural, surface and oxygen transport properties of Sm-doped Nd nickelates

Ruddlesden – Popper phases are promising materials for solid oxide fuel cell/electrolyzer air electrodes, oxygen separation membranes and other electrochemical devices due to their high oxygen mobility provided by a cooperative mechanism of oxygen migration involving both regular and highly-mobile interstitial oxygen. This work aims at studying structural, surface and oxygen transport properties of Sm-doped Nd nickelates sintered in a furnace at the temperatures in the range of 800–1250 °C and using electron beams at the temperatures in the range of 1150–1250 °C. Nd2-xSmxNiO4+δ, x = 0.2 and 0.4 are synthesized by a modified Pechini technique and characterized by X-ray diffraction, X-ray photoelectron spectroscopy and temperature-programmed isotope exchange of oxygen with C18O2 in a flow reactor. The phase composition studies show the ability to obtain single-phase materials at certain sintering conditions. Nd/Sm ratio on the surface is close to stoichiometric one, while (Nd + Sm)/Ni ratio on the surface is below stoichiometric. Such materials possess a high oxygen mobility (D⁎ up to ∼10−7 cm2/s at 700 °C).

Solvothermally Grown Oriented WO3 Nanoflakes for the Photocatalytic Degradation of Pharmaceuticals in a Flow Reactor.

Contamination by pharmaceuticals adversely affects the quality of natural water, causing environmental and health concerns. In this study, target drugs (oxazepam, OZ, 17-α-ethinylestradiol, EE2, and drospirenone, DRO), which have been extensively detected in the effluents of WWTPs over the past decades, were selected. We report here a new photoactive system, operating under visible light, capable of degrading EE2, OZ and DRO in water. The photocatalytic system comprised glass spheres coated with nanostructured, solvothermally treated WO3 that improves the ease of handling of the photocatalyst and allows for the implementation of a continuous flow process. The photocatalytic system based on solvothermal WO3 shows much better results in terms of photocurrent generation and photocatalyst stability with respect to state-of-the-art WO3 nanoparticles. Results herein obtained demonstrate that the proposed flow system is a promising prototype for enhanced contaminant degradation exploiting advanced oxidation processes.

Enhancing Aqueous Reversible Addition–Fragmentation Chain Transfer Photopolymerization in Continuous Flow Reactors with Hairy Hollow Conjugated Microporous Polymer Nanocomposites

Enhancing Aqueous Reversible Addition–Fragmentation Chain Transfer Photopolymerization in Continuous Flow Reactors with Hairy Hollow Conjugated Microporous Polymer Nanocomposites

Periodic Optimal Control of a Plug Flow Reactor Model with an Isoperimetric Constraint

We study a class of nonlinear hyperbolic partial differential equations with boundary control. This class describes chemical reactions of the type “A→\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$A \\rightarrow $$\\end{document} product” carried out in a plug flow reactor (PFR) in the presence of an inert component. An isoperimetric optimal control problem with periodic boundary conditions and input constraints is formulated for the considered mathematical model in order to maximize the mean amount of product over the period. For the single-input system, the optimality of a bang-bang control strategy is proved in the class of bounded measurable inputs. The case of controlled flow rate input is also analyzed by exploiting the method of characteristics. A case study is performed to illustrate the performance of the reaction model under different control strategies.

Carbon foam to enhance the performance of a slurry flow energy system used for hydrogen storage and transportation: An experimental investigation

A novel idea of using carbon foam (CF) is introduced to enhance the electrochemical performance of a slurry electrode system in a proton flow reactor system. Steam-activated and acid-washed Norit from peat is used as active charge carrier particles to prepare 15 wt% carbon slurry to be used in this study. The slurry flow rates in the experimental electrochemical system can be varied from 0 to 200 ml min−1, while using two channel widths of 1.6 cm and 2 cm to facilitate the slurry flow. Two sets of CFs with 10 pores per inch (PPI) and 5 PPI are used to understand the effect of introducing CFs with different pore sizes on the performance of slurry electrode. Slurry is charged slurry up to 100 C under constant application of 10 mA and 30 mA. After adding CF, the results show a significant drop in charging potential to generate both levels of current of 25% after using 5 PPI and 41% with 10 PPI. Furthermore, using the narrow channel flow of 1.6 cm and increasing the slurry flow rate from 100 ml min−1 to 150 ml min−1 lower the charging potential considerably by 19% and 21% (compared to base slurry) for 5 PPI and 10 PPI CF, respectively. Application of CF further enables the system to attain higher discharging time during the discharge cycle, and a maximum of 336% and 115% discharging capacity improvement is observed with 10 PPI and 5 PPI CF, respectively.

An optimization-free Fisher information driven approach for online design of experiments

Developing mathematical models used to elucidate reaction kinetics plays a crucial role in the design, control, and optimization of chemical processes. One of the most challenging tasks in kinetic model identification is the precise estimation of unknown kinetic model parameters. This challenge can be effectively addressed through the application of Model-Based Design of Experiments (MBDoE) techniques, which enable the design of experiments facilitating precise model parameter estimation with minimal runs and analytical resources. Nevertheless, MBDoE techniques rely on an optimization procedure that is susceptible to parametric uncertainty, making the design procedure computationally intensive and prone to issues of local optimality. MBDoE techniques are also employed in online procedures to expedite the identification of kinetic models in autonomous platforms. As a result, ensuring rapid convergence becomes imperative to mitigate numerical issues during operational processes. In this paper a Fisher Information Matrix Driven (FIMD) approach is introduced to tackle these challenges. The methodology integrates a sampling-based experimental design approach with experiment ranking based on FIM to select the most informative experiment at each iteration. The effectiveness of the proposed design methodology is examined and discussed via two different case studies of increasing complexity: a fed-batch reactor in which the fermentation of baker’s yeast is carried out and a nucleophilic aromatic substitution in a flow reactor system.

Selective Hydrogenation of Diethyl Malonate to 1,3-Propanediol Over Ga-Promoted Cu/SiO2 Catalysts With Enhanced Activity and Stability.

Cu catalysts with different compositions and different Cu and promoter contents were prepared by precipitation-gel method and studied for the selective hydrogenation of syngas or biomass-based diethyl malonate (DEM) to valuable 1,3-propanediol (1,3-PDO). The Ga-promoted 70Cu6Ga/SiO2 catalyst was found to exhibit the highest catalytic performance, achieving 100 % DEM conversion and 76.6 % 1,3-PDO selectivity under reaction conditions of 160 °C and 8 MPa H2. The 70Cu6Ga/SiO2 bimetallic catalyst also presented obviously better stability than that of the monometallic 70Cu/SiO2 catalyst in a continuous flow reactor over 180 h time-on stream. Characterization results showed that the incorporation of Ga increased the interaction between Cu and Ga species, hindered the full reduction of Cu2+ species, and thus increased the proportion of Cu+ and the number of Lewis acidic sites on the catalyst surface. The synergistic effect between Cu0 and Cu+ enhanced the adsorption and activation of ester carbonyl groups and their subsequent hydrogenation, eventually contributed to the outstanding performances of the CuGa/SiO2 bimetallic catalysts.

Measurement and Temperature Prediction from Ash Disposed in Landfills Using a Quasi-Adiabatic Flow Reactor

Measurement and Temperature Prediction from Ash Disposed in Landfills Using a Quasi-Adiabatic Flow Reactor

On the synthesis of diphenhydramine: Steady state kinetics, solvation effects, and in-situ Raman and benchtop NMR as PAT

Diphenhydramine is a first-generation antihistamine that is available over-the-counter to treat maladies such as allergic reactions and insomnia. Despite its ubiquity in society and high demand, the kinetics for either step of diphenhydramine synthesis have not been explored in detail. In this work, for the first step, a methodology has been devised to obtain kinetics from the heterogeneous halogenation of benzhydrol with hydrochloric acid in a batch reactor equipped with in-situ Raman probe and further verified with ex-situ low-field NMR spectroscopy. For the second step, the kinetics of etherification have been explored using a microfluidic flow reactor and at-line NMR spectroscopy in a variety of solvents. Arrhenius and Eyring parameters are determined for Step 2. We find that the reaction performance is well correlated with the acceptor number of the solvent indicating that the Lewis acidity of the solvent plays a significant role in the overall performance.