Synthesis of adipic acid (AA) through the oxidation of cyclohexanol and cyclohexanone (K/A oil) with nitric acid was conducted in a capillary microreactor system. Effects of the temperature, the nitric acid concentration, the volumetric flow rate ratio of nitric acid to K/A oil, and the capillary length on the selectivity and the product yield were investigated systematically to achieve optimal reaction conditions. Notably, a high yield of adipic acid (i.e., 90%) was achieved just in 6 seconds at 85℃ with the use of 55 wt% nitric acid. Gas components produced in this oxidation process and its total volumetric flow rate were determined under various operating conditions, which was beneficial for reaction mechanism characterization and process optimization. Finally, a kinetic model was established, which was of crucial theoretical significance and practical value for optimizing the reactor design and better understanding such fast and highly exothermic multiphase processes with abundant gas production.
Molecular mechanisms and process kinetics of crystallizing concomitant polymorphs remain poorly understood. Solvent-mediated phase transformation is often mistaken as concomitant crystallization, mainly due to the two processes sharing similar kinetic profiles. Herein, we developed a population balance model to simulate a concomitant crystallization process of two polymorphs of tolfenamic acid (TFA). The kinetic modeling aims to better understand concomitant crystallization and help guide form selection of such a molecular system. Crystallization kinetics of ethanolic TFA solutions were uncovered from induction time measurements, as well as seeded and unseeded crystallization experiments. Both experimental and simulation results demonstrate that the stable form I crystallizes concomitantly with the metastable form II. The faster growing form II results in an intermediate decline in the kinetic profile of form I composition in crystallized samples, a characteristic feature of the concomitantly crystallized system. A four-quadrant scheme of attainable polymorph outcome was simulated under various crystallization conditions.
We study the evaporation dynamics of multiple water droplets deposited in ordered arrays or randomly distributed (sprayed) on superhydrophobic substrates (SHP) and smooth silicone wafers (SW). The evaluation of mass of the droplets as a function of time shows a power-law behavior with exponent 3/2, and from the prefactor of the power-law an evaporation rate can be determined. We find that the evaporation rate on a SHP surface is slower than a normal surface for both single droplet and collection of droplets. By dividing a large droplet into more smaller ones, the evaporation rate increases and the difference between the evaporation rates on SHP and SW surfaces becomes higher. The evaporation rates depend also on the distance between the droplets and increase with increasing this distance.
Charged clay surfaces can impact the storage and mobility of hydrocarbon and water mixtures. Here, we use equilibrium molecular dynamics (MD) and nonequilibrium MD simulations to investigate hydrocarbon-water mixtures and their transport in slit-shaped illite nanopores. We construct two illite pore models with different surface chemistries: potassium-hydroxyl (PH) and hydroxyl-hydroxyl (HH) structures. In HH nanopore, we observe water adsorption on the clay surfaces. In PH nanopores, however, we observe the formation of water bridges because of the existence of a local, long-range electric field. Our NEMD simulations demonstrate that the velocity profiles across the pore depends strongly on water concentration, pore width and the presence or absence of the water bridge. This fundamental study provides a theoretical basis for understanding nanofluidics with charged surfaces and can be applied in such as biological processes, chemical and physical fields, and the oil and gas extraction in clay-rich formations.
Enzyme immobilization enhances the catalytic activity and stability of the enzyme, and also improves reusability. Metal organic frameworks (MOFs), which possess diversified structures and porosity, have been used as excellent carriers for enzyme immobilization. Pseudomonas fluorescens lipase (PFL) has been successfully immobilized onto MOFs by covalent cross-linking to obtain a series of immobilized lipase (PFL@MOFs). PFL@MOFs are used for catalytic enantioselective hydrolysis of 2-(4-hydroxyphenyl) propionic acid ethyl ester enantiomers (2-HPPAEE) in aqueous medium and transesterification of 4-methoxymandelic acid enantiomers (4-MMA) in organic medium. The experimental results indicated that PFL@Uio-66(Zr) exhibits excellent enzymatic catalysis performances and high enantioselectives. In addition, to increase catalytic activity and reusability, PFL is modified by the polyethylene glycol (PEG) to prepare PEG-modified lipase (PFL-PEG), then PFL-PEG is immobilized onto Uio-66(Zr) to prepare PFL-PEG@Uio-66(Zr), demonstrating better reusability and catalytic activity compared with PFL@Uio-66(Zr).
A new transport model is proposed for paraffin wax deposition onto a cold finger from flowing wax-containing oils. The model solves transient energy and mass balances simultaneously for a reversible first-order kinetic rate for precipitation of pseudo-single-component wax, and the effects of yield stress using a critical solid wax concentration to withstand flow-induced stress at the deposit-fluid interface, Cpi. The model can predict the time evolution of the deposit thickness, and the spatial and temporal evolution of temperature and wax concentration and was validated using experiments involving a cylindrical cold finger. We found that for oils with Cpi close to zero, the deposit thickness growth is dominated by heat transfer. However, mass transfer cannot be neglected as diffusion of wax into the deposit continues to take place even after the deposit has stopped growing. For oils with non-zero Cpi, the deposit growth is slow and accompanied by occasional sloughing.
Interfacial tension is an essential physical property in two phase flow and it changes due to the mass transfer. The measurement of dynamic interfacial tension (DIFT) in such condition is a difficult problem. In previous study (Zhou at al., Chem Eng Sci. 2019; 197:172-183), we presented the quantitative relation between the droplet breakup frequency function (DBFF) and interfacial tension. It is found that the DBFF is highly depends on interfacial tension. Therefore the DBFF is a suitable parameter to quantitatively characterize the interfacial tension. Based on this concept, the DIFT in the column is determined by regression method after the DBFF under mass transfer condition is measured. It is found that the DIFT is smaller than the static interfacial tension. This result indicates that interphase mass transfer leads to decreasing of the interfacial tension. The decreasing extent of the DIFT has a positive correlation with the mass transfer flux.
In this letter, we investigate the rebound dynamics of two equally sized droplets simultaneously impacting a superhydrophobic surface via lattice Boltzmann method (LBM) simulations. We discover three rebound regimes depending on the droplet distance: a complete-coalescence-rebound (CCR) regime, a partial-coalescence-rebound (PCR) regime, and a no-coalescence-rebound (NCR) regime. We demonstrate that the rebound regime is closely associated with dynamic behaviors of the formed liquid ridge or bridge between two droplets. We also present the contact time in the three regimes. Intriguingly, although partial coalescence takes places, the contact time is still dramatically shortened in the PCR regime, which is even smaller than that of a single droplet impact. These findings provide new insights into the contact time of multiple droplets impact, and thereby offering useful guidance for some application such as anti-icing, self-cleaning, and so forth.
Bubble formation from a downward-pointing capillary nozzle was investigated in this study. The experiments were conducted at gas flow rate of 40-5400 mL/h and inner nozzle radius of 0.030-0.255 mm. Experimental results show that microbubbles were formed continuously at moderate Weber number, which was not reported in pervious investigations with injecting gas through an upward-pointing capillary nozzle. High-speed visualization indicates that the formation of microbubbles arises from the convergence of the capillary waves induced by the partial coalescence of larger bubbles. A bubbling regime map is given to identify the critical conditions for the formation of microbubbles. In the present air-water experiments, the generated microbubbles are 20-170 μm in diameter. From experimental data, a scaling law for microbubble size is proposed as a function of Weber and Bond numbers.
Bubble size distribution and bubble ellipticity were measured as a function of axial position in a vertically oriented semi-batch gas-liquid Taylor vortex reactor with varying gas flow rate and inner cylinder rotation speed producing axial Reynolds numbers in the range 23.8-119 and azimuthal Reynolds numbers up to 4.2×104. The mean bubble size increases monotonically with axial distance from the bottom of the reactor at the location of gas injection. The functional form of the growth of the mean bubble size with axial position depends upon the azimuthal Reynolds number. Specifically, when the azimuthal Reynolds number is less than 1.3×104, the mean bubble size increases linearly with axial distance from the bubble injection point. In contrast, for azimuthal Reynolds numbers greater than this critical value, the mean bubble size increases with axial distance in a sigmoidal manner.
A self-wiping co-rotating twin-screw extruder (TSE) is operated in a starved state where the screws are partially filled with resin. Understanding resin distribution on the screw surface is essential for the design, operation, and maintenance of the twin-screw extrusion process. In this study, the circumferential and axial distribution of pressure, temperature, and resin in a TSE are calculated using a novel method combining the mathematical formulation of Hele–Shaw flow, the finite element method, and a newly developed down-wind pressure update scheme. The experimental results were in good agreement with the measured results. This calculation method enables us to visualize, in detail, the resin distribution, pressure, and temperature for the entire axial and circumferential direction over the TSE.
Particle-laden flows in a vertical channel were simulated using an Eulerian–Eulerian, Anisotropic-Gaussian (EE-AG) model. Two sets of cases varying the overall mass loading were done using particle sizes corresponding to either a large or small Stokes number. Primary and turbulent statistics were extracted from these results and compared with counterparts collected from Eulerian–Lagrangian (EL) simulations. The statistics collected from the small Stokes number particle cases correspond well between the two models, with the EE-AG model replicating the transition observed using the EL model from shear-induced turbulence to relaminarization to cluster-induced turbulence as the mass loading increased. The EE-AG model was able to capture the behavior of the EL simulations only at the largest particle concentrations using the large Stokes particles. This is due to the limitations involved with employing a particle-phase Eulerian model (as opposed to a Lagrangian representation) for a spatially intermittent system that has a low particle number concentration.
We investigated the flow characteristics in a tank of H/T=1.5 stirred by a novel multi-blade combined agitator (MBC) by using time-resolved PIV and LES approach. The predictions were assessed by Y+ values and power spectrum analysis, as well as experimental validation of velocity distributions. Results demonstrate that the MBC agitator can load the energy into the system effectively with a power number of 12.5 in a turbulent regime, resulting in improved axial and radial mass exchange. The upper and lower short blades produce an axial down-flow in the top half and an axial up-flow in the bottom half, respectively. Part of axial flows change to radial flows by the radial pumping of the long blades, meanwhile, the impingement of two axial flows improves the axial mass exchange. These flow characteristics leads to an obvious improvement in the turbulent kinetic energy distribution uniformity.
Multiple breakdown phenomena may take place when operating dielectric elastomers. Thermal breakdown, which occurs due to Joule heating, becomes of special importance when using multilayered stacks of dielectric elastomers, due to the large volume-to-surface-area-ratio. In this article, a 2D axisymmetric finite-element model of a multilayered stack of dielectric elastomers is set up in \comsol. Both the electro-thermal and electro-mechanical couplings are considered, allowing for determination of the onset of thermal breakdown. Simulation results show that an entrapped particle in the dielectric elastomer drastically reduces the possible number of layers in the stack. Furthermore, the possible number of layers is greatly affected by the ambient temperature and the applied voltage. The performance of three hyperelastic material models for modelling the elastomer deformation are compared, and it is established that the Gent model yields the most restrictive prediction of breakdown point, while the Ogden model yields the least restrictive estimation.
The flow characteristics of the blade unit of a tridimensional rotational flow sieve tray was investigated experimentally in this study. First, the flow patterns are defined under different liquid arrangement methods. They are bilateral film flow, continuous perforated flow, and dispersion-mixing flow in overflow distribution and film and jet flow and jet and mixed flow in spray distribution. Second, the time and frequency domain analysis of the differential pressure pulsation signal in the blade unit is carried out. The influence of perforation and mixing intensity on the flow pattern transition is clarified. Third, the rotational flow ratio of the gas-liquid phase is measured. The influence of the operating conditions on the distribution of the rotational and perforated flow for the gas-liquid phase is investigated. Finally, a prediction model for the rotational flow ratio is proposed. The prediction results agree well with the experimental data.
We present a new family of fast and robust methods for the calculation of the vapor-liquid equilibrium at isobaric-isothermal (PT-flash), isochoric-isothermal (VT-flash), isenthalpic-isobaric (HP-flash), and isoenergetic-isochoric (UV-flash) conditions. The framework is provided by formulating phase-equilibrium conditions for multi-component mixtures in an effectively reduced space based on the molar specific value of the recently introduced volume function derived from the Helmholtz free energy. The proposed algorithmic implementation can fully exploit the optimum quadratic convergence of a Newton method with the analytical Jacobian matrix. This paper provides all required exact analytic expressions for the general cubic equation of state. Computational results demonstrate the effectivity and efficiency of the new methods. Compared to conventional methods, the proposed reduced-space iteration leads to a considerable speed-up as well as to improved robustness and better convergence behavior near the spinodal and coexistence curves of multi-component mixtures, where the preconditioning by the reduction method is most effective.