Study of Liquid–Solid Mass Transfer and Hydrodynamics in Micropacked Bed with Gas–Liquid Flow

The volumetric liquid–solid (L-S) mass transfer coefficient under gas–liquid (G-L) two-phase flow in a silicon-chip-based micropacked bed reactor (MPBR) was studied using the copper dissolution method and was related to the reactor hydrodynamic behavior. Using a high-speed camera and a robust computational image analysis method that selectively analyzed the bed voidage around the copper particles, the observed hydrodynamics were directly related to the L-S mass transfer rates in the MPBR. This hydrodynamic study revealed different pulsing structures inside the packed copper bed depending on the flow patterns established preceding the packed bed upon increasing gas velocity. A “liquid-dominated slug” flow regime was associated with an upstream slug flow feed. A “sparse slug” flow regime developed with an upstream slug-annular flow feed. At higher gas velocity, a “gas continuous with pulsing” regime developed with an annular flow feed, which had similar features to the pulsing flow in macroscale packed beds, but it was sensitive and easily destabilized by disturbances from upstream or downstream pressure fluctuations. The volumetric L-S mass transfer coefficient decreased with increasing gas velocity under the liquid-dominated slug flow regime and became rather less affected under the sparse slug flow regime. By resolving the transition from the liquid-dominated slug flow to the sparse slug flow and capturing the onset of the gas-continuous with pulsing regime, we gained new insights into the hydrodynamic effects of G-L flows on the L-S mass transfer rates in a MPBR

Quantification of the oxygen uptake rate in a dissolved oxygen controlled oscillating jet-driven microbioreactor

BACKGROUND: Microbioreactors have emerged as a new tool for early bioprocess development. The technology has advanced rapidly in the last decade and obtaining real-time quantitative data of process variables is nowadays state of the art. In addition, control over process variables has also been achieved. The aim of this study was to build a microbioreactor capable of controlling dissolved oxygen (DO) concentrations and to determine oxygen uptake rate in real time. RESULTS: An oscillating jet driven, membrane-aerated microbioreactor was developed without comprising any moving parts. Mixing times of ∼7 s, and kLa values of ∼170 h−1 were achieved. DO control was achieved by varying the duty cycle of a solenoid microvalve, which changed the gas mixture in the reactor incubator chamber. The microbioreactor supported Saccharomyces cerevisiae growth over 30 h and cell densities of 6.7 gdcw L−1. Oxygen uptake rates of ∼34 mmol L−1 h−1 were achieved. CONCLUSION: The results highlight the potential of DO-controlled microbioreactors to obtain real-time information on oxygen uptake rate, and by extension on cellular metabolism for a variety of cell types over a broad range of processing conditions. © 2015 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry

Highly reproducible, high-yield flow synthesis of gold nanoparticles based on a rational reactor design exploiting the reduction of passivated Au(III)

Reproducibility in the synthesis of nanomaterials is a crucial aspect for their real-life applications. It is particularly pertinent in the context of gold nanoparticles, where a plethora of seeded-growth methods are being developed to control particle morphology and size. The translation of such methods to manufacturing can be hindered by poor reproducibility of the seed production step. This study focuses on the development of a highly reproducible platform for the synthesis of gold nanoparticles, as potential substrates for glucose sensing. A flow reactor was designed, starting from a detailed study of the synthesis in batch. The well-established Turkevich synthesis was investigated via in situ time-resolved UV-vis spectroscopy. In order to enhance the reproducibility of the synthesis the effect of passivating the gold precursor stock before its use in the synthesis was investigated. It is shown that starting from a pre-passivated precursor provided improved control over the initial reaction stage, at the expense of a small increase in the reaction time. At the optimal reaction conditions, the proposed modified Turkevich method allowed for the synthesis in batch of ∼12 nm monodisperse (RSD ∼10%) particles, with a variability from batch to batch of only ∼5%. The information gathered from the batch study, in particular the reaction time, was used to translate the synthesis from batch to flow. The system utilized for the flow synthesis consisted of a segmented flow reactor, where an organic stream was employed to segment the reactive aqueous stream to avoid reactor fouling and improve monodispersity. The use of segmented flow enables treating each droplet as a “travelling batch”, hence allowing the direct use of the kinetic data obtained in batch to design the flow reactor, leading to the rapid identification of the minimum residence time to allow for reaction completion. The flow reactor enabled the synthesis of ∼11 nm monodisperse (RSD ∼10%) particles, with full precursor conversion and reproducibility between reactor runs higher than that obtained in batch (variability of ∼2%). The flow-produced gold nanoparticles were tested for glucose sensing, exploiting their glucose oxidase-mimicking behaviour and demonstrated satisfactory glucose detection in the range of 1–10 mM

In Situ Ultrasound Acoustic Measurement of the Lithium-Ion Battery Electrode Drying Process

The electrode drying process is a crucial step in the manufacturing of lithium-ion batteries and can significantly affect the performance of an electrode once stacked in a cell. High drying rates may induce binder migration, which is largely governed by the temperature. Additionally, elevated drying rates will result in a heterogeneous distribution of the soluble and dispersed binder throughout the electrode, potentially accumulating at the surface. The optimized drying rate during the electrode manufacturing process will promote balanced homogeneous binder distribution throughout the electrode film; however, there is a need to develop more informative in situ metrologies to better understand the dynamics of the drying process. Here, ultrasound acoustic-based techniques were developed as an in situ tool to study the electrode drying process using NMC622-based cathodes and graphite-based anodes. The drying dynamic evolution for cathodes dried at 40 and 60 °C and anodes dried at 60 °C were investigated, with the attenuation of the reflective acoustic signals used to indicate the evolution of the physical properties of the electrode-coating film. The drying-induced acoustic signal shifts were discussed critically and correlated to the reported three-stage drying mechanism, offering a new mode for investigating the dynamic drying process. Ultrasound acoustic-based measurements have been successfully shown to be a novel in situ metrology to acquire dynamic drying profiles of lithium-ion battery electrodes. The findings would potentially fulfil the research gaps between acquiring dynamic data continuously for a drying mechanism study and the existing research metrology, as most of the published drying mechanism research studies are based on simulated drying processes. It shows great potential for further development and understanding of the drying process to achieve a more controllable electrode manufacturing process

Nonlinear dynamics of gas-liquid separation in a capillary microseparator

Copyright © 2018 ASME. Micro-engineered devices (MED) are seeing a significant growth in performing separation processes1. Such devices have been implemented in a range of applications from chemical catalytic reactors to product purification systems like microdistillation. One of the biggest advantages of these devices is the dominance of capillarity and interfacial tension forces. A field where MEDs have been used is in gas-liquid separations. These are encountered, for example, after a chemical reactor, where a gaseous component being produced needs immediate removal from the reactor, because it can affect subsequent reactions. The gaseous phase can be effectively removed using an MED with an array of microcapillaries. Phase-separation can then be brought about in a controlled manner along these capillary structures. For a device made from a hydrophilic material (e.g. Si or glass), the wetted phase (e.g. water) flows through the capillaries, while the non-wetted dispersed phase (e.g. gas) is prevented from entering the capillaries, due to capillary pressure. Separation of liquid-liquid flows can also be achieved via this approach. However, the underlying mechanism of phase separation is far from being fully understood. The pressure at which the gas phase enters the capillaries (gas-to-liquid breakthrough) can be estimated from the Young-Laplace equation, governed by the surface tension (γ) of the wetted phase, capillary width (d) and height (h), and the interface equilibrium contact angle (θeq). Similarly, the liquid-to-gas breakthrough pressure (i.e. the point at which complete liquid separation ceases and liquid exits through the gas outlet) can be estimated from the pressure drop across the capillaries via the Hagen-Poiseuille (HP) equation. Several groups reported deviations from these estimates and therefore, included various parameters to account for the deviations. These parameters usually account for (i) flow of wetted phase through 'n' capillaries in parallel, (ii) modification of geometric correction factor of Mortensen et al., 20052and (iii) liquid slug length (LS) and number of capillaries (n) during separation. LShas either been measured upstream of the capillary zone or estimated from a scaling law proposed by Garstecki et al., 20063. However, this approach does not address the balance between the superficial inlet velocity and net outflow of liquid through each capillary (qc). Another shortcoming of these models has been the estimation of the apparent contact angle (θapp), which plays a critical role in predicting liquid-to-gas breakthrough. θappis either assumed to be equal to θeqor measured with various techniques, e.g. through capillary rise or a static droplet on a flat substrate, which is significantly different from actual dynamic contact angles during separation. In other cases, the Cox-Voinov model has been used to calculate θappfrom θeqand capillary number. Hence, the empirical models available in the literature do not predict realistic breakthrough pressures with sufficient accuracy. Therefore, a more detailed in situ investigation of the critical liquid slug properties during separation is necessary. Here we report advancements in the fundamental understanding of two-phase separation in a gas-liquid separation (GLS) device through a theoretical model developed based on critical events occurring at the gas-liquid interfaces during separation

Particle Size Evolution during the Synthesis of Gold Nanoparticles Using In Situ Time-Resolved UV–Vis Spectroscopy: An Experimental and Theoretical Study Unravelling the Effect of Adsorbed Gold Precursor Species

The quantitative analysis of nanomaterials synthesis kinetics is valuable both for understanding the synthesis and for development of manufacturing processes, and it usually requires the use of synchrotron-based instrumentation, making it challenging to perform experiments in the large parametric space needed to develop quantitative kinetic models. UV–vis spectroscopy represents a convenient technique to circumvent such difficulties, as it is available in most chemistry laboratories and allows fast data acquisition. This technique can in theory be used for the characterization of plasmonic nanomaterials synthesis kinetics. However, linking UV–vis spectra with characteristic features of the produced nanomaterials, such as size and shape, is a challenging task. This work presents a detailed spectroscopic analysis of gold nanoparticles syntheses via in situ time-resolved UV–vis spectroscopy, with emphasis on the role of gold precursor adsorption on the particle surface during nanoparticle growth. We show that the classic Turkevich synthesis and the growth of preformed gold nanoparticles with two different methods exhibit significant commonalities in the spectra evolution, explained in terms of the interaction between gold precursor species and the nanoparticle surface. Such interaction was accounted for in a model based on the Mie theory, describing the growing nanoparticles as core–shell spheres with an outer shell of few Ångströms characterized by reduced conductivity and increased electron damping rate. The proposed model led to the determination of the nanoparticle size and concentration evolution throughout the synthesis with good quantitative agreement against literature SAXS data. Furthermore, the core–shell model enabled the reproduction of the progressive blue-shift in the SPR peak position observed during the synthesis. Thus, this work reconciles the “seed-mediated growth” mechanism for the Turkevich synthesis with the temporal evolution of the spectra within the framework of the Mie theory, showing that the distinctive purple-greyish hue observed during the synthesis can be related to the interaction of gold precursor with the growing gold nanoparticles

Motion-enhancement assisted digital image correlation of lithium-ion batteries during lithiation

For the first time, a motion enhancement and registration technique (MERt) – an advanced phase based motion enhancement method combined with an optical flow based digital image correlation process is used to investigate batteries. This, in combination with the non-invasive investigative nature of X-ray computed tomography, makes for a powerful tool to examine the mechanism behind (de)lithiation of Li-ion cells. Through MERt, which magnifies the displacement of electrodes and tracks any internal changes, it is generally observed that the electrode expands outwards, but once encountering the solid barrier that is the cell casing, the electrode has nowhere to expand but inwards, which is why the electrode deformations initiate at the cell core. The technique clearly affirms that the greatest movement of electrodes during lithiation occurs at pre-existing inflection points in the jelly roll, which are a result of the manufacturing process, and eventually leads to the large deformations observed in this and previous works. MERt also indicates a contortion of the cell casings during lithiation which may be caused by the uneven expansion of the electrodes, but requires further studies to confirm

Catalytic Teflon AF-2400 membrane reactor with adsorbed ex situ synthesized Pd-based nanoparticles for nitrobenzene hydrogenation

Among the unconventional approaches of supporting catalyst nanoparticles, the layer-by-layer assembly of polyelectrolyte multilayers for nanoparticle adsorption represents an easy and convenient method. It enables the deposition of singularly adsorbed nanoparticles and prevents them from aggregating. In this work, polydopamine was grafted on the internal surface of a Teflon AF-2400 tubular membrane, known for its excellent permeability to light gases and inertness to chemicals. Poly(acrylic acid) and poly(allylamine hydrochloride) were sequentially adsorbed on the modified surface of the membrane. Ex situ synthesised spherical, cubical, truncated octahedral palladium and dendritic platinum-palladium nanoparticles were then incorporated. The catalytic membranes were assembled in a tube-in-tube configuration and tested for 6 h of continuous nitrobenzene hydrogenation with molecular hydrogen. Stable conversion was observed for the truncated octahedral and dendritic nanoparticles, while a progressive deactivation was observed for the other nanoparticles. Due to their small size, the 3.7 nm spherical nanoparticles exhibited the highest reaction rate, 629 molreactant/(molcatalyst⋅h), while the cubical nanoparticles showed the highest turnover frequency, ∼3000 h−1. The reactor concept developed in this work demonstrates how such a tool can serve as platform for conducting continuous multiphase catalytic reactions in flow using singularly adsorbed and finely tuned nanoparticles. The small volume of pressurised gas present in the tube-in-tube reactor offers improved process safety compared to batch, while the Teflon AF-2400 membrane provides control over the gas permeation during reaction