Pressure drop through platinized titanium porous electrodes for cerium‐based redox flow batteries

The pressure drop, , across a redox flow battery is linked to pumping costs and energy efficiency, making fluid properties of the electrolyte important in scale‐up operations. The at diverse platinized titanium electrodes in Ce‐based redox flow batteries is reported as a function of mean linear electrolyte velocity measured in a rectangular channel flow cell. Darcy's friction factor and permeability vs. Reynolds number are calculated. Average permeability values are: 7.10 × 10^?4 cm² for Pt/Ti mesh, 4.45 × 10^?4 cm² for Pt/Ti plate + turbulence promoters, 1.67 × 10^?5 cm² for Pt/Ti micromesh, and 1.31 × 10^?6 cm² for Pt/Ti felt. The electrochemical volumetric mass transport coefficient, , is provided as a function of . In the flow‐by configuration, Pt/Ti felt combines high values with a relatively high , followed by Pt/Ti micromesh. Pt/Ti mesh and Pt/Ti plate gave a lower but poorer electrochemical performance. Implications for cell design are discussed. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1135–1146, 2018     

全钒液流电池电解液分布的数值模拟

为了提高全钒液流电池双极板流道电解液分布均匀性,考察流体流动行为,本文基于计算流体力学,在传统平直并联流道基础上通过增加倾斜挡板和入口流堰,改进流道结构;同时探究钒电池用电解液在分段式多通道蛇形流道内流体水力学特征。数值模拟结果表明：分段式多通道蛇形流道既可以保持传统蛇形流道流体均匀分配的性能,又能有效降低流阻,减少泵耗;合适的电解液流速及其均匀分布可以优化电解液活性物质浓度分布,提高电解液稳定性,增大钒电池能量效率。     

Corrosion behavior of a positive graphite electrode in vanadium redox flow battery

The graphite plate is easily suffered from corosion because of CO₂ evolution when it acts as the positive electrode for vanadium redox flow battery. The aim is to obtain the initial potential for gas evolution on a positive graphite electrode in 2 mol dm⁻³ H₂SO₄ + 2 mol dm⁻³ VOSO₄ solution. The effects of polarization potential, operating temperature and polarization time on extent of graphite corrosion are investigated by potentiodynamic and potentiostatic techniques. The surface characteristics of graphite electrode before and after corrosion are examined by scanning electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. The results show that the gas begins to evolve on the graphite electrode when the anodic polarization potential is higher than 1.60 V vs saturated calomel electrode at 20 °C. The CO₂ evolution on the graphite electrode can lead to intergranular corrosion of the graphite when the polarization potential reaches 1.75 V. In addition, the functional groups of COOH and CO introduced on the surface of graphite electrode during corrosion can catalyze the formation of CO₂, therefore, accelerates the corrosion rate of graphite electrode.     

Simulating multiphase flow in a two-stage pusher centrifuge using computational fluid dynamics

The design of two-stage pusher centrifuges have developed rapidly, but a good understanding of the theory behind their practice is a long-standing problem. To better understand centrifugal filter processes, the computational fluid dynamics (CFD) software program FLUENT has been used to model the three-dimensional geometry and to simulate multiphase flows based on Euler-Euler, moving mesh, dynamic mesh and porous media models. The simulation tangential velocities were a little smaller than those for rigid-body motion. In the stable flow region, the radial velocities were in good agreement with the theoretical data. Additionally, solid concentration distribution were obtained and also showed good agreement with the experimental data. These results show that this simulation method could be an effective tool to optimize the design of the two-stage pusher centrifuge.     

Investigation of Ir-modified carbon felt as the positive electrode of an all-vanadium redox flow battery

Porous graphite felts have been used as electrode materials for all-vanadium redox flow batteries due to their wide operating potential range, stability as both an anode and a cathode, and availability in high surface area. In this paper, the carbon felt was modified by pyrolysis of Ir reduced from H₂IrCl₆. ac impedance and steady-state polarization measurements showed that the Ir-modified materials have improved activity and lowered overpotential of the desired V(IV)/V(V) redox process. Ir-modification of carbon felt enhanced the electro-conductivity of electrode materials. The Ir-material, when coated on the graphite felt electrode surface, lowered the cell internal resistance. A test cell was assembled with the Ir-modified carbon felt as the activation layer of the positive electrode, the unmodified raw felt as the activation layer of the negative electrode. At an operating current density of 20 mA cm⁻², a voltage efficiency of 87.5% was achieved. The resistance of the cell using Ir-modified felt decreased 25% compared to the cell using non-modified felt.     

Comparative study of dry pressure drop and flow behaviour of gas flow through sieve plate packing

Sieve plate packing is a newly developed packing that has been used in several industries due to its simple structure and operating flexibility, and no liquid flooding. In this work, first, systematic experiments were conducted to measure the pressure drop of gas flow through six sieve plate packings. The results indicated that the geometric characteristics of the packing have complicated effects on the pressure drops. Based on this, CFD simulations on the gas flow field were conducted using the realizable k-ε model, and flow behaviours such as the pressure drop, pressure nephogram, and velocity distributions within different packings were obtained. The simulation results clearly showed interesting flow patterns, including the contraction and expansion of the gas stream through the sieve hole, the flow separation on the sharp edge of the hole, and the vortexes formed when gas impacts the downstream plate. By comparing the flow patterns and the pressure drop under different packings operating at different conditions, the effects of the geometric characteristics of the packing on the pressure drop could be clearly distinguished from the flow behaviours, so that the variations in pressure drop with various packing structures were clearly indicated. Finally, based on the experimental data and the simulated results, correlations for the prediction of the pressure drops were proposed. This work will provide a useful basis for understanding the flow behaviour of gas and liquid two-phase flow in sieve plate packing.     

A method to calculate the multiphase flow properties of heterogeneous porous media by using network simulations

A method is suggested to compute the capillary pressure and relative permeability curves of heterogeneous porous media. The broad pore radius distribution (PRD) and throat radius distribution (TRD) are decomposed into relatively narrow component distribution functions which are used for the computer‐aided construction of pore‐and‐throat networks. The quasi‐static motion of menisci in pores and throats is tracked by accounting for capillary forces. The presence of fractal roughness along pore walls ensures the coexistence of both phases in pores. The calculation of the hydraulic conductance of each phase is based on the concept of constricted unit cell. Simulations in component pore networks constructed from narrow PRD and TRD produce a set of capillary pressure and relative permeability functions, the arithmetic averaging of which yields the corresponding functions for a heterogeneous synthetic pore network. This information is used by a dynamic simulator of drainage in permeability networks to predict experimental results of soil columns. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Simulations of photodegradation of toluene and formaldehyde in a monolith reactor using computational fluid dynamics

In this study, simulations were conducted on a monolith reactor for the photodegradation of toluene and formaldehyde. The monoliths in the reactor were treated as porous zones and the photocatalytic oxidation occurring on the monolith surfaces was modeled using Langmuir–Hinshelwood kinetics. A discrete ordinates model was used to simulate the light intensity with a novel approach, which involved an adjustable parameter—the absorption coefficient of the channel wall, for modeling the local light intensity across the porous media. The advantage of this approach was that despite its simplicity, it was able to capture and visualize the local light profile across the monolith channels and to integrate it into the reaction kinetics. Although it required a trial‐and‐error to determine the correct value of the channel wall absorption coefficient, the proposed model achieved a reasonable agreement between the simulation results and published experimental data. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Validation of pressure drop prediction and bed generation of fixed-beds with complex particle shapes using discrete element method and computational fluid dynamics

Catalytic fixed-bed reactors with a low tube-to-particle diameter ratio are widely used in industrial applications. The heterogeneous packing morphology in this reactor type causes local flow phenomena that significantly affect the reactor performance. Particle-resolved computational fluid dynamics has become a predictive numerical method to analyze the flow, temperature, and species field, as well as local reaction rates spatially and may, therefore, be used as a design tool to develop new improved catalyst shapes. Most validation studies which have been presented in the past were limited to simple particle shapes. More complex catalyst shapes are supposed to increase the reactor performance. A workflow for the simulation of fixed-bed reactors filled with various industrially relevant complex particle shapes is presented and validated against experimental data in terms of bed voidage and pressure drop. Industrially relevant loading strategies are numerically replicated and their impact on particle orientation and bed voidage is investigated.     

新型径向叶片式旋转床压降分析及气相流场模拟

针对折流式旋转床压降高、能耗大的问题,提出了一种新型超重力旋转床设备--径向叶片式旋转床。首先,对该旋转床的压降进行了理论分析和建模,并利用水-空气体系进行了实验研究。通过改变气量、转速和液量探究了新型径向叶片式旋转床压降的变化规律,结果表明压降随气量、转速和液量的增加而增加,且随着气量和转速的增加,液量对压降的贡献逐渐减小。压降模型的预测值与实验数据的相对偏差基本在10%以内,表明模型可以较好地预测新型径向叶片式旋转床的压降。另外,通过计算流体力学（CFD）软件的模拟获得了旋转床内气相流场和压力分布的结果,发现转子内压降是总压降的主要部分;气体进入转子后会因叶片作用使得周向速度变大,并在转子外缘处达到最大值;气体的进口流速将会影响旋转床内的气相分布。利用实验数据对CFD模拟结果进行了验证,两者的相对偏差在10%左右。     

Influence of the boundary conditions on capillary flow dynamics and liquid distribution in a porous medium

After depositing a wetting liquid onto a porous medium surface, and under the influence of the capillary pressure, the liquid is imbibed into the porous medium creating a wetted imprint. The flow within the porous medium does not cease once all the liquid is imbibed but continues as a secondary capillary flow, where the liquid flows from large pores into small pores along the liquid interface. The flow is solved using the capillary network model, and the influence of the boundary condition on the liquid distribution within the porous medium is investigated. The pores at the porous medium boundaries can be defined as open or closed pores, where an open pore is checked for the potential threshold condition for flow to take place. In contrast, the closed pore is defined as a static entity, in which the potential condition for flow to take place is never satisfied. By defining the pores at distinct porous medium boundaries as open or closed, one is able to obtain a very different liquid distribution within the porous medium. The liquid saturation profiles along the principal flow direction, ranging from constant to steadily decreasing, to the profile with a local maximum, are found numerically. It is shown that these saturation profiles are also related to the geometrical dimension that is perpendicular to the flow principal direction, and changing the boundary type from open to closed allows the liquid distribution within the porous medium to be controlled. In addition to the liquid distribution, the influence of the boundary conditions on capillary pressure and relative permeability is investigated, where both parameters are not influenced by variation of the boundary condition types. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Discussion on the pressure drop calculation for oil‐water separated flow using a one dimensional two‐fluid model

The purpose of this work is to seek the key factors influencing the pressure drop calculation for oil‐water separated flow using a one dimensional two‐fluid model. Closure relations published for the two‐fluid model such as interface configuration, wall, and interfacial shear stress correlations are summarized. Interface configurations are established by numerically solving the Young‐Laplace equation, correlated with the Bond number, contact angle, and water holdup. Results show that the interface transforms from concave to convex with the enlargement of the contact angle and becomes flat as the Bond number increases. For the pressure drop calculation, a limited difference of predicted accuracy between the curve and flat interface is found. Discussions of both the wall and interfacial friction factor correlation on the pressure drop calculation are performed. In contrast to the effect of the interfacial friction factor, the correlation of the wall friction factor is found to have more contributions. We validate the prediction accuracy of different wall frictions factors using eight groups of published experiment results, and one correlation is recommended and being further extended.     

Dynamic effects in capillary pressure relationships for two‐phase flow in porous media: Experiments and numerical analyses

Well defined experiments and numerical analyses are conducted to determine the importance of dynamic effect in capillary pressure relationships for two‐phase flow in porous media. Dynamic and quasi‐static capillary pressure‐saturation (P^c‐S_w) and, ?S_w/?t‐t curves are determined. These are then used to determine the dynamic effects, indicated by a dynamic coefficient (τ) in the porous domains which establishes the speed at which flow equilibrium (?S_w/?t = 0) is reached. τ is found to be a nonlinear function of saturation which also depends on the medium permeability. Locally determined τ seems to increase as the distance of the measurement point from the fluid inlet into the domain increases. However, the functional dependence τ‐S_w follows similar trends at different locations within the domain. We argue that saturation weighted average of local τ‐S_w curves can be defined as an effective τ‐S_w curve for the whole domain which follows an exponential trend too. © 2012 The Authors. AIChE Journal, published by Wiley on behalf of the AIChE. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. AIChE J, 58: 3891–3903, 2012     

锑离子添加剂对低共熔溶剂(DES)电解液液流电池的性能改善研究

非水系氧化还原液流电池（NARFB）的广泛应用受制于其较低的性能。在电解液中加入一些金属离子添加剂是一种可能的解决方案。实验研究了Sb³⁺离子对低共熔溶剂（DES）电解液液流电池电化学性能的影响。结果表明,添加Sb³⁺离子可以强化V（Ⅲ）/V（Ⅱ）氧化还原离子对的电化学反应动力学（最高可达22.6％）过程,钒离子在DES中的扩散系数提高了63.3％,并且电荷转移电阻降低了11.9％。场发射扫描电子显微镜表明,Sb³⁺离子电沉积在石墨毡的表面,对电化学反应起催化作用,从而改善了电化学性能。考虑增强的动力学和降低的活性比表面积之间的平衡,确定了Sb³⁺的最佳浓度为15 mmol·L^-1。此外,当使用含有Sb³⁺的负极电解液液流电池时,液流电池的功率密度提高了31.2%,从含原始电解质的3.08 mW·cm^-2到含15 mmol·L^-1 Sb³⁺离子的4.04 mW·cm^-2。这些结果为改善NARFB的电池性能提供了一个便捷而有前景的方法。     

Ce(III)/Ce(IV) in methanesulfonic acid as the positive half cell of a redox flow battery

The characteristics of the Ce(III)/Ce(IV) redox couple in methanesulfonic acid were studied at a platinum disk electrode (0.125 cm²) over a wide range of electrolyte compositions and temperatures: cerium (III) methanesulfonate (0.1–1.2 mol dm⁻³), methanesulfonic acid (0.1–5.0 mol dm⁻³) and electrolyte temperatures (295–333 K). The cyclic voltammetry experiments indicated that the diffusion coefficient of Ce(III) ions was 0.5 × 10⁻⁶ cm² s⁻¹ and that the electrochemical kinetics for the oxidation of Ce(III) and the reduction of Ce(IV) was slow. The reversibility of the redox reaction depended on the electrolyte composition and improved at higher electrolyte temperatures. At higher methanesulfonic acid concentrations, the degree of oxygen evolution decreased by up to 50% when the acid concentration increased from 2 to 5 mol dm⁻³. The oxidation of Ce(III) and reduction of Ce(IV) were also investigated during a constant current batch electrolysis in a parallel plate zinc–cerium flow cell with a 3-dimensional platinised titanium mesh electrode. The current efficiencies over 4.5 h of the process Ce(III) to Ce(IV) and 3.3 h electrolysis of the reverse reaction Ce(IV) to Ce(III) were 94.0 and 97.6%, respectively. With a 2-dimensional, planar platinised titanium electrode (9 cm² area), the redox reaction of the Ce(III)/Ce(IV) system was under mass-transport control, while the reaction on the 3-dimensional mesh electrode was initially under charge-transfer control but became mass-transport controlled after 2.5–3 h of electrolysis. The effect of the side reactions (hydrogen and oxygen evolution) on the current efficiencies and the conversion of Ce(III) and Ce(IV) are discussed.     

纳米银在饱和多孔介质含水层中迁移主控机理和影响特征

纳米银（AgNP）作为应用最广、生态毒性最强的工程纳米材料之一,一旦进入地下水环境,将引发环境问题。目前,环境因素对纳米银在地下水环境中运移的影响机理尚不清楚。通过室内柱实验,研究了流速（1、2 ml·min^-1）和介质粒径特征（0.605、0.115 mm以及混合粒径的玻璃珠）对纳米银在饱和多孔介质中迁移的影响。研究结果表明纳米银在粒径较大（0.605 mm）的介质中的迁移主要受吸附沉降控制;在小粒径介质中（0.115 mm以及混合粒径玻璃珠）,迁移过程同时受吸附沉降和阻塞沉降两种机理的控制,且阻塞效应主要受小粒径部分介质控制。水流速度提高能降低大粒径介质中纳米银颗粒的沉降效率,从而提高其迁移能力。而对于小粒径介质和混合粒径介质,流速提高除了降低纳米银的沉降效率,还能降低阻塞效应和促进尺寸排除效应,不但能更显著地降低纳米银在介质中的衰减,还能提高纳米银在介质中的穿透速度。研究成果对于理解复杂的场地条件下纳米材料的迁移分布动态具有理论价值。     

Prediction of gas density effects on bubbly flow hydrodynamics: New insights through an approach combining population balance models and computational fluid dynamics

Detailed measurements and computational fluid dynamics (CFD) investigation of the hydrodynamics in a bubble column containing internal features causing flow disturbances are presented for both air and helium gases. An optical needle probe has been used to measure profiles of bubble size, bubble velocity, and gas holdup at different locations across the cross section of the column. An approach combining CFD with population balances is able to represent observed multiphase flow phenomena such as the effect of the pipes to remix and redistribute the gas as well as the tendency of the gas to channel through a slit in the pipes rather than go around the pipes. The comparison of CFD simulation to experimental measurements reveal that the overall decrease in gas holdup observed when switching from air to helium gas can be explained by swarm effects, whereas the steeper decrease in the gas holdup profile across the column is due to coalescence effects. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3764–3774, 2018     

旋转填料床气液两相流场的仿真分析

通过合理简化旋转填料床(RPB)结构,建立了三维物理模型,利用商用软件Fluent的计算平台,采用欧拉两相流模型和多孔介质模型对旋转填料床内的气液两相流场进行了仿真分析,深入分析了其压力场分布和速度场分布,并在此基础上对比了气相压降随旋转床转速变化的仿真结果与实验结果,两者变化趋势一致,表明所建立模型能近似地模拟旋转填料床的流场分布,并指导理论研究和实验研究进一步深入。     

Characterization of the reaction environment in a filter-press redox flow reactor

The characteristics of a divided, industrial scale electrochemical reactor with five bipolar electrodes (each having a projected area of 0.72 m²) were examined in terms of mass transport, pressure drop and flow dispersion. Global mass transport data were obtained by monitoring the (first order) concentration decay of dissolved bromine (which was generated in situ by constant current electrolysis of a 1 mol dm⁻³ NaBr_(aq)). The global mass transport properties have been compared with those reported in the literature for other electrochemical reactors. The pressure drop over the reactor was calculated as a function of the mean electrolyte flow velocity and flow dispersion experiments showed the existence of slow and fast phases, two-phase flow being observed at lower velocities.