Synergistic effects of sulfur poisoning and gas diffusion on polarization loss in anodes of solid oxide fuel cells

Poisoning effects of sulfur compounds on the performances of solid oxide fuel cells are non‐trivial. However, the synergistic effects of gas diffusion, adsorption, desorption and reaction in anodes are typically neglected. In this work, an analytical model is derived to quantitatively evaluate the poisoning effects of H₂S. The results show that sulfur poisoning correlates closely with inefficient gas diffusion for small anode pore size, small porosity/tortuosity, and low working temperatures. As compared with concentration polarization, H₂S‐diffusion‐induced activation polarization in thin anodes with a large is detrimental, especially for low‐temperature operations with a high H₂S concentration and a low current density. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1127–1134, 2018     

A highly selective polybenzimidazole‐4,4′‐(hexafluoroisopropylidene)bis(benzoic acid) membrane for high‐temperature hydrogen separation

A polymeric gas separation membrane utilizing polybenzimidazole based on 4,4′‐(hexafluoroisopropylidene)bis(benzoic acid) was prepared. The synthesized membrane has an effective permeating area of 8.3 cm² and a thickness of 30 ± 2 µm. Gas permeation properties of the membrane were determined using H₂, CO₂, CO, and N₂ at temperatures ranging from 24°C to 200°C. The PBI‐HFA membranes not only exhibited excellent H₂ permeability, but it also displayed superior gas separation performance particularly for H₂/N₂ and H₂/CO₂. The permeation parameters for both permeability and selectivity [ and α(H₂/N₂); and α(H₂/CO₂)] obtained for the new material were found to be dependent on trans‐membrane pressure difference as well as temperature, and were found to surpass those reported by Robeson in 2008. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42371.     

Sandwiched liquid metal membrane (SLiMM) for hydrogen purification

Palladium‐based membranes are currently the most advanced membranes for hydrogen separation and are on the verge of practical application. However, the search for alternative membranes continues in an effort to lower their cost and susceptibility to poisons. Here for the first time we report a novel sandwiched liquid metal membrane (SLiMM) for hydrogen separation. Permeation experiments indicate that the Ga/SiC SLiMM has a permeability of at 500°C, which is 35 time higher than that for Pd under similar conditions. This promises a potential for application of SliMM in hydrogen purification. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1483–1488, 2017     

Oxygen mass transfer in a gas/membrane/liquid system surrogate of membrane blood oxygenators

Oxygen mass transfer in a membrane blood oxygenator (MBO) surrogate system has been addressed in this work. It consists of a slit for water circulation as a surrogate blood flow channel and a constant pressure oxygen chamber separated by an integral asymmetric hemocompatible polyurethane‐based membrane. The oxygenated stream enters a well‐mixed reservoir of constant volume, V, for the oxygen average concentration, , measurement as a function of time, t. In a range of short times, the linearity of vs. t allows the direct determination of the permeation fluxes , with no recourse to dimensionless correlations for the determination of mass‐transfer coefficients. The experimental fluxes are in very good agreement with the predictions based in unidimensional axial convection and unidimensional transversal diffusion. This custom‐made benchmark system allows the optimization of the flow and oxygen mass transfer for the design of a novel flat‐sheet MBO. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3756–3763, 2018     

Analysis and optimization of pressure retarded osmosis for power generation

Model‐based analysis and optimization of pressure retarded osmosis (PRO) for power generation is focused. The effects of membrane properties (hydraulic permeability and mass‐transfer characteristics), design conditions (inlet osmotic pressures, inlet flows, and membrane area) and operating condition (applied pressure) on power density and efficiency are systematically investigated. A dimensionless design parameter , originally developed in analysis and optimization of reverse osmosis, is used to quantify the effect of dilution in draw solution (DS) as water permeates through membrane. An optimization method is developed to maximize PRO performance. It is shown that dilution and concentration polarization significantly reduce the maximum power density, and the optimal shifts away from . Moreover, power density and efficiency follow opposite trends when varying process conditions including DS flow rate and membrane area. Enhancing membrane properties is crucial to improve the economic feasibility of PRO. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1233–1241, 2015     

Ionic Liquid Confined in Nafion: Toward Molecular‐Level Understanding

In this article, multiscale simulation methods were used to study structural and transport properties of Nafion–ionic liquid composite membranes that are novel proton conducting materials for fuel cells. Coarse‐grained model for 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([bmim][BF₄]) ionic liquid was first developed in the framework of BMW‐MARTINI force field. Coarse‐grained simulation results of bulk [bmim][BF₄] ionic liquid show good agreement with all‐atom simulation results and experimental data. Nafion–[bmim][BF₄] composite membranes were then simulated using all‐atom and coarse‐grained models. Ionic liquid cluster formation inside Nafion was revealed by coarse‐grained simulations. Diffusion coefficients of both [bmim]⁺ cations and anions are reduced by one to two orders of magnitude depending on their concentrations in Nafion membrane. [Bmim]⁺ cations have faster self‐diffusion coefficient than anions, while this phenomenon is more pronounced when ionic liquids are confined in Nafion. This work provides molecular basis for understanding Nafion–ionic liquid composite membranes. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2630–2639, 2013     

Quantitative relationships between microstructure and effective transport properties based on virtual materials testing

The microstructure influence on conductive transport processes is described in terms of volume fraction ε, tortuosity τ, and constrictivity β. Virtual microstructures with different parameter constellations are produced using methods from stochastic geometry. Effective conductivities are obtained from solving the diffusion equation in a finite element model. In this way, a large database is generated which is used to test expressions describing different micro–macro relationships such as Archie's law, tortuosity, and constrictivity equations. It turns out that the constrictivity equation has the highest accuracy indicating that all three parameters are necessary to capture the microstructure influence correctly. The predictive capability of the constrictivity equation is improved by introducing modifications of it and using error‐minimization, which leads to the following expression: with intrinsic conductivity . The equation is important for future studies in, for example, batteries, fuel cells, and for transport processes in porous materials. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1983–1999, 2014     

Enhanced gas migration through permeable bubble networks within consolidated soft sediments

Many consolidated sediments experience in situ gas generation from methanogenesis, corrosion, or radiolysis reactions and can retain bubbles for long periods. Particular interest is motivated by the retention and acute release of flammable hydrogen from nuclear legacy waste sludge. X‐ray computed tomography was employed to observe 0.07–10 mm bubble populations within 30–1112 Pa yield strength Mg(OH)₂ sediments. High rates of partial coalescence were observed among sub‐millimeter microvoids, forming extensive bubble networks which spanned the 32 mm field of view. Lattice Boltzmann and Monte Carlo modeling demonstrated these networks to be highly pervious to gas, with effective diffusivities for hydrogen of 3.7–12.5 × 10^?5 m² s^?1. Continuous vessel‐spanning bubble networks, dynamic connectivity between ganglia of coalesced bubbles, Haines jumps, and composite diffusion through the gas and aqueous phase can account for enhanced gas migration over length‐scales of several meters, thus enabling chronic gas release from low‐intermediate strength sediments ( kPa) too strong for buoyant bubble ebullition and too weak for vertical channel formation. © 2018 The Authors. AIChE Journal published by Wiley Periodicals, Inc. on behalf of American Institute of Chemical Engineers. AIChE J, 64: 4131–4147, 2018     

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     

Dynamics adsorption of the enhanced CH4 recovery by CO2 injection

The dynamic adsorption isotherms of CO₂-EGR were measured by using an Intelligent Gravimetric Analysis system. In the initial CO₂ injecting stage, all the injected CO₂ enters into the adsorbent and the mole fraction of CH₄ in the gas phase () is maintained at 1.0. The CH₄ recovery factor () increases. The duration of this stage (t_CD) depends on the selectivity of CO₂ over CH₄ (). An adsorbent with large has long t_CD. In the second stage, the injected CO₂ competes with CH₄ for adsorption. The cumulative of the second stage is much larger than that of the initial stage. However, decreases sharply. in the whole CO₂ injection is always larger than that before CO₂ injection, suggesting that CH₄ desorption results from the displacement of CO₂ rather than from pressure depletion.     

Experimental determination of maximum effective hydrodynamic stress in multiphase flow using shear sensitive aggregates

Maximum effective hydrodynamic stress, , responsible for the breakup of aggregates with size comparable to Kolmogorov eddies, was experimentally determined in an aerated stirred tank. The proposed method is based on the measurement of the maximum stable aggregates size consisting of poly(methyl methacrylate) nanoparticles. The fractal aggregates were broken under various operating conditions in an aerated stirred tank and calibrated with known flow conditions using contracting nozzles to convert the measured aggregate sizes into hydrodynamic stress. It was found that can vary substantially among studied conditions and its magnitude depends on the controlling mechanism including gas jet during bubble formation, bubble rise, bubble burst at the gas–liquid interface or the turbulence generated by the impeller. The measured values are in good agreement with literature data which supports the applicability of this method to characterize the maximum effective hydrodynamic stress in complicated multiphase flow. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1735–1744, 2015     

On the steady‐state drop size distribution in stirred vessels. Part I: Effect of dispersed phase viscosity

Previous studies on emulsification have used the maximum drop size (d_max) or Sauter mean diameter ( ) to investigate the effect of viscosity on the drop size distribution (DSD), however, these parameters fall short for highly polydispersed emulsions. In this investigation (Part I), the steady‐state DSD of dilute emulsions is studied using of silicon oils with viscosities varying across six orders of magnitude at different stirring speeds. Different emulsification regimes were identified; our modeling and analysis is centered on the intermediate viscosity range where interfacial cohesive stresses can be considered negligible and drop size increases with viscosity. The bimodal frequency distributions by volume were well described using two log‐normal density functions. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3293–3302, 2018     

Kinetics of the absorption of carbon dioxide into aqueous ammonia solutions

Experiments were performed in a customized double stirred tank reactor to study the kinetics of CO₂ absorption into NH₃ solutions at concentrations ranging from 0.42 to 7.67 kmol·m^?3 and temperatures between 273.15 and 293.15 K. The results show that the reactive absorption was first order with respect to CO₂ but fractional order (1.6–1.8) with respect to ammonia. Experimental data can be satisfactorily interpreted by a termolecular mechanism using and . © 2016 American Institute of Chemical Engineers AIChE J, 62: 3673–3684, 2016     

Framework for correlating the effect of temperature on nonelectrolyte and ionic liquid activity coefficients

A power‐law expression is proposed for correlating the temperature dependence of infinite‐dilution activity coefficients ( ) for nonelectrolyte solute–solvent binary pairs and for pairs including an ionic liquid: , where θ_ij = 0 for Lewis–Randall ideal solutions, θ_ij = 1 for classic enthalpy‐based Scatchard–Hildebrand regular solution and van Laar models, and ?5 < θ_ij < 5 for most real binaries. The exponent θ_ij is a function of partial molar excess enthalpy ( ) and entropy ( ) such that . Real binaries are classified into seven types corresponding to distinct domains of and θ_ij. The new method provides a framework for correlating phase‐equilibrium driven temperature effects for a wide variety of chemical and environmental applications. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3675–3690, 2014     

Mass transfer coefficient of tubular ultrafiltration membranes under high‐flux conditions

The effect of suction flow on the mass transfer coefficient of tubular ultrafiltration membranes, in particular that under a high‐flux condition, was studied. We pointed out that is proportional to under turbulent conditions, and that the proportional constant, b, exceeds 0.023 when the effect of suction flow is not negligible. We conducted the velocity variation method using ultrafiltration membranes with MWCOs of 20k and 100k and dextrans having molecular weights of 40,000 and 70,000 at the conditions, where exceeded . We demonstrated that the effect of suction flow includes not only flux but also the diffusion coefficient of solute, and that the ratio of the flux to the diffusion coefficient, expressed as , is an important index. Finally, we concluded that , when is smaller than , giving the Deissler equation itself, and that , when exceeds . © 2017 American Institute of Chemical Engineers AIChE J, 64: 1778–1782, 2018     

Investigation mechanism of DEA as an activator on aqueous MEA solution for postcombustion CO2 capture

In this work, Diethanolamine (DEA) was considered as an activator to enhance the CO₂ capture performance of Monoethanolamine (MEA). The addition of DEA into MEA system was expected to improve disadvantages of MEA on regeneration heat, degradation, and corrosivity. To understand the reaction mechanism of blended MEA‐DEA solvent and CO₂, ¹³C nuclear magnetic resonance (NMR) technique was used to study the ions (MEACOO^‐, DEACOO^–, MEA, DEA, MEAH⁺, DEAH⁺, , ) speciation in the blended MEA‐DEA‐CO₂‐H₂O systems with CO₂ loading range from 0 to 0.7 mol CO₂/mol amine at the temperature of 301 K. The different ratios of MEA and DEA (MEA: DEA = 2.0:0, 1.5:0.5, 1.0:1.0, and 0:2.0) were studied to comprehensively investigate the role of DEA in the system of MEA‐DEA‐CO₂‐H₂O. The results revealed that DEA performs the coordinative role at the low CO₂ loading and the competitive role at high CO₂ loading. Additionally, the mechanism was also proposed to interpret the reaction process of the blended solvent with CO₂. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2515–2525, 2018     

Predicting effective conductivities based on geometric microstructure characteristics

Empirical relationships between effective conductivities in porous and composite materials and their geometric characteristics such as volume fraction , tortuosity τ and constrictivity β are established. For this purpose, 43 virtually generated 3D microstructures with varying geometric characteristics are considered. Effective conductivities are determined by numerical transport simulations. Using error‐minimization the following relationships have been established: and (simplified formula) with intrinsic conductivity σ₀, geodesic tortuosity and relative prediction errors of 19% and 18%, respectively. We critically analyze the methodologies used to determine tortuosity and constrictivity. Comparing geometric tortuosity and geodesic tortuosity, our results indicate that geometric tortuosity has a tendency to overestimate the windedness of transport paths. Analyzing various definitions of constrictivity, we find that the established definition describes the effect of bottlenecks well. In summary, the established relationships are important for a purposeful optimization of materials with specific transport properties, such as porous electrodes in fuel cells and batteries. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1834–1843, 2016     

ZrO2 和Al2O3支撑的MFI 型沸石分子筛膜:支撑体材料对膜性能的影响

采用水热合成法，以纯SiO2为源物质，在介孔Y2O3掺杂的ZrO2(YZ)及大孔α-Al2O3支撑体上制备出高质量的MFI型沸石分子筛膜，通过H2／n-C4H10气体混合物的渗透分离和p-xylene的蒸发研究了不同支撑体上MFI型沸石分子筛膜分离性能，在较低温度范围，YZ支撑的MFI型沸石分子筛膜中n-C4H10的渗透率比Al2O3支撑的膜高很多，最大n-C4H10与H2的分离率达到500，Al2O3支撑的膜中py-xylene的蒸发流量随时间下降很快，而YZ支撑的膜中的蒸发流量则变化缓慢，用XRD对膜的晶体结构进行分析，通过多种温度下热处理不同支撑体上的膜样品研究了其热稳定性与支持体材料的关系，YZ支撑的MFI型沸石分子筛膜的MFI结构在1000摄氏度后仍能保持，而Al2O3支撑的膜950摄氏度时已完全转变为石英相，研究结果表明，YZ支撑的MFI型沸石分子筛膜比Al2O3支撑的膜表现出更好的厌不性，热稳定性以及抗阻塞性。     

Convective condensation in a stator–rotor–stator spinning disc reactor

Centrifugal intensification of condensation heat transfer in the rotor–stator cavities of a stator–rotor–stator spinning disc reactor (srs‐SDR) is studied, as a function of rotational velocity ω, volumetric throughflow rate , and average temperature driving force . For the current range of ω, heat transfer from the vapor bubbles to the condensate liquid is limiting, due to a relatively low gas–liquid interfacial area a_GL. For rad s^?1, a strong increase of a_GL, results in increasing the reactor‐average condensation heat transfer coefficient h_c from 1600 to 5600 W m^?2 K^?1, for condensation of pure dichloromethane vapor. Condensation heat transfer in the srs‐SDR is enhanced by rotation, independent of the vapor velocity. The intensified condensation comes at the cost of relatively high energy dissipation rates, indicating condensation in the srs‐SDR is more suited as a means to supply heat (e.g. in an intensified reactor‐heat exchanger), rather than for bulk cooling purposes. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3784–3796, 2016