Simulation studies on a rotating ring disk electrode: Effects of ionic migration with kinetic complication-disk results

In continuation to my previous work (Guha S. AIChE J. 2013;59(4):1390-1399), in this work, effects of ionic migration are evaluated for disk region of a rotating ring disk electrode system by numerically solving complex differential equations, developed for mass transfer along with kinetic complication in presence of ionic migration under limiting current condition. The system for simulation is 0.01 M Fe₂(SO₄)₃ solution with H₂SO₄ as supporting electrolyte. Simulation cases are presence and absence of ionic migration with kinetic complication (oxidation of Fe²⁺ to Fe³⁺ under O₂ pressure). Results show that concentration boundary layer thickness of reactant Fe³⁺ reduces appreciably and steady-state disk current reduces substantially in presence of migration. Simulated steady-state disk current in absence of migration case agrees well with published data. Results indicate higher Fe²⁺ concentration in presence of migration and thereby higher rate of oxidation of Fe²⁺ to Fe³⁺ at all rate constant values.     

Effects of structural parameters on water film properties of transpiring wall reactor

Corrosion and salt deposition problems severely restrict the industrialization of supercritical water oxidation. Transpiring wall reactor can effectively weaken these two problems by a protective water film. In this work, methanol was selected as organic matter, and the influences of vital structural parameters on water film properties and organic matter removal were studied via numerical simulation. The results indicate that higher than 99% of methanol conversion could be obtained and hardly affected by transpiration water layer, transpiring wall porosity and inner diameter. Increasing layer and porosity reduced reactor center temperature, but inner diameter's influence was lower relatively. Water film temperature reduced but coverage rate raised as layer, porosity, and inner diameter increased. Notably, the whole reactor was in supercritical state and coverage rate was only approximately 85% in the case of one layer. Increasing reactor length affected slightly the volume of the upper supercritical zone but enlarged the subcritical zone.     

Impact of high-intensity ultrasound on physical properties and degree of oxidation of lipase modified menhaden oil with caprylic acid and/or stearic acid

The purpose of this research was to determine the effect of high-intensity ultrasound (HIU) on physical properties, degree of oxidation, and oxidative stability of structured lipids (SLs). Caprylic acid (C) and stearic acid (S) were incorporated into menhaden oil using Lipozyme® 435 lipase to obtain five samples: (1) LC 20 (menhaden oil with 20% of C), (2) LC 30 (menhaden oil with 30% C), (3) LS 20 (menhaden oil with 20% S), (4) LS 30 (menhaden oil with 30% S), and (5) Blend C (menhaden oil with 16.24% C and 13.04% S). Samples were crystallized for 90 min at the following temperatures: (1) LC 20 at 15.5°C, (2) LC 30 at 17.5°C, (3) LS 20 at 24°C, (4) LS 30 at 30°C, and (5) Blend C at 18.0°C, and HIU was applied at the onset of crystallization. Physical properties, degree of oxidation, and oxidative stability were evaluated in sonicated and nonsonicated samples. All SLs had statistically higher G′ after sonication. Sonicated LS 30, LC 30, and Blend C had a higher melting enthalpy than the nonsonicated ones, while enthalpy values in sonicated LS 20 and LC 20 samples were not statistically different than the nonsonicated ones. No significant difference between sonicated and nonsonicated samples was observed in peroxide values (1.2 ± 0.1 meq/kg, p > 0.05) and in the oxidative stability index (6.3 ± 0.2 h, p > 0.05). These results showed that HIU was effective at changing physical properties without affecting the oxidation of the samples.     

LPNN-based approach for LASSO problem via a sequence of regularized minimizations

In compressive sampling theory, the least absolute shrinkage and selection operator (LASSO) is a representative problem. Nevertheless, the non-differentiable constraint impedes the use of Lagrange programming neural networks (LPNNs). We present in this article the -LPNN model, a novel algorithm that tackles the LASSO minimization together with the underlying theory support. First, we design a sequence of smooth constrained optimization problems, by introducing a convenient differentiable approximation to the non-differentiable -norm constraint. Next, we prove that the optimal solutions of the regularized intermediate problems converge to the optimal sparse signal for the LASSO. Then, for every regularized problem from the sequence, the -LPNN dynamic model is derived, and the asymptotic stability of its equilibrium state is established as well. Finally, numerical simulations are carried out to compare the performance of the proposed -LPNN algorithm with both the LASSO-LPNN model and a standard digital method.     

Synthesis,structure, CO oxidation,and H2 production activities of CaCu3−xMnxTi4−xMnxO12 (x = 0, 0.5, and 1.0)

Synthesis of nanocrystalline pristine and Mn-doped calcium copper titanate quadruple perovskites, CaCu_3?xMn_xTi_4?xMn_xO₁₂ (x = 0, 0.5, and 1.0) by modified citrate solution combustion method has been reported. Powder X-ray diffraction patterns attest the phase purity of the perovskite materials. Average particle sizes of all the materials obtained from the Scherrer's formula are in the range of 55–70 nm. The specific surface areas for all the perovskites obtained from BET isotherms are found to be low as expected for the condensed oxide systems and fall in the range of 13–17 m² g^?1. Transmission electron microscopy studies show a reduction in particle size of CaCu₃Ti₄O₁₂ with increase in Mn doping. Ca and Ti are present in +2 and +4 oxidation states in all the materials as demonstrated by X-ray photoelectron spectroscopy analyses. Cu²⁺ gets reduced in CaCu₃Ti₄O₁₂ with higher Mn content. Mn is observed to be present only in +3 oxidation state. All the materials have been examined to be active in CO oxidation as well as H₂ production from methanol steam reforming. CaCu₃Ti₄O₁₂ with ~14 at.% Mn is found to show best catalytic activities among these materials. A comprehensive analysis of the catalytic activities of these perovskites toward CO oxidation and H₂ production from MSR reveal the cooperative activity of copper-manganese in the doped perovskites and it is more effective at lower manganese content.     

Preparation of a CeO2–ZrO2 based nano-composite with enhanced thermal stability by a novel chelating precipitation method

In this study, a chelating agent is introduced to prepare CeO₂–ZrO₂ nano-composite through a precipitation process. The physicochemical properties of the oxide precursors, nano composite materials are strongly dependent on the preparation method and whether a chelating agent is used. Adding an appropriate quantity of chelating agent SO₄²⁻ can facilitate thermal stability and phase structure uniformity of CeO₂–ZrO₂ mixed oxides. The calculation results showed that the Gibbs free energy of chelating complex of [ZrSO₄]²⁺ (ΔG = −127.2469 kJ/mol) is higher than the [Ce(III)SO₄]⁺ (ΔG = -29.8279 kJ/mol). The precipitation chemical potential of Zr⁴⁺ moves close to the precipitation chemical potential of Ce³⁺. The novel and low-cost chelating precipitation method can modify the homogeneity of the compounds at the atomic scale, which can offer a powerful opportunity for, and provide direction in, the design of materials with exceptional properties.     

Boosting the activity of FeOOH via integration of ZIF-12 and graphene to efficiently catalyze the oxygen evolution reaction

Transition metal oxyhydroxides have been used as promising electrocatalysts for water splitting however, their catalytic activity is restricted due to low surface area and poor conductivity. Herein, we report novel composite FeOOH@ZIF-12/graphene composite as electrocatalyst for water oxidation, whereby ZIF-12 provide extra surface for the FeOOH dispersion whilst graphene act as excellent electron mediator. The composite shows a low overpotential value of 291 mV to attain a current density of 10 mA cm^?2 and a low Tafel slope value of 78 mV dec^?1. The catalyst offers a maximum current density of 101 mA cm^?2, while it gives a turnover frequency (TOF) value of 0.031 s^?1 at an overpotential of 291 mV only. The excellent activity and remarkable stability of composite is attributed to highly conductive and porous support.     

高碘酸盐的活化及降解水体有机污染物研究进展

根据高碘酸盐活化方式、活化机理和相关自由基种类等方面,叙述了国内外高碘酸盐高级氧化体系降解水体有机污染物方面的工作。基于氧化剂为高碘酸盐的高级氧化技术氧化能力强,能在较宽的pH范围内高效降解包括抗氧化能力极强的全氟辛酸(PFOA)在内的多种有机污染物,在水处理领域具有较好的应用潜力。依据目前的研究现状,结合实际需求,认为进行废水处理的小试或者中试、优化活化理论研究,以及明确各活性物质对有机物选择性降解的机理,是将来需要关注的问题以及研究方向。     

基于Matlab的制芯机器人夹持器稳定性研究与分析

由于铸造厂制芯机器人的工作环境恶劣,机器人抓取砂芯的稳定性较差,时常出现掉砂芯、夹伤砂芯的问题。针对上述问题建立以夹持器、气压、机械振动的系统数学模型,采用高阶系统极点在[s]平面的分布法来判定该系统的稳定性。在确保高阶系统极点值不变的情况下,通过改变系统的零点值来观察零点值对系统稳定性、振荡衰减时间的影响。用Matlab的pzmap和impulse函数分别对系统的零点、极点分布和零点值的不同对系统响应进行仿真,运用仿真结果与现场试验进行优化参数,结果表明采用一种刚度与柔度各为1/2的夹持器对制芯机器人的稳定性具有较好优化效果。     

Improved synergetic excitation control for transient stability enhancement and voltage regulation of power systems

This paper proposes decentralized improved synergetic excitation controllers (ISEC) for synchronous generators to enhance transient stability and obtain satisfactory voltage regulation performance of power systems. Each generator is considered as a subsystem, for which an ISEC is designed. According to the control objectives, a manifold, which is a linear combination of the deviation of generator terminal voltage, rotor speed and active power, is chosen for the design of ISEC. Compared with the conventional synergetic excitation controller (CSEC), a parameter adaptation scheme is proposed for updating the controller parameter online in order to improve the transient stability and voltage regulation performance simultaneously under various operating conditions. Case studies are undertaken on a single-machine infinite-bus power system and a two-area four-machine power system, respectively. Simulation results show the ISEC can provide better damping and voltage regulation performance, compared with the CSEC without parameter adaptation scheme and the conventional power system stabilizer.