Investigation of La0.6Sr0.4Co1-xNixO3-δ (x=0, 0.2, 0.4, 0.6, 0.8) catalysts on solid oxide fuel cells anode for biogas dry reforming

The introduction of catalyst on anode of solid oxide fuel cell (SOFC) has been an effective way to alleviate the carbon deposition when utilizing biogas as the fuel. A series of La_0.6Sr_0.4Co_1-xNi_xO_3-δ (x = 0, 0.2, 0.4, 0.6, 0.8) oxides are synthesized by sol-gel method and used as catalysts precursors for biogas dry reforming. The phase structure of La_0.6Sr_0.4Co_1-xNi_xO_3-δ oxides before and after reduction are characterized by X-ray diffraction (XRD). The texture properties, carbon deposition, CH₄ and CO₂ conversion rate of La_0.6Sr_0.4Co_1-xNi_xO_3-δ catalysts are evaluated and compared. The peak power density of 739 mW cm^?2 is obtained by a commercial SOFC with La_0.6Sr_0.4Co_0.4Ni_0.6O_3-δ catalyst at 850 °C when using a mixture of CH₄: CO₂ = 2:1 as fuel. This shows a great improvement from the cell without catalyst for internal dry reforming, which is attributed to the formation of NiCo alloy active species after reduction in H₂ atmosphere. The results indicate the benefits of inhibiting the carbon deposition on Ni-based anode through introducing the La_0.6Sr_0.4Co_0.4Ni_0.6O_3-δ catalyst precursor. Additionally, the dry reforming technology will also help to convert part of the exhaust heat into chemical energy and improve the efficiency of SOFC system with biogas fuel.     

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.     

Numerical modeling of hydrogen catalytic reactions over a circular bluff body

This paper was intended to delineate numerical research for hydrogen catalytic combustion over a circular cylinder. The wire/rod-type catalytic reactor is a simple geometry reactor with an economical design with less pressure loss. For the single rod in the reaction channel, the flow characteristic and the difference of conversion efficiency between non-gas-phase reaction and gas-phase reaction have been delineated in the present study. The flow field and the chemical reactions were numerically modeled using 2D Large Eddy Simulation combined with the gas-phase and surface reaction mechanisms. The results show that the current numerical simulation has been validated to precisely predict the vortex shedding and its frequency in the cold flows. Despite the variation trends being dominated by the upstream flow, the vortex shedding phenomena were affected by the flue gas generated from the rod surface. It can be seen from the linear relationship between the vortex shedding frequency of reacting flow and Reynolds Number. It is noted that the vortex shedding vanished if the gas-phase reaction was ignited in the reaction channel. In addition, the geometric modified conversion efficiency was proposed to delineate an indicator that could be potential for the optimization of rod-type catalytic reactor. In summary, the fundamental study of a rod in a 2D flow channel can provide information for optimizing the catalytic design or the rod array arrangement in the reactor. Moreover, the rod can also be a partial catalytic flame holder to ignite and stabilize the gas-phase reaction. The obtained results could be the potential for practical applications of rod-type catalytic combustion, catalytic gas turbine, hydrogen generation, partially catalytic reaction flame holder, and other catalytic reactions that can be appreciated.     

Techno-economic-environmental evaluation of a combined tri and dry reforming of methane for methanol synthesis with a high efficiency CO2 utilization

Production of methanol, as a green energy, from syngas is coming into focus. However, natural gas based methanol plants, which are used steam reforming of methane for syngas production, have a high CO₂ emission resulting in the global warming. In this study, a novel process for methanol synthesis is proposed to reduce CO₂ emission. In this regard, natural gas and flue gas are fed to a parallel-series system with tri and dry reforming of methane for syngas production with the optimized stoichiometric number. Then, the produced syngas is converted to methanol in a reactor. Finally, the produced methanol is purified by two distillation towers. The proposed method is compared to a referenced method in the view of technological, economic and environmental metrics. The techno-economic-environmental analysis of the processes reveals that not only the proposed method, as compared to the referenced one, increases CO₂ conversion from 20.93% to 99.22%, but also it is more economical and environmentally friendly. In addition, the global warming potential of the proposed method is almost 60% lower than that for the referenced method due to the lower CO₂ emission. Therefore, the proposed method can save above MUS$ 8 a year by CO₂ capture.     

Hydrogen-rich gas generation via the exhaust gas-fuel reformer for the marine LNG engine

Reformed exhaust gas recirculation technology has attracted great attention in internal combustion engines. A platform of an exhaust gas-fuel reformer connected with the marine LNG engine was set up for generating on-board hydrogen. Based on the platform, effects of the methane to oxygen ratio (M/O) and reformed exhaust gas ratio (R_EG) from the reformer and excess air ratio (λ) from the engine on the components, hydrogen yield, thermal efficiency and reforming process of the reformer were experimentally investigated. Results shown that hydrogen-rich gases (reformate) can be generated by reforming the mixture of engine exhaust gas (about 400 °C) and methane supplied via the reformer with Ni/Al₂O₃ catalyst, and the hydrogen concentration of reformate was between 6.2% and 12.6% by volume. The methane supplied rate and λ affected the components and temperature of the reactant in the reformer, while R_EG changed the gas hour space velocity during the exhaust gas-fuel reforming processes, resulting in the difference in the components of the reformate and thermal efficiency. At the present experimental condition, the highest H₂ concentration reformate was generated under the M/O of 2.0, λ of 1.55 and R_EG of 6%.     

Effect of catalytic washcoat shape and properties on mass transfer characteristics of microstructured steam-methanol reformers for hydrogen production

Many attempts have been made to improve mass transfer by reducing the size of reactors. However, such reduction will fairly quickly reach practical limitations and numerous difficulties still remain. Catalytic washcoat shape and properties may be critical design factors, but the mechanisms for their effects on mass transfer characteristics are still not fully understood. To effectively eliminate problems associated with mass transport phenomena in microstructured steam-methanol reformers, the effects of washcoat shape and properties were investigated in various situations by performing computational fluid dynamics simulations. The dependence of the solution on mass transfer characteristics was reduced to a small number of dimensionless parameters. A dimensionless mass transfer analysis was carried out in terms of the Sherwood, Schmidt, and pore Reynolds numbers. The results indicated that the rate of mass transfer is predominantly controlled by washcoat properties, and porosity and effective thermal conductivity are fundamentally important. The rate of the reforming reaction is typically controlled by kinetics at a temperature of 480 K and limited by mass transfer at a temperature of 580 K. The shape of washcoats affects the overall mass transfer characteristics, depending on the structural and thermal properties of washcoats. The shape effect is limited by heat transfer. A three-fold increase in effectiveness factor can be achieved by increasing the effective thermal conductivity of the washcoat. Design recommendations were finally made to improve transport characteristics for the systems.     

Synergetic photocatalytic and thermocatalytic aqueous phase reforming of methanol for hydrogen production based on noble metal/photosensitive supports catalysts

To overcome high Gibbs free energy and low reaction rate of thermal catalytic and photocatalytic hydrogen production from methanol-H₂O mixture, photo-thermal synergistic catalysis (PC-TC) reforming has proved to be an effective strategy owing to the photo-assited thermal synergistic effect to accelerate the step controlling kinetic behavior. In order to efficiently produce H₂, proper photosensitive catalysts which absorb light energy and also show efficient thermal catalytic (TC) performance need to be developed. To study the designing principle for catalysts, herein we incorporate Pt/Pd and three different supports which show similar band gaps (ZnO, CeO₂, and P25) through the in-situ photo-deposition, which act as catalysts for PC-TC methanol aqueous reforming. The resultant 0.1%Pt/P25 catalyst exhibits H₂ evolution activity ～3.1 times than that of the TC condition and ～5.5 times than that of the photocatalytic reforming (PC) condition in the proposed PC-TC process; meanwhile 0.1%Pt/ZnO and 01%Pt/CeO₂ under PC-TC condition show ～1.3 times and ～2.0 times than that of the catalytic performance under TC condition. The physical characterizations prove that the metal-support interaction and the supports may be key factors for the catalytic performance. The active intermediate trapping experiments demonstrate possible intermediates in the PC-TC process and established reaction mechanisms to explain the synergetic effect for improved efficiency of hydrogen production. These findings may open up a new avenue of designing catalysts based on semiconductors for the PC-TC reforming of methanol-water to produce hydrogen in a high-efficiency and low-cost way, serving the needs of the future hydrogen economy.     

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.     

堆本体抗震试验动力相似关系推导与验证

为确保堆本体抗震试验中流体对流效应、脉冲效应和堆本体结构响应的准确性，需保证重力、流体与固体惯性力、结构弹性力和结构应变的相似性。本文从固体结构的振动方程、不可压牛顿流体的动力学方程、流固交界面的边界条件和环形柱体域内液体线性晃动的动力学公式出发，基于控制方程的量纲分析法，推导了考虑液体晃动效应的堆本体地震响应动力相似关系。基于上述相似关系建立了堆容器堆内构件和堆容器内自由液面流体域的缩尺模型，通过有限体积法分析堆容器堆内构件原型和缩尺模型中液体的晃动固有频率、晃动波高、压力以及液体晃动对堆容器支承裙的倾覆力矩。结果表明本文动力相似关系具有合理性和准确性，可用于堆本体缩尺模型的抗震试验研究。