Hydrogen generation in a Pd membrane fuel processor: Productivity effects during methanol steam reforming

Performance analyses are carried out for the palladium membrane fuel processor for catalytic generation of high purity hydrogen. The reactor model includes detailed particle-scale multi-component diffusion, multiple reversible reactions, flow, and membrane transport. Using methanol steam reforming on Cu/ZnO/Al₂O₃ catalyst as the test reaction, a systematic examination of the effects of operating and reactor design parameters on key performance metrics is presented. Single particle simulations reveal a complex interplay between nonisobaric transport and the reversible reactions (methanol reforming and decomposition, and water-gas shift), which impact overall reactor performance. An analysis of characteristic times helps to identify four different productivity controlling regimes: (i) permeation control, encountered with thick membranes and/or insufficient membrane area; (ii) catalyst pore diffusion control encountered with diffusion of reacting species in larger particles; (iii) reaction control, encountered when intrinsic catalytic rates are too low because of inadequate activity or catalyst loading; and (iv) feed control, encountered when the limiting reactant feed rate is inadequate. The simulations reveal that a maximum in the hydrogen productivity occurs at an intermediate space velocity, while the hydrogen utilization is a decreasing function of space velocity, implying a trade-off between productivity and hydrogen utilization. The locus of productivity maxima itself exhibits a maximum at an intermediate membrane surface to volume ratio, the specific value of which is dependent on the particle size, membrane thickness and reaction conditions. At moderate temperature and total pressure (, 10 bar), particles smaller than 2 mm diameter, Pd membranes with thickness less than , and membrane surface to volume ratio exceeding are needed to achieve viable productivity . A comparison between the packed-bed membrane reactor and conventional packed-bed reactor indicates a modest improvement in the conversion and productivity due to in situ hydrogen removal.     

Magnetoelectric,magnetodielectric effect and dielectric,magnetic properties of microwave-sintered lead-free x(Co0.9Ni0.1Fe2O4)-(1-x)[0.5(Ba0.7Ca0.3TiO3)-0.5(BaZr0.2Ti0.8O3)] particulate multiferroic composite

Materials with two distinct (magnetostrictive-ferroelectric) phases, i.e., x (Co_0·9Ni_0·1Fe₂O₄) -(1-x) [0.5 (Ba_0·7Ca_0·3TiO₃) −0.5 (BaZr_0·2Ti_0·8O₃)], combined at ratios of 10:90, 20:80, 30:70, and 40:60 were prepared using a hydroxide coprecipitation method. These multiferroic composites were subjected to sintering via the hybrid microwave sintering technique at 1200 °C for 20 min. Ni-substituted CFO exhibited excellent magnetic properties at room temperature, with Ms ≈ 80 emu/g, μB ≈ 3.37, Mr ≈ 19.05 emu/g, and Hc ≈ 599 Oe, as well as a high value of the magnetostriction coefficient (λ12 ≈ −118 ppm). The magnetostrictive-ferroelectric crystal phases in each composite were confirmed via X-ray diffraction analysis. The highest value of the linear magneto-electric coefficient was α = 21.6 mV/cm-Oe at a frequency of 1 kHz for the 40CNFO-60(BCT-BZT) composite, and a similar sample had the highest value of the magnetodielectric coefficient, which was approximately 3.3% at f = 1 kHz with an applied magnetic field of 1 T. The typical ferromagnetic and ferroelectric nature of each composite was confirmed by M − H and P–E hysteresis loops, respectively at room temperature. Two anomalies were observed in the temperature-dependent dielectric permittivity one at ~140 °C and another above 500 °C confirming the coexistence of two materials with distinct transition points, i.e., BCT-BZT and CNFO, respectively.     

Mechanical,electrical and thermal performance of hybrid polyethylene-graphene nanoplatelets-polypyrrole composites: a comparative analysis of 3D printed and compression molded samples

ABSTRACT

The paper focuses on the investigation of the 3D printing of multi-functional composites using graphene nanoplatelets (GNP), polypyrrole (PPY) and linear low-density polyethylene (LLDPE). A holistic approach was performed and characterization methods to assess the properties of 3D printed composites and compared with those of compression molded composites and neat LLDPE to understand the factors affecting their performance. It has been noted that the 3D printed composites have superior mechanical and electrical properties than neat LLDPE, but slightly lower compared to those of compression molded composites having high packing density of fillers. The nominal increases were 13.2% (tensile strength), 31.9% (flexural strength), 29.4% (flexural modulus) and 24.7% (storage modulus).     

上流式反应器气液相间传质特性的实验研究

上流式反应器设置在固定床渣油加氢反应器前有利于提高渣油原料适用性,延长装置运行时间。实验研究了上流式反应器气液相间传质,采用五齿柱形氧化铝催化剂模拟工业催化剂颗粒,水溶液模拟渣油,空气模拟氢气,采用无氧水物理吸收和亚硫酸钠化学吸收的方法,测定了在高气液比的条件下上流式反应器床层气液相间传质特性实验。考察了表观气速、表观液速、填料粒径、内构件、催化剂级配和床层高径比对液相体积传质系数和气液相界比表面积的影响规律。实验数据表明,液相体积传质系数随着气、液速的增大而增大;随填料颗粒增大而减小;在床层内安装合适的内构件或增大反应器高径比,能够促进气液相间传质。基于实验数据拟合了适合上流式反应器液相体积传质系数和气液相界比表面积的经验关联式,拟合误差最大分别为12%和24%;表明所建气液相间传质的经验关联式能更好地预测上流式反应器中的气液相间传质特性。     

不同反应器中氧化反应与水蒸气气化反应协同作用差异性

在?80mm×3000mm气流床和?40mm×200mm流化床中进行了O₂、H₂O、H₂O+O₂气氛下800℃胜利褐煤气化实验，同时在流化床中进行了O₂、H₂O、H₂O+O₂气氛下半焦原位气化实验和H₂O气氛下半焦完全气化实验。比较了2种反应器中氧化反应与水蒸气气化反应协同作用的大小（强弱）；结合实验条件利用缩核模型分别推导了2种反应器中协同作用影响下水蒸气气化反应速率方程；同时，从传质（扩散）速率、动力学、半焦-挥发分相互作用3方面探讨了2种反应器中协同作用存在显著差异的原因。结果发现，气流床中H₂O+O₂气氛下褐煤转化率明显大于H₂O和O₂单独气氛下褐煤转化率之和，其差值稳定在2.11%～4.01%，而在流化床中差值仅为0～0.75%，相对流化床，气流床中协同作用更明显。这是由于，在流化床中水蒸气向炭粒表面扩散的传质速率约为气流床的11%～25%，水蒸气气化过程受气膜扩散控制，炭粒表面水蒸气全部参与气化反应，炭粒表面无“多余”水分子，氧气开孔/扩孔作用提供的活性位“闲置”，而气流床中气化反应为速控步，炭粒表面有“富裕”水分子，可充分利用氧气开孔/扩孔作用提供的活性位，促进作用显著；挥发分-半焦相互作用不是流化床反应器中协同作用不显著的原因。     

填料生物转盘对农村家庭生活污水的处理

根据目前我国农村生活污水处理的现状以及农村家庭污水水量、水质的特点,提出了一种家庭生活污水处理装置-填料生物转盘。该装置采用生物膜法工艺,结合生物转盘与生物滤池工艺的特点,运用设备一体化的设计理念,设计了一种运行管理简单、结构紧凑的一体化装置。通过实际运行考察了装置用于农村家庭生活污水处理的挂膜启动情况,以及污染物的去除效果。结果表明:填料生物转盘生物膜的驯化培养需要20天的时间,稳定运行期间对COD、NH4+-N、TN、TP的平均去除率分别稳定在75%、85%、65%和75%以上,出水COD、NH4+-N、TN优于城镇污水处理厂污染物排放标准(GB 18918-2002)一级A标准,出水TP达到一级B标准。装置运行管理操作简单,不需要专业技术人员,适合农村家庭污水的处理。     

不同尺寸反应器内H2O2热分解氧化NO特性与氧化产物分析

采用实验方法研究了不同尺寸滴管炉反应器内H₂O₂热分解氧化NO特性。对比了不同H₂O₂蒸发条件对NO氧化率的影响规律。分析了气体温度、H₂O₂溶液浓度、H₂O₂：NO摩尔比、NO初始浓度及气体流量对NO氧化率的影响。检测了氧化产物并分析了产物的生成路径。结果表明：H₂O₂的快速蒸发是其热分解氧化NO的前提。减小H₂O₂液滴尺寸或液膜厚度可加速H₂O₂蒸发与分解,提高NO氧化率,扩宽NO氧化的温度范围。保证蒸发速率可削弱H₂O₂浓度对NO氧化率的影响。当H₂O₂：NO < 10时,NO氧化率随H₂O₂：NO的增加而增加;当H₂O₂：NO>10时,NO氧化率几乎不随H₂O₂：NO变化。H₂O₂热分解对于较高浓度的NO具有更高的氧化效率。H₂O₂热分解氧化NO的主要产物为NO₂。HO₂·直接将NO氧化为NO₂,·OH则先将NO转化为HONO,然后进一步氧化为NO₂。     

间歇釜式反应器控制策略与最优操作方案的研究

采用数学模拟方法 ,以不同控制策略综合研究了间歇釜式反应器中进行不同反应过程的最优反应操作时间和操作温度 ,可用于指导反应过程的开发及生产操作控制。