Influence of metal-support interactions on reaction pathways over Ni/CeZrOx–Al2O3 catalysts for ethanol steam reforming

This work investigates selective Ni locations over Ni/CeZrO_x–Al₂O₃ catalysts at different Ni loading contents and their influences on reaction pathways in ethanol steam reforming (ESR). Depending on the Ni loading contents, the added Ni selectively interacts with CeZrO_x–Al₂O₃, resulting in the stepwise locations of Ni over CeZrO_x–Al₂O₃. This behavior induces a remarkable difference in hydrogen production and coke formation in ESR. The selective interaction between Ni and CeZrO_x for 10-wt.% Ni generates more oxygen vacancies in the CeZrO_x lattice. The Ni sites near the oxygen vacancies enhance reforming via steam activation, resulting in the highest hydrogen production rate of 1863.0 μmol/g_cat·min. In contrast, for 15 and 20-wt.% Ni, excessive Ni is additionally deposited on Al₂O₃ after the saturation of Ni–CeZrO_x interactions. These Ni sites on Al₂O₃ accelerate coking from the ethylene produced on the acidic sites, resulting in a high coke amount of 19.1 mg_c/g_cat·h (20Ni/CZ-Al).     

Recent trends in the development of reactor systems for hydrogen production via methanol steam reforming

Hydrogen is currently receiving significant attention as an alternative energy resource, and among the various methods for producing hydrogen, methanol steam reforming (MSR) has attracted great attention because of its economy and practicality. Because the MSR reaction is inherently activated over catalytic materials, studies have focused on the development of noble metal-based catalysts and the improvement of existing catalysts with respect to performance and stability. However, less attention has been paid to the modification and development of innovative MSR reactors to improve their performance and efficiency. Therefore, in this review paper, we summarize the trends in the development of MSR reactor systems, including microreactors and membrane reactors, as well as the various structured catalyst materials appropriate for application in complex reactors. In addition, other engineering approaches to achieve highly efficient MSR reactors for the production of hydrogen are discussed.     

Motion trajectory prediction model of hydrogen leak and diffusion in a stable thermally-stratified environment

The motion trajectory of hydrogen leakage is an essential safe issue for the application of hydrogen energy. A dimensionless fast-running motion trajectory prediction model is proposed to predict the dispersion characteristics of the buoyant jet of hydrogen leakage for the accident. The impact of different leakage angles, leakage velocity and thermal stratification of ambient air on hydrogen leakage behavior was analyzed. The new developed model was verified by experimental results in literatures. Leakage hydrogen can flow upwards freely in a uniform environment. However, it shows an oscillating trajectory at a certain height in a thermally stratified environment, which is so called “locking phenomenon”. The trajectory of hydrogen leakage is upward and hydrogen gathers at the top of the space to form stratification in a uniform environment, while the hydrogen leakage shows an oscillating trajectory at a certain height in a thermal stratification environment. With the increase of Froude number Fr, it shows that the stable height and maximum height of the leakage airflow have a trend of rising first and then falling in a thermally stratified environment. The findings are expected to give guidance in real-world situations, for example, a larger Fr value and a larger temperature gradient can lead to a decrease in the stable height in the thermally stratified environment. It is found that the fitting of the stable height with different temperature gradients satisfies the power function relationship. This work is expected to be helpful for reducing hydrogen leakage accumulation and explosion risk.     

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.     

Novel core-shell-like Ni-supported hierarchical beta zeolite catalysts on bioethanol steam reforming

Hierarchical-Beta zeolites have been hydrothermally synthesized by adding a new gemini organic surfactant. The used gemini surfactant play the role of a “pore-forming agents” on the mesoscale, on the same time, providing alkaline environment for the system. With this hierarchical Beta zeolite as the core support, we successfully prepared a shell layer of Ni-containing (22 wt%) petal-like core-shell-like catalyst and applied it to bioethanol steam reforming. At the reaction temperature of 350 °C–550 °C, the conversion rate of ethanol and the selectivity of hydrogen were always above 85% and 70%. After reaction of 100 h on stream at 400 °C, there were not obvious inactivation could be observed on NiNPs/OH-MBeta catalyst.     

Numerical investigation of a multichannel reactor for syngas production by methanol steam reforming at various operating conditions

A novel multichannel reactor with a bifurcation inlet manifold, a rectangular outlet manifold, and sixteen parallel minichannels with commercial CuO/ZnO/Al₂O₃ catalyst for methanol steam reforming was numerically investigated in this paper. A three-dimensional numerical model was established to study the heat and mass transfer characteristics as well as the chemical reaction rates. The numerical model adopted the triple rate kinetic model of methanol steam reforming which can accurately calculate the consumption and generation of each species in the reactor. The effects of steam to carbon molar ratio, weight hourly space velocity, operating temperature and catalyst layer thickness on the methanol steam reforming performance were evaluated and discussed. The distributions of temperature, velocity, species concentration, and reaction rates in the reactor were obtained and analyzed to explain the mechanisms of different effects. It is suggested that the operating temperature of 548 K, steam to carbon ratio of 1.3, and weight hourly space velocity of 0.67 h⁻¹ are recommended operating conditions for methanol steam reforming by the novel multichannel reactor with catalyst fully packed in the parallel minichannels.     

一种2,6-二甲基苯甲酸的改进合成方法

以2,6-二甲基苯胺为原料,通过重氮化反应制备2,6-二甲基苯腈,经水蒸汽蒸馏法提纯后,采用75%硫酸酸化,再经酸碱法对产物进行脱色和纯化得产物2,6-二甲基苯甲酸,总收率68.4%。工艺简单、操作安全、适合工业化生产。     

埋地管道泄漏内封堵装置设计与研究

针对流体输送埋地管道泄漏问题,设计了一种利用管道机器人携带封堵气囊进行快速应急封堵修复的埋地管道泄漏内封堵装置。采用矩阵变换方法建立了牵引系统驱动轮过弯方程,利用MATLAB软件对过弯方程进行了验证,同时利用ADAMS软件仿真分析过弯路径与驱动轮转角对牵引系统行走速度的影响。研究结果表明:由两个串联封堵器组成的应急封堵系统可满足复杂工况下的管道泄漏封堵要求;牵引系统驱动轮在弯管内部行走时,单轮速度呈周期性变化,但三个驱动轮整体周期运动特性一致;驱动轮转角在25°~40°时,牵引系统行走速度与驱动轮转角成正比,且转角为30°时驱动效果最好。该内封堵装置的结构设计可为管道泄漏应急封堵领域装备的研发提供重要参考。     

基于热负荷自动调节的延迟焦化加热炉三点注汽量智能优化

针对国内某炼油厂延迟焦化加热炉三点注汽问题，采用热负荷自动调节的算法进行了研究。运用该模型方法，分析了三点注汽量对加热炉热负荷和炉管结焦系数的影响，发现三点注汽量的改变均会对热负荷和炉管结焦系数产生影响，主要表现为提高注汽量将会提高热负荷，同时降低结焦系数；第1点注汽量和第2点注汽量对热负荷和结焦系数的影响较强，第3点注汽量对热负荷和结焦系数的影响较弱。在实际操作中，加热炉中的结焦程度既不能太强也不能太弱，合适的结焦系数能够保证正常开工周期里炉管不结焦，也能保证瓦斯、注汽量等参数的合理分配。通过对热负荷、注汽量的智能分配，可得到不同原料油加工负荷条件下更加合理的装置运行方案。