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.     

Enhanced wide-activated residual network for efficient and accurate image deblocking

To save bandwidth and storage space as well as speed up data transmission, people usually perform lossy compression on images. Although the JPEG standard is a simple and effective compression method, it usually introduces various visually unpleasing artifacts, especially the notorious blocking artifacts. In recent years, deep convolutional neural networks (CNNs) have seen remarkable development in compression artifacts reduction. Despite the excellent performance, most deep CNNs suffer from heavy computation due to very deep and wide architectures. In this paper, we propose an enhanced wide-activated residual network (EWARN) for efficient and accurate image deblocking. Specifically, we propose an enhanced wide-activated residual block (EWARB) as basic construction module. Our EWARB gives rise to larger activation width, better use of interdependencies among channels, and more informative and discriminative non-linearity activation features without more parameters than residual block (RB) and wide-activated residual block (WARB). Furthermore, we introduce an overlapping patches extraction and combination (OPEC) strategy into our network in a full convolution way, leading to large receptive field, enforced compatibility among adjacent blocks, and efficient deblocking. Extensive experiments demonstrate that our EWARN outperforms several state-of-the-art methods quantitatively and qualitatively with relatively small model size and less running time, achieving a good trade-off between performance and complexity.     

Hydraulic reactivity and cement formation of baghdadite

In this study, the hydraulic reactivity and cement formation of baghdadite (Ca₃ZrSi₂O₉) was investigated. The material was synthesized by sintering a mixture of CaCO₃, SiO₂, and ZrO₂ and then mechanically activated using a planetary mill. This leads to a decrease in particle and crystallite size and a partial amorphization of baghdadite as shown by X-ray powder diffraction (XRD) and laser diffraction measurements. Baghdadite cements were formed by the addition of water at a powder to liquid ratio of 2.0 g/ml. Maximum compressive strengths were found to be ~2 MPa after 3-day setting for a 24-h ground material. Inductively coupled plasma mass spectrometry (ICP-MS) measurements showed an incongruent dissolution profile of set cements with a preferred dissolution of calcium and only marginal release of zirconium ions. Cement formation occurs under alkaline conditions, whereas the unground raw powder leads to a pH of 11.9 during setting, while prolonged grinding increased pH values to approximately 12.3.     

胡萝卜丁中维生素C在热风辅助射频干燥过程中降解的动力学模型

目的研究热风辅助射频(hot air-assisted radio frequency,HA-RF)干燥过程中维生素C随温度变化的降解动力学模型。方法在6.5 cm极板间距和60℃热风系统条件下进行HA-RF干燥,重点研究胡萝卜丁中维生素C在干燥过程中的降解动力学,包括脱氢抗坏血酸(dehydroascorbic acid,DHAA)和抗坏血酸(ascorbic acid,AA)。总维生素C含量采用2,4-硝基苯肼分光光度法测定,AA采用2,6-二氯吲哚酚滴定法测定。结果HA-RF干燥过程中维生素C的降解规律符合一级可逆模型,其降解活化能为40.54 kJ/mol。DHAA活化能为35.83 kJ/mol,表明DHAA的稳定性低于AA。结论本研究使用的干燥温度为62.5~77.5℃,较高的干燥温度下维生素C降解速率较高,较低处理温度下的降解过程具有更好的模型适应度(R2>0.98)。     

Preparation of α-cordierite through mechanochemical activation of MgO–Al2O3–SiO2 ternary system

Samples of the ternary system MgO–Al₂O₃–SiO₂ with stoichiometric composition in relation to α-cordierite (Mg₂A_l4Si₅O₁₈), consisting of 22.2 mol% MgO, 22.2 mol% Al₂O₃, and 55.6 mol% SiO₂, were activated in a low energy mill with a constant speed of 100 rpm, in an aqueous medium. The precursors used were corundum (Al₂O₃), silica gel HF254 type 60 (SiO₂), and periclase (MgO). The objective of the present study was to evaluate the effect of mechanochemical activation on the solid-state synthesis of α-cordierite, using a low energy ball mill. Another objective was to shed light on the effect of mechanochemical activation on the steps of α-cordierite formation. For this end several grinding conditions were evaluated, varying the time and mass ratio of precursors/grinding elements, as well as calcination at different temperatures between 950 °C and 1350 °C for 2 h. The samples were analyzed for the determination of the formed phases by Infrared (IR) and X-ray Diffraction (XRD). The phases identified in uncalcined samples were brucite (Mg(OH)₂), forsterite (Mg₂SiO₄), enstatite (MgSiO₃), spinel (MgAl₂O₃), amorphous silica (SiO₂), corundum (α-Al₂O₃), and zirconia (monoclinic and tetragonal ZrO₂). The lowest temperature corresponding to the formation of α-cordierite (α-Mg₂Al₄Si₅O₁₈) was 1150 °C and a considerable amount of this phase (16.2%) was observed at this temperature, for the sample with the higher mechanochemical activation. In a solid-state reaction, α-cordierite is normally obtained at around 1400 °C, therefore, the formation of this phase at 1150 °C confirms that the mechanochemical activation method, using a low-cost ball mill, is efficient in reducing the solid-state reaction temperature.     

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.