对硝基苯胺水相加氢合成对苯二胺

以对硝基苯胺为原料,水为溶剂,考察了水相中负载型镍催化剂催化对硝基苯胺加氢还原的反应性能,并开展了中试实验。考察了反应温度、压力、保温时间、对硝基苯胺浓度、废水套用等因素对催化加氢反应性能的影响。实验结果表明,产品对苯二胺质量分数较高,催化剂和水可循环使用。得到较佳的工艺条件为:温度110℃,保温时间1 h,压力2.0 MPa,搅拌转速800 r/min,起始催化剂用量10%(以对硝基苯胺的质量为基准,下同),催化剂损耗0.2%(以起始添加催化剂的质量为基准)。在该工艺条件下,对苯二胺产率达99.5%以上。废水套用后排放废水量很少,且对催化剂催化活性、产品质量等没有影响。     

Regenerable Sorbents for High-Temperature Desulfurization of Syngas from Biomass Gasification

Single-metal high-temperature solid sorbents for syngas cleaning using Mn, Ca, Fe, Cu, or Mo supported on γ-Al₂O₃ were synthesized, characterized, and tested in a fixed-bed reactor. H₂S and SO₂ concentrations in the gas after treatment at T = 400 to 700 °C were compared with thermodynamic calculations. The Mn-based sorbent showed the best ability to achieve a low sulfur residual in the gas, especially at temperatures above 600 °C. Sorbents with Fe, Cu, and Mo gave SO₂ formation in the initial phase, but this could be avoided by a pre-reduction treatment of the sorbent material.     

Preparation and characterization of highly stable protic-ionic-liquid membranes

A highly durable proton exchange membranes (PEM)s based on covalently supported ionic liquid (IL) bearing sulfonic acid imidazolium groups were successfully fabricated. The membrane preparation involved radiation induced grafting of 1-vinyl imidazole (1-VIm) onto poly(ethylene-co-tetraflouroethene) (ETFE) film, followed by covalent immobilization of 3-sulfopropyl and subsequent treatment with trifluoromethanesulfonic acid. The ionic conductivity of the supported IL membranes was increased with the increase in the concentration of IL and reached a maximum value of 138 mS cm⁻¹ in a fully hydrated state with an ion exchange capacity of 4.82 mmol g⁻¹ that is higher than Nafion with a similar thickness. The membranes displayed excellent chemical and mechanical stability. In addition, the dimensional and thermal stability of supported IL-membranes were significantly higher than commercial Nafion membranes.     

Synthesis of highly active and stable Pd/C catalysts toward HCOOH dehydrogenation by a simple NH3 adsorption method

Pd catalysts supported on activated carbon (Pd/C–NH₃) toward HCOOH dehydrogenation were prepared by a simple adsorption method using ammonia (NH₃) and Ar as the working gas. The results show that the TOF_initial of Pd/C–NH₃ was 459.8 h⁻¹ at 50 °C. When the reaction was carried out for 4 h, the HCOOH dehydrogenation ratio over Pd/C–NH₃ was about 81.2%, which was 1.15 and 1.13 times, respectively, as that of the as-prepared Pd/C catalyst without any treatment (Pd/C–As) and the Pd/C catalyst purchased from Sigma-Aldrich (Pd/C-CM). The total amount of H₂ and CO₂ produced by using Pd/C–NH₃ to decompose HCOOH in the third cycle was 99.4% of the gas produced by the first reaction cycle, and 1.80 and 12.60 times, respectively, as that of Pd/C–As and Pd/C-CM. The characterization results indicated that the Pd active species in Pd/C–NH₃ migrated to the outer surface of the carbon support during the reaction, and the pore volume of the carbon support became larger, which were beneficial to the reaction. These factors made Pd/C–NH₃ exhibit excellent HCOOH dehydrogenation activity and stability. NH₃ adsorption is a simple and effective method for preparing high-performance Pd/C HCOOH dehydrogenation catalysts, and has important guiding significance for the preparation of other carbon supported noble metal catalysts.     

A Dijkstra-like method computing all extreme supported non-dominated solutions of the biobjective shortest path problem

We address the problem of determining all extreme supported solutions of the biobjective shortest path problem. A novel Dijkstra-like method generalizing Dijkstra׳s algorithm to this biobjective case is proposed. The algorithm runs in O(N(m+n log n)) time to solve one-to-one and one-to-all biobjective shortest path problems determining all extreme supported non-dominated points in the outcome space and one supported efficient path associated with each one of them. Here n is the number of nodes, m is the number of arcs and N is the number of extreme supported points in outcome space for the one-to-all biobjective shortest path problem. The memory space required by the algorithm is O(n+m) for the one-to-one problem and O(N+m) for the one-to-all problem. A computational experiment comparing the performance of the proposed methods and state-of-the-art methods is included.     

RSVP与SSVEP混合脑电信号刺激与多类事件检测

提出一种新的基于快速序列视觉呈现（Rapid Serial Visual Presentation,RSVP）与稳态视觉诱发电位（Steady-State Visually Evoked Potential,SSVEP）组合范式的脑电信号（Electroencephalogram,EEG）刺激与多类事件检测方法。对诱发的原始脑电信号通过电位重参考、基线去除、空间滤波等预处理操作去除数据的伪迹和噪声,通过自举聚合决策树（Bagging Tree,BT）和支持向量机（Supported Vector Machine,SVM）等机器学习算法,对14名受试者双重刺激诱发的脑电信号进行目标与频率相结合的多类事件检测,通过实验验证了该组合范式诱发的脑电信号具有良好的多类可分性,为开发基于RSVP和SSVEP两种范式的混合型脑-机接口应用提供了一种新的有效途径。同时,实验结果还表明,基于机器学习的BT和SVM模型对RSVP和SSVEP组合范式诱发的EEG信号进行多类识别的性能明显优于传统的典型关联分析（Canonical Correlation Analysis,CCA）算法的性能。     

Surface structure and catalytic performance of supported PtSn catalysts

The valence states of tin in supported PtSn catalysts after reduction were tracked by in situ Mössbauer spectroscopy. Combined with catalytic evaluation, it is suggested that only when tin is in oxidative states, the catalytic performance can be greatly improved. The changes of surface structure of PtSn/Al₂O₃ during repeated coking-regeneration-reduction (CRR) cycles were also studied.     

Oxidative dimerisation of methane on a supported Pd-Ag catalyst using a diffusion controlled ceramic wall reactor

Supported palladium-silver oxides were used as catalysts for the partial oxidation of methane by molecular oxygen in a tubular reactor with ceramic wall separation. The ceramic wall controls the O₂ supply in the catalyst bed. The results indicate that the reactor configuration can play an important role in methane oxidation. C₂H₆, C₂H₄, CO₂ and H₂O were obtained at temperatures less than 300 °C. At this temperature any contribution from homogeneous gas phase reaction can be ruled out.     

The catalytic activity of FeOx/ZrO2 for the abatement of NO with propene in the presence of O2

FeO_x/ZrO₂ samples, prepared by impregnation with Fe(NO₃)₃, were characterised by means of DRS, XRD, FTIR, redox cycles and volumetric CO adsorption. Volumetric CO adsorption, combined with FTIR, showed that 45% of iron in the sample containing 2.8 Fe atoms nm⁻² was capable of forming iron carbonyls. DRS evidenced Fe₂O₃ on samples with Fe-content≥2.8 atoms nm⁻². The selective catalytic reduction of NO with C₃H₆ in the presence of O₂ was studied with a reactant mixture containing NO=4000 ppm, C₃H₆=4000 ppm, O₂=2%. The dependence on iron-content suggests that only isolated iron, prevailing in dilute FeO_x/ZrO₂, is active for NO reduction, whereas iron on the surface of small oxide particles, prevailing in concentrated FeO_x/ZrO₂, is active for C₃H₆ combustion.     

Microstructural investigations of tubular α-Al2O3-supported γ-Al2O3 membranes and their hydrothermal improvement

γ-Al₂O₃ meso-porous membranes supported by tubular α-Al₂O₃ substrates were prepared by using the sol-gel method and their nanostructural characterizations were performed for the first time with high-resolution transmission electron microscopy (HRTEM) before and after hydrothermal treatment at 500 °C. The HRTEM images and pore size distribution (PSD) analyses revealed that the morphologies as well as the characteristics of the powder and membrane samples prepared from the same boehmite are not identical. γ-Al₂O₃ and La₂O₃-Ga₂O₃ doped-γ-Al₂O₃ (LGA) membranes supported by α-Al₂O₃ were also fabricated and characterized under thermal and hydrothermal conditions for the purpose of comparisons. Finally, two type α-Al₂O₃/γ-Al₂O₃/SiO₂ (AA-SiO₂) and α-Al₂O₃/La₂O₃-Ga₂O₃-γ-Al₂O₃/SiO₂ (ALGA-SiO₂) membranes have been synthesized and the gas permeance of the membrane were measured in the temperature range 100–500 °C.