The order with respect to oxygen and the activation energy for the burning of an anthracitic char in O2 in a fluidised bed, as measured using a rapid analyser for CO and CO2

Measurements of the oxidation of a coal char in a fluidised bed have the advantages that the rates of heat and mass transfer to and from a reacting particle are large and characterised well. However, problems have arisen from a combination of the slow, but typical, response–time (4 s) of the analysers for CO and CO₂ and the slow mixing of gases when filling a fairly large fluidised bed. The resulting time constant for the sampling system was 8 s and comparable to the time for combustion at 900 °C or above. The purpose of this work was to measure the kinetics of oxidation of a char in a smaller fluidised bed (with a shorter mixing time) using an analyser for CO and CO₂ with a response time as low as 0.1 s. The result is that the oxidation of an anthracitic char is now found to be first order in O₂ between 700 and 900 °C; at 900 °C the order previously measured was almost zero. The activation energy is now measured here to be 145 ± 25 kJ/mol, in agreement with some early work.     

纳米TiO_2用于甲基橙溶液的光催化氧化研究

本实验采用纳米级的二氧化钛,对甲基橙溶液进行了紫外光催化氧化处理,探讨了pH的影响和添加Fe3+的效果及反应动力学方程,结果表明,采用UV/O3/TiO2工艺对其进行处理,pH4-5时,10W紫外灯光照60min,CODcr去除率达84%,脱色率达96%以上。添加Fe3+,对溶液的催化降解速度提高不明显。动力学研究表明,CODcr降解速度对CODcr的浓度为一级反应。     

强电场电离放电产生羟基等离子体反应过程的研究

从强电场等离子体反应室结构、电介质材料及加工工艺等方面出发．研究了在建立强电场并把O2、H2O电离后在分子层次上加工成OH^ 、eaq^-(水合电子)等自由基的等离子体反应过程。用这种方法产生的自由基的浓度、产成量均能满足工程上的需要．达到绿色化学12条原则要求,从源头上解决了环境污染问题。着重研究了羟基治理烟气SO2的绿色资源化的新方法．在无吸收剂、催化剂条件下,仅在0．8s内就能把烟气中SO2、H2O和O2电离后在分子层次上加工成H2SO4。     

3,7-二硝基亚氨基-2,4-二氮杂双环[3,3,0]辛烷的放热分解反应动力学

在程序升温条件下 ,用DSC研究了标题化合物的放热分解反应动力学 .用线性最小二乘法、迭代法以及二分法与最小二乘法相结合的方法 ,以积分方程、微分方程和放热速率方程拟合DSC数据 .在逻辑选择建立了微分和积分机理函数的最可几一般表达式后 ,用放热速率方程得到相应的表观活化能 (Ea)、指前因子 (A)和反应级数 (n)的值 .结果表明 :该反应的微分形式的经验动力学模式函数、Ea 和A值分别为 (1-α) 0 .44、2 30 .4kJ/mol和 10 18.16s-1.借助加热速率和所得动力学参数值 ,提出了标题化合物放热分解反应的动力学方程 .该化合物的热爆炸临界温度为 30 2 .6℃ .上述动力学参数对分析、评价标题化合物的稳定性和热变化规律十分有用 .     

生物质洁净能源研究中的流化床动力学模型

分别对最小流化床、鼓泡流化床和腾涌流化床及相应的全混模型、鼓泡模型、气泡汇集模型等加以综述 ,分析其优缺点 ,并在此基础上提出动力学模拟研究的新思路 .根据流化床内在的本质———流化态的不同 ,将流化床分为最小流化床、鼓泡流化床和腾涌流化床三种 .总结了前人针对各种流化床提出的全混模型、鼓泡模型、气泡汇集模型等思想 ,建议今后可以在以下几个方面进行深入研究 :⑴使得模型更有普适性 .⑵由于气泡有效直径尚不能在理论上求得 ,可以在理想气泡直径变化公式的基础上 ,加入非线性化学的计算 .⑶确定不同情况下的参数 ,使得工作更有延续性 ,也使得模型更加具有生命力 .⑷从高压的角度去进行模型的计算 ,并得到相应的试验数据支持 .     

Aharonov–Bohm oscillations observed in nanoscale open-dot structures fabricated in an InAs surface inversion layer

We fabricated nanoscale open-dot structures in an InAs surface inversion layer using an atomic-force-microscope oxidation process. Due to its superior nanofabrication capability, small open-dot structures with the feature size ranging between 100 and 300 nm were successfully fabricated. The magnetoresistance signal measured at 4.2 K showed reproducible fluctuations and a periodic oscillation component that varies in both amplitude and periodicity depending on the dot size. We show that the period of the oscillations corresponds to that of the Aharonov–Bohm effect and propose that the possible mechanism for the oscillations is due to the formation of a one-dimensional electron channel enclosing the open-dot structure as a result of the electron transfer from the InAs oxide to InAs.     

Analysis of surface layers of an iron axe from Early Medieval Age

An ancient axe from Early Medieval Age which was unearthed on a territory of the archaeological excavation site near the village Borovce (Slovakia) is investigated. The surface of the axe was supposed to be covered with a sort of glassy system. Mössbauer effect measurements performed in backscattering and transmission geometry upon original as well as powdered pieces of the axe confirmed that the surface layers of the axe consist of goethite, lepidocrite, akageneite, and/or magnetite. After temperature treatment at 400°C/100 min hematite and maghemite were found; these are products of thermal decomposition of the above mentioned iron phases. These findings ruled out the hypothesis that the surface covering substance was put on the axe by intention.     

利用甲醇氧化烟气中NO的实验研究

对利用甲醇氧化烟气中NO的反应开展了系统的实验研究。研究了反应时间、反应温度、甲醇用量比例、烟气中O2、SO2及夹带的固体颗粒对NO氧化率的影响。结果表明,在一定的条件下,甲醇能够氧化烟气中的NO;NO氧化率受反应时间和反应温度的综合影响,随着反应时间的增加,有效反应温度区域向低温方向移动,最大NO氧化率降低;随着甲醇用量比例的增加, NO氧化率增加;O2浓度增加可促进NO氧化;烟气中的SO2对反应有催化作用,可显著提高NO氧化率;烟气中固体颗粒的存在阻碍了自由基反应的进行,显著降低了NO的氧化率。     

Catalytic partial oxidation of methane using RhSr- and Ni-substituted hexaaluminates

This paper reports the results of experimental and modeling efforts to characterize partial oxidation of methane to produce synthesis gas (H₂ and CO) using metal-substituted hexaaluminate catalysts in short-contact-time reactors. Hexaaluminate catalysts offer excellent high-temperature stability compared to the equivalent metal-based catalysts. The hexaaluminates are synthesized by a metal-exchange process using alumoxane precursors that enable a wide range of metal substitutions. Of all the combinations tested, RhSr-substituted hexaaluminates yielded the best performance. The catalysts are supported on alumina porous-foam structures, which are positioned within a tube furnace to control the operating temperature. Two-stage combinations of RhSr- and Ni-substituted hexaaluminates are shown to improve conversion activity and selectivity compared to a single-catalyst system.     

Influence of pretreatment methods on adsorption and catalytic characteristics of toluene over heterogeneous palladium based catalysts

The adsorption and catalytic characteristics of heterogeneous palladium based catalyst and its modified catalysts with gases (air and hydrogen) and acidic aqueous solution (HCl) were studied for evaluating the influence of pretreatment methods for toluene. The structural and energetic adsorption properties of the parent and pretreated catalysts were analyzed by means of nitrogen adsorption isotherms and gravimetric methods. The light-off curve and the XPS investigation were used for analyzing the catalytic activity and the surface state of palladium. It was clearly shown from the experimental results that hydrogen pretreated catalysts having metallic surface state exhibited the highest adsorption capacity and catalytic activity compared to that of parent and modified catalysts. The adsorption equilibrium data for toluene were obtained at three different temperatures and correlated successfully with the two-site Langmuir molecular isotherm model (L2m). It was also found that the palladium phase has more adsorption affinity for toluene molecules than the alumina support. The isosteric heat of adsorption calculated by using the Clausius-Clapeyron equation significantly changed with the coverage and the lateral interactions between the adsorbate-adsorbate molecules control the system. Furthermore, comparative analysis of the adsorption energy distribution revealed that the parent and its modified catalysts have different types of surface energetic heterogeneities.