超薄型钢结构防火涂料的热解动力学研究

利用岛津DTG-60H型热重分析仪,在氮气气氛、升温速率为15 ℃/min条件下,对自行配制的一种超薄型钢结构防火涂料的热分解过程进行了分析,发现该防火涂料的热解过程可分为5个阶段.用Coats-Redfern积分方法分阶段对TG曲线数据进行了处理,并用常见的12种反应机理方程进行拟合,发现各阶段反应机理不尽相同: 第一阶段属于一维扩散反应机理D1,第二、第三阶段为1.5级化学反应模型RO(1.5),第四阶段为二级化学反应模型RO(2),第五阶段为一级化学反应模型RO(1).同时,求解出了各阶段的热解动力学参数及动力学方程.     

二氧化锰氧化降解五氯酚

以二氧化锰为氧化剂,研究了pH 4.12的水溶液中五氯酚氧化降解的反应动力学,并讨论了反应溶液的pH对反应动力学的影响.结果表明,五氯酚对二氧化锰的氧化作用具有较强的反应感受性.在pH一定和二氧化锰充分过量的条件下,随着反应的进行,五氯酚的降解速度变慢,遵循的不是简单的准一级反应动力学而是复合的反应动力学.此外,随溶液pH由3.5升高6.6,五氯酚的降解速度发生显著地下降.运用溶剂萃取和气质联用仪的分析方法,检测到2个主产物和1个次产物.其中,次产物是由四氯-1,4-氢醌与四氯儿茶酚组成的混合物;2个主产物是由五氯酚氧自由基偶合而成的二聚体,且是同分异构体.在观测到的表面反应动力学和降解产物的基础上,提出了五氯酚被二氧化锰氧化降解的反应流程图.     

Effect of SO2 on the performance of Ag-Pd/Al2O3 for the selective catalytic reduction of NOx with C2H5OH

The influence of SO2 on the performance of Ag-Pd/Al2O3 for the selective catalytic reduction （SCR） of NOx with C2H5OH was investigated experimentally. The activity test results suggest that Ag-Pd/Al2O3 shows a small activity loss in the presence of SO2 when using C2H5OH as a reductant. In situ DRIFTS spectra show that the activity loss originates from the formation of surface sulphate species on the Ag-Pd/Al2O3. The surface sulphate species formation inhibits the formation of nitrate, whereas hardly changes the partial oxidation of C2H5OH. Compared with the NOx reduction by C3H6, an obvious suppression of the surface sulphate species formation was observed by DRIFTS experiment when using C2H5OH as a reductant. This phenomenon reveals the better catalytic performance and strong SO2 tolerance of Ag-Pd/Al2O3-C2H50H system.     

Upscaling heterogeneity in aquifer reactivity via the exposure-time concept: inverse model

A novel inverse technique is proposed to quantitatively characterize macroscopic variability in aquifer reactivity in a Lagrangian representation. Reactivity heterogeneity is expressed in terms of distributions of flux over cumulative time of exposure of the solution to reactive surface area, termed here 'cumulative reactivity'. In cases involving single aqueous species the combined effects of physical and reactivity heterogeneity on reactive solute transport can often be established and further investigated through joint distributions of flux over travel time and cumulative reactivity. The inverse technique requires the breakthrough curve of a passive tracer to determine the distribution of flux over travel time, and additional breakthrough curves of reactive tracers provide additional moments of the distribution of flux over cumulative reactivity given travel time. Thus breakthroughs of one passive and two reactive tracers can provide the mean and variance of the distribution of flux over cumulative reactivity. This Lagrangian characterization is achieved with knowledge of the types of reactive surfaces present, but not their spatial locations. The distributions can subsequently be applied via forward modeling using the same technique to predict breakthrough curves of other solutes undergoing first-order reactions in similar physically and chemically heterogeneous configurations.     

Reaction zone structures and propagation mechanisms of flames in stearic acid particle clouds

Reaction zone structures and propagation mechanisms of two representative flames established in stearic acid (CH₃(CH₂)₁₆CO₂H) particle clouds have been investigated. The reacting zone structure was examined by using a micro-electrostatic probe and a high-speed schlieren system. A distinct difference was observed in the ion current fluctuations recorded across the two representative flames propagating through the clouds of the same total mass density of particles and different mass densities of the particles smaller than 60 μm in diameter. When the mass density of smaller particles was high, a single peak was recorded in the ion current fluctuation. On the other hand, when the mass density of smaller particles was low, multi-peaks of various heights and widths were recorded. In the former case, the single peak was considered to be attributable to a unitary and a relatively thin flame started burning in vapor generated by the evaporation of smaller particles in the preheat zone. The flame propagation mechanism in this case was inferred to be similar to that of a usual hydrocarbon–air premixed flame, although the reaction zone thickness is much larger than that of the premixed flame. In the latter case, the multi peaks of various shapes were considered to be attributable to strong combustion at blue spots far behind the schlieren front. The flame propagation in this case was inferred to be supported by the heat release due to combustion at the blue spots.     

阻抑动力学测定痕量砷（Ⅲ）的研究

在硫酸介质中，痕量Ａｓ（Ⅲ）能阻抑溴酸钾、镍化钾和锆试剂之间的褪色反应，研究了阻抑褪色反应的最佳佳实验条件，建立了测定初量Ａｓ（Ⅲ）的方法，本方法的最低检测限为３．６×１０＾－５μｇ·ｍｌ＾－１，测定范围为０．０－１．０μｇ·２５ｍｌ＾－１，用于测定工业废水中的Ａｓ（Ⅲ），获得了满意的结果。     

Alpha-thalassaemia prenatal diagnosis by two PCR-based methods

In Cyprus all couples carrying α⁰-thalassaemia mutations are detected in the course of the thalassaemia carrier screening program and prenatal diagnosis is offered to all of them. Prenatal diagnosis for α-thalassaemia is routinely done by two independent molecular methods. With the first method, the mutations of the parents are directly determined by gap-PCR and then the chorionic villus sample (CVS) is examined for the presence of these mutations. With the other method, a (CA)_n repeat polymorphic site located between the ψα₁- and α₂-globin genes is used for determining the presence or absence of the normal and mutant alleles. In the period from 1995 to 1999, molecular analysis of 46 couples in which haematological data were consistent with deletion of two α-globin genes in both partners indicated that only 13 of them were actually at risk for haemoglobin (Hb) Bart's hydrops fetalis and prenatal diagnosis was provided in 16 pregnancies. The molecular diagnosis was possible in all cases with the use of both gap-PCR and (CA)_n repeat polymorphisms analysis. No misdiagnosed cases for α-thalassaemia have been reported to date. Copyright © 2001 John Wiley & Sons, Ltd.     

CuBr2分解缓释-膜催化对零价汞的氧化性能研究

以置于多孔陶瓷膜中的CuBr2受热分解所释放的Br2为氧化剂,利用膜催化装置对Hg0氧化效率进行研究,并设计反应-就地检测一体化装置,避免下游气体管壁效应对实验结果带来的影响.结果表明,MnO x/α-Al2O3催化膜对CuBr2分解所产生Br2的释放有较好的"缓释"作用.Hg0和Br2在催化膜表面的吸附和反应可用Langmuir-Hinshelwood机制描述.Hg0氧化效率随Br2浓度增大而升高,但在达到一定浓度后,Hg0和Br2的吸附速率及两者在催化膜表面的反应速率成为限速因素.473~573 K时Hg0氧化效率变化较稳定.烟气中SO2对Hg0氧化有一定抑制作用,NO无明显影响.     

铸铁还原氯乙酸的影响因素与机制研究

氯乙酸是地表水与饮用水中一种常见的微量氯代有机污染,具有致癌性,浓度较高时对人体健康会产生一定的危害.为了更经济地去除水体中的氯乙酸,研究了铸铁废料去除氯乙酸的可行性,讨论了铁类型、预处理方法,振荡方式以及溶解氧等条件对还原效果的影响.结果表明传质过程比铁类型与酸处理对氯乙酸还原速率的影响更大.铸铁无氧去除三氯乙酸(TCAA)的主要产物为二氯乙酸(DCAA)而有氧存在时为一氯乙酸(MCAA).在纵向翻转下铸铁对氯乙酸的去除过程符合伪一级动力学,TCAA、DCAA与MCAA的无氧速率常数分别为0.46 h-1、0.03 h-1与0,有氧速率常数依次为1.24 h-1、0.79 h-1与0.28 h-1.不同氧含量环境中铸铁对氯乙酸的去除机制不同,无氧时为连续氢解,有氧时可能包括连续氢解与直接转化过程.