亚硫酸盐溶液中氧气泡吸收过程的实验研究

采用CCD对单个氧气泡在亚硫酸钠溶液中的吸收过程进行拍照,并用软件进行图像边界识别来研究单个纯氧气泡同亚硫酸钠溶液发生的强制氧化反应过程。实验结果表明反应速度与气泡半径有关。在动力学控制阶段,反应速率与气泡的半径成0阶关系;在扩散控制阶段,反应速率与气泡的半径成-1阶关系。     

基于简单碰撞理论煤粉燃烧动力学模型的研究--PART Ⅱ:颗粒表面的氧气浓度分布模型

为了较准确地预报炉内煤粉燃烧速率,正确区分TGA中滞止煤粉表面与炉内载流煤粉表面氧气浓度的变化规律是非常关键的。从TGA中非稳态条件下坩埚内颗粒表面氧气浓度分布的数理解知,煤样的氧化过程是同时进行的,只是上部的氧化速率大一些,底部的氧化速率小一些;同一样品,同一升温速率,试样的堆积厚度的差异,会影响实验结果的重复性。分析表明,在初始和反应结束时,坩埚内颗粒表面氧气浓度等于环境浓度;反应速率达到最大值时,颗粒表面氧气浓度达到最小值。颗粒在炉内流动燃烧过程中,环境中氧气浓度值是单调减少的,煤焦表面氧的浓度是非线性变化的。     

气液两相流速度及粒径分布激光干涉测量方法的研究

为了实现对气液两相流的粒子粒径、空间分布及其速度测量。对激光干涉气液两相流测量技术（ILIDS）进行了深入研究,该技术是一种应州于气液两相流测量的新技术,其主要优点是不干扰流场和颗粒粒径、位置测量精度高。基于该技术所开发的图像自动处理方法可以利用普通粒子成像测量技术系统拍摄气液两相流的激光散射干涉图像。并利用图像卷积定位、傅里叶变换频率分析及其图像互相关测速等图像处理手段从干涉图像中自动提取粒子的位置、直径和速度信息。为了验证该方法的测量精度,对喷嘴生成的气水两相流进行了测量实验,得到了喷嘴出口处不同区域的粒径、速度矢量的空间分布,并将测得的速度矢量与用粒子成像测量技术方法测得的结果进行对比,证明两种方法测量的平均速度差别仅为0．38％。     

TiO_2一维纳米阵列电极表面氧气泡发展规律研究

光电化学分解水反应驱动的氧气泡生长,是发生在固液表面典型的物理化学过程。本文通过搭建的光电化学分解水反应体系,利用显微拍摄系统,探究了氧气泡在光电极表面的发展规律,结果表明气泡大小与生长时间遵循关系;并通过改变反应溶液的浓度和激发光源的光照强度,总结了溶液浓度和光照强度对气泡的生长时间与脱离直径的影响规律。     

OH与蒎烯醇和柠檬烯醇液相反应动力学的实验和理论研究

蒎烯醇与柠檬烯醇分别是α-蒎烯和柠檬烯大气氧化反应的重要产物,它们的挥发性很低,因而容易进入大气的液相粒子,在颗粒相中被大气氧化剂引发液相氧化反应. 通过实验和理论计算研究,首次在304±3 K和大气压下测得这两种醇与OH的液相反应速率,其速率常数分别为(3.05±0.5)×109和(4.57±0.2)×109 L/(mol·s). 采用量子化学密度泛函法计算这两个液相反应的速率常数,计算中考虑了溶剂化效应的影响,计算结果与实验值符合得较好,并用液质联用和理论计算证实了一些反应产物.     

基于格子Boltzmann方法的二维气泡群熟化过程模拟

Ostwald熟化(ripening)是指局部热力学平衡状态下,颗粒/液滴/气泡系统为了减小界面能而自发地进行颗粒群尺度分布调整的过程,具有重要研究价值.针对目前数值模拟研究不充分的现状,本文采用格子Boltzmann方法,对相变速率主控的二维蒸气泡系统演化开展了数值模拟研究.模拟结果与本文推导的二维气泡群演化标度律符合较好,证实了格子Boltzmann方法对复杂相变-物质输运过程捕捉的准确性.研究同时表明,蒸气泡系统演化过程中物质输运为液相压力不平衡所驱动,并且在小气泡“溃灭”过程中水动力学作用会影响气泡群半径分布函数的局部细节;气-液状态方程参数对熟化过程的影响效果分析显示,气液两相比内能差是驱动相变的核心要素,此差异越大相变速率越快,该结论进一步诠释了化学势驱动熟化过程的物理图像.     

复合胺砜溶液吸收CO_2传质动力学研究

利用湿壁塔法测量复合胺砜溶液吸收CO_2的动力学特性,实验工况包括不同的反应温度(293.15～323.15 K)和不同的溶液浓度(0.5～6.6 mol/L)。本文简化了气液传质模拟,计算了不同工况下的吸收速率常数、总反应速率常数、二级反应速率常数及增强因子等动力学参数,同时根据实验结果拟合得到了二级反应速率常数和增强因子的经验公式,并得到了复合胺砜溶液与CO_2反应的表观反应活化能为为20.38 kJ/mol。     

低温气液两相流流型识别及相关测量技术

介绍了目前高沸点液体气液两相流流型识别常用的理论和方法 ,并分析了它们在低温气液两相流型识别中的适用性 ;同时介绍了可用于低温气液两相流流型识别的相关测量仪器。最后指出 ,低温下气液两相流流型的研究及测试技术远没有完善 ,应积极开发基于物理机制的研究方法。     

光电催化过程中氧气泡成核—生长—脱离特性研究

光电催化过程中的气泡动力学特性是研究气液两相流动行为的重要参数,对光电分解水的效率及反应过程中的传热、传质产生重要影响。本文针对TiO_2光电极表面析出氧气泡的动力学特性展开研究,通过独立设计的实验系统,得到了氧气泡整个演化过程的生长规律符合d∝(?)~s,气泡形成10 ms以内x为0.5～0.85,10 ms之后x≈0.33,捕捉到了气泡成核初期的图像,得到了光学手段能观察到的气泡成核时间和空间尺度,给出了激光功率和恒定偏压对气泡脱离直径的影响规律。     

石墨电极气体开关中等离子体弧区碳氧反应效率研究

氧气是石墨电极气体开关中必不可少的组分,用于氧化石墨电极在高温电弧冲击下形成的石墨蒸汽,防止熄弧后石墨蒸汽凝华成固体粉末给开关带来绝缘危害。为提高石墨蒸汽的氧化比例,研究了背景气体组分和氧气浓度对石墨氧化反应的影响,选取3种气体N₂,Ar,He作为背景气体,研究不同气氛电弧的氧化反应特征;在传统的类空气气体（80%的N₂＋20%的O₂）的基础上,提高氧气浓度至40%和60%,研究氧气浓度对碳质氧化比例的改善作用。基于不同气体组分的热力学参数和输运系数,通过电弧磁流体动力学计算模型得到开关温度特征,将电弧与电极界面的热流强度作为石墨电极质量损失速率的评估依据。实验结果表明,随着氧气浓度的升高,石墨蒸汽的氧化比例逐步提高,但当氧气浓度高于40%时,存在电弧引燃石墨电极的风险。当氧气浓度恒定20%时,以Ar作为背景气体时石墨电极质量损失速率较小,且碳蒸汽在电弧中氧化更加充分。因此,相比于传统的开关气体介质,将背景气体替换为Ar或将氧气浓度提高至约40%均能提升碳氧反应效率,降低开关中的杂质残余量。     

亚硫酸盐氧化气液反应过程模型研究

亚硫酸盐氧化是湿法烟气脱硫的重要反应过程,本文建立了该反应过程的物理模型,包括氧的相间传质扩散、本征化学反应和亚硫酸根扩散这三个步骤,宏观反应速率由其中最慢的一个步骤来决定,反应分为不同的控制阶段。在双膜理论和质量守恒理论的基础上,建立了稳态单气泡吸收过程的数学模型。在动力学控制阶段,反应速率与气泡的半径呈0阶关系;在...     

空气电极/AC作载体对TiO2光催化性能的影响

研究了空气电极和活性碳 (AC)作载体对TiO2 光催化氧化活性艳红 (K 2BP)性能的影响 .实验结果表明 ,用空气电极 /AC作载体能显著提高TiO2 的光催化反应速度 ;空气电极不仅具有良好的合成H2 O2 的性能 ,而且对TiO2 光催化剂可产生大约 +0 .5V的偏压作用 ,大大减小了TiO2 光生电荷的复合几率 ;AC对有机物分子良好的吸附作用提高了有机物分子在TiO2 表面及周围的富集浓度 ,其含量在 2 1%左右可使光催化剂达到最佳的催化效果 .复合电极工作电流密度对活性艳红的氧化脱色速度有影响 ,i=15mA/cm2 ,速度达到最大 ;活性艳红分子在复合电极表面的吸附受溶液pH值的影响 ;提出了复合电极的工作原理 .     

Electrocatalytic determination of sulfite using a modified carbon nanotubes paste electrode: application for determination of sulfite in real samples

This paper introduces a carbon paste electrode modified with ferrocene and carbon nanotubes as a voltammetric sensor for determination of sulfite at pH 7.0. The results showed that under the optimum condition (pH 7.0) in cyclic voltammetry, the oxidation of sulfite occurred at a potential about 280?mV less positive than the unmodified carbon paste electrode. Kinetic parameters such as electron transfer coefficient (??) and heterogeneous rate constant (k) for sulfite were also determined using electrochemical approaches. Under the optimized conditions, the electrocatalytic oxidation peak current of sulfite showed two linear dynamic ranges with a detection limit of 0.1???M for sulfite. The proposed method was examined as a selective, simple, and precise method for voltammetric determination of sulfite in some real samples such as weak liquor from wood and paper industry, boiler water, river water, industrial water, and tap water.     

两亲性金属酞菁的催化性能研究

采用耗氧法研究了4种金属酞菁配合物[α-四(对羧基苯氧基)金属酞菁(Zn,Co)、β-四(对羧基苯氧基)金属酞菁(Zn,Co)]对0.1mol.L-1亚硫酸钠的催化氧化性能,考察了配合物中心金属和取代基的位置对催化活性的影响。研究结果表明中心离子相同时,β位四取代(对羧基苯氧基)金属酞菁的催化活性优于α位;取代基位置相同时,酞菁钴的催化氧化性优于酞菁锌。且β-四(对羧基苯氧基)酞菁钴的浓度为1.00×10-4mol.L-1时,对亚硫酸钠的催化氧化性能最高。     

Photocatalytic Oxidation of Hydrosulfide Ions by Molecular Oxygen Over Cadmium Sulfide Nanoparticles

Photocatalytic activity of CdS nanoparticles in hydrosulfide-ions air oxidation was revealed and thoroughly investigated. HS⁻ photooxidation in the presence of CdS nanoparticles results predominantly in the formation of SO₃ ²⁻ and SO₄ ²⁻ ions. Photocatalytic activity of ultrasmall CdS crystallites in HS^– photooxidation is much more prononced as compared to bulk CdS crystals due to high surface area of nanoparticles, their negligible light scattering, improved separation of photogenerated charge carriers etc. It was shown that hydrosulfide ions can be oxidized in two ways. The first is HS⁻ oxidation by the CdS valence band holes. This process rate depends on the rate of comparatively slow reaction between molecular oxygen and CdS conduction band electrons. The second reaction route is the chain-radical HS⁻ oxidation induced by photoexcited CdS nanoparticles and propagating in the bulk of a solution. In conditions favourable to chain-radical oxidation of HS⁻(i.e. at low light intensities and CdS concentration and high oxygen and Na₂S concentrations) quantum yields of the photoreaction reach 2.5.     

Oxidation and faceting of polycrystalline tungsten ribbons

We have measured the oxidation rate of tungsten and the evaporation rate of tungsten oxide in the temperature range from 900 to 1200 K at an oxygen pressure from 5 × 10^?4 to 5 × 10^?3 Torr. The oxidation rate increases steadily with coverage in the whole range studied. The evaporation rate decreases at high pressure and is strongly dependent on the initial conditions of the experiments. These kinetic measurements support a qualitative model of oxidation. The surface is composed of oxide islands surrounded by oxide-free regions covered only by chemisorbed oxygen atoms. On the bare regions beside the chemisorbed oxygen atoms we suppose the existence of a dilute chemisorbed oxide layer which can either enter the condensed oxide phase or evaporate. The number of the growing islands is set up at the beginning of the reaction and does not increase further. This model, consistent with kinetic results during oxidation, has been proposed first to explain results obtained by Auger electron spectroscopy and thermal desorption spectroscopy under vacuum. Faceting is particularly important in the early stages of the experiment because it can hinder the nucleation of the oxide which is a necessary step for growth. In a narrow range of temperature and oxygen pressure this inhibited nucleation leads to an enhanced evaporation rate so that the growth rate is lower. Recording this growth rate allows us to follow faceting. The parameters studied are the oxygen coverage and the temperature, experimental results are in agreement with LEED and RHEED results. Reconstruction and faceting are discussed and are believed to be caused by a smoothing of the surface during the chemisorption step.     

The influence of aliovalent impurities on the oxidation kinetics of nickel at high temperatures

The influence of chromium and sodium on the nickel oxidation kinetics has been studied as a function of temperature (1373-1673 K) and oxygen activity (10−10⁵ Pa O₂), using microthermogravimetric techniques. It has been shown that the oxidation of Ni-Cr and Ni-Na alloys, like that of pure nickel, follows strictly the parabolic rate law being thus diffusion controlled. In agreement with the defect model of Ni_1−yO, it has been found that the oxidation rate of the Ni-Cr alloy is higher than that of pure nickel, the reaction rate is pressure independent and the activation energy of this process is lower. This implies that the concentration of double ionized cation vacancies in a Ni_1−yO-Cr₂O₃ solid solution is fixed on a constant level by trivalent chromium ions, substitutionally incorporated into the cation sublattice of this oxide. In the case of the Ni-Na alloy, on the other hand, the oxidation rate is lower than that of pure nickel, the activation energy is higher and the oxidation rate increases more rapidly with oxygen pressure. These results can again be explained in terms of the doping effect, by assuming that univalent sodium ions dissolve substitutionally in the cation sublattice of nickel oxide.     

Wastes Treatment: Hydrothermal electrolytic oxidation of wastewater

Abstract

Electrochemical evolution of hydrogen gas, oxygen gas and chlorine at the electrodes is the usual reaction in conventional electrolysis of aqueous salt solution. However, here we demonstrate that the electrolysis governing reaction in hydrothermal solutions is different from the electrolysis performed at atmospheric pressure and temperatures up to 100°C. Experimental electrolytic reaction of aqueous salt solution carried out inside a sealed 300-mL batch autoclave showed that; accumulation of hydrogen gas, oxygen gas and chlorine is highly suppressed under hydrothermal (250°C and 7 MPa) conditions. We have also observed that, when organics are present in the aqueous salt solution being hydrothermally electrolyzed, an effective oxidation of organics is accomplished. Furthermore, for hydrothermal electrolytic oxidation (HEO) with oxygen gas added, experimentally observed TOC removal profile demonstrates apparent anodic oxidation electrical current efficiency of almost 200% for highconcentrated acetic acid solutions.