含氧氢气钢瓶释放过程危险性分析及处置

针对一起空气误充入氢气钢瓶而导致使用时发生多起爆炸的事故,详细分析了氢氧混合气钢瓶在释放过程中的主要危险性,对释放过程中最可能存在的点火源即静电的产生机理及静电的放电条件进行了详细的论述,应用TNT当量法对可能发生的氢气钢瓶爆炸事故的破坏强度进行了估算。针对爆炸事故的高危险性,制定了以电机作为开阀动力的远距离放空方案,并提出了接地、洒水增湿等预防静电产生的有效措施,综合考虑冲击波超压伤害和人员操作的方便,确定了合理的安全操作距离,为防止爆炸产生的碎片对周围人员、建筑的伤害,在释放场所周围及人员操作场所设置了沙包墙作为防爆掩体。     

Practical applications of the fenton reaction to the removal of chlorinated aromatic pollutants

BACKGROUND: Chlorophenols (CPs) constitute a group of organic pollutants that are introduced into the environment as a result of several man-made activities, such as uncontrolled use of pesticides and herbicides, and as byproducts in the paper pulp bleaching. Promising removal technologies of chlorinated aromatics consist in the application of advanced oxidation processes (AOPs) that can provide an almost total degradation of a variety of contaminants. Among these, wide application find Fenton systems based on generation of reactive species having a high oxidizing power, such as hydroxyl radical HO*. Our objective was that of determining the overall degradation efficiency of the model compound 2,4-dichlorophenol (DCP) by thermal Fenton-type oxidation systems with a view toward defining in more details relevant process parameters, the effect of reaction temperature and of co-catalyst Cu2+. METHODS: Reaction conditions were similar to those generally adopted as optimal in many practical applications, i.e. pollutant/Fe2+ (as FeSO4) ratio ca. 20, Fe2+/Cu2+ (co-catalyst) 2:1, pH adjusted and controlled at pH 3, and H2O2 in excess (up to four-fold over the stoichiometric amount required for complete mineralization). RESULTS AND DISCUSSION: The results demonstrate that it is advantageous to carry out the reaction at a temperature markedly higher (70 degrees C) than ambient. The stepwise addition of H2O2 in aliquots yields an efficient transformation, while allowing a convenient control of the reaction exothermicity. Under these conditions, the essentially complete removal of the initial DCP is accomplished using just one equiv of H2O2 during 15 min; excess H2O2 (5 equivalents) yields extensive substrate mineralization. Also relevant, at 70 degrees C dechlorination of the initial DCP (and of derived reaction intermediates) is remarkably extensive (3-5% residual TOX), already with the addition of 1 equiv of H2O2. At the end of the reaction, IC and IC-MS analyses of the solution reveal that only low-molecular weight carboxylic acid (acetic, formic, oxalic, malonic, tartaric, etc.) contribute to the residual TOC. CONCLUSIONS: The whole of the results herein point to the advantage of performing the process at temperatures substantially higher than ambient (70 degrees C). Under the conditions adopted, almost complete degradation of the initial toxic compound can be achieved using hydrogen peroxide in fair excess (e.g., 3.5 equiv H2O2). RECOMMENDATIONS AND OUTLOOK: In applying practical Fenton-type degradation systems to heavily polluted wastes, either for the pre-treatment of waters with a high COD value prior to biodegradation or for complete mineralization of pollutants, the set up of appropriate reaction conditions appears to be a key factor. Also, it is desirable to keep the concentration of iron salts within the lower limits in order to minimize the production and disposal of iron oxide sludges.     

气体中硫化氢催化焚烧催化剂的制备和性能研究

考察了制备方法对催化剂活性的影响，评价了活性组分的添加量，操作温度和空速对催化剂活性和选择性的影响，在温度290℃，空速5000h^-1条件下，催化剂连续使用200h性能稳定，H2S转化率为SO2生成率在99．9％以上，该催化剂具有优良的性能，适合在硫化氢焚烧装置上使用。     

东深供水工程生化预处理挂膜过程分析

介绍东深供水工程生化预处理挂膜启动过程中，氨氮，CODMn去除效果和填料上生物膜变化的特点。根据氨氮去除（≥50．0％），生物膜形状，生物膜上动物种类和数量可判断挂膜启动过程是否完成。本试验挂膜启动25天，比小型试验增加了10天左右，气温低是该工程挂膜启动过程时间延长的主要原因。     

天然气中的硫资源及其开发

天然气中的硫化氢(H_2S)是硫的重要资源,许多国家都很重视从含硫天然气中回收硫。我国天然气中普遍含 H_2S,而 H_2S 为剧毒气体,对人体有害,对设备有强烈的腐蚀作用,易堵塞采油气管柱和气层,故开采含硫天然气有别于一般的天然气,在钻井、采气、集输、净化和加工方面均有其特殊性。随着天然气工业的高速发展,含硫气藏愈来愈多,因此研究天然气中硫资源的特点及其开发技术具有现实意义。     

Thermodynamic-dynamic analysis of gamma type free-piston stirling engine charged with hydrogen gas as working fluid

ABSTRACT

In this study, the combined thermodynamic and dynamic model of a new concept of gamma type free-piston Stirling engine is conducted. The engine consists of two identical displacer cylinders, a power cylinder, a linear alternator, and three-cushion pistons. Two displacer cylinders are symmetrically positioned on each side of the power cylinder for minimizing the rotational vibrations. Hydrogen is used as the working gas and the effect of gas temperature on the specific heat capacity is considered. The analysis carried out in this study involves the prediction of the thermodynamic-dynamic performance characteristics of the engine. In the thermodynamic section of the analysis, the working space of the engine is divided into 31 nodal volumes and the gas pressures in nodal volumes are assumed to be equal to each other. The conservation of mass and energy equations is obtained for each nodal volume. Instantaneous gas temperatures of nodal volumes are calculated by the first law of thermodynamics given for the unsteady open systems. The dynamic section of the analysis involves the motion equations of displacer, power and cushion pistons. The motion equations are derived using the Newton method. In the calculations done for variable specific heat capacity, it has been determined that there is 1% cyclic work reduction compared to the constant heat capacity. It is estimated that the maximum effective power that can be produced by the linear alternator will be around 1.6 kW. The working frequency range of the proposed engine is found to be suitable to generate electrical power.     

Fenton反应助催化剂碳基黄铁矿型纳米二硫化钴的合成

以水热与化学气相沉积方法制备了碳基黄铁矿型纳米CoS₂薄膜,对其组成、形貌进行了表征,并对其Fenton反应助催化性能进行了研究。实验结果表明：在罗丹明B模拟废水的Fenton处理过程中,添加CoS₂助催化剂的Fenton体系具有更高的反应活性,20 s内的脱色率达到98%,相比于普通Fenton体系的反应速率提高了近3倍;在类Fenton体系中的反应速率最高增加了约350%。CoS₂的加入显著提高了H₂O₂的利用效率以及催化氧化反应的反应速率。     

大气中过氧化氢的生成、污染特征及其影响因素

过氧化氢(H₂O₂)是自由基的源和汇,是对流层大气中重要的氧化剂. 采用文献研究法对1990年以来H₂O₂的文献进行搜集整理,对其生成途径、污染特征及其影响因素进行了研究. 结果表明:H₂O₂在大气、云水和颗粒物中均有存在,大气中的H₂O₂主要通过O₃和甲醛光解、VOC同OH·/O₃等反应生成. 大气中φ(H₂O₂)一般在nd～8×10-9内波动,晴天φ(H₂O₂)呈早晚低、午后高的日变化特征;φ(H₂O₂)随φ(O₃)、太阳辐射和气温的增加而升高,随φ(NO_x)、φ(VOCs)和相对湿度的升高而降低;H₂O₂氧化SO₂为SO₄2-是液相化学中最重要的反应,可以导致酸沉降以及二次气溶胶浓度的升高. 在气相光化学反应中,H₂O₂/HNO₃(体积分数比)可以指示O₃生成是VOCs控制还是NO_x控制. 今后需对OH·浓度、NO₂和O₃的光解速率等影响H₂O₂关键因素开展监测研究,此外,还需对我国特殊大气环境下H₂O₂对SO₄2-生成的贡献、不同地区H₂O₂/HNO₃指示O₃生成对NO_x或VOCs敏感性等方面开展更多的研究.      

ZrxMg1-xO supported cobalt catalysts for methane decomposition into COx-free hydrogen and carbon nanotubes

Zirconia-magnesia supported cobalt catalysts with various Zr/Mg atomic ratios were prepared and evaluated for non-oxidative catalytic decomposition of methane to produce CO_x-free hydrogen and carbon nanotube. The catalytic performance of the catalysts was performed in a continuous fixed bed flow reactor at 700°C under atmospheric pressure. The fresh and spent catalysts were characterized by XRD, TPR, BET, TEM, and Raman spectroscopy. The results showed that the change in Zr/Mg ratio of the mixed oxide support has a significant effect on the catalytic performance of the active Co metal. The catalyst 30%Co/Zr_0.8Mg_0.2 showed the highest activity and stability within the used series of catalysts with hydrogen yield reached up to 79%. Both Co/Mg_1.0 and Co/Zr_1.0 showed poor stability due to strong Co-Mg interaction and aggregation of Co species on Zr support, respectively. All catalysts produced mainly MWCNTs with different diameters depending on the Zr/Mg ratio. The outer diameter increased with increasing Zr content in the catalyst due to the enlargement of the particle size of cobalt as a result of aggregation.     

Relationship between liquid depth and the acoustic generation of hydrogen: design aspect for large cavitational reactors with special focus on the role of the wave attenuation

Understanding the effect of the liquid depth (z) on the acoustic generation of hydrogen is highly required for designing large-scale sonoreactors for hydrogen production because acoustic cavitation is the central event that initiates sonochemical reactions. In this paper, we present a computational analysis of the liquid-depth effect on the generation of H₂ from a reactive acoustic bubble trapped in water irradiated with an attenuating sinusoidal ultrasound wave. The computations were made for different operating conditions of frequency (355–1000 kHz), acoustic intensity (1–5 W/cm²), and liquid temperature (10–30°C). The contribution of the acoustic wave attenuation on the overall effect of depth was appreciated for the different conditions. It was found that the acoustic generation of hydrogen diminished hardly with increasing depth up to z = 8 m, and the depth effect was strongly operating parameter-dependent. The sound wave attenuation played a crucial role in quenching H₂ yield, particularly at higher z. The reduction of the H₂ yield with depth was more pronounced at higher frequency (1000 kHz) and lower temperature (10°C) and acoustic intensity (1 W/cm²). The attenuation of the sound wave may contribute up to 100% in the overall reductive effect of depth toward H₂ production rate. This parameter could be imperatively included when studying all aspects of underwater acoustic cavitation.