用改性活性碳纤维去除CO2原料气中的H2S

采用固定床动态吸附实验，用改性活性碳纤维（ACF）吸附去除CO2原料气中的H2S。通过改变改性剂种类、反应温度和原料气中CO2浓度，找出用改性ACF去除CO2原料气中H2S的规律。实验结果表明：常温下，可用NaON改性的ACF来消除CO2的酸性对去除H2S的不利影响；随着反应温度的升高，CO2与ACF形成的C（O＊）中间产物增多，CO2的存在有利于改性ACF去除H2S；而当反应温度过高时，CO2与ACF形成的C（O＊）中间产物发生分解，导致ACF碳化，不利于H2S的吸附去除。     

多因素耦合条件下硫化矿自燃神经网络动态预测模型研究

硫化矿石自燃是多种因素、多场耦合综合作用的结果,是一典型的非线性问题。笔者应用人工神经网络技术,以Matlab软件为平台,通过现场调查和理论分析,建立了矿石含硫量、通风强度、环境温度3因素与硫化矿石自燃之间的预测模型;通过数据样本学习与部分现场监测数据相结合进行模拟,研究表明预测数据与实测结果基本吻合,误差控制在10%以内,取得了较好的效果。该研究为预防硫化矿石自燃提供一个新的思路和方法,具有一定的理论意义和应用价值。     

钠盐量影响下DD6单晶高温合金的高温热腐蚀规律研究

目的 开展镍基单晶高温合金DD6在950 ℃下的热盐腐蚀试验(95%Na2SO4+5%NaCl)，探明涂盐量和涂盐方式(周期涂盐和单次涂盐)对DD6高温热腐蚀的影响规律和机理。方法 结合扫描电子显微镜、X射线能量色散谱、X射线衍射等设备，对不同涂盐量及涂盐方式下DD6的表面及横截面形貌进行观察分析，分析不同涂盐量和涂盐方式下DD6的高温热腐蚀机理。结果 DD6在950 ℃下主要发生碱性熔融热腐蚀，同时伴随氧化、硫化和氯化等过程。高温热腐蚀使得DD6合金表面生成的保护性氧化膜被熔融态的腐蚀介质破坏，导致O、S、Cl等外部元素通过氧化膜的缺陷进入DD6基体中，在合金的亚表面发生内氧化、内硫化以及内氯化反应，横截面上出现明显的腐蚀层，其主要由氧化物以及硫化物组成。随着热腐蚀的进行，DD6表面物质发生了剥蚀，沉积盐量的增加导致剥蚀现象越加严重，合金内部致密的组织结构也被破坏，横截面上出现了大量孔洞、裂纹等缺陷。在相同涂盐量下，周期涂盐法使得DD6的腐蚀程度高于单次涂盐法。结论 DD6高温热腐蚀行为与涂盐量及涂盐方式密切相关，相同涂盐方式下，涂盐量越大，DD6热腐蚀更加严重。涂盐量一定时，周期涂盐法使得DD6的热腐蚀剧烈程度大于单次涂盐法，且DD6在上述热腐蚀条件下均发生剥蚀破坏。     

On the implementation of an International Curriculum on Hydrogen Safety Engineering into higher education

This paper describes the implementation of an International Curriculum on Hydrogen Safety Engineering into higher education. The curriculum is being developed as part of the educational and training activities of the European Network of Excellence Safety of Hydrogen as an Energy Carrier (HySafe) and has been implemented into a 1-year Postgraduate Certificate Course in Hydrogen Safety Engineering by the University of Ulster. The course is taught in the distance learning mode and comprises of two 30 CATS-point modules, namely, ‘Principles of Hydrogen Safety’ and ‘Applied Hydrogen Safety’. The first delivery of this course began in January 2007 and the second delivery will commence in September 2007.     

Ag~+改性复合钛铌酸钾盐对二甲基硫醚和乙硫醇吸附与光催化氧化研究

采用高温固相法合成具有不同Nb/Ti摩尔比的复合钛铌酸钾盐,通过Ag+离子交换对其进行改性。在静态下评价了Ag+改性复合钛铌酸钾盐对二甲基硫醚(DMS)和乙硫醇(EM)的吸附与紫外光催化氧化作用,使用红外光谱技术对催化剂表面滞留物种进行表征。结果表明,Ag+改性复合钛铌酸钾盐对DMS的吸附作用力比EM弱。随着Nb/Ti摩尔比增加,Ag+改性复合钛铌酸钾盐对EM的吸附作用力增强。在紫外光辐射下,Ag+改性的复合钛铌酸钾盐将DMS氧化为亚砜、砜和硫酸盐,而EM则被氧化为磺酸和单齿硫酸盐。     

Influence of Na2S on the degradation kinetics of CCl4 in the presence of very pure iron

This paper presents the results of kinetic studies to investigate the effect of FeS film formation on the degradation rate of CCl(4) by 99.99% pure metallic iron. The film was formed by submersing metallic iron grains in an oxygen free HCO(3)(-)/CO(3)(2-) electrolyte solution. When the grains had reached a quasi steady-state value of the corrosion potential, Na(2)S((aq)) was injected. Upon injection, a microm thick poorly crystalline FeS film formed immediately on the iron surface. Over time, the iron became strongly corroded and both the FeS film and the metallic iron grains began to crack leading to exposure of bare metallic iron to the solution. The effect of the surface film on the degradation rate of CCl(4) was investigated following four periods of aging, 1, 10, 30, and 60 days. Relative to the controls, the 1-day sulfide-aged iron showed a substantial decrease in rate of degradation of CCl(4.) However, over time, the rate of degradation increased and surpassed the degradation rate obtained in the controls. It has been proposed that CCl(4) is reduced to HCCl(3) by metallic iron by electron transfer. The FeS film is substantially less conducting than the bulk iron metal or non-stoichiometric magnetite and from the results of this study, greatly decreases the rate of CCl(4) degradation relative to iron that has not been exposed to Na(2)S. However, continued aging of the FeS film results in breakdown and stress-induced cracking of the film, followed by dissolution and cracking of the iron itself. The cracking of the bulk iron is believed to be a consequence of hydrogen embrittlement, which is promoted by sulfide. The increase in CCl(4) degradation rate, as the FeS films age, suggests that the process of hydrogen cracking increases the surface area available for charge transfer.     

Numerical simulation of hydrogen–air detonation for damage assessment in realistic accident scenarios

An accidental hydrogen release within an equipment enclosure may result in the presence of detonable mixture in a confined environment. From a safety standpoint, it is then useful to assess the potential for damage. In that context, numerical simulation of the sequence of events subsequent to detonative ignition provides a useful tool, although with obvious limitations. This article describes the procedure, summarizes two case studies, and reviews the limitations. First, a hydrogen dispersion pattern is obtained from numerical simulation of dispersion, using a commercial package designed primarily for incompressible flow. This dispersion cloud is then used as the initial condition in an inviscid, compressible, reactive flow simulation. To force detonative ignition, a sufficiently large amount of energy is deposited in a small region that corresponds to the ignition location. Chemistry is modeled using a single step Arrhenius model. Because the wave thickness is small compared with the computational domain, a fine mesh is needed, limiting the practicality of the process to two-dimensional geometries. This is the most significant limitation; it is conservative. The two cases described in the paper include an electrolyzer, in which a small release occurs, leading potentially to some damage to the enclosure, and a reformer, in which the consequences are potentially more serious.     

对环境空气氯化氢浓度限值的探讨

通过对环境空气中氯化氢的毒理作用,各类标准比较、标准来源、评价标准的计算方法等,对现有的环境空气质量标准进行了探讨,提出了需要对现行标准进行修订的建议.     

Variability of tropospheric hydroperoxides at a coastal surface site in Antarctica

The annual cycles of hydrogen peroxide (H₂O₂) and methylhydroperoxide (MHP) have been investigated at a remote site in Antarctica in order to study seasonal variations as well as chemical processes in the troposphere. The measurements have been performed from March 1997 to January 1998 and in February 1999 at the German Antarctic research station Neumayer which is located at 70°39′S, 8°15′W. The obtained time series for hydrogen peroxide and methylhydroperoxide in near-surface air represents the first all-year measurements in Antarctica and indicates clearly the occurrence of seasonal variations. During polar night mean values of 0.054±0.046 ppbv (range<0.03–0.11 ppbv) for hydrogen peroxide and 0.089±0.052 ppbv (range<0.05–0.14 ppbv) for methylhydroperoxide were detected. At the sunlit period higher Mixing ratios were found, 0.20±0.13 ppbv (range<0.03–0.91 ppbv) for hydrogen peroxide and 0.19±0.10 ppbv (range<0.05–0.89 ppbv) for methylhydroperoxide. Occasional long-range transport of air masses from mid-latitudes caused enhanced peroxide concentrations at polar night. During the period of stratospheric ozone depletion we observed peroxide mixing ratios comparable to typical winter levels.     

Enhanced stability of hydrogen peroxide in the presence of subsurface solids

The stabilization of hydrogen peroxide was investigated as a basis for enhancing its downgradient transport and contact with contaminants during catalyzed H(2)O(2) propagations (CHP) in situ chemical oxidation (ISCO). Stabilization of hydrogen peroxide was investigated in slurries containing four characterized subsurface solids using phytate, citrate, and malonate as stabilizing agents after screening ten potential stabilizers. The extent of hydrogen peroxide stabilization and the most effective stabilizer were solid-specific; however, phytate was usually the most effective stabilizer, increasing the hydrogen peroxide half-life to as much as 50 times. The degree of stabilization was nearly as effective at 10 mM concentrations as at 250 mM or 1 M concentrations. The effect of stabilization on relative rates of hydroxyl radical activity varied between the subsurface solids, but citrate and malonate generally had a greater positive effect than phytate. The effect of phytate, citrate, and malonate on the relative rates of superoxide generation was minimal to somewhat negative, depending on the solid. The results of this research demonstrate that the stabilizers phytate, citrate, and malonate can significantly increase the half-life of hydrogen peroxide in the presence of subsurface solids during CHP reactions while maintaining a significant portion of the reactive oxygen species activity. Use of these stabilizers in the field will likely improve the delivery of hydrogen peroxide and downgradient treatment during CHP ISCO.