控制污水中硫化氢的生成──减轻大气污染和设备腐蚀

石油和石化企业所排放的含硫污水给水环境带来的污染是众所周知的，但它对大气环境的间接污染却常被人们忽视。而含硫污水中逸出的硫化氢是引起恶臭的主要原因之一，与水共存时又会对金属设备造成严重腐蚀，因此，控制污水中硫化氢的生成可有效地减轻污水所带来的大气污染和腐蚀现象。     

Catalytic hydrolysis of gaseous HCN over Cu–Ni/γ-Al2O3 catalyst: parameters and conditions

? The Cu–Ni/γ-Al₂O₃ catalyst was prepared to study HCN hydrolysis ? On catalyst calcined at 400°C, the HCN removal efficiency reaches a maximum. ? HCN removal is the highest at 480 min at a H ₂ O/HCN volume ratio of 150 ? The presence of CO facilitates HCN hydrolysis and increases NH ₃ production. ? O ₂ increases the HCN removal and NO_x production but decreases NH ₃ production GRAPHIC ABSTRACT To decompose efficiently hydrogen cyanide (HCN) in exhaust gas, g-Al₂O₃-supported bimetallic-based Cu–Ni catalyst was prepared by incipient-wetness impregnation method. The effects of the calcination temperature, H₂O/HCN volume ratio, reaction temperature, and the presence of CO or O₂ on the HCN removal efficiency on the Cu–Ni/g-Al₂O₃ catalyst were investigated. To examine further the efficiency of HCN hydrolysis, degradation products were analyzed. The results indicate that the HCN removal efficiency increases and then decreases with increasing calcination temperature and H₂O/HCN volume ratio. On catalyst calcined at 400°C, the efficiency reaches a maximum close to 99% at 480 min at a H₂O/HCN volume ratio of 150. The HCN removal efficiency increases with increasing reaction temperature within the range of 100°C–500°C and reaches a maximum at 500°C. This trend may be attributed to the endothermicity of HCN hydrolysis; increasing the temperature favors HCN hydrolysis. However, the removal efficiencies increases very few at 500°C compared with that at 400°C. To conserve energy in industrial operations, 400°C is deemed as the optimal reaction temperature. The presence of CO facilitates HCN hydrolysis andincreases NH₃ production. O₂ substantially increases the HCN removal efficiency and NO_x production but decreases NH₃ production.     

Effects of hydrogen addition on the confined and vented explosion behavior of methane in air

Multi-component gas mixture explosion accidents occur and recur frequently, while the safety issues of multi-component gas mixture explosion for hydrogen–methane mixtures have rarely been addressed.Numerical simulation study on the confined and vented explosion characteristics of methane-hydrogen mixture in stoichiometric air was conducted both in the 5 L vessel and the 64 m³ chamber, involving different mixture compositions and initial pressures. Based on the results and analysis, it is shown that the addition of hydrogen has a negative effect on the explosion pressure of methane-hydrogen mixture at adiabatic condition. While in the vented explosion, the addition of the hydrogen has a significant positive effect on the explosion hazard degree. Additionally, the addition of hydrogen can induce a faster reactivity and enhance the sensitivity of the mixture by reducing the explosion time and increasing the rate of pressure rise both in confined and vented explosion. Both the maximum pressure and the maximum rate of pressure rise increase with initial pressure as a linear function, and also rise with the increase of hydrogen content in fuel. The increase in the maximum rate of pressure rise is slight when hydrogen ratio is lower than 0.5, however, it become significant when hydrogen ratio is higher than 0.5. The maximum rate of pressure rise for stoichiometric hydrogen-air is about 10 times the one of stoichiometric methane-air.Furthermore, the vent plays an important role to relief pressure, causing the decrease in explosion pressure and rate of pressure rise, while it can greatly enhance the flame speed, which will extend the hazard range and induce secondary fire damages. Additionally it appears that the addition of hydrogen has a significant increasing effect on the flame speed. The propagation of flame speed in confined explosion can be divided into two stages, increase stage and decrease stage, higher hydrogen content, higher slope. But in the vented explosion, the flame speed keeps increasing with the distance from the ignition point.     

Relative yields of monomeric and dimeric adducts induced by sulphur mustard in isolated and cellular DNA as determined by HPLC/tandem mass spectrometry

Sulphur mustard (SM) is known as an efficient vesicating agent as well as a carcinogenic chemical. This warfare agent remains a threat for both civilians and militaries. DNA alkylation is one of the critical molecular pathways at the origin of the symptoms associated with SM exposure. SM forms monoadducts with guanine and adenine as well as a biadduct between two guanine bases. The aim of the present work is to determine the relative yields of these three lesions in DNA samples after SM exposure without using radiolabeled SM as in earlier works. For this purpose, we have developed a high performance liquid chromatography/tandem mass spectrometric method to simultaneously quantify the SM monoadducts and biadduct in the same DNA sample. We observed in isolated and cellular DNA that the guanine monoadduct was the predominant lesion, while the biadduct was present in twofold lower yield. The adenine monoadduct was generated in lowest amounts. The analytical approach was extended to 2?chloroethyl ethyl sulphide, a widely used SM analog. Again, the adenine adduct was much less frequent than the guanine derivative. The developed assay will allow performing studies involving large numbers of samples.     

Catalytic degradation of PP with an Fe/activated carbon catalyst

We investigated the function of Fe and activated carbon (AC) as a catalyst by comparing Fe/AC with Fe/SiO₂ or AC, and also the effect of H₂ as a reaction gas on the product distribution in the catalytic degradation of polypropylene. Supported Fe promotes H₂ consumption to decompose solid residues, and AC support degrades heavy oil to produce light oil. As a result, using Fe/AC as a catalyst gives the maximum yield of the liquid product. For the reaction conditions, with a high reaction temperature or a long reaction time, the product distribution is more influenced by the thermal degradation than by the catalytic degradation. For the amount of Fe to load, 5wt% is the optimum condition in our reaction system. We demonstrated the mechanism of the degradation of polyolefins with hydrogen-capping catalysts.     

Biogeochemistry and isotope geochemistry of a landfill leachate plume

The biogeochemical processes were identified which improved the leachate composition in the flow direction of a landfill leachate plume (Banisveld, The Netherlands). Groundwater observation wells were placed at specific locations after delineating the leachate plume using geophysical tests to map subsurface conductivity. Redox processes were determined using the distribution of solid and soluble redox species, hydrogen concentrations, concentration of dissolved gases (N(2), Ar, and CH(4)), and stable isotopes (delta15N-NO(3), delta34S-SO(4), delta13C-CH(4), delta2H-CH(4), and delta13C of dissolved organic and inorganic carbon (DOC and DIC, respectively)). The combined application of these techniques improved the redox interpretation considerably. Dissolved organic carbon (DOC) decreased downstream in association with increasing delta13C-DOC values confirming the occurrence of degradation. Degradation of DOC was coupled to iron reduction inside the plume, while denitrification could be an important redox process at the top fringe of the plume. Stable carbon and hydrogen isotope signatures of methane indicated that methane was formed inside the landfill and not in the plume. Total gas pressure exceeded hydrostatic pressure in the plume, and methane seems subject to degassing. Quantitative proof for DOC degradation under iron-reducing conditions could only be obtained if the geochemical processes cation exchange and precipitation of carbonate minerals (siderite and calcite) were considered and incorporated in an inverse geochemical model of the plume. Simulation of delta13C-DIC confirmed that precipitation of carbonate minerals happened.     

GIS与大气污染扩散模型的整合研究

大气扩散模型与GIS整合是当前的重要发展趋势。文章分析了该技术存在的主要问题和可行的解决路线,并指出了其主要发展方向。主张采用GIS二次开发工具和大气污染模型进行整合。详细介绍了开发“硫化氢应急专家系统”的工作中,解决二者整合所取得的研究进展和成果。将GIS、大气模型与应急救援工作三者有机的整合,实现了GIS数据和应急数据的紧密结合及对硫化氢扩散的预测。     

Effect of self-inhibition at a flame propagation in rich gaseous mixtures of combustible–air–diluent

An analysis of published experimental data characterizing the influence of diluents of various chemical nature (both halogenated and chemically inert) on upper flammability limits of flammable gases in air (methane and hydrogen have been considered as examples) has been done. Dependences of critical oxygen concentration and critical fuel equivalence ratio _cr for mixtures combustible–air–diluent at upper flammability limits on diluent concentration were determined. The obtained data were interpreted on the basis of the concept of self-inhibition at combustion of rich mixtures of organic combustibles in air. A method for evaluation of relative effectiveness of various inhibitors and for determination of availability of self-inhibitive properties of a combustible gas has been proposed.     

Hazard evaluation of hydrogen–air deflagration with flame propagation velocity measurement by image velocimetry using brightness subtraction

Deflagration phenomena in hydrogen–air mixtures initially filled in 1.4 m³ spherical latex balloons were measured using a high-speed digital video camera and pressure transducers. The image velocimetry using brightness subtraction was introduced to eliminate the background effects for obtaining accurate time evolution records of flame propagation velocity. The maximum flame propagation velocity of about 100 m/s was observed with maximum overpressure 15 kPa at 1 m from ignition point. According to the detailed flame propagation velocity records, there were long deceleration durations. The observed maximum overpressure was smaller than the overpressure estimated by the basis of the observed maximum flame propagation velocity and the pressure wave theories of spherical flames. A new blast curve plot of scaled overpressure vs. distance was tentatively proposed.     

Safety distances for hydrogen filling stations

In the context of spatial planning the Dutch Ministry of Housing, Spatial Planning and the Environment asked the Centre for External Safety of the National Institute for Public Health and the Environment (RIVM) to advice on safe distances pertaining to hydrogen filling stations. The RIVM made use of failure modeling and parameters for calculating the distance in detail. An imaginary hydrogen filling station for cars is used in the determination of ‘external safety’ or third party distances for the installations and the pipe work for three different sizes of hydrogen filling stations. For several failure scenarios ‘effect’ distances are calculated for car filling at 350 and 700 bar. Safe distances of filling stations from locations where people live and work appear to be similar for compressed hydrogen, gasoline/petrol and compressed natural gas. Safe distances for LPG are greater. A filling unit for hydrogen can be placed at gasoline/petrol-filling stations without increasing safety distances.