Influence of concentration distribution of hydrogen in air on measured flammability limits

There is a clear difference between exiting data on the measured flammability limits of hydrogen-air mixture. The non-uniformity of concentration distribution of hydrogen in air is a contributor to deviations of the upper flammability limit (UFL) and the lower flammability limit (LFL) measured in different experiments. This paper presents a numerical model to simulate the gas mixing process from start to stability, to predict the concentration distribution, and to research the influence of concentration distribution of hydrogen in air on measured UFLs and LFLs. The commercial software package Fluent was used to carry out the numerical simulation for the concentration distribution of hydrogen in air in the vessels with length-to-diameter ratios (L: D) of 1:1, 3:1, 5:1 and 7:1 respectively. Based on the numerical simulation and analysis, the influence of concentration distribution on measured flammability limits was demonstrated for hydrogen in air in the vessel. It is found that the deviations of measured flammability limits of hydrogen in air are the minimum in the vessel with length-to-diameter ratio of 1:1, and augment with the augmentation of vessel length-to-diameter ratio. Moreover, it is presented that the deviations of measured flammability limits of hydrogen in the center of the vessel are lower than that in the top and the bottom.     

Bioreduction of vanadium (V) in groundwater by autohydrogentrophic bacteria: Mechanisms and microorganisms

As one of the transition metals, vanadium (V) (V(V)) in trace amounts represents an essential element for normal cell growth, but becomes toxic when its concentration is above 1 mg/L. V(V) can alter cellular differentiation, gene expression, and other biochemical and metabolic phenomena. A feasible method to detoxify V(V) is to reduce it to V(IV), which precipitates and can be readily removed from the water. The bioreduction of V(V) in a contaminated groundwater was investigated using autohydrogentrophic bacteria and hydrogen gas as the electron donor. Compared with the previous organic donors, H₂ shows the advantages as an ideal electron donor, including nontoxicity and less production of excess biomass. V(V) was 95.5% removed by biochemical reduction when autohydrogentrophic bacteria and hydrogen were both present, and the reduced V(IV) precipitated, leading to total-V removal. Reduction kinetics could be described by a first-order model and were sensitive to pH and temperature, with the optimum ranges of pH 7.5–8.0 and 35–40°C, respectively. Phylogenetic analysis by clone library showed that the dominant species in the experiments with V(V) bioreduction belonged to the β-Proteobacteria. Previously known V(V)-reducing species were absent, suggesting that V(V) reduction was carried out by novel species. Their selective enrichment during V(V) bioreduction suggests that Rhodocyclus, a denitrifying bacterium, and Clostridium, a fermenter known to carry out metal reduction, were responsible for V(V) bioreduction.     

Propagation and intensity of blast wave from hydrogen pipe rupture due to internal detonation

The coupled fluid-structure-rupture model was developed to study the propagation and intensity of blast wave from hydrogen pipe rupture due to internal detonation. The dynamic rupture of pipe and propagation of blast wave were well coupled together in every timestep during the simulation. The numerical model was validated with experiments in terms of both typical rupture profiles and blast overpressures. Results reveal that crack branching of pipe can dramatically increase the rupture opening rate which controls the intensity and shape of the resultant blast wave. Due to the process of crack initiation and extension, the blast wave out of the pipe first forms and then is strengthened by the subsequent compression waves. This makes the maximum peak overpressure appears at a certain standoff distance above the rupture. Despite consuming some percentages of energy, the dynamic rupture of pipe generally presents positive effects (up to 2–3 times) on the blast wave intensity along the jetting direction due to the convergence effect of rupture opening on the release of internal high-pressure gas. Finally, through defining normalized overpressure and impulse based on the same hydrogen detonation in open spaces, the quantitative influences of pipe rupture on the blast wave intensity in cases of different detonation pressures and standoff distances are clarified.     

H2O2 treatment boosts activity of NiFe layered double hydroxide for electro-catalytic oxidation of urea

Urea oxidation reaction (UOR) provides a method for hydrogen production besides wastewater treatment, but the current limited catalytic activity has prevented the application. Herein, we develop a novel H₂O₂ treatment strategy for tailoring the surface oxygen ligand of NiFe-layered double hydroxides (NiFe-LDH). The sample after H₂O₂ treatment (NiFeO-LDH) shows significant enhancement on UOR efficiency, with the potential of 1.37 V (RHE) to reach a current density of 10 mA/cm². The boost is attributed to the richness adsorption O ligand on NiFeO-LDH as revealed by XPS and Raman analysis. DFT calculation indicates formation of two possible types of oxygen ligands: adsorbed oxygen on the surface and exposed from hydroxyl group, lowered the desorption energy of CO₂ product, which lead to the lowered onset potential. This strategy is further extended to NiFe-LDH nano sheet on Ni foam to reach a higher current density of 440 mA/cm² of UOR at 1.8 V (RHE). The facile surface O ligand manipulation is also expected to give chance to many other electro-catalytic oxidations.     

新型聚乙烯填料生物滴滤床净化硫化氢气体的启动研究

研究了新型高密度聚乙烯改良型拉西环填料生物滴滤床净化硫化氢气体的启动过程,重点比较了启动过程中不同的挂膜方式对启动时间及效能的影响.结果表明,采用液相连续流强化挂膜法成膜时间短,在环境温度20～28℃时7 d可以挂膜成功.在启动过程中,随着工艺参数的突然改变(GRT缩短)和入口浓度波动,液相连续流强化挂膜后反应器的硫化氢去除率更稳定.在进气浓度最高为343 mg/m³时硫化氢去除率稳定在95%以上.试验过程中还发现,将SO₄^2-浓度作为活性污泥驯化完成的监测指标、液相S^2-去除率作为挂膜完成的监测指标更合理.启动结束后,通过2种途径减去喷淋液中的碳源并未影响硫化氢的去除率,这进一步表明生物滴滤床中硫化氢的净化主要由自养菌完成.     

The influence of ClO− and acidity in the reaction between H2O2 and CuCl2

The potentially explosive reaction of hydrogen peroxide (H₂O₂) and copper chloride (CuCl₂) was investigated. Pressure tests revealed that the reaction was strongly temperature - dependent and can easily undergo runaway reaction. Nevertheless, there was only a slight pressure increase at the low temperatures studied or when using low concentrations of CuCl₂. Under the conditions generating the slight pressure increase, hypochlorite anions (ClO⁻) are generated and the acidity increases. As the reaction reaches completion, ClO⁻ disappears, and the acidity decreases. Interestingly, the addition of phosphate buffer to maintain the weakly acid conditions led to a runaway reaction, and the use of basic ClO⁻ promoted the exothermic reaction. Based on the results, acidity has a strong impact on the reaction behaviour.     

管道截面对氢气/空气预混爆炸影响的实验研究

为研究管道截面对氢气/空气预混火焰形状与传播速度的影响,选用三个长度都为1m而截面尺寸不同的方形管道进行实验。实验结果表明,在截面为80mm×80mm的管道中,四种氢气浓度下预混火焰都发展形成了郁金香火焰。火焰传播速度呈现上升,下降,再上升的波动。在截面为100mm×100mm和150mm×150mm的管道中,只有在氢气浓度20%下形成郁金香火焰,并且传播速度也出现上述的波动。而在氢气浓度25%,30%,40%下,预混火焰都呈指尖形传至管口,未出现郁金香火焰,传播速度都是不断上升。三个管道对比中,截面为100mm×100mm的管道内火焰平均传播速度最快,且压力波第一峰值最大。     

Fe和Fe2+对混合细菌产氢发酵的影响

在研究Fe粉剂量和Fe²⁺浓度对混合细菌产氢发酵的影响基础上,确定Fe和Fe²⁺促进混合细菌产氢能力的最佳阈值,并对乙醇型发酵菌群在不同Fe粉和Fe²⁺浓度下的产氢量和最大比产氢速率进行考察和对比.结果表明,Fe粉和Fe²⁺对乙醇型发酵菌群的产氢能力均有明显的促进作用.以葡萄糖为底物,投加Fe²⁺试验中,Fe²⁺浓度200mg/L获得最大产氢量143.7mL/g,较对照组提高32%;Fe²⁺浓度50mg/L获得单位VSS最大比产氢速率21.2 mL/(h·g),较对照组提高33%.投加单质Fe试验中,Fe粉剂量1000mg/L获得最大产氢量156.1mL/g,较对照组提高44%;Fe粉剂量500mg/L获得单位VSS最大比产氢速率23.5mL/(h·g),较对照组分别提高47%.单质Fe浓度高于50mg/L时,对发酵菌群产氢的促进作用要优于同浓度下的Fe²⁺.同时对混合细菌中铁的全量和形态分布进行了考察.     

Thermal hazard accident investigation of hydrogen peroxide mixing with propanone employing calorimetric approaches

Hydrogen peroxide (H₂O₂), historically, due to its broad applications in the chemical industries, has caused many serious fires and explosions around the world. Its thermal hazards may also be incurred by an incompatible reaction with other chemicals, and a runaway reaction may be induced in the last stage. This study applied thermal analytical methods to explore the H₂O₂ leading to these accidents by incompatibility and to discuss what might be formed by the upset situations. Thermal hazard analysis contained a solvent, propanone (CH₃COCH₃, so-called acetone), which was deliberately selected to mix with H₂O₂ for investigating the degree of thermal hazard. Differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2) were employed to evaluate the thermal hazard of H₂O₂. The results indicated that H₂O₂ is highly hazardous while mixed with propanone, as a potential contaminant. The time to maximum rate (TMR) was used as emergency response time in the chemical industries. Therefore, TMR of H₂O₂ was calculated to be 70 min for runaway reaction (after T₀) and TMR of H₂O₂/propanone was discovered to be 27 min only. Fire and explosion hazards could be successfully lessened if the safety-related data are properly imbedded into manufacturing processes.     

Acidification of groundwater in water-filled gravel pits -- a new environmental and geomedical threat

Swimmers and users of motor boats frequenting old, water-filled gravel pits in Kiiminki, Northern Finland, found in August 1993 that they were suffering from painful irritation of the eyes and that their boats had developed a finely polished surface on their aluminium hulls, evidently due to the corrosive action of the water. Subsequent measurements carried out by the water authority showed that the pH of the water in some of the pits was extremely low, reaching a value of 3.4 at its lowest. To find out the causes of the abnormally low pH values, the present authors began systematic measurements of the pH and determination of the chemical composition (Si, Al, Ca, Mg, K, Na, Fe, Mn, Cu, Pb, Ni, Cd, Cl^-, NO₃ ^-, SO₄ ^2-) of the water in 23 gravel pits. In addition, a series of laboratory experiments was carried out to examine the interaction of water with samples of the soil and bedrock of the area to evaluate the role of this process as a possible cause of the acidification. The results show that the reaction of water with the moderately to intensively weathered sulphide and jarosite-bearing black schists, typical of the bedrock of the area, can bring about aqueous solutions similar in pH and sulphate--nitrate ratios to those found naturally in the gravel pits. The contribution of other possible mechanisms, e.g. acidic precipitation as such or combined with enhanced evaporation, the possible use of the pits as dumping sites for acidic waste or the flow or seepage of acidic peat-bog waters into the pits from the surrounding wetlands, cannot be ruled out entirely, but their contribution seems to be of minor importance. Since the concentrations of several heavy metals (notably Pb, Cd, Ni, Fe and Mn) and of sulphate and aluminium has increased in the pit water as a result of the acidification process and exceed the norms laid down in the EU Drinking Water Directive, acidification of water in gravel pits due to the oxidation of sulphides must be regarded as a new, serious environmental and geomedical threat which has so far remained poorly known or unrecognised.