Analyzing effective factors on leakage-induced hydrogen fires

Currently, novel energy resources are receiving increasing attention as a response to the limitation in fossil fuels as well as their adverse effects on human health. Hydrogen, one of the most abundant elements on the earth, can be regarded as a new energy source to replace fossil fuels. Therefore, safety assessment of the relating processes is very crucial by increasing use of hydrogen as a fuel source. In this regard, consequence analysis for risk assessment and power reduction is very important. The present study aims at modeling hydrogen dispersion along with consequence analyses for such events as jet fire and flash fire. The model was validated by using the data derived from a study on hydrogen leakage in supply pipelines in the laboratory of the University of Pisa. Modeling results reveal that ambient conditions will impose a milder impact on leakage consequences if internal pressure is high in release source. The safe distance was also estimated to be 14 m. Dispersion consequence modeling was performed, followed by the evaluation of the effect of environmental (i.e., stability, ambient temperature, surface roughness, wind speed, and humidity) and process (i.e., vessel temperature and pressure, leakage diameter, and releasing point height) parameters on maximum size flammable vapor cloud and maximum level jet fire radiation on the ground. The size of flammable vapor cloud (consequence dispersion index) and the maximum flux of radiation were affected by process parameters more than ambient parameters. Leakage diameter and the vessel pressure were found to have the highest impact on the operational parameters.     

Persistence of fensulfothion in a sandy‐loam soil and uptake by rutabagas,carrots and radishes using microplots

Abstract

Field microplots were treated with 141 and 282 ppm fensulfothion and 37.1 and 74.2 ppm fensulfothion sulfone. These concentrations are equivalent to field treatment rates of 8.48 and 16.96 kg Al/ha, fensulfothion, and 2.23 and 4.47 kg Al/ha, fensulfothion sulfone, respectively, for banded application (10 cm wide, rows 80 cm apart). The half‐lives in a sandy loam soil were 30–39 and 14–23 days, respectively. Fensulfothion sulfone and sulfide were the main derivatives found in fensulfothion treated soil.

The maximum levels of these derivatives were 21.22 and 22.95 ppm, respectively for the 8.48 kg/ha treatment and 33.90 and 42.45 ppm, respectively, for the higher treatment, which occurred between 30–60 days.

Carrots appeared to take up more fensulfothion from soil than rutabagas or radishes. The residue levels at harvest decreased in the order carrot peel > pulp > rutabagas root > peel > pulp. Residue levels of fensulfothion and sulfone in radishes were similar to those found in rutabagas. The ratio sulfoxide/sulfone in rutabagas ranged from 0.4–1.5 and in carrots from 1.7–7.6. This phenomenon is thought to be due to oxidative enzyme systems present in rutabagas. Dimethyl phosphorothioic acid, but not dimethyl phosphoric acid was detected (max. 1.33 ppm) in some rutabagas samples but not in carrots.     

常温下铁的硫化产物自燃性

含硫油品储运过程中H2S腐蚀产物是常温下硫铁化合物的主要来源,以H2S与铁粉反应制备的硫铁化合物来模拟设备内H2S的腐蚀产物,利用自然氧化的方法测定了硫化反应产物的一次氧化升温和二次氧化升温,考察了铁粉含水量对硫化反应及硫化反应产物自燃性的影响,采用XRD和SEM手段对硫化反应产物进行了表征。结果表明:H2S与铁粉的硫化反应产物为FeS,呈微小颗粒状,覆盖在铁粉表面;硫化反应产物具有自燃性,一次氧化升温最高达到87℃;未被完全氧化的硫化反应产物密封放置一段时间后自燃性明显增加,其二次氧化升温速率最高超过39℃/min;铁粉中含有适量的水可以增加硫化反应速率,提高硫化反应产物的自燃性。     

Extinguishment of hydrogen laminar diffusion flames by water vapor in a cup burner apparatus

Transient computations with full hydrogen chemistry were performed to reveal the flame structure and extinguishment process of co-flow, hydrogen diffusion flame suppressed by water vapor. As the concentration of water vapor was increased, the flame detached away from the burner brim and formed an edge flame at the flame base. Water vapor showed larger chemical inhibition effect than nitrogen when extinguishing hydrogen flame, which was attributed to its enhanced third body effect in the reaction H + O₂ + M = HO₂ + M. The minimum extinguishing concentration (MEC) of water vapor and nitrogen was predicted by Senecal formula and perfectly stirred reactor (PSR) model respectively. The MECs predicted by PSR model agree with the MECs calculated by Fluent, which shows that 1) the flame extinction is controlled by the flame base, and 2) radiation absorption is negligible. The measured MECs are in a reasonable agreement with the values calculated by Fluent, which demonstrates the accuracy of the CFD model. A simple model was used to investigate the relative importance of extinguishing mechanisms of water vapor. The results show that in a co-flow configuration the thermal cooling and chemical inhibition effect are the main extinguishing mechanisms in suppressing hydrogen diffusion cup burner flame.     

Reuse of nickel recovered from spent Ni–Cd batteries for the preparation of C/Ni and C/Ni/Pd layered electrodes for energy sources

Nickel recovered in the recycling process of Ni–Cd batteries was used as a main component of bath for electrodeposition of nickel onto carbon fabric in order to obtain C/Ni composite. A part of the obtained composite was additionally coated with a thin layer of palladium (C/Ni/Pd composite). All the materials were investigated to assess the possibility of their use in the processes of electrochemical storage (sorption/desorption) of hydrogen and electrochemical oxidation of methanol. The obtained results showed the composites to be active electrode materials in these processes. The electrodes exhibited high activity and cyclability, especially in the process of methanol oxidation due to electrocatalytic activity of both nickel deposited onto carbon fabric and the outer layer of porous palladium coating nickel substrate.     

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 p H and temperature, with the optimum ranges of p H 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 theβ-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.     

连续流动分析法测定水中硫化物的显色剂配制方法研究

针对连续流动分析法测定水中硫化物方法中显色剂N,N-二甲基-1,4苯二胺二盐酸盐保质期短的问题,研究了不同体积比盐酸或硫酸介质对延长显色剂保质期的影响,确定了延长保质期的试剂配制方法,并对该方法的适用性进行了检验.结果显示,体积比10％硫酸介质的显色剂优于盐酸介质显色剂,可以存放一周.使用此显色剂进行硫化物分析检出限为0.003 mg/L,线性范围0.000 mg/L ～2.00 mg/L,平行测定相对偏差0.0％ ～11.8％,加标回收率82.0％～102％,可以满足环境样品分析需求.     

n(NO3--N)/n(NO2--N)对混培养菌与纯培养菌同步脱氮除硫的影响

在温度30℃、pH为7、硫氮比为5/3、厌氧条件下,对比研究了不同n(NO-3-N)/n(NO-2-N)对荧光假单胞菌和铜绿假单胞菌混培养菌同步脱氮除硫影响.随着n(NO-3-N)/n(NO-2-N)减小,荧光假单胞菌、铜绿假单胞菌对NOx-N去除率逐渐增高,而S2-去除率却依次减少,混培养菌对NOx-N去除效率先增加后趋于平稳.n(NO-3-N)/n(NO-2-N)对混培养菌去除S2-几乎没有影响.荧光假单胞菌能迅速将NO-3-N转化为NO-2-N,但NO-2-N转为N2却相对缓慢,培养液中出现NO-2-N累积;而铜绿假单胞菌将NO-2-N还原N2的能力明显比荧光假单胞菌强,培养液未反应的NOx-N以NO-3-N为主,未出现NO-2-N累积.混培养菌对NOx-N转化的情况介于荧光假单胞菌与铜绿假单胞菌之间.荧光假单胞菌同时获得较高NOx-N、S2-去除的n(NO-3-N)/n(NO-2-N)为5/5,铜绿假单胞菌为10/0,混培养菌为5.0/5.0.混培养菌对NOx-N、S2-的同步去除效果优于单菌株荧光假单胞菌和铜绿假单胞菌.     

黄河三角洲翅碱篷湿地硫化氢和羰基硫排放动态研究

利用静态箱/气相色谱法,观测了生长季(5~10月)黄河三角洲翅碱篷湿地H2S和COS的释放动态.结果表明,H2S、COS的排放通量具有明显的季节和日变化规律,在生长季,黄河三角洲翅碱篷湿地是H2S和COS的释放源,其中H2S的平均释放通量为4.97μg·(m2·h)-1,COS的平均释放通量为0.92μg·(m2·h)-1.在探讨的环境因子中,不同环境因子对翅碱篷湿地H2S和COS释放通量的影响不同,其中土壤SO2-4含量是影响H2S释放通量的主要因素,土壤含水量是影响COS释放通量的主要因素.含硫气体的排放可能还受到其它因素如植物、潮汐状况等多种因素的影响.     

铈插层黏土负载铁催化剂在H2S选择性催化氧化过程中催化性能的研究

合成了铈插层的Laponite黏土材料(Ce-Lap),并以此材料为载体,分别负载质量分数为3%、5%、8%、10%的Fe制备Fe/Ce-Lap催化剂,通过XRD、氮气吸脱附曲线、XRF、TG、FT-IR、O2-TPD、H2-TPR、XPS等手段,对催化剂的物理化学性质进行了表征测试,并考察了催化剂在H2S选择性催化氧化反应过程中的活性.结果表明,5%的Fe/Ce-Lap在180℃时表现出最好的催化活性,能达到96%的硫产率,这归因于Fe与Ce之间的相互作用,改善了Fe3+的氧化还原能力.此外,较高的氧吸附能力及铁物种的高分散度促进了氧化反应的进行.