Catalytic decomposition of hydrogen peroxide in the presence of alkylpyridines: Runaway scenarios studies

A number of runaway scenarios of the excess of hydrogen peroxide used during the N-oxidation of alkylpyridines, under closed and open conditions, were examined. It was found that, in most cases, if the volume of the liquid hydrogen peroxide solution occupies more than 10% of the total volume of a closed system (e.g. reactor and vent line between reactor and blockage), the production of gases raises the pressure so quickly that evaporation is completely suppressed. Higher than 70% filling levels result in complete expansion of the liquid. The MTSR(t) of the system falls rapidly if the normal process temperature is high, but if a runaway occurs exactly at the end of dosing, MTST will be very high and secondary decompositions will rapidly develop. The results of this study are currently being used to critically assess the current approaches and further the study of inherently safer designs.     

原子荧光光谱法测定空气中硒化氢的不确定度评定

依据JJF1059.1-2012,确立测量结果和不确定度评价的数学模型,从采集气样体积和采气后滤膜消解液待测物浓度和定容体积三个部分,A类不确定度和B类不确定度二个方面评定测量过程的不确定度,量化各不确定度分量。本次测量相对合成标准不确定度为0.024,较大的不确定度是样品浓度测量过程中的A类不确定度,主要由标准曲线测量和样品测量随机偏差引入,分量值分别为0.013和0.011。本次测量结果为0.169±0.008mg/m3(包含区间在0.161～0.177mg/m3),k=2。即在包含概率约为95%的条件下,可以判定该工作场所空气中硒化氢的含量已经超过了PC-TWA标准限值。     

Hydrogen island: the story and motivations behind the Icelandic hydrogen society experiment

The paper describes the background, motivations and action plan for an extensive experiment with hydrogen (H) as an energy carrier in Iceland. The energy consumption of Iceland is described as well as the role of fossil fuel imports in the otherwise renewable energy scenario. The paper goes on describing the academic/political reasons for the drive towards the H economy experiment and the international consortium created to herald the work. Finally the paper describes the ongoing projects in Iceland and the anticipated development of H research and development in the country.     

有障碍物半开口管道内氢气燃烧数值模拟研究

基于有障碍物氢气燃烧实验装置进行数值模拟研究,采用Fluent软件分析了半开口管道内障碍物对氢气/空气燃烧特性的影响。结果表明:障碍物会促进实验管段内氢气火焰加速,随着障碍物阻塞率和数量的增加,火焰加速更快且燃烧压力峰值更大;在相同阻塞率下,障碍物形状对氢气火焰速度和燃烧压力峰值的影响很小;燃烧压力随障碍物间距的增大先增大后减小,障碍物间距为3倍管道内径时产生的燃烧压力峰值最大。     

氢气爆燃作用下核电站安全壳力学响应数值模拟分析

在核电站严重事故中,由氢气爆燃产生的压力载荷会危及安全壳完整性致其失效,进而造成放射性物质泄漏的严重危害。通过ANSYS/Fluent有限元数值模拟软件,建立了安全壳有限元模型,并对安全壳内氢气爆燃过程以及其力学特性进行了数值模拟研究,获得了氢气爆炸过程中的超压值、升压速率、安全壳变形以及压应力分布。结果表明:爆燃波传递引起压强升高,火焰阵面处压强最高,爆燃波所经区域超压疾速上升随后快速下降;爆燃作用下,顶部壳体和下部筒体连接区域混凝土位移最大,最大压应力也集中分布在该区域,最易受到破坏。获得的结论可为安全壳结构抗爆设计和安全性研究提供理论参考。     

Thermal hazard in a batch process involving hydrogen peroxide

Hydrogen peroxide is a versatile and interesting reagent for many industrial processes; nevertheless, it is very sensitive to impurities that can catalyze its decomposition, so that the desired reaction could be accompanied by undesired parallel and consecutive reactions. As an example, the butadiene free radical polymerization with hydrogen peroxide in the presence of an organic solvent was studied. Batch polymerization occurs in the liquid phase at about 120 °C. Because of the involved reactive compounds and the relatively high temperature, this is an intrinsically dangerous reaction. Therefore calorimetric data can give important information about safety and process optimization during the scale-up. The aim of this research project was to study the influence of impurities on the overall heat of reaction. The experiments were made in a high-pressure reaction calorimeter. The study has revealed that impurities do indeed affect the reaction course. Most importantly, the presence of carboxylic acids and/or ionic iron must be avoided and the recycle of unreacted reagents must be carefully controlled to minimize the build-up of these impurities.     

Effect of inert species on the laminar burning velocity of hydrogen and ethylene

The maximum laminar burning velocity (LBV) of a fuel-air mixture is an important input parameter to vapor cloud explosion (VCE) blast load prediction methods. In particular, the LBV value has a significant impact on the predicted blast loads for high reactivity fuels with the propensity to undergo a deflagration-to-detonation transition (DDT). Published data are available for the maximum LBV of many pure fuel-air mixtures. However, little test data are available for mixtures of fuels, particularly for mixtures of fuels and inert species. Such mixtures are common in the petroleum refining and chemical processing industries. It is therefore of interest to be able to calculate the maximum LBV of a fuel/inert mixture based on the mixture composition and maximum LBV of each component.This paper presents measured test data for the maximum LBV of H₂/inert and C₂H₄/inert mixtures, with both nitrogen and carbon dioxide as the inert species. The LBV values were determined using a constant-volume vessel and the pressure rise method. This paper also provides a comparison of the measured LBV values with simplified LBV prediction methods.     

Control of hydrogen sulphide in digestor gas using iron salts

Different dosages of ferrous chloride and ferric chloride were added to digestors separately, and the volumes of methane and hydrogen sulphide contained in the digestor gas (biogas) were monitored. It was noted that the effects of adding of 16, 18 and 32 kg ferrous chloride/ tonne volatile solids, and 16 and 18 kg ferric chloride/tonne volatile solids were similarly effective in controlling the hydrogen sulphide levels.

According to an average amount of undigested sludge (primary sludge mixed with surplus activated sludge) of 41 tonne volatile solids produced each day during the sewage treatment process in Shatin sewage treatment works, and the required dosage of 16 kg ferric chloride/ tonne volatile solids, the amount of iron salts required should be 656 kg/day or 3.3 mg/L for the actual application, based on an average sewage flow of 200,000 m³/day.     

Solubility and calorimetric study of the effects of gas environment on the decomposition of o-nitrobenzoyl chloride

When ortho-nitrated benzoic acids are chlorinated in xylene and acetonitrile, the product gases, HCl and SO₂, dissolve in the solvent mixture. Previously measured solubilities [Lever, S. D., Papadaki, M. (2004a). o-Chlorination of 2-nitrobenzoic acid with thionly chloride in xylene and acetonitrile. Solubility study of hydrogen chloride and sulphur dioxide in xylene and acetonitrile, IChemE transactions part B. Process Safety and Environmental Protection. 48–60.] were compared to other published data and found to be in very good agreement. The heat of solution of SO₂ in xylene was evaluated calorimetrically and compared to the value obtained from our previous experimental work. In our previous work [Lever, S. D., Papadaki, M. (2004b). Study of condition-dependent decomposition reactions—the thermal behaviour and decomposItion of 2-nitrobenzoyl chloride part_I. Journal of Hazardous Materials. 115; pp. 91–100], it was reported that the products of the decomposition are condition dependent. The current study showed that the decomposition is extensively promoted by the presence of HCl. This has important safety implications should the process operating temperature be reduced and HCl solution in the solvent mixture be increased. If a thermal runaway began in the increased availability of HCl, an undesirable escalation of the runaway could occur.     

生物质能利用技术-厌氧消化技术的研究新进展

厌氧消化技术是最重要的生物质能利用技术之一。厌氧消化技术是实现废物污染防治和能源回收利用的有效方法。本文综述了厌氧消化技术利用生物质废物回收利用生物质能的最新研究进展,分别介绍了生物质废物厌氧发酵产乳酸,氢气和甲烷的机理,研究现状和存在的问题,并对其进一步发展和未来的应用前景进行了分析和展望,为寻找适合中国的垃圾处理技术提供一些参考。