A correlation of the lower flammability limit for hybrid mixtures

Hybrid mixtures are widely encountered in industries such as coal mines, paint factories, pharmaceutical industries, or grain elevators. Hybrid mixtures explosions involving dust and gas can cause great loss of lives and properties. The lower flammability limit (LFL) is a critical parameter when conducting a hazard assessment or developing mitigation methods for processes involving hybrid mixtures. Unlike unitary dust or gas explosions, which have been widely studied in past decades, only minimal research focuses on hybrid mixtures, and data concerning hybrid mixtures can rarely be found. Although methods to predict the LFL have been developed by using either Le Chatelier's Law, which was initially proposed for homogeneous gas mixtures, or the Bartknecht curve, which was adopted for only certain hybrid mixtures, significant deviations still remain. A more accurate correlation to predict an LFL for a hybrid mixtures explosion is necessary for risk assessment. This work focuses on the study of hybrid mixtures explosions in a 36 L dust explosion apparatus including mixtures of methane/niacin, methane/cornstarch, ethane/niacin and ethylene/niacin in air. By utilizing basic characteristics of unitary dust or gas explosions, a new formula is proposed to improve the prediction of the LFL of the mixture. The new formula is consistent with Le Chatelier's Law.     

Evaluating relief events in binary mixtures with dynamic simulations

Relieving rates in ethanol/water and ethylene glycol/water mixtures were investigated using dynamic models of an emergency relief scenario due to an external heat source. A commonly used shortcut method was compared to two rigorous calculation methods—one using ideal conditions and another using non-ideal conditions. In several cases, the shortcut method provides a reasonable estimate compared to the rate predicted by the more rigorous methods. However, in many cases the shortcut method over or under-predicts the required relieving rate—sometimes by a significant amount. Several discrepancies are also noted between non-ideal and ideal conditions. This study demonstrates that each multi-component mixture must be carefully considered before sizing emergency relief systems and devices.     

Flash points measurements and prediction for binary miscible mixtures

Flash point is one of the most important parameters used to characterize the potential fire and explosion hazards for flammable liquids. In this study, flash points of twenty eight binary miscible mixtures comprised eighteen flammable pure components with different compositions were measured by using the closed cup apparatus. The obtained experimental data are further employed to develop simple and accurate models for predicting the flash points of binary miscible mixtures. Based on the vapor–liquid equilibrium theory, the normal boiling point, the standard enthalpy of vaporization, the average number of carbon atoms, and the stoichiometric concentration of the gas phase were selected as the dominant physicochemical parameters that were relevant to the overall flash point property of liquids. With these parameters for pure components as well as the compositions of mixtures, the new form of characteristic physicochemical parameters for mixtures were developed and used as the input parameters for the flash point prediction of mixtures. Both the modeling methods of multiple linear regression (MLR) and multiple nonlinear regression (MNR) were employed to model the possible quantitative relationships between the parameters for mixtures and the flash points of binary miscible mixtures. The resulted models showed satisfactory prediction ability, with the average absolute error for the external test set being 2.506 K for the MLR model and 2.537 K for the MNR model, respectively, both of which were within the range of the experimental error of FP measurements. Model validation was also performed to check the stability and predictivity of the presented models, and the results showed that both models were valid and predictive. The models were further compared to other previously published models. The results indicated the superiority of the presented models and revealed which can be effectively used to predict the FP of binary miscible mixtures, requiring only some common physicochemical parameters for the pure components other than any experimental flash point or flammability limit data as well as the use of the Le Chatelier law. This study can provide a simple, yet accurate way for engineering to predict the flash points of binary miscible mixtures as applied in the assessment of fire and explosion hazards and the development of inherently safer designs for chemical processes.     

Ventilation theory and dispersion modelling applied to hazardous area classification

Critical formulae given in the current Explosive Atmospheres Hazardous Area Classification Standard IEC 60079-10-1 (2008) [BS EN 60079-10-1, 2009] to determine the expected gas cloud volume which is used to determine area classification do not have any scientific justification. The standard does allow the alternative use of Computational Fluid Dynamics (CFD) methods, which serve to compound the concern with these formulae: the predicted volume of the gas cloud from CFD models being several orders of magnitude smaller than that given by the formulae in question. To resolve such major discrepancies, replacement of the current formulae with a scientifically validated approach is proposed. Integral models of dispersion and ventilation have been used routinely for many years in the analysis of major hazards in the chemical industry. This paper presents an adaptation of these models to determine the expected volume of a gas cloud arising from a release of gas from a pressurised source. A very simple integral jet model is presented for outdoor dispersion, extended to the case of indoor dispersion, from which the volume of the gas cloud is derived. The single free parameter, an entrainment coefficient, is fixed by comparison with data on a free jet, and then predictions of the model are compared with CFD calculations (which themselves have been validated against experimental data) for dispersion within an enclosed volume. The results of this simple integral model are seen to agree very well with the CFD predictions. The methodology presented here is therefore proposed as a scientifically validated approach to Hazardous Area Classification.     

粉胶比对沥青混合料安全性能影响的试验研究

为研究出合理的、适合大兴安岭通县公路沥青混凝土路面的粉胶比,选用大兴安岭本地石材、大庆AH-130基质沥青,按密级配AC-16Ⅰ上限配比,通过标准马歇尔、浸水马歇尔、车辙、小梁低温弯曲等试验对沥青混合料的安全性能进行了研究。结果表明：最佳沥青用量OAC为6.0%,沥青混合料的抗水侵性能满足要求;在同一油石比的条件下,随着粉胶比的增大,动稳定度有显著增大的趋势,但当粉胶比超过1.0时,增长趋势逐渐缓慢,并且在粉胶比达到1.3之后达到峰值,然后开始下降;随着粉胶比的逐渐增大,弯拉应变有增大的趋势,粉胶比在1.0-1.1左右沥青混合料低温抗弯拉性能最佳。     

Fugitive Gas Emissions from Fuel Tanks

Many fuel installations and industrial operations often are associated with the release, whether deliberately or inadvertently, of fuel vapors into the surrounding atmosphere. Most of these releases may be considered to be relatively small on a thermal basis, but they do represent collectively a serious source of unburned hydrocarbon emissions into the atmosphere. Moreover, the emissions of methane from various sources of natural gas contribute significantly to green house gas emissions.

The paper presents computed results of the transient dissipation of a fixed mass of methane when released within vertical cylindrical vessels containing air, which are open to the outside atmosphere under ambient conditions. Particular attention is given to the rates of emission of gas into the outside atmosphere and how it is affected by the composition and mass of the fuel released and the size and configuration of the fuel retaining cylindrical tank. The corresponding transient formation, growth and subsidence of flammable zones within such a vessel are also described. Some guidelines for reducing the hazards associated with such releases are presented.     

Experimental investigation of fast flame propagation in stratified hydrogen–air mixtures in semi-confined flat layers

This paper presents results of an experimental investigation on fast flame propagation and the deflagration-to-detonation transition (DDT) and following detonation propagation in a semi-confined flat layer filled with stratified hydrogen–air mixtures. The experiments were performed in a transparent, rectangular channel open from below. The combustion channel has a width of 0.3 m and a length of 2.5 m. The effective layer thickness in the channel was varied by using different linear hydrogen concentration gradients. The method to create quasi-linear hydrogen concentration gradients that differ in the range and slope is also presented. The ignited mixtures were accelerated quickly to sonic flame speed in the first obstructed part of the channel. The interaction of the fast flame propagation with different obstacle set-ups was studied in the second part of the channel. The experimental results show an initiation of DDT by one additional metal grid in the obstructed semi-confined flat layer. Detonation propagation and failed detonation propagation were observed in obstructed and unobstructed parts of the channel.     

Comparative study on standardized ignition sources used for explosion testing

For the determination of safety characteristics of gases, vapors and dusts different types of ignition sources are used in international standards and guidelines. The paper presents test results of a comparative calorimetric and visual study between four different types of ignition sources. The ignition procedures were analyzed visually with a high-speed camera and electric recordings. In addition to that, the influence of the electrode-orientation, -distance as well as ignition energy on the reproducibility of the exploding wire igniter was tested.The exploding wire is already in use for standardized determination of safety characteristics of gases, first tests on the suitability of the exploding wire igniter for dust testing have been carried out but are not standardized yet. Using the exploding wire, the ignition energy can be varied from 2 J to 10 000 J (2 x 5000 J) and thus it could be used for gases, vapors, dusts and hybrid mixtures. Moreover it can be used at high initial pressures and it is the only ignition source with an easily measurable ignition energy release. Furthermore, it does not introduce another chemical reaction into the system.Finally, a proposal for a standard ignition source for explosion tests on hybrid mixtures is derived from the test results.     

Binary mixtures of feeding deterrents mitigate the decrease in feeding deterrent response to antifeedants following prolonged exposure in the cabbage looper, <Emphasis Type="Italic">Trichoplusia ni</Emphasis> (Lepidoptera: Noctuidae)

Summary. The effect of rearing larvae of Trichoplusia ni on individual feeding deterrents or on binary mixtures of deterrents on their subsequent gustatory sensitivity was measured in paired choice leaf disc bioassays. Our working hypothesis was that mixtures of antifeedants (pure allelochemicals) would mitigate decreased feeding deterrent response following prolonged exposure in this generalist herbivore. Neonate larvae were reared on cabbage leaves treated with individual feeding deterrents (digitoxin, thymol, toosendanin or xanthotoxin), or with binary mixtures of these until the third instar. Feeding deterrent responses to each antifeedant or mixture was then determined in a leaf disc choice bioassay. All of the mixtures produced additive deterrence when presented to naïve larvae. Larvae reared on individual antifeedants showed a significantly decreased feeding deterrent response (except to digitoxin), whereas larvae reared on binary mixtures of antifeedants did not show a decreased feeding deterrent response to any of them. Such mixtures were synergistic in terms of their feeding deterrence to experienced larvae. Our experiment supports the hypothesis (Jermy 1986) that mixtures of deterrents can prevent decreased feeding deterrent response following prolonged exposure, and provides one explanation for the multiplicity of chemical defenses found in many plants.     

有害结局路径(AOP)框架在水体复合污染监测研究中的应用

由于包含复杂的毒害化学污染物质,水体复合污染一直威胁着人类健康和水生生态安全。对复合污染水体进行监测、评估和治理是水环境管理的重点之一。监测并识别水体关键毒害污染因子是进行水质管理的前提,也是复合污染研究的难点。目前国内外在水复合污染毒性监测研究上主要基于动物活体试验或者生物体外测试。由于受限于毒理学测试方法,常见的应用通常仅关注于某方面的毒性效应或者少数的分子指标,因而受到质疑和挑战。有害结局路径(Adverse outcome pathway, AOP)的概念将化学污染物的结构、致毒的分子启动事件和生物毒性的有害结局建立关联,为污染物的毒性测试、预测和评估提供了新的模式。本文旨在论述有害结局路径在复合污染毒性评估和关键毒害物质鉴别中的指导性价值和意义。在有害结局路径的指导框架下,借助于生物体外高通量测试技术、化学分析的靶向和非靶向分析技术、和生物信息学技术,可以系统地分析化学混合物在分子、细胞水平上健康相关指标的响应水平,评估水体中复杂结构污染物,与不同生态和健康有害结局之间的关联,为水环境评价和优先污染物的筛选管理提供有效支撑。本文通过综述AOP框架在复合水体中毒害物质风险研究的现状和优势,对AOP在水环境环境管理上的应用前景提出展望。