被动采样/热脱附/GC-MS法测定环境空气中挥发性有机物暴露量

建立了吸附管被动采样-热脱附解吸气相色谱质谱联用测定环境空气中挥发性有机物暴露量的采样、分析方法。14种挥发性有机物的检出限为0.002~0.005 ng/h。该法采样无需动力,具有简单、方便、灵敏度高等特点,可广泛应用于环境气体的监测。     

Diphenylmethane diisocyanate self-polymerization: Thermal hazard evaluation and proof of runaway reaction in gram scale

Thermal analysis by differential scanning calorimetry and thermogravimetric/differential thermal analysis mass spectrometry, adiabatic calorimetry, a gram-scale heating test, and infrared spectroscopy were performed to evaluate the thermal hazards of diphenylmethane diisocyanate (MDI) and prove the occurrence of a runaway reaction. The self-polymerization of MDI was found to occur at about 340 °C under rapid heating conditions. Carbon dioxide was eliminated and heat was generated to allow polymerization. Under adiabatic and closed conditions, the runaway reaction of MDI can begin at least from 220 °C. Besides it is highly probable that the runaway reaction of MDI can begin from a lower temperature in an actual process scale. More heat was generated than in the previous case and the pressure rose rapidly. A closed 2-mm-thick glass vessel exploded because of the runaway reaction of MDI even if the temperature was lower than 300 °C. Therefore, MDI could cause fatal runaway reactions below 300 °C, where MDI had been assumed to self-polymerize by eliminating carbon dioxide previously.     

Calorimetric studies on the thermal stability of methyl ethyl ketone peroxide (MEKP) formulations

The energetic decomposition of methyl ethyl ketone peroxide (MEKP) and its formulations have long been known to present a significant risk. Indeed, MEKP has the highest number of reported decomposition incidents of all organic peroxides, many of which have led to significant numbers of fatalities, injuries and damage. It is noteworthy that incidents have been reported at all stages of the product lifecycle.This paper is derived from incident-investigation work and provides a summary of serious incidents involving MEKP, followed by details of calorimetric experiments performed to investigate thermal stability of representative MEKP formulations containing varying amounts of MEKP monomer. In particular we report the wide degree of variation that exists between commercial MEKP formulations, even between materials that are of the same nominal formulation. Such variations are detectable using differential scanning calorimetry (DSC).Follow-up studies performed on a representative MEKP formulation containing MEKP monomer indicate that a risk of decomposition exists at temperatures well below the reported self-accelerating decomposition temperature (SADT) of the products. As such, the experimental results reported here suggest that lower storage temperatures (commonly recommended by manufacturers to maximise shelf life) should be considered as being essential throughout the product lifecycle to reduce the risk of accidents in storage and transportation.     

不同自燃倾向性煤自燃氧化特性试验研究

为了研究不同自燃倾向性煤自燃特性变化规律,利用煤氧化动力学测定系统,测试了三种不同自燃性煤的氧化特征。结果表明:(1)单一气体生成量、耗氧量及耗氧速率均随着煤自燃性的增强而增大,且CO生成量和耗氧速率急剧上升的拐点温度与出现C_2H_4气体的温度相同。(2)CO、CO_2和C_2H_4产生率具有明显的阶段性,且前两种气体最大产生率所对应的温度相同;当不同自燃性煤的温度超过80℃时,两组指标CO/ΔO_2和CO/CO_2均迅速增大,表明其氧化反应加快。(3)在TG-DSC试验中,煤的氧化燃烧过程可分为5个阶段,对应于4种特征温度。其中过渡稳定阶段指煤的质量保持稳定,是失重到增重的过渡态,且不同自燃性煤每个阶段持续时间及阶段性特征温度存在显著差异。     

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.     

Thermal radiation from vented dust explosions

The fireball from a vented dust explosion presents a danger to personnel who may be within the vicinity of the event. The risk of serious injury to people caught within the fireball is great, and anyone just outside the fireball may be at risk from thermal radiation. This report describes a project in which the effects of thermal radiation from vented dust explosions was studied. The aim was to establish the areas around a fireball in which people would be at risk from thermal radiation. Six dusts were tested in a large vented vessel and external fireballs were generated under a range of conditions. The fireball geometry and the heat flux from the fireball were studied. A range of material samples were exposed to the fireball. The safe areas around the fireballs were established for each of the six dusts. Generally, the larger vent areas resulted in the larger fireballs and high heat pulse values. However, the fireball was usually too brief to ignite fabric samples unless they were very close to the fireball. The work has shown that in most cases the safe area was relatively close to the surface of the largest fireball.     

Review on fate of chlorine during thermal processing of solid wastes

Chlorine(Cl) is extensively present in solid wastes, causing significant problems during the thermal conversion of waste to energy or fuels, by combustion, gasification or pyrolysis.This paper introduces the analytical methods for determining the Cl content in solid materials and presents the concentrations of Cl in various types of wastes, as reported in literature. Then, it provides a comprehensive analysis on the Cl emission behavior and Cl species formed during the thermal processing of the inorganic and organic Cl sources. The challenges resulted from the reactions between the formed Cl species and the ferrous metals, the heavy metals and the organic matters are summarized and discussed, e.g., high temperature corrosion, heavy metal evaporation and dioxin formation. The quality degradation of products(oil, char and syngas) by Cl is analyzed. Finally, the available controlling methods of Cl emission, including pre-treatment(water washing, sorting,microwave irradiation and stepwise pyrolysis) and in-furnace(absorbents, co-treatment and catalysts) methods are assessed.     

Chip-scale calorimeters: Potential uses in chemical engineering

This work illustrates the potential use of chip-scale calorimeters in typical applications found in chemical engineering including thermal hazard screening, material characterization, and mixing compatibility screening. Experimental results were obtained from two liquid nanocalorimeters and one thermal conductivity sensor designed and commercialized by Xensor Integration, and from two microfabricated calorimeter prototypes developed at Texas A&M University and University of Louisiana at Lafayette.     

Assessing the perception and reality of arguments against thermal waste treatment plants in terms of property prices

The thermal processing of waste materials, although considered to be an essential part of waste management, is often sharply contested in the UK. Arguments such as health, depletion of resources, cost, noise, odours, traffic movement and house prices are often cited as reasons against the development of such facilities. This study aims to review the arguments and identify any effect on property prices due to the public perception of the plant. A selection of existing energy from waste (EfW) facilities in the UK, operational for at least 7 years, was selected and property sales data, within 5 km of the sites, was acquired and analysed in detail. The locations of the properties were calculated in relation to the plant using GIS software (ArcGIS) and the distances split into 5 zones ranging from 0 to 5 km from the site. The local property sale prices, normalised against the local house price index, were compared in two time periods, before and after the facility became operational, across each of the 5 zones. In all cases analysed no significant negative effect was observed on property prices at any distance within 5 km from a modern operational incinerator. This indicated that the perceived negative effect of the thermal processing of waste on local property values is negligible.     

Analysis of the boiling liquid expanding vapor explosion (BLEVE) of a liquefied natural gas road tanker: The Zarzalico accident

The road accident of a tanker transporting liquefied natural gas (LNG) originated a fire and, finally, the BLEVE of the tank. This accident has been analyzed, both from the point of view of the emergency management and the explosion and fireball effects. The accidental sequence is described: fire, LNG release, further safety valves release, flames impingement on vessel unprotected wall, vessel failure mode, explosion and fireball. According to the effects and consequences observed, the thermal radiation and overpressure are estimated; a mathematical model is applied to calculate the probable mass contained in the vessel at the moment of the explosion. The peak overpressure predicted from two models is compared with the values inferred from the accident observed data. The emergency management is commented.