膨胀聚苯乙烯热分解动力学分析和寿命预测

针对既有聚苯乙烯泡沫类外墙外保温系统的防火问题,在空气和氮气气氛下对非阻燃和阻燃型膨胀聚苯乙烯泡沫进行了热重分析。样品由10℃/min、20℃/min、40℃/min和50℃/min四个升温速率从室温加热至800℃。热分解动力学参数由Flynn-Wall-Ozawa(FWO)等转化率方法和多参数非线性回归方法(multivariate non-linear re-gression method)计算,结果表明六溴环十二烷(HBCD)阻燃剂可一定程度上提高EPS的热稳定性。EPS在空气和氮气气氛下热解可认为是单步反应。非阻燃聚苯乙烯泡沫在空气和氮气气氛下的热解过程可由自催化n阶反应机理描述。阻燃EPS在空气气氛下的热解机理为自催化n阶反应,在氮气气氛下则为n阶反应机理。基于动力学参数和反应机理,对聚苯乙烯泡沫在不同温度下的寿命进行了预测。     

Alternative method to prevent thermal runaway in case of error on operating conditions continuous reactor

Thermal runaway was studied in a continuous tubular pilot reactor under steady-state regime. Different accident scenarii were conducted by making some errors on reactant concentrations and/or temperature feed. To prevent thermal runaway, control by direct contact by solvent injection was used at different reactor locations. This injection allowed controlling the maximum reaction temperature. A simplified analytical method to estimate the maximum reaction temperature along the reactor was used.Benefit of this control method was the diminution of computational time. Furthermore, by injecting solvent to control maximum reaction temperature, there is no need to shut down the unit. The control method was validated experimentally.     

基于层次分析法的热塑性聚氨酯及其纳米复合材料火灾危险性综合评价

聚合物的火灾危险性与热、烟、毒的释放密切相关,但采用不同指标对材料的评价结果不一致。以纳米级蒙脱土(MMT)、氢氧化铝(ATH)和聚磷酸铵(APP)为添加剂的热塑性聚氨酯(TPU)纳米复合材料为研究对象,选取其在静态管式炉、稳态管式炉和锥形量热仪中的相关实验数据,以HCN总浓度作为特殊毒性危害指标,CO和CO_2浓度为一般毒性危害指标,以热释放速率峰值、平均热释放速率、总热释放量为热危害指标,以产烟速率峰值、生烟总量为烟危害指标。进一步细分了火灾烟气中不同毒性气体对于火灾风险的影响,并运用层次分析法计算指标权重,综合评价了热塑性聚氨酯及其复合材料的火灾危险性。结果表明,当添加量为6 wt%聚磷酸铵、3 wt%氢氧化铝与3 wt%蒙脱土时,此时复合材料的火灾危险最低,证明了综合热、烟、毒三个层次来降低聚合物材料火灾危险性是可行的。     

Ignition temperatures of dust layers and bulk storages in hot environments

In many industrial installations, particulate solids (cereals, agri-food products, coal, plants, etc.) are stored or processed. Self-heating of these products, which can lead to fires and explosions, can occur in a variety of situations. Examples include large storage at room temperature, formation of a layer on a hot surface, layer deposited on a surface – insulating or conductive – in a hot environment or even storage of product exposed to heating on one side.The main parameters that determine the occurrence of self-heating are the size of the container, the temperature, the residence time and the characteristics of the product. Depending on the type of situation encountered and these implementation conditions, the analysis of self-heating risks must be based on specific models and/or parameters.This paper presents the different variants and combinations of the theoretical model from the theory of thermal runaway to represent self-heating, taking into account in particular the symmetry or asymmetry of heating, reagent consumption and boundary conditions. It also discusses their adaptation to the previous identified industrial situations.Nine products were chosen to be representative of those used in the different considered industrial situations. They were subjected to self-heating basket tests in isothermal ovens in order to determine the parameters for applying the described theoretical models. These results were compared with the results of self-heating tests in layers of different thicknesses in a hot environment, on an insulating or conductive plate, using a specially developed test protocol, as well as with the results of standardized tests of minimum ignition temperature in 5 mm layers.This led to the proposal of the most appropriate theoretical model to represent the self-heating phenomenon for each of the four identified industrial situations.This analysis can promote better design of industrial equipment and production conditions (temperatures, volumes or product flows …) in order to prevent fires and explosions.     

用热分析法研究鼎湖山土壤的粘粒矿物

广东鼎湖山自然保护区的土壤主要为山地黄壤和赤红壤。本文用差热-热重-微商热重(DTA-TG-DTG)联合热分析法,对两种土壤的粘粒矿物进行了初步研究,确认两种土壤的粘粒矿物组成主要为伊利石、高岭石、三水铝石、蛭石、针铁矿等。伊利石、三水铝石、蛭石的含量山地黄壤多于赤红壤,而高岭石则相反。两种土壤的风化程度不高,土壤矿物风化主要处于幼年阶段,山地黄壤尤其明显。另外,对不同林型下的赤红壤也进行了对比研究,其粘粒矿物组成和数量差异不大。     

A very simple yet accurate solution to the thermal explosion problem

A very simple solution to the thermal explosion problem for one-dimensional solids is presented. The solution produces analytical expressions for the criticality condition. Two different solutions are used. One solution gives higher answers than those known from exact solutions and the second solution gives lower answers. This allows bracketing the expected answer with a determined tolerance. The results obtained compare quite favorably with those obtained from known exact numerical solutions. This allows the utilization of the present method for many a practical problem with an acceptable tolerances.     

Use of Airborne Thermal Imagery to Detect and Monitor Inshore Oil Spill Residues During Darkness Hours

/ Trials were conducted using an airborne video system operating in the visible, near-infrared, and thermal wavelengths to detect two known oil spill releases during darkness at a distance of 10 nautical miles from the shore in St. Vincent's Gulf, South Australia. The oil spills consisted of two 20-liter samples released at 2-h intervals, one sample consisted of paraffinic neutral material and the other of automotive diesel oil. A tracking buoy was sent overboard in conjunction with the release of sample 1, and its movement monitored by satellite relay. Both oil residues were overflown by a light aircraft equipped with thermal, visible, and infrared imagers at a period of approximately 1 h after the release of the second oil residue. Trajectories of the oil residue releases were also modeled and the results compared to those obtained by the airborne video and the tracking buoy. Airborne imagery in the thermal wavelengths successfully located and mapped both oil residue samples during nighttime conditions. Results from the trial suggest that the most advantageous technique would be the combined use of the tracking beacon to obtain an approximate location of the oil spill and the airborne imagery to ascertain its extent and characteristics.KEY WORDS: Airborne video; Thermal imagery; Global positioning; Oil-spill monitoring; Tracking beacon     

Phytotoxicity and groundwater impacts of leaching from thermal treatment residues in roadways

The use of coal fly ash (CFA), municipal solid waste incinerator bottom ash (MSWIBA) and flue gas desulfurization residue (FGDR) in road construction has become very common owing to its economical advantages. However, these residues may contain toxic constituents that pose an environmental risk if they leach out and flow through the soil, surface water and groundwater. Therefore, it is necessary to assess the ecotoxicity and groundwater impact of these residues before decisions can be made regarding their utilization for road construction. In this study, the physico-chemical characteristics, leaching and phytotoxicity of these residues were investigated. Specifically, multivariate analyses were used to evaluate the contributions of the leaching constituents of the CFA, MSWIBA and FGDR leachates to the germination index of wheat seeds. B, Ba, Cr, Cu, Fe and Pb were found to be more toxic to the wheat seeds than the other heavy metals. Furthermore, the leached concentrations of the constituents from the CFA, MSWIBA and FGDR were below the regulatory threshold limits of the Chinese identification standard for hazardous wastes. Analyses conducted using a numerical groundwater model (WiscLEACH) indicated that the predicted field concentrations of metals from the CFA, MSWIBA and FGDR increased with time up to about 30 years at the point of compliance, then decreased with time and distance. Overall, this study demonstrated that the risks resulting from MSWIBA, CFA and FGDR leaching could be assessed before its utilization for road construction, providing crucial information for the adoption of these alternative materials.     

火电湿法烟气脱硫塔模拟及优化操作分析

基于火电石灰石-石膏湿法烟气脱硫工艺,以华能福州电厂实际生产数据为依据,经对设备分别简化建模,建立了反映实际脱硫过程的脱硫塔模型,形成全工艺模拟流程,模型计算结果和实际运行数据间平均误差为0.4364%.对脱硫工艺过程进行灵敏度分析,得出循环浆液pH值、烟气流量、液气比等因素对吸收效率的影响.最后,以灵敏度分析结论为基础,借助多目标优化方法分析不同工况下各控制因素对脱硫效率的影响,得到基本优化控制范围(pH值处于5.4～5.6、烟气压力处于0～1000Pa)和相应的最优控制方案,并分析了优化操作结果的工业适用性.     

Simulation of the flow of an explosive atmosphere exposed to a hot surface

The accidental ignition of combustible atmospheres by hot surfaces is of great concern for chemical and process plant safety. In this paper, we present our research regarding the evolution of thermal plumes originating from hot hemispheres and discs. In particular, we focus on the effect of the orientation of the surface on the ignition process. The auto-ignition temperatures and ignition locations were studied experimentally. To get further insight, we conducted detailed numerical simulations and validated them with measurements. Three-dimensional simulations were performed on hot hemispheres and hot discs for different orientations ranging from 0° to 180°. The solver employs a transient, implicit scheme which is based on the coupled heat transfer and flow equations. The mesh in the vicinity of the hot surfaces is refined to resolve the steep temperature gradients and to capture the boundary layer separation. The influence of the orientation on critical hot spots in the gas mixture is analysed by examining the flow structures and the temperature evolution of the buoyancy-driven flow. Using the obtained results, we discuss the change of the onset and location of the ignition.