太空环境下锂离子电池热失控与火灾的研究展望

综述了锂离子电池的热失控机理,介绍了由于电池内部电解液、电池隔膜和电极材料分解的链式热反应过程而引发的热失控和火灾现象。同时,讨论了锂离子电池在微重力太空环境中可能产生的烟黑浓度倍增,加速火蔓延,火焰喷射等极端火行为。进而探讨了开展锂离子电池的低压、落塔和抛物飞行等地面实验模拟太空微重力燃烧的方法可行性,建立数值模型预测太空微重力环境下锂离子电池热失控临界条件与火灾行为的必要性,以及如何通过基础研究科学地指导空间站电池热管理和消防系统的设计。     

基于火探管式的锂离子电池灭火技术研究

为研究锂离子电池灭火方案,基于火探管灭火技术同时利用新型清洁灭火剂Novec 1230,组装成火探管灭火系统。在灭火测试平台上以功率为200 W的电热管作为外热源引发单电池或电池模组热失控,通过改变火探管的布置位置,记录相应的灭火行为以及灭火效率,并对实验结果进行了分析。研究结果表明,当火探管灭火系统直接布置在电池正上方时,在起火后的5.6s内控制火情;随着灭火剂用量增加可以显著降低体系温度,防止电池复燃以及连锁热失控现象发生;火探管有效覆盖区域外的失控电池作为热源将继续加热临近电池,引发连锁热失控,造成灭火系统失效;根据电池热失控后的燃烧行为以及传热行为,提出相应的火探管灭火系统复合方案。     

Thermal decomposition mechanism of 65% lysine sulfate powder and its thermal stability based on thermal analysis

Lysine is widely used in the fields of food, medicine and feed, which generally appears in the form of lysine sulfate or lysine hydrochloride dust because of the high instability of the free L-lysine. The L-lysine Sulfate is in high risk of decomposition, spontaneous ignition and even the dust explosion, because the control temperature in its production process is high up to 90 °C. Thus, the thermal behaviors and its thermal stability of 65% lysine sulfate are experimentally explored in Air and Nitrogen using the simultaneous TG-DSC measurements. Results show: (1) the decomposition of 65% lysine sulfate can be divided into three stages both in the atmospheres of air and nitrogen, and most of the weight loss occurred in the first two stages, which are related with the decarboxylation and deamination process. (2) The effects of atmosphere on the decomposition of 65% lysine sulfate mainly occur at the third stage. In this stage, the weight loss in nitrogen is only 14.2%, which is much lower than that in air (34.3%), which is related to the oxidative degradation at high temperature. Besides, the active energy is slightly increased in nitrogen compared to that in air. (3) The initial temperatures of the decomposition of the 65% lysine sulfate are 145 °C and 155 °C, for the air and nitrogen atmosphere, respectively, which are much lower than that (260 °C) of the pure lysine.     

水稻和玉米的热氧化分解特性及几种动力学方法结果的比较

利用热重分析仪在空气气氛、不同的升温速率下对带壳稻谷粉和玉米粒粉进行了热重测试,依据热重实验数据,采用多种热解动力学分析方法计算了水稻和玉米的活化能数值并进行比较,结果表明水稻和玉米的热氧化反应活化能随着转化率出现先增加后降低的趋势,并在转化率为70%左右达到了极大值。     

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.     

阿特拉津对弹琴蛙(Rana adenopleura)蝌蚪微核和核异常的影响

分别在d1、d3、d7、d14,观察空白对照(CK-)、水溶助剂0.1mL/L二甲基亚砜对照(CK )、阿特拉津0.01mg/L(ρ1)、0.1mg/L(ρ2)、1mg/L(ρ3)和10mg/L(ρ4)溶液中弹琴蛙(Ranaadenopleura)蝌蚪血红细胞微核和核异常细胞数.结果表明,d14时,ρ1、ρ2、ρ3和ρ4组蝌蚪的微核率分别是CK-的2.25、2.50、4.25、5.11倍(P<0.05),说明阿特拉津可引起蝌蚪血红细胞微核率升高;且与d1、d3、d7相比较,微核率随着时间的延长有升高的趋势.d14时,ρ2、ρ3和ρ4组蝌蚪的总核异常率(含微核率)分别是CK-的2.59、2.17、1.96倍(P<0.05),说明阿特拉津也可引起蝌蚪血红细胞总核异常率升高.图2表1参17     

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.