PPH (potassium polyacrylate & hectorite) composite materials – A new fire accident emergency method for thermal protection of adjacent tanks

When a chemical tank fire happens in a storage area, it is very important to protect adjacent tanks so as to decrease fire accident losses. In this paper, a new thermal protection method was put forward based on a PPH (potassium polyacrylate & hectorite) thermal insulation composite material spraying on an adjacent tank under fire. Firstly, the PPH material was prepared successfully by a polymerization reaction of potassium acrylate, hectorite, NaHSO₃ and (NH₄)₂S₂O₈. Secondly, thermal insulation performance of the PPH material was characterized by heat transfer process at high incident heat flux using cone calorimeter. The results show that thermal insulation performance of the PPH material is affected by a content change of (NH₄)₂S₂O₈, NaHSO₃ and hectorite in formulations. The content of (NH₄)₂S₂O₈ 0.14 wt%, NaHSO₃ 1.38 wt% and hectorite 1.4 wt% was an optimum formulation ratio to obtain best thermal insulation performance. Finally, possible thermal insulation mechanisms of the PPH material were presented using SEM, TG and TG-IR techniques. One of the thermal insulation mechanisms is the incident heat flux absorbed by water evaporation from the PPH material. Another is the thermal protection of the char formed from the PPH material at high incident thermal radiation, which can prevent heat and mass transfer.     

Pressure and temperature increase of LPG in a thermally coated pressure vessel exposed to fire: Experimental and model results

Damage caused by incidents with transport tanks with compressed liquified gas is amongst the most extreme that can be encountered with transport vessels. This is particularly the case with the Boiling Liquid Expanding Vapor Explosion (BLEVE), which may occur if such a tank is exposed to fire for a prolonged period. Therefore, the local Dutch LPG transport sector adopted a thermally insulating tank coating as a ‘standard outfit’ for their tank trailers, with the aim to delay a BLEVE for a sufficiently long period for emergency services to take appropriate measures and for people near the accident location to be evacuated. On a European scale however, no consensus has been reached on the cost-benefit of such measures.With the current drive towards “greener” and renewable energy sources, this issue has regained attention with alternative fuels such as LNG, CNG and Hydrogen and a need was felt for (better) theoretical models and experimental data concerning the behavior of transport tanks carrying these substances.In this paper a new tank thermal (equilibrium) model is described to predict pressure and temperature behavior of a multi layered, thermally insulated tank containing a compressed liquified gas exposed to heat. Results are compared with data of three bonfire experiments, in which 3 m³ tanks, filled for ca. 50% with LPG were exposed to fire. A good match between modelled and experimental pressure and temperature evolution in time could be obtained using a constant value for the thermal conductivity of the insulation layer. The modelling showed that the thermal insulation value is crucial for an accurate prediction of these parameters as well as the opening time for a pressure safety valve. As relevant temperatures may cover a very wide range (from cryogenic in LNG-tanks to over 1000 °C in a fire) knowledge of the thermal (and physical) behavior of the insulating layer over a large temperature range is essential.The same holds for the behavior of the PRV when subjected to fire. Extreme temperatures may also lead to deviating behavior from what is expected based on the initial settings.     

Fire tests on defective tank-car thermal protection systems

Many railway tank-cars carrying hazardous materials are thermally protected from fire impingement by thermal insulation and a steel jacket applied to the outside of the tank-car shell. Over time, it is possible that the thermal insulation will sag, rip, degrade, or be crushed under the steel jacket. A thermographic technique to determine whether or not a tank has insulation deficiencies has been developed, but it is necessary to determine which thermal deficiencies do not affect a tank’s survivability in a fire and which thermal deficiencies must be repaired. In order to develop a guideline in assessing thermal defects, a thermal model and experimental data would be beneficial.A series of fire tests were performed on a quarter-section tank-car mock-up to assist in developing a guideline and to provide validation data for a thermal model. Twelve fire tests, with constant, credible, simulated pool fire conditions, were performed on the tank-car mock-up with various insulation deficiencies. An infrared thermal imaging camera was used to measure the tank wall temperature. The thermal images were useful in determining the temperature profiles across the defects at different times and the transient temperature behaviour at different locations.It was seen that the properly installed thermal protection system significantly reduced the heat transfer from the fire to the tank wall. It was also seen that the steel jacket alone (i.e. 100% defect) acted as a radiation shield and provided a significant level of protection. With small defects, it was observed that the surrounding protected material provided a cooling effect by thermal conduction. A square defect greater than about 40 cm on each side should be considered significant, because unlike smaller defects, there is little benefit from the surrounding material as far as the peak defect temperature is concerned.     

On the thermal rupture of 1.9 m propane pressure vessels with defects in their thermal protection system

This paper describes the results from a series of fire tests that were carried out to measure the effect of defects in thermal protection systems on fire engulfed propane pressure vessels.

In North America thermal protection is used to protect dangerous goods rail tank-cars from accidental fire impingement. They are designed so that a tank-car will not rupture for 100 min in a defined engulfing fire, or 30 min in a defined torching fire. One common system includes a 13 mm blanket of high-temperature ceramic fibre thermal insulation covered with a 3 mm steel jacket. Recent inspections have shown that some tanks have significant defects in these thermal protection systems. This work was done to establish what levels of defect are acceptable from a safety standpoint.

The tests were conducted using 1890 l (500 US gallon) ASME code propane pressure vessels (commonly called tanks in the propane industry). The defects tested covered 8% and 15% of the tank surface. The tanks were 25% engulfed in a fire that simulated a hydrocarbon pool fire with an effective blackbody temperature of 870 °C.

The fire testing showed that even relatively small defects can result in tank rupture if the defect area is engulfed in a severe fire, and the defect area is not wetted by liquid from the inside. A wall failure prediction technique based on uniaxial high-temperature stress rupture test data has been developed and agrees well with the observed failure times.     

Experimental research in the fire resistance of the double-frame container

During the road transportation of hazardous materials (hazmat), container was usually used to protect the inner package from accidents. The conventional container is a sandwich-framed construction. When it was subjected to car fire, the combustible materials such as poly-foam interlayer would burn up in few minutes. Once the hazmat leaked out, it could result in the great loss of the public and environment. In this paper, a double-frame container mechanism was firstly proposed for loss prevention. In order to investigate the heat conduction pattern and the effect of interlayer thickness, the two-dimensional (2D) Finite Element (FE) model was developed. Based on the numerical results, the interlayer thickness was defined as 155 mm considering the ignorance of sealing. Furthermore, two small-scale containers whose interlayer were ceramic fiber and phenolic foam separately were manufactured. Pool fire experiments were carried out to evaluate the fire resistance of the mechanism and compare the insulation of the interlayer. Results show that the construction of the container remained complete after about 30-min fire exposure. The maximum temperature inside was below 100 °C during the burning process. When the fire burnt down, the temperature inside increased to 110 °C and then declined gradually during the 1000-min cooling process. Additionally, although the thermal insulation of the container with phenolic foam is relatively better, the ceramic fiber is much more suitable for the interlayer considering the sealing of the container and the stability in heat. In summary, the double-frame container could protect the product inside from car fire. It could be beneficial for the fire-resistant design of much bigger containers, which might be widely used for loss prevention in hazmat transport.     

An experimental study of an LPG tank at low filling level heated by a remote wall fire

This paper describes an experimental study of 2300 L pressure vessels exposed to remote fire heating by a natural gas fuelled wall fire simulator. The tanks were filled to 15% capacity with commercial liquid propane. The flame intensity and distance were varied to study the effect of different heating levels on the tank and its lading.The fire simulator is first characterized with tests including fire thermocouples, radiative flux meters and thermal imaging. With the appropriate positioning of a target tank it is possible to get very realistic fire heat fluxes at the tank surface.Three tests were conducted with the 2300 L tanks filled to 15% capacity with propane. The tanks were positioned at three different distances from the wall fire resulting in measured average peak heat flux at the tank surfaces ranging between 24 and 43 kW m^?2. The data shows rapid rise in vapour space wall temperatures, significant temperature stratification in the vapour space, and moderate rate of pressure rise. These results provide excellent data for the validation of computer models used to predict the response of pressure vessels exposed to moderate heating from a remote fire.     

高压开关柜阻燃绝缘件在役老化诱发着火事故的综合分析

高压开关柜长期连续运行在高温高湿环境下,内部的阻燃绝缘件会老化而导致性能劣化,进而引起电弧击穿乃至着火事故。为揭示绝缘件样品老化对其击穿与引燃特性的影响机制,针对已在役运行12年开关柜内老化阻燃固封极柱样品和同配方新样品,开展了微观形貌、热重-差示扫描量热、热重-红外光谱和微量燃烧特性综合分析。结果表明:开关柜内的长期电热应力易使环氧树脂绝缘材料的微观结构产生破坏,内部易产生孔洞和裂纹,导致其绝缘性能下降;开关柜内的高温环境易使绝缘材料内部分子链缓慢断裂,导致老化样品更易受热分解;同时,柜内高温高湿环境既可使其材料内部孔隙吸湿而降低绝缘性能,还易导致磷系阻燃剂吸潮氧化,降低其阻燃性能;最后,与新样品相比,12年老化样品在升温初期的燃烧释热更高,一旦形成击穿电弧,更易着火燃烧。研究结果为高压开关柜因绝缘件老化失效而形成击穿起火事故提供了分析要点,并可作为未来更高性能阻燃绝缘件的优化设计依据。     

火灾下匀质防火保护钢构件温度计算(II)：实际火灾环境计算

目前各国规范给出的计算火灾下有匀质防火保护的钢构件温度的公式都是基于标准火灾环境得到。标准火灾只包含升温段而实际火灾包括升温段和降温段。考察了将现有公式用于实际火灾环境计算的有效性。通过工况分析,考察了不同火灾、不同厚度、不同截面和不同防火涂料情形下的钢材温度。通过与有限元分析的结果比较,我国规范推荐的公式给出的钢材温度与有限元结果符合最好。研究同时表明欧洲规范中使用的避免升温早期负钢材温度增量的方法,即升温段当计算得到的钢材温度为负值时取增量为0,会引起最高钢材温度和降温段钢材温度的偏高,不适用于实际火灾环境计算。综合而言,我国规范最适用于实际火灾环境计算。     

基于数值模拟的外墙保温体系防火问题研究

针对国内现有的外墙外保温系统的防火性较差的现状,通过分析上海公寓楼外墙保温层的火灾,得到外墙外保温防火的三种重要因素（粘结或固定方式、防火隔离带的构造、防火保护面层）。鉴于现在流行的保温材料为膨胀聚苯板（EPS）,因而选用EPS作为模拟材料,利用数值模拟计算得出以下结论：认为火灾时有空腔的保温层比无空腔的保温层更危险;设置防火隔离带能有效得阻隔火灾的蔓延,较宽的隔离带效果更好。除此之外,外保温层防火设计中还应考虑以下三方面的问题,即遴选适当的保温材料、建议保温层也使用类似于防火分区的防火措施和保证保温效果的同时增加防火隔离带的宽度。研究结论和建议对于解决外墙保温体系防火问题具有重要的参考价值和现实意义。     

Experimental hazardous risk investigation of energetic styphnic acid analytical reagent in calorimetric analysis

Analytical reagents identify and manage metal pollution, a major environmental issue. Regrettably, these compounds' safety concerns, especially when heated, have been neglected. This research examines the thermal hazard of the extremely reactive analytical reagent styphnic acid. Differential scanning calorimetry, thermogravimetric analysis, and accelerating rate calorimetry examined styphnic acid's thermodynamics. Thermogravimetric analysis showed weight loss reactions starting at 127 °C and peaking at 208 °C. Differential scanning calorimetry showed an endothermic peak at 176 °C. The accelerating rate calorimetry test showed that styphnic acid self-accelerates at 237 °C after 196.5 °C. Kissinger, Ozawa-Flynn-Wall, and Kissinger-Akahira-Sunose thermokinetic models calculated apparent activation energy from 131.677 to 155.718 kJ/mol. A nonlinear regression analysis showed that styphnic acid undergoes a two-step autocatalytic reaction during heat degradation. Thermal safety was assessed by measuring time to conversion limit, maximum rate, total energy release, self-accelerating decomposition temperature, and adiabatic temperature rise. Styphnic acid is less stable at higher temperatures and its thermal hazards depend on heating rate. The computed SADT was 109.04 °C, with alarm and control temperatures of 104.04 and 99.04 °C, respectively. The risk matrix analysis based on T_ad and TMR_ad suggests reducing thermal instability. This study on styphnic acid's thermal risks and safe storage and transit during analytical applications is beneficial.     

玻化微珠保温砂浆在隧道防火设计中的应用研究

针对当前多发的隧道火灾,探讨玻化微珠保温砂浆在隧道防火设计中的可行性。通过有限元计算分析,对设置玻化微珠保温砂浆隔热层的隧道衬砌结构防火性能进行研究,同时对不同火灾规模下隧道温度场的影响进行了分析。研究结果表明玻化微珠保温砂浆可以很好地阻止热量的入侵,初步验证了其在隧道防火应用的可行性,可为后续隧道防火设计及相关研究提供参考。     

Thermal effects of a sonic jet fire impingement on a pipe

Although the effects of jet fires are often limited to rather short distances, if their flames impinge on a pipe or a vessel collapse can occur in very short times. In such cases, the heat flux on the affected equipment is very high and wall temperature can increase very rapidly. This can happen in parallel pipelines, if a release occurs and impinges on another one. Nevertheless, jet fire impingement has been scarcely studied. In this communication the results obtained from an experimental set-up are presented. Sonic jet fires impinged on a pipe containing stagnant air or water. The temperatures of the flames impinging on it were measured for the worst case (flame front-bright zone), as well as the evolution with time of the pipe wall temperature at different locations. Initial temperature increases up to around twenty °C/s were registered for the air inside, with maximum values of up to 600 °C reached in 2.5 min, and 800 °C in approximately 9 min. In the case of pipe containing water, in the zone of the wall in contact with the liquid the heating rates were much lower, the maximum temperature reached being up to approximately 150 °C. From the temperatures of the jet flames and of the pipe, the heat fluxes reaching the pipe and the corresponding heat transfer coefficients were obtained. The results obtained emphasized that safe distances are essential in pipelines, together with fire proofing and other safety measures.     

防火型家用救生舱舱体热环境与结构优化研究

为优化防火型家用救生舱舱体隔热设计,提出了适用于火灾工况的多重绝热结构设计方法,采用数值模拟和实验的方法研究了防火型家用救生舱舱体的温度分布,分析了12种不同围护结构形式下舱体的绝热保温性能,获得多重绝热结构的最优厚度及绝热材料的最优配比。研究成果可为防火型家用救生舱的隔热设计提供一定的理论支撑和工程设计参考。     

池火特性参数计算及其热辐射危害评价

可燃性油品池火的火焰及其产生的热辐射 ,可能导致周围人员伤亡或设备设施损坏。笔者介绍了油品池火的质量燃烧速率、火焰长度、火焰倾角及火焰后拖量等特性参数的计算方法 ,提出了池火热辐射强度的预测模型 ,给出了热辐射伤害 /破坏准则 ,并进行了模拟计算和评价。     

Evaluation of thermal properties and process hazard of three ionic liquids through thermodynamic calculations and equilibrium methods

Industrial and new energy applications of ionic liquids (ILs) may have to be used at high temperatures conditions, such as in batteries and fuel applications, which may cause thermal hazards. However, there are few studies on the thermal hazards of ILs. To ensure the thermal safety of ILs processes, three commonly used ILs were selected for analysis: 1-butyl-3-methylimidazolium nitrate ([Bmim]NO₃), 1-butyl-2,3-dimethylimidazolium nitrate ([Bmmim]NO₃), and 1,3-dimethylimidazolium nitrate ([Mmim]NO₃). The process hazards under adiabatic conditions demonstrated that [Bmmim]NO₃ and [Mmim]NO₃ have extensive explosion hazards. The self-reaction characteristics determined by the isothermal test indicated that the ILs are nth reactions, and the thermal decomposition features were also determined by thermogravimetric analysis. The data were obtained with a nonlinear thermodynamic model and used to establish the basic thermal hazards of the three ILs. In addition, based on the thermal equilibrium theory, the critical safety parameters can be inferred. The effects of heat transfer in 25.0 g and 50.0 g containers were discussed. The results show that [Mmim]NO₃ will produce a thermal runaway reaction at a lower temperature (<100 °C) and has the shortest reaction time (<1 day), which means [Mmim]NO₃ is considered to be the most hazardous material among the three ILs studied.     

局部火灾条件下某钢结构屋架的抗火保护研究

本文针对局部火灾条件下钢结构屋架的防火保护问题,结合典型案例提出了一种基于性能计算分析的抗火保护设计评估分析方法.首先通过火灾场景分析及烟气运动模拟计算,得到钢结构屋架所处的热环境,再计算各构件在不同保护条件下的温升及应力分布,并判断构件及结构在不同的保护方式下是否失效,最后得到经济合理的保护区域和防火涂层厚度.该方法可以为类似的局部火灾条件下钢结构抗火保护提供参考.     

变压器油池火燃烧规律的实验研究*

为对变压器油池火灾进行准确有效的灭火，研究不同尺寸和不同厚度下变压器油的火灾动力学特征和基本燃烧特性，具体分析变压器油的燃烧过程和变压器油燃烧速率、火焰温度以及辐射热流随油池直径以及厚度的变化规律。结果表明:整个油品的燃烧过程分为预热燃烧阶段、稳定燃烧阶段和火焰熄灭阶段。对于厚度大于10 mm的油池燃烧，稳定阶段的燃烧速率与油层厚度无关，稳定阶段的燃烧速率随着油池直径的增加而增加。同时，变压器油火灾连续火焰区温度接近750 ℃。对于稳定燃烧阶段下的变压器油燃烧，基于辐射通量可得出在燃烧过程中，辐射热量占总燃烧热的占比约为1/3。研究结果可丰富变压器油燃烧的基础数据，为变压器火灾的灭火提供参考。     

外墙保温材料在火灾中的燃烧现象小尺寸实验研究

利用外墙保温材料的小尺寸燃烧实验来研究外墙保温材料在火灾过程中的燃烧特性,分析总结外墙保温材料在火灾过程中的燃烧现象.建立外墙保温材料火灾实验模型,对外墙保温材料火灾实验的实验方法以及数据测定方式进行了介绍.采用不同阻燃性质的保温材料,研究阻燃成分阻止竖向燃烧的效果.观察不同的保温材料在燃烧过程中的点燃性能.根据材料的阻燃性能、点火位置、固定方式的不同,总结燃烧痕迹的变化规律.分析非阻燃材料在燃烧的过程中的熔滴生成,发现产生的熔滴对未燃保温材料的点燃现象.观察不同的保温材料在燃烧过程中的烟气生成及烟气层的形成.通过小尺寸火灾试验的方法来研究建筑外墙保温材料火灾的特性,提出使用阻燃型外墙保温材料的必要性.     

The study of burning behaviors and quantitative risk assessment for 0# diesel oil pool fires

The liquid fuel safety issues on fuel storage, transportation and processing have gained most attention because of the high fire risk. In this paper, some 0# diesel pool fire experiments with different diameters (0.2–1 m) were conducted with initial fuel thicknesses of 2 cm and 4 cm, respectively, to obtain liquid fuel combustion characteristics. Some key parameters including mass burning rate, flame height and the flame radiative heat flux, associated with fire risk, were investigated and determined. Subsequently, a detail quantitative risk assessment framework for 0# diesel pool fire is proposed based on the 0# diesel burning characteristics. In the framework, the probability of personal dead and the facility failure are calculated by the vulnerability models, respectively. In the end, 10 special tank fire scenarios were selected to show the whole risk calculation process. The tank diameter and the distance to pool fires were paid more attention in the cases. The safety distances in the cases are provided for the persons and nearby facilities, respectively. The paper enriches the basic experimental data and the provided framework is useful to the management of 0# diesel tank areas.