Kinetic parameter estimation for decomposition of organic peroxides by means of DSC measurements

The thermal stability of organic peroxides (cumene hydroperoxide 80 wt% and dicumyl peroxide) was studied by means of calorimetric measurement (DSC, TA Q1000) in an isotherm mode and a dynamic mode. Analysis of power profiles released in the isothermal mode was combined with the analysis of the decomposed compounds by a gas chromatograph/mass spectrometer (GC/MS) to determine the reaction mechanisms corresponding to each of the two reactions. In this work, a methodology for estimating kinetic parameters was based on the comparison of the power profile (dynamic mode) given by the model to that obtained experimentally by changing the parameters values. Parameter estimation is achieved using the mixed estimation method where a genetic algorithm is combined with a locally convergent method.     

镁粉爆炸特性和惰化抑爆的实验研究

采用20 L球形爆炸测试装置,考察了镁尘浓度、镁粉粒度、点火能量对镁粉爆炸过程热力学参数Pmax、动力学参数(dP/dt)max的影响;选取CaC03粉末作为惰化剂,考察惰化剂含量、情化剂粒度对镁粉爆炸抑制性能的影响,提出了预防镁粉爆炸、降低爆炸危害的本质化安全对策.结果表明,镁尘浓度、点火能量越高,爆炸危害越大;镁粉...     

易燃易爆气体泄漏的危险性分析

从现代社会中广泛使用和运输的易燃易爆气体着手,介绍了气体泄漏后的几种重要参数的模型,同时总结了这些气体的毒害机理、易发生火灾和爆炸的特点,同时指出了火灾和爆炸的模型,使人们可以深刻地认识其毒害性.     

易燃易爆重大危险源事故概率计算

分有人介入和无人介入重大危险源监测系统两种情况，运用马尔可夫过程研究了重大危险源发生事故的概率，并进行了实例计算。所给概率模型可用于重大危险源的安全评价。【关键词】##4易燃易爆重大危险源;;马尔可夫过程;;安全评价;;事故概率计算;;安全监测系统     

输油管道中汽油蒸汽爆炸的规律研究

综合考虑湍流及化学反应动力学机理对燃烧的影响,建立了详细流动耦合简化的详细化学反应机理的湍流燃烧模型,以有限体积法求解爆炸流动及反应控制方程,对二维压力管道中汽油蒸汽爆炸的过程及规律进行了数值模拟,模拟结果与实验数据有较好的吻合性;分析了各种组分的变化过程及对爆炸的控制作用.为汽油蒸汽爆炸特性及规律的进一步研究、工业防...     

乳化炸药生产线危险源安全措施探讨

本文从乳化炸药的原材料、工艺、设备等方面,分析探讨了乳化炸药生产线危险源所在及其危险性,并提出了相应安全技术措施,这对安全生产具有一定指导意义。     

易燃、易爆、有毒重大危险源评价方法与控制措施

论述了重大危险源和重大事故隐患的定义;介绍了易燃、易爆、有毒重大危险源评价方法;在辨识评价的基础上,提出了制定重大危险源事故应急计划,加强监控、管理等措施     

山东省民爆器材行业安全现状调查

民用爆破器材的易燃易爆属性,使得民爆生产、储存、运输、装卸过程具有较大的危险性,发生后果严重的燃烧爆炸事故概率相对较高。因此,民爆器材行业首要的任务就是搞好安全生产,保障人民生命财产的安全,维护社会的稳定。摸清行业的安全现状,研究制定切实的安全对策措施,也就成了搞好行业安全工作的重要内容。     

锅炉过热器爆漏原因的统计分析和预防措施

以100余起公开报道的锅炉过热器爆漏事故案例进行统计分析为基础,将引起过热器爆漏的直接原因归纳为长期超温、短期超温、腐蚀、磨损和焊接缺陷,对产生事故的机理和主要原因进行了探讨和归类,认为运行管理不当是造成过热器爆漏的最重要方面。分析并提出了设计、安装、制造、检修和运行管理过程中对爆漏风险贡献最大的各单因素及其成因。针对造成爆漏的根本原因提出了预防措施,为锅炉的安全运行和合理检修提供了科学依据。     

Comparisons of TGA and DSC approaches to evaluate nitrocellulose thermal degradation energy and stabilizer efficiencies

This study investigated the thermal degradation energy (activation energy, E_a) for nitrocellulose (NC) with low nitrogen content of 11.71 mass%, so-called NC3, by using two different kinds of thermal analysis instruments: thermogravimetric analyzer (TGA) and differential scanning calorimetry (DSC). A comparison of E_a for various nitrogen content NC samples at two scanning rates (5 and 10 °C min^?1) tested by TGA and DSC is also discussed in this paper. Meanwhile, our aim was to analyze the anti-degradation of E_a for NC with high nitrogen content, as so-called NC1. Thermal stability for NC1 with diphenylamine (DPA) was tested via DSC with 10 DPA concentrations in weights of 0, 0.25, 0.50, 0.75, 1.0, 1.25, 1.50, 1.75, 2.0, and 3.0 mass%. Experimental results indicated that E_a of NC3s was 319.91 kJ mol^?1. Moreover, that while dosing DPA into NC1 the best recipe could be employed to avoid any violent NC1 runaway and also can be used to distinguish the differences of thermal decomposition E_a between NC with different nitrogen contents. This study established a fast and efficient procedure for thermal decomposition properties of NC, and could be applied as an intrinsically safer design during relevant operations.     

易燃易爆危险物质泄漏扩散仿真及其应用的研究

以某轻烃厂泄漏事故为研究对象，研制并开发了一个事故后果仿真软件（ＰＣＩＭＳ）．针对仿真过程中存在的问题，如模型的复杂性、参数的不确定性等提出了处理方法．通过具体生产装置的泄漏扩散后果分析，演示了ＰＣＩＭＳ的仿真结果     

静电放电对电火工品作用机理分析与试验研究

在分析电火工品静电作用机理的基础上,利用瞬态脉冲试验原理研究了静电放电对电火工品的性能影响。分析了因电火工品个体差异导致分组不均给试验带来的影响,提出用瞬态脉冲试验得到的温升参数对样品进行分组,以保证试验样品的一致性。研究结果表明,经过静电放电试验后,电火工品温升值变大,平均作用时间变长。说明可以用瞬态脉冲试验法检测经静电放电后电火工品的性能变化。     

Thermal hazard analysis of triacetone triperoxide (TATP) by DSC and GC/MS

Thermal degradation of triacetone triperoxide (TATP) was studied using differential scanning calorimetry (DSC) and gas chromatography/mass spectrometry (GC/MS). TATP, a potential explosive material, is powerful organic peroxide (OP) that can be synthesized by available chemicals, such as acetone and hydrogen peroxide in the laboratory or industries. The thermokinetic parameters, such as exothermic onset temperature (T₀) and heat of decomposition (ΔH_d), were determined by DSC tests. The gas products from thermal degradation of TATP were identified using GC/MS technique.In this study, H₂O₂ was mixed with propanone (acetone) and H₂SO₄ catalysis that produced TATP. The T₀ of TATP was determined to be 40 °C and E_a was calculated to be 65 kJ/mol. A thermal decomposition peak of H₂O₂ was analyzed by DSC and two thermal decomposition peaks of H₂O₂/propanone were determined. Therefore, H₂O₂/propanone mixture was applied to mix acid that was discovered a thermal decomposition peak (as TATP) in this study. According to risk assessment and analysis methodologies, risk assessment of TATP for the environmental and human safety issue was evaluated as 2-level of hazard probability rating (P) and 6-level of severity of consequences ratings (S). Therefore, the result of risk assessment is 12-point and was evaluated as “Undesirable” that should be enforced the effect of control method to reduce the risk.     

沼气工程火灾爆炸定量风险分析方法研究

为减少我国沼气工程火灾爆炸事故的发生,本文基于风险的概念对我国沼气工程火灾爆炸风险的量化分析方法进行研究.首先,在事故概率方面,综合分析荷兰研究小组在COVO研究报告中公布的数据、挪威船级社(DNV)的数据库以及国内同行业研究人员的统计数据,给出我国推荐使用的沼气工程设备基础泄漏概率;然后,在事故后果方面,通过对沼气工程泄漏事件树的分析,借鉴API统计数据,提供沼气泄漏后的表现形式和事件发生概率,并结合我国石化行业标准,建立沼气工程火灾爆炸伤害分析模型;最后,在风险可接受准则方面,借鉴荷兰、英国、美国等相关机构数据,给出适合我国实际的个人风险可接受标准.这一定量风险分析方法可为沼气工程风险管理、应急救援、土地使用、安全规划等方面提供分析工具.     

粒径对镁粉爆炸特性的影响

在简要分析了镁粉爆炸的过程和特性基础上,结合在20 L球型爆炸测试装置中对粒径D50为6,47,104,173 μm镁粉的爆炸特性实验数据,着重分析了粒径对镁粉爆炸特性所产生的影响.实验结果表明,随着粒径的增大,镁粉的爆炸危险性随之减小.     

300m3易燃易爆湿式氢气贮柜爆炸事故分析

针对某动力公司300m^3易燃易爆湿式氢气贮柜发生燃烧爆炸事故的现场情况,首次给出了湿式氢气贮柜发生爆炸的可能原因和事故的技术分析过程,建立了相应的事故数学分析模型和爆炸燃烧方程,提供了湿式氢气贮柜发生爆炸事故的数学模拟计算方法,确定了300m^3湿式氢气贮柜发生爆炸事故原因,为我国类似企业开展湿式氢气贮柜火灾爆炸事故分析提供了可借鉴的理论和方法依据。     

The thermal hazard evaluation of 1,1-di (tert-butylperoxy) cyclohexane by DSC using non-isothermal and isothermal-kinetic simulations

1,1-Di (tert-butylperoxy) cyclohexane (DTBPH) has been widely employed in the chemical industry. Unfortunately, organic peroxides have been involved in many serious fires and explosions in manufacturing processes, storage, and transportation. This study investigated the thermokinetic parameters by isothermal kinetic and non-isothermal-kinetic simulation, using differential scanning calorimetry (DSC) tests. DSC was applied to assess the kinetic parameters, such as kinetic model, frequency factor (ln k₀), activation energy (E_a), reaction order, and heat of reaction (ΔH_d). Comparisons of non-isothermal and isothermal-kinetic model simulation led to a beneficial kinetic model of thermal decomposition to predict the thermal hazard of DTBPH. Simulations of a 0.5 L Dewar vessel and 25 kg barrel commercial package in liquid thermal explosion models were performed and compared to the results in the literature. From the results, the optimal conditions for use of DTBPH to avoid violent runaway reactions during the storage and transportation were determined. This study established the features of thermal decomposition that could be executed as a reduction of energy potential and storage conditions in view of loss prevention.     

基于DSC试验的DCP自加速分解温度的推算

采用差示扫描量热仪(DSC)对小尺度过氧化二异丙苯(DCP)的热分解过程进行试验研究,利用基于等转化率Friedman微分法对热分析试验所得数据进行动力学分析,得出DCP的反应活化能的均值为160.82 kJ· mol-1.最后运用热爆炸理论对25 kg标准包装条件下的自加速分解温度(SADT)进行推算.结果表明,利用等转化率Friedman 微分法计算所得的动力学参数在整个反应进程中并不是常数,表明DCP的热分解反应是一个固态的复杂反应过程.多重扫描速率下计算所得的动力学参数较单个扫描速率法可信度更高,推算所得DCP的SADT值与美式全尺寸试验值基本一致.     

改性活性炭纤维吸附炸药废水中TNT实验研究

本文研究了改性活性炭纤维对炸药废水中TNT的吸附行为。研究表明:1 mol/L HNO3改性的活性炭纤维吸附效果最好,其对炸药废水中TNT的最佳吸附条件为:吸附剂用量为0.6 g/25 m L,吸附平衡时间为60 min,升温有利于吸附进行。Langmuir和Freundlich吸附等温线均能较好地描述活性炭纤维对TNT的吸附,吸附动力学分析表明,吸附过程遵循准二级动力学规律。