Thermal explosion of autocatalytic reaction

Analytical and numerical solutions are used to determine the critical conditions for thermal explosion of autocatalytic reaction. The solutions covers both the reaction governed by the Arrhenius kinetics equation and the Frank-Kamenetskii approximation for that equation. The definition of criticality as the point at which d²θ/dβ²=0, d³θ/dβ³=0 and dθ/dβ〉0 is used here. The study is dealt with low and high exothermicity (B) of the reaction and their effects on the critical parameters. The numerical solutions cover the whole reaction from start at β = 0 up to the end at β = 1.0. All trajectories from subcritical, critical to supercritical are offered. The effects of different parameters such as B, ψ and θ_a (ambient temperature) on the critical conditions are presented. The results showed that the lower the autocatalytic factor (β₀) is, the pronounced autocatalytic reaction explosion. The analytical solution offered analytical expressions for the critical condition and the different limits of the solutions are clarified. It was found that the numerical results confirm the analytical solution.     

Numerical simulation of the thermal inertia of an adiabatic reaction calorimeter in reaction thermal safety process

Obtaining accurate thermal risk assessment parameters of chemical processes and substance properties is essential for improving the safety of chemical production and substance use and storage, and the adiabatic reaction calorimeter (ARC) has been employed by many researchers for this purpose. However, with the improvement and upgrading of the instrument, an examination of the factors that affect its detection accuracy is warranted. A simplified reaction model of the adiabatic thermal decomposition of tert-butyl peroxyacetate was constructed using computational fluid dynamics in which the adiabatic thermal decomposition kinetic model and fluid-solid coupling model were combined to simulate heat transfer. To verify the reliability of the parameters of the numerical calculation model, the effects of the sample cell's material, wall thickness, and mass were investigated in relation to the thermal inertia of the ARC. The results indicated that the thermal inertia of the system was lowest when the sample cell was composed of titanium. When the sample pool's composition is determined, the thermal inertia of the system can be reduced to a certain extent through an approximate increase in the sample mass. Finally, an analysis of the heat flow cloud diagram of the wall of sample pools made from different materials revealed that the thermal conductivity of titanium was high; this information can assist in controlling the adiabatic process.     

三氯乙醛的光降解反应研究

研究了太阳光照下,水溶液中FeC l3-三氯乙醛的光化学反应速率,采用紫外分光光度计定时对含有不同浓度Fe（Ⅲ）的溶液进行实验测定,并根据三氯乙醛标准溶液曲线进行分析。实验结果表明,在波长为480nm的紫外光照射下：室内自然光下含有Fe（Ⅲ）和室外太阳光下不含Fe（Ⅲ）的三氯乙醛溶液中,三氯乙醛的浓度基本保持不变;但在室外太阳光下含有Fe（Ⅲ）的三氯乙醛溶液中,三氯乙醛的浓度随着Fe（Ⅲ）浓度的增加而减小。由此表明,Fe（Ⅲ）是三氯乙醛光化学反应的催化剂,FeC l3-三氯乙醛的光化学反应随着Fe（Ⅲ）浓度的增加而加快。     

氯乙烯生产装置危险性分析

电石法制氯乙烯生产装置涉及到乙炔、氯化氢、氯乙烯等众多的易燃、易爆、有毒物质,反应条件苛刻,系统一旦失控,极易发生火灾、爆炸、中毒等重大事故。因此,对氯乙烯生产装置进行危险性分析具有重要的意义。本文采用危险性和可操作性研究及故障类型影响分析方法分别对氯乙烯生产装置工艺过程及设备的危险性进行了分析,找出了可能引发系统失控的工艺偏离及原因,并提出了控制措施。     

贫烟煤氧化热解反应的动力学分析

通过运用热分析的技术研究平顶山烟煤以及郑州嵩枫贫煤氧化热解反应的动力学特性.依据转化率将煤样的TG曲线划分为两个不同的温度区间进行动力学机理函数的探讨.通过对比分析整个TG曲线的氧化受热情况,将线性较好的机理函数带入DSC曲线进行分析验证,并求解出动力学参数以分析其氧化热解反应的特点.研究得出:这两种煤的氧化热解过程相似但同等条件下反应程度不同;在不同的反应阶段其化学反应级数不同并且相应过程中的TG曲线和DSC曲线反应级数一致;煤反应的活化能随着煤与氧反应过程的深入而增加,指前因子随着活化能的增加而增加且煤氧化反应过程是个分阶段的、多步反应以及相互联系促进的过程.     

Dynamic modeling and bifurcation analysis for the methyl isocyanate hydrolysis reaction

The aim of this work was to characterize the methyl isocyanate hydrolysis reaction and to identify its operational criteria. The parametric sensitivity and dynamic stability methodologies were performed at the Bhopal disaster circumstances, over the relevant operating parameter space. Stable and unstable conditions, bifurcations points, turning points and oscillatory behavior were determined. The combined methodology give useful guidance on the operative conditions selection and the appropriate strategy to overcome hazardous situations. The obtained results demonstrated high sensitivity to small perturbations (thermal runaway) and prevalent oscillatory behavior. Moreover, the following critical parameters for the studied dynamic system were defined: the inverse residence time of 1.5700103 and the heat transfer coefficient of 752.394.     

Emergency shutdown of fluidized bed reaction systems

With several industrial applications of fluidized bed technology recently commercialized worldwide, it becomes essential to develop safe operation methods for fluidized bed reaction systems (FBRSs) to prevent any influence on their process values, which lead to accidents. To preventing any disaster or malfunction in an FBRS, an emergency shutdown system (ESD) is initiated, closing the reaction system in case of any abnormality by effectively isolating the flammable gas. However, an ESD is also prone to the “inactivation problem,” in which in the case of failure it initiates the emergency shutdown, even when the operating conditions of the reaction system are abnormal. It is also vulnerable to a “malfunction problem,” where the emergency shutdown is performed even when the operating conditions of the reaction system are normal. In this study, these problems were solved by investigating a reaction system through the monitoring of appropriate parameters and setting up of trigger levels, which reflect the uniqueness of an FBRS using an ESD. The parameters were identified by analyzing the scenario leading to an accident. The trigger levels were determined as the points at which the loss is smaller in the presence of an ESD, as compared to the value of the loss function in the presence or absence of an ESD. Furthermore, the ESD design model was applied as a case study in the ammoxidation process of propylene. The results showed that an ESD can prevent an approximately 8 billion yen of loss due to accidents in plant operations, against an investment of 200 million yen.     

基于Gaussian的甲烷爆炸微观反应计算分析*

为从微观热力学及动力学角度更深入了解甲烷爆炸微观反应机理,应用Gaussian软件DFT理论,B3LYP-D3(BJ)/6-31+G*水平对利用敏感性分析方法得出的甲烷爆炸反应简化机理中各驻点进行结构优化与频率计算,在M06-2X/def2-tzvpp水平上计算单电能,得到反应物、中间体、过渡态、产物的稳定构型及其参数、热力学数据,并计算得到各反应的焓变、吉布斯自由能变及自由能垒。研究结果表明:甲烷爆炸微观反应机理中基元反应1,9无过渡态,其他反应存在过渡态;基元反应1,4等为反应体系提供热量,保证甲烷氧化反应不断进行,反应1放热最多,焓变为-433.7 kJ·mol-1;关键自由基OH·的生成是反应3 O2+H·→OH·+O·与反应4 O·+H2→OH·+H·相互协同与促进的结果;反应3 O2+H·→OH·+O·为该甲烷爆炸机理的决速步,自由能垒为312.4 kJ·mol-1。研究结论可为深入研究甲烷爆炸微观反应机理和化学抑爆机理提供借鉴。     

BIPB的热分解动力学和失控反应模拟

为了评估双(叔丁过氧基)二异丙苯(BIPB)的热危害,对其热分解过程进行多速率的动态扫描C80热分析,用几种简单的热危害评估方法分析其热危害。然后应用模式法、无模式法(Friedman微分等转化率法)分别对试验结果进行处理,得到分解动力学数据,并用ASTM E 698法得到活化能数据,同时用C80、ARC和DSC的试验数据验证分解动力学数据的可靠性。最后利用无模式法的分解动力学数据进行BIPB绝热条件下和非绝热的2m3球形容器中的失控反应模拟,得到类似工艺条件下BIPB的安全控制温度。     

Eye movement and reaction time measures of the effectiveness of caution signs

The effectiveness of various forms of caution signs was evaluated using saccadic eye movements and reaction time as the dependent variables. Both dependent measures show that caution signs requiring specific positive actions are processed more slowly and less efficiently than signs requiring avoidance behaviors. Additionally, the data show that changing the order of the “consequences” and “instructions” elements of the caution signs did not influence the number of saccades, the speed, or accuracy of interpretation. The research shows that saccadic eye movement may be an effective method for evaluating the design of caution signs.     

反应性液体紧急泄放面积设计进展

为防止反应失控造成爆炸事故,减少事故损失,在介绍模拟反应失控的实验装置ARC、VSP以及RSST等的基础上,针对不同的紧急泄放类型,如气相系统、蒸气系统和混合系统的紧急泄放研究进展,进行了分析论述,旨在发现解决反应失控紧急泄放问题的更好方法,从而为进一步研究反应失控的紧急泄放问题打下基础.     

The differential reaction calorimeter: examples of use

A new kind of calorimeter, commercialized by SETARAM SA and operating in isoperibolic mode, appeared 2 years ago: the differential calorimeter DRC^®. This DRC was developed by Aventis Pharma in their own laboratories and has been used as standard tool for 10 years. The Swiss Institute for the promotion of safety and security (Organic Process Research and Development (2002) to be published) has also studied this calorimeter. In order to show the accuracy of this apparatus, we can compare the DRC with the RC1 from Mettler Toledo which is the reference for safety studies. We can demonstrate the exactitude of results in a wide range of reactions: with one step (neutralization) or two steps (aldolisation–crotonisation), semi-batch reactions with addition of one reagent or simultaneous additions of two reagents, slightly or very exothermic reactions. In each situation, DRC will obtain the same data and results in less time with a smaller amount of raw materials.     

Investigation of the decomposition reaction and dust explosion characteristics of crystalline dicumyl peroxide

The dicumyl peroxide (DCP) is widely used as a polymerization initiator, catalyst and vulcanizing agent in the chemical industry. A number of accidents have been caused by its thermal instability in storage or manufacturing process. Thus, its hazard characteristics have to be clearly identified. First of all, the differential scanning calorimeter (DSC) is used to measure the heat of decomposition reaction, which can contribute to understanding the reaction characteristics of DCP. The accelerating rate calorimeter (ARC) is used to measure the rates of temperature and pressure rises of decomposition reaction, and then the kinetics parameters are estimated. Furthermore, the MIKE 3 apparatus and the 20-l-Apparatus are used to measure and analyze the dust explosion characteristics of DCP at room temperature and atmospheric pressure. Finally, Semenov's thermal explosion theory is applied to investigate the critical runaway condition and the stability criterion of decomposition reaction, and to build the relationship of critical temperature, convective heat transfer coefficient, heat transfer surface area and ambient temperature. These results contribute to improving the safety in the reaction, transportation and storage processes of DCP.     

某恒温间歇反应温度参数的模拟与热危险性的分析

为得到间歇反应的温度参数,以物料平衡及热量平衡为基础,借助工艺热风险的基础知识,以文献中给出的某恒温间歇反应为例,利用计算机编程技术对其反应过程中的温度变化进行了模拟,得到了反应器温度Tr随时间的变化规律,且温度模拟情况与文献有良好的一致性.在此基础上,从工艺热风险的角度出发,对温度参数敏感性的问题进行了探讨,得出了反应器最佳冷却温度Tc.     

Thermal kinetics analysis of polymerization reaction of styrene-ethylbenzene system

To explore the reaction thermodynamics of a styrene-ethylbenzene mixed system, a differential scanning calorimetry (DSC) analysis was performed on the mixed system with styrene: ethylbenzene mass ratios of 1:0, 4:1, 3:2, and 2:3 at heating rates of 2.5, 5, 7.5, and 10 K/min. The activation energy of the mixed reaction system was calculated using the model-free Kissinger kinetic method, to determine a mixed system of relative stability mixing proportion. The thermodynamic parameters of the styrene-ethylbenzene mixture system at the optimal ratio were obtained using an adiabatic accelerating calorimeter. Further, dynamic thermal parameters such as the activation energy of the hybrid system, pre-exponential factor and order of reaction, TMR, TMRad, and T_D24 were calculated.     

空调压缩机冷媒爆炸反应特征分析

冷媒与空气的反应特征对空调压缩机安全性有重要影响.本文采用最小自由能原理,分别对两种冷媒R407C和R410A与空气的混合气体的爆炸反应参数进行了数值计算,得到了不同初始压力和不同冷媒含量条件下,混合气体爆炸反应温度和压力,分析了混合气体反应压力条件和爆炸极限范围.结果表明:初始压力低于0.2 MPa时,R407C-空气混合气体和R410A-空气混合气体均不会发生爆炸;初始压力超过0.3 MPa时,混合气体能够发生爆炸,爆炸反应温度和压力随着初始压力的升高而升高;R407C和R410A质量分数分别在34%、35%左右,混合气体反应温度和压力达到最大值.R407C和R410A易燃易爆特征相近;但爆炸范围都比氟利昂(R22)气体宽,即同样的条件下更容易发生爆炸.该计算结果能够为新型冷媒R407C和R410A的安全使用提供一定的依据.     

Effects of uncertainty, transmission type, driver age and gender on brake reaction and movement time

PROBLEM: Braking time (BT) is a critical component in safe driving, and various approaches have been applied to minimize it. This study analyzed the components of BT in order to assess the effects of age, gender, vehicle transmission type, and event uncertainty, on its two primary components, perception-reaction time and brake-movement time. METHOD: Perception-reaction time and brake-movement time were measured at the onset of lights for 72 subjects in a simulator. The six experimental conditions were three levels of uncertainty conditions (none, some, and some + false alarms) and two types of transmission (manual and automatic). The 72 subjects, half male and half female, were further divided into three age groups (mean of 23, 30, and 62 years). Each subject had 10 trials in each of the three levels of uncertainty conditions. RESULTS: Transmission type did not significantly affect either perception-reaction time or brake-movement time. Perception-reaction time increased significantly from 0.32 to 0.42 s (P < .05) as uncertainty increased but brake-movement time did not change. Perception-reaction time increased (from 0.35 to 0.43 s) with age but brake-movement time did not change with age. Gender did not affect perception-reaction time but did affect brake-movement time (males 0.19 s vs. females 0.16 s). IMPACT ON INDUSTRY: At 90 km/h, a car travels 0.25 m in 0.01 s. Consequently, even such small effects multiplied by millions of vehicle-kilometers can contribute to significant savings in lives and damages.     

Optimum parameters for fault detection and diagnosis system of batch reaction using multiple neural networks

Batch process usually differs from the continuous process because of its time-varying variables and the process parameters. An early detection and isolation of faults in the process will help to reduce the process upsets and keep it safe and reliable. This paper discusses on the application of multi-layer perceptron neural network in detecting various faults in batch chemical reactor based on an esterification process that involves the reaction of ethanol and acetic acid catalyzed by sulfuric acid. A multi-layer feed forward neural network with double hidden layers has been used in the neural network architecture. The detection was based on the different patterns generated between normal and faulty conditions. An optimum network configuration was found when the network produced the minimal error with respect to the training, testing and data validation.