Thermal hazard in a batch process involving hydrogen peroxide

Hydrogen peroxide is a versatile and interesting reagent for many industrial processes; nevertheless, it is very sensitive to impurities that can catalyze its decomposition, so that the desired reaction could be accompanied by undesired parallel and consecutive reactions. As an example, the butadiene free radical polymerization with hydrogen peroxide in the presence of an organic solvent was studied. Batch polymerization occurs in the liquid phase at about 120 °C. Because of the involved reactive compounds and the relatively high temperature, this is an intrinsically dangerous reaction. Therefore calorimetric data can give important information about safety and process optimization during the scale-up. The aim of this research project was to study the influence of impurities on the overall heat of reaction. The experiments were made in a high-pressure reaction calorimeter. The study has revealed that impurities do indeed affect the reaction course. Most importantly, the presence of carboxylic acids and/or ionic iron must be avoided and the recycle of unreacted reagents must be carefully controlled to minimize the build-up of these impurities.     

Investigation of an accidental explosion in a nitromethane rectification process

An explosion that occurred during a nitromethane rectification process is investigated. Experiments were performed in an effort to elucidate the cause of the explosion. All test samples analyzed, including reaction product, crude product, 99% pure product and raffinate, were collected from the accident site. Gas chromatography was used to analyze the components of the samples, thermal analysis determined the exothermic character of the samples and the sample evaporating experiment recorded the reaction phenomena occurring at low liquid level. Based on the experimental results, the excess heat released by the decomposition of overheated raffinate is pinpointed as the root cause of the explosion.     

Ti/SnO2-RuO2-Sb电极电氧化处理五氯苯酚模拟废水研究

采用刷涂-热解法制备了Sb、Ru掺杂的Ti/SnO2电极。通过SEM、EDX、XRD和循环伏安扫描(CV)表征了电极表面形态、组成、结构和电化学性质,并通过正交试验考察了电催化氧化降解五氯苯酚的影响因素。结果表明,各因素对五氯苯酚转化率影响的大小顺序依次为:底物初始质量浓度、反应温度、反应时间、电流密度、初始溶液pH值。在底物质量浓度为50mg.L-1,反应温度50℃,反应时间180min,电流密度40mA.cm-2,溶液初始pH值为8的条件下五氯苯酚的转化率达到97.6%。     

数值分析方法在一起高危工艺分析中的应用

以二级放热反应为研究对象,在反应体系温度、浓度均匀分布的假设基础上,根据反应速率方程和热平衡方程,建立高危工艺反应的温度和转化率随时间变化的数学模型。采用数值计算技术,以一阶差分代替微分,并结合工艺中的恒温过程、绝热过程和飞温过程,编写计算程序求得其转化率、温度在不同时间点的数值解,揭示爆炸事故的发展过程,定量分析操作参数的影响和转化率、温度随时间分布的规律。同时通过对绝热反应时间、冷凝器的冷却能力的分析,结合冷凝器的移热能力和反应放热对反应体系热积累的影响,讨论防止反应失控发生的可能性。最后探讨冷凝器热负荷余量、反应物投料浓度比等因素对控制反应失控的影响。     

Making hybrid mixture explosions a common case

Explosions of gas-dust hybrid mixtures have long been considered as particular cases encountered in specific industrial contexts. However, it should be reminded that during the explosion of an organic powder, the presence of a hybrid mixture composed of the dust itself and its pyrolysis gases is compulsory. On these premises, an experimental study to determine the role of cellulose pyrolysis products (gaseous, condensable and solid) on the global phenomenon is presented. Hybrid mixture explosion tests were exploited to carry out the investigation. The G-G furnace and the 20 L sphere were employed. Several experimental strategies were chosen to demonstrate the impact of pyrolysis reaction on the explosion of organic powders: i) the fuel equivalence ratio of the reactive mixture (case 1), or ii) the mass of reactants (case 2) were respectively kept constant, iii) the effects of water vapor, char and tar were tested. They were next compared to identify the most suitable one. The two first experimental approaches lead to significantly different results: only case 2 keeps the maximum explosion pressure almost constant, but maximum rate of pressure rises and deflagration index greatly decrease when the pyrolysis gases concentration decreases, which highlights the importance of the pyrolysis reaction on the explosion kinetics. It should also be stressed that the maximum explosion severity is not obtained for the pure gases but when a small dust content is added. The same evolution is observed when a small amount of char is introduced to pyrolysis gases, which underlines the influence of the radiative transfer. Adding small amounts of tar to cellulose tends to increase its explosion severity. However, this impact is less than that generated by the addition of pyrolysis gases.     

Application of a hydroxylamine nitrate stability model to plutonium purification process equipment

A mathematical model that predicts hydroxylamine nitrate (HAN) (NH₂OH·HNO₃) stability is applied to aqueous solutions containing HAN, nitric acid and plutonium that are used in plutonium purification processes. The model estimates the stability of these solutions with respect to the rapid, hazardous, autocatalytic reaction of HAN with nitric acid that generates heat and gas. It also accounts for reaction kinetics, temperature changes, gas generation rates, solution volumes and flow rates, and distribution of plutonium and nitric acid between aqueous and organic phases. The model is applied to three typical process vessels used in solvent extraction purification of plutonium – a countercurrent aqueous/organic plutonium stripping column, an oxidation column used for HAN and hydrazine destruction, and a plutonium rework tank. Both normal and off-normal process scenarios are modeled. Two of the off-normal scenarios lead to the rapid autocatalytic reaction of HAN with nitric acid where heat and gas are generated and that could lead to damage of the process equipment and/or release of hazardous plutonium solution from the vessel. In these two cases, stationary aqueous solutions containing HAN, Pu(III), and nitric acid were allowed to slowly react until conditions for the autocatalytic reaction were reached.     

连续搅拌釜式反应器放热反应失控事故预防

运用敏感度方法研究连续搅拌釜式反应器(CSTR)放热反应的参数敏感性行为及规律,探讨CSTR反应器的安全操作区域和敏感操作区域。研究发现:无因次活化能小于4的反应系统,其整个操作参数空间都是安全的;无因次活化能大于4的反应系统,只有选择无因次活化能小于其临界值,反应系统才能安全、稳定地运行;临界无因次反应热的值与无因次丹克莱尔数和无因次反应热有关;丹克莱尔数和无因次反应热越大,则临界无因次反应热越小,安全操作区域也越小。     

Use of bifurcation analysis for identification of a safe CSTR operability

Exothermic reactions are the most interesting systems for safety analysis because of their potential safety problems and the possibility of exotic behavior like multiple steady states. An operability and safety analysis of an exothermic reaction (hydrolysis of propylene oxide to tri-propylene glycol with consecutive reactions in a CSTR) with cooling is reported in this work. The information obtained from the bifurcation diagram is used to identify a set of unsafe operation points, which have been chosen on the base of requirement of maximal production of the process. An important information of safe reactor operation is the time in which the operator must handle a critical situation. For this reason, dynamics simulation of a failure in the cooling medium flow rate has been done and discussed for each of the selected operation points.     

Estimation of air traffic longitudinal conflict probability based on the reaction time of controllers

To estimate air traffic longitudinal conflict probability influenced by human factors, an analytic model considering the reaction time of controllers is proposed. In the model, the decelerating process of two close flights is described, and the reaction time of controllers is considered a stochastic variable. Then one hundred data of the controller reaction time are collected and analysed. Maximum likelihood estimate is used for parameter estimation. The Anderson–Darling Goodness of Fit test is used for significance test. The results show that the reaction time of controllers fits lognormal distribution at levels of significance 0.05, 0.025, 0.01 and 0.005 respectively. Case study is then performed to certify the rationality of the model, and the impact of the controller reaction time on air traffic longitudinal conflict probability is shown.     

一种化学物质的热危险性研究

以某一化学物质(ANPyO)为例,探讨了化学物质热危险性分析方法和步骤:建议首先从化学结构上对物质进行初步分析,然后根据化学结构进行理论计算预测,最后在前面研究的基础上,选择和确定采用合适的,比如:DSC/TG、ARC等小药量实验方法,研究化学物质的热危险性.对于ANPyO,通过分子结构可知其为多硝基多氨基芳烃,是具有潜在的燃烧、爆炸危险的活性化学物质.理论计算预测其属于高危险性物质.对其进行DSC/TG、ARC实验,得到绝热分解反应的热力学和动力学参数,自加速分解温度( TSADT)为199℃,热分解开始温度为310.0℃,最大反应速度出现在系统温度771.5℃时,自热分解开始到最大反应速度的时间为23.5min.文中研究可为该化学物质生产、使用和储运安全提供参考.     

Managing safety in hydropower projects in emerging markets – Experiences in developing from a reactive to a proactive approach

International companies investing in emerging markets need to address the management of safety under varying conditions. The paper presents an evaluation of the approaches taken by an international hydropower company in two different construction projects, one in India and one in the Philippines. In the first project, the company had to intervene as a reaction to poor safety and overall performance. Based on previous experiences, the company selected a proactive approach in the second project, involving use of the contracting process to ensure adequate conditions from the start of construction and onwards. The paper accounts for the safety performance results in the two projects and interprets them in relationship to external and internal influencing factors in the respective project. It is concluded that a proactive approach has the potential of delivering satisfactory safety results at moderate costs for follow-up. A reactive approach risks exposing the company to ethical and reputation risks due to a poor safety performance before the corrective actions have taken full effect. It is also resource demanding. Results demonstrate the feasibility of turning around a project’s safety performance also when preconditions are challenging.     

硝酸甲胺反应过程的安全性研究

用反应量热仪(RC1e)对硝酸溶液与一甲胺溶液在反应过程中的热安定性进行初步研究,分别测试不同反应温度、加料速度和初始硝酸浓度下反应的放热情况。实验结果表明:该中和过程反应迅速,在室温就能进行;与反应温度、加料速度相比,起始硝酸浓度对反应安全性影响最大,且硝酸浓度越高,反应的速度和反应的完全程度也越高。实验还表明:RC1e是研究反应过程中热安定性情况的有效工具,能通过反应过程的热量变化体现反应速率,所得结果对硝酸甲胺的工业化生产具有重要的参考价值。     

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.     

考虑驾驶员反应时间的车辆碰撞预警模型

为了保证车辆在行驶过程中的安全性,提出了一种考虑驾驶员反应时间的车辆碰撞预警模型,改进了传统模型中驾驶员反应时间定值化的缺点。首先,依据车辆的制动过程分析了驾驶员反应时间对制动距离的影响。其次,设计驾驶员反应时间的模糊推理算法,选取驾龄、疲劳强度和应变能力3个主要因素作为评价指标来计算反应时间。最后,采用分等级的预警策略建立考虑驾驶员反应时间的碰撞预警模型,并通过Carsim-Matlab/Simulink联合仿真与传统模型进行对比分析。结果表明,设计的预警模型可以对不同类型的驾驶员进行差异化碰撞预警,在30 km/h和80 km/h两种车速下实际停车距离与理论值的最大误差为8%。     

Simulator study of young driver's instinctive response of lower extremity to a collision

Objective: A driver's instinctive response of the lower extremity in braking movement consists of two parts, including reaction time and braking reaction behavior. It is critical to consider these two components when conducting studies concerning driver's brake movement intention and injury analysis. The purposes of this study were to investigate the driver reaction time to an oncoming collision and muscle activation of lower extremity muscles at the collision moment. The ultimate goal is to provide data that aid in both the optimization of intervention time of an active safety system and the improvement of precise protection performance of a passive safety system.

Method: A simulated collision scene was constructed in a driving simulator, and 40 young volunteers (20 male and 20 female) were recruited for tests. Vehicle control parameters and electromyography characteristics of eight muscles of the lower extremity were recorded. The driver reaction time was divided into pre-motor time (PMT) and muscle activation time (MAT). Muscle activation level (A_COL) at the collision moment was calculated and analysed.

Results: PMT was shortest for the tibialis anterior (TA) muscle (243～317 ms for male and 278～438 ms for female). Average MAT of the TA ranged from 28-55 ms. A_COL was large (5～31% for male and 5～23% for female) at 50 km/h, but small (<12%) at 100 km/h. A_COL of the gluteus maximus was smallest (<3%) in the 25 and 100 km/h tests. A_COL of RF of men was significantly smaller than that of women at different speeds.

Conclusions: Ankle dorsiflexion is firstly activated at the beginning of the emergency brake motion. Males showed stronger reaction ability than females, as suggested by male's shorter PMT. The detection of driver's brake intention is upwards of 55ms sooner after introducing the electromyography. Muscle activation of the lower extremity is an important factor for 50 km/h collision injury analysis. For higher speed collisions, this might not be a major factor. The activations of certain muscles may be ignored for crash injury analysis at certain speeds, such as gluteus maximus at 25 or 100 km/h. Furthermore, the activation of certain muscles should be differentiated between males and females during injury analysis.     

绿色技术评价磺化反应过程热危险性

反应量热仪RC1研究磺化反应过程中热危险性具有评价路线简单、易于操作、过程绿色环保等优势,近年来逐渐成为研究的热点.磺化反应过程中由于工艺的不同,不同磺化反应过程的热危险性也具有很大的差别.通过反应量热仪RC1、差示扫描量热DSC、绝热加速量热仪ARC对10种不同工艺的磺化反应过程的热危险进行了深入的研究,对企业实践生...     

长隧道韵律型视觉环境设计研究

采用心理物理试验分析公路隧道内部视觉环境对驾驶员行车安全的影响,将E-prime 2.0软件与仿真驾驶模拟器相结合,对驾驶员在隧道内长时间行车中的速度判断准确率及反应时间两个指标进行分析,提出了利用标志标线构建公路隧道内韵律型标线系统的改善措施,以改善隧道内视觉环境,并利用数理统计方法及Logistics拟合分析对设计方案进行评价。结果表明:1)公路隧道内韵律型标线系统能提升隧道内驾驶员的速度判断准确率3.33%~11.66%;2)普通公路隧道场景中,被试者反应时间与隧道内行车时间存在显著关系,公路隧道内韵律型标线系统的场景中,反应时间与隧道内的行车时间没有显著关系,能有效缓解视觉疲劳现象;3)被试者反应时间的增加同时受隧道内视觉环境与行车时间的影响。公路隧道内韵律型标线系统能有效提高驾驶员的反应时间,适用于行驶速度为80 km/h、大于1 333 m的隧道。     

甲酰吗啉生产过程中的危险因素与安全措施探讨

吗啉酰化合成甲酰吗啉(NFM)过程存在诸多安全与环保的危险、有害因素。实验室小试、中试和工业试生产研究表明:正确选择反应工艺路线是首要条件。较可取的是以甲酸为酰化剂,吗啉酰化初期强放热反应,该类反应安全操作条件是安全生产的关键。选择适宜的传热介质及时移出反应热,适当加入带水剂,采用滴加的加料方式可减缓放热速度是控制反应温度的关键。先进和规范的安全管理制度,是防止事故的保证。     

化学放热系统热爆炸潜在危险性评价

讨论化学放热系统的热稳定性和临界条件,用化学反应物无消耗的假设推导化学放热系统热失控(热爆炸)时的动力学参数临界值,得到热失控的判据、临界点火温度和熄火温度。提出用系统安全指数概念来评价放热反应系统发生热爆炸的潜在危险性,分析化学放热系统的平衡域。用硝酸甲酯分解爆炸实例,说明如何利用安全指数对具有热爆炸可能性的系统的潜在危险性进行定量评价,其预测结果与实验结果一致。     

Dilute Acid Hydrolysis of Cellulose and Cellulosic Bio-Waste Using a Microwave Reactor System

The dilute acid hydrolysis of grass and cellulose with phosphoric acid was undertaken in a microwave reactor system. The experimental data and reaction kinetic analysis indicate that this is a potential process for cellulose and hemi-cellulose hydrolysis, due to a rapid hydrolysis reaction at moderate temperatures. The optimum conditions for grass hydrolysis were found to be 2.5% phosphoric acid at a temperature of 175°C. It was found that sugar degradation occurred at acid concentrations greater than 2.5% (v/v) and temperatures greater than 175°C. In a further series of experiments, the kinetics of dilute acid hydrolysis of cellulose was investigated varying phosphoric acid concentration and reaction temperatures. The experimental data indicate that the use of microwave technology can successfully facilitate dilute acid hydrolysis of cellulose allowing high yields of glucose in short reaction times. The optimum conditions gave a yield of 90% glucose. A pseudo-homogeneous consecutive first order reaction was assumed and the reaction rate constants were calculated as: k₁ = 0.0813 s⁻¹; k₂ = 0.0075 s⁻¹, which compare favourably with reaction rate constants found in conventional non-microwave reaction systems. The kinetic analysis would indicate that the primary advantages of employing microwave heating were to: achieve a high rate constant at moderate temperatures: and to prevent ‘hot spot’ formation within the reactor, which would have cause localised degradation of glucose.