Critical runaway conditions and stability criterion of RDX manufacture in continuous stirred tank reactor

The energetic material cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX) has been widely used as explosive and propellant ingredients in the military industry. It is usually produced by hexamine nitration reaction in continuous stirred tank reactor (CSTR). This manufacturing process is quite dangerous and always causes fire incidents or explosion owing to its thermal instability in its nitration reaction or purification processes. In this investigation, we used its reaction kinetics parameters to evaluate the thermal hazard conditions and stable reaction criteria in the reaction systems of continuous stirred tank reactor.     

从全混流反应器热稳定性的角度探讨高危工艺的危险性

通过对全混流反应器(CSTR)热平衡条件下多态的分析,探讨热稳定性条件,并对一级不可逆反应在CSTR中的热稳定性进行定性分析;探讨不同反应热和活化能对反应过程热稳定性的影响,及其对反应器发生"飞温"事故要求紧急停车时的控制要求的影响,进而从反应工程的角度对高危工艺的界定提出新的思路。分析结果表明,工艺的危险性不仅与工艺的种类相关,更与工艺本身的热力学、动力学特征密切相关。通过对高危工艺的热稳定状况的分析,能够动态地揭示其在温度扰动下发生"飞温"或"熄火"的过程,从本质上把握高危工艺潜在的危险性,并能有针对性地制定自动化改造方案,提高化工企业的本质安全度。     

A general criterion to define runaway limits in chemical reactors

A general runaway criterion valid for single as well as for multiple reaction types, i.e. consecutive, parallel, equilibrium, and mixed kinetics reactions, and for several types of reactors, i.e. batch reactor (BR), semibatch reactor (SBR) and continuous stirred tank reactor (CSTR) has been developed. Furthermore, different types of operating conditions, i.e. isoperibolic and isothermal (control system), have been analysed. The criterion says that we are in a runaway situation when the divergence of the system becomes positive (div>0) on a segment of the reaction path. The results show that this is a general runaway criterion than can be used to calculate the runaway limits for chemical reactors. The runaway limits have been compared with previous criteria. A considerable advantage, over existing criteria, is that it can be calculated on-line using only temperature measurements and, hence, it constitutes the core of an early warning runaway detection system we are developing.     

Thermal risk in batch reactors: Theoretical framework for runaway and accident

Thermal safety and risk of accidents are still challenging topics in the case of batch reactors carrying exothermic reactions. In the present paper, the authors develop an integrated framework focusing on defining the governing parameters for the thermal runaway and evaluating the subsequent risk of accident. A relevant set of criteria are identified in order to find the prior conditions for a thermal runaway: failure of the cooling system, critical temperature threshold, successive derivatives of the temperature (first and second namely) vs. time and no detection in due time (reaction time) of the runaway initiation. For illustrative purposes, the synthesis of peracetic acid (PAA) with hydrogen peroxide (HP) and acetic acid (AA) is considered as case study. The critical and threshold values for the runaway accident are identified for selected sets of input data. Under the conditional probability of prior cooling system failure, Monte Carlo simulations are performed in order to estimate the risk of thermal runaway accident in batch reactors. It becomes then possible to predict the ratio of reactors, within an industrial plant, potentially subject to thermal runaway accident.     

Thermal risk in batch reactors: Case of peracetic acid synthesis

The present paper deals with accidents risk in batch reactors. It identifies the conditions for the occurrence of a thermal runaway and develops a probabilistic approach to assess the relevant risk. It investigates also the conditions for optimal synthesis of peracetic acid (PAA) with hydrogen peroxide (HP) and acetic acid (AA). The kinetic model of reversible reaction and side reaction of PAA synthesis is used to predict reactor temperature and molar ratio of PAA by ASPEN PLUS software. A sensitivity analysis is performed under different conditions such as constant temperature or adiabatic process with different concentrations of sulfuric acid. Assuming a prior cooling system failure, the conditions for reaction runaway triggering a thermal accident are identified in the case of PAA synthesis. Monte Carlo simulations are used in order to calculate the conditional probability of accident and optimize the synthesis of PAA.     

烃类流体火灾伤害破坏作用定量分析

对烃类流体火灾的伤害破坏作用进行正确的定量分析是开展重大消防目标火灾风险评估工作的基础。针对烃类流体火灾伤害破坏作用定量分析中存在的问题,系统论述烃类流体火灾伤害破坏作用的定量分析方法,分析并讨论火球、池火、喷射火和蒸气云火灾等不同火灾形式的热辐射通量计算模型及其前提条件,对不同热辐射伤害破坏作用准则及伤害概率模型的适用条件和模型基础进行了论述。     

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。     

Determination and assessment of the characteristic values for the evaluation of the thermal safety of chemical processes

Experience gained in the chemical industry in testing and assessing the thermal safety of chemical processes is published in this paper. Isothermal and adiabatic tests, which are the most important methods for both small and large quantities, are described and discussed. Methods for testing the thermal hazards of primary or desired reactions are also included, e.g. reaction calorimetry, adiabatic methods, investigations using a sampling method. More important are the criteria for assessing the test results. On the basis of energies produced by primary and secondary reactions and the temperature ranges within which they take place, thermal hazards can be predicted. If the rules for the safe design of batch and semi-batch reactions are observed, it is possible to control the thermal behaviour of reactions.     

Comparison of criteria for prediction of runaway reactions in the sulphuric acid catalyzed esterification of acetic anhydride and methanol

Loss of temperature control is one of the major reasons that can lead to runaway reaction. This occurrence is commonly named thermal runway. The aim of this paper is the application of thermal runaway criteria in order to predict the onset of runaway phenomena and define the range of stability related to operating conditions in the reactor, with specific reference to the esterification of acetic anhydride and methanol catalysed by sulphuric acid tested in isoperibolic conditions. The isoperibolic calorimeter has also been used to obtain thermodynamic, kinetic and physical chemistry data necessary to develop a model for the reaction. Some runaway criteria applied in this work require a model for the process, so a model for the analyzed system been developed.Because of the modest reaction enthalpy and low activation energy this reacting system provide a severe test to the runaway criteria.In this work, various runaway criteria have been applied to the experimental and simulated data and the results obtained have been compared.     

Safety analysis of CSTR towards changes in operating conditions

Exothermic reactions are the most interesting systems for safety analysis because of their potential safety problems and the possibility of exotic behavior such as multiple steady states. A sensitivity analysis of an exothermic reaction involving the hydrolysis of propylene oxide to propylene glycol in a CSTR with jacket cooling is presented here. The objective of this article is to determine how multiple steady states might arise. A comparison of the static and continuation method of the identification of multiple steady states and their stability is presented. Finally, the implications of safety analysis for operation and control of reactors with multiple steady states are discussed.     

细水雾阻隔火焰热辐射的模拟研究

从热辐射传递方程出发，根据Mie散射理论,考虑雾滴对热辐射的散射和吸收特性，建立细水雾阻隔火焰热辐射的两通量模型，并给出简化算法；同时建立小尺度模拟实验系统，对理论模型进行验证。结果表明，两通量模型较为合理地预测了细水雾对火焰热辐射的衰减作用。在此基础上，应用上述理论模型进一步探讨火焰温度、细水雾特性参数、雾场厚度对阻隔热辐射效率的影响，为细水雾系统的实际工程应用提供了理论和依据。     

苯和甲苯硝化及磺化反应热危险性分级研究

首先介绍了化工工艺热安全性的内涵,并从反应过程热危险性分析的方法学出发,介绍间隙、半间歇化学反应工艺热危险性分级研究的总体思路及方法。然后,围绕甲苯和苯的硝化、磺化反应,用全自动反应量热仪(RC1e)和加速度量热仪(ARC)测定其反应过程的绝热温升(△Tad)、目标反应所能达到的最高温度(TM)、分解反应最大速率到达时间(θD)等参数。运用风险评价指数矩阵法(方法1)和基于失控过程温度参数的热危险评估法(方法2)分别对其硝化和磺化反应过程的热危险性进行了分级评估。结果表明,这两种方法具有良好的一致性;给定工艺条件下甲苯和苯的一段硝化反应过程的热危险度等级较低;而磺化反应的热危险较高。尽管这两种方法还有一定的局限性,但对于间歇、半间歇合成工艺的本质安全化设计、工艺热危险性的评估具有重要的参考价值和实用意义。     

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.     

Reaction mechanism and process safety assessment of acid-catalyzed synthesis of tert-butyl peracetate

Esterification during the synthesis of tert-butyl peracetate (TBPA) is highly exothermic. Since peroxides (tert-butyl hydroperoxide TBHP and TBPA) are intrinsically thermosensitive, this synthesis process is potentially dangerous. In this work, the exothermic process and mechanism of TBPA synthesis using acetic anhydride (Ac₂O) and TBHP under the catalysis of sulphuric acid (H₂SO₄) were clarified by calorimetry, infrared spectroscopy, and high-performance liquid chromatography. To substantially alleviate the thermal risk of the reaction, and to feasibly select appropriate synthesis conditions for ensuring the process safety of the synthesized products, several sets of isothermal and isoperibol experiments were performed using calorimetry. The intermediates formed and concentration changes during the reaction were monitored using in-situ Fourier-transform infrared spectroscopy. Differential scanning calorimetry and adiabatic calorimetry were used to assess the thermal hazard of the materials during the synthesis process. The reaction mechanism was verified using density functional theory calculations. The results revealed that a controlled increase in exothermicity could be achieved by adding aqueous TBHP to Ac₂O in semi-batch experiments in isothermal mode, and accordingly, the highest yield was 95.71%. Experiments combined with theoretical calculations revealed that the primary exothermic event was the TBPA formation reaction, and the removal of a large amount of water from TBHP prior to this is favourable for the reaction. The criticality classes of this reaction were of Grade 2.     

热爆炸研究的主题聚类、趋势与影响

为全面认识国际热爆炸研究的主题聚类、趋势与影响,使用科技文本挖掘工具VOSviewer对科睿唯安SCI数据库中的1 415篇热爆炸研究论文进行了分析。结果表明:国际热爆炸研究的热点主要分布在燃烧合成、分解、点火、晶体结构、含能材料等方面;以高频关键词为中心形成了5个主要聚类,分别为热爆炸理论基础、热合成、热分解、热行为及含能材料与晶体结构。主题趋势显示热爆炸研究在整体上首先经历了热爆炸理论基础研究,并渗透到了热合成、热分解、热行为和含能材料与晶体结构等方面,高影响主题集中在热合成和热分解两个领域。热合成研究的高影响主题相比其他领域要更加显著,高影响主题涉及传播、镍铝化物、钛镍、铝、碳化及致密化等方面。相比而言,作为热爆炸研究的基础领域,热爆炸理论研究的热度及对应聚类主题的整体引用次数要显著低于目前活跃的领域。     

过氧化苯甲酰合成工艺热危险性分析

采用RC1e反应量热仪对过氧化苯甲酰(BPO)合成工艺危险性进行研究,测试不同Na OH溶液初始浓度(1.96 mol/L、3.93 mol/L、7.14 mol/L)下反应的放热历程,获得BPO合成反应过程中的热危险性参数,并采用PHI-TECⅡ绝热加速量热仪对产物进行热稳定性分析,最后评估该反应热风险。结果表明,Na OH浓度为7.14 mol/L时,反应初期放热速率慢,热累积度大,后期反应剧烈,绝热温升(ΔTad)及热失控时工艺反应达到的最高温度(MTSR)最大。热稳定性试验表明,合成的粗产物BPO初始分解温度、活化能、指前因子、最大放热速率到达时间为24 h时的对应温度(TD24)均低于纯BPO。利用合成粗产物BPO的TD24对反应进行危险度评估,该工艺热危险性等级均为5级,工艺危险性大。     

Probe into effect of the initiator on the thermal runaway hazards of methyl methacrylate bulk polymerization

The bulk polymerization of methyl methacrylate (MMA) is of great importance in chemical industry, but the polymerization process is highly hazardous, and few reports have focused on the effect of initiators on its thermal hazards. In this work, to thoroughly explore the thermal hazard characteristics, the runaway behavior of MMA bulk polymerization is investigated by a combination of thermodynamics experimental and kinetics theoretical methods. The results indicate that the presence of initiator exhibits an undesirable thermal hazard to the MMA bulk polymerization, and its exothermic behavior is also greatly influenced by the type and concentration of initiator. For azobisisoheptanenitrile (ABVN), azodiisobutyronitrile (AIBN) and dibenzoyl peroxide (BPO) initiators as examples, the AIBN-initiated reaction has the shortest adiabatic induction period (39.51 min), whereas the BPO-initiated polymerization exhibits the strongest maximum temperature-rising rate and maximum pressure-rising rate. Under adiabatic runaway, the temperature and pressure change significantly with increasing AIBN concentration, revealing a great potential risk of thermal runaway. Kinetic parameters are calculated to further understand the thermal runaway mechanisms, showing a strong agreement with the adiabatic experimental data. Finally, based on the cooling failure scenario, severity grading is determined by the evaluation criteria. The current work provides extensive data as a reference and guidance for the process design and optimization of MMA bulk polymerization from the perspective of safety.     

Essential hazard and process safety assessment of para-toluene sulfonic acid through calorimetry and advanced thermokinetics

Para-toluene sulfonic acid is a typical intermediary for the synthesis of pharmaceuticals, pesticides, and dyes and is a catalyst for organic synthesis. The consumption of para-toluene sulfonic acid used in organic synthesis has increased substantially. The toluene sulfonation process is the central path for synthesizing para-toluene sulfonic acid in China. However, the process has risks and has resulted in numerous disasters. This study utilized a reaction calorimeter 1 to reproduce the commercial toluene sulfonation process in a laboratory. The para-toluene sulfonic acid product was examined with an accelerating rate calorimeter and through differential scanning calorimetry. Both differential and integral isoconversional methods were used to determine the thermal stability of and appropriate thermokinetic models for para-toluene sulfonic acid. The safety parameters of para-toluene sulfonic acid were estimated. The research findings can be used for optimization of the toluene sulfonation process and for safe handling of para-toluene sulfonic acid.     

Azodicarboxylates: Explosive properties and DSC measurements

A large number of azodicarboxylates and their derivatives are produced and used in the chemical industries. The versatile applications of these azodicarboxylates in research institutes and in the chemical industries for chemical synthesis arouse additional hazards. The intent of this paper is to obtain first knowledge about the structure–response relationship regarding the explosive properties and the thermal hazards of different versatile used azodicarboxylates. The substances are examined with the differential scanning calorimetry (DSC). Furthermore, different laboratory test methods, based on the UN Recommendations on the Transport of Dangerous Goods, are applied to determine the explosive properties of the mentioned substances. On the basis of the obtained results, the known influence of the nitrogen content within the molecule regarding their thermal behaviour could be confirmed. The measured heat of decomposition appeared to be proportional to the nitrogen content within the group of the aliphatic and the aromatic azodicarboxylates. To emphasize this dependency, further investigations should be done. The long term objective of this research is to develop structure–response relationships of the explosive properties and the thermal hazards originating from azodicarboxylates.