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.     

Thermal hazard analysis of 1-((cyano-1-methylethyl) azo) formamide and effect of incompatible substances on its thermal decomposition

1-((cyano-1-methylethyl) azo) formamide (CABN) is an azo compound that exhibits high thermal sensitivity and self-reactivity. Because of incorrect operation, incompatible substances and other dangerous conditions, thermal explosion accidents may occur during the manufacturing, storage, and transportation of CABN. The pyrolysis characteristics of CABN and its mixture for various heating rates were assessed using differential scanning calorimetry. The results showed that incompatible substances increased the risk of CABN. Moreover, the thermal runaway of CABN under an adiabatic condition was studied using an adiabatic rate calorimeter to obtain the parameters under adiabatic condition. Based on the experimental data, the kinetic parameters of CABN and its mixtures were obtained. In addition, a thermal decomposition kinetic model of CABN was created using Thermal Safety Series. All experiments have shown that the conditions and parameters of CABN must be strictly controlled.     

Mathematical methods for application of experimental adiabatic data – An update and extension

The paper represents some results of comparative analysis of the methods used for processing and interpreting data of adiabatic calorimetry as well as applying it to practical situations. Specifically two approaches are compared – approximate method based on evaluation of simplified kinetics and a more comprehensive, simulation-based method that utilizes the evaluation of more detailed kinetic models.The analysis is focused on two important types of data processing – correction of experimental results on thermal inertia (phi-factor correction) and estimation of adiabatic time to maximum rate (TMR).The most widely cited method for phi-factor correction is considered and its improvement is proposed to enable more precise prediction of the adiabatic time scale. A procedure for phi-factor correction of pressure response is also proposed. The limitations of this enhanced Fisher's method are discussed by comparison with simulation-based method. All the illustrative materials are based on real examples.As an example of application, the simplified method will be used to predict TMR and its limitations will be discussed.     

Mg(BH_4)_2和MgH_2对RDX热分解特性的影响

在黑索今(RDX)中加入具有高热值的金属氢化物(Mg(BH4)2和MgH2)有望提高RDX的爆炸性能,但同时给RDX的安全使用带来挑战。为了探索RDX与这2种金属氢化物的相容性与安定性,采用差示扫描量热法(DSC)研究Mg(BH4)2和MgH2对RDX热分解性能的影响,并由DSC得到的数据计算动力学参数,参照GJB770B—2005的方法分析这2种金属氢化物与RDX的相容性和安定性。结果表明,加入Mg(BH4)2使RDX的表观活化能从159.22 kJ/mol增加至180.27 kJ/mol,加入MgH2使RDX的表观活化能降低至133.69 kJ/mol;Mg(BH4)2与RDX的相容性为1级,MgH2与RDX的相容性为3级,加入Mg(BH4)2使RDX的安定性有所提高,加入MgH2降低了RDX的安定性。因此,在将MgH2作为RDX的高能添加剂以前,必须首先提高其与RDX的相容性以保证试验和存储过程的安全。     

Prediction of the self-ignition temperature in lagging fires by means of isothermal calorimetry

Under certain circumstances, contamination of a porous insulation material by a combustible liquid may result in a lagging/insulation fire. In the current study, a method based on isothermal calorimetry and modelling to estimate the risk of a lagging fire, or a maximum insulation thickness for a certain system temperature, is presented. The studied system was a combination of mineral wool and rapeseed oil. Full-scale tests were performed to determine suitable ignition criteria and to validate the results from the isothermal calorimetry tests and modelling. We contaminated the lagging using two methods – a direct method and a solvent method. These methods were evaluated in the full-scale tests. The solvent method resulted in more repeatable results than the direct method, where the contaminant was poured on the insulation. Using the calorimetric measurements, we estimated the parameters for the kinetic equation. This result was used to estimate the self-ignition temperature of contaminated lagging installed on a pipe. We found that a temperature increase of 40 °C was a reasonable ignition criterion when modelling.     

Pressure relief sizing of reactive system using DIERS simplified methods and dynamic simulation method

Incidents involving uncontrolled chemical reactions continue to result in fatality, injury and economic loss. These incidents are often the result of inadequate pressure relief system designs due to a limited knowledge of the chemical reactivity hazard. A safe process design requires knowledge of the chemical reactivity of desired as well as undesired chemical reactions due to upset conditions. Simplified, cost effective methods to relief system sizing are presented by The Design Institute of Emergency Relief Systems (DIERS). They require multiple experiments, and sizing is only valid for the system composition and thermal inertia represented by the small scale experiments. Results are often conservative, especially for gassy systems. Detailed, dynamic computer simulation is highly accurate and can be used for iterative design and multiple scenario evaluation.In this study, an accelerating rate calorimeter (ARC^®) and a low thermal inertia calorimeter (automatic pressure tracking adiabatic calorimeter – APTAC™) were used to collect chemical reactivity data for the dicumyl peroxide and toluene system. Results of the pressure relief system sizing using the dynamic simulation method are presented and compared with DIERS simplified methods.     

Reaction hazard and mechanism study of H2O2 oxidation of 2-butanol to methyl ethyl ketone using DSC,Phi-TEC II and GC-MS

Methyl ethyl ketone (MEK) oxidation via H₂O₂ with tungsten-based polyoxometalate catalysts has gained much attention with an ever-growing body of knowledge focusing on the development of environmentally benign processes in chemical industry. In this study, two calorimetry techniques, differential scanning calorimetry (DSC) and Phi-TEC II adiabatic calorimetry, were employed to analyze the thermal hazards associated with the 2-butanol oxidation reaction system. Hydrogen peroxide was the oxidant and a tungsten-based polyoxometalate as the catalyst. Gas chromatography-mass spectrometry was used for identification of the organic products. Important thermal kinetic data were obtained including “onset” temperature, heat of reaction, adiabatic temperature rise and self-heat rate. From DSC results, three exothermic peaks were detected with a total heat generation of approximately 1.26 kJ/g sufficiently to induce a thermal runaway. Possible reaction pathway for three stages were proposed based on both DSC and GC-MS results. One exotherm was detected by Phi-TEC II calorimeter and the pressure versus temperature profile together with the DSC and GC-MS data demonstrate the complexity of 2-butanol reaction system under both thermal screening and adiabatic conditions.     

Processing of whey from dairy industry waste

An investigation carried out in 11 dairies in Serbia has shows that 78.75 % of whey, a by-product of cheese industry, is emitted into river systems, thus contributing to the organic pollution of the environment. This pollution can be avoided by processing of whey into food and pharmaceuticals. It is shown that low-temperature regime of whey concentration and fractionation, based on vacuum concentration and diafiltration, preserves whey proteins undenaturated, as proved by differential scanning calorimetry method. Functional native whey proteins based food products, with potentially high immunomodulatory activity, are obtained.     

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.     

乳化炸药高压热分解试验研究

为分析压力在乳化炸药泵送事故中的影响,运用高压加速量热仪对乳化炸药、硝酸铵和含有10%水分的硝酸铵样品热分解特性进行研究。结果表明:压力对于乳化炸药,硝酸铵和含有10%水分硝酸铵样品的热分解有着显著的影响,压力条件下虽然起始分解温度基本没有变化,但是样品反应速率有了显著的升高,导致放热量增大。水分的存在阻碍硝酸铵的热分解,在乳化炸药配方中适当增加水份含量可以提高乳化炸药生产安全性。分析认为相比于温度,压力对于泵送事故的影响更为关键。