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.     

Thermal hazard accident investigation of hydrogen peroxide mixing with propanone employing calorimetric approaches

Hydrogen peroxide (H₂O₂), historically, due to its broad applications in the chemical industries, has caused many serious fires and explosions around the world. Its thermal hazards may also be incurred by an incompatible reaction with other chemicals, and a runaway reaction may be induced in the last stage. This study applied thermal analytical methods to explore the H₂O₂ leading to these accidents by incompatibility and to discuss what might be formed by the upset situations. Thermal hazard analysis contained a solvent, propanone (CH₃COCH₃, so-called acetone), which was deliberately selected to mix with H₂O₂ for investigating the degree of thermal hazard. Differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2) were employed to evaluate the thermal hazard of H₂O₂. The results indicated that H₂O₂ is highly hazardous while mixed with propanone, as a potential contaminant. The time to maximum rate (TMR) was used as emergency response time in the chemical industries. Therefore, TMR of H₂O₂ was calculated to be 70 min for runaway reaction (after T₀) and TMR of H₂O₂/propanone was discovered to be 27 min only. Fire and explosion hazards could be successfully lessened if the safety-related data are properly imbedded into manufacturing processes.     

Evaluation of multiple reactions in dilute benzoyl peroxide concentrations with additives using calorimetric technology

Benzoyl peroxide (BPO) is a typical organic peroxide widely used in food processing, particularly flour bleaching. Due to the unstable nature of the oxygen-oxygen bond in BPO, it readily reacts under even mid-low-temperature conditions. Lower concentrations of BPO are also potentially explosive, even when combined with acid or alkaline additives. Given the history of both potential and documented industrial accidents, this study investigates the thermal stability of various BPO concentrations when mixed with acid or alkaline solutions. In addition, differential and integral kinetic models were applied to verify that the apparent activation energy data from the differential scanning calorimetry experiments were valid. The results of autocatalysis reactions and nth-order reaction simulations presented characteristics consistent with the experimental findings. The findings in this paper can be used as a reference for BPO products that are mediated with either an acid or an alkaline solution during production, storage, transportation, or use.     

Characterization of fulvic acids during olive mill waste composting (Elemental,Thermal and fluorescence analyses)

Elemental analysis, fluorescence spectroscopy and differential scanning calorimetry (DSC) were applied to the study of fulvic acids isolated from different stages during olive mill waste composting. The fulvic extracted acids are characterized by a high nitrogen content and O/C ratio values that may result from the high degree of humification and the synthesis of more condensed humic complexes. This was confirmed by fluorescence spectroscopy in the synchronous-scan mode by the decrease of shoulder intensities at intermediate wavelengths indicating the increase of polycondensation and conjugation of unsaturated structures and the greater uniformity of fluorophores. Fluorescence spectra in the emission, excitation and synchronous modes became simpler with compost maturation. This was confirmed by DSC results which proved the high degree of polycondensation of aromatic nuclei of fulvic acid molecules during olive mill waste composting.     

Use of thermal analysis techniques (TG-DSC) for the characterization of diverse organic municipal waste streams to predict biological stability prior to land application

The use of organic municipal wastes as soil amendments is an increasing practice that can divert significant amounts of waste from landfill, and provides a potential source of nutrients and organic matter to ameliorate degraded soils. Due to the high heterogeneity of organic municipal waste streams, it is difficult to rapidly and cost-effectively establish their suitability as soil amendments using a single method. Thermal analysis has been proposed as an evolving technique to assess the stability and composition of the organic matter present in these wastes. In this study, three different organic municipal waste streams (i.e., a municipal waste compost (MC), a composted sewage sludge (CS) and a thermally dried sewage sludge (TS)) were characterized using conventional and thermal methods. The conventional methods used to test organic matter stability included laboratory incubation with measurement of respired C, and spectroscopic methods to characterize chemical composition. Carbon mineralization was measured during a 90-day incubation, and samples before and after incubation were analyzed by chemical (elemental analysis) and spectroscopic (infrared and nuclear magnetic resonance) methods. Results were compared with those obtained by thermogravimetry (TG) and differential scanning calorimetry (DSC) techniques. Total amounts of CO₂ respired indicated that the organic matter in the TS was the least stable, while that in the CS was the most stable. This was confirmed by changes detected with the spectroscopic methods in the composition of the organic wastes due to C mineralization. Differences were especially pronounced for TS, which showed a remarkable loss of aliphatic and proteinaceous compounds during the incubation process. TG, and especially DSC analysis, clearly reflected these differences between the three organic wastes before and after the incubation. Furthermore, the calculated energy density, which represents the energy available per unit of organic matter, showed a strong correlation with cumulative respiration. Results obtained support the hypothesis of a potential link between the thermal and biological stability of the studied organic materials, and consequently the ability of thermal analysis to characterize the maturity of municipal organic wastes and composts.     

A+OSA活性污泥工艺剩余污泥减量特性研究

采用自动热量计对Anoxic (A) + oxic-settling-anaerobic(OSA)系统解偶联池进出污泥进行热值分析,以考察污泥量变动与能值变动的相互关系;通过解偶联池参数调整,了解污泥减量趋势,结合能量和物质平衡与常规水质指标测试,推测减量途径和特性.结果表明,解偶联池水力停留时间为5.56、 7.14和9 h时,整个系统污泥减量分别为1.236、 0.771和0.599 g/d.进出解偶联池的污泥含能水平发生了变化,随停留时间增加出流污泥的单位热值有高于进流污泥单位热值的趋势：5.56 h时,进出水热值没有显著差异;7.14 h时,进出水热值差值在99～113 J/g之间;9 h时,差值在191～329 J/g之间.解偶联池发生了污泥的衰减,停留时间延长,衰减程度越高.A+OSA系统污泥减量是解偶联池污泥衰减与AO主体反应区污泥产生率变化共同作用的结果.     

Characterization of fulvic acids during olive mill waste composting (Elemental, Thermal and fluorescence analyses)

Elemental analysis, fluorescence spectroscopy and differential scanning calorimetry (DSC) were applied to the study of fulvic acids isolated from different stages during olive mill waste composting. The fulvic extracted acids are characterized by a high nitrogen content and O/C ratio values that may result from the high degree of humification and the synthesis of more condensed humic complexes. This was confirmed by fluorescence spectroscopy in the synchronous-scan mode by the decrease of shoulder intensities at intermediate wavelengths indicating the increase of polycondensation and conjugation of unsaturated structures and the greater uniformity of fluorophores. Fluorescence spectra in the emission, excitation and synchronous modes became simpler with compost maturation. This was confirmed by DSC results which proved the high degree of polycondensation of aromatic nuclei of fulvic acid molecules during olive mill waste composting.     

Thermal runaway reaction for highly exothermic material in safe storage temperature

Highly exothermic materials have caused many serious accidents involving storage and transportation, due to being thermally reactive. The safe storage and management of these materials is still a critical problem in many countries. Our aim was to study the thermal hazard of thermal reactive materials, such as a propellant, by employing differential scanning calorimetry (DSC) non-isothermal tests and isothermal tests, and then comparing the kinetic parameters by isothermal and non-isothermal of kinetics. The chosen approach was to obtain reliable thermal decomposition by a safe and effective method, which acquired the kinetic and safety parameters of storage conditions that could be applied as highly exothermic materials' reduction of loss prevention and energy potential for safer design during storage transport and processing operations.     

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.     

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.