Thermal risk analysis of cumene hydroperoxide in the presence of alkaline catalysts

Many studies have been performed to clarify the basic thermal runaway hazards and kinetics of cumene hydroperoxide (CHP) decomposition. However, materials that are incompatible with CHP have not been clearly identified. Alkaline solutions have been used as a catalyst to form dimethylphenyl carbinol (DMPC) and dicumyl peroxide (DCPO); however, these solutions also affect the reaction and storage temperature of CHP. In this study, thermal calorimeters, differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2), were used to compare the effects of various bases on the decomposition of CHP in cumene. Specifically, the exothermic onset temperature, change in pressure over time, self-heating rate and heat of decomposition were evaluated. Moreover, to appraise the degree of hazard associated with the use of CHP, the compatibility of CHP with various substances was analyzed, and a risk matrix for thermal runaway reactions was obtained. The results of the present study could be used to design safety procedures for the production of CHP and its derivatives.     

Coordinability and consistency: Application of systems theory to accident causation and prevention

Recent works in the safety literature report several fruitful attempts to introduce mathematically rigorous results from systems and control theory to bear upon accident prevention and system safety. Previously, we discussed the implications on safety of the systems theoretic principles of coordinability and consistency, and we identified the lack of coordinability and/or consistency as fundamental failure modes in hierarchical multilevel systems. In this work, we further develop system safety analysis techniques based on these principles. We demonstrate that these principles not only provide a domain-independent vocabulary for expressing the results of post-mortem accident analyses, but they can also be applied to guide design and operational choices for accident prevention and system safety. We develop these ideas with the help of an illustrative case study. This case study represents a broad class of systems where operational policies and procedures of individual stakeholders in the system interact with physical processes such that new system behaviors emerge, and unanticipated safety issues arise. We argue, and illustrate our arguments using this case study, that the coordinability and consistency principles can be developed to deliver a threefold impact on accident analysis and prevention: firstly, these principles provide domain-independent procedural templates and vocabulary for post-mortem accident analysis. Secondly, these principles provide theoretical safety specifications to be met during system design and operation. Finally, these safety specifications can precipitate the formulation of a series of questions directly related to safety-oriented choices in the design, operation, and control of systems.     

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 assessment for accident of cooling loop failure (ACLF) in lunar nuclear power reactor (LNPR)

The safety assessment of an accident in the lunar base power plant is investigated for the stability of the operation. The lunar surface reactor is modeled for this study. The accident of cooling loop failure (ACLF) is one of the important scenarios for the virtual case in the moon nuclear power plant (NPP). The newly designed lunar nuclear power reactor (LNPR) is suggested for the commercial purpose. The system dynamics (SD) is used for the simulation of the safety assessment. The cyclic variation of the lunar surface temperature can affect to the physical situation of the coolant, which is expressed by the time step. The result shows the performance possibility of the long term cooling increases slightly in the short period of the time step. The dynamical simulation of the lunar environment is performed for the conceptual design of the NPP.     

Diphenylmethane diisocyanate self-polymerization: Thermal hazard evaluation and proof of runaway reaction in gram scale

Thermal analysis by differential scanning calorimetry and thermogravimetric/differential thermal analysis mass spectrometry, adiabatic calorimetry, a gram-scale heating test, and infrared spectroscopy were performed to evaluate the thermal hazards of diphenylmethane diisocyanate (MDI) and prove the occurrence of a runaway reaction. The self-polymerization of MDI was found to occur at about 340 °C under rapid heating conditions. Carbon dioxide was eliminated and heat was generated to allow polymerization. Under adiabatic and closed conditions, the runaway reaction of MDI can begin at least from 220 °C. Besides it is highly probable that the runaway reaction of MDI can begin from a lower temperature in an actual process scale. More heat was generated than in the previous case and the pressure rose rapidly. A closed 2-mm-thick glass vessel exploded because of the runaway reaction of MDI even if the temperature was lower than 300 °C. Therefore, MDI could cause fatal runaway reactions below 300 °C, where MDI had been assumed to self-polymerize by eliminating carbon dioxide previously.     

Developing a new alternative risk assessment framework in the work sites by including a stochastic and a deterministic process: A case study for the Greek Public Electric Power Provider

An individual method cannot achieve the optimum risk-assessment result in the worksites, and future perspectives should focus on the parallel application of a deterministic approach with a stochastic approach. In particular, the risk analysis and assessment techniques of the deterministic (DET) approach are classified into three main categories: (a) the qualitative, (b) the quantitative, and (c) the hybrid techniques (qualitative-quantitative, semi-quantitative). Furthermore, the stochastic (STO) approach includes the classic statistical approach (CSA) and the accident forecasting modeling (AFM). The objective of this paper is triple: (a) the presentation and classification of the main risk analysis and risk assessment methods and techniques of the deterministic approach and the stochastic approach as well, (b) the development and presentation of a new alternative risk assessment framework (called as STODET) including a stochastic and a deterministic process, and (c) the application of STODET in the Greek Public Power Corporation (PPC) by using occupational accidents that have been recorded, during the 17-year period of 1993-2009. In particular, the STODET application proves that required actions (or suppressive measures) are essential and must be taken in a medium-term period (1 working year) for abolishing the hazard sources.