Articles

Our publications in foreign magazines: 

1. A. Kossoy, I. Sheinman, Effect of temperature gradient in sample cells of adiabatic calorimeters on data interpretation,  Thermochimica Acta, V 500 2010, Pages 93-99

Abstract 

2. J-R. Chen, S-Y. Cheng, M-H Yuan, A. Kossoy and C-M Shu, Hierarchical kinetic simulation for autocatalytic decomposition of cumene hydroperoxide at low temperatures, Journal of Thermal Analysis and Calorimetry, 2009, V 96, N 3, p. 751-758

Abstract 

A hierarchical set of kinetic models were proposed and discussed for simulation of autocatalytic decomposition of cumene hydroperoxide (CHP) in cumene at low temperatures. The hierarchy leads from a formal model of full autocatalysis, which is based on conversion degree as a state variable, through a two-stage autocatalytic concentration-based model to a meticulous multi-stage model of the reaction. By the ForK (Formal Kinetics) and DesK (Descriptive Kinetics) software, developed by ChemInform Saint Petersburg (CISP) Ltd., the related kinetic parameters and their significance have also been estimated and elucidated. Through this best-fit approach, it is possible to formulate a systematic methodology on the kinetic studies for thermal decomposition of typical organic peroxides with autocatalytic nature, specifically at low temperature ranges.

3. A. Kossoy, Yu. Akhmetshin, Identification of kinetic models for the assessment of reaction hazards, Process Safety Progress, 2007, V. 26, N3 September 2007, pp. 209-220

Abstract

The assessment, control and mitigation of reaction hazards is primarily based on the use of kinetic models. These kinetic models are used for the assessment of reaction hazards, the operation and control of the reactor, the design of emergency relief systems, and estimation of the consequences of a reaction runaway, to name a few. The validity of these assessments depends highly on the validity of the kinetic model employed.  

Several steps are required to identify a suitable kinetic model. This includes:

• Selection of the model type. 
• Estimation of the model’s parameters using available data.
• Validation of the model.

This paper discusses each of these steps in detail and identifies problems associated with each step. Several practical examples are used to demonstrate these problems.

The results show that: 1) the results are sensitive to a number of assumptions, 2) mistakes may originate from misinterpretation of the thermal data, and 3) computational methods do exist to provide suitable kinetic models for hazard assessment.

The analysis employed assumes a batch reaction system, since most of the kinetic data available is derived from batch calorimetric equipment.

4. A. Kossoy, I. Sheinman. “Comparative Analysis of the Methods for SADT Determination”, Journal of Hazardous Materials, Vol 142, 2007, pp. 626-638

Abstract 

The self-accelerating decomposition temperature (SADT) is an important parameter that characterizes thermal safety at transport of self-reactive substances. A great many articles were published focusing on various methodological aspects of SADT determination. Nevertheless there remain several serious problems that require further analysis and solution. Some of them are considered in the paper.

Firstly four methods suggested by the United Nations “Recommendations on the Transport of Dangerous Goods” (TDG) are surveyed in order to reveal their features and limitations.

The inconsistency between two definitions of SADT is discussed afterwards. One definition is the basis for the US SADT test and the heat accumulation storage test (Dewar test), another one is used when the Adiabatic storage test or the Isothermal storage test are applied. It is shown that this inconsistency may result in getting different and, in some cases, unsafe estimates of SADT.

Then the applicability of the Dewar test for determination of SADT for solids is considered. It is shown that this test can be restrictedly applied for solids provided that the appropriate scale-up procedure is available. The advanced method based on the theory of regular cooling mode is proposed, which ensures more reliable results of the Dewar test application.

The last part of the paper demonstrates how the kinetics-based simulation method helps in evaluation of SADT in those complex but practical cases (in particular, stack of packagings) when neither of the methods recommended by TDG can be used.

5. M-H. Yuan, C-M. Shu and A. Kossoy, Kinetics and hazards of thermal decomposition of methyl ethyl ketone peroxide by DSC, Thermochimica Acta, Volume 430, Issues 1-2, June 2005, pp 67-71

Abstract

Historically, methyl ethyl ketone peroxide (MEKPO), a universal hardener in the rubber industries, has caused many serious explosions and fires in Taiwan, Japan, Korea and China. This study used certain thermal analytical methods to thoroughly explore both why MEKPO resulted in these accidents and what happened during the upset conditions. Potential process contaminants, such as H2SO4, KOH and Fe2O3, were deliberately selected to mix with MEKPO in various concentrations. Differential scanning calorimetry (DSC) was employed to calculate the thermokinetic parameters. Kinetics evaluation was also implemented by means of the methods and software developed by ChemInform St. Petersburg, Ltd. The results indicate that MEKPO was highly hazardous as mixed with any of the above-mentioned contaminants. The hazard of fires and explosions could be effectively controlled to a lesser extent only if safety parameters and thermokinetic parameters are properly imbedded into the manufacture processes.

6. A. Kossoy, A. Benin, Yu. Akhmetshin. An Advanced Approach to Reactivity Rating, Journal of Hazardous Materials, Vol 118, issues 1-3, 2005,  pp 9-17

 Abstract

Reactive hazards remain a significant safety challenge in the chemical industry despite continual attention devoted to this problem. The application of various criteria, which are recommended by the guidelines for assessment of reactive hazards, often causes unsafe results to be obtained. The main origins of such failures are as follows:

• reactivity of a compound is considered as an inherent property of a compound. 
• some appropriate criteria are determined by using too simple methods that cannot reveal potential hazards properly. 

Four well-known hazard indicators – time to certain conversion limit, TCL, adiabatic time to maximum rate, TMR, adiabatic temperature rise, and NFPA reactivity rating number, Nr - are analyzed in the paper. It was ascertained that they could be safely used for preliminary assessment of reactive hazards provided that:

• the selected indicator is appropriate for the specific conditions of a process;
• the indicators have been determined by using the pertinent methods.

The applicability limits for every indicator were determined and the advanced kinetics-based simulation approach, which allows reliable determination of the indicators, is proposed. The technique of applying this approach is illustrated by two practical examples.

7. Kossoy A., Sheinman I., Evaluating thermal explosion hazard by using kinetics-based simulation approach, Process Safety and Envir. Protection. Trans IchemE, V. 82, Issue B6, November 2004, p.421-430. (B6 Special Issue: Risk Management);

A. Benin, A. Kossoy, I. Sheinman and P.Grinberg. Evaluating Thermal Explosion Hazard of Self-Reactive Substances by Using Kinetics-Based Simulation Approach.// International Journal of Self-Propagating High-Temperature Synthesis.-  2006, V.15, N 4, P. 297 - 307.

abstract

Analysis of possible development of runaway at production, storage and use of a chemical product, and subsequent choice of measures that can prevent an accident or mitigate its consequences is one of the main tasks of reaction hazards assessment. A kinetic model evaluated from calorimetric data gives the reliable basis for implementing the analysis by means of numerical simulation. The purpose of this paper is to discuss some features of the approach as applied to such typical problems as determination of critical conditions of thermal explosion and the SADT for solid and liquid reactive chemicals.

Firstly the brief survey of some popular simplified theories is discussed to reveal their main limitations.

Secondly the mathematical models of thermal explosion in solid and liquid reacting systems are presented followed by a basic sketch of the numerical methods chosen for solving the problems.

Finally the practical usefulness of the kinetics-based simulation approach for analyzing influence of various factors on explosion development is illustrated with several examples.

The discussed models and methods were embodied in the ThermEx and ConvEx program packages developed by CISP. All the presented results have been obtained by means of this software.

8. A. Kossoy, T. Hofelich, Methodology and software for Reactivity Rating, Process Safety Progress. v22, N4, December 2003, p.235-240

ABSTRACT

To resolve various problems in creating a process, or conducting stability analysis, and\or yazard assessment, one needs to know the reactivity of a chemical system. The National Fire Protection Association (NFPA) requires use of a reactivity rating number (RRN) to describe such reactivity potentials as thermal stability, interaction with water, and gas generation. For assessing thermal stability of a substance, NFPA has recently a new quantitative approach based on the idea of "Instantaneous Power Density”. Though it has many advantages compared to the largely qualitative previous approach, the new method has one serious drawback - it doesn’t take into account the peculiarities of such complex cases as self-accelerating or multi-stage reactions. This, in turn, can lead to a less-than-safe, or unsafe, design.

In this paper, we propose a method to generalize the concept of instantaneous power density by considering the maximal power density as the quantitative measure of the reactivity, allowing one to take proper account of kinetics complexity. We also briefly discuss the ReRank software which was developed to assess reactivity ratings in general, and, specifically, to calculate reactivity rating numbers.

9. Misharev P., Kossoy A., Benin A. Methodology and software for numerical simulation of thermal explosion. Process Safety and Envir. Protection. Trans IChemE, v.74, part B, February (1996)17.

ABSTRACT

The importance of the computer simulation for the prediction of a thermal explosion in reacting substances is beyond any doubt nowdays. Special software for solving this problem has been developed. This article describes comprehensively the THERMAL EXPLOSION program that provides simulation of explosion for systems with conductive heat transfer and forms a part of this software. Mathematical formulation, numerical method, several examples are discussed.

10. Kossoy A., Koludarova E. Specific features of kinetics evaluation in calorimetric studies of runaway reactions. J. Loss Prev. Process Ind., v.8, N.4,(1995)229.

 ABSTRACT

This paper is dedicated to the problem of the adequacy of the kinetics evaluation methods used in calorimetric investigation of reaction kinetics. The problem is especially important for adiabatic calorimetry because in this case application of usual methods may lead to obtaining non-correct kinetic models and, hence, to serious mistakes in hazard assessment of runaway reactions. The essence of the problem is being considered by method of mathematical simulation. The basic features and advantages of the appropriate method are discussed on the basis of real experimental data processing for kinetics evaluation.

11. Kossoy A., Belochvostov V. and Gusttin J.-L. Methodological aspects of the application of adiabatic calorimetry for thermal safety investigation. J. Loss Prev. Process Ind., v.7, N.5,(1994)397.

ABSTRACT

The method of mathematical simulation was used for analysis of some methodological problems related with adiabatic calorimetry application: correctness of the procedure of initial temperature determination, influence of thermal inertia on temperature distribution in a reacting system,  features of data interpretation in the case of a complicated reaction mechanism and some others.

The efficiency of the approach based on the use of mathematical simulation and appropriate software has been illustrated by several examples.

12. Kossoy A.A., Benin A.I., Smikalov P.Yu., Kasakov A.N. A computerized system for research into thermal safety of chemical processes. Thermoch. Acta, 203 (1992), 77-92.

ABSTRACT

Ensuring thermal safety of chemical processes is an important practical problem. Thermal safety means the processes' safety from the view point of possible development of thermal explosion caused by heat evolving during the chemical processes.

The computerized system developed for solving this complicated problem is described as based on the complex of thermoanalytical and calorimetric devices of "SETARAM".  Structure, purpose and possibilities of the system are considered. Methodological questions of kinetic experiments, kinetic analysis, thermal explosion simulation and organization of software are also discussed.

13. Benin A.I., Kossoy A.A., Sharikov F.Yu. Automated system of kinetic research in thermal analysis. II. Organization of kinetic experiment in ASKR. JTA, Vol.38 (1992), 1167-1180.

ABSTRACT

Correctness of kinetic experiment is an essential condition for obtaining of reliable results in kinetic investigation. Methods for provision and testing of thermo-physical and concentrational  correctness are discussed in the present article.

Problems connected with non-isothermal mode of real thermoanalytical experiment caused by programming as well as by heat release in the sample are considered. Application analysis of combined partial-linear heating laws in kinetic investigations is given. Results of correctness analysis are presented in relation to heat flux calorimeters "SETARAM".

14. Benin A.I., Kossoy A.A., Smikalov P.Yu. Automated system of kinetic research in thermal analysis. I. General description of automated system. JTA, Vol.38 (1992), 1151-1165.

ABSTRACT

Kinetic research with employment of thermal analysis methods comprises a complicated multi-stage procedure. Its successive implementation is impossible without the automation of all the stages with regard to their interconnections. Development of the automated system of kinetic researches (ASKR) in thermal analysis is the solution of this problem.

ASKR is described as based on the set of thermoanalytical devices of "SETARAM" firm. The system allows shortening of time of a study and provides high quality and reliability of the results.

Structure, purpose and possibilities of ASKR are considered. Methodological questions of kinetic experiments and kinetic data analysis, organization of software are also discussed.