Cheminform St-Petersburg (CISP) Ltd. Offers integrated solutions for reaction hazard assessment and chemical engineering

N.A. Podlevskikh, A.A. Kossoy ChemInform Saint-Petersburg, The annual meeting of European DIERS User's group (EDUG), Amsterdam, The Netherlands, 11,12 March 2002

A. Kossoy, Yu. Akhmetshin. (CISP Ltd.), The annual meeting of European DIERS User's group (EDUG), Ispra, Italy, 26-27 Apr 2001.

N. Podlevskikh, A. Kossoy, A. Sokolov, The Fall DIERS meeting, Boston, USA, 16-18 Oct 2000.

P. Grinberg, (To be published in "Chemical Engineering Science").

P. Grinberg, (To be published in "Chemical Engineering Science").

A. Kossoy (RSC AP), T. Hofelich (The Dow Chemical Company), (To be published in "Thermochimica Acta").

A. Kossoy, N. Podlevskikh, I. Sheinman. ChemInform Saint-Petersburg (CISP) Ltd., International Conference "Assessment and Control of Chemical Processing Hazards", London, England, 24-25 Oct, 2000.

N. Podlevskikh, A. Kossoy, A. Sokolov (CISP Ltd.), The annual meeting of European DIERS User's group (EDUG), Ludvigshafen, Germany, 18-19 May 2000.

P. Smykalov, P. Grinberg, M. Minkin (RSC AP), J. Bouillard (Rhone Poulenc Ind.) The 16^th International Symposium on Chemical Reaction Engineering (ISCRE-16), Krakow, Poland, 10-13 Sep 2000.

S. Dobychin, K. Malakhov, The annual meeting of European DIERS User's group (EDUG), Saint-Petersburg, Russia, Jun 1999.

N. Podlevskikh, The 1^st International Conference Reaction hazards assessment and vent sizing (RHV 99), Saint-Petersburg, Russia, Jun 1999.

I. Sheinman, E. Shwalev, P. Misharev, A. Monastyrenko, A. Kossoy The 1^st International Conference Reaction hazards assessment and vent sizing (RHV 99), Saint-Petersburg, Russia, Jun 1999.

A. Kossoy, V. Belohvostov, A. Ahmedshin, The 1^st International Conference Reaction hazards assessment and vent sizing (RHV 99), Saint-Petersburg, Russia, Jun 1999.

A. Benin, A. Posecelski, D. Rozmanov, V. Tihonov, P. Smykalov, The 3^rd International Conference of Unsteady-State Processes in Catalysis (USPC-3), 30 Jun-3 Jul, 1998, Saint-Petersburg, Russia.

A. Kossoy, P. Misharev, V. Belohvostov, 53^rd Annual Calorimetry Conference, Midland, Michigan, USA, 9-14 Aug, 1998.

A. Kossoy, A. Benin. Minutes of 21^st Meeting of DIERS Users Group of the AIChE, Pittsburdh, Pennsilvania, USA, 27-29 Oct, 1997.

P. Misharev, A. Kossoy, A. Benin, Process Safety and Environmental Protection. Trans IChemE, v.74, part B, Feb (1996) 17.

A. Kossoy, E. Koludarova, Journal of Loss Prevention in Process Industries, v.8, N.4, (1995) 229.

A. Kossoy, V. Belohvostov, J-L. Gustin. Journal of Loss Prevention in Process Industries, v.7, N.5, (1994) 397.

A. Kossoy, A. Benin, P. Smykalov, A. Kasakov. Thermochimica. Acta, 203 (1992), 77-92.

A. Benin, A. Kossoy, F. Sharikov. Journal of Thermal Analysis, Vol.38 (1992), 1167-1180.

A. Benin, A. Kossoy, P. Smykalov. Journal of Thermal Analysis, Vol.38 (1992), 1151-1165.

Sizing of safety valves.Comparative analysis of applicability of simplified methods and more adequate sizing methods.

N.A. Podlevskikh, A.A. Kossoy ChemInform Saint-Petersburg, The annual meeting of European DIERS User's group (EDUG), Amsterdam, The Netherlands, 11,12 March 2002.

This report considers some results obtained after a trial application of the simplified vent sizing methods described in Prof. Leung’s works, and compares these methods with those used in the BST software, which is intended to solve the same problems.

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Software for design of inherently safer processes.

A. Kossoy, Yu. Akhmetshin. (CISP Ltd.), The annual meeting of European DIERS User's group (EDUG), Ispra, Italy, 26-27 Apr 2001.

The paper describes the task positing and features of the InSafer program developed by ChemInform Saint-Petersburg (CISP) Ltd. and intended for design of inherently safer processes. InSafer provides optimization of the normal mode of semi-BATCH or CSTR process in such a manner that in case of cooling failure the adiabatic course of a process in the worst case would be as safe as possible. Several examples presented in the paper illustrate effectiveness of the approach.

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BST and SuperChems: Comparative analysis of the functionality of the software.

N. Podlevskikh, A. Kossoy, A. Sokolov, The Fall DIERS meeting, Boston, USA, 16-18 Oct 2000.

Nowadays the chemical industry is developing rapidly. Lots of chemical reactors are designed and produced by a number of companies. Evidently, they must be safe enough to prevent an accident or at least to mitigate the consequences. In many cases, a real experiment is too expensive and usually gives insufficient information. So, the computer simulation of a thermal accident is of high interest. This paper is aimed at considering and comparing two codes, namely they are BST 3.11 and SuperChems 4.0, both designed for Windows 95/98. It is a result of the thorough tests. BST is a part of the software set developed by ChemInform Saint-Petersburg (CISP) Ltd., Russia, for studying chemical reaction kinetics and hazard assessment. It is intended to simulation of a thermal explosion in a reactor caused by chemical reaction or external heating and also solves the vent-sizing problem. SuperChems 4.0 is a current version of the well-known SuperChems software by Arthur D. Little Inc. This is a multipurpose program. In addition to solving the problems mentioned above it analyzes the consequences of an accident. Nevertheless, these features are out of scope of this paper.

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Methodology of algorithm for automatic structure identification and kinetic parameters estimation of stoichiometric models.

P. Grinberg, (To be published in "Chemical Engineering Science").

The paper describes a new methodology and software for structure identification and kinetic parameters estimation of the stoichiometric model for complex reaction systems. The method is based on the analysis of measured data of concentration evolution of the reaction mixture in batch reactor. The method allows the formatting of the complete stoichiometric model (stoichiometric equations and all the kinetic parameters). The idea of the algorithm is to enumerate all of the 'significant' sets of stoichiometric equations and find the best set of kinetic parameters for each stoichiometric set using the short-cut technique. The general law of mass action and irreversibility are the main assumptions of the algorithm. This algorithm is coded in FORTRAN and it is planned to be implemented in the ReactOp software.

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Methodology of SVD-algorithm for automatic identification of stoichiometric models.

P. Grinberg, (To be published in "Chemical Engineering Science").

A new methodology and software are described that have been developed for identifying stoichiometric models for complex reaction systems. The method is based on the analysis of the experimental data of concentration evolution of the reaction mixture in batch reactor. The method allows to determine the maximum number of independent reactions and to derive a family of stoichiometric models with number of reaction stages ranging from 1 to the maximum. If composition of reaction species allows satisfying the atomic balances, the algorithm determines a family of stoichiometric models with integer coefficients. Otherwise, the user obtains a family of stoichiometric models with real coefficients. This algorithm is implemented in FORTRAN and is available as part of the ReactOp software.

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Calorimetric data processing for kinetics evaluation in reaction hazard assessment.

A. Kossoy (RSC AP), T. Hofelich (The Dow Chemical Company), (To be published in "Thermochimica Acta").

Calorimetry of various types (adiabatic, DSC, isothermal, etc.) is one of the main experimental techniques applied for kinetics investigation in reaction hazard assessment. The important peculiarity of this study is that reliability of resultant data depends strongly on the accuracy of calorimetric experiment and correctness of initial processing of original data. Some minor drawbacks in methodology, often inessential in general practice, become crucial when reaction hazards are investigated. Influence of the correctness of processing data of the adiabatic and scanning calorimetry on the resultant kinetics is discussed. Appropriate methods of preparing data for kinetics evaluation are proposed that allow obtaining more reliable kinetic models. Discussion is illustrated by the results of processing of real experimental data.

From calorimetric data via kinetic modeling to runaway simulation and reactor optimization (methodology and software).

A. Kossoy, N. Podlevskikh, I. Sheinman. ChemInform Saint-Petersburg (CISP) Ltd., International Conference "Assessment and Control of Chemical Processing Hazards", London, England, 24-25 Oct, 2000.

The presentation describes main ideas and features of the problem-oriented methodology and software developed by ChemInform for reaction hazard assessment. The approach proposed is principally grounded on systematic application of the kinetics-based mathematical simulation. The numerous examples demonstrate both the limitations of customary semi-empirical way of interpreting calorimetric data and efficiency of mathematical simulation methods when solving various practical problems.

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Validation of the BST-software for ERS-design.

N. Podlevskikh, A. Kossoy, A. Sokolov (CISP Ltd.), The annual meeting of European DIERS User's group (EDUG), Ludvigshafen, Germany, 18-19 May 2000.

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A new approach to grey-box kinetics modeling.

P. Smykalov, P. Grinberg, M. Minkin (RSC AP), J. Bouillard (Rhone Poulenc Ind.) The 16^th International Symposium on Chemical Reaction Engineering (ISCRE-16), Krakow, Poland, 10-13 Sep 2000.

The report describes a new methodology and associated software for grey-box kinetic modeling for homogenous complex reaction systems. There are as many as four methods discussed. One of them is considered in details. The methods are based on the analysis of measured data of concentration evolution of the reaction mixture in batch or semi batch reactor. These methods allow investigator to formulate a stoichiometric model. In this paper, we analyze the applicability conditions, effectiveness and drawbacks of gray-box kinetic modeling methods developed in the literature. Salient features of the newly developed Grey-Box modeling approach implemented in the new ReactOp software are discussed. In light of this discussion, new developments are proposed.

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Estimation of main physical-chemical properties of pure organic liquids with the use of some parameters related to structural and chemical molecular features.

S. Dobychin, K. Malakhov, The annual meeting of European DIERS User's group (EDUG), Saint-Petersburg, Russia, Jun 1999.

Chemical industries are known to be potentially dangerous due to a possibility of thermal explosion of a reactor under abnormal conditions. To prevent such explosions, various types of Pressure Relief Systems are used. If there is a liquid in a reactor, pressure relief will lead to extra coolness due to evaporation. Experimental works on modeling of hazardous thermal regimes are rather costly. So mathematical modeling is very important in this case. And to build a good mathematical model one should know temperature dependencies of equilibrium vapor pressure, vapor density, liquid density and evaporation heat. It's also important to know critical parameters of liquids because many values necessary to build a complete model may be estimated on the basis of them.

As a rule, values of the required properties cannot all be found in modern databases and thus there is always a need for estimation methods to get the missing values. Ideal estimation methods should be based on the minimal molecular information. It's quite natural to choose as a basis the information about the structure of a molecule that is considered as a combination of functional groups. And every group independently of other ones contributes a constant value to the final chemical property. Such group contribution methods are widely used not only in particular engineering calculations but also in rather complex models of chemical processes. Usually the normal boiling temperature is used as a main parameter that determines the quality of estimation. Knowledge of the normal boiling point makes it possible to determine the critical temperature and pressure and then to restore the vapor pressure dependence, etc. But by some serious reasons this approach may lead to obtaining quite unsafe estimates of vapor pressure dependency on temperature.

An alternative approach is resented in the report. The task of determination of the critical parameters and vapor pressure equation coefficients was solved for two cases. In the first one it's necessary to know one experimentally determined 'vapor pressure - temperature' point. In the second one it is assumed that the critical 'pressure - temperature' point is known. But as a matter of fact critical data are estimated too by the use of the Fedors group contribution method. Authors added to the proposed Fedors method a large quantity of group contributions and correction coefficients that ensure its reliability for considerably greater number of compounds including halogenated hydrocarbons.

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Runaway simulation and vent sizing for batch stirred tank. Methodology and software.

N. Podlevskikh, The 1^st International Conference Reaction hazards assessment and vent sizing (RHV 99), Saint-Petersburg, Russia, Jun 1999.

The Batch Stirred Tank (BST) software is a part of the software system developed by RSC AP and CISP Ltd. for study of chemical reaction kinetics and hazard assessment. BST is designed for computer simulation of physical and chemical processes in well-stirred batch tanks with pressure relief systems.

The main methodological matters dealt with simulation of a runaway in the multi component reacting mixture are discussed as well as numerous problems related with calculation of multi phase flow through vent system. The technical statement of the problem of simulation or runaway in a BATCH equipped with emergency relief system is considered. Structure and functionality of the software developed is presented and its abilities are illustrated by results of simulation of some benchmarks.

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Software for numerical simulation of thermal explosion in solids.

I. Sheinman, E. Shwalev, P. Misharev, A. Monastyrenko, A. Kossoy The 1^st International Conference Reaction hazards assessment and vent sizing (RHV 99), Saint-Petersburg, Russia, Jun 1999.

Application of the developed software for simulation of thermal explosions in solids is shown. The critical parameters of thermal explosion are found numerically in the context of complicated chemical kinetics for several types of the reactor geometry, various boundary conditions, and with the possibility to set inert partitions or shells. Comparison of analytical and computer-based methods for thermal explosion hazard assessment is made, the weakness of the analytical approach and the necessity of using the full numerical investigation are shown.

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Specific features of kinetics evaluation in reaction hazard assessment.

A. Kossoy, V. Belohvostov, A. Ahmedshin, The 1^st International Conference Reaction hazards assessment and vent sizing (RHV 99), Saint-Petersburg, Russia, Jun 1999.

Kinetics evaluation aimed for solving various problems of reaction hazard assessment has some specific features that are defined by peculiarities of experimental methods used for reaction study as well as the final problem, which is to be analyzed. The paper considers the following topics:

• influence of initial processing of calorimetric data on the reliability of resultant kinetics;
• choice of the class of kinetic models most appropriate for solving certain practical problem, and discrimination of a model within a group of competing models;
• choice of the most appropriate method for estimating kinetic parameters of a model.

All the matters are discussed on the basis of real experimental data.

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Swing flow reactor for investigation of transient kinetics of heterogeneous catalytic processes.

A. Benin, A. Posecelski, D. Rozmanov, V. Tihonov, P. Smykalov, The 3^rd International Conference of Unsteady-State Processes in Catalysis (USPC-3), 30 Jun-3 Jul, 1998, Saint-Petersburg, Russia.

The new experimental setup for study of heterogeneous catalytic reactions is described. The design of the setup ensures extraction of kinetic information about chemical processes and adsorption on the catalyst surface within the wide range of degrees of conversion.

The new proposed concept is based on the use of reverse flow through a short fixed bed reactor. Every pulse is characterized by small residence time and low conversion that allows avoiding undesirable interfacial gradients. As the number of pulses (cycles) during a single experiment can be big enough one can provide the summary residence time as big as necessary. Thus the pulse flow mode ensures obtaining reliable transient data for creation of a reaction model (kinetics evaluation). Results of use of the setup for investigation of fluorination of dichloromethane are presented.

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Peculiarities of calorimetric data processing for kinetics evaluation in reaction hazard assessment.

A. Kossoy, P. Misharev, V. Belohvostov, 53^rd Annual Calorimetry Conference, Midland, Michigan, USA, 9-14 Aug, 1998.

Calorimetry is a reach source of data for evaluating reaction kinetics in reaction hazard assessment. The resultant kinetics allows solution of miscellaneous problems of thermal safety by applying mathematical modeling. The most typical problem to be solved is runaway simulation, and the results are extremely sensitive to small variations of kinetic parameters. The reliability of kinetics in its turn depends on the elaboration of the methodology of calorimetric experiment. Therefore, some drawbacks of methodology, often inessential in general practice, become crucial when reaction hazards are investigated. This paper describes some issues of this kind as applied to the data from scanning and adiabatic calorimetry.

Two features of DSC experiment are considered - sample overheating and heat inertia of a cell. Both of them result in rather small distortions of a calorimetric response but, if not taken into account, may lead to erroneous kinetics and incompatibility of DSC and adiabatic data. As for the adiabatic data, the problem of uncertainty of initial conditions at the onset temperature of the adiabatic mode is discussed.

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Developments in the field of methodology and software for thermal hazards assessment.

A. Kossoy, A. Benin. Minutes of 21^st Meeting of DIERS Users Group of the AIChE, Pittsburdh, Pennsilvania, USA, 27-29 Oct, 1997.

The report presents some results of developments achieved by Cheminform Saint-Petersburg (CISP) Ltd. in methodology and software for thermal hazard assessment. The approach is considered which is based on intensive and consequent application of methods of mathematical simulation.

In the first part, some methodological aspects of experimental study by using calorimetric technique are discussed such as adequate data processing procedures, statistical analysis of data, metrological assessment of research system based on modeling experiment.

Second part is devoted to the problem of kinetics evaluation and runaway simulation. The basic requirements to the methodology of creation of kinetic models are discussed; formulation of general approach to the simulation of thermal explosion in solid and liquid chemicals is given.

Last part contains the overview of structure and functionality of the software for hazard assessment developed by CISP Ltd.

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Methodology and software for numerical simulation of thermal explosion.

P. Misharev, A. Kossoy, A. Benin, Process Safety and Environmental Protection. Trans IChemE, v.74, part B, Feb (1996) 17.

The importance of the computer simulation for the prediction of a thermal explosion in reacting substances is beyond any doubt nowadays. 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.

Specific features of kinetics evaluation in calorimetric study of runaway reactions.

A. Kossoy, E. Koludarova, Journal of Loss Prevention in Process Industries, v.8, N.4, (1995) 229.

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 unsafe or even erroneous 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.

Some methodological aspects of adiabatic calorimetry application for thermal safety investigation.

A. Kossoy, V. Belohvostov, J-L. Gustin. Journal of Loss Prevention in Process Industries, v.7, N.5, (1994) 397.

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 interpretation of data in case of a complex reaction mechanism, etc. The efficiency of the approach based on the use of mathematical simulation and appropriate software is illustrated by several examples.

Computerized system for research of chemical processes' thermal safety.

A. Kossoy, A. Benin, P. Smykalov, A. Kasakov. Thermochimica. Acta, 203 (1992), 77-92.

Ensuring thermal safety of chemical processes is an important practical problem. Thermal safety means the processes' safety from the viewpoint of possible evolution of thermal explosion caused by heat generation 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 the software are also discussed.

Automated system of kinetic researches in thermal analysis. Organization of kinetic experiment in ASKR.

A. Benin, A. Kossoy, F. Sharikov. Journal of Thermal Analysis, Vol.38 (1992), 1167-1180.

Correctness of kinetic experiment is an essential condition for obtaining reliable results in kinetic investigation. Methods for providing and testing 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. Analysis of applicability of combined partial-linear heating laws in kinetic investigations is given. Results of correctness analysis are presented in relation to heat flux calorimeters SETARAM.

Automated system of kinetic researches in thermal analysis. General description of automated system.

A. Benin, A. Kossoy, P. Smykalov. Journal of Thermal Analysis, Vol.38 (1992), 1151-1165.

Kinetic research based on thermal analysis methods comprises a complex multi-stage procedure. The full performance of that is impossible without 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 the SETARAM firm. The system provides reducing of the investigation time, 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.