www.icheme.org/cherd doi: 10.1205/cherd.

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02638762/06/$30.00+0.00 # 2006 Institution of Chemical Engineers Trans IChemE, Part A, July 2006 Chemical Engineering Research and Design, 84(A7): 543 552

REVIEW PAPER

SAFETY AND RUNAWAY PREVENTION IN BATCH AND SEMIBATCH REACTORSA REVIEW

K. R. WESTERTERP1 and E. J. MOLGA2
2 1 , Barcelona, Spain Ramon Llull University, Institut Quimic de Sarria Warsaw University of Technology, Chemical and Process Engineering Department, Warsaw, Poland

n this paper a review of recent developments on safety and runaway prevention in batch and semibatch reactors is given. To prevent thermal runaways in chemical reactors usually three lines of defense have to be considered: choice of the right operating conditions, early warning detection system and system to handle running away reactions. Because of its too specic nature, the last line of defense is not discussed in this review, while the former two are considered in detail. Firstly the capability and applicability of the reaction calorimeter for safety assessments are reviewed, then fundamental safety criteria for safe operation of batch and semibatch reactors are reported and discussed. A review of the most useful and efcient methods for a correct choice of safe operating conditions is split into two cases: one, when the reaction kinetics are known, and when kinetic information is not available. Also several promising recent developments of an early warning detection system for the on-line detection of unexpected situations leading to a thermal runaway are presented. Keywords: safety of chemical reactors; criteria of thermal runaway; reaction calorimetry; early warning detection of runaway; batch and semibatch reactors.

INTRODUCTION In this paper we will review the developments in the last 25 years in the study of safety and runaway prevention of batch and semi-batch reactors. We will do so from the view point of the science of reaction engineering and therefore, we will leave a number of relevant studies untouched that belong to the elds of chemistry, mechanical engineering and/or organizational sciences. In Table 1 we give statistical data on the prime causes of batch reactor incidents as they have been reported in three different studies (Verwijs, 1994). We can observe that at least more than 60% of the incidents could probably be avoided, if a proper design of the reactor plant and choice of the safe operating conditions has been performed. The number of incidents per month seems to increase in time according to Table 1, this is not the case in reality: the numbers of reports and methods of reporting have increased and improved very much over the period from 1960 to 1990. We may feel that a number of two incidents per month for a few thousands of reactors considered in the surveys leads to a rather small percentage of incidents. However, more than 80%

Correspondence to: Professor E. J. Molga, Warsaw University of Technology, Chemical and Process Engineering Department, ul. Warynskiego 1, 00-645 Warsaw, Poland. E-mail: molga@ichip.pw.edu.pl

of the reactions executed daily do not have a heat effect large enough to cause a runaway, so that the chance of a runaway, nevertheless, is not hypothetical. To prevent reactor incidents and runaways in general three lines of defense have to be considered in the design and operation of a (semi-)batch reactor. The rst line of defense is the choice of the right operating conditions. This refers to the degree of mixing, the cooling capacity, the choice of the coolant temperature, the dosing rate of the reactant(s) and so on. In the course of the years many papers have been written on the choice of the operating conditions; moreover, we should realize that the studies on tubular reactors also can be translated to batch reactors. Most recommendations are based on the knowledge of the kinetics of the reaction. Regretfully batch reactors are almost exclusively used in the ne chemicals industry, where usually time and money are serious constraints for the costly and time-consuming study of reaction kinetics. For highly exothermic reactions the use of inaccurate kinetic information often leads to a too prudent selection of operating conditions with low reactor productivities. In the last decennia the Reaction Calorimeter has become widely accepted as a tool for the selection of operating conditions, so that we will also dedicate some space to the discussion of this piece of very useful laboratory equipment. The second line of defense is an early warning detection system. As is clear from Table 1, a correct choice of 543

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WESTERTERP and MOLGA entitled Reaction Calorimetry, in a series of contributions the expanding role of reaction calorimetry is demonstrated and its theoretical principles, methods of modelling as well as areas of application are indicated and widely discussedsee a.o. Landau (1996), Rowe (1996) and Zaldivar et al. (1996). Following Landau (1996), three basic areas of application of reaction calorimetry can be distinguished: Process Safety, Process Development and Basic Research. All of them contribute signicantly to the evaluation of safety aspects of batch and semibatch reactors by thermal and kinetic analysis of chemical reactions. In a more recent review by Zogg et al. (2004), the most important calorimetric principles are presented and discussedincluding heat ow, heat balance, power compensation and the Peltier principleas well as a classication and a comparison of the available reaction calorimeters. Among numerous relevant papers on the contribution of reaction calorimetry to safe operation of chemical reactors, e.g., the following publications should be mentioned: Ubrich et al. (2001) and Gesthuisen et al. (2005). A few commercial applications of standard heatow reaction calorimeters are available on the market for both laboratory and research purposes. To avoid promoting any particular producer the reader is referred to the papers cited above as well as to the webpage HarsNet (HarsBook). In principle each heat-ow reaction calorimeter measures the heat evolution with time of a reaction under isothermal, isoperibolic or adiabatic conditions. A schematic diagram of a typical bench-scale reactor is shown in Figure 1. The principles of reaction calorimetry are based on the determination of mass and energy balances carried out over the reaction vessel. In the general casetaking into account the behaviour of a semi-batch reactor, even with evaporation of solvent or reactantsthe molar balance for each reactant in the reacting mixture has to be formulated, including the molar ow rates due to evaporation and reuxing of certain components. Their ow rates have to be determined from a heat balance around the condenser as well as from a mass balance around the reux collector (see Figure 1). The reaction heat-ow rate qR(t) can be found easily using only temperatures measured inside the reactor and in the coolant jacket. Values of parameters such as the overall heat transfer coefcient U and the specic heat capacity of the reaction mixture CP, can be determined in a separate series of calibration experiments. An accurate estimation of heat ow through the reactor wall is essential for this type of reaction calorimeters and can be found from the following relationship: qflow UATR TA (1)

Table 1. Prime causes of batch reactor incidents (Verwijs, 1994). 19621984 19621987 References Nolan and Barton (1987) 21.4% 7.9% 22.3% 22.2% 9.5% 16.7% 0.46 Barton and Nolan (1989) 20.1% 8.9% 21.3% 18.9% 10.1% 20.7% 0.54 19861990

Incident cause Thermo-reaction chemistry Raw material quality Maintenance/other factors Temperature control Loss of mixing/agitation Mischarging of reactants Incident rate (#/month)

Etchells (1993) 14.8% 9.8% 22.2% 13.9% 13.1% 26.2% 2.03

Data obtained from Health and Safety Executive records (HSE, UK).

operating conditions is not enough for the safe running of a reactor section in the plant. Human errors like mischarging of reactants, maintenance troubles, agitator break down and so on always may occur. Therefore, it would be a god send if we could provide industry with a piece of equipment or a procedure, that can give an early warning to the operator to anticipate a runaway to occur within a shorter period, say for example, 20 to 200 min in advance of reaching the maximum runaway temperatures. In this eld in the last ten years great advances have been made. The third line of defense is a suitable system to handle running away reactions. Such systems depend on the reactants and reactions at hand. If vapors are developed, we need a blow down system with catch tanks; or in another case, reactor contents must be discharged to refrigerated cellars loaded with ice to stop the reaction by freezing. In practice, many different approaches can be found. We will not discuss this aspect in this paper, because the measures to be taken to handle a reaction mass, that is heating up towards a runaway, are too specic for each particular case. In this paper we will discuss rst the capabilities of the reaction calorimeter, then the criteria based on known kinetics to operate a batch reactor safely and after that the methods developed to achieve safe operation without knowing reaction kinetics. At the end we will dedicate some space to the promising recent developments of an early warning detection system. THE REACTION CALORIMETER The reaction calorimeter has been developed and now is in full use at almost every process development laboratory in ne chemicals industry. In commercial applications of reaction calorimetry the operation of batch and semibatch reactions is supported in many ways apart from controlled heating and cooling, stirring and mixing, distillation and reuxing, dosing of reactants and measurement and control of process parameters (pressure, pH, turbidity, chemical content by FTIR analysis and so on). An extensive review of the application of the reaction calorimetry is given in the special issue of Thermochimica Acta 289, 1996, edited by R.N. Landau. In this issue

where TA is a corrected jacket temperature, Tc, to take into account the heat capacity of reactor walls (Zaldivar et al., 1996; Molga, 1997). Having determined the power generated due to the reaction progress, qR(t), the total heat effect, QT, can be calculated as well as the reaction enthalpy: QT DHA D nA tF
0

qR (t)dt D nA

(2)

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Figure 1. Schematic diagram of a typical bench-scale (semi-)batch reactor or a reaction calorimeter: 1basic unit containing reactor control and regulation systems, 2reactor vessel with jacket, head assembly and stirrer, 3dosing pumps, 4electronic weights, 5computer for controlling the system and acquisition of data, 6cryostat, 7distillation and reux set.

Then, for a single reaction, the conversion rate of the compound A can be estimated as a function of the reaction time: RA t qR t DHA (3)

. Process Development (Schmidt and Reichert, 1988; am Ende et al., 1996; Ferguson and Puga, 1997; Erwin et al., 2001; Clark et al., 2001). . Basic Research (Nomen et al., 1997; Stoessel, 1997; Singh, 1997; LeBlond et al., 1996; Ubrich et al., 1999; Nogent and Le Tacon, 2002).

and further the conversion of the compound A as: qR tdt XA t 0 QT t (4) CRITERIA FOR SAFE OPERATION AND RUNAWAY PREVENTION OF (SEMI-)BATCH REACTORS, BASED ON KNOWN KINETICS Runaway prevention has drawn the attention of chemical engineers for many decennia. We refer to the early work of Semenov and others already before the Second World War, specially in the eld of combustion engineering, and also to the work of Barkelew (1959). He demonstrated that for rst order reactions in a batch reactor the reactor remains thermally stable provided the temperature difference between coolant and reacting mixture is not higher than: 2 =E . TR Tc RTc Provided this condition is fullled a runaway will not occur. Later Van Welsenaere and Froment (1970) demonstrated this also holds for a temperature difference smaller 2 /E and that an even somewhat higher (TR 2 Tc) than RTR can be applied without a runaway. In the period under consideration Balakotaiah et al. (1995) demonstrated that the above criterion must be corrected for the heat taken up by the mass of the reactor vessel. They introduced the ratio of the heat capacity of the reactor vessel and its contents compared to that of the reactor mixture only and called this arbitrarily a Lewis number Le mcp R m cp w 1 mcp f m cp f

Based on the mass balance and the stoichiometric reaction equation as well as using the conversion rate, the concentration of the ith reactant in the reacting mixture can be found as a function of the reaction time. So, based on data for the reaction rate and the reactant concentrations, both as a function of time, the reaction kinetics can be studied and the safety of the process can be analysed. As can be seen from equations (2) (4), even with a single run the reaction enthalpy can be determined, while by carrying out the reaction at isothermal conditions at least at two different temperatures, the activation energy can be obtained. So, with the reaction calorimeter the parameters DHR, E, DTad and Cp, required for process safety assessment, can be estimated. They can be directly used for safe designing of the reactor performance on an industrial scale. Apart from the references mentioned before in this section, some other representative examples of practical applications of reaction calorimetry are listed below. They have been here arbitrarily grouped according to the categories proposed by Landau (1996), although all of them can be directly related to safety of processes: . Process Safety (Zaldivar et al., 1992; Schuler and Schmidt, 1992; Regenass, 1997a, b; Serra et al., 1997; Lerena et al., 1996; De Filippis et al., 2002; Molga et al., 2004).

This factor, called also thermal inertia, had been used earliere.g. see the paper by Townsend and Tou (1980),

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WESTERTERP and MOLGA In general the batch reactor can be applied only for reactions with a low adiabatic temperature rise. For more exothermic reactions the semi-batch reactor is used, in which one or more reactants are loaded into the reactor and the balance of the recipe items are fed with a desired mass rate prole (usually but not always linear with time) over a dened period. Doing so, we can keep the heat evolution by a very exothermic reaction in hand by the dosing rate of the second reactant. After the Seveso incident in 1976 much research was started to understand what the real cause of the runaway in a semi-batch reactor may have been. The authors Hugo and Steinbach (1985, 1986) deserve the honour for the observation that an accumulation of the dosed component at too low reactor temperatures is the cause of the runaway in homogeneous semi-batch reactors. They presented a line in a diagram, which separates the region with a runaway from the region with a smoothly operating semi-batch reactor with only a small harmless accumulation of the dosed reactant. They did so for modied Stanton numbers of 5, 10 and 15, where this number reads as St (U A tdos =V r cP ). They also determined empirically from their calculations thatin their range of Stanton numbersin the boundary between the two regions the hler number Da kcBo tdos must be equal to or Damko higher than the modied Stanton number. In their paper Hugo and Steinbach (1986) derived empirical relations for the operating conditions in a homogeneous semi-batch reactor. They found that the thermal 2 ) must reaction number B (E DTad =R TR p 2 be smaller than the limit value B St 2G 1:2 , where G mA/m is the ratio of the mass of the reactant A to the nal mass of the reactor content, which represents the volume increase due to the dosage of the second reactant, and that the coolant temperature must be higher than the limit value Td, which can be found from the following equation: DaTd St (6)

where its inuence on runaway trajectories as well as on thermal stability is also discussed. So, the acceptable adiabatic temperature rise for the batch wise executed reaction can be a factor Le higher. In practice it is difcult to estimate the value of Le: for instance the agitator will have the same temperature as the reaction mixture, but the wall of the reactor not so, because it will have a temperature somewhere in between TR and Tc. These authors considered a well mixed batch reactor with a homogeneous, single and irreversible, exothermic reaction A ! B, with n . Assuming that the reaction a rate given by r k(T )cA heat generated is removed only by cooling, they gave the following operation equation, which can be easily derived from the set of general mass and heat balance equations after introducing dimensionless variables and parameters: Le du a u u c 1 B dX B1 X n expu=1 u=g (5)

It holds for the reactant conversion 0 X , 1 and after integration with u 0 at X 0 gives the reaction paths in the temperature-conversion plane. Particularly useful can be an observation of the reactor temperature trajectory at assumed operating conditions in relation to the adiabatic trajectory. A typical plot is shown in Figure 2. Because in many practical cases the adiabatic temperature is unacceptably high as the limiting temperature, Balakotaiah et al. (1995) referred to the work of Adler and Enig (1964) to have a sharp and realistic criterion for the prevention of runaway. At some special conditionsi.e., for uc 0 and g 1the results are presented in an operating diagram, in which the lines separating runaway and safe regions are plotted in a plane with the coordinates a/B and B/Le (see gure 2 in the cited paper). Heiszwolf and Fortuin (1996) executed an experimental study with a rst order reaction and demonstrated that the predictions of Adler and Enig (1964) are on the dot to predict for a certain set of operating and design conditions at what reactant concentration in the feed a runaway will occur in a batch reactor with a homogeneous reaction mixture.

Figure 2. Temperature trajectories calculated with the operation equation [Equation (5)] according to the criterion by Balakotaiah et al. (1995). Calculations carried out at: Le 1, B 2, n 1, uc 0, g 20 for different values of dimensionless external heat transfer coefcient a.

Specially their last relation is very simple. Hugo et al. (1988) studied the danger of a runaway after an agitator breakdown, because after a breakdown the reaction proceeds adiabatically. They demonstrate that the most dangerous situation prevails if the breakdown occurs at the moment of just reaching the stoichiometric dosage of the second reactant, because at that condition the concentrations of the two reactants reach such values that the reaction rate of a second order reaction just has its highest value, that is the highest value of the product cA cB. They found that the nal temperature of the adiabatic reaction mixture will exhibit a minimum value as a function of the reaction temperature chosen in a particular case, provided the value for B is larger than 2. Steensma and Westerterp (1990, 1991) developed full safety diagrams for the same range of cooling numbers for heterogeneous liquid liquid semi-batch reactions and for reactions both in the dispersed phase as well as in the continuous phase. They have studied slow reactions and also fast reactions, where the mass transfer is enhanced by the chemical reaction. They show that also for chemically enhanced reactions, where the supplied reactant is

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SAFETY AND RUNAWAY PREVENTION already consumed in the lm around the drops, still a dangerous accumulation can occur in its own phase, causing a runaway. In their safety diagrams they plotted the Reactivity, Ry, as a function of the Exothermicity, Ex, and surrounded the region of runaways by a boundary line. These dimensionless groups are dened as: DTad,o E=R Ex 2 Tc RH U Da=11 (nA =nB )mDac Ry RH U Da=11 (7) (8)

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caution about blindly applying of each safety criteria to reactions that may be autocatalytic, is very important.

SAFE OPERATION OF (SEMI-)BATCH REACTORS WITHOUT KINETIC INFORMATION Gygax (1988, 1990) discusses in two concise papers the available methods to determine the danger of runaways in batch and semi-batch reactors and how we can use chemical engineering principles to cope with these dangers. Stoessel and Ubrich (2001) for homogeneous reactors demonstrate how the operation of a semi-batch reactor can be improved by modulating the feed rate to a semibatch reactor, proving that the reactor productivity can be sharply increased. They also demonstrate how in their case the appropriate information can be obtained with a reaction calorimeter and without knowing the kinetics of the reactions involved. They illustrate their method with an example of a set of consecutive reactions. Westerterp and Molga (2004a) demonstrate that the Cooling number is the key parameter, that determines the difference in behavior of the large scale, industrial reactor and the laboratory reactor. The Cooling number is dened as: Co U Ao tdos 1V rcP o (9)

Further regions with no accumulation, harmless reactions and insufcient ignitions are distinguished. The boundary diagrams (see Figure 3) depend on the value of the cooling numberwhich is similar to the modied Stanton number of Hugo and Steinbach (1986)and on whether the reaction takes place in the continuous phase or in the dispersed phase in the reactor. Van Woezik and Westerterp (2000, 2002) publish experimental work on a very exothermic nitration reaction system with consecutive reactions and with a secondary heat effect, which is 3.25 times higher than that of the desired reaction. They determined very accurately the kinetics of their consecutive reaction scheme. They also determined the interfacial areas in the reactor. They conclude that the set of differential equations as used by Westerterp and coworkers to describe the behaviour of such reactors are conrmed accurately by their experiments. For safe operation much higher Cooling numbers are required than in the previous work (Steensma and Westerterp, 1990, 1991) and they introduce the concept of the inherently safe operating region, in which the heat evolution is still harmless and the accumulation of the dosed reactant remains very small (see Figure 3). Maestri and Rota (2005a and 2005b) calculate safety diagrams for kinetics different from those used by Hugo, Westerterp and coworkers. The diagrams are inuenced indeed by a difference in kinetics, regretfully they do not discuss when and where their kinetics occurs in practical semibatch reactor operations. Hugo (1990) determined that a description by second order reaction always gives satisfactory results, except for autocatalytic reactions. A special

Figure 3. Inherently safe operating conditions for slow reaction in the continuous phase.

They indicate how this Co number must be determined for laboratory reactors as well as for industrial reactors. Further they elaborate on the concept of inherently safe reactor operation and how this must be achieved in practice. See Figure 3 for the indication of the inherently safe operation region in a safety diagram for a slow liquid liquid reaction in the continuous phase. They determine the full range of values of Cooling numbers for all liquid liquid reactors of all sizes in a laboratory or in an industrial plant. They also determine the maximum of the Exothermicity values below which, and the minimum values of the Reactivity above which, never a runaway can occur. They state that the necessary information can be obtained in a few days in a laboratory in a reaction calorimeter, provided the calorimeter is used in the semi-batch mode. They argue that their method for liquid liquid reactions can be used for single as well as for multiple reactions of any reaction scheme with the exception of autocatalytic reactions. They also discuss how incidents like agitator breakdown can be handled without any danger of a runaway. The elaborated practical procedure to determine the inherently safe operating conditions in semi-batch reactors is summarized in Table 2 (Westerterp and Molga, 2004b). Westerterp and Molga (2004a) in their paper give data on the practical values of the dimensionless groups of the Reactivity, the Exothermicity and the Cooling numbers for both laboratory and industrial reactors. We should realize that laboratory reactors usually have much higher Cooling numbers than industrial reactors. Specially, for heterogeneous liquid liquid and gas liquid reactions Cooling numbers necessarily are high in order to achieve good dispersions with large interfacial areas. In order to simulate industrial conditions often reaction calorimeters are equipped with

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WESTERTERP and MOLGA

Table 2. Procedure for the determination of safe operating conditions Method used to determine

Value (or group) determined

In laboratory reactor I. The Exothermicity criterion for a single reaction

In industrial reactor

DTad,o E RH 1 Co Ex Yield

Measured or calculated Measured in reaction calorimeter or DSC Calculated Calculated Measured (cooling curve for originally loaded batch)

Measured (cooling curve for originally loaded batch) Calculated as a function of tdos, and at realistic Tc For Ex Exmin check for the reactor productivity at the chosen tdos

II. The Reactivity criterion for a single reaction Co Tta f (t) RyQFS,min Tc Measured (cooling curve for batch originally loaded) Calculated Calculated Calculated Calculated Tc,ind - see below Eq. T1 III. Multiple reactions See original article. The following holds: (a) for parallel reactions an apparent activation energy should be determined, then the procedure above can be directly applied; (b) for consecutive reactions the following method should be applied: Heat evolution curves Yield Ex E1/E2 Ex criterion RyQFS criterion " # 2 RTc,lab RyQFS, min ind ln Tc,lab E RyQFS, min lab Measured as a function of T Measured For the rst reaction, the second reaction or for the sum of heat effects Estimated Calculated Calculated Calculated

Tc,ind

(T1)

stirrers with low agitation speeds to reduce the Cooling numbers. This helps indeed for homogeneous reactions, but is unacceptable for heterogeneous reactions leading to phase separations. EARLY WARNING DETECTION SYSTEMS As has been mentioned before, even a correct choice of reactor operating conditions does not totally protect the plant against a thermal runaway. So, apart from the offline activities, which help to dene safe operating conditions, also on-line prevention measures are necessary to detect any unexpected situation leading to a runaway scenario (see Figure 4). Among others under the on-line safety measures as listed in Figure 4, an early warning detection system (EWDS) is indispensable to detect and evaluate unexpected dangerous situations, which may occur in batch and semibatch reactors e.g., due to a failure of the cooling or stirring systems or to a human mistake. The development of an efcient and robust EWDS for batch and semi-batch reactors is very difcult due to the complexity of the processes carried out in such reactors and their strongly nonlinear dynamics. The main problem of a detection of dangerous situations in discontinuous reactors is the fast recognition of deviations from safe

operation, because we must provide sufcient time for the plant operator or an automatic protection system to take appropriate protective countermeasures to stop a thermal excursion. Such countermeasures may be a pressure relief, full cooling or quenching (i.e., addition of inhibitor or cold inert liquid as well as dumping of the reactor content into a cold catch tank). At the same time to avoid false alarms, a warning system must be able to precisely distinguish between dangerous and non-dangerous reactor states. So, an essential element of any EWDS is a robust safety criterion, which works on-line and is practically independent of the actual process carried out in the reactor. Numerous criteria for the safe operation of batch and semibatch reactions have been developed and can be found in literature, some of them are discussed in this paper in the sections above. The sensitivity towards the initial and the operating parameters has been extensively studied(see Varma et al. 1999) and a new series of safety criteria based on parametric sensitivity has been developed (e.g., see Morbidelli and Varma, 1986, 1988, 1989; Vajda and Rabitz, 1992; Shukla and Pushpavanam, 1994). Unfortunately, these criteria can not be used for an on-line early warning detection of a runaway. A detailed discussion of the applicability of the existing safety criteria for an early detection system can be found in a series of

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Figure 4. Prevention measures developed to avoid situations that may lead to loss of thermal control and runaway scenario, see also Zaldivar (1991a) as well as Westerterp and Molga (2004a).

can be found in the paper by Strozzi et al. (1999), while further theoretical developments as well as practical applications and considerations are published in a series of papers by Strozzi, Zaldivar and their coworkers, which report on the results obtained in an EU funded project AWARD (2001 2005) (see Zbilut et al., 2002; Bosch et al., 2004c; Zaldivar et al., 2005, 2003; Bosch et al., 2004 a, b, d), respectively. Based on the results of the studies carried out within the frame of the AWARD project, several prototypes of an Early Warning Detection System for batch and semibatch reactors have been produced (for details see AWARD, 2001 2005). In the mentioned method a new runaway criterion has been dened and the onset of loss of control has been identied at the point where the divergence of the reactor behavior becomes positive on a segment of the reaction path: div Fu, X1 , X2 . 0 (11)

papers by Strozzi and Zaldivar (e.g., see Strozzi et al., 1999; Zaldivar et al., 2003). The general conclusion arising from this analysis indicates that most of the existing safety criteria can not be directly used for an EWDS, because either they work off-line or they are model-based; so expensive and time consuming kinetic studies are required, which are seldom applied to processes carried out in batch and semi-batch reactors. A simple on-line safety criterion has been based on measurements of the reactor and cooling jacket temperatures and some their derivatives: for the recognition of a dangerous situation it is enough to check the following expressions (Hub and Jones, 1986): d2 TR .0 dt2 and dTR Tc .0 dt (10b) (10a)

This criterion does not require any detailed information on the process carried out in the reactor and it can be also applied for the detection of thermal runaway in other equipment, e.g., in storage tanks. Its main disadvantage is that the noise, always measured in experimental signals, is amplied and signicantly affects the results of evaluations, so false alarms may be triggered. A very useful discussion of practical tests of this method as well as the results obtained is given by (Zaldivar, 1991b). Strozzi and Zaldivar developed a new method for assessing the thermal stability of batch and semibatch chemical reactors (e.g., see Strozzi and Zaldivar, 1994a; Strozzi et al., 1994b; Alos et al., 1996a,b). In their method the Lyapunov exponents were used to calculate the sensitivity and to formulate a new safety criterion. An essential advantage of this method, in comparison to the previous ones, is that it can be applied for on-line runaway detection. This was made possible by applying a phase-space reconstruction technique and resulted in the fact that the divergence of the system can be evaluated from the measurement of one system variable only. The background of this method

The research group led by Strozzi and Zaldivar developed a method to calculate the divergence on-line, using one representative measurable variable of the system. State reconstruction techniques and a theory of embedding have been applied for this purpose. The method based on a delayed temperature vector turned out as the most robust one with respect to noised experimental data, but also pressure measurements have been successfully tested (e.g., see Bosch et al., 2004d and a). The divergence criterion developed has been tested and successfully validated for different types of reactors (batch, semibatch and CSTR), different operating modes (isothermal, isoperibolic and adiabatic) as well as for different schemes of reaction kineticsa.o. for simple and complex (parallel, consecutive, mixed and equilibrium) reactions, homogenous liquid and heterogeneous liquid liquid reactions, polymerization reactions and so on (see the references cited above). Several methods employing the state reconstruction technique with use of one or more temperature sensors have been developed and successfully tested for early detection of runaway (see Bosch et al., 2004b; Zaldivar et al., 2005). It has been found that for all considered batch and semi-batch runs only one temperature sensor is usually sufcient to reconstruct the divergence with a reasonably accuracy, so to detect runaway. The developed method of runaway detection, employing only one temperature sensor, simplies considerably an application of the EWDS in industrial practice. In case of one single temperature sensor we have to be sure that the measured temperature is representative for the entire reactor, i.e., that perfect mixing has been achieved. In case of failure of the stirring system signicant non-uniformities of temperature and reactants concentrations inside the reactor will occur, so a proper location of the required number of the temperature sensors is essential. Computational uid dynamics (CFD) have been used to investigate this EWDS method and to identify hot-spots appearing in the reaction mass (see Rudniak et al., 2004; Molga et al., 2004; Milewska et al., 2005). The CFD models of stirred tank reactors for bench and industrial scale reactors and also for both homogeneous and heterogeneous reaction systems, enable a determination of local and instantaneous values of reactor temperatures and reactant concentrations in badly mixed vessels.

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WESTERTERP and MOLGA reactor temperature. In this area a very promising approach, developed and tested by Zaldivar, Strozzi, Westerterp and their collaborators, must be noticed. From this approach, initially based on the divergence criterion and then subjected to several modications, a universal and robust EWDS has been developed. In these transformations the state space reconstruction has been employed, so the detection of runaway with the developed EWDS has become possible by on-line measurement of one single operating parameter such as the reactor temperature or the reactor pressure, provided the latter can be considered as a variable representing the state of the reactor. The presented review can be concluded with the following corroborations, which are particularly useful and signicant for the ne chemicals industry: . Off-line safety assessments for batch and semibatch reactors, to determine inherently safe operating conditions, should be carried out on the basis of the boundary diagram. This approach does not demand for detailed kinetic investigations, only a few measurements with a laboratory reaction calorimeter are needed. . For on-line runaway detection in reactors operated according to the state of the art, the EWDS system elaborated by Zaldivar, Strozzi and their collaborators should be employed. It is a robust early warning detection system, for which only an on-line, single point measurement of the reactor temperature (and/or the reactor pressure) is needed. NOMENCLATURE
A E DHcAo VRo B RTc mcp f Tc ci cp Cp Co Da kc cBotdos E Ex k m m n q Q r R R RH (rcP )d =(rcP )c Ry St UAtdos =V rCp tdos T 1:05DTad,0 Tta Tc 1RH Co1 1t U heat exchange surface area, m2 dimensionless adiabatic temperature rise concentration of the ith component, mol m23 mass specic heat capacity, J kg21 K2 1 molar specic heat capacity, J mol21K21 Cooling number, see equation (9) for denition hler number Damko activation energy, J mol21 exothermicity number, see equation (7) for denition reaction rate constant, m3 mol21 s21 mass, kg distribution coefcient (liquid liquid system) number of moles, reaction order heat ow, W amount of energy, J reaction rate, mol m23 s21 conversion rate, mol s21 gas constant, J mol21 K21 ratio of heat capacities of the dispersed and the continuous phase reactivity number, see equation (8) for denition modied Stanton number dosing time, s temperature, K target temperature, K overall heat transfer coefcient, W m22K21

In off-line applications the results from CFD simulations can be directly converted into a spatial map of the local divergence of the system so, a detection of local hot spots and their propagation into a global runaway may be indicated. It can be particularly important for a socalled computer experimentation, during which different types of failures occurring in industrial reactors can be safely investigated. However, it must be clearly distinguished, that for industrial reactors of complex geometry local CFD predictions are difcult for experimental verications, so the results of CFD simulations should be treated as preliminary indications. SUMMARY AND CONCLUSIONS From statistical data, which report on the prime causes of incidents in batch and semibatch chemical reactors carrying out strongly exothermic reactions, the general conclusion arises that a thermal runaway in these reactors is still a problem of great importance. So, a robust safety assessment is always indispensable. Usually three lines of defense have to be considered to prevent thermal runaways in chemical reactors: choice of the right operating conditions, application of early warning detection system and methods to handle running away reactions. Because of its too specic nature, the last line of defense was not discussed in this review, while the former two have been considered in detail. The choice of safe or inherently safe reactor operating conditions is usually performed in an off-line analysis. Two main approaches can be here distinguished: the model-based analysis in which a detailed knowledge of the reaction kinetics is indispensable and the most recent approach based on the boundary diagram, which is particularly useful for the reacting systems with unknown reaction kinetics. In the last approach, based on the work of Westerterp and his collaborators which are published in the series of cited papers, safety boundary diagrams are employed to distinguish the inherently safe operating conditions for batch and semibatch reactors with liquid and liquid liquid reacting systems, respectively. In these safety diagrams in a plot of the coordinates Reactivity versus Exothermicity numbers, runaway and non-runaway regions can be easily distinguished (see Figure 3). In these safety diagrams the boundary lines are still a function of the Cooling number. The most relevant advantage of this approach is that even for the case, when a detailed reaction kinetics is not know, the problem of safety assessments can be tackled in a few days with use of the reaction calorimeter. Also the capability and applicability of the reaction calorimeter for safety assessments have been reviewed. Several applications, useful particularly for direct process safety improvement as well as for supporting assessments based on the use of boundary diagrams, have been indicated. Due to a failure of the cooling/stirring systems or a human mistake, different unexpected dangerous situations, which can lead to a runaway scenario, may occur even in a reactor operated along a safe trajectory. Taking into account that even a correct choice of safe operating conditions does not totally protect the reactor against a thermal runaway, the recent developments of early warning detection system have been reported. Such a warning detection system makes possible an early on-line prediction of the reactor states, which may lead to the uncontrolled rise of

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U (U A)0/(r cP VR k cB)0 V X Greek symbols UA a n1 mcP f kTc cAo dimensionless cooling capacity volume, m3 conversion

551

dimensionless external heat transfer coefcient dimensionless activation energy reaction enthalpy, J mol21 adiabatic temperature rise, K relative volume increase dimensionless temperature stoichiometric coefcient dimensionless time

g E=RTc DH DTad 1 E T Tc u RTc Tc n t t=tdos

Subscripts 0 c f F ow QFS R w

initial jacket, cooling, at cooling temperature uid (liquid reactor content) nal ow through the reactor wall quick onset, fair conversion, smooth temperature prole reactor, reaction reactor walls and inserts (stirrer and bafes)

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