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10.1016@S0950 42309900061 3 PDF
10.1016@S0950 42309900061 3 PDF
www.elsevier.com/locate/jlp
a
Safety and Environmental Technology Group, Chemical Engineering Department, ETH Zentrum, CH 8092 Zürich, Switzerland
b
Aventis Research and Technologies (former Hoechst AG), Frankfurt a. M., Germany
Abstract
Recently, a method for estimating the time to maximum rate under adiabatic conditions (TMRad) from non-isothermal DSC
measurements was presented by Keller, A., Stark, D., Fierz, H., Heinzle, E., & Hungerbühler, K. (1997). J. Loss. Prev. Process.
Ind., 10, 31–41. The method was tested on the basis of isoperibolic data only, because data from adiabatic experiments were not
available. In this study we used results from 180 Dewar vessel experiments with an adiabatic shield and the corresponding dynamic
DSC measurements provided by Aventis Research and Technologies (former Hoechst AG) to test the estimation method suggested.
The data were obtained for reaction mixtures, bottom residuals, reaction residuals, and products. We found that in all cases the
predicted TMRad at a given temperature was shorter than the experimental value determined from adiabatic measurements. This
result shows that the TMRad estimation method is useful as a screening tool for the assessment of thermal risk. Furthermore, the
estimation method introduced by Keller et al., is more on the safe side than other common and often applied estimation methods
like the so-called 100 degree rule or the 50 degree rule. We also describe how to derive adiabatic induction times for different
temperatures by using a minimum number of adiabatic experiments. 1999 Elsevier Science Ltd. All rights reserved.
Keywords: Safety screening; DSC; Adiabatic Dewar experiments; Time to maximum rate
0950-4230/00/$ - see front matter 1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 5 0 - 4 2 3 0 ( 9 9 ) 0 0 0 6 1 - 3
8 J. Pastré et al. / Journal of Loss Prevention in the Process Industries 13 (2000) 7–17
Nomenclature
ADT 24 Temperature at which TMRad is 24 h derived from adiabatic measurements [K]
c Concentration [mol m⫺3]
cp Heat capacity [J kg⫺1 K ⫺1]
cp,cor Corrected Heat capacity [J kg⫺1 K ⫺1]
cp,sample Heat capacity of sample [J kg⫺1 K ⫺1]
Dewarcor Correction for Dewar vessel [J K ⫺1]
DSC Differential Scanning Calorimetry
Ea Arrhenius activation energy [J mol⫺1]
⌬hR Specific Enthalpy of reaction [J kg⫺1]
k0 Preexponential factor
m Mass of sample [kg]
q̇ Heat release rate [W kg⫺1]
q̇0 Heat release rate at T0 [W kg⫺1]
q̇onset Heat release rate at Tonset [W kg⫺1]
R Universal gas constant [J mol⫺1 K ⫺1]
T Temperature [K]
⌬Tad Adiabatic temperature rise [K]
T0 Temperature at which TMRad is calculated [K]
TMRad Time to maximum rate at adiabatic conditions [s]
Tonset Temperature were heat release rate signal can be differentiated from baseline [K]
To,24 Temperature at which TMRad is 24 h derived from dynamic DSC measurements [K]
Tq̇=0.1 W/kg Temperature at which q̇=0.1 W/kg [K]
Tq̇=0.5 W/kg Temperature at which q̇=0.5 W/kg [K]
Texo Temperature which is concerned as safe in the German guidelines (1994) [°C]
t Time [s]
suggested. The data were provided by Aventis Research Usually the value of Ea is unknown. One possibility
and Technologies and comprise reaction mixtures, bot- to estimate an activation energy is by measuring the heat
tom residuals, reaction residuals, and products. We also release rate at different temperatures in a number of isop-
used experimental data measured by Grewer and Klais eribolic DSC measurements. The logarithmic heat
(1988, 1992), which were obtained for pure substances. release rate has then to be plotted against the correspond-
ing inverse temperature to derive the activation energy
1.1. Estimation of TMRad from dynamic DSC as the slope of the resulting line (Grewer & Klais, 1988).
measurements Instead of using this procedure, a very conservative esti-
mation of Ea,m=50 kJ/mol was used in this study. This
Many decomposition reactions can be described by an is a rather low value for a decomposition reaction. To
Arrhenius model. Assuming a zeroth order reaction, the obtain the heat release rate q̇0 at a certain initial tempera-
following expression for TMRad can be derived (Frank- ture T0, the conditions at the onset (q̇onset and Tonset) of
Kamenetzkii, 1969; Townsend & Tow, 1980): a dynamic DSC curve are used. The temperature of the
onset point Tonset is defined as the temperature where the
cp·R·T 20
TMRad⫽ (1) heat rate signal can first be differentiated from the base-
q̇0·Ea line temperature reading by visual inspection. Keller et
where T0 [K] is the start temperature, q̇0 [W kg⫺1] the al. (1997) assumed that the heat release rate at the onset
corresponding heat release rate, Ea [J mol⫺1] the Arrhen- point q̇onset is of the order of 20 W/kg (Townsend &
ius activation energy, R [J mol⫺1 K ⫺1] the gas constant, Tow, 1980). This minimal detectable heat release rate
and cp [J kg⫺1 K ⫺1] the specific heat of the reaction depends on the sensitivity of the instrument and on the
mass. In this model the concentration decrease is neg- curvature of the baseline. The conversion at the onset
lected, so that the calculated TMRad is always shorter point is negligibly small, so it can be neglected. By
than the real adiabatic value and, thus, is on the con- using q̇onset (20 W/kg) and assuming an Arrhenius model
冉 冊
servative side. To calculate TMRad not only the heat
release rate q̇0 but also an Arrhenius activation energy Ea
q̇⫽k0·exp ⫺ ·f(c)·(⫺⌬hR) (2)
Ea are needed. RT
J. Pastré et al. / Journal of Loss Prevention in the Process Industries 13 (2000) 7–17 9
q̇0⫽q̇onset·exp 冉冉
Ea 1
⫺
1
R Tonset T0 冊冊 (3)
Using this value for q̇0 and an estimated value for the
activation energy it is possible to calculate TMRad using
Eq. (1). The resulting estimated TMRad is a conservative
value, because the extrapolation is based on a zeroth
order Arrhenius model and a low activation energy
which leads to an overestimated value of q̇0 (Keller et
al., 1997). Inserting Eq. (1) into Eq. (3) a temperature
with a time to maximum rate of more than 24 h can be
defined, referred to as To,24:
To,24⫽ 冉 1 R
⫺ · ln
Tonset Ea 冉 T 2o,24·R·cp
Ea·TMRad·q̇onset 冊冊 −1
(4)
2. Experimental
of a technical apparatus with a volume of about 1 to 5 given below. The next step is to measure the adiabatic
m3 (Grewer et al., 1989), the Dewar test can simulate in pressure and temperature profiles of the sample and the
a very easy way the thermal behaviour of large sample corresponding oven temperature. Then the differential
mass. This means that the results can be transferred temperature (dT/dt) and pressure (dp/dt) increases are
directly to the plant conditions without substantial cor- plotted against inverse temperature to obtain information
rection of the experimental data. on the reaction rate and the amount of gas which is pro-
This method uses a massive autoclave around the duced at a certain temperature.
Dewar flask. An aluminium block oven with electrical The last step is the extrapolation of the experiment to
heaters produces a homogeneous temperature distri- a storage temperature at which TMRad will be 24h (ADT
bution resulting in an adiabatic shield (Fig. 2) around 24) as shown in the following example, in which the
the Dewar flask. The top of the vessel is closed with an evaluation of the Pressure increase is not discussed,
insulating lid. A magnetic stirrer is used for the investi- because this information is not needed to obtain ADT
gation of heterogeneous liquids. 24 values.
The storage temperature of the adiabatic experiments Temperature and pressure profiles of adiabatic experi-
and the inserted mass are determined using the former ments normally look as shown in Fig. 4. The reaction
DSC results like onset temperature and heat of reaction. mass reaches the oven temperature very slowly because
Normally about 200 g of the test substance is the start of the isolation of the Dewar. This temperature is called
material in the Dewar vessel. The sample- and oven tem- storage temperature T0, which is 160°C in this example.
perature and the pressure are measured and recorded The time-span in going from the oven temperature to
using a computer. The external heat flow leads to a tem- runaway is called induction time or time to maximum
perature equilibrium between the autoclave and the sam- rate. It is important that the time span of the adiabatic
ple. If self heating is registered after reaching the storage temperature rise is sufficient for allowing observation of
temperature, the oven temperature follows the sample the kinetic behaviour. The induction time should be
temperature with less then 0.3 K difference. The appar- between 10 and 40 hours. This is necessary since extra-
atus is able to determine heat production rates of 100 polation is more robust when regression is done over a
mW/kg. longer time period. On the other hand, if adiabatic induc-
tion time takes too long there is a possibility that the
2.1. Evaluation procedure reaction mixture is heated up very slowly by an unin-
tended heat input caused by a controller.
2.1.1. Determination of ADT 24 In Fig. 5 the logarithm of dT/dt is plotted against
In this chapter we present the method of evaluating inverse temperature Eq. (8) in a typical Arrhenius dia-
the ADT 24 at Aventis by using an example (Figs. 3– gram.
5). The first step is to carry out a DSC measurement of
a sample (Fig. 3) to decide which amount of substance dT ⬘ Ea
ln ⫽k 0⫺ (8)
(derived from specific heat of reaction) and which stor- dt R·T
age temperature (derived from the onset temperature)
should be used in the Dewar experiment. A detailed dis-
cussion on how to determine the onset temperature is The lowest self heating rate can be observed at storage
temperature. Below this temperature the sample is heated
resulting in a larger dT/dt than at the storage tempera-
ture. The measurement is reliable and extrapolations are
allowed if a straight line describes the behaviour
between ln dT/dt and the inverse temperature is visible.
In this simple example the plot shows a linear depen-
dency between 160°C and 260°C. A zeroth order kinetic
model is fitted to the linear part as shown in Fig. 5. This
kinetic model is on the safe side because the reaction is
not becoming slower at higher degrees of conversion. It
is also possible to fit a first order kinetic model to the
data when the curve of temperature increase versus
inverse temperature flattens for higher temperatures.
From the slope of the straight line a value for the acti-
vation energy can be calculated.
Finally, a simulation of heat production q̇ is done by
multiplying the rate of temperature increase with the cor-
Fig. 2. Experimental set up of a Dewar test with an adiabatic shield. rected specific heat of the sample cp,cor.
J. Pastré et al. / Journal of Loss Prevention in the Process Industries 13 (2000) 7–17 11
Fig. 4. Representative courses of oven temperature (grey line), sample temperature (black line) and pressure (dashed line) as a function of time
in an adiabatic Dewar experiment corresponding to Fig. 3.
Fig. 5. Semi-logarithmic plot of temperature increase versus inverse temperature (䉬) corresponding to Fig. 3. Simulation of the heat production
(grey line) and a fit of zeroth order kinetics (black line) are shown. A Celsius scale is included for easier reading.
Fig. 6. Semi-logarithmic plot of the induction time (䉬) versus the inverse temperature corresponding to Fig. 3. Straight line: Extrapolation of
the induction time to lower temperatures. A Celsius scale is included for easier reading.
J. Pastré et al. / Journal of Loss Prevention in the Process Industries 13 (2000) 7–17 13
observed. In the example shown in Fig. 6 linear behav- exotherm because in most cases the first exothermic pro-
iour can be observed between 160 and 200°C. The point cess has a rather small reaction heat and often the adia-
of intersection of the line representing an induction time batic measurement has to be done at temperatures above
of 1440 min (dashed line in Fig. 6) and the extrapolated the onset of the first process, so that the kinetic behav-
line yields the temperature where TMRad is 24 h, which iour of the first process is not visible in the adiabatic
is 158°C for the chosen example. measurement. In dubious cases it is important to use the
Another check to decide whether the chosen model first exotherm to be on the safe side. In the next chapter
(zeroth or first order) is consistent and an extrapolation we will discuss what happens when the different onsets
is possible is the following one: The activation energy are chosen.
which results by multiplying the slope of the linear part
of Fig. 6 by R should be of the same order of magnitude
as the activation energy obtained by the model determ- 3. Results and discussion
ined in Fig. 5. The results obtained for the example are
given in Table 1. In Fig. 9 the ADT 24 values obtained from 180 adia-
The determination of ADT 24 is only allowed if the batic experiments are plotted versus the onset tempera-
earlier described kinetic fitting is feasible and if the adia- tures of the corresponding DSC measurements. Two dif-
batic time to maximum rate is of the order of one day ferent data sets are shown. The open symbols represent
or at least greater than 600 minutes. data measured and evaluated by Grewer and Klais
(1992). The closed symbols represent measurements
2.1.2. Determination of Tonset done at Aventis in the last three years and are presented
For the determination of the onset temperature a tem- above. In the plot three straight lines are shown which
perature programmed DSC plot is used and the onset of represent the model based estimation method, the 100
the first exothermic reaction is visually determined. A degree rule, and the 50 degree rule given in Eqs. (5)–
typical example is shown in Fig. 3. (7), respectively. The slope of the line which represents
When different choices for the baseline exist, the read- the estimation method Eq. (5) is smaller than the slope
ing of the onset temperature becomes more difficult as of the two other parallel lines. At onset temperatures
shown in Fig. 7. When an endothermic process occurs over 170°C the suggested estimation method Eq. (5)
before the exothermic decomposition reaction it will gives a much more conservative prediction of ADT 24.
generally be difficult to decide when the exothermic pro- Below onset temperatures of 170°C this behaviour is dif-
cedure starts. In our example the onset is chosen to be ferent. At low temperatures the 100 degree rule Eq. (6)
145°C because the exothermic process is separated from is more conservative than the estimation method Eq. (5).
the endothermic process. If a separation of these two For a reliable prediction ADT 24 values derived from
processes was not possible we always used the minimum estimation rules must be smaller than values derived
of the endotherm in order to be on the safe side. from adiabatic experiments. This means that all data
There are samples which may lead to difficulties when points should lie above the lines representing the rules.
calculating ADT 24 from dynamic DSC curves, namely This requirement is not fulfilled by the 50°C rule Eq.
those with an additional exotherm before the main exo- (7) in many cases (Fig. 9).
thermic process as shown in Fig. 8. For our kinetic Also the condition Tonset minus 100°C Eq. (6) will lead
evaluation we often chose the onset of the main to ADT 24 values which in some cases are not safe
Table 1
Parameters characterising the example shown in Figs. 3–6
Fig. 7. A dynamic DSC measurement with an endothermic process preceding an exothermic process. Possible choices of onset temperatures
are shown.
Fig. 8. A dynamic DSC measurement with a small exotherm before the main exotherm. The resulting data points derived by using different
onsets are shown in Fig. 9.
enough. Eight points lie under the line representing the From Fig. 9 some remarkable measurements can be
100 degree rule and quite a few points are situated very identified. One is acroleine, which is from the data set
close to that rule, especially at higher temperatures. On compiled by Grewer and Klais (1992). In that special
the other hand, the suggested model based estimation case the onset is at 70°C while the sample could be
method fulfils the requirement for all samples. For the stored for 24 hours at 110°C until the runaway occurs.
data investigated in this study it would not always be We think this behaviour is due to a polymerisation.
appropriate to use the 100 degree rule even though the Another substance measured by Grewer and Klais
onsets of the first exotherm were used. (1992) produces the highest onset of all. It is sodium
J. Pastré et al. / Journal of Loss Prevention in the Process Industries 13 (2000) 7–17 15
Fig. 9. The ADT 24 values are plotted against the corresponding onset temperatures (䉬: new data; 䉫: data of Grewer & Klais, 1988, 1992). The
100 degree rule (grey line) (Cronin, Nolan & Barton, 1987; Hofelich & Thomas, 1989), the 50 degree rule (dashed line) and the model based
estimation method (black line) as given in Eq. (5) of Keller et al. (1997) are shown.
To show what happens when the wrong onset is used, reaction. The two possible onsets are marked in Fig. 9.
we plotted an adiabatic measurement using different When the onset of the first exotherm is used the corre-
onset temperatures of the DSC. The DSC plot in Fig. 8 sponding experimental ADT 24 values are further away
shows a small exotherm before the main decomposition from the estimation methods and, thus, move on the safe
16 J. Pastré et al. / Journal of Loss Prevention in the Process Industries 13 (2000) 7–17
3.2. Outlook
suggestions, valuable discussions and corrections. We Gimzewski, E., & Audley, G. (1993). Thermochimica Acta, 214,
also would like to thank D. Mank and F. Ernst for their 129–140.
Grewer, T. (1994). Thermal hazards of chemical reactions. Amster-
help in making data available. dam: Elsevier.
Grewer, T., & Klais, O. (1988). Exotherme zersetzung. Düsseldorf:
VDI-Verlag.
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