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Transcript of 1 Bertrand Roduit 1, Franz Brogli 2, Francesco Mascarello 3, Mischa Schwaninger 3, Thomas Glarner 4,...
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Bertrand RoduitBertrand Roduit11, Franz Brogli, Franz Brogli22, Francesco Mascarello, Francesco Mascarello33, Mischa Schwaninger, Mischa Schwaninger33, Thomas Glarner, Thomas Glarner44, , Jacques WissJacques Wiss55, Markus Luginbühl, Markus Luginbühl66, Craig Williams, Craig Williams66, Pierre Reuse, Pierre Reuse77
11AKTS AG Advanced Kinetics and Technology Solutions, TECHNOArk 1, 3960 Siders, SwitzerlandAKTS AG Advanced Kinetics and Technology Solutions, TECHNOArk 1, 3960 Siders, Switzerland22Ciba Schweizerhalle AG, P.O. Box, CH-4002 Basel, SwitzerlandCiba Schweizerhalle AG, P.O. Box, CH-4002 Basel, Switzerland
33DSM Nutritional Products Ltd., Safety laboratory, 4334 Sisseln, SwitzerlandDSM Nutritional Products Ltd., Safety laboratory, 4334 Sisseln, Switzerland44F. Hoffmann-La Roche Ltd, Safety laboratories, 4070 Basel, SwitzerlandF. Hoffmann-La Roche Ltd, Safety laboratories, 4070 Basel, Switzerland
55Novartis Pharma AG, Novartis Campus, WSJ-145.8.54, 4002 Basel, SwitzerlandNovartis Pharma AG, Novartis Campus, WSJ-145.8.54, 4002 Basel, Switzerland66Syngenta Crop Protection Münchwilen AG, WMU 3120.1.54, 4333 Münchwilen, SwitzerlandSyngenta Crop Protection Münchwilen AG, WMU 3120.1.54, 4333 Münchwilen, Switzerland
77Swiss Safety Institute, Schwarzwaldallee 215, WRO-1055.5.02, 4002 Basel, SwitzerlandSwiss Safety Institute, Schwarzwaldallee 215, WRO-1055.5.02, 4002 Basel, Switzerland
www.akts.com
APSS 2009APSS 200920-23 October, 2009, Osaka, Japan20-23 October, 2009, Osaka, Japan
Estimation of Time to Maximum Rate under Adiabatic Conditions (TMRad) Using Kinetic Parameters Derived
from DSC - Investigation of Thermal Behavior of 3-methyl-4-nitrophenol
2
Adiabatic Runaway Scenario
Example of adiabatic runaway scenarioExample of adiabatic runaway scenario
Before :Before :
3
Example of adiabatic runaway scenarioExample of adiabatic runaway scenario
After :After :
Adiabatic Runaway Scenario
4
Analysis samples:
3-methyl-4-nitrophenol
CAS No: 2581-34-2
Objective: Determine the initial temperature for Time To Maximum Rate under adiabatic conditions TMRad = 24h
- Different suppliers (different batches) - DSC or ARC techniques were applied - Different DSC apparatus (various manufacturers)
Analysis Samples
5
Temperature (°C)325300275250225200175150125
Hea
tFlo
w (
W/g
)
5
4
3
2
1
0
-1
-2
-3
-4
ExoHeat : -2,194.016 (J/g) T : 198.92 and 344.13 (°C) Top of Peak : 294.34 (°C) Peak Height : 4.41 (W/g) Baseline Type : Tangential Sigmoid
128.16 (°C)
.
Typical DSC trace of Typical DSC trace of 3-methyl-4-nitrophenol 3-methyl-4-nitrophenol recorded at 4 K/min and recorded at 4 K/min and
sigmoid baseline construction. sigmoid baseline construction.
3-methyl-4-nitrophenol at 4 K/min
6
Temperature (°C)340320300280260240220200
Rea
ctio
n ra
te (
-/s)
2E-3
1.5E-3
1E-3
5E-4
0
.
The reaction rates for all samples at 4K/min. The reaction rates for all samples at 4K/min. Despite of the different experimental setups and sample origins the Despite of the different experimental setups and sample origins the
reproducibility of the DSC traces is acceptable. reproducibility of the DSC traces is acceptable.
Reproducibility of the DSC traces
7
22
TR
EConst
dt
d 1ln
11
22
33
33
=
ln
Theory: isoconversional
analysis &
baseline optimization
Differential isoconversional method
8Temperature (°C)340320300280260240220200
Rea
ctio
n ra
te (
-/s)
0.003
0.002
0.001
0
Rea
ctio
n pr
ogre
ss (
-)
1
0.8
0.6
0.4
0.2
0
1
.
.
2
4
8
0.50.25
4
0.250.5
12
48
4
.
Reaction rates dReaction rates d/dt and progresses /dt and progresses corresponding to the normalized DSC-signals for the corresponding to the normalized DSC-signals for the decomposition of all decomposition of all 3-methyl-4-nitrophenol samples under 3-methyl-4-nitrophenol samples under non-isothermal non-isothermal conditions. conditions. The The
values of the heating rates are marked on the curves. The comparison of the experimental and values of the heating rates are marked on the curves. The comparison of the experimental and simulated signals at chosen experimental conditions is shown in the respective insets.simulated signals at chosen experimental conditions is shown in the respective insets.
Reactions rate and progress: Non-isothermal
9Time (h)1614121086420
Rea
ctio
n ra
te (
-/s)
6E-4
5E-4
4E-4
3E-4
2E-4
1E-4
0
Rea
ctio
n pr
ogre
ss (
-)
1
0.8
0.6
0.4
0.2
0
240
260
250
190
230
220
210
200
190200210
220230
240
250
260
.
.
220
220
.
Reaction rates dReaction rates d/dt and progresses /dt and progresses corresponding to the normalized DSC-signals for the corresponding to the normalized DSC-signals for the decomposition of all decomposition of all 3-methyl-4-nitrophenol samples under 3-methyl-4-nitrophenol samples under isothermal isothermal conditions. conditions. The values The values
of the temperatures are marked on the curves. The comparison of the experimental and of the temperatures are marked on the curves. The comparison of the experimental and simulated signals at chosen experimental conditions is shown in the respective insets.simulated signals at chosen experimental conditions is shown in the respective insets.
Reactions rate and progress: Isothermal
10
Isothermal validationIsothermal validation
ARC validationARC validation
Initial temperature for TMRad 24h = ? °CInitial temperature for TMRad 24h = ? °C
Experimental Validation
11
=0=0 Or Or ==
=1=1 ==TTadad
From DSCFrom DSC
> 1000 kg> 1000 kgTheoryTheory
Determination of time to maximum rateDetermination of time to maximum rate under adiabatic conditions (TMRunder adiabatic conditions (TMRadad))
Adiabatic Adiabatic ConditionsConditions
Link between kinetics and TMRad
12
Temperature profile of an adiabatic Temperature profile of an adiabatic runaway reaction,runaway reaction,
TT
ad
iab
ati
cad
iab
ati
c
Tem
pera
ture
/Tem
pera
ture
/°C°C
Time /hTime /h
Determination of Determination of time to maximum rate under adiabatic conditions (TMRtime to maximum rate under adiabatic conditions (TMRadad))
Key parameters obtained from adiabatic experimentsKey parameters obtained from adiabatic experiments
=1=1 ==TTadad
TheoryTheory
Key parameters in adiabatic experiments
13
Temperature profile of an adiabatic Temperature profile of an adiabatic runaway reaction,runaway reaction,
corresponding self-heating ratecorresponding self-heating rate
TT
ad
iab
ati
cad
iab
ati
c
Time to Maximum RateTime to Maximum Rateadiabaticadiabatic
Maxim
um
Maxim
um
Self
heat
Self
heat
rate
rate
Self
heat
rate
/°C
/min
Self
heat
rate
/°C
/min
Tem
pera
ture
/Tem
pera
ture
/°C°C
Time /hTime /h
=1=1 ==TTadad
TheoryTheory
Determination of Determination of time to maximum rate under adiabatic conditions (TMRtime to maximum rate under adiabatic conditions (TMRadad))
Key parameters obtained from adiabatic experimentsKey parameters obtained from adiabatic experiments
Key parameters in adiabatic experiments
14Time (h)1614121086420
Rea
ctio
n P
rogr
ess
(-)
10.8
0.6
0.4
0.20
Tem
pera
ture
(°C
)
500
450
400
350
300
250
200
150
100
50 Reaction Progress: 0.0095 (-)
t: 11.29 (h)T: 183.81 (°C)
t: 15.67 (h)T: 421.65 (°C(
Typical ARC test for Typical ARC test for 3-methyl-4-nitrophenol 3-methyl-4-nitrophenol carried out in HWS mode. Having the kinetic carried out in HWS mode. Having the kinetic description of the reaction rate from the DSC data, one can estimate that the reaction description of the reaction rate from the DSC data, one can estimate that the reaction
progress a after ca. 11.3 h of HWS testing amounts to about 0.0095 (ca. 1%). From the time progress a after ca. 11.3 h of HWS testing amounts to about 0.0095 (ca. 1%). From the time at which the temperature of the detection limit (183.81°C) was reached the value of TMR at which the temperature of the detection limit (183.81°C) was reached the value of TMR
amounts to ca. 4.4h (15.67-11.29h). Solid line depicts the simulation being in a good amounts to ca. 4.4h (15.67-11.29h). Solid line depicts the simulation being in a good agreement with the experimental HWS-ARC data presented as symbols.agreement with the experimental HWS-ARC data presented as symbols.
Experimental Validation
15
Isothermal validationIsothermal validation
ARC validationARC validation
Initial temperature for TMRad 24h = ? °C Initial temperature for TMRad 24h = ? °C (F =1)(F =1)
Experimental Validation
16
Participant of round
robin test
Heating rates applied
(non-isothermal)
Temperatures applied(isothermal)
Hr ± Initial temperature for TMRad =
24 h
Sum of all correl. coeff.
0.25, 0.5, 1, 2, 4 200, 210, 220, 240 1961.2± 151.8 156.4 9960
0.5, 1, 2, 4, 8 2070.5 ± 166.7 153.6 9894
4, 4 220, 240, 260 2143.2 ± 115.1 148.9 9932
0.5, 2, 4, 8 210, 220, 230, 240 2133.8 ± 144.7 149.4 9934
2.5, 2.5 148
190, 200, 210, 220 2112.1 ± 76.5 152.5 9978
5 220, 230, 240, 250, 260 1655.8 ± 141.9 150.1 9972
Summary of the results of determination of the initial temperatures leading to Summary of the results of determination of the initial temperatures leading to TMRTMRadad = 24 h with AKTS-Thermokinetics Software by using all DSC data = 24 h with AKTS-Thermokinetics Software by using all DSC data
collected in round robin test.collected in round robin test.
Mean value for TMRMean value for TMRadad 24h = 151.27 ±3.01°C 24h = 151.27 ±3.01°C
TMRad 24 h
17
Isothermal validationIsothermal validation
ARC validationARC validation
Initial temperature for TMRInitial temperature for TMRadad 24h = 151°C 24h = 151°C ((=1) =1)
Experimental Validation
18
The correct determination of TMRThe correct determination of TMRadad based on DSC data based on DSC data requiresrequires
two important parameters two important parameters
(i) an advanced kinetics of the investigated reaction (i) an advanced kinetics of the investigated reaction and and
(ii) an adiabatic heat balance of the system.(ii) an adiabatic heat balance of the system.
‘‘Safety through calculations not by accidents’Safety through calculations not by accidents’
Conclusion
19
Advanced Kinetics and Technology Solutions
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armasuisse, Dr. P. Folly, Dr. A.Sarbach and B. Bergerarmasuisse, Dr. P. Folly, Dr. A.Sarbach and B. BergerSwiss Federal office of Public Health, Dr. V. DudlerSwiss Federal office of Public Health, Dr. V. Dudler
Univ. of Western Switzerland, Prof. J.N. Aebischer, Univ. of Western Switzerland, Prof. J.N. Aebischer, S. Gomez, B. AlonsoS. Gomez, B. Alonso
Swiss Institute of Safety and Security,Swiss Institute of Safety and Security,Dr. P. Reuse, Prof. F. Stoessel, Dr. H. Fierz Dr. P. Reuse, Prof. F. Stoessel, Dr. H. Fierz
Nitrochemie Wimmis AG, Dr. M. Ramin, Dr. U. Schädeli, Nitrochemie Wimmis AG, Dr. M. Ramin, Dr. U. Schädeli, Dr. B. VogelsangerDr. B. Vogelsanger
Acknowledgements Acknowledgements Our partners and friendsOur partners and friends