Thermal analysis and calorimetry solutions - Setaram

T h e r m a l a n a l y s i s a n d c a l o r i m e t r y
s o l u t i o n s
calvet

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Process Safety
Our Products
The DSC131 evo is a highly robust and flexible DSC designed for busy laboratories
with a wide range of applications and users. This entry level DSC features a unique
and user changeable sensor, as well as a range of crucibles suitable for even the
most energetic materials:
The SENSYS evo is the premier DSC solution for Process Safety lab, the only DSC
with a truly representative sample size - more than 10 times that of traditional DSC
which allows for the accurate studies of heterogeneous mixtures and solutions.
The unique Calvet detector also provides Cp measurements with precision of 1%.
-120 to 830 (or 600)°C Temperature Range •
Phi-Tec
DSC 131 evo
Sensys evo
- 170 to 700 °C Temperature Range •
0.01 to 100°C/min •
+/- 0.5% calorimetric precision •
30 & 100 µl crucibles, up to 500 bar (7500 psi) •
0.01 to 30°C/min •
+/- 0.1% calorimetric precision •
Full autosampler option •
120 to 320 µl crucibles, up to 500 bar (7250 psi) •
Adiabatic Calorimetry is the final step in the design of
a safe and efficient process and HEL provides both
low and high Phi-Factor calorimeters which are critical
for determining the heat and pressure evolved during
uncontrolled runaway reactions. The NEW Phi-Tec I
(a modern alternative to the classic Dow developed
Accelerated Reaction Calorimeter) provides a unique
bench-top system for optimal lab design.
Both PHI-TEC I and II systems feature highly robust designs,
including solid copper heaters, for long term operation and fast
scan rates. The Phi-Tec II is a low Phi-Factor adiabatic calorimeter
for simulation of true plant conditions and therefore precise
calculations of vent sizes and emergency relief design.
The C80 Calvet Calorimeter is one of the most
powerful yet flexible tools available for the Process
Safety laboratory. The C80 has a wide range
of cells with a nominal volume of 12.5ml and as such
can be used for truly representative samples, high
precision Cp and also pressure measurement during
decomposition. The range of cells includes ability
to perform batch and semi-batch reactions under
atmospheric pressure, applied pressure or for
reactions that generate pressure. In scanning mode the
C80 accurately asses chemical runaways. The range
of sample cells include pressure up to 1000 bar (14600
psi), high pressure mixing and even batch cells with a
pressure transducer to measure evolved pressure.
• Ambient to 300° °C Temperature Range
• 0.001 to 2°C/min scanning rate
• +/- 0.1% calorimetric precision
• 350, 600 and 1000 bar (5075, 8700 and 14600 psi)
pressure vessels
• Mixing by membrane or reversal cell
• High pressure reactions up to 200 bar (3000 psi)
C80
Advanced Kinetics Software from AKTS provides model free isoconversional
kinetics for the precise modelling of runaway reactions.
Using only 4 or 5 DSC or C80 signals recorded at different heating
rates or at different isothermal temperatures a fully scaleable model
of the decomposition is generated which is then used to predict
such parameters as Time to Maximum Rate, SADT and stability in
different thermal environments. Using AKTS software it is possible to
use your adiabatic calorimeter as a single experiment verification, and
not a series of experiments at the start of a process evaluation.
• Automatic baseline optimization and construction
to DSC, nano and microDSC,
C-80, DTA, HFC, TG, TG-MS
• Model free kinetics : differential isoconversional
(Friedman), integral isoconversional
(Ozawa-Flynn-Wall), ASTM A698
• Model fitting kinetics : all common kinetic
models (i.e. autocatalytic and n-th order reactions (Fn),
nucleation (Avrami-Erofeev, An), diffusion (Dn)…etc)
AKTS
• Thermal aging: prediction of reaction progress at any temperature profiles:
isothermal, non-isothermal, stepwise,
temperature modulation, NATO/STANAG 2895
• Thermal safety: prediction of the reaction progress under adiabatic
(TMR ad
, thermal safety diagram and self heating rate curves) and
non-adiabatic conditions (Finite Element Analysis for critical design parameters:
SADT, critical radius and hot discharge temperature, cook-off, etc.)
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Applications
DSC
Customer Testimonial
Screening DSC : Analysis of propergol
The thermal decomposition of Propergol was
studied in a tightly closed high pressure crucible and
in an open crucible with milligram-scale samples.
Both experiments were run at a scanning rate of
3°C/min, under inert gas conditions.
It was observed that if the pressure rises during
decomposition (closed crucibles), both total heat
and reaction schemes are different. However,
three peaks remain at similar positions and shape
(cf. arrows), which was confirmed by built-in
deconvolution module of Calisto data treatment
software. The flexibility of SETARAM DSC’s allows
gaining fast access to the behaviour under varying
gaseous conditions (ex: ambient pressure vs. high
pressure, oxidizing vs. inert conditions, etc…)
“If I was setting up a new process safety laboratory, I would start
with a Calvet C80 Calorimeter because, even if it can’t solve each
process safety problem, it can be used for both synthesis reactions
(mixing cell) and decomposition reactions, by offering an
appreciable advantage, namely pressure measurement.
I would start with a Calvet C80 Calorimeter, even if it meant
supplementing it later on:
- with a reaction calorimeter that would give a more representative
measurement of the reactant accumulation and the heat release
rate of the synthesis reaction.
- with a DSC that offers greater screening productivity (scanning
rate) and a wider temperature range (>300°C).”
Prof. Francis STOESSEL,
Swiss Institute for the Promotion of Safety, Basle, SWITZERLAND.
Calvet 3D Calorimetry
Adiabatic Calorimetry
C80 : Analysis of diethyl sulfatel
The thermal decomposition of diethyl
sulfate was studied in a tightly closed high
pressure cell equipped with a pressure
measurement system.
The experiment was run at a scanning rate
of 0.5°C/min.
It was observed that the biggest
contribution to the pressure increase was
due to a first decomposition at about 175°C.
At the contrary, the second decomposition
peak is probably consuming part of the
gas produced at the first stage. More
information can be extracted from
this signal like pressure release rate,
condensable / non condensable gas ratio.
Phi-Tec
This curve shows the decomposition
reaction of 20% solution of N-nitroso-nmethyl-p-toluenesulfonamide
(NMTS)
in 1,4 Dioxane studied using Phi-Tec I
and Phi-Tec II calorimeters.
The decomposition was detected at
71°C by Heat-Wait-Search method.
Values of thermal inertia (Phi Factor)
close to one (perfect adiabaticity) can
be achieved with Phi-Tec II. It allows
simulating true plant conditions, where
heat accumulation strongly overcomes
heat evacuation.
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C80 : Polymerization study
The polymerization reaction of Vinyl Pyrrolidone in
presence of 4, 4’-azobis-cyanovaleric acid was
studied using a C80 Calorimeter with membrane
mixing cells.
Pyrrolidone and 4, 4’-azobis-cyanovaleric acid were
placed in the two chambers of the cell, separated by
a thin membrane.
The calorimeter was run under isothermal mode at
50 °C. In-situ mixing was provided by piercing of the
membrane.
It was observed that a first, sharp peak, probably linked
with the initiation of the reaction, was followed
by a slower kinetics and higher heat process.
This second peak is linked with the polymerization of
Vinyl Pyrrolidone.
Deconvolution of these peaks allows having access
to the heat of the initiation, and by difference, the
heat of polymerization could be calculated.
Kinetics
Advanced Kinetics
(A) The decomposition of 3-methyl-4-
nitrophenol was studied using DSC and C80.
Heat flow (W/g)
0.4 0.6 0.8 Heat flow (W/g)
0.2
Temperature (C°)
Time (h)
200 220 240 260 280 16 20 24 28 32
0.2
DSC
Heat : -1,864.7 (J/g)
A
SADT
360
320
Kinetics
TMR 280
ad 24h
B
240
Φ=1
Φ=3.2
200
D 160
0
180 200 220 240 260 280 0 5 10 15 20 25
Temperature (C°)
C
Time (h)
TMR ad 24h
165
160
155
150
Temperature (C°) Temperature (C°)
(B) The experiments at different
heating rates were treated with
AKTS - software.
(C) The variation of the runaway
time under true adiabatic mode
(Phi Factor = 1) can be calculated
for any process temperature.The
critical value TMR ad
= 24 hours is
obtained at 153°C. Dashed lines
depict the confidence interval.
(D) An adiabatic experiment with
a Phi factor = 3.2 was performed
for the final validation of the
simulation, and compared to
adiabatic data. SADT can be
determined applying “Finite
Element Analysis”.
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Some International references
Akzo Nobel - Netherlands
Aqura GmbH - Germany
Ashland Chemical Company - USA
Astra Zeneca - Sweden, UK
Bayer - Germany
Boehringer - Germany
Boehringer Ingelheim Chemicals - USA
Boehringer Ingelheim Pharmaceuticals - USA
Bristol-Myers Squibb - USA
Centre d’études de Gramat - France
ChemInform Saint-Petersbourg (CISP) – Russia
Chimex - France
Diosynth - Netherlands
DSM Nutritional Products AG - Switzerland
Firmenich Inc - USA
INERIS - France
Institute of Safety and Security - Switzerland
KOSHA - Korea
LG Chem - Korea
L’Oréal - France
Merck - USA
Mitsubishi Chemicals - Japan
National Research Institute of Fire & Disaster - Japan
NAVSEA (US Navy) - USA
Nestec - Switzerland
Novartis - Switzerland
Organon - Netherlands
Oril Industrie, Groupe Servier - France
Pfizer - UK, USA
Sanofi Aventis - France
Stazione Sperimentale per i Combustibili - Italy
Syngenta - UK
Synkem - France
The Dow Chemical Company - USA
Wacker Chemie - Germany
Zambon - Italy
Offices in United Kingdom, Germany,
Italy, Switzerland and Singapore
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SETARAM INSTRUMENTATION
7 rue de l’Oratoire
69300 Caluire - France
Phone +33(0)4 72 10 25 25
Fax +33(0)4 78 28 63 55
SETARAM Inc.
8430 Central Ave. Suite 3D
Newark, CA 94560 - USA
Phone +1 (510) 793 3345
Fax +1 (510) 402 4705
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Rm 1808, 618 Shangcheng Rd,
Shanghai, 200120 - China
Phone +86 21 50620017
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PIRANA.net • Specifications are given as indications only and are not contractual • 09/09
I n s p i r i n g I m a g i n a t i o n f o r M a t e r i a l S c i e n c e