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

Transcription

1 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

2 2 3

3 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%. Phi-Tec DSC 131 evo Sensys evo 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) -120 to 830 (or 600) C Temperature Range 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 to 2 C/min scanning rate +/- 0.1% calorimetric precision 350, 600 and 1000 bar (5075, 8700 and 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.) 4 5

4 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. 6 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) Heat flow (W/g) 0.2 Temperature (C ) Time (h) DSC Heat : -1,864.7 (J/g) A SADT Kinetics TMR 280 ad 24h B 240 Φ=1 Φ= D Temperature (C ) C Time (h) TMR ad 24h 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. 7

5 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 w w w. s e t a r a m. c o m s a l e s e t a r a m. c o m SETARAM INSTRUMENTATION 7 rue de l Oratoire Caluire - France Phone +33(0) Fax +33(0) SETARAM Inc Central Ave. Suite 3D Newark, CA USA Phone +1 (510) Fax +1 (510) SETARAM China Rm 1808, 618 Shangcheng Rd, Shanghai, China Phone Fax 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