Reaction Calorimetry in Continuous Flow Mode: A New Approach for the Thermal Characterization of High Energetic and Fast Reactions

Mortzfeld, Frederik B.; Polenk, Jutta; Guélat, Bertrand; Venturoni, Francesco; Schenkel, Berthold; Filipponi, P

doi:10.1021/acs.oprd.0c00117

Cited by 15 publications

(34 citation statements)

References 39 publications

(15 reference statements)

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“…Organometallic reactions and nitrations also fall into the category of type A reactions. Examples include the investigation of an organometallic reaction using flow calorimetry by Mortzfeld et al 19 and the nitration of phenol with concentrated HNO 3 as investigated by Glotz et al 22 Type B reactions, which are characterized by reaction halflives between 1 s and 10 min, are suitable for flow calorimetry only to a limited extent. Since in most cases microreactors are used for flow chemistry, a certain residence time is given by the reactors' internal volume and feeding rate of reactants.…”

Section: ■ Classification Of Calorimetersmentioning

confidence: 99%

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Advances in Continuous Flow Calorimetry

Frede

Maier

Kockmann

et al. 2022

Org. Process Res. Dev.

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Calorimetric data from chemical reactions such as reaction enthalpy, adiabatic temperature rise, and activation energy are essential for reaction safety and scale-up from laboratory investigations to reactor design and operation. Typically, these data are gained from batch calorimeters with sophisticated setups and elaborate measurement procedures. Continuous flow calorimeters, compared with batch setups, have different mixing and heat transfer characteristics and enable harsh reaction conditions, particularly within microstructured reactors with their enhanced heat transfer capability. This review provides an overview of currently investigated and applied flow calorimeters in research and development in relation to existing concepts. Novel approaches for heat flux measurements as well as integrated sensors are presented. Safety aspects of flow chemistry are a main driver, but additionally, low material consumption is important in early process development. Limitations of the concepts are presented with a comprehensive literature overview of flow calorimetry to show that continuous flow calorimeters form a new tool in process development and safety engineering, particularly with microstructured devices and novel sensing techniques.

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Section: ■ Classification Of Calorimetersmentioning

confidence: 99%

“…The development of flow calorimeters is therefore of great interest for the design and operation of flow reactors. 19 In summary, the combination of microreactors and reaction calorimetry offers the following advantages:…”

Section: ■ Introductionmentioning

confidence: 99%

Advances in Continuous Flow Calorimetry

Frede

Maier

Kockmann

et al. 2022

Org. Process Res. Dev.

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“…The closer this determination is to the industrial process, the more robust safety data are obtained. For example, Mortzfeld et al [7] found deviations in non-selective reactions when they were investigated using batch calorimeters or continuous flow calorimeters. Several flow calorimeters have been developed measuring the enthalpy of reaction using thermoelectric heat flow [8][9][10], infrared thermography [11], or segmental temperature sensors [7].…”

Section: Introductionmentioning

confidence: 99%

Simultaneous determination of enthalpy of mixing and reaction using milli-scale continuous flow calorimetry

Steinemann

Rütti

Moser³

et al. 2022

J Flow Chem

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A simultaneous determination of the enthalpy of mixing and reaction in a scalable continuous milli-scale flow calorimeter is investigated. As obtained calorimetric data is pivotal for the safety assessment of chemical reactions and processes. The acid-catalysed selective, homogeneous hydrolysis of acetic anhydride with half-lives from a few seconds to a few minutes is investigated as a model reaction. For the enthalpy of mixing 7.2 ± 2.8 kJ/mol and for the enthalpy of reaction −60.8 ± 2.5 kJ/mol were determined. For reactions that show complete conversion in the continuous reactor, a technique is introduced to further improve the accuracy of the reaction enthalpy determination. Thereby, the resolution of the observed temperature profile is increased by measuring the profile at different flow rates. Applying this procedure, the reaction enthalpy of −62.5 kJ/mol was determined which is in good agreement with literature values for this model reaction. Graphical abstract

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“…For the development of accurate kinetic models that assist chemical reactor development, design and optimization, extensive knowledge of interaction between reaction kinetics and hydrodynamics is essential [4]. Thus, the interest in the development of continuous flow calorimeter increases constantly [5][6][7][8]. Moreover, the miniaturization of calorimetry enables the investigation of fast and highly exothermic reactions under safe conditions due to the superior temperature control when compared to standard batch equipment [9].…”

Section: Introductionmentioning

confidence: 99%

Software-guided microscale flow calorimeter for efficient acquisition of thermokinetic data

2021

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Fast chemical process development is inevitably linked to an optimized determination of thermokinetic data of chemical reactions. A miniaturized flow calorimeter enables increased sensitivity when examining small amounts of reactants in a short time compared to traditional batch equipment. Therefore, a methodology to determine optimal reaction conditions for calorimetric measurement experiments was developed and is presented in this contribution. Within the methodology, short-cut calculations are supplemented by computational fluid dynamics (CFD) simulations for a better representation of the hydrodynamics within the microreactor. This approach leads to the effective design of experiments. Unfavourable experimental conditions for kinetics experiments are determined in advance and therefore, need not to be considered during design of experiments. The methodology is tested for an instantaneous acid-base reaction. Good agreement of simulations was obtained with experimental data. Thus, the prediction of the hydrodynamics is enabled and the first steps towards a digital twin of the calorimeter are performed. The flow rates proposed by the methodology are tested for the determination of reaction enthalpy and showed that reasonable experimental settings resulted. Graphical abstract A methodology is suggested to evaluate optimal reaction conditions for efficientacquisition of kinetic data. The experimental design space is limited by thestepwise determination of important time scales based on specified input data.

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Reaction Calorimetry in Continuous Flow Mode: A New Approach for the Thermal Characterization of High Energetic and Fast Reactions

Cited by 15 publications

References 39 publications

Advances in Continuous Flow Calorimetry

Advances in Continuous Flow Calorimetry

Simultaneous determination of enthalpy of mixing and reaction using milli-scale continuous flow calorimetry

Software-guided microscale flow calorimeter for efficient acquisition of thermokinetic data

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