Abstract
Reaction calorimetry of flow processes is important for scale-up and safety in flow chemistry. Due to the increasing number of flow processes, corresponding flow calorimeters are required as an alternative or addition to high-precision batch calorimeters. In this work, a milli-scale isoperibol continuous flow calorimeter was used to measure the heat of reaction based on an elaborated heat transfer model. This allows for reaction calorimetry without calibration. The model was tested with a selective, fast and exothermic neutralization reaction of acetic acid and sodium hydroxide at different flow rates, concentrations and viscosities. Deviations of the mean heats of reaction from the literature values were only about 2%. The calorimetric data can further be used for direct scale-up with tube bundle mixer heat exchangers having similar heat transfer characteristics. In addition, a reaction screening at different flow rates allows to find the maximum temperature and maximum heat generation. This data is useful in safety analyses of continuous processes. For these reasons, continuous reaction calorimetry provides a practical scale-up tool for flow processes.
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Abbreviations
- AcOH:
-
Acetic acid
- H2O:
-
Water
- h. visc.:
-
High viscous
- HTM:
-
Heat transfer medium
- M:
-
Molar
- NaOAc:
-
Sodium acetate
- NaOH:
-
Sodium hydroxide
- PFR:
-
Plug flow reactor
- SD:
-
Standard deviation
- VDI:
-
Verein Deutscher Ingenieure
- α :
-
Heat transfer coefficient [W m−2 K−1]
- α inside, i :
-
Heat transfer coefficient in the tube [W m−2 K−1]
- α outside, a :
-
Heat transfer coefficient in the shell [W m−2 K−1]
- β :
-
Flow factor [ml min−1 °C]
- η :
-
Viscosity [Pa s]
- η W :
-
Viscosity at the wall [Pa s]
- λ :
-
Thermal conductivity [W m−1 K−1]
- λ W :
-
Thermal conductivity of the wall [W m−1 K−1]
- ρ :
-
Density [kg m−3]
- τ :
-
Residence time [s]
- A a :
-
Heat transfer surface at the outside of the tube [m2]
- A i :
-
Heat transfer surface at the inside of the tube [m2]
- A m :
-
Mean heat transfer surface [m2]
- c A,0 :
-
Initial concentration of the limiting reactant A [mol m−3]
- c p :
-
Specific heat capacity [J kg−1 K−1]
- D :
-
Diameter [m]
- D i :
-
Inner diameter [m]
- ΔH r :
-
Reaction enthalpy [J mol−1]
- k :
-
Overall heat transfer coefficient [W m−2 K−1]
- L :
-
Length [m]
- \(\dot{\textit{m}}\) :
-
Mass flow rate [kg s−1]
- Q :
-
Heat [J]
- \({\dot{\textit{Q}}}_{\text{ex}}\) :
-
Exchanged heat flow [W]
- \({\dot{\textit{Q}}}_{\text{nex}}\) :
-
Not exchanged heat flow [W]
- Q r :
-
Specific heat of reaction [J kg−1]
- \({\dot{\textit{Q}}}_{\text{r}}\) :
-
Heat flow of reaction [W]
- s :
-
Wall thickness [m]
- t :
-
Time [s]
- t 1/2 :
-
Reaction half-life [s]
- t mix :
-
Mixing time [s]
- T :
-
Temperature [K]
- ΔT :
-
Temperature difference [K]
- ΔT ad :
-
Adiabatic temperature rise [K]
- V :
-
Volume [m3]
- V void :
-
Void volume [m3]
- \(\dot{\textit{V}}\) :
-
Volume flow rate [m3 s−1]
- w :
-
Flow velocity [m s−1]
- Nu :
-
Nusselt number [-]
- Nu inside :
-
Nusselt number in the tube [-]
- Nu outside :
-
Nusselt number in the shell [-]
- Pe :
-
Péclet number [-]
- Pr :
-
Prandtl number [-]
- Pr W :
-
Prandtl number at the wall [-]
- Re :
-
Reynolds number [-]
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Acknowledgements
The authors thank the Swiss Government and Innosuisse for their funding and Berthold Schenkel, Francesco Venturoni, Bertrand Guélat, Jutta Polenk, Paolo Filipponi and Frederik Mortzfeld from Novartis Pharma AG for helpful discussions.
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Highlights
• Flow calorimetry was achieved for a fast and selective reaction without the need for calibration
• The mean heat of reaction of the flow screening deviates only about 2% from the literature value
• Low pressure drop in the milli-scale flow reactor allows the use of high viscous process fluids
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Moser, M., Georg, A.G., Steinemann, F.L. et al. Continuous milli-scale reaction calorimeter for direct scale-up of flow chemistry. J Flow Chem 11, 691–699 (2021). https://doi.org/10.1007/s41981-021-00204-y
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DOI: https://doi.org/10.1007/s41981-021-00204-y