Abstract
A series of green deep eutectic solvents (DESs: ChCl-PTSA, ChCl-2PTSA and ChCl-3PTSA) prepared by mixing choline chloride (ChCl) and p-toluenesulfonic acid monohydrate (PTSA) were applied to catalyze the esterification of methanol and cinnamic acid to synthesize methyl cinnamate. ChCl-3PTSA showed an excellent catalytic effect, hence it was adopted to explore the effects of agitation speed, catalyst loading, molar ratio of reactants and temperature on the conversion of cinnamic acid in detail. After that, the data obtained by kinetic experiments at 331.15–351.15 K were dynamically correlated by the activity-based pseudo-homogeneous (PH) model, and the kinetic parameters were compared with those obtained adopting p-toluenesulfonic acid and sodium bisulfate as catalysts. The relative deviations between the experimental values of cinnamic acid conversion catalyzed by ChCl-3PTSA and the calculated results by PH model are ~ 5%, which indicates that the model is applicable. Furthermore, the activity of ChCl-3PTSA did not decrease significantly after being conducted five cycles, indicating ChCl-3PTSA has the prospect of industrial application for the esterification reaction.
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Abbreviations
- ChCl:
-
Choline chloride
- PTSA:
-
P-Toluenesulfonic acid monohydrate
- DESs:
-
Deep eutectic solvents
- z :
-
The number of moles of PTSA relative to per 1 mol of ChCl
- K x :
-
Equilibrium constant base on mole fraction
- K e :
-
Equilibrium constant based on activity
- a i :
-
Activity of component i
- r :
-
Reaction rate (mol min−1 g−1)
- M cat :
-
Catalyst weight (g)
- γ i :
-
Activity coefficient of component i
- x i :
-
Mole fraction of component i
- k 1 :
-
Forward reaction rate constant (mol min−1 g−1)
- k 2 :
-
Reverse reaction rate constant (mol min−1 g−1)
- SRS:
-
Sum of residual squares
- T :
-
Temperature (K)
- E ai :
-
Activation energy (kJ mol−1)
- Δr G 0 :
-
Gibbs energy change (kJ mol−1)
- Δr S 0 :
-
Reaction entropy (J mol−1 K−1)
- Δr H 0 :
-
Reaction enthalpy (kJ mol−1)
- R 2 :
-
Linear regression coefficient
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All authors whose names appear on the submission made substantial contributions to the conception and design of the work. The first draft of the manuscript was written by LT, and JX made great contributions to the revision of the manuscript. All authors read and approved the final manuscript.
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Tang, L., Guo, Y., Xu, J. et al. Synthesis of methyl cinnamate catalyzed by deep eutectic solvents based on choline chloride: kinetic studies. Braz. J. Chem. Eng. 39, 715–726 (2022). https://doi.org/10.1007/s43153-022-00221-x
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DOI: https://doi.org/10.1007/s43153-022-00221-x