Abstract
As a green plasticizer, the industrial production of dioctyl terephthalate (DOTP) is still facing the problem of high energy consumption. To optimize the production process and reactor, it is essential to understand the kinetic behavior of reaction system. In this work, the two-step consecutive esterification of solid terephthalic acid (PTA) and 2-ethylhexanol (2-EH) catalyzed by tetrabutyl titanate was studied. First, the equilibrium constants and enthalpies of the two-step reaction were experimentally determined and validated by the group contribution methods. Then, a pseudohomogeneous kinetic model was developed, and the reaction order of PTA was corrected to reflect its solid phase characteristic. Non-isothermal kinetic experiments were carried out under different initial feed molar ratios and catalyst concentrations, and the kinetic parameters in the model were estimated by mathematical regression. The model predicted data agreed well with the experimental data. Finally, the analyses of reaction rate showed that the first-step reaction was the rate-controlling step of the whole esterification process.
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Abbreviations
- 2-EH:
-
2-ethylhexanol
- PTA:
-
terephthalic acid
- DOTP:
-
dioctyl terephthalate
- MEHTP:
-
mono-2-ethylhexyl terephthalate
- Mi :
-
molar mass of component i [g·mol−1]
- Ci :
-
concentration of component i [mol·L−1]
- C 0i :
-
initial concentration of component i [mol·L−1]
- C eqi :
-
equilibrium molar concentration of component i [mol·L−1]
- Cp :
-
constant pressure heat capacity [J·mol−1]
- Vsys :
-
volume of reaction system [L]
- R:
-
gas constant
- K:
-
equilibrium constant of reaction
- ΔHr :
-
enthalpy of reaction [kJ·mol−1]
- ΔH 0r :
-
standard enthalpy of reaction [kJ·mol−1]
- ΔH 0f :
-
standard enthalpy of formation [kJ·mol−1]
- ΔHvap,T :
-
enthalpy of vaporization at temperature T [kJ·mol−1]
- ΔHvap, b :
-
enthalpy of vaporization at the normal boiling point [kJ·mol−1]
- T:
-
absolute temperature [K]
- Tref :
-
reference temperature [K]
- Tc :
-
critical temperature [K]
- Tb :
-
boiling point temperature [K]
- Ea :
-
activation energy of reaction [kJ·mol−1]
- t:
-
reaction time [min]
- r:
-
reaction rate [mol−1·L−1·min−1]
- r0 :
-
initial reaction rate [mol−1·L−1·min−1]
- k:
-
forward reaction rate constants [mol−1.37·L1.37·min−1]
- kref :
-
forward reaction rate constant at the reference temperature [mol−1.37·L1.37·min−1]
- ml :
-
mass of liquid in the system [g]
- n 0i :
-
initial molar number of component i [mol]
- υ i :
-
stoichiometric coefficient of component i
- α :
-
reaction order of PTA
- ω i :
-
mass fraction of component i
- xDOTP :
-
mole fraction of DOTP
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Pseudo-homogeneous kinetic modeling of dioctyl terephthalate (DOTP) production by esterification of terephthalic acid and 2-ethylhexanol over tetrabutyl titanate catalyst
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Zhou, F., Cai, J., Mao, X. et al. Pseudo-homogeneous kinetic modeling of dioctyl terephthalate (DOTP) production by esterification of terephthalic acid and 2-ethylhexanol over tetrabutyl titanate catalyst. Korean J. Chem. Eng. 39, 2324–2333 (2022). https://doi.org/10.1007/s11814-022-1161-9
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DOI: https://doi.org/10.1007/s11814-022-1161-9