Industrial & Engineering Chemistry Research, Vol.55, No.45, 11664-11671, 2016
Kinetic Model Development for Dehydration of 2,3-Butanediol to 1,3-Butadiene and Methyl Ethyl Ketone over an Amorphous Calcium Phosphate Catalyst
A reaction network and kinetic model for the dehydration of 2,3-butanediol (2,3-BDO) to 1,3-butadiene (1,3-BD) and methyl ethyl ketone (MEK) on an amorphous calcium phosphate catalyst are proposed. The kinetic parameters of the model were estimated using experimental data obtained from a laboratory-scale fixed-bed reactor operated under isothermal conditions. Experiments were performed using a mixture of 2,3-BDO, 3-buten-2-ol (3B2OL), and N2 as feed, at temperatures ranging from 304 to 334.5 degrees C and gas hourly space velocity (GHSV) ranging from 1780 to 2222 h(-1). 2,3-BDO conversion varied from 6 to 100%; the selectivity of 1,3-BD ranged from 5 to 33 wt %, and the selectivity of MEK ranged from 31 to 34 wt %. Kinetic models based on the simple power law and Langmuir-Hinshelwood-Hougen-Watson model were developed to describe the dehydration of 2,3-BDO to 1,3-BD and MEK. Statistical and physicochemical criteria are used to contrast the performance of the two kinetic approaches. The power law model showed the highest capacity to represent the tendency of experimental data obtained by changing temperature and GHSV. The kinetic parameters indicate the following: (0 The reaction orders (n(1), n(3), n(4) = 0.0187; n(2) = 0.146) are very close to 0, meaning that reactor performance for 2,3-BDO dehydration is mainly determined by the temperature of the reactor not by the concentrations of reactants. (ii) The reaction routes that produce 1,3-BD demand activation energy that is higher than that of the others, explaining the quickly changing rate of 3B2OL and 1,3-BD selectivity and slowly changing rate of MEK and 2MPL selectivity with increasing temperature.