Chemical Engineering Science, Vol.202, 15-25, 2019
Study on phenol sulfonation by concentrated sulfuric acid: Kinetics and process optimization
Sulfonation process usually exhibit high reaction rate and low yield and selectivity of product in common reactors for its insufficient micromixing. This work employed a rotating packed bed (RPB) to intensify the micromixing of the phenol sulfonation process to improve the yield and selectivity of p-hydroxybenzenesulfonic acid (p-HBSA). Experiments and kinetic study on the sulfonation of phenol by concentrated sulfuric acid were carried out in a stirred tank reactor (STR). The reaction rate constant k and activation energy E at certain temperature was tested. The values of pre-exponential factor and activation energy were obtained as follows: k(1) = 5.74 x 10(3), E-1 = 8.17 kJ/mol, k(-1) = 6.95 x 10(3), E-1 = 6.18 kJ/mol, k(2) = 1.43 x 10(10), E-2 = 69.35 kJ/mol, k(-2) = 0.05 x 10(3), E-2 = 14.17 kJ/mol. The effects of various operating conditions including reaction temperature (T), sulfuric acid/phenol molar ratio (eta), solvent/phenol molar ratio (zeta), concentrated sulfuric acid feeding rate (Q'), stirring speed (P), ageing time (tau), on the content of p-HBSA were investigated in an attempt to obtain the optimal operating conditions in the STR. The yield of p-HBSA is 89.85% at the optimal operating conditions. On the basis of the results in STR, further experiments were performed in a rotating packed bed (RPB) to improve the sulfonation reaction selectivity and p-HBSA yield. The effects of rotation speed (N), cycle time (t) and concentrated sulfuric acid feeding rate (Q) were investigated. Results show that the yield of p-HBSA can reach up to 96.52% in RPB at the optimal operating conditions of N = 2250 rpm, Q = 300 mL/min, T = 100 degrees C, eta = 1.1, tau = 25 min, zeta = 1.25 and t = 3 min. The yield of p-HBSA obtained in the RPB is 6.67% higher than that in the STR. The research exhibits that RPB can obviously improve the yield of p-HBSA. (C) 2019 Elsevier Ltd. All rights reserved.
Keywords:p-Hydroxybenzenesulfonic acid (p-HBSA);Rotating packed bed (RPB);Stirred tank reactor (STR);Yield;Reaction rate constant;Activation energy