The performance of batch reactive distillation process involving the esterification of acetic acid with methanol to produce methyl acetate and water is considered in this work. Two cases studies with varying amount of the reactants are considered. The reflux ratio (single time interval) is selected as the control variable to be optimised (treated as piecewise constant) for different but fixed batch time ranging from 5 to 15 h, so as to maximise the conversion of methanol subject to product purity of methyl acetate. The dynamic optimisation problem is converted to a nonlinear programming problem by Control Vector Parameterization (CVP) technique and is solved by using efficient SQP method. The optimisation results show that as the methanol and methyl acetate are wide boiling, the separation of methyl acetate is easier without losing much of methanol reactant. The conversion improves by 6.4 % due to sufficient amount of acetic acid being reacted with methanol. Moreover an excess of acetic acid leads to high operation temperature and therefore high reflux operation (to reduce loss of methanol from the top of the column) to maximise the conversion.