Vapor-liquid equilibrium (VLE) and liquid-liquid equilibrium (LLE) data of binary and ternary acrylic systems were systematically measured. Subsequently, VLLE phase diagrams of binary systems, tridimensional VLE phase diagrams of methyl acrylate (MA)-methanol (Me)-H2O ternary system, and quaternary LLE phase diagrams of MA-Me-H2O-methyl acetate (MeOAc) system were constructed. These diagrams clearly demonstrated the effects of temperature on phase equilibrium. The experimental data was fitted by the NRTL and UNIQUAC models, and the best-fitted parameters were used to predict interaction properties of ternary and quaternary mixture. Therefore, the phase equilibrium data were provided as reference for the design of acrylic systems rectification or extraction process. Residue curve was mapped out for MA-Me-H2O system through Aspen plus software. Finally, using thermodynamics and residue curve as theoretical basis, two novel separation processes were proposed and applied to the quaternary acrylic systems. (C) 2015 American Institute of Chemical Engineers