Kinetic modeling of methyl methacrylate gas-phase decomposition and its impact on polymethyl methacrylate pyrolysis yields

Chemical recycling of polymethyl methacrylate (PMMA) to its monomer, methyl methacrylate (MMA), requires balancing primary depolymerization with the suppression of secondary gas-phase reactions. This study investigates non-oxidative MMA decomposition in a fluidized bed reactor across a temperature range of 623 K to 1073 K using online FTIR spectroscopy. Experimental results reveal a significant shift in product selectivity: low temperatures favor a low-energy decarboxylation pathway (yielding CO 2 and methanol), while high temperatures promote radical cracking (yielding CO and light hydrocarbons). To describe this, a two-competing-reactions model (CRM) is used, outperforming the traditional single first-order approaches. The CRM identifies two distinct activation energies: E a,1 = 76.5 kJ mol −1 for decarboxylation and E a,2 = 269.9 kJ mol −1 for cracking. The research further demonstrates that the classical sequential decomposition model (PMMA → MMA → light gases) overpredicts monomer yields at low temperatures. By integrating a direct solid-to-gas pathway to account for side-chain break-off and incorporating multi-volume reactor hydrodynamics, the model’s predictive accuracy significantly improved. This integrated framework identifies an optimal recovery window near 723 K, achieving MMA yields over 95 %.