Thermodynamic and economic analysis of a deployable and scalable process to recover Monomer-Grade styrene from waste polystyrene

Less than 5% of polystyrene is recycled, motivating a search for energy efficient and economical methods for polystyrene recycling that can be deployed at scale. One option is chemical recycling, consisting of thermal depolymerization and purification to produce monomer-grade styrene (>99%) and other co-products. Thermal depolymerization and distillation are readily scalable, well-established technologies; however, to be considered practical, they must be thermodynamically efficient, economically feasible, and environmentally responsible. Accordingly, mass and energy balances of a pyrolysis reactor for thermal depolymerization and two distillation columns to separate styrene from α-methyl styrene, styrene dimer, toluene, and ethyl benzene co-products, were simulated using ASPEN to evaluate thermodynamic and economic feasibility. These simulations indicate that monomer-grade styrene can be recovered with energy inputs <10MJ/kg, comparable to the energy content of pyrolysis co-products. Thermodynamic sensitivity analysis indicates the scope to reduce these values and enhance the robustness of the predictions. A probabilistic economic analysis of multiple scenarios combined with detailed sensitivity analysis indicates that the cost for recycled styrene is approximately twice the historical market value of fossil-derived styrene when styrene costs are fixed at 15% of the total product cost or less than the historical value when feedstock costs are assumed to be zero. A Monte Carlo and Net Present Value-based economic performance analysis indicates that chemical recycling is economically viable for scenarios assuming realistic feedstock costs. Furthermore, the CO ₂ abatement cost is roughly $1.5 per ton of averted CO ₂, relative to a pyrolysis process system to produce fuels. As much as 60% of all polystyrene used today could be replaced by chemically recycled styrene, thus quantifying the potential benefits of this readily scalable approach.