Abstract

This study develops technology for mitigation of NOx formed in thermal processes using recycled plastics such as polyethylene (PE). Experiments involve sample characterization, and thermogravimetric decomposition of PE under controlled atmospheres, with NOx concentration relevant to industrial applications. TGA-Fourier transform infrared (FTIR) spectroscopy and NOx chemiluminescence serve to obtain the removal efficiency of NOx by fragments of pyrolyzing PE. Typical NOx removal efficiency amounts to 80%. We apply the isoconversional method to derive the kinetic parameters, and observe an increasing dependency of activation energy on the reaction progress. The activation energies of the process span 135 kJ/mol to 226 kJ/mol, and 188 kJ/mol to 268 kJ/mol, for neat and recycled PE, respectively, and the so-called compensation effect accounts for the natural logarithmic pre-exponential ln (A/min-1) factors of ca. 19-35 and 28-41, in the same order, depending on the PE conversion in the experimental interval of between 5 and 95%. The observed delay in thermal events of recycled PE reflects different types of PE in the plastic, as measurements of intrinsic viscosity indicate that, the recycled PE comprises longer linear chains. The present evaluation of isoconversional activation energies affords accurate kinetic modeling of both isothermal and nonisothermal decomposition of PE in NOx-doped atmosphere. Subsequent investigations will focus on the effect of mass transfer and the presence of oxygen, as reburning of NOx in large-scale combustors take place at higher temperatures than those included in the current study.

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