Co-pyrolysis of wheat straw with polyester-based polyurethane for nitrogenous compounds: pyrolysis kinetic properties and synergistic effects

Abstract

To re-utilize agricultural waste straw and waste plastic, the co-pyrolysis process of wheat straw (WS) and high-nitrogen polymer polyester-based polyurethane (PU) and the synergistic effects were studied. The results showed that PU facilitated pyrolysis to occur at lower temperatures. The effective apparent activation energies（Eα）of different samples were calculated at different conversion rates with three methods (Kissinger, KAS and Starink). It was found that PU decreased the Eα values and enthalpy change of WS and increased the reactivity. Both ΔG and ΔS results indicate that a heating rate of 5 ℃/min is more favorable for co-pyrolysis. PU greatly promoted the production of pyrolysis oil. Co-pyrolysis oil doped with 75% PU gave the highest yield of 77wt%. Co-pyrolysis effectively suppressed the production of acids, aldehydes, and phenols in pyrolysis oils. It increased the levels of alcohols and ketones, improving the pyrolysis oil's stability and calorific value. α, β-unsaturated aldehydes produced by WS during pyrolysis reacted with hydrazine derivatives produced by PU pyrolysis to produce pyrazole compounds after dehydration. In the co-pyrolysis of 50% doped PU, the reaction of methyl and methylene produced by WS with amines (-NH2) produced by the pyrolysis of PU promotes the production of trimethylamine. The yield of amines in the nitrogenous compounds reached a maximum at this time. PU increased the yield of nitrogenous compounds and their variety. It favored the output of high-value chemicals. FT-IR analyses of pyrolytic charcoal showed that the addition of PU promoted the cleavage of WS and the dehydration and decarboxylation reactions of C-O and C-O-C. Finally, synergistic effects and nitrogen conversion mechanisms in the co-pyrolysis process are proposed. This work provided a theoretical basis for the resource utilization of WS waste and PU waste.