Co-pyrolysis of Baltic wheat straw and low-density polyethylene bags and its kinetic and thermodynamic behaviour

Abstract

Wheat cultivation represents about 42 % of the total cereal cultivation area in the Baltic Sea region, generating huge amounts of wheat straw (WS) that needs to be optimally managed. In this context, this research aims to investigate the extent of using pyrolysis process in WS valorization. The experiments were performed using a thermogravimetric (TG) analyzer on WS and its mixtures with low-density polyethylene (LDPE) bags at different mixing ratios (1:1, 1:2, 1:3, 1:4). The released TG vapours were monitored using TG-Fourier transform infrared spectroscopy (TG-FTIR) and chromatography-mass spectrometry (GC-MS). The thermochemical activation energy (Ea) were studied by Kissinger-Akahira-Sunose, Flynn-Wall-Ozawa, Friedman, and Vyazovkin models. The pyrolysis results showed that WS and LDPE could be completely decomposed as a single reaction up to 600 °C and 520 °C, respectively. Aromatic-carbonyl and CO2 were the main FTIR functional group for WS vapour versus -CH2- for LEDP vapour. The GC/MS analysis of WS showed various compounds such as sec-Butylamine (11.88 %), acetic acid (10.68 %), etc., while LDPE showed many compounds without specific trend even when the heating rate was changed. While the co-pyrolysis results showed that WS/LDPE could be decomposed individually in two successive reactions at 335 °C (WS) and 495 °C (LDPE). These results were confirmed by FTIR and GC/MS which showed that the functional groups and chemical compounds of vapour generated at these decomposition zones have similar characteristics to those obtained from pyrolysis of WS and LDPE. Finally, kinetic analysis showed that WS-Baltic (227–250 kJ/mol) is more complex compared to WS-Asian (163–217 kJ/mol) due to its higher ash content. While Ea of WS/LDPE was increases upto 274–291 kJ/mol (1:1), 266–297 kJ/mol (2:1), 268–289 kJ/mol (3:1), and 278–299 kJ/mol (1:4). Also, the enthalpy, and Gibbs free energy coefficients of WS were increased by mixing (1:1) up to 272 J/mol K, while its entropy does not change much by mixing (367 J/mol K). Accordingly, the co-pyrolysis process is a key technology in valorization of WS and convert into value-added chemicals and a sustainable energy source.