Co-pyrolysis of pretreated cotton stalk and low-density polyethylene: Evolved products and pyrolysis mechanism analysis

Abstract

The preparation of bio-oil from cotton stalks and agricultural residue films using co-pyrolysis technology can achieve resource recovery and energy conversion, which has important research value and significance. In this study, cotton stalks were subjected to different chemical pretreatments using NaOH, HCl, and H₂O solutions to understand their structural changes and pyrolysis characteristics. In addition, the lower H/C ratio of cotton stalks resulted in higher oxygen content in the pyrolysis oil, which limited its efficient and clean utilization. Therefore, the characteristics and pyrolysis kinetics of the pyrolysis products of pretreated cotton stalks and LDPE (low-density polyethylene) were studied. The results showed that the ash content of alkali pretreatment cotton stalks decreased by 1.24 %, and the dense structure of cotton stalks significantly relaxed. NaOH pretreatment effectively removed hemicellulose sugars and cracked them. During the co-pyrolysis process, when the ratio of NaOH-CS/LDPE was 50/50, the synergistic effect was more pronounced, and the oil yield increased by 2 % compared to the theoretical value. The oxygen content of CO and CO₂ in the pyrolysis gas was higher than the theoretical value, at 10.4 % and 14.1 % respectively. The synergistic effect of bio-oil on hydrocarbons was the most significant, reaching 18.9 %. More hydrogen and less oxygen migrated into the co-pyrolysis oil, resulting in an increase in hydrocarbons and a decrease in oxygen-containing compounds, and improving the quality of bio-oil. Results from electron paramagnetic resonance (EPR) indicated that adding LDPE might raise the quantity of stable free radicals. The evolution mechanism of functional groups of NaOH-CS and LDPE co-pyrolysis behavior was analyzed by Fourier in-situ infrared spectrometry (FTIR), and it was found that C–O–C, C=O, and O–H decreased due to dehydroxylation, decarboxylation, decarbonylation, and demethoxy reactions with the increase of temperature, indicating that there was a synergistic effect between NaOH-CS and LDPE co-pyrolysis. The pyrolysis kinetics of NaOH-CS, LDPE and their blends were determined by the model-free method. The introduction of LDPE can reduce the activation energy of NaOH -CS pyrolysis alone, and the 3D diffusion (D3) model is suitable for their blends.