CO2-assisted catalytic pyrolysis of cellulose acetate using Ni-based catalysts

Highlights: • A new technical platform for valorizing waste cellulose acetate (CA) was proposed. • CO₂ was suggested to maximize the carbon utilization and H₂ production. • Ni catalysts expedited effectiveness of CO₂ on CA pyrolysis with CO production. • CO₂ suppressed coke deposition on Ni catalyst. Cellulose acetate (CA) is one of widely used polymers for chemical and medical applications due to its versatile physico-chemical functionalities. Although its recycle is available after a deacetylation process, the recycle process releases a huge amount of wastewater. Thus, this study investigated a direct disposal process of CA with its valorization to syngas (H₂ and CO) through pyrolysis. To construct more environmentally benign process, CO₂ was used as a co-feedstock with CA to simultaneously convert them into syngas. Pyrolysis of CA in N₂ was performed as a reference study to examine the effectiveness of CO₂ on valorization of CA. Acetic acid and methyl acetate were main volatile pyrolysates (VPs) from CA pyrolysis, and the further thermal cracking of VPs resulted in syngas and CH₄ formations under both N₂ and CO₂ conditions. To expedite syngas formations, multi-stage pyrolysis (two-stage pyrolysis) and catalytic pyrolysis were employed. With the increased thermal energy through two-stage pyrolysis, four times more production of syngas was shown, comparing to the result of a single-stage pyrolysis. With Ni catalysts, the syngas formation was the two orders of magnitude higher than the single-stage pyrolysis, and the significant enhancement of CO formation was shown in the presence of CO₂ due to combined effects of CO₂ and the Ni-based catalysts. This CO enhancement resulted from catalytically expedited gas phase reactions between CO₂ and VPs evolved from CA. In addition, the CO₂ contributed to the suppression of coke deposition on the catalyst, thereby suggesting more technical and environmental benefits of CO₂ as a reactive co-feedstock of pyrolysis in reference to N₂. Therefore, this study proved the direct and versatile technical platform to convert CA and CO₂ into syngas.