Search for: All records

Polyvinyl chloride (PVC) containing municipal solid waste (MSW) streams are difficult to recycle and mostly landfilled due to various detrimental effects PVC causes to waste recycling. In this work, a single-step upcycling of PVC-containing commingled wastes in tetrahydrofuran was investigated using cellulose, PVC, polyethylene (PE), polypropylene (PP), and polystyrene (PS) to model the wastes. During the co-conversion, in-situ produced HCl derived from PVC decomposition acted as an acid catalyst to selectively decompose cellulose into liquid mainly containing levoglucosan (LGA) and furfural. It was also found that the presence of PE, PP, and PS in the mixture synergistically enhanced the cellulose-derived monomer productions and increased the reaction rate for producing the monomers by suppressing secondary reactions of HCl in the solvent. The maximum LGA yield from co-conversion of cellulose, PVC, and PS was 35.4% after a 5 min reaction compared to the 31.7% obtained without PS in the mixture. In addition to converting cellulose to chemicals, PVC-derived polyaromatics and partly decomposed PE, PP, and PS were recovered as solids. The dechlorinated solids had higher heating values up to 46.11 MJ/kg, achieved by co-converting cellulose, PVC, and PP. When used as oil absorbents in water, the solid recovered from converting cellulose, PVC, and PE mixture showed the highest absorption capability. Overall, the presented approach offers a promising way for upcycling PVC-containing wastes in which PVC properties and its molecular structure are leveraged to enhance the conversion. 

Herein, we report a novel method to obtain oxygenated chemicals and high-quality lignin from biomass in one-pot using a single step process. Plasma electrolysis of red oak was conducted by applying high-voltage alternating current electricity in γ-valerolactone using sulfuric acid as the electrolyte. Red oak was completely solubilized to produce levoglucosenone and furfural as the two major monomers with the respective yields of up to 44.9 mol% and 98.0 mol%. During the conversion, an oxidized lignin was also simultaneously produced in high purity. The valorization potential of the plasma electrolysis-derived lignin evaluated using the pyrolysis method showed that depolymerization of this lignin could produce significantly higher yields of phenolic monomers than the natural lignin or the lignin isolated during conventional solvolysis. Our investigation showed that benzylic carbon of the natural lignin was selectively modified during plasma electrolysis to limit the formation of interunit C–C bonds, significantly improving the subsequent lignin valorization to aromatic monomers. Overall, this study demonstrated a simple green approach to improve chemical production without using costly catalysts or tedious biomass fractionation. This study also presented a novel and highly efficient way to modify lignin for enhanced valorization. 

Atmospheric pressure nonthermal plasma treatment can be a novel, green and low energy method to convert biomass to biobased chemicals. The unique physiochemistry of plasma discharge enables reactions within biomass that otherwise could not possibly occur under traditional conditions. In this study, we present a simple method of producing a high yield of levoglucosan from cellulose without using any catalysts, chemicals, solvents or vacuum, but by using plasma treatment to control the depolymerization mechanism of cellulose. Cellulose was first pretreated in a dielectric barrier discharge reactor operating in ambient air or argon for 10–60 s, followed by pyrolysis at 350–450 °C to produce up to 78.6% of levoglucosan. Without the plasma pretreatment, the maximum yield of levoglucosan from cellulose pyrolysis was 58.2%. The results of this study showed that the plasma pretreatment led to homolytic cleavage of glycosidic bonds. The resulting free radicals were then trapped within the cellulose structure when the plasma discharge stopped, allowing subsequent pyrolysis of the plasma-pretreated cellulose to proceed through a radical-based mechanism. The present results also revealed that although the radical-based mechanism is highly selective to levoglucosan formation, this pathway is usually discouraged when the untreated cellulose is pyrolyzed due to the high energy barrier for homolytic cleavage. Initiating homolytic cleavage during the plasma pretreatment also helped the pretreated cellulose to produce higher yields of levoglucosan using lower pyrolysis temperatures. At 375 °C, the levoglucosan yield was only 53.2% for the untreated cellulose, whereas the yield reached 77.6% for the argon-plasma pretreated cellulose.