The degradation of cellulose in ionic mixture solutions under the high pressure of carbon dioxide

Abstract

This work aims to study the product characteristics of cellulose degradation not only by a hydrothermal process but also in combination with a sonication process. Herein, 4.3 mL of oxalic acid (H₂C₂O₄)–sodium chloride (NaCl) solution containing cellulose was placed into a stainless steel reactor (or the mixture was placed into the reactor after the sonication process for 1 hour); then, carbon dioxide (CO₂) was released for pressurization. Degradation was performed under certain pressures (70 and 200 bar) and temperatures (125 °C and 200 °C) at various times. Scanning Electron Microscopy (SEM) results indicated that the sonication pretreatment process affected the solid cellulose, making it rougher or fibrous than the non-sonicated process. XRD characterization results indicated that both process types caused changes in the crystallinity and composition of cellulose I and II with pressure, temperature, and time. The combination of sonication and hydrothermal processes resulted in lower crystallinity. Changes in crystallinity showed different characteristics in swelling, reduced the interaction between chains, and even broke the polymer chains inside the particles. In a hydrothermal process at 200 bar and 200 °C, a maximum reducing sugar concentration of 5.1 g L⁻¹ was obtained, while 3.2 g L⁻¹ was obtained in the combined sonication and hydrothermal process under the same operating condition, which is below the value attained at 200 °C and 70 bar. These results indicated the existing competition between the formation and further degradation of the reducing sugar, a phenomenon explained by the presence of a monomer (reducing sugar), an oligomer (cellotriose), and 5-HMF (5-hydroxymethyl-2-furaldehyde) in a liquid product processed under hydrothermal conditions.