Insights on the Effect of Heavy Metals on Subcritical Hydrothermal Recycling of Heavy Metal-Contaminated Biomass and Its Derived Porous Carbon Properties Using Cu as a Case

Abstract

Subcritical hydrothermal liquefaction (HTL) technique has shown great potential in recycling heavy-metal-contaminated biomass derived from phytoremediation and biosorption. However, the effect of heavy metals on the physicochemical characteristics of HTL products and their derivatives has not been elaborated so far. Herein, various Cu content-contaminated derived biomass was recycled by HTL. We found that over 99% of Cu was enriched in hydrochar at 300 °C, enabling us to obtain clean chemicals (e.g., levulinic acid and acetic acid). Furthermore, a large amount of Cu(0) was formed, especially at high temperatures, because HTL products acted as electron donors. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry analysis showed that Cu catalyzed the depolymerization and deoxygenation of macromolecular lignins/carboxylic-rich alicyclic molecule-like compounds, resulting in the production of more levulinic acid. Two-dimensional FTIR correlation spectroscopy analysis indicated that the intensity of C═C increased first, and the intensity of C–O–C decreased later as the Cu content increased. Notably, the low-risk hydrochar could be upgraded into porous carbon (PC) with excellent CO2 capture performance (up to 6.64 mmol/g), whereas Cu enhanced the CO2 capture capacity of PC by increasing its porosity. Undoubtedly, such findings have important implications for recycling heavy-metal-contaminated biomass into high value-added products.