Breaking the temperature limit of hydrothermal carbonization of lignocellulosic biomass by decoupling temperature and pressure

Hydrothermal carbonization (HTC) of lignocellulosic biomass is a promising technology for the production of carbon materials with negative carbon emissions. However, the high reaction temperature and energy consumption have limited the development of HTC technology. In conventional batch reactors, the temperature and pressure are typically coupled at saturated states. In this study, a decoupled temperature and pressure hydrothermal (DTPH) reaction system was developed to decrease the temperature of the HTC reaction of lignocellulosic biomass (rice straw and poplar leaves). The properties of hydrochars were analyzed by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, X-ray diffraction (XRD), thermogravimetric analyzer (TGA), etc. to propose the reaction mechanism. The results showed that the HTC reaction of lignocellulosic biomass could be realized at a low temperature of 200 °C in the DTPH process, breaking the temperature limit (230 °C) in the conventional process. The DTPH method could break the barrier of the crystalline structure of cellulose in the lignocellulosic biomass with high cellulose content, realizing the carbonization of cellulose and hemicellulose with the dehydration, unsaturated bond formation, and aromatization. The produced hydrochar had an appearance of carbon microspheres, with high calorific values, abundant oxygen-containing functional groups, a certain degree of graphitization, and good thermal stability. Cellulose acts not only as a barrier to protect itself and hemicellulose from decomposition, but also as a key precursor for the formation of carbon microspheres. This study shows a promising method for synthesizing carbon materials from lignocellulosic biomass with a carbon-negative effect. A decoupled temperature and pressure hydrothermal (DTPH) reaction system was developed to break the temperature limit of the hydrothermal carbonization of lignocellulosic biomass, realizing a low-temperature carbonization at 200 °C. [Display omitted] •HTC of biomass is achieved at a lower temperature.•The temperature and pressure are decoupled in the reaction system.•Cellulose acts as a barrier to protect itself and hemicellulose from carbonization.•The barrier of the crystalline structure of cellulose in biomass is breached.•Biomass with high cellulose content tends to produce well-shaped carbon spheres.