Mid Sweden University

In order to explore the utilization of natural microalgae, the natural Scenedesmus was selected to carry out hydrothermal carbonization experiments, and the characterization of its hydrochars was determined using Fourier transform infrared spectroscopy, X-ray diffraction analysis, X-ray fluorescence spectroscopy, environmental scanning electron microscopy and thermogravimetric analyzer. The results showed that the ash content of natural Scenedesmus was 44.66%, and the lipid and protein content of natural Scenedesmus were 1.4% and 15.1%, respectively. The natural microalgae ash components were mostly water-insoluble components. The main components included (Mg0.064Ca0.936CO3), SiO2, NaCl, Al2O3, CaSO4, Mg3S2O8(OH)2. After hydrothermal carbonization treatment, NaCl was dissolved in water, and the water-insoluble components were enriched in hydrochars. Compared with the natural Scenedesmus, the ash content of hydrochars increased, in the range from 57.41% to 71.47%. It was worth noting that the natural Scenedesmus and its derived hydrochars had no fixed carbon. With the increase of hydrothermal temperature, the hydrothermal carbon yield decreased from 47.29% (180℃) to 43.01% (240℃). This phenomenon was on account of the organic components in the natural Scenedesmus underwent hydrolysis, dehydration, decarboxylation, aromatization, condensation and polymerization. The carbon remaining ratio was the largest, the oxygen was the smallest, and the remaining ratios of carbon, hydrogen and oxygen decreased as the hydrothermal temperature increased. For HC-240, the removal rates of H and O were 69.88% and 93.88%, respectively, and the C remaining ration rate was 33.97%. The O/C molar ratio of hydrochars decreased from 1.45 to 0.28. Dehydration and decarboxylation were the main pathways in hydrothermal carbonization of the natural Scenedesmus, and the demethylation pathway was negligible. Oxygen was removed in the form of H2O and CO2. The degree of carbonization was enhanced and hydrochars had the potential to be applied to solid fuels. Since hydrochars contained a large amount of ash, its calorific value was in the range of 8.43-9.67 MJ/kg. Hence, the pretreatment of deashing was a necessary process. The hydrothermal carbonization treatment effectively improved the pore structure of hydrochars, and the absorption-desorption capacity of hydrochars was obviously enhanced. Compared with natural Scenedesmus (4.36 m2/g), the specific surface area of hydrochars was in the range of 28.7-35.26 m2/g. The natural Scenedesmus had a dense block-like without pores or pathways. However, the morphologies of hydrochars changed significantly. The fragmentation and porosity of hydrochars increased, which attributed to the release of volatile matter during hydrothermal carbonization process and chemical bond decomposition of feedstock. The thermogravimetric analysis experiments were carried out to reveal the pyrolysis characteristics of hydrochars. It was found that the weight loss peak at 300℃ gradually disappeared with the increased of hydrothermal temperature. This was owing to the degree of natural Scenedesmus increased and the volatile matter content decreased. When the hydrothermal temperature was higher than 220℃, the maximum weight loss rate peak moved to the high temperature zone. The pyrolysis kinetics results showed that the thermal stability of hydrochars increased with the increase of hydrothermal temperature. The hydrochars were more hydrophobic than that of the natural Scenedesmus. The research results provide a theoretical reference for the resource utilization of natural microalgae.