Utilization of papermaking black liquor as liquid phase for hydrothermal carbonization of corn stalks: The unique role of alkali for production of hydrochar

Papermaking black liquor (BL) contains a large amount of organic matter, alkali, and salt, which has high value in industrial and agricultural production. In the present paper, hydrothermal carbonization (HTC) technology has been employed to deal with BL and corn stalk (CS) under various conditions. A variety of analytical technologies, including Fourier Transform Infrared Spectrometer, X-Ray Diffraction, element analyzer, comprehensive thermal analyzer, scanning electron microscope, chromatography/mass spectrometry, TOC analyzer, and density functional theory (DFT), were used to characterize the physicochemical properties of hydrochar and aqueous phase product. The effects of experimental parameters (temperature, solid-liquid ratio, and time) on the HTC of BL and CS were systematically investigated. The higher energy yield and densification of hydrochar prepared by our HTC technology were obtained at 260 ℃ in 30 min with a solid-liquid ratio of 1:3. Mechanism study indicates that NaOH, which comes from the original BL, could effectively facilitate the cleavage of β–O–4 bond in lignin and β–1–4 glycosidic bond in cellulose and hemicellulose molecules. Hemicellulose and cellulose are more susceptible to degradation relevant to the lignin in the presence of NaOH. Elementary analysis shows that the dosage of BL is important for improving energy densification of hydrochar. The combustion characteristics show that hydrochar presents a thermochemical behavior, which is close to bituminous coal. Owing to hydroxyl ion in NaOH ion pair was consumed in the series of dehydrogenation reactions, pH of HTC aqueous phase product significantly decreases from 11-13 in original BL to 4.8-5. Such results indicate that a completely change for the components of BL could be obtained by our HTC technology, which provide a novel idea for the treatment of Papermaking BL without concentration.