NMR studies of stock process water and reaction pathways in hydrothermal carbonization of furfural residue

Hydrothermal carbonization(HTC) is a valuable approach to convert furfural residue(FR) into carbon material. The prepared biochars are usually characterized comprehensively, while the stock process water still remains to be studied in detail. Herein, a NMR study of the main components in stock process water generated at different HTC reaction conditions was reported. Various qualitative and quantitative NMR techniques(~1H and ^(13)C NMR,~1H-~1H COSY and ~1H-^(13)C HSQC etc.) especially 1D selective gradient total correlation spectroscopy(TOCSY NMR) were strategically applied in the analysis of HTC stock process water. Without separation and purification, it was demonstrated that the main detectable compounds are 5-hydroxymethylfurfural, formic acid, methanol, acetic acid, levulinic acid, glycerol, hydroxyacetone and acetaldehyde in this complicate mixture. Furthermore, the relationship between the concentration of major products and the reaction conditions(180-240 ℃ at 8 h, and 1-24 h at 240 ℃) was established. Finally, reasonable reaction pathways for hydrothermal conversion of FR were proposed based on this result and our previously obtained characteristics of biochars. The routine and challenging NMR methods utilized here would be an alternative other than HPLC or GC for biomass conversion research and can be extended to more studies.

Converting furfural residue wastes to carbon materials for high performance supercapacitor

Sustainable development based on the value-added utilization of furfural residues(FRs)is an effective way to achieve a profitable circular economy.This comprehensive work highlights the potential of FRs as precursor to prepare porous carbons for high performance supercapacitors(SCs).To improve the electrochemical performance of FR-based carbon materials,a facile route based on methanol pretreatment coupled with pre-carbonization and followed KOH activation is proposed.More defects could be obtained after methanol treatment,which is incline to optimize textural structure.The activated methanol treated FR-based carbon materials(AFRMs)possess high specific surface area(1753.5 m^(2) g^(-1)),large pore volume(0.85 cm^(3) g^(-1)),interconnected micro/mesoporous structure,which endow the AFRMs with good electrochemical performance in half-cell(326.1 F g^(-1) at 0.1 Ag^(-1),189.4 Fg^(-1) at 50 A g^(-1) in 6 mol L^(-1) KOH).The constructed symmetric SCs based on KOH,KOH–K_(3)Fe(CN)_(6) and KOH-KI electrolyte deliver energy density up to 8.9,9.9 and 10.6 Wh kg^(-1) with a capacitance retention of over 86%after 10,000 cycles.Furthermore,the self-discharge can be restrained by the addition of K_(3)Fe(CN)_(6) and KI in KOH electrolyte.This study provides an effective approach for high-valued utilization of FR waste.