The aim of this work was to characterize the natural low transition temperature mixtures (LTTMs) as promising green solvents for biomass pretreatment with the critical characteristics of cheap, biodegradable and renewable, which overcome the limitations of ionic liquids (ILs). The LTTMs were derived from inexpensive commercially available hydrogen bond acceptor (HBA) and l-malic acid as the hydrogen bond donor (HBD) in distinct molar ratios of starting materials and water. The peaks involved in the H-bonding shifted and became broader for the OH groups. The thermal properties of the LTTMs were not affected by water while the biopolymers solubility capacity of LTTMs was improved with the increased molar ratio of water and treatment temperature. The pretreatment of oil palm biomass was consistence with the screening on solubility of biopolymers. This work provides a cost-effective alternative to utilize microwave hydrothermal extracted green solvents such as malic acid from natural fruits and plants.
Identified green solvents of current interest for biomass pretreatment. • Discussed formation, types, materials and design methodologies of green solvents. • Reviewed potential applications of choline chloride (ChCl) based green solvents. • Existing challenges of green solvents are emphasized for future research.
Natural hydro-low-transition-temperature mixtures (NH-LTTMs) tend to be the most favorable next-generation green solvents for biomass pretreatment, as they are cheap and environmental friendly. The amount of water bound into the NH-LTTMs greatly affected their thermal stability, whereby the highest thermal stability was observed with the water content of 7.6 wt%. It is worth noting that, the highest molar transition energy of NH-LTTMs (47.57 kcal mol), which indicated the highest solubility, was optimized with the molar ratio of hydrogen bond donor (HBD)-hydrogen bond acceptor (HBA)-water (2:4:3) at a temperature of 60 °C. Hydrogen bonding networks of the NH-LTTMs, which led to the dissolution of biomass, were confirmed by the alteration in the peaks of the involved bonds and resonance signal to lower field through FTIR and H NMR spectra, respectively. The components evidenced in high-resolution mass spectra of extracted lignin showed its high potential to be valorized into useful fuels and chemicals.
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