Softwood is an abundantly available feedstock for the bio-based industry. However, achieving cost-effective sugar release is particularly challenging, owing to its guaiacyl-only lignin. Here, we report the highly effective pretreatment of the softwood pine (Pinus sylvestris) using ionoSolv pretreatment, a novel ionic liquid-based lignocellulose fractionation technology. Three protic, low-cost ionic liquids, 1-butylimidazolium hydrogen sulfate, triethylammonium hydrogen sulfate and N,N-dimethylbutylammonium hydrogen sulfate, were used to fractionate the biomass into a carbohydrate-rich pulp and a lignin. The carbohydrate-rich pulp was hydrolysed into fermentable sugars by enzymatic saccharification. Under the most successful pretreatment conditions, quantitative glucose release from the pulp was achieved, which equates to a projected glucose release of 464 mg per gram of pine wood entering the process. We further intensified the process by increasing the solid to solvent ratio up to 1 : 2 g g⁻¹ while maintaining saccharification yields of 75% of the theoretical maximum. We also demonstrate for the first time that N,N-dimethylbutylammonium hydrogen sulfate, [DMBA][HSO₄], is an excellent low-cost pretreatment solvent, surpassing the pretreatment effectiveness of its symmetrically substituted analogue triethylammonium hydrogen sulfate. This shows that ionoSolv pretreatment with protic hydrogen sulfate ionic liquids is a truly feedstock-independent pretreatment option, further increasing the commercial potential of this pretreatment technology.

Sugarcane bagasse is an abundant and geographically widespread agro-industrial residue with high carbohydrate content, making it a strong candidate feedstock for the bio-based economy. This study examines the use of the low-cost protic ionic liquid triethylammonium hydrogen sulfate ([TEA][HSO4]) to fractionate a range of South African sugarcane bagasse preparations into a cellulose-rich pulp and lignin. The study seeks to optimize pretreatment conditions and examine the necessity of applying a depithing step on bagasse prior to pretreatment. Pretreatment of five bagasse preparations, namely whole, industrially depithed, laboratory depithed (short and long fiber) and pith bagasse with [TEA][HSO4]:[H2O] (4:1 w/w) solutions produced highly digestible cellulose-rich pulps, as assessed by residual lignin analysis and enzymatic hydrolysis. Pretreatment under the optimized condition of 120 °C for 4 h produced a pretreated cellulose pulp with up to 90% of the lignin removed and enabled the release of up to 69% glucose contained in the bagasse via enzymatic hydrolysis. Glucose yields from whole and depithed bagasse preparations were very similar. Significant differences in lignin recovery were obtained for laboratory depithed bagasse compared with whole and industrially depithed bagasse. The silica-rich ash components of bagasse were seen to partition mainly with the pulp, from where they could be easily recovered in the post-hydrolysis solids. The five bagasse preparations were compared but did not show substantial differences in composition or cellulose digestibility after pretreatment. Evidence was presented that a depithing step appears to be unnecessary prior to ionoSolv fractionation, potentially affording significant cost and energy savings. Instead, lignin re-deposition onto the pulp surface (and, in turn, particle size and shape) appeared to be major factors affecting the conditioning of bagasse with the applied IL. We show that pith bagasse, a common by-product of paper making, can be successfully conditioned for high glucose release while allowing recovery of lignin and silica-rich ash. The glucose yields obtained for bagasse using [TEA][HSO4]-water mixtures were ~ 75% as high as for conventional aprotic ionic liquids such as [Emim][OAc]; this result is highly promising for commercialization of ionoSolv processing given [TEA][HSO4] is 40 times less expensive, thermally stable and recyclable.

The pretreatment of lignocellulosic biomass with protic low-cost ionic liquids is shown, resulting in a delignified cellulose-rich pulp ...

Agricultural residues from rice, wheat and sugarcane production are annually available at the gigaton-scale worldwide, particularly in Asia. Due to their high sugar content and ash compositions, their conversion to bioethanol is an attractive alternative to their present disposal by open-field burning and landfilling. In this work, we demonstrate application of the low-cost protic ionic liquid triethylammonium hydrogen sulfate ([TEA][HSO₄]) for pretreatment of rice straw, rice husk, wheat straw and sugarcane bagasse. The feedstocks had high ash (up to 13 wt%) and lignin content (up to 28 wt%). Pretreatment effectiveness was examined at 150 and 170°C and an optimal pretreatment time was identified and characterized by glucose release following enzymatic saccharification (i.e., hydrolysis), biomass delignification observed by compositional analysis, and lignin recovery. The isolated lignin fractions were analyzed by 2D HSQC NMR to obtain insights into the structural changes occurring following ionic liquid pretreatment. After treatment at 170°C for 30–45 min, enzymatic hydrolysis of three agroresidues gave near-quantitative glucose yields approaching 90% while rice husk gave 73% yield. Glucose release from the pulps was enhanced by saccharifying wet pulps without an air-drying step to reduce hornification. According to pulp compositional analysis, up to 82% of lignin was removed from biomass during pretreatment, producing highly digestible cellulose-rich pulps. HSQC NMR of the extracted lignins showed that delignification proceeded via extensive cleavage of β-O-4′ aryl ether linkages which was accompanied by condensation reactions in the isolated lignins. The high saccharification yields obtained indicate excellent potential for valorization of low-cost agroresidues in large volumes, which is promising for commercialization of biofuels production using the ionoSolv pretreatment technology.