Abstract
This paper examines the efficacy of ionic liquid (IL) pretreatment on seven different commercially harvested biomass types: corn stover, miscanthus, pine, sorghum, sugarcane bagasse, switchgrass, and wheat straw in an effort to improve the production of renewable fuels and chemicals from biomass derived sugars. Initial experiments screened the pretreatment of lodgepole pine, a particularly recalcitrant biomass feedstock, with nine different imidazolium based ionic liquids. After screening, one hydrophilic and one hydrophobic ionic liquid was selected for pretreatment tests on six commercially harvested biomasses. Ultimately, the hydrophilic ionic liquid functioned better for biomass pretreatment than the hydrophobic ionic liquid. These results were then compared to a traditional dilute acid pretreatment to examine the relative effectiveness of ionic liquid pretreatment across a variety of biomass and ionic liquid types. Total theoretical sugar yields after IL pretreatment varied widely by IL and biomass type and ranged from 4.9 to 90.2%. Dilute acid pretreatment showed consistent sugar yields for herbaceous material (from 71.4 to 80.8%) but low yield for lodgepole pine (22.8%). Overall, ILs showed the potential to reach slightly higher sugar yields than dilute acid and were particularly effective for woody feedstocks. More importantly, the sugar release kinetics for IL pretreatment were three times faster than dilute acid and gave maximum sugar yields after about 24 hours. Additional characterization of IL treated materials included scanning electron microscopy (SEM), x-ray diffraction (XRD), and compositional analysis. SEM and XRD showed qualitative and quantitative reductions in cellulose crystallinity (respectively) that correlated well to improved sugar release during enzymatic hydrolysis for hydrophilic ionic liquids. However, reductions in crystallinity associated with hydrophobic ionic liquids resulted in lower sugar release during enzymatic hydrolysis. Compositional analysis generally showed increased sugars content for hydrophilic ILs and increased lignin content for hydrophobic ILs.
Highlights
Clean and domestic energy is an important issue for the development of sustainable and secure global communities
The pine samples were treated with the nine ILs shown in Table 1 which was comprised of a set of imidazolium based ionic liquids
Results from scanning electron microscopy (SEM), x-ray diffraction (XRD) and enzymatic hydrolysis show that the most effective ionic liquids for biomass dissolution has three attributes: (1) fewer functional groups, (2) polar protic anions (as seen with the acetate anion compared with the chlorine anion for Emim Ac vs. Emim Cl, and (3) hydrophilic anions
Summary
Clean and domestic energy is an important issue for the development of sustainable and secure global communities. While various biomass pretreatment strategies have been developed (Mosier et al, 2005; Alvira et al, 2010) this paper focuses on the comparison between a traditional dilute acid pretreatment and emerging ionic liquid pretreatments to understand, and evaluate, the effectiveness of ionic liquids. To date both dilute acid and IL pretreatment have been used for a variety of biomass types. The percent of total sugars yielded from the combined pretreatment and enzymatic hydrolysis of these samples tends to be in the range of 40 to 90% but often averages 65%. The range of conditions and yields given above are represented in the references for the individual feedstocks
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