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Here, we report a novel ammonia : ammonium salt solvent based pretreatment process that can rapidly dissolve crystalline cellulose into solution and eventually produce highly amorphous cellulose under near-ambient conditions. Pre-activating the cellulose I allomorph to its ammonia–cellulose swollen complex (or cellulose III allomorph) at ambient temperatures facilitated rapid dissolution of the pre-activated cellulose in the ammonia-salt solvent ( i.e. , ammonium thiocyanate salt dissolved in liquid ammonia) at ambient pressures. For the first time in reported literature, we used time-resolved in situ neutron scattering methods to characterize the cellulose polymorphs structural modification and understand the mechanism of crystalline cellulose dissolution into a ‘molecular’ solution in real-time using ammonia-salt solvents. We also used molecular dynamics simulations to provide insight into solvent interactions that non-covalently disrupted the cellulose hydrogen-bonding network and understand how such solvents are able to rapidly and fully dissolve pre-activated cellulose III. Importantly, the regenerated amorphous cellulose recovered after pretreatment was shown to require nearly ∼50-fold lesser cellulolytic enzyme usage compared to native crystalline cellulose I allomorph for achieving near-complete hydrolytic conversion into soluble sugars. Lastly, we provide proof-of-concept results to further showcase how such ammonia-salt solvents can pretreat and fractionate lignocellulosic biomass like corn stover under ambient processing conditions, while selectively co-extracting ∼80–85% of total lignin, to produce a highly digestible polysaccharide-enriched feedstock for biorefinery applications. Unlike conventional ammonia-based pretreatment processes ( e.g. , Ammonia Fiber Expansion or Extractive Ammonia pretreatments), the proposed ammonia-salt process can operate at near-ambient conditions to greatly reduce the pressure/temperature severity necessary for conducting effective ammonia-based pretreatments on lignocellulose.
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Understanding the effect of Deep Eutectic Solvent (DES) pretreatment on the utilization of corn stover
Pretreatment is an important step to reduce the recalcitrance factors in biomass for effective biomass utilization. In particular, the choice of processing solvents in the pretreatment influences the quantity and quality of the final products. Although conventional organosolv pretreatments are effective, they are typically performed under harsh conditions. Compared to those approaches, recent studies have shown that the use of Deep Eutectic Solvents (DES) made up of a hydrogen bond donor and acceptor at the eutectic point can be a promising alternative as biomass processing solvents because of their good thermal stability and compatibility with natural components. In this study, DES pretreatment was applied to corn stover, which is the largest agricultural residue in the United States. The performance of the pretreatments was assessed by measuring the removal of xylan and lignin from the corn stover, as well as the production of glucose and xylose by subsequent enzymatic hydrolysis. The results indicated that the DES pretreatment resulted in significantly higher delignification rates (75%) than an organosolv pretreatment (35%) at the same processing temperature. The DES pretreatment also resulted in a more effective conversion of glucan (81%) and xylan (56%) than the organosolv pretreatment. The results indicated that DES pretreatment is a promising processing strategy for biomass utilization.
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- Award ID(s):
- 2239299
- PAR ID:
- 10559363
- Publisher / Repository:
- Journal of high school science
- Date Published:
- Journal Name:
- Journal of high school science
- ISSN:
- 2575-6206
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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A thermophilic Geobacillus bacterial strain, WSUCF1 contains different carbohydrate-active enzymes (CAZymes) capable of hydrolyzing hemicellulose in lignocellulosic biomass. We used proteomic, genomic, and bioinformatic tools, and genomic data to analyze the relative abundance of cellulolytic, hemicellulolytic, and lignin modifying enzymes present in the secretomes. Results showed that CAZyme profiles of secretomes varied based on the substrate type and complexity, composition, and pretreatment conditions. The enzyme activity of secretomes also changed depending on the substrate used. The secretomes were used in combination with commercial and purified enzymes to carry out saccharification of ammonia fiber expansion (AFEX)-pretreated corn stover and extractive ammonia (EA)-pretreated corn stover. When WSUCF1 bacterial secretome produced at different conditions was combined with a small percentage of commercial enzymes, we observed efficient saccharification of EA-CS, and the results were comparable to using a commercial enzyme cocktail (87% glucan and 70% xylan conversion). It also opens the possibility of producing CAZymes in a biorefinery using inexpensive substrates, such as AFEX-pretreated corn stover and Avicel, and eliminates expensive enzyme processing steps that are used in enzyme manufacturing. Implementing in-house enzyme production is expected to significantly reduce the cost of enzymes and biofuel processing cost.more » « less
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