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.
more »
« less
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.
more »
« less
- 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
More Like this
-
-
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
-
Abstract Biomass‐derived deep eutectic solvents (DESs) have been introduced as promising pretreatment and fractionation solvents because of their mild processing conditions, easy synthesis, and green solvent components from biomass. In recent DES studies, solvent‐based third constituents like water, ethanol, and others improve the processibility of typical binary DESs. However, the impacts of these components are not well understood. Here, two solvent‐based constituents, including water and ethylene glycol, were applied to 3,4‐dihydroxybenzoic acid (DHBA)‐based DES system for improving the conversion efficiency of cellulose‐rich fraction and the properties of lignin fraction. Chemical composition, enzymatic digestibility, degree of polymerization of cellulose and physicochemical properties of lignin were used to evaluate the impact of each third constituent on biomass processing. Ternary ChCl‐DHBA DESs exhibited better performances in delignification, fermentable sugar production, and preservation of β‐O‐4 ether linkage in lignin compared with binary ChCl‐DHBA DES.more » « less
-
Abstract Integrating multidisciplinary research in plant genetic engineering and renewable deep eutectic solvents (DESs) can facilitate a sustainable and economic biorefinery. Herein, we leveraged a plant genetic engineering approach to specifically incorporate C6C1monomers into the lignin structure. By expressing the bacterialubiCgene in sorghum,p‐hydroxybenzoic acid (PB)‐rich lignin was incorporated into the plant cell wall while this monomer was completely absent in the lignin of the wild‐type (WT) biomass. A DES was synthesized with choline chloride (ChCl) and PB and applied to the pretreatment of the PB‐rich mutant biomass for a sustainable biorefinery. The release of fermentable sugars was significantly enhanced (∼190 % increase) compared to untreated biomass by the DES pretreatment. In particular, the glucose released from the pretreated mutant biomass was up to 12 % higher than that from the pretreated WT biomass. Lignin was effectively removed from the biomass with the preservation of more than half of the β‐Ο‐4 linkages without condensed aromatic structures. Hydrogenolysis of the fractionated lignin was conducted to demonstrate the potential of phenolic compound production. In addition, a simple hydrothermal treatment could selectively extract PB from the same engineered lignin, showing a possible circular biorefinery. These results suggest that the combination of PB‐based DES and engineered PB‐rich biomass is a promising strategy to achieve a sustainable closed‐loop biorefinery.more » « less
-
Lignin‐derived deep eutectic solvents (DESs) have been investigated as sustainable green media for biomass processing. However, the properties and processability of DESs have not been fully understood with the chemical structures of their constituents for biomass fractionation. In this article, the properties of the phenolic DESs are discussed with different numbers of functional groups, such as –OCH3and –CHO in their hydrogen bond donor (HBD) structures. The formation of DES is significantly related to the hydrogen bond between its constituents, identified by nuclear magnetic resonance (NMR) analysis and density functional theory calculation (DFT). Lower viscosity and net basicity of DES are achieved with fewer –OCH3on HBD structures, resulting in enhanced processability and fractionation efficiency. The thermal stability of the DES is also influenced by the –OCH3and –CHO of HBD, as indicated by its onset temperature. The recyclability of the phenolic DES is confirmed by the fractionation performance of the recycled DES. Understanding the structural impacts of DES constituents on the properties and performance is crucial for designing solvents in biorefinery applications.more » « less
An official website of the United States government

