RESUMEN
Adsorption method is an effective approach to treat wastewater containing methylene blue. Herein, a cost-effective and eco-friendly lignin-based network composite hydrogel adsorbent (PAA@SML) was constructed by using polyacrylic acid (PAA) to crosslink with sulfomethylated lignin (SML) via free radical polymerization for adsorption of methylene blue (MB) from wastewater. The constructed PAA@SML-0.2 exhibited remarkable adsorption performance towards removal of MB, with a maximum theoretical adsorption capacity of 777.1 mg·g-1. The improved efficiency can be attributed to the well-established network structure and abundant hydrophilic functional groups present in the adsorbent, promoting the interaction between methylene blue (MB) molecules and the adsorption sites of the adsorbent. The adsorption process of the adsorbent for MB followed the pseudo-second-order kinetic and the Langmuir isotherm models, which illustrated the adsorption process attributed to monolayer chemisorption. Mechanism investigation confirmed that the adsorption of MB by PAA@SML-0.2 primarily relied on hydrogen bonding and electrostatic interactions. Moreover, the recyclability test demonstrated excellent regeneration usability and stability of PAA@SML-0.2, and the adsorption capacity maintained above 74.0 % after five cycles. This constructed lignin-based network composite hydrogel is considered to have great potential in the treatment of organic dye in wastewater.
Asunto(s)
Aguas Residuales , Contaminantes Químicos del Agua , Lignina/química , Azul de Metileno/química , Adsorción , Hidrogeles , Contaminantes Químicos del Agua/química , CinéticaRESUMEN
Deep eutectic solvents (DESs) have emerged as promising and eco-friendly solvents for the efficient extraction of lignin from biomass due to their low cost and environmental benefits. Nevertheless, the prevalent use of acidic DESs in lignin extraction often results in excessive depolymerization and recondensation of lignin, thereby impeding its downstream applications. In this study, we developed a range of alkaline DESs (ADESs), both pure and peroxide-containing, for the extraction of high-quality lignin from bamboo. Moreover, carbon dioxide (CO2) was employed for the precipitation and regeneration of the extracted lignin. The obtained lignin fractions were comprehensively characterized in terms of yield, purity, morphology, solubility, structural features, and anti-UV/oxidant activity. The results showed that the monoethanolamine-based ADES demonstrated superior performance among the pure ADESs. Structural analysis confirmed the well-preserved substructures of lignin fractions obtained using ADESs, with ß-O-4 bond retention ranging from 49.8 % to 68.4 %. The incorporation of a suitable amount of peroxide improved lignin yield, morphology, solubility, and anti-UV/oxidant activity. Additionally, the anti-UV/oxidant activity of lignin exhibited a positive correlation with its phenolic hydroxyl content. This study provides a valuable reference for the green and sustainable production and valorization of lignin within the existing biorefinery framework.
Asunto(s)
Disolventes Eutécticos Profundos , Lignina , Lignina/química , Solventes/química , Antioxidantes , Biomasa , Oxidantes , HidrólisisRESUMEN
Increasing application for lignin due to its unique aromatic structures has encouraged the development of pretreatment techniques for lignin separation and recovery. In this work, the integration of microwave-assisted hydrothermal pretreatment (MW-HTP) and alkaline post-treatment was proposed for separating lignin from poplar wood and revealing its structural characteristics. Results showed that the yields of the lignins fractionated via the integrated treatment based on MW-HTP were increased up to 52.6%, and their associated sugars contents were clearly decreased to 0.19-0.09%, as compared to the fractionated lignins without the microwave pretreatment (29.8% and 0.29%). Interestingly, the integrated treatment based on MW-HTP promoted the cracking of ß-O-4 ethers in the lignin macromolecules of poplar wood, resulting in the raise of their phenol OH groups up to 2.36 mmol/g. Overall, the fulfillment of this work will be conducive to improve the fractionation and efficient utilization of lignin in biorefinery industry.
Asunto(s)
Lignina/química , Microondas , Populus/química , Temperatura , Agua/química , Espectroscopía de Resonancia Magnética con Carbono-13 , Fraccionamiento Químico , Peso Molecular , Espectroscopía Infrarroja por Transformada de Fourier , Azúcares/análisisRESUMEN
BACKGROUND: In view of the natural resistance of hemicelluloses in lignocellulosic biomass on bioconversion of cellulose into fermentable sugars, alkali extraction is considered as an effective method for gradually fractionating hemicelluloses and increasing the bioconversion efficiency of cellulose. In the present study, sequential alkaline extractions were performed on the delignified ryegrass material to achieve high bioconversion efficiency of cellulose and comprehensively investigated the structural features of hemicellulosic fractions for further applications. RESULTS: Sequential alkaline extractions removed hemicelluloses from cellulose-rich substrates and degraded part of amorphous cellulose, reducing yields of cellulose-rich substrates from 73.0 to 27.7% and increasing crystallinity indexes from 31.7 to 41.0%. Alkaline extraction enhanced bioconversion of cellulose by removal of hemicelluloses and swelling of cellulose, increasing of enzymatic hydrolysis from 72.3 to 95.3%. In addition, alkaline extraction gradually fractionated hemicelluloses into six fractions, containing arabinoxylans as the main polysaccharides and part of ß-glucans. Simultaneously, increasing of alkaline concentration degraded hemicellulosic polysaccharides, which resulted in a decreasing their molecular weights from 67,510 to 50,720 g/mol. CONCLUSIONS: The present study demonstrated that the sequential alkaline extraction conditions had significant effects on the enzymatic hydrolysis efficiency of cellulose and the investigation of the physicochemical properties of hemicellulose. Overall, the investigation the enzymatic hydrolysis efficiency of cellulose-rich substrates and the structural features of hemicelluloses from ryegrass will provide useful information for the efficient utilization of cellulose and hemicelluloses in biorefineries.
RESUMEN
To reveal the structural characteristics and physicochemical properties of perennial ryegrass lignin, sequential alkali extractions or double ball-milling and enzymatic hydrolysis on the basis of ultrasonic and hydrothermal pretreatments were proposed in this study. Results revealed that sequential alkali extractions released 89.4% of original lignin from the ryegrass cell walls and 0.75-4.16% of associated carbohydrates as compared to the double ball-milling and enzymatic hydrolysis (96.0% and 18.39%). It was observed that the two types of lignin prepared were SGH-type and had different amounts of p-coumarates and ferulates, and primarily consisted of ß-O-4' linkages combined with minor amounts of ß-ß' and ß-5' linkages. Besides, alkali-soluble lignins exhibited relatively fewer ß-O-4' linkages, higher S/G ratios and H-type units, and abundant phenolic OH groups as compared to the double enzymatic lignin. Overall, the deeper investigation of the lignin structure of ryegrass will provide useful information for the efficient utilization of lignin macromolecules in biorefineries.
Asunto(s)
Lignina/química , Lolium/química , Álcalis/químicaRESUMEN
An integrated treatment coupling ultrasonic and hydrothermal pretreatments with sequential alkali post-extractions was performed to isolate and characterize hemicelluloses from perennial ryegrass and improve the enzymatic hydrolysis efficiency of cellulose. The yield, chemical composition, and structure of water-soluble and alkali-soluble hemicelluloses obtained from the hydrothermal supernatant and hydrothermally pretreated ryegrass as well as the enzymatic hydrolysis efficiency of cellulose were comprehensively investigated by gel permeation chromatograph, high-performance anion exchange chromatography, Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectra. Results showed that more than 90 % of the original hemicelluloses in ryegrass were released during the integrated treatment and all hemicellulosic fractions obtained were mainly composed of Ê-arabino-(4-O-methyl-á´ -glucurono)-á´ -xylans, galactoanrabinoxylans and ß-glucans. In addition, the effective removal of amorphous hemicelluloses and lignin significantly increased the cellulose enzymatic hydrolysis rate of ryegrass from 43.8 to 91.1 %. These results provided new insights into the collaborative utilization of hemicelluloses and cellulose in ryegrass.
Asunto(s)
Lolium/química , Polisacáridos/química , Álcalis , Celulasa/metabolismo , Celulosa/química , Celulosa/metabolismo , Cristalización , Hidrólisis , Peso Molecular , Resonancia Magnética Nuclear Biomolecular , Polisacáridos/aislamiento & purificación , Polisacáridos/metabolismo , Solubilidad , Espectroscopía Infrarroja por Transformada de Fourier , UltrasonidoRESUMEN
Hereon, tobacco stalk was deconstructed by lyophilization, ball-milling, ultrasound-assisted alkali extraction, hydrothermal pretreatment (HTP), and alkali presoaking, respectively, followed by dilute alkali cooking to both improve its enzymatic digestibility and isolate the hemicellulosic streams. It was found that a maximum cellulose saccharification rate of 93.5% was achieved from the integrated substrate by ball-milling and dilute alkali cooking, which was 4.4-fold higher than that from the raw material. Interestingly, in this case, 76.9% of hemicelluloses were simultaneously recovered during the integrated treatment. Structural determination indicated that the hemicelluloses released from tobacco stalk by dilute alkali cooking were mixed polysaccharides, and the (1 â 4)-linked ß-D-Xylp backbone branched with L-Araf units at O-2/O-3 and 4-O-Me-α-D-GlcpA units at O-2 of the xylose residues was the main structure. In comparison, ultrasound-assisted alkali extraction, ball-milling, and HTP favored the extraction of hemicelluloses with less branched structure and lower molecular weights in the following alkali cooking.