16 research outputs found
Characterization and Hydrothermal Conversion of Lignin Produced from Corncob Acid Hydrolysis Residue
Lignin is one of the main components of corncob acid hydrolysis residue (CAHR). It can be used as a feedstock for biomaterial and biochemical production via biorefining. In this study, CAHR lignin was extracted, and enzymatic/mild acidolysis lignin (EMAL) was produced to ensure efficient lignin recovery. Next, hydrothermal conversion of the EMAL was carried out. The influences of process conditions including the temperature, time, and mass ratio of deionized water to EMAL on the hydrothermal conversion were thoroughly investigated to quantify analysis of the aromatics. EMAL produced from CAHR had a structure of the G-S-H type, in which the p-hydroxyphenyl unit was the primary structural unit, followed by the guaiacyl structural unit. The syringyl structural unit was less common. The yields (wt. %) of phenol, guaiacol, and 4-ethyl-phenol reached maxima of 1.26%, 0.75%, and 1.16%, respectively, at a reaction temperature of 310 °C and time of 30 min with a mass ratio of 80:1
Catalysis of Glucose to 5-Hydroxymethylfurfural using Sn-Beta Zeolites and a Brønsted Acid in Biphasic Systems
Selective and efficient dehydration of glucose to 5-hydroxymethylfurfural (HMF) has been a widely explored concept recently, especially from the perspective of employing environmentally benign heterogeneous catalysts. However, there has been a relative paucity of data regarding the application of Sn-Beta zeolites, a category of catalysts that are very innocuous, inexpensive, and effective, toward evaluating bio-based conversions. Sn-Beta was shown to possess good Lewis acidity for catalyzing glucose isomerization to fructose in aqueous media at low pH and accelerating dehydration of glucose to HMF in a biphasic system with high yields. Sn-Beta zeolite with NH4F as the mineralizing agent (Sn-Beta-F) was a more effective catalyst for the selective dehydration of glucose to HMF. An optimal HMF yield of 53.0% was obtained over Sn-Beta-F zeolite in an acidic environment (pH 1) after 70 min at 190 °C. The reaction system was also effective for conversion of cellulose to HMF with a yield of 32.2% preliminarily
Ionic Liquid-Mediated Homogeneous Esterification of Cinnamic Anhydride to Xylans
A new functional biopolymer was synthesized through an ionic liquid-mediated homogeneous grafting of cinnamic anhydride to xylans. The ionic liquid used was 1-allyl-3-methylimidazolium chloride (AMIMCl) ionic liquid. Xylans with degrees of substitution (DS) between 0.11 and 0.57 were accessible in a completely homogeneous system by changing catalysts (NaOH, KOH and LiOH), time, reaction temperature, and cinnamic anhydride/xylan molar ratio. The chemical structure and the thermal stability of the derivatives were characterized by Fourier transform infrared spectroscopy (FT-IR), 13C-NMR spectroscopy, and thermogravimetry. The thermal stability of the derivatives was reduced compared with the original xylan. Possible applications of the cinnamic anhydride-acylated xylan derivatives include wet-end papermaking, organic–inorganic composite films, and hydrogels
Supercritical Water-induced Lignin Decomposition Reactions: A Structural and Quantitative Study
The use of supercritical water for the decomposition of lignin and evaluation of its influence on lignin decomposition and conversion to various products was the thrust of the current study. Poplar alkali lignin (AL), corncob-to-xylitol residue lignin (XRL), and cornstalk-to-ethanol residue lignin (ERL) were the lignin species studied because they constitute the main residual lignins available in the biomass refinery industry. The lignins were characterized by elementary analysis, Fourier transform infrared spectrometry (FT-IR), phosphorus nuclear magnetic resonance (31P-NMR), and X-ray diffraction (XRD), and their hydrothermal depolymerization products were analyzed by gas chromatography-mass spectrometer (GC–MS). The results showed that the residual lignin is a potential source for valuable aromatics. The XRL had the best total phenolics yield, 140 mg/g, while AL had the lowest, 90 mg/g. The maximum yields of phenol (28.94 mg/g) and 4-ethylphenol (36.21 mg/g) were obtained from XRL depolymerization at 375 °C for 30 min, and the optimal yields of guaiacol (14.34 mg/g) and 2,6-dimethoxyphenol (15.67 mg/g) were achieved by AL at 375 °C for 30 min. The information here provides some insights toward developing selective biorefinery methods for lignin-to-organic products conversion processes
Preparation and Characterization of Size-Controlled Lignin Nanoparticles with Deep Eutectic Solvents by Nanoprecipitation
Lignin nanomaterials have wide application prospects in the fields of cosmetics delivery, energy storage, and environmental governance. In this study, we developed a simple and sustainable synthesis approach to produce uniform lignin nanoparticles (LNPs) by dissolving industrial lignin in deep eutectic solvents (DESs) followed by a self-assembling process. LNPs with high yield could be obtained through nanoprecipitation. The LNPs were characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC). Distinct LNPs could be produced by changing the type of DES, lignin sources, pre-dropping lignin concentration, and the pH of the system. Their diameter is in the range of 20–200 nm and they show excellent dispersibility and superior long-term stability. The method of preparing LNPs from lignin–DES with water as an anti-solvent is simple, rapid, and environmentally friendly. The outcome aids to further the advancement of lignin-based nanotechnology
Characterization of Lignin Extracted from Willow by Deep Eutectic Solvent Treatments
Purity, morphology, and structural characterization of synthesized deep eutectic solvent (DES)-lignins (D6h, D9h, D12h, D18h, D24h) extracted from willow (Salix matsudana cv. Zhuliu) after treatment with a 1:10 molar ratio of choline chloride and lactic acid at 120 °C for 6, 9, 12, 18, and 24 h were carried out. The purity of DES-lignin was ~95.4%. The proportion of hydrogen (H) in DES-lignin samples increased from 4.22% to 6.90% with lignin extraction time. The DES-lignin samples had low number/weight average molecular weights (1348.1/1806.7 to 920.2/1042.5 g/mol, from D6h to D24h) and low particle sizes (702–400 nm). Atomic force microscopy (AFM) analysis demonstrated that DES-lignin nanoparticles had smooth surfaces and diameters of 200–420 nm. Syringyl (S) units were dominant, and total phenolic hydroxyl content and total hydroxyl content reached their highest values of 2.05 and 3.42 mmol·g−1 in D12h and D6h, respectively. β-Aryl ether (β-O-4) linkages were eliminated during DES treatment
Lignin Nanoparticles and Alginate Gel Beads: Preparation, Characterization and Removal of Methylene Blue
A novel and effective green system consisting of deep eutectic solvent (DES) was proposed to prepare lignin nanoparticles (LNPs) without any lignin modification. The LNPs are obtained through the dialysis of the kraft lignin-DES solution. The particle size distribution, Zeta potential and morphology of the LNPs are characterized by using dynamic light scattering (DLS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The average diameter of LNPs is in the range 123.6 to 140.7 nm, and the LNPs show good stability and dispersibility in water. The composite beads composed of LNPs and sodium alginate (SA) are highly efficient (97.1%) at removing methylene blue (MB) from the aqueous solution compared to 82.9% and 77.4% by the SA/bulk kraft lignin composite and pure SA, respectively. Overall, the LNPs-SA bio-nanocomposite with high adsorption capacity (258.5 mg/g) could be useful in improving water quality and other related applications
Deep Eutectic Solvents (DESs) for the Isolation of Willow Lignin (Salix matsudana cv. Zhuliu)
Deep eutectic solvents (DESs) are a potentially high-value lignin extraction methodology. DESs prepared from choline chloride (ChCl) and three hydrogen-bond donors (HBD)—lactic acid (Lac), glycerol, and urea—were evaluated for isolation of willow (Salix matsudana cv. Zhuliu) lignin. DESs types, mole ratio of ChCl to HBD, extraction temperature, and time on the fractionated DES-lignin yield demonstrated that the optimal DES-lignin yield (91.8 wt % based on the initial lignin in willow) with high purity of 94.5% can be reached at a ChCl-to-Lac molar ratio of 1:10, extraction temperature of 120 °C, and time of 12 h. Fourier transform infrared spectroscopy (FT-IR) , 13C-NMR, and 31P-NMR showed that willow lignin extracted by ChCl-Lac was mainly composed of syringyl and guaiacyl units. Serendipitously, a majority of the glucan in willow was preserved after ChCl-Lac treatment
Mechanistic Investigation of Rice Straw Lignin Subunit Bond Cleavages and Subsequent Formation of Monophenols
Lignin is a superb
renewable feedstock for deriving petroleum-analogous
biochemicals and value-added bioproducts. However, proper elucidation
of its original biosynthetic structure and subsequent deconstruction
is necessary to facilitate proper exploitation. Herein, its chemical
substructure and linkages within an important global feedstock, rice
straw, were interrogated by spectroscopy. Pyrolysis was chosen to
cleave it and obtain guaiacyl (G), syringyl (S), and hydroxyphenyl
(H) monophenols distributions at various temperatures. A unique relationship
between product substructures and lignin depolymerization was revealed.
The overall scope of the depolymerization mechanism into monophenols
by cleavage of β-O-4 and β-5 in phenylcoumaran subunits
were explored experimentally and through bond dissociation energy
(BDE) theory