Thermodynamic and Kinetic Equilibrium for Adsorption of Cellulosic Xylose of Commercial Cation-Exchange Resins.

The development of low-cost purification technology is an indispensable need for industrial biorefinery. Xylose is easily obtained from hydrothermal pretreatment of lignocellulosic biomass. This current study emphasizes the chromatographic monosaccharide separation process using commercial cation-exchange resins (CER) including Amberlite 120 and Indion 225 to separate xylose from a mixture of hydrolysates. To understand the performance of the two CER, the studies of equilibrium, thermodynamics, and kinetics were evaluated. In this study, with different xylose concentrations, the adsorption equilibrium was found to follow the Freundlich isotherm model well (R2 > 0.90 for both CER). The results indicated that a pseudo-second-order model represented the xylose adsorption kinetics. In addition, the activation energy of xylose adsorption onto both CER, i.e., Amberlite 120 and Indion 225 was 34.9 and 87.1 kJ/mol, respectively. The present adsorption studies revealed the potential of these commercial CER to be employed as effective adsorbents for monosaccharide separation technology.

Fiber Melt Spinning and Thermo-Stabilization of Para-Rubber Wood Lignin: An Approach for Fully Biomass Precursor Preparation.

Para-rubber wood (PRW) lignin, extracted from agricultural waste, was successfully melt-spun to fibers and thermo-stabilized without employing auxiliary additives. 31P NMR analysis revealed that PRW-lignin contained mainly a syringyl unit of phenolic C5-substituted OH group, which enabled melt flow during fiber spinning, as well as a guaiacyl unit which offered the ability to cross-link during thermo-stabilization. Thermo-stabilized fibers with no fusion were achieved at 250 °C with the heating rate of 0.1 °C/min. Structural changes in the fibers during stabilization were systematically investigated using FTIR and XPS analyses. From the results, changes in the intensities of characteristic bands relating to C-H stretching, aromatic C-H stretching, and C=O stretching indicated structural changes of lignin toward aromaticity via oxidation reactions. XPS analysis of the fibers carbonized at 900, 1000, and 1200 °C revealed an increase in carbon content from 72 to 87 wt %. and a decrease in oxygen content from 28 to 13 wt %. with the increasing carbonization temperature. The weight loss of carbonized fibers was in the range of 73.6 to 88.7%. The high weight loss of fibers carbonized at 1200 °C was explained partly due to the thermal decomposition of disordered carbon. The tensile strength and modulus of carbonized fibers were 163.0 and 275.1 MPa, respectively. This study demonstrates an approach to prepare a fully biomass precursor fiber and contributes to the exploration of the potential use of lignin from biomass waste.

Physicochemical characteristics of organosolv lignins from different lignocellulosic agricultural wastes.

Lignin is a promising alternative to petrochemical precursors for conversion to industrial-needed products. Organosolv lignins were extracted from different agricultural wastes including sugarcane bagasse (BG) and trash (ST), corncob (CC), eucalyptus wood (EW), pararubber woodchip (PRW), and palm wastes (palm kernel cake (PKC), palm fiber (PF), and palm kernel shell (PKS), representing different groups of lignin origins. Physicochemical characteristics of lignins were analyzed by several principal techniques. Most recovered lignin showed high purity of >90 % with trace sugar contamination, while lower purities were found for lignin from palm wastes. Hardwood lignins (EW and PRW) mainly contained guaiacyl (G) and syringyl (S) units with a minor fraction of p-hydroxyphenyl units (H) with high molecular weight, glass transition temperature, phenolic hydroxy group and low aliphatic hydroxy group. Grass-type lignins (BG, ST, CC) and palm lignins (PKC, PF, and PKS) contained three monolignols of H, G, and S units with lower molecular weights and C5-substituted hydroxy of S unit. Among the grass-type lignins, PKC lignin contained the highest nitrogen and lipophilic components with the lowest molecular weight, thermal stability, and glass transition temperature. This provides insights into properties of organosolv lignin as basis for their further applications in chemical, polymer and material industries.

Characterization of Cellulose-Chitosan-Based Materials from Different Lignocellulosic Residues Prepared by the Ethanosolv Process and Bleaching Treatment with Hydrogen Peroxide.

Cellulose-based composites are promising biomaterials with potent applications in absorbents, cosmetics, and healthcare industries. In this study, the cellulose fractions from various agricultural residues, including bagasse (BG), rice straw (RS), corncob (CC), and palm fiber (PF), were prepared by the organosolv process using 70% v/v ethanol, followed by bleaching and forming with chitosan powder. Organosolv treatment at 180 °C of BG, RS, and PF and at 190 °C of CC for 60 min using H2SO4 as the catalyst was optimal for high cellulose recovery (87.9-98.9%) with efficient removals of the hemicellulose (59.3-86.0%) and lignin (61.1-73.7%). High cellulose purity in the solids (76.9-86.8%) was obtained after bleaching with 4% v/v H2O2 compared with that of 84.9% for commercial cellulose. The isolated celluloses were incubated with 2% w/v chitosan solution in acetic acid for the formation of the hydrogen-bonding interaction between the cellulose fiber and chitosan. The pieces of evidence of the obtained sheet materials were characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction analysis, and thermogravimetric analysis. All cellulose-chitosan materials absorbed water fraction in the range of 54.3-94.2 g/m2. Efficient oil absorption was observed for cellulose-chitosan sheets prepared from PF (96.3 g/m2) and CC (81.1 g/m2). This work demonstrated the preparation of potent biobased absorbents with a promising application in waste treatment and healthcare industries.

Effects of alkaline catalysts on acetone-based organosolv pretreatment of rice straw.

Organosolv is an effective pretreatment strategy for increasing digestibility of lignocellulosic materials owing to selectivity of solvents on separating biopolymeric constituents of plant biomass. In the present work, a novel low-temperature alkali-catalyzed organosolv pretreatment of rice straw was studied. The effects of alkaline catalysts (i.e., NaOH, ammonia, and tri-ethylamine) and solvent types (i.e., acetone, ethanol, and water) were carried out. Addition of alkalis led to increasing sugar from enzymatic hydrolysis while acetone was found to be superior to ethanol and water on selectivity towards cellulose preservation. The optimal alkaline-catalyzed pretreatment reaction contained 5% (w/v) NaOH in an aqueous-acetone mixture (1:4) at 80 °C for 5 min. A glucose yield of 913 mg/g of pretreated biomass was achieved, equivalent to a maximal glucose recovery of 93.0% from glucan in the native biomass. Scanning electron microscope revealed efficient removal of non-cellulosic components, resulting in exposed cellulose microfibers with a reduced crystallite size as determined by X-ray diffraction. With potential on obtaining high-quality lignin, the work demonstrated potential of the novel low-temperature alkaline-catalyzed acetone-based organosolv process for pretreatment of lignocellulosic materials in biorefineries.

Biocatalytic synthesis of starch esters by immobilized lipase on magnetic microparticles.

Enzymatic esterification is an efficient approach for modifying starch to functionalized biomaterials. In this study, conversion of cassava starch to fatty acid acyl esters using immobilized Thermomyces lanuginosus lipase on Fe3O4 microparticles modified with 3-aminopropyltriethoxysilane and covalently linked by 1-ethyl-3-(3-dimethyl aminopropyl) carbodiimide and N-hydroxysuccinimide (Fe3O4-AP-ED-lipase) in a solvent-free system was studied. An optimized reaction containing 5% w/v gelatinized starch, 1% v/v Triton X-100, and 1% w/v biocatalyst with 2.5% w/v of fatty acids (palmitic, oleic, or linoleic acid) resulted in esterified products with a degree of substitution (DS) of 0.12-0.14, while a slightly lower DS was observed using crude palm fatty acid distillate as the acyl donor with 42.9-59.6% recovery yield. Increasing DS led to lower glass transition temperature and higher viscosity of the esterified products. The enzyme showed high operational stability with 85% retaining in activity after recycling in three consecutive batches with simple separation by magnetization, leading to improved process economics.

Biocatalytic methanolysis activities of cross-linked protein-coated microcrystalline lipase toward esterification/transesterification of relevant palm products.

Biocatalysis by immobilized lipase is an efficient alternative process for conversion of crude vegetable oil with high free fatty acid content to biodiesel, which is the limit of the conventional alkaline-catalyzed reaction. In this study, influences of solid-state organic and inorganic buffer core matrices with different pKa on catalytic performance of cross-linked protein coated microcrystalline biocatalysts prepared from Thermomyces lanuginosus lipase (CL-PCMC-LIP) toward esterification of palmitic acid (PA), transesterification of refined palm oil (RPO), and co-ester/transesterification of crude palm oil (CPO) to fatty acid methyl ester (FAME) was studied. Glycine, CAPSO (3-(cyclohexylamino)-2-hydroxy-1-propanesulfonic acid), and TAPS ([(2-hydroxy-1,1-bis(hydroxymethyl)ethyl)amino]-1-propanesulfonic acid) were shown to be potent core matrices for these reactions. The optimal reaction contained 4:1 [methanol]/[fatty acid] molar equivalence ratio with 20% (w/w) CL-PCMC-LIP on glycine in the presence of tert-butanol as a co-solvent. Deactivation effect of glycerol on the biocatalyst reactive surface was shown by FTIR, which could be alleviated by increasing co-solvent content. The maximal FAME yields from PA, RPO, and CPO reached 97.6, 94.9, and 95.5%, respectively on a molar basis under the optimum conditions after incubation at 50°C for 6h. The biocatalyst retained >80% activity after recycling in five consecutive batches. The work demonstrates the potential of CL-PCMC-LIP on one-step conversion of inexpensive crude fatty acid-rich feedstock to biodiesel.