On the Effect of Hot-Water Pretreatment in Sulfur-Free Pulping of Aspen and Wheat Straw.
ABSTRACT: In modern biorefineries, low value lignin and hemicellulose fractions are produced as side streams. New extraction methods for their purification are needed in order to utilize the whole biomass more efficiently and to produce special target products. In several new applications using plant-based biomaterials, the native-type chemical and polymeric properties are desired. Especially, production of high-quality native-type lignin enables valorization of biomass entirely, thus making novel processes sustainable and economically viable. To investigate sulfur-free possibilities for so-called "lignin first" technologies, we compared alkaline organosolv, formic acid organosolv, and ionic liquid processes to simple soda "cooking" using wheat straw and aspen as raw materials. All experiments were carried out using microwave-assisted pulping approach to enable rapid heat transfer and convenient control of temperature and pressure. The main target was to evaluate the advantage of a brief hot water extraction as a pretreatment for the pulping process. Most of these novel pulping methods resulted in high-quality lignin, which may be valorized more diversely than kraft lignin. Lignin fractions were thoroughly analyzed with NMR (13C and HSQC) and gel permeation chromatography to study the quality of the collected lignin. The cellulose fractions were analyzed by determining their lignin contents and carbohydrate profiles for further utilization in cellulose-based products or biofuels.
Project description:During biomass fractionation, any native acetylation of lignin and heteropolysaccharide may affect the process and the resulting lignin structure. In this study, Typha capensis (TC) and its lignin isolated by milling (MWL), ionosolv (ILL) and organosolv (EOL) methods were investigated for acetyl group content using FT-Raman, ¹H NMR, 2D-NMR, back-titration, and Zemplén transesterification analytical methods. The study revealed that TC is a highly acetylated grass; extractive free TC (TCextr) and TC MWL exhibited similar values of acetyl content: 6 wt % and 8 wt % by Zemplén transesterification, respectively, and 11 wt % by back-titration. In contrast, lignin extracted from organosolv and [EMIm][OAc] pulping lost 80% of the original acetyl groups. With a high acetyl content in the natural state, TC could be an interesting raw material in biorefinery in which acetic acid could become an important by-product.
Project description:In order to make better use of lignocellulosic biomass for the production of renewable fuels and chemicals, it is necessary to disrupt its recalcitrant structure through pretreatment. Specifically, organosolv pretreatment is a feasible method. The main advantage of this method compared to other lignocellulosic pretreatment technologies is the extraction of high-quality lignin for the production of value-added products. In this study, bamboo was treated in a batch reactor with 70% ethanol at 180 °C for 2 h. Lignin fractions were isolated from the hydrolysate by centrifugation and then precipitated as ethanol organosolv lignin. Two types of milled wood lignins (MWLs) were isolated from the raw bamboo and the organosolv pretreated residue separately. After the pretreatment, a decrease of lignin (preferentially guaiacyl unit), hemicelluloses and less ordered cellulose was detected in the bamboo material. It was confirmed that the bamboo MWL is of HGS type (p-hydroxyphenyl (H), vanillin (G), syringaldehyde (S)) associated with a considerable amount of p-coumarate and ferulic esters of lignin. The ethanol organosolv treatment was shown to remove significant amounts of lignin and hemicelluloses without strongly affecting lignin primary structure and its lignin functional groups.
Project description:Hybrid poplar genetically engineered to possess chemically labile ester linkages in its lignin backbone (zip-lignin hybrid poplar) was examined to determine if the strategic lignin modifications would enhance chemical pulping efficiencies. Kraft pulping of zip-lignin and wild-type hybrid poplar was performed in lab-scale reactors under conditions of varying severity by altering time, temperature and chemical charge. The resulting pulps were analyzed for yield, residual lignin content, and cellulose DP (degree of polymerization), as well as changes in carbohydrates and lignin structure. Statistical models of pulping were created, and the pulp bleaching and physical properties evaluated. Under identical cooking conditions, compared to wild-type, the zip-lignin hybrid poplar showed extended delignification, confirming the zip-lignin effect. Additionally, yield and carbohydrate content of the ensuing pulps were slightly elevated, as was the cellulose DP for zip-lignin poplar pulp, although differences in residual lignin between zip-lignin and wild-type poplar were not detected. Statistical prediction models facilitated comparisons between pulping conditions that resulted in identical delignification, with the zip-lignin poplar needing milder cooking conditions and resulting in higher pulp yield (up to 1.41?% gain). Bleaching and physical properties were subsequently equivalent between the samples with slight chemical savings realized in the zip-lignin samples due to the enhanced delignification.
Project description:Fractionation of lignocellulose into its three main components, lignin, hemicelluloses, and cellulose, is a common approach in modern biorefinery concepts. Whereas the valorization of hemicelluloses and cellulose sugars has been widely discussed in literature, lignin utilization is still challenging. Due to its high heterogeneity and complexity, as well as impurities from pulping, it is a challenging feedstock. However, being the most abundant source of renewable aromatics, it remains a promising resource. This work describes a fractionation procedure that aims at stepwise precipitating beech wood (Fagus sp.) lignin obtained with OrganoCat technology from a 2-methyltetrahydrofuran solution, using n-hexane and n-pentane as antisolvents. By consecutive antisolvent precipitation and filtration, lignin is fractionated and then characterized to elucidate the structure of the different fractions. This way, more defined and purified lignin fractions can be obtained. Narrowing down the complexity of lignin and separately valorizing the fractions might further increase the economic viability of biorefineries.
Project description:Background:Lignocellulosic biomass will progressively become the main source of carbon for a number of products as the Earth's oil reservoirs disappear. Technology for conversion of wood fiber into bioproducts (wood biorefining) continues to flourish, and access to reliable methods for monitoring modification of such fibers is becoming an important issue. Recently, we developed a simple, rapid approach for detecting four different types of polymer on the surface of wood fibers. Named fluorescent-tagged carbohydrate-binding module (FTCM), this method is based on the fluorescence signal from carbohydrate-binding modules-based probes designed to recognize specific polymers such as crystalline cellulose, amorphous cellulose, xylan, and mannan. Results:Here we used FTCM to characterize pulps made from softwood and hardwood that were prepared using Kraft or chemical-thermo-mechanical pulping. Comparison of chemical analysis (NREL protocol) and FTCM revealed that FTCM results were consistent with chemical analysis of the hemicellulose composition of both hardwood and softwood samples. Kraft pulping increased the difference between softwood and hardwood surface mannans, and increased xylan exposure. This suggests that Kraft pulping leads to exposure of xylan after removal of both lignin and mannan. Impact of enzyme cocktails from Trichoderma reesei (Celluclast 1.5L) and from Aspergillus sp. (Carezyme 1000L) was investigated by analysis of hydrolyzed sugars and by FTCM. Both enzymes preparations released cellobiose and glucose from pulps, with the cocktail from Trichoderma being the most efficient. Enzymatic treatments were not as effective at converting chemical-thermomechanical pulps to simple sugars, regardless of wood type. FTCM revealed that amorphous cellulose was the primary target of either enzyme preparation, which resulted in a higher proportion of crystalline cellulose on the surface after enzymatic treatment. FTCM confirmed that enzymes from Aspergillus had little impact on exposed hemicelluloses, but that enzymes from the more aggressive Trichoderma cocktail reduced hemicelluloses at the surface. Conclusions:Overall, this study indicates that treatment with enzymes from Trichoderma is appropriate for generating crystalline cellulose at fiber surface. Applications such as nanocellulose or composites requiring chemical resistance would benefit from this enzymatic treatment. The milder enzyme mixture from Aspergillus allowed for removal of amorphous cellulose while preserving hemicelluloses at fiber surface, which makes this treatment appropriate for new paper products where surface chemical responsiveness is required.
Project description:The production of chemicals and various materials from black liquor lignin will greatly improve the economics of biomass refining. In the present work, organosolv lignin residues (OLRs) from the organosolv pulping process were used to fabricate submicron lignin spheres using ethanol/water mixtures as an antisolvent, in conjunction with homogenization. Both the ethanol content in the ethanol/water mixture and the applications of homogenization were investigated as key factors affecting the agglomeration of OLRs. The results show that the solubility of the amphiphilic OLRs in ethanol was approximately 28 and 32 times greater than those of alkali lignin and kraft lignin, respectively. Using the optimal percentage of ethanol together with homogenization enhanced the nucleation of lignin macromolecules, such that the colloidal spheres of OLR were spontaneously assembled via gradual hydrophilic-lipophilic aggregation. The resulting OLR colloidal spheres had a yolk-shell structure and a mean particle diameter of around 200 nm, when the ethanol content was 50% and the homogenization time was 15 min or more. This study demonstrates a simple means of utilizing OLRs to produce lignin-based spheres. The lignin spheres generated in this work are thought to have potential applications in many fields as porous carbon precursors for energy storage, sensitive functional materials, and controlled-release fertilizer carriers.
Project description:A shift towards a sustainable and green society is vital to reduce the negative effects of climate change associated with increased CO2 emissions. Lignocellulosic biomass is both renewable and abundant, but is recalcitrant to deconstruction. Among the methods of pretreatment available, organosolv (OS) delignifies cellulose efficiently, significantly improving its digestibility by enzymes. We have assessed the hydrolysability of the cellulose-rich solid fractions from OS-pretreated spruce and birch at 2% w/v loading (dry matter). Almost complete saccharification of birch was possible with 80 mg enzyme preparation/gsolids (12 FPU/gsolids), while the saccharification yield for spruce was only 70%, even when applying 60 FPU/gsolids. As the cellulose content is enriched by OS, the yield of glucose was higher than in their steam-exploded counterparts. The hydrolysate was a transparent liquid due to the absence of phenolics and was also free from inhibitors. OS pretreatment holds potential for use in a large-scale, closed-loop biorefinery producing fuels from the cellulose fraction and platform chemicals from the hemicellulose and lignin fractions respectively.
Project description:In order to obtain accurate information about the ultrastructure of cellulose from native biomass by 13C cross polarization magic angle spinning (CP/MAS) NMR spectroscopy the cellulose component must be isolated due to overlapping resonances from both lignin and hemicellulose. Typically, cellulose isolation has been achieved via holocellulose pulping to remove lignin followed by an acid hydrolysis procedure to remove the hemicellulose components. Using 13C CP/MAS NMR and non-linear line-fitting of the cellulose C? region, it was observed that the standard acid hydrolysis procedure caused an apparent increase in crystallinity of ~10% or less on the cellulose isolated from Populus holocellulose. We have examined the effect of the cellulose isolation method, particularly the acid treatment time for hemicellulose removal, on cellulose ultrastructural characteristics by studying these effects on cotton, microcrystalline cellulose (MCC) and holocellulose pulped Populus. 13C CP/MAS NMR of MCC indicated that holocellulose pulping and acid hydrolysis has little effect on the crystalline ultrastructural components of cellulose. Although any chemical method to isolate cellulose from native biomass will invariably alter substrate characteristics, especially those related to regions accessible to solvents, we found those changes to be minimal and consistent in samples of typical crystallinity and lignin/hemicellulose content. Based on the rate of the hemicellulose removal, as determined by HPLC-carbohydrate analysis and magnitude of cellulose ultrastructural alteration, the most suitable cellulose isolation methodology utilizes a treatment of 2.5 M HCl at 100 °C for a standard residence time between 1.5 and 4 h. However, for the most accurate crystallinity results this residence time should be determined empirically for a particular sample.
Project description:Background:The forest biorefinery plays an important part in the evolving circular bioeconomy due to its capacity to produce a portfolio of bio-based and sustainable fuels, chemicals, and materials. To tap into its true potential, more efficient and environmentally benign methods are needed to fractionate woody biomass into its main components (cellulose, hemicellulose, and lignin) without reducing their potential for valorization. This work presents a sequential fractionation method for hardwood based on steam pretreatment (STEX) and hydrotropic extraction (HEX) with sodium xylene sulfonate. By prehydrolyzing the hemicellulose (STEX) and subsequently extract the lignin from the cellulose fraction (HEX), the major wood components can be recovered in separate process streams and be further valorized. Results:Using autocatalyzed STEX and HEX, hemicellulose (>?70%) and lignin (~?50%) were successfully fractionated and recovered in separate liquid streams and cellulose preserved (99%) and enriched (~?twofold) in the retained solids. Investigation of pretreatment conditions during HEX showed only incremental effects of temperature (150-190 °C) and hold-up time (2-8 h) variations on the fractionation efficiency. The hydrolyzability of the cellulose-rich solids was analyzed and showed higher cellulose conversion when treated with the combined process (47%) than with HEX alone (29%), but was inferior to STEX alone (75%). Protein adsorption and surface structure analysis suggested decreased accessibility due to the collapse of the fibrillose cellulose structure and an increasingly hydrophobic lignin as potential reasons. Conclusion:This work shows the potential of sequential STEX and HEX to fractionate and isolate cellulose, hemicellulose, and a sulfur-free lignin in separate product streams, in an efficient, sustainable, and scalable process.
Project description:A one-step formic acid-catalyzed organosolv process using a low-boiling point acid-solvent system was studied for fractionation of sugarcane bagasse. Compared to H2SO4, the use of formic acid as a promoter resulted in higher efficiency and selectivity on removals of hemicellulose and lignin with increased enzymatic digestibility of the cellulose-enriched solid fraction. The optimal condition from central composite design analysis was determined as 40 min residence time at 159 °C using water/ethanol/ethyl acetate/formic acid in the respective ratios of 43:20:16:21%v/v. Under this condition, a 94.6% recovery of cellulose was obtained in the solid with 80.2% cellulose content while 91.4 and 80.4% of hemicellulose and lignin were removed to the aqueous-alcohol-acid and ethyl acetate phases, respectively. Enzymatic hydrolysis of the solid yielded 84.5% glucose recovery compared to available glucan in the raw material. Physicochemical analysis revealed intact cellulose fibers with decreased crystallinity while the hemicellulose was partially recovered as mono- and oligomeric sugars. High-purity organosolv lignin with < 1% sugar cross-contamination was obtained with no major structural modification according to Fourier-transform infrared spectroscopy. The work represents an alternative process for efficient fractionation of lignocellulosic biomass in biorefineries.