Optimization of oxalic acid pretreatment of moso bamboo for textile fiber using response surface methodology

In this article, samples of moso bamboo were pretreated with oxalic acid under various process conditions. Response surface methodology was applied to optimize the pretreatment conditions. A three-variable quadratic polynomial regression model was obtained to predict the cellulose content, lignin removal and hemicellulose solubilization. The reliability of the model was also evaluated by the key elements obtained from analysis of variance of the coefficients. The surface response plot and contour plot of the effects were studied to further examine the interactions of the three factors and determine the optimum levels of each factor. Finally, the optimized conditions for oxalic acid pretreatment were temperature 178.4 °C, 3.68 % oxalic acid and 28.4 min, respectively. The maximum predicted value of cellulose content in the residue fraction was 64.98 %, along with 79.43 % lignin removal and 96.71 % hemicellulose solubilization after the oxalic acid pretreatment.     

Enhancement of the Enzymatic Digestibility and Ethanol Production from Sugarcane Bagasse by Moderate Temperature-Dilute Ammonia Treatment

In this study, sugarcane bagasse was pretreated with ammonium hydroxide, and the effectiveness of the pretreatment on enzyme hydrolysis and ethanol production was examined. Bagasse was soaked in ammonium hydroxide and water at a ratio of 1:0.5:8 for 0–4 days at 70 °C. Approximately, 14–45 % lignin, 2–6 % cellulose, and 13–22 % hemicellulose were removed during a 0.5- to 4-day ammonia soaking period. The highest glucan conversion of sugarcane bagasse soaked in dilute ammonia at moderate temperature by cellulase was accomplished at 78 % with 75 % of the theoretical ethanol yield. Under the same conditions, untreated bagasse resulted in a cellulose digestibility of 29 and 27 % of the theoretical ethanol yield. The increased enzymatic digestibility and ethanol yields after dilute ammonia pretreatment was related to a combined effect of the removal of lignin and increase in the surface area of fibers.     

Compositional Changes in Sugarcane Bagasse on Low Temperature, Long-term Diluted Ammonia Treatment

Sugarcane bagasse is the major by-product of the sugar industry. It has a great potential for the production of biofuels and chemicals due to its considerable amount of cellulose and hemicellulose. In this study, we investigated a simple and economic pretreatment process using dilute ammonia for the storage of sugarcane bagasse. Sugarcane bagasse was stored in 0, 0.03, and 0.3% (w/w) ammonium hydroxide in a closed bottle for 40 days at 30 °C under atmospheric pressure without any agitation or circulation. Samples were taken every 10 days and analyzed for changes on lignin, cellulose, hemicellulose composition, ammonia concentration, and microbial counts. Biomass storage for 40 days at 0.3% ammonium hydroxide removed 46% of lignin and retained 100% cellulose and 73% hemicellulose.     

Solid/liquid- and vapor-phase interactions between cellulose- and lignin-derived pyrolysis products

Solid/liquid- and vapor-phase interactions between cellulose- and lignin (Japanese cedar milled wood lignin)-derived pyrolysis products were studied under the conditions of N₂/600 °C/40–80 s. A dual-space closed ampoule reactor was used to eliminate the solid/liquid-phase interactions, and careful comparison of the resulting data with those of the pyrolysis of the mixed samples gave some insights into the solid/liquid- and vapor-phase interactions separately. With the solid/liquid-phase interactions, the tar yields from both cellulose and lignin increased with the decreasing yields of the char fractions in a short pyrolysis time of 40 s (primary pyrolysis stage). Most of the identified tar components from cellulose and lignin increased in their yields. The vapor-phase interactions were significant at a longer pyrolysis time of 80 s (secondary reaction stage) when the methoxyl groups of the lignin-derived volatiles were cleaved homolytically. The vapor-phase interactions accelerated the gas formation from the cellulose-derived volatiles with suppressing the vapor-phase char formation of the lignin-derived volatiles. The yields of methane and catechols from lignin also increased greatly instead of the formation of o-cresols. Most of these influences are explained with a proposed interaction mechanism, in which the cellulose-derived volatiles act as H-donors while the lignin-derived volatiles (radicals) act as H-acceptors.     

Extraction and Characterization of Cellulose Nanowhiskers from Balsa Wood

Summary: In this study cellulose nanowhiskers were obtained from balsa wood. For this purpose, fibers of balsa wood were exposed to hydrolysis reactions for lignin and hemicellulose digestion and acquisition of nano-scale cellulose. Transmission electron microscopy (TEM) results demonstrated that the obtained cellulose nanocrystals had average length and thickness of 176 (±68 nm) and 7.5 (±2.9 nm), respectively. Infrared spectroscopy (FTIR) and wide angle x-ray diffraction (WAXD) showed that the process for extracting the nanowhiskers digested nearly all the lignin and hemicellulose from the balsa fiber and still preserved the aspect ratio and crystallinity satisfactory enough for future application as nanofillers in polymer nanocomposites. The thermogravimetric analysis (TGA) showed that the onset temperature of thermal degradation of the cellulose nanocrystals (226 °C) was higher than the onset temperature of the balsa fiber (215 °C), allowing its use in molding processes with polymers melts.     

Dielectric properties of lignin and glucomannan as determined by spectroscopic ellipsometry and Lifshitz estimates of non-retarded Hamaker constants

We present in this study a quantitative estimate of the dispersive interactions between lignin, hemicellulose and cellulose, which are the dominating components in wood and also extensively used to produce paper and packaging materials. The dielectric properties in the UV-visible region of spin-coated films of pure lignin and glucomannan were determined by spectroscopic ellipsometry. The non-retarded Hamaker constants were estimated from the determined spectral parameters using Lifshitz theory for lignin and glucomannan interacting with cellulose, titania and calcium carbonate in vacuum, water and hexane. The Hamaker constants for the different combinations of cellulose, lignin and glucomannan fall within a relatively narrow range of 35–58 and 8–17 zJ, for the values in vacuum (air) and water, respectively. The estimated Hamaker constants for the interactions of the wood components with TiO₂ and CaCO₃, common additives in paper, in water range from 3 to 19 zJ, thus being similar in magnitude as the interactions between the wood components themselves. In contrast, the Hamaker constant is essentially zero for glucomannan interacting with calcium carbonate in hexane. The Hamaker constants for lignin, hemicellulose and cellulose determined in this study can provide information regarding the surface interactions important for e.g. adhesion, friction, swelling and wetting in paper processing as well as for the resulting behavior of paper products.     

On-line product analysis of pine wood pyrolysis using synchrotron vacuum ultraviolet photoionization mass spectrometry

The pyrolysis process of pine wood, a promising biofuel feedstock, has been studied with tunable synchrotron vacuum ultraviolet photoionization mass spectrometry. The mass spectra at different photon energies and temperatures as well as time-dependent profiles of several selected species during pine wood pyrolysis process were measured. Based on the relative contents of three lignin subunits, the data indicate that pine wood is typical of softwood. As pyrolysis temperature increased from 300 to 700 °C, some more details of pyrolysis chemistry were observed, including the decrease of oxygen content in high molecular weight species, the observation of high molecular weight products from cellulose chain and lignin polymer, and potential pyrolysis mechanisms for some key species. The formation of polycyclic aromatic hydrocarbons (PAHs) was also observed, as well as three series of pyrolysis products derived from PAHs with mass difference of 14 amu. The time-dependent profiles show that the earliest products are formed from lignin, followed by hemicellulose products, and then species from cellulose.

Kinetic study of wood chips decomposition by TGA

Pyrolysis of a wood chips mixture and main wood compounds such as hemicellulose, cellulose and lignin was investigated by thermogravimetry. The investigation was carried out in inert nitrogen atmosphere with temperatures ranging from 20°C to 900°C for four heating rates: 2 K min⁻¹, 5 K min⁻¹, 10 K min⁻¹, and 15 K min⁻¹. Hemicellulose, cellulose, and lignin were used as the main compounds of biomass. TGA and DTG temperature dependencies were evaluated. Decomposition processes proceed in three main stages: water evaporation, and active and passive pyrolysis. The decomposition of hemicellulose and cellulose takes place in the temperature range of 200–380°C and 250–380°C, while lignin decomposition seems to be ranging from 180°C up to 900°C. The isoconversional method was used to determine kinetic parameters such as activation energy and pre-exponential factor mainly in the stage of active pyrolysis and partially in the passive stage. It was found that, at the end of the decomposition process, the value of activation energy decreases. Reaction order does not have a significant influence on the process because of the high value of the pre-exponential factor. Obtained kinetic parameters were used to calculate simulated decompositions at different heating rates. Experimental data compared with the simulation ones were in good accordance at all heating rates. From the pyrolysis of hemicellulose, cellulose, and lignin it is clear that the decomposition process of wood is dependent on the composition and concentration of the main compounds.     

The effect of chemical and physical characteristics of spruce SEW pulps on enzymatic hydrolysis

Conifers, which are the most abundant biomass species in Nordic countries, USA, Canada and Russia, exhibit strong resistance towards depolymerization by cellulolytic enzymes. At present, it is still not possible to isolate a single structural feature which would govern the rate and degree of enzymatic hydrolysis. On the other hand, the forest residues alone represent an important potential for biochemical production of biofuels. In this study, the effect of substrate properties on the enzymatic hydrolysis of softwood was studied. Stem wood spruce chips were fractionated by SO₂–ethanol–water (SEW) treatment to produce pulps of varying composition by applying different operating conditions. The SEW technology efficiently fractionates different types of lignocellulosic biomass by rapidly dissolving hemicelluloses and lignin. Cellulose remains fully in the solid residue which is then treated by enzymes to release glucose. The differences in enzymatic digestibility of the spruce SEW pulp fibers were interpreted in terms of their chemical and physical characteristics. A strong correlation between the residual lignin content of SEW pulp and enzymatic digestibility was observed whereas cellulose degree of polymerization and hemicellulose content of pulp were not as important. For the pulps containing about 1.5 % (w/w) lignin, 90 % enzymatic digestibility was achieved at 10 FPU enzyme charge and 24 h of hydrolysis time.     

Microbial Pretreatment of Corn Stovers by Solid-State Cultivation of Phanerochaete chrysosporium for Biogas Production

The microbial pretreatment of corn stover and corn stover silage was achieved via the solid-state cultivation of Phanerochaete chrysosporium; pretreatment effects on the biodegradability and subsequent anaerobic production of biogas were investigated. The peak levels of daily biogas production and CH₄ yield from corn stover silage were approximately twice that of corn stover. Results suggested that ensiling was a potential pretreatment method to stimulate biogas production from corn stover. Surface morphology and Fourier-transform infrared spectroscopy analyses demonstrated that the microbial pretreatment of corn stover silage improved biogas production by 10.5 to 19.7 % and CH₄ yield by 11.7 to 21.2 % because pretreatment could decrease dry mass loss (14.2 %) and increase substrate biodegradability (19.9 % cellulose, 32.4 % hemicellulose, and 22.6 % lignin). By contrast, the higher dry mass loss in corn stover (55.3 %) after microbial pretreatment was accompanied by 54.7 % cellulose, 64.0 % hemicellulose, and 61.1 % lignin degradation but did not significantly influence biogas production.     

The Influence of Different Strategies for the Saccharification of the Banana Plant Pseudostem and the Detoxification of Concentrated Broth on Bioethanol Production

Pseudostem of the Musa cavendishii banana plant was submitted to chemical pretreatments with acid (H₂SO₄ 2%, 120 °C, 15 min) and with alkali (NaOH 3%, 120 °C, 15 min), saccharified by commercial enzymes Novozymes® (Cellic CTec2 and HTec2). The influences of the pretreatments on the degradation of the lignin, cellulose and hemicellulose, porosity of the surface, particle crystallinity, and yield in reducing sugars after saccharification (Y _RS), were established. Different concentrations of biomass (70 and 100 g/L in dry matter (dm)), with different physical differences (dry granulated, crushed wet bagasse, and whole pseudostem), were used. The broth with the highest Y _RS among the different strategies tested was evaporated until the concentration of reducing sugars (RS) was to the order of 100 g/L and fermented, with and without prior detoxification with active carbon. Fermentation was carried out in Erlenmeyer flasks, at 30 °C, initial pH 5.0, and 120 rpm. In comparison to the biomass without chemical pretreatment and to the biomass pretreated with NaOH, the acid pretreatment of 70 g/L of dry granulated biomass enabled greater digestion of hemicellulose, lower index of cellulose crystallinity, and higher Y _RS (45.8 ± 0.7%). The RS increase in fermentation broth to 100 g/L, with posterior detoxification, presented higher productivity ethanol (Q _P = 1.44 ± 0.02 g/L/h) with ethanol yield (Y _P/RS) of 0.41 ± 0.02 g/g. The value of Q _P was to the order of 75% higher than Q _P obtained with the same broth without prior detoxification.     

Dilute Ammonia Pretreatment of Sorghum and Its Effectiveness on Enzyme Hydrolysis and Ethanol Fermentation

A new pretreatment technology using dilute ammonium hydroxide was evaluated for ethanol production on sorghum. Sorghum fibers, ammonia, and water at a ratio of 1:0.14:8 were heated to 160 °C and held for 1 h under 140–160 psi pressure. Approximately, 44% lignin and 35% hemicellulose were removed during the process. Hydrolysis of untreated and dilute ammonia pretreated fibers was carried out at 10% dry solids at an enzyme concentration of 60 FPU Spezyme CP and 64 CBU Novozyme 188/g glucan. Cellulose digestibility was higher (84%) for ammonia pretreated sorghum as compared to untreated sorghum (38%). Fermentations with Saccharomyces cerevisiae D₅A resulted in 24 g ethanol /100 g dry biomass for dilute ammonia pretreated sorghum and 9 g ethanol /100 g dry biomass for untreated sorghum.     

Cellulose microfibril angles and cell-wall polymers in different wood types of Pinus radiata

Four corewood types were examined from sapling trees of two clones of Pinus radiata grown in a glasshouse. Trees were grown either straight to produce normal corewood, tilted at 45° from the vertical to produce opposite corewood and compression corewood, or rocked to produce flexure corewood. Mean cellulose microfibril angle of tracheid walls was estimated by X-ray diffraction and longitudinal swelling measured between an oven dry and moisture saturated state. Lignin and acetyl contents of the woods were measured and the monosaccharide compositions of the cell-wall polysaccharides determined. Finely milled wood was analysed using solution-state 2D NMR spectroscopy of gels from finely milled wood in DMSO-d ₆/pyridine-d ₅. Although there was no significant difference in cellulose microfibril angle among the corewood types, compression corewood had the highest longitudinal swelling. A lignin content >32 % and a galactosyl residue content >6 % clearly divided severe compression corewood from the other corewood types. Relationships could be drawn between lignin content and longitudinal swelling, and between galactosyl residue content and longitudinal swelling. The 2D NMR spectra showed that the presence of H-units in lignin was exclusive to compression corewood, which also had a higher (1 → 4)-β-d-galactan content, defining a unique composition for that corewood type.     

Pretreatment of corn stover using wet oxidation to enhance enzymatic digestibility

Corn stover is an abundant, promising raw material for fuel ethanol production. Although it has a high cellulose content, without pretreatment it resists enzymatic hydrolysis, like most lignocellulosic materials. Wet oxidation (water, oxygen, mild alkali or acid, elevated temperature and pressure) was investigated to enhance the enzymatic digestibility of corn stover. Six different combinations of reaction temperature, time, and pH were applied. The best conditions (60g/L of corn stover, 195°C, 15 min, 12 bar O₂, 2 g/L of Na₂CO₃) increased the enzymatic conversion of corn stover four times, compared to untreated material. Under these conditions 60% of hemicellulose and 30% of lignin were solubilized, whereas 90% of cellulose remained in the solid fraction. After 24-h hydrolysis at 50°C using 25 filter paper units (FPU)/g of dry matter (DM) biomass, the achieved conversion of cellulose to glucose was about 85%. Decreasing the hydrolysis temperature to 40°C increased hydrolysis time from 24 to 72 h. Decreasing the enzyme loading to 5 FPU/g of DM biomass slightly decreased the enzymatic conversion from 83.4 to 71%. Thus, enzyme loading can be reduced without significantly affecting the efficiency of hydrolysis, an important economical aspect.     

Enhanced Saccharification of Biologically Pretreated Wheat Straw for Ethanol Production

The biological pretreatment of lignocellulosic biomass with white-rot fungi for the production of bioethanol is an alternative to the most used physico-chemical processes. After biological treatment, a solid composed of cellulose, hemicellulose, and lignin—this latter is with a composition lower than that found in the initial substrate—is obtained. On the contrary, after applying physico-chemical methods, most of the hemicellulose fraction is solubilized, while cellulose and lignin fractions remain in the solid. The optimization of the combination of cellulases and hemicellulases required to saccharify wheat straw pretreated with the white-rot fungus Irpex lacteus was carried out in this work. The application of the optimal dosage made possible the increase of the sugar yield from 33 to 54 %, and at the same time the reduction of the quantity of enzymatic mixture in 40 %, with respect to the initial dosage. The application of a pre-hydrolysis step with xylanases was also studied.     

Optimization of steam pretreatment of corn stover to enhance enzymatic digestibility

Among the available agricultural byproducts, corn stover, with its yearly production of 10 million t (dry basis), is the most abundant promising raw material for fuel ethanol production in Hungary. In the United States, more than 216 million to fcorn stover is produced annually, of which a portion also could possibly be collected for conversion to ethanol. However, a network of lignin and hemicellulose protects cellulose, which is the major source of fermentable sugars in corn stover (approx 40% of the dry matter [DM]). Steam pretreatment removes the major part of the hemicellulose from the solid material and makes the cellulose more susceptible to enzymatic digestion. We studied 12 different combinations of reaction temperature, time, and pH during steam pretreatment. The best conditions (200°C, 5 min, 2% H₂SO₄) increased the enzymatic conversion (from cellulose to glucose) of corn stover more then four times, compared to untreated material. However, steam pretreatment at 190°C for 5 min with 2% sulfuric acid resulted in the highest overall yield of sugars, 56.1 g from 100 g of untreated material (DM), corresponding to 73% of the theoretical. The liquor following steam explosion was fermented using Saccharomyces cerevisiae to investigate the inhibitory effect of the pretreatment. The achieved ethanol yield was slightly higher than that obtained with a reference sugar solution. This demonstrates that baker's yeast could adapt to the pretreated liquor and ferment the glucose to ethanol efficiently.     

Influence of the interaction of components on the pyrolysis behavior of biomass

There has been much interest in the utilization of biomass-derived fuels as substitutes for fossil fuels in meeting renewable energy requirements to reduce CO₂ emissions. In this study, the pyrolysis characteristics of biomass have been investigated using both a thermogravimetric analyzer coupled with a Fourier-transform infrared spectrometer (TG-FTIR) and an experimental pyrolyzer. Experiments have been conducted with the three major components of biomass, i.e. hemicellulose, cellulose, and lignin, and with four mixed biomass samples comprising different proportions of these. Product distributions in terms of char, bio-oil, and permanent gas are given, and the compositions of the bio-oil and gaseous products have been analysed by gas chromatography-mass spectrometry (GC-MS) and gas chromatography (GC). The TG results show that the thermal decomposition of levoglucosan is extended over a wider temperature range according to the interaction of hemicellulose or lignin upon the pyrolysis of cellulose; the formation of 2-furfural and acetic acid is enhanced by the presence of cellulose and lignin in the range 350-500 °C; and the amount of phenol, 2,6-dimethoxy is enhanced by the integrated influence of cellulose and hemicellulose. The components do not act independently during pyrolysis; the experimental results have shown that the interaction of cellulose and hemicellulose strongly promotes the formation of 2, 5-diethoxytetrahydrofuran and inhibits the formation of altrose and levoglucosan, while the presence of cellulose enhances the formation of hemicellulose-derived acetic acid and 2-furfural. Pyrolysis characteristics of biomass cannot be predicted through its composition in the main components.     

Valorization of industrial waste lignin via pyrolysis in the presence of additives: Formation,characterization, and application of fuel valued bio-oil and activated char

The annual production of over 50 million tonnes of industrial waste kraft lignin and scant utilization invites environmental concern. To explore the potential of simultaneously produced bio-oil and modified char (Activated char), lignin from industrial effluents was subjected to pyrolytic degradation at 380 °C using various additives, viz., H₃BO₃, ZnCl₂, and KOH yielding encouraging quantities of bio-oils besides substantial quantities of char. Quantitative and qualitative analyses of gaseous products (by GC-TCD) indicated a mixture of CO, CO₂, H₂, and methane, with some variation in volumetric composition suggesting potential for gaseous fuel/syngas. Gaseous products obtained in the presence of H₃BO₃ have the highest methane percentage. The bio-oils obtained in the presence of H₃BO₃, ZnCl₂, KOH, and only pure lignin under otherwise similar conditions were respectively 37%, 21%, 27%, and 11 wt%. In all cases, mainly bio-oils contain phenols, cyclic esters, and carboxylic acids, as indicated by GC-MS analysis. Elemental (C, H, O) Analyses of bio-oils obtained in the presence of (H₃BO₃, ZnCl₂, and KOH) indicated decreasing oxygen content compared to original lignin, suggesting their prima facie potential to lead to fuel additives/supplements. Similarly, the Char obtained in the presence of H₃BO₃, ZnCl₂, KOH, and only pure lignin were respectively, 40%, 53%, 48%, and 33 wt% with a high calorific value. Char obtained from KOH application demonstrated good uptake of Carbofuran (pesticide) from the aqueous solution. Less modified, cost-effective activated char was characterized using FTIR, TG-DTA, XRD, SEM, and BET-BJH, indicating 188.798 m²/g; this explores the role of KOH to form a microporous structure. Pseudo-second-order kinetics explain chemisorption to be dominant in the adsorption process. Thus, pyrolysis at selected temperatures/additives/and further treatments provides a much better way to utilize industrial waste lignin.     

Application of sequential aqueous steam treatments to the fractionation of softwood

The FIRST (Feedstock Impregnation and Rapid Steam Treatment) approach was used in this study to isolate extractives, hemicellulose, lignin, fibers, and cellulosic fines of softwood. With hydrolysis and fermentation of the hemicellulose and cellulosic fines fractions, this approach produces four co-products: extractives, cellulose, lignin, and ethanol. The first unit operation uses aqueous/alcohol to remove and recover the extractive rich fraction. The second unit operation uses steam treatment to destructure the matrix and solubilize a large fraction of the hemicelluloses. The third unit operation uses alkaline delignification to dissolve a lignin fraction. The fourth unit operation uses the refining process to separate fibers from cellulosic fines. The fibers are bleached. The yields of lignin and bleached cellulose were about 20.0 kg and 38.3 kg out of 100 kg initial dry pine, respectively. The recovered hemicelluloses were 23.3 kg (containing 16.1 kg hexoses and 5.0 kg pentoses) and the cellulose fines derived hexoses amounted to 3.4 kg out of 100 kg initial dry pine. When the two liquors containing the hemicellulose sugars and the cellulose fines-derived hexoses were fermented for ethanol production, an ethanol yield of 6.8 kg was obtained.     

Characterization of low molecular weight organic acids from beech wood treated in supercritical water

Japanese beech (Fagus crenata Blume), its cell wall components, and model compounds were treated by supercritical water (380°C, 100 MPa) for 5 s using a batch-type reactor to investigate the production behavior of low molecular weight organic acids. It was found that cellulose and hemicellulose were decomposed to formic acid, pyruvic acid, glycolic acid, acetic acid, and lactic acid, whereas lignin was barely decomposed to such organic acids under the given conditions. However, after prolonged treatment (380°C, 100 MPa, 4 min) of lignin, some organic acids were recovered owing perhaps to the decomposition of the propyl side chain of lignin. It was additionally revealed that the predominant organic acid recovered was acetic acid, which might be derived from the acetyl group of hemicellulose in Japanese beech.