Modulating the properties and structure of lignins produced by alkaline delignification of sugarcane bagasse pretreated with two different mineral acids at pilot-scale.

Sugarcane bagasse was pretreated with dilute phosphoric acid or sulfuric acid to facilitate cellulose hydrolysis and lignin extraction. With phosphoric acid, only 8 % of the initial cellulose was lost after delignification, whereas pretreatment with sulfuric acid resulted in the solubilization of 38 % of the initial cellulose. After enzymatic hydrolysis, the process using phosphoric acid produced approximately 35 % more glucose than that using sulfuric acid. In general, the lignins showed 95-97 % purity (total lignin, w/w), an average molar mass of 9500-10,200 g mol-1, a glass transition temperature of 140-160 °C, and a calorific value of 25 MJ kg-1. Phosphoric acid lignin (PAL) was slightly more polar than sulfuric acid lignin (SAL). PAL had 13 % more oxidized units and 20 % more OH groups than SAL. Regardless of the acid used, the lignins shared similar properties, but differed slightly in the characteristics of their functional groups and chemical bonds. These findings show that pretreatment catalyzed with either of the two acids resulted in lignin with sufficiently good characteristics for use in industrial processes.

Fermentation of cellulosic hydrolysates obtained by enzymatic saccharification of sugarcane bagasse pretreated by hydrothermal processing.

This work aims to evaluate the fermentability of cellulosic hydrolysates obtained by enzymatic saccharification of sugarcane bagasse pretreated by hydrothermal processing using Candida guilliermondii FTI 20037 yeast. The inoculum was obtained from yeast culture in a medium containing glucose as a carbon source supplemented with rice bran extract, CaCl(2)·2H(2)O and (NH(4))(2)SO(4) in 50 mL Erlenmeyer flasks, containing 20 mL of medium, initial 5.5 pH under agitation of an orbital shaker (200 rpm) at 30°C for 24 h. The cellulosic hydrolysates, prior to being used as a fermentation medium, were autoclaved for 15 min at 0.5 atm and supplemented with the same nutrients employed for the inoculum, except the glucose, using the same conditions for the inoculum, but with a period of 48 h. Preliminary results showed the highest consumption of glucose (97%) for all the hydrolysates, at 28 h of fermentation. The highest concentration of ethanol (20.5 g/L) was found in the procedure of sugarcane bagasse pretreated by hydrothermal processing (195°C/10 min in 20 L reactor) and delignificated with NaOH 1.0% (w/v), 100°C, 1 h in 500 mL stainless steel ampoules immersed in an oil bath.

Characterization of coffee (Coffea arabica) husk lignin and degradation products obtained after oxygen and alkali addition.

The full use of biomass in future biorefineries has stimulated studies on utilization of lignin from agricultural crops, such as coffee husk, a major residue from coffee processing. This study focuses on characterizing the lignin obtained from coffee husk and its further wet oxidation products as a function of alkali loading, temperature and residence time. The lignin fraction after diluted acid and alkali pretreatments is composed primarily of p-hydroxylphenyl units (≥49%), with fewer guaiacyl and syringyl units. Linkages appear to be mainly ß-O-4 ether linkages. Thermal degradation of pretreated lignin during wet oxidation occurred in two stages. Carboxylic acids were the main degradation product. Due to the condensed structure of this lignin, relatively low yields of aromatic aldehydes were achieved, except with temperatures over 210 °C, 5 min residence time and 11.7 wt% NaOH. Optimization of the pretreatment and oxidation parameters are important to maximizing yield of high-value bioproducts from lignin.

Characterization and application of cellulose acetate synthesized from sugarcane bagasse.

The synthesis and application of cellulose acetate (CA) from sugarcane bagasse were investigated. Firstly, cellulose was extracted by a sequential treatment with H2SO4 (10% v/v), NaOH (5% w/v), EDTA (0.5% w/V), and H2O2 (5% v/v), and characterized by X-ray diffraction (DRX). After the acetylation of the extracted cellulose, CA was characterized using Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and thermogravimetry analysis (TGA), and was applied in the membrane production. The membranes were analyzed by DSC and atomic force microscopy (AFM), and tested in the flux of water vapor to determinate the best conditions for membrane manufacturing. FTIR analysis proved the replacement of free OH groups by acetyl groups, and the thermal analysis showed that sugarcane bagasse CA possessed thermal properties compared to commercial grade CA. The best conditions to prepare membrane were: 3% (w/v) of polymer/solvent relation, 10min of solvent evaporation time, and 20°C as temperature for the coagulation bath. These results show that CA can be successfully synthesized from sugarcane bagasse and applied in membrane preparation.

Obtainment of chelating agents through the enzymatic oxidation of lignins by phenol oxidase.

Oxidation of lignin obtained from acetosolv and ethanol/water pulping of sugarcane bagasse was performed by phenol oxidases: tyrosinase (TYR) and laccase (LAC), to increase the number of carbonyl and hydroxyl groups in lignin, and to improve its chelating capacity. The chelating properties of the original and oxidized lignins were compared by monitoring the amount of Cu2+ bound to lignin by gel permeation chromatography. The Acetosolv lignin oxidized with TYR was 16.8% and with LAC 21% higher than that of the original lignin. For ethanol/water lignin oxidized with TYR was 17.2% and with LAC 18% higher than that of the original lignin.

Reuse of the xylanase enzyme in the biobleaching process of the sugarcane bagasse acetosolv pulp.

In this work, pretreatment-enzymatic series of the bagasse-sugarcane pulp and alkaline extraction of enzyme treated pulp were carried out. In the pretreatment an enzyme dose was utilized and acetosolv pulp suspension of 3% (w/v) with different solvents (distilled water, 0.05 mol/L acetate buffer pH 5.5 and 0.05 mol/L phosphate buffer pH 7.25) stirred at 85 rpm for 2 or 4 h. The enzymes used were pulpzyme and cartazyme, both commercial. The accompaniment of the enzymatic activity was carried out through measurement in initial and finish of each enzymatic pretreatment. The xylanase-treated pulps and xylanase-alkaline-extracted pulps were analyzed regarding kappa number and viscosity. Pulpzyme recovery was better in phosphate buffered medium (84, 46, and 23% for first, second, and third enzymatic treatment, respectively) although in aqueous medium reached only 2% for every treatments. However, the improvement of pulp properties was evidenced only in aqueous medium for pulpzyme. Cartazyme recovery was similar for both solvents (water and acetate buffer), reaching values around 19% for first enzymatic treatment and 9% for second one. Nevertheless, the pulp properties increased only in acetate buffered medium.

Ceriporiopsis subvermispora used in delignification of sugarcane bagasse prior to soda/anthraquinone pulping.

Sugarcane bagasse was pretreated with the white-rot fungus Ceriporiopsis subvermispora for 30 d of incubation. The solid-state fermentation of 800 g of bagasse was carried out in 20-L bioreactors with an inoculum charge of 250 mg of fungal mycelium/kg of bagasse. The oxidative enzymes manganese peroxidase (MnP), lignin peroxidase (LiP), and laccase (Lac) and the hydrolytic enzyme xylanase (Xyl) were measured by standard methods and related to the fungus's potential for delignification. Among the lignocellulolytic assayed enzymes, Xyl was detected in larger quantity (4478 IU/kg), followed by MnP (236 IU/kg). LiP and Lac were not detected. The results of chemical analysis and mass component loss showed that C. subvermispora was selective to lignin degradation. Pretreated sugarcane bagasse and control pulps were obtained by soda/anthraquinone (AQ) pulping. Pulp yields, kappa number, and viscosity of all pulps were determined by chemical analysis of the samples. Yields of soda/AQ ranged from 46 to 54%, kappa numbers were 15-25, and the viscosity ranged from 3.6 to 7 cP for pulps obtained from pretreated sugarcane bagasse.

Sugarcane bagasse pulps: biobleaching with commercial cartazyme HS and with Bacillus pumilus xylanase.

Organosolv (ethanol/water and acetosolv) pulps were treated with Bacillus pumilus xylanase for 4, 8, and 12 h and compared with commercial Cartazyme HS xylanase-treated pulps. Treatment of ethanol/water pulps with B. pumilus xylanase increased viscosity by 40% in 8 h of treatment compared with pulps treated without enzyme. However, acetosolv pulps treated with B. pumilus xylanase lost viscosity. Ethanol/water pulps treated with Cartazyme had a viscosity of 18.5 cP in 4 h of treatment. In the acetosolv pulps treated with commercial enzyme, the loss of viscosity was 20% compared with pulps treated without enzyme. Ethanol/water pulps treated with B. pumilus and Cartazyme had similar effects: a 44% reduction in kappa number for pulps treated with enzyme followed by alkaline extraction compared with pulps treated with alkaline extraction. In acetosolv pulps treated with B. pumilus, the kappa number was from 12 to 18, compared with pulps treated without enzyme, which had a 40% reduction in 4 and 12 h and a 60% reduction in 8 h. Cartazyme-treated acetosolv pulps had a kappa number of 14 in 4 and 8 h of treatment. For 12 h of treatment, the kappa number was 8. Fourier transform infrared spectra of the pulps showed that enzyme-treated pulps had changes in the 1000 cm-1 absorption owing to a C-O bond present in esters. Using principal component analysis, it is possible to differentiate the unbleached pulps and enzyme-treated pulps.

Enzymatic bleaching of organosolv sugarcane bagasse pulps with recombinant xylanase of the fungus Humicola grisea and with commercial Cartazyme HS xylanase.

Organosolv (ethanol/water and acetosolv) pulps were treated with Humicola grisea var. thermoidea and compared with Cartazyme HS xylanase-treated pulp. The ethanol/water pulps treated with H. grisea had the same viscosity as unbleached pulps (8 cP). Ethanol/water pulps treated with Cartazyme had higher viscosity than H. grisea-treated pulps (12 cP). Acetosolv pulps treated with H. grisea and Cartazyme presented a reduction in viscosity; however, the pulps treated with H. grisea had a lower reduction in viscosity than Cartazyme-treated pulps. Ethanol/water pulps treated with H. grisea had a 23% reduction in kappa number in 4 and 8 h of treatment, compared with the unbleached pulps. Cartazyme-treated pulps had a kappa number similar to that of the control pulps for 4 h of treatment. Extending the treatment time to 12 h resulted in a reduction of 33%. The acetosolv pulp treated with H. grisea had a kappa number reduced to 23% in 4 h. Cartazyme treatment resulted in a reduction of 55 and 44% in kappa number for 4 and 8 h of treatment, respectively, when compared with control pulp. Extending the treatment time to 12 h decreased the kappa number 72%. Fourier transform infrared spectra and principal component analysis showed differences among unbleached, H. grisea-treated, and Cartazyme-treated pulps.

Integrated processes for use of pulps and lignins obtained from sugarcane bagasse and straw: a review of recent efforts in Brazil.

Sugarcane bagasse and straw can be converted into pulps, oils, controlled-release formulations, chelating agents, and composites. This article reviews bagasse and straw conversion efforts in Brazil. Laboratory-scale processes were developed aiming at the integral use of these biomass byprod ucts. Organosolv pulping and oxidation of lignin are the most promising processes for the rational use of sugarcane residues. Fungal pretreatment and spectroscopic characterization are also discussed.

Hydrogenolysis of lignins: influence of the pretreatment using microwave and ultrasound irradiations.

Hydrolytic eucalyptus lignin was converted to oils by hydrogenolysis. The lignin was obtained by acid hydrolysis of eucalyptus chips from two semi-industrial sources in Brazil: FTI and Coalbra. Hydrogenolysis was performed in an 1-L reactor using lignin/water ratio 1/4 (w/v), pH 9 (adjusted with NaOH), 0.1 g sodium formate/g lignin, 20 MPa (argon pressure) at 280 degrees C for 15 min. After reaction, the products were filtered and the solids extracted with chloroform/ethanol 3/1 (v/v). The solvent was evaporated from the organic phase and a dark oil was obtained. The solid remaining after extraction was weighed to calculate the conversion. Without pretreatment conversions were 41.3 and 47.9% for Coalbra and FTI, respectively. The oil yields were 22.7-27.6% for Coalbra and FTI, respectively. Using microwave pretreatment (30 min of irradiation at 490 W) the conversions were 41.6-50.5% and the oil yields increased slightly to 25.2-31.4%. The polymeric chains in the lignin breakdown due to the action of water near the boiling point under microwave irraditation. On the other hand, by using ultrasound (30 min at 50 degrees C in a ultrasound bath of 25 kHz and 0.8 W/cm2) the conversions were 35.2-46.9% and oil yields were 22.0-27.1%. Ultrasound favors the formation of radicals that probably caused the reticulation of lignins, decreasing the conversion and yield. Oils analyzed by infrared spectroscopy showed an increase in C=O bond intensities, compared with the original lignins.

Effect of dose of xylanase on bleachability of sugarcane bagasse ethanol/water pulps.

Pulps obtained from the ethanol/water cooking of sugarcane bagasse were bleached with the xylanase enzyme obtained from the fungus Thermomyces lanuginosus IOC-4145 and with the commercial enzyme Cartazyme HS from Sandoz. By changing the enzyme dose from 4.3 to 36 IU/g of pulp, kappa number and viscosity were maintained when the xylanase from T. lanuginosus was used. On the other hand, by using Cartazyme HS, kappa number decreased by 17%, reaching 35.5. This pulp was further extracted with NaOH without a decrease in viscosity (10 cP), and pulp with a kappa number of 13 was obtained. Xylanases had no significant effect on the ethanol/water pulps.

Influence of pressure in ethanol/water pulping of sugarcane bagasse.

The influence of the pressure in the ethanol/water pulping of sugarcane bagasse was studied using argon pressure varying from 0.5 to 1.5 MPa. The reaction volume and activation volume were studied. For the reaction volume, temperature and time were constant and pressure was varied, and for the activation volume, temperature was constant and pressure and time were varied. The degradation of cellulose was not promoted by the pressure with positive reaction volume (4100 cm(3)/mol). On the other hand, degradation of xylan (polyoses) and lignin was strongly favored by the pressure and reaction volume ranged from -1000 to -3000 cm(3)/mol.

Action of white-rot fungus Panus tigrinus on sugarcane bagasse: evaluation of selectivity.

Biological pretreatments with three selected strains of Panus tigrinus were used for delignification of sugarcane bagasse. The fungi with potential for delignification were analyzed by determining the chemical composition of the decayed bagasse samples, and the selectivity in terms of weight loss of the different components was evaluated. All the strains grow abundantly on bagasse as unique carbon source. After determining the chemical composition of degraded bagasse, P. tigrinus FTPT-4745 was selected as the most efficient strain on a 6-g scale, since the carbohydrates were preserved. P. tigrinus FTPT-4741 and FTPT-4742 were the most efficient strains on a large scale (100 g).

Production of chelating agents through the enzymatic oxidation of acetosolv sugarcane bagasse lignin.

Oxidation of lignin obtained from Acetosolv pulping of sugarcane bagasse was performed by polyphenoloxidase (PPO) using glycerol or polyethyleneglycol to increase the number of carbonyl and hydroxyl groups in lignin, and to improve its chelating capacity. Increase in the absorption in UV-spectrum related to alpha-carbonylphenolic and alpha,beta-unsaturated structures was observed in all the experiments. The chelating properties of the original and oxidized lignins were compared by monitoring the amount of Cu2+ bound to lignin by gel permeation chromatography. The chelating capacity of original Acetosolv lignin was 354 mg Cu2+/g lignin. On the other hand, lignin oxidized with PPO/O2 showed an increase of 73% in chelating capacity in relation to the original lignin. The chelating capacity of lignin oxidized with PPO/O2/glycerol was 110% higher than that of the original lignin. Glycerol stabilizes PPO, increasing its half-life. Average molecular weight (MW), measured by size-exclusion chromatography, was smaller for the oxidized lignins than for the original Acetosolv lignin. This result suggests that quinones can eventually be formed through the action of PPO, but are not polymerized. The chelating capacity of oxidized lignins increases with the incorporation of vicinal hydroxyl groups.

Panus tigrinus strains used in delignification of sugarcane bagasse prior to kraft pulping.

Three strains of the white-rot fungus Panus tigrinus (FTPT-4741, FTPT-4742, and FTPT-4745) were cultivated on sugarcane bagasse prior to kraft pulping. Pulp yields, kappa number, and viscosity of all pulps were determined and Fourier transform infrared (FTIR) spectra from the samples were recorded. The growth of P. tigrinus strains in plastic bags increased the manganese peroxide and xylanase activities. Lignin peroxidase was not detected in the three systems (shaken and nonshaken flasks and plastic bags). FTIR spectra were reduced to their principal components, and a clear separation between FTPT-4742 and the control was observed. Strain FTPT-4745 decayed lignin more selectively in the three systems utilized. Yields of kraft pulping were low, ranging from 20 to 45% for the plastic bag samples and from 12 to 38% for the flask samples. Kappa numbers were 1-18 and viscosity ranged from 2.3 to 6.8 cP.

Modeling of 2,4-dichlorophenoxyacetic acid controlled-release kinetics from lignin-based formulations.

The second Fick's law of diffusion, considering boundary conditions that at both slab faces the concentration of herbicide is equal to zero (sink conditions), has been adequate to describe our kinetic data obtained from experiments on 2,4 -dichlorophenoxyacetic acid, (2,4 - D) released from lignin-based formulations in a water static bath system. However, the same model proved to be invalid in describing the experimental data obtained with ametryn (2-ethylamino-4-isopropylamino-6-methylthio-1,3,5-triazine) and diuron (3-[3,4-dichlorophenyl]-1,1-dimethylurea) formulations in a water dynamic bath system. For ametryn and diuron formulations, because of the lower aqueous solubility of these herbicides, it was necessary to model a stagnant film at the formulation surface to describe better the release kinetics because the model incorporating sink conditions is insufficient. This study presents a new mathematical modeling of experimental data obtained with 2,4-D formulations in a water static bath system. The new model incorporates a stagnant film as the boundary condition at the formulation surface, and its diffusion coefficient value is more precise than the one estimated by the model employing sink conditions.

Estimation of solubility effect on the herbicide controlled-release kinetics from lignin-based formulations.

Understanding the main phenomena involved in the controlled-release kinetics of herbicides in a water bath is a very important requisite for diffusive- parameter estimation, because, some mathematical models based on Fick's second law for diffusion have been developed to describe the controlled-release kinetic data. However, the validity of these models is restricted to the following assumptions: (1) the formulation is an isothermal slab; (2) the release occurs through the two faces of the slab; (3) the herbicide is dissolved in the water contained in the slab pores at a concentration less than the saturation concentration (cis); (4) the total sum of the individual volumes of the pores is epsilonAL (epsilon is the slab porosity, A is the slab area, and L is the slab thickness); and (5) the initial concentration of herbicide in the pores is M0/epsilonAL (M0 is the initial amount of herbicide in the matrix). The fourth assumption may be invalid for mathematical description of systems in which the herbicide concentration in the slab may be above the saturation concentration. If this were true, the final assumption would also be invalid, because the initial concentration of herbicide in the pores is cis in this case. This work presents a study of the solubility effect on the controlled-release kinetics of herbicides from lignin matrices.

Tissue-specific cell wall hydration in sugarcane stalks.

Plant cell walls contain water, especially under biological and wet processing conditions. The present work characterizes this water in tissues of sugarcane stalks. Environmental scanning electron microscopy shows tissue deformation upon drying. Dynamic vapor sorption determines the equilibrium and kinetics of moisture uptake. Thermoporometry by differential scanning calorimetry quantifies water in nanoscale pores. Results show that cell walls from top internodes of stalks are more deformable, slightly more sorptive to moisture, and substantially more porous. These differences of top internode are attributed to less lignified walls, which is confirmed by lower infrared spectral signal from aromatics. Furthermore, cell wall nanoscale porosity, an architectural and not directly compositional characteristic, is shown to be tissue-specific. Nanoscale porosities are ranked as follows: pith parenchyma > pith vascular bundles > rind. This ranking coincides with wall reactivity and digestibility in grasses, suggesting that nanoscale porosity is a major determinant of wall recalcitrance.

Industrial-scale steam explosion pretreatment of sugarcane straw for enzymatic hydrolysis of cellulose for production of second generation ethanol and value-added products.

Steam explosion at 180, 190 and 200°C for 15min was applied to sugarcane straw in an industrial sugar/ethanol reactor (2.5m(3)). The pretreated straw was delignificated by sodium hydroxide and hydrolyzed with cellulases, or submitted directly to enzymatic hydrolysis after the pretreatment. The pretreatments led to remarkable hemicellulose solubilization, with the maximum (92.7%) for pretreatment performed at 200°C. Alkaline treatment of the pretreated materials led to lignin solubilization of 86.7% at 180°C, and only to 81.3% in the material pretreated at 200°C. All pretreatment conditions led to high hydrolysis conversion of cellulose, with the maximum (80.0%) achieved at 200°C. Delignification increase the enzymatic conversion (from 58.8% in the cellulignin to 85.1% in the delignificated pulp) of the material pretreated at 180°C, but for the material pretreated at 190°C, the improvement was less remarkable, while for the pretreated at 200°C the hydrolysis conversion decreased after the alkaline treatment.