Estimating Glucan,Xylan, and Methylglucuronic Acids in Kraft Pulps of Eucalyptus globulus Using FT-NIR Spectroscopy and Multivariate Analysis

Abstract

Fourier transform near infrared (FT-NIR) associated with multivariate analysis was used to estimate glucan, xylan, 4-O-Methyl-α -D-glucuronic acid (MeGlcA) content, and pulp yield in kraft pulps of Eucalyptus globulus Labill. Several models were applied to correlate chemical composition in samples with the NIR spectral data by means of principal components regression (PCR) or partial least square (PLS) algorithms. Calibration models were built and validated by using all the spectral data and cross-validation methodology. The r_c ² values for the best calibration models for quantification of glucan, xylan, MeGlcA contents and pulp yield were between 0.71–0.92. The model was validated using a set of external samples. The amount of glucan (64–77%), xylan (12–18%), and MeGlcA (204–363 mmol kg pulp^–1) in pulps were predicted with a root mean square error of prediction (RMSEP) of 0.91%, 0.46%, and 15.21% for glucan, xylan, and MeGlcA, respectively. Pulp yield (in the range of 46–70%) was also predicted with good accuracy with a RMSEP of 1.63%. These results suggest that glucan, xylan, MeGlcA composition, and pulp yield in kraft pulps of E. globulus can be adequately estimated by NIR spectroscopy for laboratory or industrial applications. NIR predictions can also provide useful and cost-effective tools for the rapid screening of large numbers of samples.     

The Potential of Hydrothermally Pretreated Industrial Barks From E. globulus as a Feedstock for Pulp Production

This study focused on the use of industrial eucalyptus globulus bark as an alternative fiber source for bleached pulp and paper production. Bark has high extractives and ash contents (7.7% and 3.5%, respectively) but a mild hydrothermal pretreatment was tested, decreasing its values to 2.8% and 2.4%, respectively. Untreated and pretreated bark were kraft pulped at 15% and 20% (as Na₂O) active alkali conditions. The pretreatment improved delignification when using low active alkali; kappa number 25.4 vs 17.5, and shives 3.1% vs 0%, respectively, with untreated and pretreated bark. The pretreatment resulted in a lower chemical demand to obtain pulps with similar yield and kappa number. It was possible to produce bleached pulps with good handsheet optical, physical, and mechanical properties with slightly lower values than those of industrial eucalypt wood pulps; e.g., brightness > 85% vs 87%, tear index > 4.2 vs 5.6 mn.m².g^?1, tensile index > 62 vs 69 n.m.g^?1 for bark and wood pulps, respectively.     

Isolation,characterization and enzymatic modification of water soluble xylans from Eucalyptus grandis wood and sugarcane bagasse

BACKGROUND: There is growing interest in utilizing xylans as biodegradable polymers to replace synthetic additives, coatings and encapsulation matrices. However, techniques are required to reduce the water solubility of the xylan for such applications. The study objective was to isolate and characterize water soluble xylans from Eucalyptus grandis wood and sugarcane (Saccharum officinarum L) bagasse for subsequent precipitation in water by enzymatic modification. RESULTS: The water soluble xylans were extracted from E. grandis and bagasse using two mild alkali‐low‐temperature extraction methods in which the xylan was recovered either by ultra‐purification (Hoije) or ethanol precipitation (Lopez). Yields of 66 and 35% were obtained for the xylan extracted from bagasse and E. grandis, respectively, using the Hoije method and 28 and 12%, respectively, using the Lopez method. The xylans were hydrolysed by selective removal of arabinose and 4‐O‐methylglucuronic acid (4‐O‐MeGlcA) side chains by treatment with α‐L ‐arabinofuranosidase and α‐D ‐glucuronidase, respectively. The α‐L ‐arabinofuranosidase removed about 14% of the available arabinose in the xylans extracted from bagasse using the Hoije method, which led to precipitation in water. However, the α‐D ‐glucuronidase removed only 2% 4‐O‐MeGlcA of the available 4‐O‐MeGlcA from the xylans extracted from bagasse and E. grandis using both the Hoije and Lopez methods, and failed to show visible precipitation of the xylan in water. CONCLUSION: The xylans extracted from bagasse suited the substrate specificities of the α‐L ‐arabinofuranosidase for side chain removal and precipitation in water. However, the dosage of α‐D ‐glucuronidase for precipitating the xylan would need to be increased. Copyright © 2012 Society of Chemical Industry     

Ethanol‐based pulping from Cynara cardunculus L

A non‐conventional pulping process based on the delignification of cardoon (Cynara cardunculus L) in ethanol–water mixtures has been studied to evaluate its pulping potential and to establish the optimum pulping conditions for this lignocellulosic material. The variables analyzed were the concentration of ethanol in the cooking liquor, the pulping time and temperature. Variable optimization was performed by a central composite design. High viscosity, low kappa number and acceptable screened yield were used as pulp quality criteria to optimize cooking conditions. Pulps having low kappa numbers and viscosities greater than 900 cm³/g^?1 were obtained. The total pulp yield was low compared with wood pulping due to the high contents of extractives and ash in cardoon. The amount of rejects in the pulp is of importance, especially for pulps with a high kappa number. The most suitable pulping conditions were 188 °C, 135 min and 50% (w/w) ethanol concentration. In these conditions the kappa number of the pulp was around 26, the pulp viscosity greater than 1100 cm³ g^?1 and a screened pulp yield of about 31% was obtained. Copyright © 2005 Society of Chemical Industry     

Alkaline sulfite/anthraquinone pulping of pine wood chips biotreated with Ceriporiopsis subvermispora

Pine wood chips were treated for 30 days with Cemporiopsis subvermispora in 20 dm³ bioreactors. A typical selective biodelignification was observed. The biotreated wood chips and undecayed controls were subjected to modified alkaline sulfite/anthraquinone (ASA) cooking at 170 °C or 175 °C applying varying cooking times ranging from 30 to 270 min. In all cases, the residual lignin content of the pulps prepared from biologically pretreated wood chips was lower than that of the control pulp. With increasing cooking time, however, the differences in kappa number became smaller. Wood chips cooked for a short time required mechanical refining for fiber liberation. A disk‐refining step resulted in pulps with low reject content (0.4%) and high screened yield (56–60%). In this case, the use of biotreated wood chips provided pulps with significantly lower kappa numbers than for the control pulp (71 and 83, respectively). The pulp from biologically pretreated wood fibrillated rapidly, reaching 20° SR in only 38 min beating time in a Jokro mill, while the control pulp required 56 min to reach the same beating degree. Although easier to beat, the biopretreated pulps showed tensile and burst indices similar to those of the control samples. However, their tear indices were always lower. Easier delignification after wood biotreatment was not observed for the reactions performed at long cooking times. Oxygen delignification of biotreated and conventional ASA pulps with low kappa numbers reduced kappa number and improved brightness considerably with the biotreated pulps being favored by a better preservation of viscosity. Copyright © 2004 Society of Chemical Industry     

Optimization of beech wood pulping in catalyzed acetic acid media

Fagus sylvatica wood samples were treated in HCl‐catalyzed, acetic acid solutions. The effects of selected operational variables (catalyst concentration, reaction time and liquor to wood ratio) on pulp yield, composition of pulps and composition of pulping liquors were assessed using incomplete, second‐order, centred, factorial designs. Pulp composition was measured by the contents in cellulose, xylan and lignin. The concentrations of glucose, xylose and furfural in pulping liquors were also considered as experimental variables. Under selected conditions, pulps with 5.8% to 7.5% Klason lignin (kappa numbers in the range 25 to 33), 77.2% to 85.3% cellulose and 3.3% to 6.1% xylan were obtained at 45.8% to 50.0% pulp yield. The selected pulps showed good SCAN viscosity (723 to 814 mL/g) and alkaline resistances which were affected by the acetyl group content of samples (6.6 to 7.6 weight percent).     

Delignification of Pinus taeda wood chips treated with Ceriporiopsis subvermispora for preparing high‐yield kraft pulps

Pinus taeda wood chips were treated with the white‐rot fungus Ceriporiopsis subvermispora in 20‐dm³ bioreactors for periods varying from 15 to 90 days. Decayed samples, non‐inoculated controls and extractive‐free wood samples were submitted to kraft pulping using 25% of sulfidity and different active alkali concentrations in the cooking liquor. Cooking reactions were carried out isothermally at 170 °C. Residual lignin contents of pulps prepared from biotreated wood chips were lower than those observed in pulps from the undecayed control. Delignification kinetic studies showed that the initial delignification phase was accelerated and shortened by the fungal pretreatment. At a cooking time fixed before the end of the bulk delignification phase, the fungal pretreatment provided pulps with significantly lower kappa numbers or pulps with a fixed kappa number were obtained by reducing the amount of active alkali added to the liquor. Pulps of kappa 80 were obtained both from the undecayed control cooked with 20.8% of active alkali and from the 15‐day‐biotreated sample cooked with only 15% of active alkali. The biopulping benefits were neither proportional to the extent of the biodelignification nor to the biological removal of some specific wood component. DFRC‐determination (derivatization followed by reductive cleavage) of the amount of aryl–ether linkages in residual lignins of biotreated samples indicated an extensive depolymerization during the initial stages of biodegradation, which suggested that bio‐depolymerized lignin was easily released during the first stages of cooking, resulting in a faster and shorter initial delignification phase. © 2002 Society of Chemical Industry     

Nitrogen containing additives in soda pulping of bagasse pith

Unbleached soda pulp was prepared from Egyptian bagasse pith by varying the alkali concentration and the time of heating at the boiling point of the liquor under atmospheric pressure. A linear relationship was observed between the dissolved pith and the dissolved lignin. Pulping with alkali concentration higher than 10% but not exceeding 16% was more effective, since more delignification took place with lower dissolved pith percentage. p- And m-nitrobenzoic acids and also hydroxylamine hydrochloride had a slight or no effect on the yield of the pulps. The alkali solubility percentage of the pulps prepared in the presence of any of the additives was lower than the control pulp. The delignification was enhanced more on the addition of hydroxylamine hydrochloride than p-nitrobenzoic acid, while m-nitrobenzoic acid seemed to have no effect. The yield of the pulps thus prepared, as determined by weighing, showed lower values than those determined by a chemical method. The soda delignification rate was shown to be proportional to the amount of unremoved lignin and the concentration of alkali in the liquor. The delignification reaction was found to follow approximately first-order kinetics.     

Comparison of Sample Preparation Methods for NIR Analysis of Carbohydrate Content of Unbleached Eucalyptus Pulps

Abstract

The formation of hexenuronic acid groups during kraft pulping via demethylation of the 4‐O‐methylglucuronic acid groups attached to the wood xylan backbone was discovered a long time ago. In recent years, the formation of hexenuronic acid groups has attracted new interest and it has been stated that they represent the majority of the uronic acid groups in kraft pulps. However, the values reported in the literature are scattered. Furthermore, the data reported recently are partly in conflict with the earlier observations, which are based on analytical methods of a different type. It is obvious that more reliable and quantitative methods are needed for the determination of hexenuronic acids in pulps in order to assess their influence on factors associated with the bleaching process and pulp quality.     

Kraft pulping of Drimys winteri wood chips biotreated with Ganoderma australe

Drimys winteri, a native hardwood from Chile, presents some interesting characteristics that make it suitable for the pulp and paper industry. In this work, the potential of D winteri for the conventional kraft and biokraft pulp production was evaluated. For biokraft pulping, wood chips were biotreated with the white‐rot fungus Ganoderma australe. During the biotreatment, a selective pattern of biodelignification was observed and the wood chips biotreated for 15, 30 and 45 days were submitted to kraft cooking. At low cooking severity (H‐factor below 1500 h^?1, 15% active alkali and 25% sulfidity), all biopulps presented lower kappa numbers than control pulps and approximately the same screened pulp yield. Biopulps were easily refined in a PFI mill, requiring less PFI revolutions to achieve the same fibrillation degree. The strength properties of the biopulps were similar to those of the control pulps. Copyright © 2005 Society of Chemical Industry     

Soda Pulping of Hardwoods Catalyzed by Anthraquinone and Methyl Substituted Anthraquinones

Abstract

Black liquor gasification (BLG) as well as the recovery of lignin and other organic compounds from pulping black liquor would be aided if an efficient sulfur‐free pulping process could be developed. This has provided new impetus for research on soda pulping with redox catalysts instead of sodium sulfide that is presently used in the kraft process. Soda/anthraquinone (AQ) pulping afforded white birch (Betula papyrifera) and sugar maple (Acer saccharum) pulps with equal if not superior strength to kraft pulps. However, the delignification rate was significantly lower for soda/AQ pulping. When AQ was replaced by 2‐methylanthraquinone (2‐MAQ) a delignification rate only slightly lower than that of kraft pulping was obtained at the same effective alkali (EA). At a kappa number of ～20, a soda/2‐MAQ pulp was produced from sugar maple at a higher yield (1.2% on chips) than for a kraft pulp. 2‐MAQ was synthesized, as a powder, at 75% yield using an AlCl₃–mediated Friedel‐Crafts reaction that is one of the methods used for commercial production of AQ.     

Charge Density of Lignin Samples from Kraft Cooking of Birch Wood

Abstract

Black liquor, isolated dissolved lignin and residual lignin samples corresponding to different cooking times were obtained from flow-through kraft cooking of birch wood. Dissolved lignin was isolated from black liquor by acid precipitation and residual lignin was isolated from pulp by acid-dioxane extraction. The average mobility (μav) of the lignin-containing samples was determined by capillary zone electrophoresis. The lignin samples have a broad mobility distribution that reflects the charge-to-size ratio of the molecules. At pH 12, i.e. when lignin is completely dissociated, the μav of each type of sample increases during the cook, reflecting an increase in charge density of the lignin. For samples corresponding to the initial and beginning of the bulk delignification phases, the μav decreases in the order dissolved lignin>black liquor>residual lignin. The lower charge density of black liquor compared to dissolved lignin is proposed to be caused by associations between lignin and carbohydrate fragments dissolved in the black liquor. As from the middle of the bulk delignification phase, the μav of the three series of samples is quite similar. The decrease in mobility on lowering the pH is an indication of the degree of dissociation of the lignin phenol groups. At pH 10, i.e. about the pK_a of lignin, the μav of black liquor is highest throughout the cook. The relative order of μ_av is then black liquor>dissolved lignin≈residual lignin.     

Extractive Profiles in the Production of Sulfite Dissolving Pulp from Eucalyptus Globulus WOOD

The profile of major families of extractives soluble in acetone and dichloromethane during the production of acid sulfite dissolving pulp from Eucalyptus globulus wood was assessed. Nearly 85% of total extractives were removed from wood during pulping and nearly 11% in the course of E-O-P pulp bleaching and secondary pulp screening. Unlike extractives of polyphenolic origin that were almost completely removed after the alkaline extraction stage (E), fatty acids were the main retained component in fully bleached pulp followed by sterols and fatty alcohols. Throughout the bleaching steps, the profiles of extractives were not necessarily decreasing and depended on their reactions with bleaching reagents and the presence of auxiliary chemicals (e.g. antifoams). In this context, the content of fatty acids and fatty alcohols was mostly vulnerable. It has been suggested that Fock reactivity of dissolving pulps is unaffected by extractives at concentrations up to 0.3%.     

TCF BLEACHED PULPS FROM MISCANTHUS SINENSIS BY THE IMPREGNATION RAPID STEAM PULPING (IRSP) PROCESS

ABSTRACT

The production of bleached cellulose pulps from elephant grass (Miscanthus sinensis) via a two-stage soda pulping process and a TCF bleaching sequence is evaluated in this work. The impregnation rapid steam pulping process (IRSP) involves impregnating of the lignocellulosic material with the pulping liquor, withdrawing the excess liquor and rapidly steaming the impregnated material at 180–200°C for a short time. In this paper the process variables and their effect on the kappa number, yield and viscosity of the unbleached pulps are discussed. Bleaching by an ozone-based TCF sequence was tested, and the papermaking properties of the bleached pulp were determined. A kappa number of 19 was obtained by impregnating at an alkali charge of 30 + 0.1% anthraquinone carboxylic acid (AQCA) and pulping at 180°C for only 15 min. Kappa was reduced to 16 by extending pulping time to 26 min. The alkali consumption during impregnation and pulping was 10.2 g NaOH/100 g of dry Miscanthus. Screened pulp yield, viscosity and brightness for this pulp were 54.6%, 913 mL/g and 37.3%, respectively. After bleaching, the pulp had an ISO brightness of 87.4% and a viscosity of 700 mL/g. Refining in a PFI mill provided optimal strength properties of the bleached pulp at 4500 revolutions (71°SR): breaking length 7.2 km, tensile index 72 N m/g, and burst index 4.3 kN/g. Tear index was 7.9 mN m²/g at this degree of refining.     

Oxygen Delignification Chemistry and Its Impact on Pulp Fibers

Abstract

Two southern pine kraft pulps with kappa numbers of 30.0 (SW1-0) and 48.0 (SW2-0) were oxygen delignified by 30–60% by varying the reaction temperature (78–110°C) and charge of sodium hydroxide (1.6–4.4%). O-bleachability was found to be correlated to the incoming kappa number and charge of sodium hydroxide employed. In general, a lower charge of caustic and a higher brownstock kappa number improved pulp bleachability. The residual lignin in the brownstocks and O-delignified kraft pulp samples was isolated and characterized by ¹³C and ³¹P NMR. ¹³C NMR analysis of the residual lignin samples indicated that the post-oxygen delignified pulps were enriched with α-carbonyl groups and carboxylic acid groups. The content of β-O-aryl structures was increased by 23–36% depending on the extent of oxygen delignification. The post-oxygen delignified pulps were also shown to have increased substituted aryl carbons. ³¹P NMR indicated that the relative content of condensed phenolic units increased by 9–20% after the oxygen delignification, depending on the severity of the O-stage. This observation was probably due to the accumulation or formation of 5,5-biphenyl structures in the process. The physical strength properties of brownstock and post-oxygen delignified pulps were assessed in terms of zero-span strength, tensile strength, tear strength, and burst strength. Oxygen delignification led to a slight increase in the curls and kinks of the pulp fibers. The O-stage was shown to cause a 4.8–15.6% decrease in zero-span strength. In contrast, oxygen delignification increased tensile strength. This result could be explained as the improvement of fiber bonding after the oxygen bleaching.     

Kraft pulping of Eucalyptus nitens wood chips biotreated by Ceriporiopsis subvermispora

Eucalyptus nitens and E. globulus are wood species used in kraft pulping in Chile and Australia. Although E. nitens adapts very well to cold regions it requires more severe cooking conditions to produce bleachable kraft pulps. An attempt was made to find out whether a pre‐treatment with Ceriporiopsis subvermispora would improve its performance during kraft pulping and the pulp properties. The biotreatment of the chips carried out for a period of 15 days resulted in 13.3% lignin loss and a limited glucan degradation (2%). The pulping of biotreated samples required lower active alkali charge to reach the target kappa number compared to the control untreated sample and exhibited better pulping selectivity. The pulp yield increased by 3% and 1.5% for the pulps of 22 and 16 kappa numbers, respectively. The biotreated pulp's strength properties were improved and were similar to those of E. globulus reference pulp. Copyright © 2006 Society of Chemical Industry     

Dissolution of Ethylenediamine Pretreated Pulp with High Lignin Content in LiCl/DMSO without Milling

Abstract

Various hardwood and softwood chemical pulps, including those with relatively high lignin content (up to ca. 10.5%), were completely dissolved without milling in lithium chloride/dimethyl sulfoxide (LiCl/DMSO) after a pretreatment with ethylenediamine (EDA). Because milling of the sample is not required, degradation of the cell wall components caused by milling does not take place. After the EDA pretreatment, the crystallinity of the pulps remained as high as the original pulps, although the crystal structure changed. This is the first time that transparent solutions of underivatized pulps with high lignin content were obtained in a simple organic solvent system. Interestingly, even in the case of coarse wood meal (40–80 mesh) about 70% could be dissolved after repeating the dissolving procedure two times. The formation of a pulp–EDA or wood–EDA complex seems to be critical for the dissolution in LiCl/DMSO. The nuclear magnetic resonance (NMR) spectrum of the EDA treated pulp solution had good resolution even though the degree of polymerization (DP) of the cellulose in the pulp is very high.     

Alkaline sulfite/anthraquinone pretreatment followed by disk refining of Pinus radiata and Pinus caribaea wood chips for biochemical ethanol production

BACKGROUND: Alkaline sulfite/anthraquinone (ASA) cooking of Pinus radiata and Pinus caribaea wood chips followed by disk refining was used as a pretreatment for the production of low lignified and high fibrillated pulps. The pulps produced with different delignification degrees and refined at different energy inputs (250, 750 and 1600 Wh) were saccharified with cellulases and fermented to ethanol with Saccharomyces cerevisiae using separated hydrolysis and fermentation (SHF) or semi‐simultaneous saccharification and fermentation (SSSF) processes. RESULTS: Delignification of ASA pulps was between 25% and 50%, with low glucans losses. Pulp yield was from 70 to 78% for pulps of P. radiata and 60% for the pulp of P. caribaea. Pulps obtained after refining were evaluated in assays of enzymatic hydrolysis. Glucans‐to‐glucose conversion varied from 20 to 70%, depending on the degree of delignification and fibrillation of the pulps. The best ASA pulp of P. radiata was used in SHF and SSSF experiments of ethanol production. Such experiments produced maximum ethanol concentration of 20 g L^?1, which represented roughly 90% of glucose conversion and an estimated amount of 260 L ethanol ton^?1 wood. P. caribaea pulp also presented good performance in the enzymatic hydrolysis and fermentation but, due to the low amount of cellulose present, only 140 L ethanol would be obtained from each ton of wood. CONCLUSION: ASA cooking followed by disk refining was shown to be an efficient pretreatment process, which generated a low lignified and high‐fibrillated substrate that allowed the production of ethanol from the softwoods with high conversion yields. Copyright © 2012 Society of Chemical Industry     

BEHAVIOR OF EUCALYPTUS GLOBULUS LIGNIN DURING KRAFT PULPING. II. ANALYSIS BY NMR,ESI/MS,AND GPC

ABSTRACT

Residual and dissolved lignin from different phases of kraft delignification of Eucalyptus globulus wood were isolated and characterized by 1D and 2D ¹H NMR, ¹³C NMR, Electrospray Ionization Mass Spectrometry (ESI/MS), and gel permeation chromatography (GPC). During the temperature rise period, below 70°C, about 20% of the lignin was dissolved without significant structural changes. Above 70°C, the lignin suffered significant degradation/fragmentation in the cell wall prior to dissolution. The lignin ether-linked syringyl units were the most susceptible to alkaline degradation. Through the course of pulping, the residual lignin (RL) revealed a gradual increase of aliphatic moieties of unknown structure, as well as a decrease of native structures such as phenylcoumaran and pino-/syringaresinol lignin units. A significant decrease of the β-O-4 structures content in RL was detected only at the final cooking temperature. The lignin dissolved in the black liquor (BL) consisted of highly branched oligomers with rather low molecular weight (average mass 800–1000 u). A part of BL (about 30%) was chemically linked to carbohydrates and possessed a large molecular weight distribution (500–4000 u). BL showed a progressive decrease in β-O-4 and pino-/syringaresinol structures and formation of enol ether and stilbene structures. The GPC analyses showed a continuous decrease of the molecular weight of both the residual and dissolved lignins during the pulping process, particularly in the residual stage.     

Methanol-based pulping of eucalyptus globulus

The autocatalyzed pulping of Eucalyptus globulus wood with methanol-water mixtures was studied. A surface response design was employed to develop mathematical models describing the pulp properties as a function of cooking time, cooking temperature and methanol concentration. The ranges studied for these variables were 40–120 min, 170-200°C and 30-70% (w/w), respectively. The pulp properties modeled were kappa number, total yield, screenings content, screened yield and viscosity. Under the optimum cooking conditions pulps with low kappa number and acceptable viscosity can be obtained with a high yield.