Reductive degradation of residual chromophores in kraft pulp with sodium dithionite

TAPPI Journal ◽  
2012 ◽  
Vol 11 (3) ◽  
pp. 59-67 ◽  
Author(s):  
HÉLIO J. M. CARREIRA ◽  
PEDRO E. G. LOUREIRO ◽  
M. GRAÇA V.S. CARVALHO ◽  
DMITRY V. EVTUGUIN
Keyword(s):  
Kraft Pulp ◽  
Unknown Origin ◽  
Sodium Dithionite ◽  
Carboxyl Groups ◽  
Kraft Pulps ◽  
Model Compounds ◽  
Muconic Acid ◽  
Reduction Stage ◽  
Reductive Degradation ◽  
Vis Spectroscopy

The focus of this study is the chemistry of reductive bleaching of kraft pulps with sodium dithionite. A set of model compounds mimicking quinone structures, residual lignin structures with conjugated carbonyl/carboxyl groups and muconic acid, among others, was reduced with sodium dithionite and monitored by ultraviolet-visible (UV-vis) spectroscopy. Depending on the chromophore models, either reductive or sulfonation reactions are thought to be responsible for the degradation. No reductive degradation of hexeneuronic acid (HexA) residues was detected, but unsaturated structures of unknown origin were eliminated from the xylan. Additionally, the potential of the reductive stage with either sodium dithionite or sodium borohydride was tested using an industrial pine kraft pulp bleached by OOZEDD sequence. This pulp, with a 88.8% ISO brightness ceiling, exhibited a brightness increase to 90 ± 0.5% in the final reduction stage.

scholarly journals Contribution of xylan to the brightness development and stability in the final ECF bleaching of eucalypt (Eucalyptus globulus Labill.) kraft pulp

Holzforschung ◽  
2013 ◽  
Vol 67 (5) ◽  
pp. 497-503 ◽  
Author(s):  
Pedro E.G. Loureiro ◽  
Joana I.T. Sousa ◽  
M. Graça. V.S. Carvalho ◽  
Dmitry V. Evtuguin
Keyword(s):  
Analytical Methods ◽  
Kraft Pulp ◽  
Resonance Raman Spectroscopy ◽  
Size Exclusion ◽  
Kraft Pulps ◽  
Vis Spectroscopy ◽  
Exclusion Chromatography ◽  
Uv Resonance Raman Spectroscopy ◽  
Modern Analytical

Abstract Xylans isolated from eucalypt kraft pulps have been characterized by modern analytical methods. The pulps were partially bleached (DEOPD) and fully bleached with either a final ClO2 (DEOPDD) or an alkaline H2O2 (DEOPDP) bleaching stage. Alternatively, xylan isolated from the DEOPD pulp was treated with ClO2 or with H2O2 under the same conditions as pulps in a final bleaching stage and were further characterized. 1H nuclear magnetic resonance, size exclusion chromatography, UV-vis spectroscopy in cadoxen solution, and UV-resonance Raman spectroscopy were applied as analytical methods. The final ClO2 stage generated new unsaturated moieties in xylan, whereas H2O2 was very effective in the removal of xylan-related chromophores. The role of xylan to the delay of brightness development in the final ClO2 stage was highlighted by means of a pretreatment with xylanase Pulpzyme HC before the final bleaching stage. By this approach, the final bleachability of the pulp was boosted and the brightness stability of the fully bleached pulp was improved.

Alkaline peroxide treatment of ECF bleached softwood kraft pulps. Part 1. Characterizing the effect of alkaline peroxide treatment on carboxyl groups of fibers

Holzforschung ◽  
2007 ◽  
Vol 61 (4) ◽  
pp. 445-450 ◽  
Author(s):  
Zheng Dang ◽  
Thomas Elder ◽  
Arthur J. Ragauskas
Keyword(s):  
Carbonyl Group ◽  
Intrinsic Viscosity ◽  
Sodium Borohydride ◽  
Kraft Pulp ◽  
Carboxyl Groups ◽  
Kraft Pulps ◽  
Peroxide Bleaching ◽  
Bleached Kraft Pulp ◽  
Alkaline Peroxide ◽  
Group Content

Abstract The influence of alkaline peroxide treatment has been characterized on elementally chlorine-free (ECF) bleached softwood (SW) kraft pulp. The results indicate that fiber charge increased with an increase in peroxide charge: a maximum fiber charge increment of 16.6% was obtained with 8.0% more peroxide charge on oven-dried (o.d.) pulp at 60.0°C. Two primary bleaching temperatures of 60.0°C and 90.0°C were investigated during peroxide treatment. Copper number decreased for peroxide charges of 0.5% and 1.0% at 60.0°C and 90.0°C, respectively, then increased with increasing peroxide charge. Both fiber charge and copper number approached constant values when 4.0% or higher peroxide charge was applied. Peroxide treatment on a bleached kraft pulp at 90.0°C resulted in lower fiber charge and lower intrinsic viscosity compared to treatment at 60.0°C. Sodium borohydride (NaBH4) pretreatment was able to protect the fibers from being degraded during peroxide bleaching. Fiber charge and copper number were compared after peroxide treatment of ECF bleached kraft pulp to NaBH4-reduced ECF bleached kraft pulp. The results indicate that the carbonyl group content of fibers is favorable for improving fiber charge after peroxide treatment.

Prebleaching of eucalypt kraft pulp with OP stages: Effect of an acid pretreatment or chelation step

TAPPI Journal ◽  
2012 ◽  
Vol 11 (6) ◽  
pp. 31-38
Author(s):  
TATIANA M. PÓVOAS ◽  
DINA A.G. ANGÉLICO ◽  
ANA P.V. EGAS ◽  
PEDRO E.G. LOUREIRO ◽  
LICÍNIO M. GANDO-FERREIRA ◽  
...  
Keyword(s):  
Eucalyptus Globulus ◽  
Comparative Evaluation ◽  
Kraft Pulp ◽  
Kraft Pulps ◽  
Acid Pretreatment ◽  
High Brightness ◽  
Pulp Viscosity ◽  
Brightness Reversion

We conducted a comparative evaluation of different treatments for the bleaching of eucalypt kraft pulps beginning with OP stages. The treatments tested were (1) an acid chelation stage with DTPA (OQP sequence); (2) a hot acid stage (AOP sequence); and (3) a chelant addition into the alkaline oxygen stage ((OQ)P and A(OQ)P sequences). The latter strategy was also studied for environmental reasons, as it contributes to the closure of the filtrate cycle. The OQP sequence leads to the highest brightness gain and pulp viscosity and the lowest peroxide consumption caused by an efficient metals control. Considering that the low biodegradability of the chelant is a problem, the A(OQ)P sequence is an interesting option because it leads to reduced peroxide consumption (excluding OQP) while still reaching high brightness values and similar brightness reversion to OQP prebleaching, with only a viscosity loss of 160 dm3/kg. Therefore, a hot acid stage could be considered when a separate acid Q stage is absent in a prebleaching sequence of Eucalyptus globulus kraft pulps involving OP stages.

Optimization of elemental chlorine-free bleaching for a softwood kraft pulp • part 2: economic analysis of chemical and steam consumption

TAPPI Journal ◽  
2010 ◽  
Vol 9 (9) ◽  
pp. 47-53 ◽  
Author(s):  
BRIAN N. BROGDON
Keyword(s):  
Chlorine Dioxide ◽  
Previous Investigation ◽  
Kraft Pulp ◽  
Energy Costs ◽  
Alkaline Extraction ◽  
Stage Versus ◽  
Kraft Pulps ◽  
Steam Consumption ◽  
Elemental Chlorine ◽  
Softwood Kraft Pulp

Our previous investigation [1] re-analyzed the data from Basta and co-workers (1992 TAPPI Pulping Conference) to demonstrate how oxidative alkaline extraction can be augmented and how these changes affect chlorine dioxide consumption with elemental chlorine-free (ECF) sequences. The current study manipulates extraction delignification variables to curtail bleaching costs with a conventional U.S. Southern softwood kraft pulp. The economic advantages of ~0.35% to 0.65% H2O2 peroxide reinforcement in a 70°C (EOP)-stage versus 90°C (EO)-stage are predisposed to the brightness targets, to short or long bleach sequences, and to mill energy costs. Minimized bleaching costs are generally realized when a 90°C (EO) is employed in D0(EO)D1 bleaching, whereas a 70°C (EOP) is economically advantageous for D0(EOP)D1E2D2 bleaching. The findings we disclose here help to clarify previous ECF optimization studies of conventional softwood kraft pulps.

scholarly journals Cellulose Nanofibril (CNF) Films and Xylan from Hot Water Extracted Birch Kraft Pulps

2019 ◽  
Vol 9 (16) ◽  
pp. 3436 ◽  
Author(s):  
Marc Borrega ◽  
Hannes Orelma
Keyword(s):  
Food Packaging ◽  
Kraft Pulp ◽  
Barrier Properties ◽  
Hot Water ◽  
Kraft Pulps ◽  
Cellulose Nanofibril ◽  
Vapour Permeability ◽  
Transparent Films ◽  
Cnf Films ◽  
Birch Kraft Pulp

The effects of xylan extraction from birch kraft pulp on the manufacture and properties of cellulose nanofibril (CNF) films were here investigated. Hot water extractions of bleached and unbleached kraft pulps were performed in a flow-through system to remove and recover the xylan. After the extraction, the pulps were oxidized with 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) and fibrillated in a high-pressure microfluidizer. Compared to CNF from bleached kraft pulp, the CNF dispersions obtained from water-extracted pulps were less viscous and generally contained a higher amount of microfiber fragments, although smaller in size. In all cases, however, smooth and highly transparent films were produced from the CNF dispersions after the addition of sorbitol as plasticizer. The CNF films made from water-extracted pulps showed a lower tensile strength and ductility, probably due to their lower xylan content, but the stiffness was only reduced by the presence of lignin. Interestingly, the CNF films from water-extracted bleached pulps were less hydrophilic, and their water vapour permeability was reduced up to 25%. Therefore, hot water extraction of bleached birch kraft pulp could be used to produce CNF films with improved barrier properties for food packaging, while obtaining a high-purity xylan stream for other high-value applications.

Reactions of aromatic structures in brightness reversion of fully-bleached eucalyptus kraft pulps

Holzforschung ◽  
2009 ◽  
Vol 63 (3) ◽  
Author(s):  
Anna-Stiina Jääskeläinen ◽  
Katri Toikka ◽  
Anni Lähdetie ◽  
Tiina Liitiä ◽  
Tapani Vuorinen
Keyword(s):  
Resonance Raman ◽  
Kraft Pulps ◽  
Brightness Reversion ◽  
Vis Spectroscopy ◽  
Uv Resonance Raman ◽  
Hexenuronic Acid

Abstract The role of aromatic structures in brightness reversion of fully bleached pulps was studied by UV resonance Raman (UVRR) and reflectance UV-Vis spectroscopy. The results clearly showed that ageing increased the aromatic band at approximately 1600 cm-1 in the UVRR spectra and the lignin band at approximately 280 nm in the UV-Vis spectra. This increase was probably due to increased conjugation of lignin and it was observed for all pulps regardless of the bleaching sequence. In addition to these lignin reactions, other unsaturated structures, such as hexenuronic acid groups, reacted during ageing.

scholarly journals Strong paper from spruce CTMP – Part II: Effect of pressing at nip press temperatures above the lignin softening temperature

2018 ◽  
Vol 33 (1) ◽  
pp. 142-149 ◽  
Author(s):  
Sven Norgren ◽  
Gunilla Pettersson ◽  
Hans Höglund
Keyword(s):  
Compression Strength ◽  
Kraft Pulp ◽  
Softening Temperature ◽  
Strength Properties ◽  
Kraft Pulps ◽  
Cationic Starch ◽  
Tensile Index ◽  
Very High

Abstract The main objective of the current study was to demonstrate that it is possible to enhance strength properties of sheets from spruce HT-CTMP and CTMP furnishes up to the same level as is common on sheets from softwood kraft pulps by changing conditions in papermaking. To achieve that, sheets of spruce HT-CTMP and CTMP were consolidated at densities close to that of the reference bleach kraft pulp by pressing at press nip temperatures well above the tack and softening temperatures of lignin. On sheets from spruce CTMP (CSF 420 ml), where the fibers were surface treated with cationic starch, it was possible to reach tensile index at the same level as on sheets from the untreated reference kraft pulp. The compression strength (SCT) of CTMP and HT-CTMP sheets, which were achieved at the highest press nip temperature (200 °C) in the study, was equal to or higher than that of the reference kraft pulp sheets. The results show that there is a great yet unexploited potential in papermaking from spruce HT-CTMP and CTMP furnishes, which could be utilized in manufacturing of products where very high requirements upon strength is demanded.

Investigations into Laccase-Mediator Delignification of Kraft Pulps

Holzforschung ◽  
1999 ◽  
Vol 53 (5) ◽  
pp. 498-502 ◽  
Author(s):  
J. Sealey ◽  
A.J. Ragauskas ◽  
T.J. Elder
Keyword(s):  
Bond Dissociation Energy ◽  
Dissociation Energy ◽  
Kraft Pulp ◽  
Substituent Effects ◽  
Computational Results ◽  
Kraft Pulps ◽  
Bond Dissociation ◽  
Structure Activity ◽  
Softwood Kraft Pulp

SummaryThe structure activity effects of 1-hydroxy benzotriazole and phthalimide derivatives as mediators for laccase were studied. Using a softwood kraft pulp it was shown that the N-hydroxy unit is a key component of 1-hydroxybenzotriazole for efficient laccase mediator delignification to occur. It was also found that the 1-hydroxybenzotriazole structure was very sensitive to substituent effects with respect to laccase-mediator delignification. Computational results from PM3 indicate that the bond dissociation energy, and electronic factors of the radical may contribute to the efficiency of the mediator for LMS delignification.

Evidence for the formation of lignin-hexenuronic acid-xylan complexes during modified kraft pulping processes

Holzforschung ◽  
2006 ◽  
Vol 60 (2) ◽  
pp. 137-142 ◽  
Author(s):  
Zhi-Hua Jiang ◽  
Jean Bouchard ◽  
Richard Berry
Keyword(s):  
Acid Hydrolysis ◽  
Kraft Pulp ◽  
Kraft Pulping ◽  
Order Kinetic ◽  
Kraft Pulps ◽  
First Order ◽  
Pseudo First Order ◽  
Hexenuronic Acid ◽  
Kinetics Of ◽  
Hydrolysis Of

Abstract The finding that hexenuronic acid (HexA) groups can be selectively removed from kraft pulps by acid hydrolysis has provided an opportunity to reduce bleaching chemicals. However, there is evidence that the acid hydrolysis is not uniform. In this report, we evaluate the kinetics of acid hydrolysis of HexA in a xylan sample enriched with HexA, a conventional kraft pulp, and three modified kraft pulps: anthraquinone pulp (Kraft-AQ), polysulfide pulp (PS), and polysulfide-anthraquinone pulp (PS-AQ). We found that HexA present in the xylan and conventional kraft pulp behaved similarly toward the acid hydrolysis throughout. On the other hand, HexA present in the Kraft-AQ, PS-AQ and PS pulps was heterogeneous toward acid hydrolysis and the reaction can be separated into two pseudo-first-order kinetic phases, each of which has a different rate constant. The kinetic data provide evidence for the formation of lignin-HexA-xylan complexes during modified kraft pulping processes.

Fate of Residual Lignin during Delignification of Kraft Pulp by Trametes versicolor

1998 ◽  
Vol 64 (6) ◽  
pp. 2117-2125 ◽  
Author(s):  
Ian D. Reid
Keyword(s):  
Trametes Versicolor ◽  
Kraft Pulp ◽  
Lignin Degradation ◽  
Water Soluble ◽  
Kraft Pulps ◽  
Residual Lignin ◽  
Spruce Wood ◽  
Single Ring ◽  
Enzyme Bleaching ◽  
By Products

ABSTRACT The fungus Trametes versicolor can delignify and brighten kraft pulps. To better understand the mechanism of this biological bleaching and the by-products formed, I traced the transformation of pulp lignin during treatment with the fungus. Hardwood and softwood kraft pulps containing 14C-labelled residual lignin were prepared by laboratory pulping of lignin-labelled aspen and spruce wood and then incubated with T. versicolor. After initially polymerizing the lignin, the fungus depolymerized it to alkali-extractable forms and then to soluble forms. Most of the labelled carbon accumulated in the water-soluble pool. The extractable and soluble products were oligomeric; single-ring aromatic products were not detected. The mineralization of the lignin carbon to CO2 varied between experiments, up to 22% in the most vigorous cultures. The activities of the known enzymes laccase and manganese peroxidase did not account for all of the lignin degradation that took place in the T. versicolor cultures. This fungus may produce additional enzymes that could be useful in enzyme bleaching systems.

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