Voltammetric analysis of the bleachability of softwood kraft pulps

Holzforschung ◽  
2004 ◽  
Vol 58 (6) ◽  
pp. 581-587 ◽  
Author(s):  
Robert Bourbonnais ◽  
Loredana Valeanu ◽  
Michael G. Paice
Keyword(s):  
Chlorine Dioxide ◽  
Acid Content ◽  
Black Spruce ◽  
Kappa Number ◽  
Western Hemlock ◽  
Kraft Pulps ◽  
Residual Lignin ◽  
Redox Mediators ◽  
Voltammetric Analysis ◽  
Hexenuronic Acid

Abstract Kraft and oxygen delignified pulps with various kappa numbers were prepared from black spruce and western hemlock chips. The bleachability (ratio of kappa number decrease to chlorine dioxide applied) of the different pulps at the same kappa number varied with both wood furnish and delignification process. Thus, unbleached kappa number alone is not a reliable indicator of bleachability for these pulps. This may be due in part to the variable hexenuronic acid content of the pulps; those with higher ratio of hexenuronic acid content to kappa number (HexA/kappa) are harder to bleach. Voltammetric analysis of the same kraft pulps in the presence of redox mediators was found to measure both the content and reactivity of residual lignin. Peak current ratios of redox mediators correlated with pulp bleachability for all pulps. These ratios may therefore provide a more accurate prediction of bleachability than unbleached kappa number.

Bleaching of eucalyptus kraft pulps with chlorine dioxide: Factors affecting the efficiency of the final D stage

TAPPI Journal ◽  
2012 ◽  
Vol 11 (3) ◽  
pp. 43-53 ◽  
Author(s):  
OLENA SEVASTYANOVA ◽  
ANNBRITT FORSSTRÖM ◽  
EVA WACKERBERG ◽  
MIKAEL E. LINDSTRÖM
Keyword(s):  
Carboxylic Acid ◽  
Chlorine Dioxide ◽  
Ph Value ◽  
Eucalyptus Grandis ◽  
Conductometric Titration ◽  
Kappa Number ◽  
Kraft Pulps ◽  
Factors Affecting ◽  
Hexenuronic Acid ◽  
A Minor

We investigated the bleaching efficiency of the final chlorine dioxide (D2) stage in the D0(EP)D1D2 bleaching sequence, focusing on the effect of pH in relation to the bleaching history of pulp samples. The samples used were unbleached kraft Eucalyptus grandis pulps with kappa no. 14.8 and the same pulp oxygen-delignified to kappa nos. 12 and 9.8. The samples were bleached according to the D0(EP)D1 sequence to a brightness of about 86% ISO and then submitted to the final D2 stage under identical conditions (e.g., chlorine dioxide charge, time, temperature, and final pH). The target final brightness was 90.5% ISO. Changes in the kappa number, brightness, viscosity, and contents of hexenuronic acid, 4-O-methylglucuronic acid, and the total amount of carboxylic acid (COOH) groups in pulps were monitored during the bleaching sequence. The final brightness of eucalyptus kraft pulps increased when the terminal pH of the D2 stage was raised from 3.0 to 6.5. The 90.5% ISO target brightness in the D2 stage was achieved for all pulps within a pH range of 4.5–6.5, but this required adjusting final pH for individual samples. The optimal pH value with respect to pulp viscosity was between 3 and 5. Despite dissimilar conditions applied in previous bleaching stages, the samples after the D1 stage revealed similar residual lignin contents as shown by kappa number analysis. The content of hexenuronic acid in the samples, however, varied broadly, from 2 to 26 mmol/kg. Conductometric titration showed different amounts of carboxylic acid groups in pulps after the D1 stage, of which hexenuronic acid accounted for only a minor part. The variations in the fiber charge resulted from the different bleaching conditions applied before the D2 stage. The fiber charge affected the alkali demand in the final D2 stage, whereas variations in the alkali demand affected the initial pH and associated process kinetics. Lower total fiber charge was found to be beneficial for improved final brightening and viscosity when bleached at higher final pH.

Effects of lignin chemistry on oxygen delignification performance

TAPPI Journal ◽  
2018 ◽  
Vol 17 (07) ◽  
pp. 373-381 ◽  
Author(s):  
Valeria Juste Gomes ◽  
Hasan Jameel ◽  
Hou-Min Chang ◽  
Robert Narron ◽  
Jorge Colodette ◽  
...  
Keyword(s):  
Molecular Oxygen ◽  
Chemical Properties ◽  
Kappa Number ◽  
Kraft Pulps ◽  
Residual Lignin ◽  
Reactive Site ◽  
Oxygen Delignification ◽  
Hardwood Species ◽  
Hexenuronic Acid ◽  
The Relationship

The present work focused on characterizing the chemical and structural properties of isolated lignin from six hardwoods and their kraft pulps in an attempt to better understand the relationship between lignin’s chemical properties and resultant oxygen delignification performance. Several hardwood samples were cooked under the same conditions with varying alkali charges to obtain unbleached pulps with kappa numbers between 19 and 20. These pulps were then subjected to an oxygen delignification stage. Both processes were evaluated for pulp quality, residual lignin, and O-stage delignification efficiency. The oxygen delignification stage was carried out under fixed conditions and evaluated with regards to kappa number, which was corrected for hexenuronic acid (HexA) contributions.Results revealed that different hardwood species exhibited differing oxygen delignification efficiencies. A high correlation was found between the O-stage delignification efficiency and the content of phenolic groups in the unbleached lignin, which confirmed that free phenolic groups are the reactive site for molecular oxygen attack. When different hardwood species were compared, the HexA contents were not found to affect O-stage delignification efficiencies.

Pre-bleaching of kraft acacia pulp

2019 ◽  
Vol 34 (2) ◽  
pp. 165-172 ◽  
Author(s):  
Moinul Haque ◽  
Moumita Nanjiba ◽  
M. Sarwar Jahan ◽  
M. A. Quaiyyum ◽  
M. Zahangir Alam ◽  
...  
Keyword(s):  
Acacia Mangium ◽  
Kappa Number ◽  
Acacia Auriculiformis ◽  
Kraft Pulps ◽  
Oxygen Delignification ◽  
Acid Pretreatment ◽  
Acacia Hybrid ◽  
Pre Treatment ◽  
Hexenuronic Acid ◽  
Peroxyformic Acid

Abstract Kraft pulps from acacia hybrid, Acacia mangium of 8 years old and Acacia auriculiformis of 6, 8 and 10 years old were pre-treated with oxygen, peroxyformic acid and acid treatment prior to bleaching. The kappa number reduction was 52–63 % by oxygen delignification, 31–35 % by peroxyformic acid (PFA) pre-treatment and 11–13 % by acid pre-treatment. Oxygen delignified pulp required less chlorine dioxide charge to reach target brightness. At the consumption of 30 kg ClO2/ton of pulp, the pulp brightness reached to 65–71 % for the untreated pulp, 81–85 % for the oxygen delignified pulp, 81–82 % for the PFA treatment and 79–80 % for acid pre-treated pulp. COD load in bleached effluent was much lower in oxygen delignified pulp. Cold alkali extraction of unbleached and oxygen delignified pulps was also carried out with varying alkali charge to remove hexenuronic acid (HexA) from the pulp. Xylan removal from the pulp was insignificant and resulted in no removal of HexA. Acid pretreatment removed 55.7 % to 17.8 % HexA from acacia hybrid, 57.5 % to 16.3 % from A. auriculiformis of 10 years and 58.6 % to 20.1 % from A. auriculiformis of 6 years old, resulting in improved final pulp brightness.

Changes in the lignin-carbohydrate complex in softwood kraft pulp during kraft and oxygen delignification

Holzforschung ◽  
2004 ◽  
Vol 58 (6) ◽  
pp. 603-610 ◽  
Author(s):  
Martin Lawoko ◽  
Rickard Berggren ◽  
Fredrik Berthold ◽  
Gunnar Henriksson ◽  
Göran Gellerstedt
Keyword(s):  
Kraft Pulp ◽  
Kappa Number ◽  
Kraft Pulps ◽  
Residual Lignin ◽  
Oxygen Delignification ◽  
Number Range ◽  
Morphological Aspects ◽  
Carbohydrate Complex ◽  
Softwood Kraft Pulp ◽  
Hydrolysis Of

Abstract Three kraft pulps in the kappa number range between 50 and 20 and the same pulps oxygen-delignified to similar lignin contents (kappa approximately 6) were analyzed for lignin-carbohydrate complexes (LCC) by a method based on selective enzymatic hydrolysis of the cellulose, and quantitative fractionation of the LCC. Between 85 and 90% of residual lignin in the unbleached kraft pulp and all residual lignin in the oxygen-delignified pulps were isolated as LCC. Three types of complexes were found; viz., xylan-lignin, glucomannan-lignin-xylan and glucanlignin complexes. After pulping to a high kappa number, most of the residual lignin was linked to xylan. Different delignification rates were observed so that most of the residual lignin was linked to glucomannan when the pulping was extended to a low kappa number. With increasing degree of oxygen delignification, a similar trend in the delignification rates of LCC was observed so that the residual lignin was increasingly linked to glucomannan. Complex LCC network structures seemed to be degraded into simpler structures during delignification. The differences in delignification rates are discussed with reference to the solubility properties and structural differences of LCC, and to morphological aspects of the pulp.

scholarly journals Assessment of Q(OP)D(PO) bleachability of softwood kraft pulp

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Sara Starrsjö ◽  
Maria Boman ◽  
Olena Sevastyanova ◽  
Mikael E. Lindström ◽  
Juha Fiskari
Keyword(s):  
Kraft Pulp ◽  
Kappa Number ◽  
Carbohydrate Content ◽  
Residual Lignin ◽  
Three Samples ◽  
Softwood Kraft Pulp ◽  
Pulp Sample ◽  
Yield Gain ◽  
Hexenuronic Acid

Abstract Bleachability is evaluated as how easily a pulp sample is bleached and it depends on the structure of residual lignin and carbohydrates. Also, the bleachability varies depending on the bleaching sequence. ECF light sequences have been improved significantly in the recent years. However, we still don’t fully understand how ECF light bleach plants are optimally run. This work studies the bleachability of softwood kraft pulp in an ECF light bleaching sequence, (OO)Q(OP)D(PO). Three pulp samples with brown stock kappa number 27, 32 and 35 were bleached and studied for residual lignin, hexenuronic acid and carbohydrate content. It was found that in the bleaching stages that are highly delignifying, it is beneficial with a higher kappa number for the delignifying bleachability. However, in the bleaching stages where the objective is brightness increase, the brightness gain bleachability is improved by a lower kappa number. We also intended to determine which of the three samples had the best suited kappa number for this particular bleaching sequence. According to our results, the bleaching was most effective with kappa number around 32. Although an even higher kappa number resulted in higher yield after cooking, it seemed that this bleaching sequence cannot preserve the yield gain.

Extension of a steady-state chlorine dioxide brightening model for Z-ECF bleaching of softwood kraft pulps

TAPPI Journal ◽  
2021 ◽  
Vol 20 (3) ◽  
pp. 186-197
Author(s):  
BRIAN N. BROGDON ◽  
LUCIAN A. LUCIAN
Keyword(s):  
Steady State ◽  
Linear Relationship ◽  
Chlorine Dioxide ◽  
Current Model ◽  
Kappa Number ◽  
Kraft Pulps ◽  
Current Investigation ◽  
Elemental Chlorine ◽  
Steady State Model ◽  
Ecf Bleaching

Earlier studies developed a steady-state model to predict the brightness and/or bleach consumption during the chlorine dioxide brightening (D1) of softwood pulps produced by conventional elemental-chlorine-free (ECF) sequences. This model relates the chlorine dioxide consumed to the brightness gains predicated upon an asymptotic D1 brightness limit, an incoming D1 pulp brightness, and an equation parameter (β11). The current investigation examines the application of this model to ECF sequences that use ozone delignification (Z-ECF). Literature D1 data from various Z-ECF bleaching studies, which investigated OZ, OD0/Z, and OZ/D0 delignification, were fitted to the model. The β11 parameter was found to be linearly correlated to the entering kappa number. Interestingly, this linear relationship was found to be identical to the relationships observed when modeling the D1 stage for conventional ECF and chlorine-based bleach sequences. Subtle differences in D1 brightening response in the model among the various bleach sequences are reflected by incoming pulp brightness (at the same kappa number). The current model is used to illustrate how alterations to Z-ECF delignification affect D1 brightening and chlorine dioxide consumption.

Stoichiometric model of chlorine dioxide delignification of hardwood kraft pulps with oxidant-reinforced extraction effect,

TAPPI Journal ◽  
2013 ◽  
Vol 12 (2) ◽  
pp. 17-26 ◽  
Author(s):  
BRIAN N. BROGDON
Keyword(s):  
Steady State ◽  
Chlorine Dioxide ◽  
Empirical Relationship ◽  
Kappa Number ◽  
Published Data ◽  
Kraft Pulps ◽  
Mathematical Transformation ◽  
Stoichiometric Model ◽  
Hardwood Species ◽  
Steady State Model

A generalized, steady-state model for hardwoods is proposed for predicting bleaching delignification and/or chlorine dioxide (ClO2) consumption for sequences that use oxidant-reinforced extraction. Published data for various hardwood species and mixtures were analyzed to develop the model. The kappa number data from these studies were normalized to their respective pre-D0 kappa number, and the normalized kappa numbers were plotted against the bleach demand. This mathematical transformation allowed for various brownstocks and oxygen-delignified pulps with different kappa numbers to be modeled as a single curve based on an empirical relationship with fitted equation parameters. One of the two equation parameters could be expressed as simple functions of oxidant-reinforced extraction conditions (i.e., peroxide dosage). The model forecasts ClO2 usage reasonably well (±0.20% ClO2 on pulp) for conventional ClO2 delignification with extraction. Attempts to incorporate modified bleaching delignification processes that eliminate hexenuronic acids into the model were unsuccessful; data were insufficient to develop a relationship. This straightforward stoichiometric model contains relatively few fitted parameters to be determined. The model could be used with other steady-state brightening-stage models to predict bleach usage.

High-consistency ozonation of hardwood kraft pulp

Holzforschung ◽  
2006 ◽  
Vol 60 (6) ◽  
pp. 685-690 ◽  
Author(s):  
Ai Van Tran
Keyword(s):  
Kraft Pulp ◽  
Kappa Number ◽  
Second Phase ◽  
Residual Lignin ◽  
Two Phase ◽  
Elemental Chlorine ◽  
Ozonation Time ◽  
Shrinking Core ◽  
High Consistency ◽  
Hexenuronic Acid

Abstract At present, ozone is one of the main chemicals in elemental chlorine-free (ECF) and totally chlorine-free (TCF) bleaching sequences. High consistency (HC) and medium consistency (MC) technologies are in use. This study shows that HC ozonation of hardwood kraft pulp, as expressed by the overall kappa number encompassing both hexenuronic acid groups and residual lignin, is a two-phase path. The reaction rate of the first phase is two- to three-fold higher than that of the second phase. We propose that the first phase is due to ozonation of both hexenuronic acid groups and residual lignin, whereas the second phase involves only residual lignin. The fiber width and wall thickness were relatively unchanged during ozonation. These results are in contrast to the “shrinking core kinetic model” frequently discussed in the context of HC ozonation. The development of pulp brightness and the decrease in pulp viscosity with the ozonation time are well correlated with the overall kappa number or the kappa number due to residual lignin alone.

Inter-laboratory comparisons of hexenuronic acid measurements in kraft eucalyptus pulps using a UV-Vis spectroscopic method

TAPPI Journal ◽  
2014 ◽  
Vol 13 (1) ◽  
pp. 57-61 ◽  
Author(s):  
J.Y. ZHU ◽  
H.F. ZHOU ◽  
X.S. CHAI ◽  
DONNA JOHANNES ◽  
RICHARD POPE ◽  
...  
Keyword(s):  
Acid Content ◽  
Spectroscopic Method ◽  
The Other ◽  
Kraft Pulps ◽  
Chemical Pulp ◽  
Three Samples ◽  
Hexenuronic Acid ◽  
Replicate Measurements ◽  
The Comparative Study ◽  
Measurement Repeatability

An inter-laboratory comparison of a UV-Vis spectroscopic method (TAPPI T 282 om-13 “Hexeneuronic acid content of chemical pulp”) for hexeneuronic acid measurements was conducted using three eucalyptus kraft pulps. The pulp samples were produced in a laboratory at kappa numbers of approximately 14, 20, and 35. The hexeneuronic acid contents of the three pulps were approximately 55–65 μmol/g, or with a variation of approximately 15%. Five laboratories from four different countries participated in this round-robin study as part of the evaluation of the TAPPI provisional method for upgrading to a TAPPI standard method. The comparative study showed that the orders of hexeneuronic acid content from low to high among the three pulp samples produced by four laboratories were in agreement. Replicate measurements were not conducted at the laboratory that produced an inconsistent order of hexeneuronic acid among the three pulp samples compared with the other four laboratories. The differences in hexeneuronic acid contents from different laboratories were systematic and consistent; that is, some laboratories consistently produced high values of hexeneuronic acid for all three samples. The comparative data of three pulp samples concluded that the measurement repeatability (within a laboratory) was less than 3% and reproducibility (among laboratories) was less than 16%.

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