Optimization of elemental chlorine-free bleaching for a softwood kraft pulp – part 1: impact of oxidative extraction on chlorine dioxide stoichiometry

TAPPI Journal ◽  
2010 ◽  
Vol 9 (8) ◽  
pp. 27-35 ◽  
Author(s):  
BRIAN N. BROGDON

The present investigation meticulously analyzes how oxidative alkaline extraction can be augmented through process changes, and how these augmentations can be leveraged to optimize chlorine dioxide usage with elemental chlorine-free (ECF) sequences for a conventional softwood kraft pulp. Bleaching data from Basta and co-workers (1992 TAPPI Pulping Conference) are re-examined and re-interpreted in this study. We determined that ~60% to 65% of the overall ClO2 charge should be applied in the D0-stage. Peroxide addition to an (EOP) can replace 0.6 to 2.5 Kg. ClO2 per Kg H2O2. Boosting the (EO) temperature to 80°C is equivalent to a 70°C (EOP) with 0.25% to 0.30% H2O2,whereas a 90°C (EO) is equivalent to 0.50% – 0.75% H2O2 in a 70°C (EOP). The stoichiometric bleaching data from this study can guide decision-making for lowering chemical usage and minimize costs to reach target brightness levels with three- and five-stage sequences.

TAPPI Journal ◽  
2010 ◽  
Vol 9 (9) ◽  
pp. 47-53 ◽  
Author(s):  
BRIAN N. BROGDON

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.


TAPPI Journal ◽  
2016 ◽  
Vol 15 (4) ◽  
pp. 285-295 ◽  
Author(s):  
UMIT SEZGI ◽  
JANAINA RESENDE ◽  
LEWIS SHACKFORD ◽  
JORGE COLODETTE ◽  
MARCELA ANDRADE

Mills have largely used chlorine dioxide (ClO2) for eucalyptus kraft pulp bleaching. Different mills have observed significant variation in ClO2 demand to reach full brightness (≥90 ISO). These large differences in ClO2 consumption derive from many factors. The most significant include differences in carryover loads and hexenuronic acid (HexA) contents and the level of chlorate formation across bleaching. Handling of pulp with high HexA content and ClO2 losses to chlorate can be minimized by proper operation of the ClO2 stages across the bleach plant. An oxygen delignified eucalyptus kraft pulp with a kappa of 10-12 units contains only 4-6 units actually derived from lignin. This scarce amount of lignin (0.6%-0.9%) is not able to consume high ClO2 doses and, as a consequence, the excess ClO2 applied can end up being converted into chlorate. Hence, proper optimization of ClO2 bleaching stages can save significant amounts of this oxidant. This study focused on optimizing ClO2 bleaching for a typical oxygen delignified eucalyptus kraft pulp of kappa number 11.7. Elemental chlorine free bleaching was carried out with the D0-(EP)-D1 sequence. The following conditions were varied in the D0 stage: temperature, end pH, and kappa factor. The results indicated that maximum ClO2 bleaching efficiency is achieved when minimum chlorate is formed, especially when ClO2 bleaching is adjusted in such a way that residual active chlorine is maintained to a minimum. The most significant variable affecting chlorate formation is pH; however, ClO2 doses (ClO2 concentration) also play a very important role. Chlorate formation is more intense in the D1 stage in relation to the D0 stage. Optimum conditions to run the D0 stage were 90°C, 3.5 pH, and 0.22 kappa factor.


TAPPI Journal ◽  
2013 ◽  
Vol 12 (10) ◽  
pp. 33-41 ◽  
Author(s):  
BRIAN N. BROGDON

This investigation evaluates how higher reaction temperatures or oxidant reinforcement of caustic extraction affects chlorine dioxide consumption during elemental chlorine-free bleaching of North American hardwood pulps. Bleaching data from the published literature were used to develop statistical response surface models for chlorine dioxide delignification and brightening sequences for a variety of hardwood pulps. The effects of higher (EO) temperature and of peroxide reinforcement were estimated from observations reported in the literature. The addition of peroxide to an (EO) stage roughly displaces 0.6 to 1.2 kg chlorine dioxide per kilogram peroxide used in elemental chlorine-free (ECF) bleach sequences. Increasing the (EO) temperature by Δ20°C (e.g., 70°C to 90°C) lowers the overall chlorine dioxide demand by 0.4 to 1.5 kg. Unlike what is observed for ECF softwood bleaching, the presented findings suggest that hot oxidant-reinforced extraction stages result in somewhat higher bleaching costs when compared to milder alkaline extraction stages for hardwoods. The substitution of an (EOP) in place of (EO) resulted in small changes to the overall bleaching cost. The models employed in this study did not take into account pulp bleaching shrinkage (yield loss), to simplify the calculations.


Holzforschung ◽  
2014 ◽  
Vol 68 (7) ◽  
pp. 733-746 ◽  
Author(s):  
Susanna Kuitunen ◽  
Ville Tarvo ◽  
Tiina Liitiä ◽  
Stella Rovio ◽  
Tapani Vuorinen ◽  
...  

Abstract A comprehensive model for alkaline extraction (E) of chlorine dioxide delignified (D0) softwood kraft pulp (KP) is presented. The dynamics of the process is modeled by taking into account both irreversible and reversible chemical reactions and gas-liquid and liquid-liquid mass transfer. Equations linking molecular-scale composition (amounts of monomeric lignin and carbohydrate structures) and general engineering parameters [κ number (KN), brightness, intrinsic viscosity, total organic carbon (TOC), chemical oxygen demand (COD), etc.] are presented. The model is capable of reproducing the development of KN and brightness from the molecular-level kinetics. Reactions responsible for the darkening of chlorine dioxide bleached (D0) pulp in alkali, brightening of pulp due to the action of hydrogen peroxide and oxygen, and reduction in KN were identified. The model predicts the chemical composition of both fiber wall and filtrate. This feature enables studies concerning the interaction of the AE chemistry with upstream (D0 washing) and downstream (D1 stage) processes. Quantitative physicochemical modeling approach also points out shortcoming in the present knowledge.


2011 ◽  
Vol 18 (7) ◽  
pp. 1049-1056 ◽  
Author(s):  
Jukka Kukkola ◽  
Juha Knuutinen ◽  
Jaakko Paasivirta ◽  
Sirpa Herve ◽  
Piia Pessala ◽  
...  

2013 ◽  
Vol 634-638 ◽  
pp. 386-390
Author(s):  
Zhi Li ◽  
Jun Li ◽  
Jun Xu

Elemental Chlorine Free (ECF) bleaching sequence of O1/O2D0EOPD1D2 was adopted to bleach the pro-hydrolyzed Larix kraft pulp, where O1/O2 was two-stage oxygen delignification without interstage treatment, D was chlorine dioxide bleaching, EOP was pressurized alkaline extraction strengthened by hydrogen peroxide. Keeping bleaching temperature and time unchanged, sodium hydroxide charge(NaOH) in O1 stage, chlorine dioxide(ClO2) charge in D0 stage and D2 stage were studied, pulp properties such as brightness, kappa number, alpha-cellulose, pentosan and polymerization degree were measured and compared to establish optimal bleaching conditions. Results show that the optimal charge of NaOH in O1 stage is 2.5%, ClO2 in D0 and D2 stage are 2.5%, 0.6%, and the pulp gained at the optimal bleaching conditions has the properties of 93.9% of alpha-cellulose, 2.60% of pentosan, 375.5 ml/g of viscosity and 86.6%ISO of brightness.


Holzforschung ◽  
2003 ◽  
Vol 57 (5) ◽  
pp. 503-512 ◽  
Author(s):  
C. S. R. Freire ◽  
A. J. D. Silvestre ◽  
C. Pascoal Neto

Summary The structural changes of E. globulus wood extractives during bleaching with chlorine dioxide (D), oxygen (O), ozone (Z) and hydrogen peroxide (P) were studied. The detailed characterisation of the extractive derivatives detected in the partially bleached D, O, P and Z pulps was achieved by performing reactions of pure reference compounds with the different bleaching agents. The results show that the unsaturated sterols and fatty acids are extensively degraded during chlorine dioxide and ozone bleaching and only partially degraded during oxygen and hydrogen peroxide bleaching. The corresponding saturated extractives as well as the long chain aliphatic alcohols and ω-hydroxyfatty acids were stable during bleaching. The main oxidation products of β-sitosterol and oleic and linoleic acids, including one chlorinated derivative of linoleic acid, were identified here for the first time in E. globulus bleached pulps and bleaching filtrates.


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