Susanna Kuitunen

The Effect of Process Variables in Chlorine Dioxide Prebleaching of Birch Kraft Pulp. Part 1. Inorganic Chlorine Compounds, Kappa Number, Lignin, and Hexenuronic Acid Content

Abstract This study investigated the effects of temperature, chlorine dioxide dosage, and filtrate circulation on various filtrate and pulp properties in chlorine dioxide prebleaching of birch kraft pulp. Also the effect of a preceding A-stage was examined. Kappa number, delignification, and hexenuronic acid removal were unaffected by the used dilution media and temperature. Increasing ClO2 charge resulted in a lower kappa number, increased hexenuronic acid removal, and more efficient delignification. With a preceding A-stage the kappa number was lower throughout the D0-stage, but the kappa number reduction and the removal of hexenuronic acid were slightly decreased. Chlorine dioxide consumption was practically independent of the tested variables; only dosage had an effect. The formation of chlorate and chloride was increased with higher dosages of ClO2, but the stoichiometry remained unchanged. The concentration of chlorite + chlorous acid during bleaching depended on temperature, used dilution medium, and the presence of an A-stage.

Lignin oxidation mechanisms under oxygen delignification conditions. Part 2: Advanced methods for the detailed characterization of lignin oxidation mechanisms

Abstract Advanced analysis methods have been developed to follow the reactions of lignin during alkaline oxygen delignification conditions more comprehensively than before. This aim was attained by monitoring both the lignin macromolecule and the dissolved reaction products. Softwood (SW) and hardwood (HW) kraft spent liquor lignins were studied as substrates under various reaction conditions. The decrease in the contents of different types of free phenolic hydroxyl groups and the concurrent formation of carboxylic acids was followed by 31P NMR of the phosphitylated products. In addition, the formation of acidic degradation products with low molecular weight was determined by capillary zone electrophoresis (CE). This way, it was possible to distinguish the carboxylic acids bound to the lignin macromolecule from the cleaved reaction products, even if they partly co-precipitated during sample preparation. Peak deconvolution was applied to get information on syringyl type phenolic structures and on C(5) condensed guaiacyl structures in hardwood lignin. Pyrolysis-GC/MS was applied to provide additional information about the distribution of guaiacyl/syringyl/p-hydroxyphenyl (G/S/H) type lignin subunits, as well as changes in the phenylpropane side chain.

The Effect of Process Variables in Chlorine Dioxide Prebleaching of Birch Kraft Pulp. Part 2. AOX and OX Formation

Abstract Chlorine dioxide prebleaching (D0-stage) is known to produce some chlorinated organic compounds. This article presents the development of AOX and OX as a function of time under various prebleaching conditions for oxygen delignified hardwood pulp. It was observed that OX is formed more rapidly than AOX and its amount was less affected by a preceding A-stage. Temperature had little effect on chlorination. Using mill filtrate instead of water for dilution increased the amount of AOX formed while the amount of OX remained unchanged. Higher charges of chlorine dioxide expectedly increased chlorination during a D0-stage.

A model for chlorine dioxide delignification of chemical pulp

Abstract A phenomenon based model for chlorine dioxide delignification of chemical pulp is introduced. The pulp suspension environment is modeled using the concept of two liquid phases, one inside and the other external to the fiber wall. Physico-chemical processes taking place during delignification are implemented with thermodynamic, mass transfer and reaction kinetic models. A broad library of chemical reactions is introduced. Inclusion of each reaction is justified. The model response is tested against experimental laboratory delignification results (o-delignified birch pulp). The experimental data consists of kappa number, hexenuronic acid, inorganic oxy-chlorine compound, and organochlorine (AOX, OX) measurements at several time points during five delignification experiments. The model predictions are mainly in good agreement with the experimental results. The predictions regarding hypochlorous acid driven processes (HexA removal, organochlorine formation, chlorite and chlorate concentration) are somewhat incoherent, indicating that knowledge regarding the intermediately formed hypochlorous acid is presently insufficient.

Reactions of aldehydes with chlorous acid and chlorite in chlorine dioxide bleaching

Abstract The role of chlorine (III) compounds, i.e. chlorous acid (HClO2) and chlorite (ClO2 -), in chlorine dioxide bleaching were investigated by treating different pulps with Cl(III). It was discovered that in addition to its fully inorganic reactions, chlorous acid is consumed by organic structures present in the pulp. These structures were assumed to be aldehydes. The aldehydes might exist already in unbleached pulps, but chlorine dioxide bleaching was also found to generate new aldehyde groups. The reactive groups were concluded to originate both from carbohydrates and lignin.

The role of Donnan effect in kraft cooking liquor impregnation and hot water extraction of wood

Abstract In this article, a phenomenological model is proposed for alkali impregnation and hot water extraction of wood. Elementary reaction kinetics, ion exchange (IE) equilibrium, and mass transfer rates are considered in the model. IE is a consequence of the dissociation of the covalently bound uronic acid and phenolic groups in the wood fiber wall (FW). Due to this effect, the molality of cations is higher in the FW liquid than in the liquid external to the FW, whereas the opposite is true for anions. For the development of kinetic models under the participation of hydroxyl and hydrogen ions, the estimation of their molalities in these two liquid phases is crucial because of their ubiquitous presence in chemical reactions. This study applies a recently developed physicochemical modeling environment in which alkali impregnation and hot water extraction processes are considered. The simulations revealed that the IE effect is significant and affects the chemical reaction kinetics in both processes in focus. Furthermore, the IE effect does not remain constant but varies as a function of treatment time.

Chlorate Formation in Chlorine Dioxide Delignification—An Analysis via Elementary Kinetic Modeling

Abstract Elementary kinetic modeling was used to study the mechanism of chlorate formation in chlorine dioxide delignification. Reaction conditions reflecting typical industrial processes (T = 50°C, pH 1.5–4) were examined. Fe mediated Cl(III) decomposition and a reaction between hypochlorous acid and chlorous acid (or their equilibrium counterparts) were found to be the major reaction routes responsible for chlorate formation at pH < 3. The latter route accounts for chlorate formation at pH ≥ 3. The rate of chlorous acid (HClO2) self-decomposition was too slow either to compete against the other routes (pH < 3) or to yield notable amounts of chlorate within the given time frame (pH ≥ 3). The results suggest that chlorate formation could be suppressed, without adverse effects on chlorine dioxide regeneration, by aiming for end pH 3–3.5, ensuring a moderate chloride ion concentration and by favoring concentrated solutions/suspensions.

Reaction kinetics of strong nucleophiles with a dimeric non-phenolic lignin model compound with α-carbonyl functionality (adleron) in aqueous alkali solution

Abstract The degradation kinetics of a non-phenolic lignin model compound with α-carbonyl functionality (adlerone) has been studied by varying temperature and concentrations of sodium hydroxide, sodium hydrogen sulfide, and sodium sulfite. The kinetics of adlerone degradation and formation of its reaction products were monitored by UV-Vis spectroscopy and their structures were analyzed by GC/MS. The two step degradation of adlerone was studied in two separate experimental setups. In the first alkali catalyzed step, adlerone is converted to a β-elimination product that reacts further in the second step with hydrogen sulfide or sulfite ion. The Arrhenius kinetic parameters were derived by the KinFit software. The activation energy for the 1st step was 69.1 kJ mol-1, and for the 2nd step with sulfide 42.4 kJ mol-1 and with sulfite ion 35.8 kJ mol-1. The reaction mechanisms presented are in line with those published earlier: β-ether bonds of structures having α-carbonyl functionality do not cleave under soda pulping conditions, whereas in kraft and sulfite pulping the cleavage of β-ether bonds proceeds via nucleophile attack and addition. The combination of hydroxyl and sulfite ions gives the fastest cleavage of β-ether bonds in non-phenolic lignin structures with the α-carbonyl functionality.

Modeling of alkaline extraction chemistry and kinetics of softwood kraft pulp

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.

Implementation aspects of modeling equilibrium reactions and thermodynamics data in a flowsheet simulator

Abstract The paper presents systematic treatment and implementation of the equilibrium reactions between the liquid phase components and what kind of data needs to be stored into the database of a steady state unit modular flowsheet simulator. The examples consider chemical systems of alkanolamines and wood polymers, which are both important topics from the sour gas capture and biochemical production point of view. The paper further shows how the fact that some thermodynamic properties are missing is tackled.