The use of Fenton chemistry for reducing the refining energy during TMP production : the effect of free ferrous and free or chelated ferric ions

• Main Author: Walter, Karin
• Format: Doctoral Thesis
• Language: English
• Published: Mittuniversitetet, Avdelningen för kemiteknik 2013
• Online Access: http://urn.kb.se/resolve?urn=urn:nbn:se:miun:diva-20737; http://nbn-resolving.de/urn:isbn:978-91-87557-15-6

The potential of using acid hydrogen peroxide under Fenton conditions to lowerthe electrical energy consumed during the production of Black spruce (Piceamariana) thermomechanical pulp (TMP) was investigated in pilot scale. Thechemical system, which consisted of ferrous sulphate, hydrogen peroxide andoptionally an enhancer (such as a chelating agent), was evaluated as an inter-stagetreatment. The produced TMPs were thoroughly characterised in order to explainthe effect of the chemical system on fibre development and to be able to propose amechanism for the impact on refining energy reduction. The possibility to improvethe optical properties by washing, chelating and sodium dithionite or hydrogenperoxide bleaching the treated pulps was evaluated. The system of lignocellulosicmaterial, a Norway spruce (Picea abies) TMP, and Fenton chemistry was alsoevaluated in a model study to understand more about how conditions such as e.g.initial pH, dissolved organic material and reaction time affect the reactions.Ferrous and ferric ions (free and chelated) and different anions were evaluated.Moreover, it was examined whether hydroxyl radicals could be detected andmonitored.The results obtained in pilot scale showed that it is possible to significantly reducethe specific energy consumption by approximately 20% and 35% at a freenessvalue of 100 ml CSF or a tensile index of 45 Nm/g by using 1% and 2% hydrogenperoxide respectively. The energy reduction was obtained without any substantialchange to the fractional composition of the pulp, although tear strength wasslightly reduced, as were brightness and pulp yield. No major differences betweenthe reference pulp and the chemically treated pulps were found with respect tofibre length, width or cross-sectional dimensions. However, the acid hydrogenperoxide-treated pulps tended to have more collapsed fibres, higher flexibility, alarger specific surface area and a lower coarseness value. The yield lossiiiaccompanying the treatment was mainly a consequence of degradedhemicelluloses. It was also found that the total charge of the chemically treatedpulps was higher compared to the reference pulps; something that may haveinfluenced the softening behaviour of the fibre wall.A washing or chelating procedure could significantly reduce the metal ion contentof the chemically treated TMPs. The amount of iron could be further reduced to alevel similar to that of untreated pulps by performing a reducing agent-assistedchelating stage with dithionite. The discoloration could not, however, becompletely eliminated. The brightness decrease of the treated pulps was thereforenot only caused by the greater iron content in the pulp, but was also dependent onthe type of iron compound and/or other coloured compounds connected with theacid hydrogen peroxide treatment. Oxidative bleaching using hydrogen peroxidewas more effective than reductive bleaching using sodium dithionite in regainingthe brightness that was lost during the energy reductive treatment.From the model study and by using a chemiluminescence method, it could beconcluded that hydroxyl radicals were present in the system of Fenton chemicalsand lignocellulosic material (TMP). Initial pH, retention time, pulp consistency,type of catalyst (free or chelated) and dissolved organic material had an impact onthe reactions between TMP and acid hydrogen peroxide. Different anions(sulphate, nitrate and chloride) of ferric ion salt gave a similar catalytic effect.There appeared to be more reactions with the TMP when there was less dissolvedorganic material in the liquid phase from the start. A catalyst of ferrous sulphatehad a greater impact on the pulp (increased total fibre charge and carbonyl groups,more dissolved organic material in filtrate) than ferric ions chelated withethylenediaminetetraacetic acid at an initial pH of about 3-7. If using ferric-EDG(ethanol diglycinic acid) as catalyst, the measured effect on the pulp was similar orless compared to using ferrous sulphate. Ferric-EDG, however, gave higherhydrogen peroxide consumption and more detectable hydroxyl radicals than usingferrous sulphate (initial pH 5-8). It is likely that the iron catalyst must bind to theTMP, or be in close proximity to it, for the hydroxyl radicals to be able to react withthe material.A mechanism was proposed: the hydroxyl radicals generated in the Fentonreaction will probably attack and oxidise the available outer fibre surfaces,weakening these layers, and simultaneously dissolve some of the organic material.This can facilitate fibre development, give a better bonding pulp and reduce theelectrical energy required during refining.