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Improvement of kraft pulp bleaching by treatments with laccase, urea, and refining
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Wood Chemistry and Pulp Technology.
Instituto Nacional de Investigacion y Tecnologias Agrarias y Alimentarias.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Wood Chemistry and Pulp Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
2013 (English)In: Holzforschung, ISSN 0018-3830, Vol. 67, no 6, 651-658 p.Article in journal (Refereed) Published
Abstract [en]

Unbleached Eucalyptus kraft pulps were treated by three methods and the bleaching effects have been evaluated. The treatments were performed by a laccase mediator system (LMS), refining (R), and urea (U) alone and in combination of these methods. The bleached pulps were characterized in terms of κ number, hexenuronic acid content, brightness, and viscosity. In addition, the lignin-carbohydrate complexes (LCCs) were fractionated and characterized with regard to the fractionation yield, lignin content, and carbohydrate composition. Moreover, the 1 H nuclear magnetic resonance spectra were recorded and the thioacidolysis-gas chromatography and thioacidolysis-size exclusion chromatography analyses were performed. The LMS treatment resulted mainly in a slightly better delignification as manifested by a κ number (K no.) reduction of 0.8 units. The effects of the U treatment included delignification (1.4 κ units), hexenuronic acid removal (3 μ mol g-1), and improved pulp brightness (3.4 ISO units). The R treatment darkened the pulp (3 ISO units), whereas the bleaching of the R-pulp by subsequent LMS or U treatment enhanced the brightness (0.5 unit more) or delignification (0.3 unit more). The residual lignin in the pulp samples was present mainly as xylan-lignin. The Klason lignin content from the xylan lignin fraction decreased as the degree of delignification increased. The pulp darkening followed by the R treatment was interpreted as the result of the formation of condensed lignin structures, but these condensed lignins were substantially removed by the subsequent LMS or U treatment.

Place, publisher, year, edition, pages
2013. Vol. 67, no 6, 651-658 p.
Keyword [en]
bleaching, Eucalyptus, laccase-mediator system, lignin-carbohydrate complex (LCC), refining, thioacidolysis, urea
National Category
Chemical Engineering
URN: urn:nbn:se:kth:diva-126277DOI: 10.1515/hf-2012-0140ISI: 000324719100005ScopusID: 2-s2.0-84904999585OAI: diva2:642052

QC 20131017

Available from: 2013-08-20 Created: 2013-08-20 Last updated: 2013-10-17Bibliographically approved
In thesis
1. Deepening the insights of lignin structure: Lignin-carbohydrate complex (LCC) fractionation and characterization and Kraft lignin amination
Open this publication in new window or tab >>Deepening the insights of lignin structure: Lignin-carbohydrate complex (LCC) fractionation and characterization and Kraft lignin amination
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Improvement of kraft pulping delignification efficiency and value-addition of industrial kraft lignin are two attractive topics. The proposal that delignification is deteriorated by the presence of lignin-carbohydrate complex (LCC) is still being debated. Therefore, it is theoretically and practically important to investigate various LCC structures from native wood and their changes during different treatments. Currently, however, there is no effective LCC fractionation method that could quantitatively isolate all LCC fractions and be applicable for all types of lignocellulosic materials. The fractionation should also be followed by comprehensive and reliable structural characterisation. Additionally the Kraft lignin has a heterogeneous structure and poor properties. Structural modification is therefore one possible solution for creating more economical benefits than the presently direct combustion for heat.

In this work, an LCC fractionation method has been developed, which preserves original lignin and lignin-carbohydrate (LC) bonding structures and is nearly quantitative. It is universally applicable for hardwood, softwood or non-wood species. A whole set of subsequent analytical tools for the comprehensive elucidation of the different LCC fractions has also been established and applied. After applying the LCC fractionation and characterisation:

1). spruce wood was found to consist of 49.5% glucan-lignin (GL), 30.9% glucomannan–lignin (GML) and 12.0% xylan–lignin (XL). Although the LC and lignin-lignin (LL) linkage signals could not be directly observed by a 400 MHz NMR instrument, these linkages have been clearly observed by a 600 MHz NMR instrument equipped with a cryogenic probe after enzymatic hydrolysis. The LC bondings include phenyl glycoside, benzyl ether and γ-ester. Based on the LL bond frequencies, GML is less condensed than XL.

2). a general lignin biodegradation mechanism by the laccase-mediator system (LMS) has been proposed, which mainly involves Cα oxidation and Cα-Cβ bond cleavage of the lignin side chain and eventually aromatic ring cleavage. The LMS delignification efficiency depends largely on the species of the applied laccase and mediator. Some LMS has been proven to possess an obvious capacity for hexenuronic acid (HexA) removal. For Kraft pulp bleaching, there are potential benefits of various combinations among biological treatment (by LMS), non-oxidative chemical (by urea treatment, U), and mechanical treatment (by refining, R).

In addition, it has been demonstrated in this work that the structures and properties of industrial softwood Kraft lignin (LignoBoost lignin) could largely be upgraded by amination via the Mannich reaction. With or without a phenolation pretreatment, the aminated lignins obtained are promising polycationic materials, especially in the application as colloidal suspensions. During this investigation of kraft lignin amination, NMR methods have been developed for the quantification of the N content introduced and for the deepened insights of the structural changes of the lignin. 

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2013. 65 p.
Trita-CHE-Report, ISSN 1654-1081 ; 2013:30
National Category
Polymer Chemistry
urn:nbn:se:kth:diva-126279 (URN)978-91-7501-818-8 (ISBN)
Public defence
2013-09-10, Sal F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)

QC 20130820

Available from: 2013-08-20 Created: 2013-08-20 Last updated: 2013-08-20Bibliographically approved

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Du, XueyuLi, Jiebing
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