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Investigation of the Molecular Weight Increase of Commercial Lignosulfonates by Laccase Catalysis
KTH, Skolan för kemivetenskap (CHE), Fiber- och polymerteknik, Träkemi och massateknologi.
KTH, Skolan för kemivetenskap (CHE), Fiber- och polymerteknik, Träkemi och massateknologi.
KTH, Skolan för kemivetenskap (CHE), Fiber- och polymerteknik, Träkemi och massateknologi.
KTH, Skolan för kemivetenskap (CHE), Fiber- och polymerteknik, Träkemi och massateknologi.
2010 (Engelska)Ingår i: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 11, nr 4, s. 904-910Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

Lignosulfonates are by-products from the sulfite pulping process. During this process, lignin is liberated from pulp fibers through sulfonation and washed away. As a consequence, the lignosulfonate molecules contain both hydrophobic and hydrophilic moieties. Lignosulfonates are low-value products with limited performance and are used as such as binders, surfactants, and plasticizers in concrete. Lignosulfonates face strong competition from synthetic petroleum-based plasticizers with superior quality. Therefore, increasing the performance of lignosulfonates is desirable not only from a sustainability point of view but also to expand their usage. One important aspect that describes how well lignosulfonates can act as plasticizers is the molecular weight. In this paper, the molecular weight of four commercial lignosulfonates is increased through oxidation by two laccases without utilization of mediators. Different parameters to obtain maximal molecular weight increase were identified and the technical significance of the experiments is discussed.

Ort, förlag, år, upplaga, sidor
2010. Vol. 11, nr 4, s. 904-910
Nyckelord [en]
spruce wood, lignin, delignification, biosynthesis, oxidation, model, pulp
Nationell ämneskategori
Polymerkemi
Identifikatorer
URN: urn:nbn:se:kth:diva-19391DOI: 10.1021/bm901258vISI: 000276557300010Scopus ID: 2-s2.0-77950824209OAI: oai:DiVA.org:kth-19391DiVA, id: diva2:337438
Anmärkning
QC 20100525Tillgänglig från: 2010-08-05 Skapad: 2010-08-05 Senast uppdaterad: 2017-12-12Bibliografiskt granskad
Ingår i avhandling
1. Structural Modifications of Lignosulphonates
Öppna denna publikation i ny flik eller fönster >>Structural Modifications of Lignosulphonates
2011 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
Abstract [en]

Lignosulphonates are by‐products from the sulphite pulping process for the manufacture ofspecialty dissolving pulps and paper. During the liberation of the cellulose, the lignin isfractionated and solubilised through covalent addition of sulphonic acid groups at variouspositions in the structure. The formed sulphonated lignin, lignosulphonate is then furtherisolated and refined.

The amphiphilic nature of lignosulphonates has enabled them to be used as additives to varioussuspensions to improve their dispersion and stability. The by far largest utilisation oflignosulphonates is as dispersants in concrete. Here, lignosulphonates act by dispersing cementparticles to prevent flocculation, un‐even particle distribution and reduced strengthdevelopment. The dispersion is achieved through steric and electrostatic repulsion of the cementparticles by the lignosulphonate polymer. This behaviour is intimately linked with the overallsize and amount of charged groups in the dispersing polymer. Traditional modifications oflignosulphonates have been limited to removal of sugars, filtration and fractionation. Thesemodifications are not sufficient for utilisation of lignosulphonates in high‐strength concrete. Heresynthetic dispersants and superplasticisers are used which are considerably more efficient evenat low dosages. To compete with these, additional modifications of lignosulphonates are likely tobe necessary. The molecular weight and functional group composition have been identified anddescribed as the most interesting parameters that can be modified.

Currently, no suitable method exists to increase the molecular weight of lignosulphonates.Oxidation by the natural radical initiating enzyme laccase is an interesting tool to achieve suchmodifications. In this thesis several aspects of the mechanism through which this enzyme reactswith lignin and lignosulphonate structures have been elucidated through model compoundstudies. Further studies showed that laccase alone was a highly efficient tool for increasing themolecular weight of commercial lignosulphonates at low dosages and in short incubation times.Immobilisation of the laccase to a solid support to enable re‐utilisation was also investigated.

Modification of functional group composition of lignosulphonates was achieved throughozonolysis and the Fenton’s reagent, a mixture of hydrogen peroxide and iron(II)acetate.Introduction of charged carboxylic groups was achieved through opening of the benzyl rings oflignosulphonates. It was found that a two‐stage process consisting of laccase oxidation followedby ozonolysis was an efficient technique to create a polymer enriched with carboxylic acidgroups with a sufficient molecular size.

Oxidation by the Fenton’s reagent was shown to yield similar modifications as the combinedlaccase/ozonolysis treatment albeit with less pronounced results but with a large level of controlthrough variation of a number of reaction parameters. The Fenton’s reagent can therefore be aninteresting alternative to the aforementioned two‐stage treatment.

These modifications are interesting for large‐scale applications not only because of theirsimplicity in terms of reaction parameters but also because of the ubiquity of the used enzymeand the chemicals in the pulp and paper industry.

Ort, förlag, år, upplaga, sidor
Stockholm: KTH Royal Institute of Technology, 2011. s. 55
Serie
Trita-CHE-Report, ISSN 1654-1081 ; 2011:26
Nationell ämneskategori
Polymerkemi
Identifikatorer
urn:nbn:se:kth:diva-32881 (URN)978-91-7415-923-3 (ISBN)
Disputation
2011-05-13, D3, Lindstedsvägen 3, Stockholm, 10:00 (Engelska)
Opponent
Handledare
Anmärkning
QC 20110427Tillgänglig från: 2011-04-27 Skapad: 2011-04-26 Senast uppdaterad: 2011-09-01Bibliografiskt granskad

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Areskogh, DimitriLi, JiebingGellerstedt, GöranHenriksson, Gunnar
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