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Structural Modifications of Lignosulphonates

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Structural Modifications of Lignosulphonates Structural Modifications of Lignosulphonates Dimitri Areskogh Doctoral Thesis Royal Institute of Technology School of Chemical Science and Engineering Department of Fibre & Polymer Technology Division of Wood Chemistry and Pulp Technology Stockholm 2011 AKADEMISK AVHANDLING Som med tillstånd av Kungliga Tekniska Högskolan framläggs till offentlig granskning för avläggande av teknologie doktorsexamen, fredagen den 13 maj 2011 kl. 10.00 i sal D3, Lindstedsvägen 3, KTH, Stockholm. Avhandlingen försvaras på engelska. Fakultetsopponent: Prof. Arthur J Ragauskas Georgia Institute of Technology, Atlanta, Georgia, USA © Dimitri Areskogh Stockholm 2011 TRITA‐CHE Report 2011:26 ISSN 1654‐1081 ISBN 978‐91‐7415‐923‐3 “Reading is the basics for all learning.” —Presidential candidate George W. Bush, Reston, Virginia, March 28, 2000 Abstract Lignosulphonates are by‐products from the sulphite pulping process for the manufacture of specialty dissolving pulps and paper. During the liberation of the cellulose, the lignin is fractionated and solubilised through covalent addition of sulphonic acid groups at various positions in the structure. The formed sulphonated lignin, lignosulphonate is then further isolated and refined. The amphiphilic nature of lignosulphonates has enabled them to be used as additives to various suspensions to improve their dispersion and stability. The by far largest utilisation of lignosulphonates is as dispersants in concrete. Here, lignosulphonates act by dispersing cement particles to prevent flocculation, un‐even particle distribution and reduced strength development. The dispersion is achieved through steric and electrostatic repulsion of the cement particles by the lignosulphonate polymer. This behaviour is intimately linked with the overall size and amount of charged groups in the dispersing polymer. Traditional modifications of lignosulphonates have been limited to removal of sugars, filtration and fractionation. These modifications are not sufficient for utilisation of lignosulphonates in high‐strength concrete. Here synthetic dispersants and superplasticisers are used which are considerably more efficient even at low dosages. To compete with these, additional modifications of lignosulphonates are likely to be necessary. The molecular weight and functional group composition have been identified and described 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 such modifications. In this thesis several aspects of the mechanism through which this enzyme reacts with lignin and lignosulphonate structures have been elucidated through model compound studies. Further studies showed that laccase alone was a highly efficient tool for increasing the molecular 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 through ozonolysis 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 of lignosulphonates. It was found that a two‐stage process consisting of laccase oxidation followed by ozonolysis was an efficient technique to create a polymer enriched with carboxylic acid groups with a sufficient molecular size. Oxidation by the Fenton’s reagent was shown to yield similar modifications as the combined laccase/ozonolysis treatment albeit with less pronounced results but with a large level of control through variation of a number of reaction parameters. The Fenton’s reagent can therefore be an interesting alternative to the aforementioned two‐stage treatment. These modifications are interesting for large‐scale applications not only because of their simplicity in terms of reaction parameters but also because of the ubiquity of the used enzyme and the chemicals in the pulp and paper industry. Sammanfattning Lignosulfonater är bi‐produkter från sulfitprocessen som används för framställning av ren dissolvingmassa för vidare produktion av regenererad cellulosa. Under denna process löses ligninet upp i kokvätskan genom introduktion av sulfonsyragrupper, vilket medför att ligninet blir vattenlösligt och kan därför separeras från massan. Den amfifatiska strukturen hos lignosulfonaterna som innehåller både hydrofila och hydrofoba grupper har gett lignosulfonaterna unika egenskaper. Lignosulfonater används idag som dispergeringsmedel för olika typer av suspensioner för att förbättra deras dispersion och stabilitet. Det överlägset största användningsområdet av lignosulfonater är som dispergeringsmedel för betongtillverkning. Här används lignosulfonaterna för att dispergera cementpartiklarna för att ge betongen bra flyt och undvika partikelaggregation. Denna dispersion sker främst genom sterisk och elektrostatisk repulsion av de laddade cementpartiklarna. Dessa två fenomen är intimt förknippade med storleken och laddningen hos den dispergerande polymeren. De traditionella modifieringarna av lignosulfonater har varit begränsade till eliminering av socker, filtrering och fraktionering. I högstyrke‐betong ställs andra krav på dispersion vilket medför att man använder syntetiska dispergeringsmedel med väldigt specifika egenskaper vilka är avsevärt effektivare. För att konkurrera med dessa, är ytterligare modifieringar av lignosulfonater nödvändiga. Molekylvikten och andelen laddade grupper har därför identifierats som de två mest lämpliga egenskaperna för modifiering av lignosulfonater. För tillfället finns det inga metoder för att öka molekylvikten hos lignosulfonater. En intressant metod är polymerisering genom enzymatisk oxidering med hjälp av det radikal‐initierande enzymet lackas. I denna avhandling har flera aspekter av reaktionsmekanismen hos detta enzym undersökts och kartlagts via studier med modellkomponenter. Oxidation av tekniska lignosulfonater visade att detta enzym är mycket kapabelt till att öka molekylvikten markant även vid låga doseringar. Tekniker för att tillåta återanvändning av enzymet genom immobilisering till en support har undersökts. Modifiering av mängden laddade grupper hos lignosulfonater skedde genom ozonering och reaktion med Fentons reagens, en blandning av väteperoxid och järn(II)acetat. Laddade karboxylgrupper visade sig bildas genom reaktioner där bensylgrupper i lignosulfonaterna bröts upp. En kombination av oxidation med lackas följt av ozonering visade sig vara en mycket intressant tvåstegsmodifiering vilket gav upphov till en högmolekylär polymer berikad med laddade karboxylgrupper. Oxidering med Fentons reagens visade sig ge liknande resultat som en kombinerad lackas och ozonbehandling med märkbart lägre effektivitet men dock med en större grad av kontroll. Detta reagens skulle kunna vara ett intressant alternativ till den ovan nämnda tvåstegsmodifieringen. Dessa modifieringar är intressanta för storskalig användning då dessa är bör vara lätta att implementera men också eftersom både enzymet och kemikalierna är väl bekanta för pappers‐ och massaindustrin. List of Publications This thesis is based on the following papers: I. Oxidative polymerisation of models for phenolic lignin end‐groups by laccase Areskogh, D.; Li, J.; Nousiainen, P.; Gellerstedt, G;, Sipilä, J. and Henriksson, G. Holzforschung, 2009, 64, 21–34. II. Sulfonation of phenolic end groups in lignin directs laccase‐initiated reactions towards cross‐linking. Areskogh, D,; Li, J.; Nousiainen, P.; Gellerstedt, G.; Sipilä, J. and Henriksson, G. Industrial Biotechnology 2010, 6, 50‐59. III. Investigation of the Molecular Weight Increase of Commercial Lignosulfonates by Laccase Catalysis. Areskogh, D.; Li, J.; Gellerstedt, G. and Henriksson, G. Biomacromolecules, 2010, 11, 904–910. IV. Structural modification of commercial lignosulphonates through laccase catalysis and ozonolysis. Areskogh, D.; Li, J.; Gellerstedt, G. and Henriksson, G. Industrial Crops and Products 2010, 32, 458‐466. V. Immobilisation of laccase for polymerisation of commercial lignosulphonates. Areskogh, D. and Henriksson, G. Process Biochemistry 2011, 46, 1071‐1075 VI. Fenton’s reaction: a simple and versatile method to structurally modify commercial lignosulphonates. Areskogh, D. and Henriksson, G. Nordic Pulp & Paper Research Journal, 2011, 26, 90‐98 Author’s Contribution Paper I‐VI: Principal author. Formulated research strategies with Prof. Gunnar Henriksson. Abbreviations In alphabetical order: C3A Calcium aluminate, (CaO)3Al2O3. C2S Dicalcium silicate, (CaO)2SiO2 C3S Tricalcium silicate, (CaO)3SiO2 C‐S‐H Calcium silicate tetrahydrate (CaO)3(SiO2)2∙4∙H2O ECF Elemental Free Chlorine FT‐IR Fourier Transform Infrared Spectroscopy GC/MS Gas Chromatography/Mass Spectrometry Gypsum Calcium sulphate dihydrate, CaSO2⋅2∙(H2O) HSQC‐NMR Heteronuclear Single Quantum Coherence Nuclear Magnetic Resonance LCC Lignin‐carbohydrate complex LMS Laccase‐mediatory system MALDI‐TOF MS Matrix‐Assisted Laser Desorption/Ionisation Time‐of‐Flight Mass Spectrometry Me‐ Methyl group, CH3‐ MeO‐ Methoxy group, CH3O‐ MtL Myceliophthora thermophila laccase SEC Size Exclusion Chromatography TCF Totally Chlorine Free TvL Trametes villosa laccase Table of Contents I Introduction .........................................................................................................................................
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