Valorization of Kraft Lignin by Fractionation and Chemical Modifications for Different Applications
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Valorization of Kraft Lignin by Fractionation and Chemical Modifications for Different Applications Selda Aminzadeh Doctoral Thesis Wallenberg Wood Science Center (WWSC) Department of Fiber and Polymer Technology School of Engineering Sciences in Chemistry, Biotechnology and Health KTH Royal Institute of Technology Stockholm, Sweden 14th December 2018, Stockholm, Sweden I Principal Supervisor Prof. Mikael Lindström Co-supervisors Assoc.Prof. Olena Sevastyanova Prof. Gunnar Henriksson Copyright © Selda Aminzadeh, Stockholm, 2018 All rights reserved Paper I © 2017 Springer Paper II © 2017 Elsevier Paper III © 2018 Accepted to Nanomaterials Journal Paper IV © 2018 Elsevier Paper V © 2018 Springer Paper VI © 2018 Manuscript ISBN: 978-91-7873-046-9 TRITA-CBH-FOU-2018-61 ISSN:1654-1081 Tryck: US-AB, Stockholm 2018 Akademisk avhandling som med tillstånd av Kungliga Tekniska Högskolan framläggs till offentlig granskning för avläggande av teknisk doktorsexamen i fiber och polymerteknologi fredagen den 14:e december 2018, Lindstedtsvägen 26, Stockholm, kl. 14:00 i sal F3. Avhandlingen försvaras på engelska. Opponent: Professor Hasan Jameel, North Carolina State University, USA II “Dedicated to my mother and father.” III Abstract Lignin is one of the most abundant biopolymers. Approximately 70 million tons of technical lignin is generated annually, but only little is used for products other than energy. The complexity of lignin hinders full utilization in high-value products and materials. In spite of the large recent progress of knowledge of lignin structure and biosynthesis, much is still not fully understood, including structural inhomogeneity. We made synthetic lignin at different pH’s and obtained structural differences that might explain the structural inhomogeneity of lignin. Technical lignins from the chemical pulping are available in large scale, but the processes result in alterations, such as oxidation and condensation. Therefore, to utilize technical lignin, modifications, such as fractionation and/or chemical modifications are necessary. Fractionation with ceramic membranes is one way to lower the polydispersity of lignin. The main advantage is their tolerance towards high temperature and harsh conditions. We demonstrated that low Mw lignin was extracted from industrially produced LignoBoost lignin aiming: i) to investigate the performance of the membrane over time; ii) to analyze the antioxidant properties of the low Mw lignin. Chemical modification can also improve the properties of lignin. By adding moieties, different properties can be obtained. Amination and methacrylation of kraft lignin were performed, as well as lignin-silica hybrid materials with potential for the adsorption were produced and investigated. Non-modified and methacrylated lignin were used to synthesize lignin-St-DVB porous microspheres to be utilized as a sorbent for organic pollutants. The possibility to substitute styrene with methacrylated lignin was evaluated, demonstrating that interaction between lignin and DVB, and porosity increased. Lignin has certain antibacterial properties. Un-modified and modified (aminated) lignin samples and sphere nanoparticles of lignin were tested for IV their effect against gram-positive and gram-negative bacteria’s and an injectable hydrogel was developed with encapsulated lignin for being used as an injectable gel for the open wounds. Results demonstrated promising antibacterial efficiency of lignins against gram-positive, more especially better inhibition with aminated lignins against gram-positive and negative bacterium. V SAMMANFATTNING Lignin är en av de mest förkommande biopolymererna och ca 70 miljoner ton av tekniskt lignin produceras årligen, men endast en mindre del används till andra applikationer än energiproduktion. Ett hinder för användning av lignin i mer komplexa produkter och material är dess komplexa struktur. Trotts senare års stora framsteg när det gäller kunskap om ligninets struktur, är mycket alltjämt dåligt förstått, exempelvis angående den strukturella inhomogeniteten hos lignin. Vi har studerat detta genom att göra syntetiskt lignin vid olika pH, och erhöll strukturella skillnader som kan vara en förklaring till den strukturella inhomogeniteten. Tekniska ligniner från kemisk massatillverkning är tillgängliga i stor skala, men processerna resulterar i strukturella modifieringar hos ligninet, såsom oxidationer och kondensationer. Därför är fraktionering och modifiering av tekniskt lignin lämpligt. Fraktionering med hjälp av keramiska membran är ett sätt att minska polydisperiteten hos lignin. Den största fördelen är membranens stora tolerans mot höga temperatur och aggressiva kemikalier. Vi använde filtrering på keramiska membran för att framställa lågmolekylärt lignin från den industriella kvaliteten LignoBoost, för att utvärdera membranens prestanda över tid, och analysera antioxidantegenskaperna hos det lågmolekylära ligninet. Kemisk modifiering kan också användas för att förbättra egenskaperna hos lignin. Genom att koppla på grupper, kan egenskaperna ändras. Amidering och metakrylering av sulfatlignin utfördes liksom tillverkning av lignin-silikon- hybridmaterial, med potential för adsorption, och materialen undersöktes. Omodifierat och metakrylerat lignin användes tillsammans med styren för att syntetisera porösa mikrosfärer som testades som absorbent för organiska föroreningar. Utvärdering visade att metakrylering ökade interaktionen mellan lignin och polystyren och ökade porositeten. VI Lignin har viss antimikrobiell aktivitet. Omodifierade och amiderade ligninprover och sfäriska nanopartiklar av lignin testades för sin verkan mot gram-positiva och gram-negativa bakterier. Resultaten visade lovande resultat för antimikrobiell aktivitet, och särskilt för amiderade ligniner när det gäller grampositiva bakterier. En injicerbar hydrogel med inkapslat lignin utvecklades också för behandling av öppna sår. VII List of papers This thesis is a summary of following publications: Paper I: A possible explanation for the structural inhomogeneity of lignin in LCC networks. Aminzadeh. S., Zhang. L., Henriksson. G. Wood Sci Techn., 2017, 51, 1365- 1376. DOI: 10.1007/s00226-017-0941-6 Paper II: Membrane filtration of kraft lignin: Structural characteristics and antioxidant activity of the low-molecular-weight fraction. Aminzadeh. S., Lauberts. M., Dobele. G., Ponomarenko. J., Tuve Mattsson. T., Lindström. E. M., Sevastyanova. O. Industrial Crops & Products., 2018, 112, 200-209 DOI: 10.1016/j.indcrop.2017.11.042 Paper III: Peculiarities of synthesis and properties of lignin-silica nanocomposites prepared by sol-gel method Budnyak. T., Aminzadeh. S., Pylypchuk. I., Riazanova. A., Tertykh. V., Lindström. M., Sevastyanova. O. Accepted to Nanomaterials Journal Paper IV: Methylene Blue dye sorption by hybrid materials from technical lignins Budnyak. T., Aminzadeh. S., Pylypchuk. I., Sternike. D.,Tertykh. V., Lindström. M., Sevastyanova. O. Journal of Environmental Chemical Engineering, 2018, 6, 4997-5007. DOI: 10.1016/j.jece.2018.07.041 Paper V: Synthesis and structure characterization of polymeric nanoporous microspheres with lignin Goliszek. M., Podkoscielna. B., Fila. K., Riazanova. V. A., Aminzadeh. S., Sevastyanova. O., Gun’ko. V. M. Cellulose, 2018. DOI: 10.1007/s10570-018- 2009-7 Paper VI: Lignin based hydrogel for the antibacterial application Aminzadeh. S., Haghniaz. R., Ottenhall. A., Sevastyanova. O., Lindström. E. M., Khademhosseini. A. (Manuscript) VIII The author’s contributions to the appended papers are the following: Paper I, II: Principal author. Performed most of the experiments and most of the manuscript preparations. (Pyrolysis and antioxidant studies were made in Riga). Paper VI: Principal author. Performed the planning and designing the project, all of the experiments and manuscript preparation. Paper III and IV: Second author. Performed most of the experiments, participated in discussions and prepared some parts of the manuscript. Paper V: Fourth author. Performed part of the experiments (synthesis, 13C NMR, thermal analysis and SEM), participated in discussions and partly in the preparation and revision of the manuscript. Paper VI: First author. Performed most of the experiments and most of the manuscript preparation (design of this project, sample preparations, Instron test, cell studies, nanoparticle preparations were performed in the US, Harvard-MIT medical centre-UCLA Uni). Conference Publications: 1. On the Crossflow Membrane Fractionation of Lignoboost Kraft Lignin - Characterization of Low Molecular Weight Fractions. Aminzadeh. S., Sevastyanaova. O., Mattsson. T., Lindström. M. 251th ACS National Meeting, Oral Proceeding, 13th March, 2016, San Diego, USA. 2. Membrane Filtration of LignoBoost Kraft Lignin: Fouling Phenomena and Properties of the Low Molecular Weight Fraction. Aminzadeh, S., Lauberts, M., Dobele, G., Ponomarenko, J., Mattsson, T., Sevastyanova, O., Lindström, M.E., Nordic Wood Biorefinery Conference (NWBC), Poster Proceedings pp. 220-222, March 28th-30th, 2017, Stockholm, Sweden. IX 3. Membrane Filtration of LignoBoost Kraft Lignin: Properties of the Low Molecular Weight Fraction Aminzadeh, S., Lauberts, M., Dobele, G., Ponomarenko, J., Mattsson, T., Sevastyanova, O., Lindström, M.E.: 19th International Symposium on Wood Fibre and Polymer Chemistry (ISWFPC), Oral Proceedings pp. 246-250, August 31th – September 1st, 2017, Porto Seguro, Brazil; 4. Novel Lignin/Silica Hybrids: Peculiarities of Synthesis and Application Budnyak, T.M., Aminzadeh, S., Pylypchuk,