Pensando em um melhor aproveitamento para o excedente do bagaço de cana, esse trabalho tem como objetivo a obtenção de membranas de acetato de celulose composta com ligninas oxidadas, ambos isolados do bagaço da cana. Para tal, os componentes macromoleculares do bagaço foram separados, aplicando-se um pré-tratamento de explosão a vapor para retirada da parte hemicelulósica e um tratamento com hidróxido de sódio para a separação da lignina e obtenção da polpa bruta de celulose. Essa polpa foi branqueada e acetilada e, posteriormente, foram sintetizadas membranas deste acetato de celulose, incorporando-se lignina oxidada a estas membranas com o objetivo de aumentar a capacidade de retenção de metais destas membranas. Assim, pretende-se obter um produto com maior valor comercial, que tem aplicações em tratamento de água e efluentes, podendo contribuir ainda mais para a manutenção do ambiente. As membranas foram sintetizadas por inversão de fase, utilizando dois métodos distintos: I. por evaporaçãoprecipitação e, II. por imersão em banho de coagulação. O material acetilado foi analisado por IR, confirmando-se a acetilação pelo aparecimento de bandas características do acetato e analisadas quanto ao grau de substituição, caracterizando um diacetato. As membranas sintetizadas pelo método I foram analisadas por MEV, constatando-se membranas de estrutura densa para todas as composições, e mais rígidas que uma membrana preparada a partir de um triacetato comercial, de acordo com os dados da análise dinâmico-mecânica. Foram realizados ainda, testes de permeabilidade e retenção de cobre. Apesar de rígidas, resistiram a pressões de até 20 bar. A membrana aditivada com lignina oxidada por lacase foi a que apresentou melhor desempenho nesse teste, atingindo maior fluxo necessitando menor pressão. No teste de retenção de cobre, apresentaram uma capacidade média de 15%, correspondendo a 50,5 mg Cu2+/g lignina. As membranas sintetizadas pelo método II foram analisadas por MEV, constatando-se diferenças na morfologia quando a lignina é adicionada dissolvida em NaOH. As análises térmicas mostraram a Tg do material perto de 80°C, além de evidenciar uma maior estabilidade térmica do material aditivado com lignina oxidada, comparado ao material sem lignina e com lignina original. No teste de permeabilidade, realizado aqui à pressão constante de 10 bar, a membrana sintetizada apenas com o acetato de celulose de bagaço de cana não apresentou fluxo. As membranas aditivadas com lignina original e lignina oxidada apresentaram fluxo, de 3,5 e 6,1 L/h.m2 respectivamente. O fato foi atribuído à morfologia das membranas, dado que as duas últimas, que apresentaram fluxo, possuem estrutura porosa, enquanto a outra possui estrutura densa. No teste de retenção de cobre, foi possível visualizar o efeito da adição da lignina na membrana, que aumenta 3,5 vezes a capacidade de retenção de cobre e, ainda, o efeito da oxidação da lignina, que aumenta em mais 50 % essa capacidade de retenção em comparação à adição apenas da lignina original. Contudo, os resultados indicam que as membranas sintetizadas, principalmente as membranas aditivadas com lignina oxidada, são promissoras para o objetivo proposto. / Thinking of a better use for the surplus of sugarcane bagasse, this study aims to obtain membranes of cellulose acetate composite with oxidized lignins, both isolated from sugarcane bagasse. To this purpose, the macromolecular components of bagasse were separated by applying a steam explosion pre-treatment for removal of hemicellulose and a treatment with sodium hydroxide to separate the lignin and obtaining of crude cellulose pulp. This pulp was bleached and acetylated, and subsequently cellulose acetate membranes were synthesized incorporating oxidized lignin in these membranes in order to increase the metal retention capacity of them. Thus, we intend to obtain a product with higher commercial value, which has applications in water and effluent treatment, which can further contribute to the maintenance of the environment. The membranes were synthesized by phase inversion, using two different methods: I. evaporation-precipitation and II. immersion in coagulation bath. The acetylated material was analyzed by FTIR, confirming the acetylation by the appearance of bands characteristic of acetate and analyzed for degree of substitution, featuring a diacetate. The membranes synthesized by method I were analyzed by SEM, verifying dense structure for the membranes in all compositions, and more rigid than a membrane prepared from a commercial triacetate, according to the data of dynamic mechanical analysis. Tests about permeability and copper retention also were done. Although rigid, they resisted to pressures up to 20 bar. The membrane added with lignin oxidized by laccase showed the best performance in this test, reaching higher flow requiring less pressure. In the test of copper retention, they showed an average retention capacity of 15%, corresponding to 50.5 mg Cu2+/ g lignin. The membranes synthesized by method II were analyzed by SEM, noting differences in morphology when the lignin is added dissolved in NaOH. Thermal analysis showed the Tg of the material near 80 °C, besides showing a higher thermal stability of the material added with oxidized lignin compared to material without lignin and with original lignin. In the permeability test, held at constant pressure of 10 bar, the membrane synthesized with only cellulose acetate cane bagasse showed no flow. The membranes added with original lignin and oxidized lignin showed flow of 3.5 and 6.1 L/h.m2, respectively. The fact was attributed to the morphology of the membranes, since the two latter, which showed flow, have porous structure, while the other has a dense structure. In the test of copper retention, it was possible to visualize the effect of the addition of lignin in the membrane, which increases 3.5 times the cupper retention capacity and, the effect of lignin oxidation, with increases in more 50% this retention capacity in comparison to the addition of the lignin in the original form. However, the results indicate that the synthesized membranes, mainly membranes added with oxidized lignin, are promising for the proposed objective.

O rápido declínio da qualidade nutricional de P. maximum com o avanço da maturidade é um dos maiores limitantes do desempenho animal em pastagens. Devido ao modo de reprodução apomítica da espécie, a engenharia genética surge como importante ferramenta para o desenvolvimento de novas cultivares. Sendo assim, a identificação de genes responsáveis pela queda da digestibilidade da fibra é um passo importante para a geração de cultivares transgênicas. Objetivou-se neste estudo determinar a produtividade, composição bromatológica, digestibilidade in vitro das frações folha e colmo de 11 genótipos de P. maximum colhidos em três idades de corte: 30, 60 e 90 dias de crescimento, bem como quantificar a expressão de seis enzimas da via de lignificação da parede celular. Objetivou-se ainda a classificação dos genótipos em grupos de acordo com suas características produtivas e de qualidade nutricional. Utilizou-se delineamento de blocos ao acaso, em esquema de parcela subdividida, com três repetições, no qual a parcela experimental foi composta de seis linhas com 4 m de comprimento, espaçadas de 0,5 m, sendo a data de corte a parcela e os genótipos as sub-parcelas. A produção de MS diferiu entre os genótipos somente com 90 dias de crescimento. Houve ainda variação entre os genótipos quando à porcentagem de folhas, colmos e material morto. Os genótipos não diferiram quanto à composição química e digestibilidade da fração folha, porém apresentaram grande variação quanto à composição química e digestibilidade da fração colmo. A fração colmo apresentou maiores valores de FDN, FDA e lignina, e menores valores de PB do que a fração folha. Entretanto, a fração colmo apresentou maior digestibilidade da MS com 60 dias de crescimento e maior digestibilidade da FDN com 30 e 60 dias de crescimento. O agrupamento detectou 4 grupos de genótipos de acordo com produtividade e DIVFDN do colmo. Os acessos PM39 e PM47 se destacaram por boa produtividade, elevada digestibilidade da FDN do colmo, enquanto as cultivares Milênio e Mombaça apresentaram alta produção de massa, porém baixa digestibilidade da fibra do colmo. A cultivar Massai e os acessos PM39 e PM47 foram selecionados como genótipos com boa manutenção da digestibilidade da fibra (LENTA), enquanto os genótipos Tanzânia, Milênio e Mombaça foram selecionados como genótipos com rápida queda da digestibilidade da fibra do colmo (RÁPIDA) para quantificação da expressão gênica. Foi realizada uma quantificação da expressão relativa de seis genes de interesse (CCR, COMT, C4H, 4CL, CAD e PAL) e um gene controle (GAPDH) nas três idade de corte. Houve interação tratamento idade para os genes C4H e COMT, com aumento da expressão dos genes de 30 para 60 dias de crescimento somente no grupo de RÁPIDA queda da digestibilidade. No grupo com LENTA queda da digestibilidade não houve alteração da expressão com 60 dias. O gene PAL mostrou comportamento semelhante, porém a interação tratamento idade não foi significativa. Estas características posicionam estes três genes como possíveis moduladores da digestibilidade do colmo de P. maximum. Conclui-se que a maturidade tem maior efeito sobre a qualidade nutricional da fração colmo do que sobre a fração folha e que há grande variação entre os genótipos em relação ao efeito da maturidade sobre a digestibilidade da fração colmo, indicando a possibilidade de seleção de cultivares com maior digestibilidade de colmos, e a dificuldade de se selecionar genótipos com maior digestibilidade de folhas. Identificou-se os genes C4H, COMT e PAL como possíveis candidatos à engenharia genética para produção de cultivares transgênicas. / The rapid decline of nutritional quality of P. maximum with advanced maturity is an important limiting factor for animal performance in pastures. Because of the apomitic reproduction of the species, genetic engineering arises as an important tool for development of new cultivars. Therefore, the identification of genes responsible for the decline in fiber digestibility is an important step towards generating transgenic cultivars. The objective of this study was to determine the yield, chemical composition, in vitro digestibility of leaf and stem fractions of 11 P. maximum genotypes harvested at three stages: 30, 60 and 90 days of regrowth, as well as to quantify the expression of six enzymes from the cell-wall lignification pathway. Another objective was to classify the genotypes in groups according to their productive and nutritional characteristics. A randomized block design in a split plot arrangement with three replications was used, in which the experimental plot was composed of six lines with 4 m length, spaced 0.5 m, being the harvest age the plot and the genotypes the sub-plots. The DM production differed between genotypes only after 90 days of regrowth. There was variation among genotypes in the percentage of leaves, stems and dead material. The genotypes did not differ in chemical composition and digestibility of the leaf fraction, but there was great variation in chemical composition and digestibility of the stem fraction. The stem fraction had higher NDF, ADF and lignin content, and lower CP content than the leaf fraction. However, the stem fraction had higher DM digestibility with 60 days of regrowth, and higher NDF digestibility after 30 and 60 days. The clustering procedure separated the genotypes in four groups cording to DM yield, stem NDF digestibility and percentage of leaves. The accessions PM39 and PM47 stood out for their good productivity and high stem NDF digestibility, while the cultivars Milênio and Mombaça had high DM yield but lower stem NDF digestibility. For quantification of gene expression, the Massai cultivar and the accessions PM39 and PM47 were selected as genotypes with good maintenance of fiber digestibility (SLOW), while the genotypes Tanzânia, Milênio and Mombaça were selected as ones with fast decline in stem fiber digestibility (FAST). The relative expression of six genes of interest (CCR, COMT, C4H, 4CL, CAD and PAL), and one control gene (GAPDH) was determined in the three harvested ages. There was a treatment age interaction for the C4H and COMT genes, with an increase in gene expression from 30 to 60 days of regrowth only in the group with FAST decline in digestibility. In the group with SLOW decline in digestibility, there was no difference in expression from 30 to 60 days of regrowth. The gene PAL had similar profile of expression; however the treatment age interaction was not significant. These characteristics place these three genes as possible modulators of stem digestibility in P. maximum. We conclude that maturity has a great effect over the stem nutritional quality than over leaves, and there was great variation among genotypes in the effect of maturity on stem fiber digestibility, indicating the possibility to select cultivars with higher stem digestibility, and also the difficulty to select genotypes with higher leaf digestibility. We identified the genes C4H, COMT and PAL as possible candidates for genetic engineering aiming the production of transgenic cultivars.

O cultivo da cana-de-açúcar é uma das atividades agrícolas mais importantes no Brasil, produzindo após a moagem o caldo, utilizado para a produção de açúcar e etanol, e o bagaço, resíduo lignocelulósico. O bagaço é recalcitrante à hidrólise enzimática, em parte pela baixa porosidade, resultante do recobrimento das fibrilas de celulose com lignina e hemicelulose. Neste estudo, o bagaço foi pré-tratado com sulfito alcalino nas concentrações de 2,5% de NaOH e 5% de Na2SO3 versus 5% de NaOH e 10% de Na2SO3 para produzir substratos para hidrólise enzimática. Ambos pré-tratamentos produziram substratos com teor de hemicelulose, grupos ácidos, grau de retenção de água e área superficial semelhantes. O conteúdo de lignina foi bem diferente nos bagaços pré-tratados com 5% de sulfito (21% de lignina) e 10% de sulfito (13% de lignina). A hidrólise da celulose e hemicelulose do bagaço com alto teor de lignina, utilizando a carga enzimática de 40 FPU/g e 80 U/g de ?-glicosidase foram próximas a 50% em 48 horas e, mesmo no bagaço com pouca lignina a conversão dos polissacarídeos não foi completa (90%). Considerando a importância do tipo de enzimas para a conversão dos polissacarídeos dos bagaços pré-tratados, realizou-se um planejamento experimental 24 com 6 pontos centrais ampliado em estrela, para avaliar uma mistura de enzimas partindo de 5 FPU/g do extrato comercial de Trichoderma reesei (celluclast) combinado com enzimas purificadas comerciais: xilanase de Neocallimastix patriciarum (família 10), xilanase de Thermotoga maritima (família 11), ?-xilosidase de Selelomonas ruminantium e ?-glicosidase de Aspergillus niger. A aplicação da mistura de enzimas otimizada no bagaço pré-tratado com alta carga de sulfito aumentou a conversão de celulose e hemicelulose em 6,6% e 15% respectivamente, comparado com a mistura de referência (5FPU de celluclast e 10UI de Novozyme 188 por grama de bagaço). A suplementação da celluclast com ?-xilosidase e ?- glicosidase foi estatisticamente significativa em 24 horas de hidrólise a um nível de 95% de confiança e a interação da xilanase 10 e 11 foi significativa com um nível de confiança de 90%. Quando foram realizados os mesmos ensaios do planejamento com o substrato com alto teor de lignina, as hidrólises da celulose e hemicelulose com a mistura de enzimas foram inferiores à obtida com a referência. A suplementação com xilanases e ?-xilosidase aumentou a conversão enzimática da hemicelulose apenas do substrato com pouca lignina, entretanto nos hidrolisados de ambos os substratos foi detectada a presença de xilooligossacarídeos, indicando a necessidade de adição de mais ?-xilosidase à mistura enzimática. As velocidades iniciais de hidrólise da celulose e hemicelulose foram pouco alteradas quando a lignina do bagaço reduziu de 21% para 13%, porém a conversão em 48 h de reação foi o dobro. Este estudo mostrou que o acesso das enzimas à hemicelulose foi limitado pelo alto teor de lignina do substrato, e que o benefício do uso de xilanases para a conversão de celulose foi obtido no substrato pré-tratado com alta carga de sulfito. / The cultivation of sugarcane is one of the most important agricultural activities in Brazil. The juice obtained from the crushed stalks of sugarcane is used to produce sugar and ethanol and the dry, fibrous residue remaining is the bagasse. Bagasse is recalcitrant to enzymatic hydrolysis, in part by low porosity due to the partial filling of space between the cellulose microfibrils by lignin and hemicelluloses. In this study, bagasses were pretreated with alkaline sulfite at concentrations of 2.5% NaOH and 5% Na2SO3 NaOH versus 5% and 10% Na2SO3 to produce substrates for enzymatic hydrolysis. Both substrates presented similar hemicellulose content, acid groups, water retention and specific surface area. Lignin content differed between pretreated bagasse with 5% sulfite (21%) and 10% sulfite (13%). The hydrolysis of cellulose and hemicellulose of bagasse with high lignin content, using 40 FPU/g and 80 U/g of ?-glucosidase was aproximately 50% in 48 hours and even on bagasse with low lignin content, the polysaccharides conversion was not complete (90%). Considering the importance of the type of enzymes for the conversion of polysaccharides of pretreated bagasses, a 24 full factorial experimental design with six central points was performed to evaluate a mixture of enzymes. A load of 5 FPU/g of Trichoderma reesei extract (celluclast) was combined with purified commercial enzymes: Neocallimastix patriciarum xylanase (family 10), Thermotoga maritima xylanase (family 11), Selelomonas ruminantium ?-xylosidase and ?-glucosidase from Aspergillus niger. The optimized mixture improved the conversion of cellulose and hemicellulose of the substrate with low lignin content in 6.6% and 15% respectively, when compared to the reference mixture (5FPU of celluclast and 10 IU of novozyme 188 per gram of bagasse). Supplementation with ?-xylosidase and ?-glucosidase was statistically significant at 24 hours of reaction and also the interaction of xylanases 10 and 11. When the same assays were performed with the substrate with low lignin, hydrolysis of the cellulose and hemicellulose with a mixture of purified enzymes was inferior to that obtained by the reference. Supplementation with xylanase and ?-xylosidase improved the enzymatic conversion only for substrate with low lignin content, however in supernatants of both substrates was detected the presence of xylo-oligosaccharides, suggesting the need for further addition of ?-xylosidase to the enzyme mixture. Initial rate of cellulose and hemicellulose hydrolysis changed very little when the lignin in the bagasse was reduced from 21% to 13%, but the conversion at 48 h conversion time was twice higher. This study showed that access of enzymes to the hemicellulose was limited by the high lignin content of the substrate, and that the benefit of using xylanases for the conversion of cellulose was obtained on the substrate pretreated with high sulfite load.

Lignin, the second most abundant naturally occurring polymer found in plant cell wall has the potential of becoming an alternative source for the production of chemical synthons for the pharmaceuticals and other chemical industries. While much gain has been made towards the development of degradation methods to break down lignin, effective analytical methods are still required to rapidly and accurately identify the products of lignin breakdown experiments. The goal of this work was to develop mass spectrometric methods for the characterization of lignin oligomers based on the study of model lignin compounds. Unlike peptides and oligosaccharides, lignin model compounds that could serve as analytical standards for methods developments are not commercially available, and hence, the first project of this dissertation focused on the synthesis of lignin model compounds containing the β-O-4 bond. The priority was to synthesize compounds containing all important functionalities that reflect the structure of native lignin. By employing the known Aldol reaction, lignin oligomers containing the β-O-4 were synthesized. The synthesized β-O-4 lignin oligomers contained the characteristic functional groups of native β-O-4 lignin, that is, the phenolic functionality, the aryl glycerol β-O-4 aryl ether bond and the unsaturated side chain. The second project was aimed at developing alternative ionization methods for the characterization of lignin in the negative ion mode mass spectrometry. A chloride adduct ionization method was developed and used for characterizing and sequencing lignin oligomers. This method proved to be very useful in stabilizing the adduct ion in the full scan spectrum mode and also providing useful structural information upon tandem mass spectrometry. In the third project, a cationization technique was developed to unambiguously assign the sequence in which β-O-4 lignin oligomers are connected. A simple and easy to use sequencing chart was designed and could serve as a guide for predicting the sequence of larger lignin oligomers. This method offers an alternative approach for the characterization of lignin oligomers in the positive ion mode mass spectrometry. The fourth project focused on the ionization response of a new class of β-O-4 lignin compounds. β-O-4 compounds having the same skeletal backbone but different non-polar groups at the a-position were synthesized, and their ESI response studied. Results from this study show that a slight change in the structure of a β-O-4 lignin model compound can change the cationization response to several order of magnitude. Most importantly, this work for the first time has shown a direct correlation between lignin ionization response and lignin structure. The fifth project was aimed at studying the chromatographic behavior of the diastereomer pair in β-O-4 lignin model compounds. Using three commercially available HPLC columns, the chromatographic behavior and factors that affect the separation of the diastereomer pair of the β-O-4 lignin diastereomer on an HPLC column were studied. By performing tandem mass spectrometry on each of the diastereomers, a fragmentation mechanism was developed that could be used to unambiguous assign the configuration (erythro or threo) for the pair of diastereomer in a β-O-4 model. The results presented in this dissertation adds significant knowledge to the lignin mass spectrometry literature, and it offers new ionization techniques for the characterization of lignin oligomers, most importantly, an alternative approach for lignin analysis using adduct ionization mass spectrometry. The developed methods could easily be extended for the characterization of larger lignin oligomers.

To date, most lignocellulosic biorefinery strategies have focused on optimizing conversion of cellulose to ethanol, leaving lignin as an underutilized biomass constituent. Lignin is engineered by nature with the intent to protect plants from chemical and biological attack; this leaves lignin with high structural irregularity and recalcitrance, rendering conversion of the lignin macromolecule to valuable products particularly challenging. Nevertheless, given that the economics of cellulosic ethanol production are strongly dependent on the value that can be obtained for the lignin co-product, the successful valorization of lignin is a crucial step in the transition towards a bio-based economy. This thesis focuses on lignin depolymerization using oxidative methods, specifically, the oxidation and cleavage of the β-O-4 linkage. Heterogeneous catalysis in this case is more desirable than homogenous catalysis as the catalyst easily recovered, and it is better suited for industrial applications. Initially, layered double hydroxide (LDH) supported gold nanoparticles were characterized and screened in the oxidation of various lignin model compounds using molecular oxygen, leading to the discovery of an Au/Li-Al LDH heterogeneous catalyst active for oxidative cleavage of the β-O-4 linkage. The Au/Li-Al LDH catalyst was then applied to oxidatively depolymerize Indulin AT kraft lignin and γ-valerolactone (GVL) extracted lignin, high yields of monomers being observed when the oxidized lignins underwent subsequent base-catalyzed hydrolysis. Thereafter, different literature oxidative lignin depolymerization methods were tested on kraft lignin and GVL lignin, and the results compared to the Au/Li-Al LDH catalyst (coupled with hydrolysis) system to determine the most effective oxidative depolymerization method.

Effective analytical techniques need to be developed to characterize the products of lignin degradation experiments to be able to generate renewable products from lignin. Mass spectrometry is an valuable analytical approach for lignin characterizaion, but it is hindered by lignin’s poor ionization efficiency, especially in the positive ion mode. In this work, we attempt to improve lignin’s ionization by utilizing electrospray and laser desorption mass spectrometry coupled with the addition of cations and chemical derivatives. We confronted the ionization problem from both a top-down and bottom-up analytical approach by analyzing synthesized monomers, dimers, and polymers along with natural lignin extracts from switchgrass. We also utilized tandem mass spectrometry to sequence lignin dimers and determine their bonding motifs from their fragmentation patterns. We believe that resolving the ionization issues with lignin will open the door for easier and more efficient lignin break-down techniques and ultimately more accessible renewable products from lignin.

Le but de cette thèse a été de trouver de nouveaux systèmes catalytiques pour l'oxydation de la lignine. Dans ce but, deux stratégies ont été abordées : une méthodologie directe, où différents systèmes catalytiques à base de sels métalliques et de peroxydes d'hydrogène ont été testés. Dans ce cas, le système Na2WO4,2H2O/H2O2 s'est avéré le plus efficace en dépolymérisant la lignine avec des rendements modérés. Une méthodologie indirecte via l'utilisation de molécules modèles de la lignine. Dans ce cas, des catalyseurs plus complexes ont été évalués notamment le Fe(TAML)Li. Ce dernier en combinaison avec le DAIB comme oxydant a montré une activité intéressante avec les molécules modèles, mais décevante avec la lignine. Enfin cette thèse a permis d'évaluer l'activité du Fe(TAML)Li dans l'oxydation d'alcools et d'alcane benzyliques / The goal of the thesis was to find new catalytic systems for lignin oxidation. Two strategies were chosen to reach this objective: a direct methodology, which implied the test of different catalytic systems based on metal salts and hydrogen peroxide. In that case the system Na2WO4,2H2O/H2O2 permitted to obtain the best results, with moderate depolymerization yields. An indirect methodology through the use of lignin model compounds. In that case, more complex catalysts were tested. The system Fe(TAML)Li/DAIB implied the best results with model compounds, but quite disappointing with lignin. Finally, the thesis have permitted to evaluate the activity of Fe(TAML)Li for the oxidation of alcohols and benzylic alkanes

<p>There is a strong driving force to increase the competitiveness of the pulping industry by finding new business opportunities. In this context full utilisation of the wood raw material used in conventional pulping mills is of vital importance. One focus area is to increase the utilisation areas of lignin. LignoBoost is a new method to obtain kraft lignin of high purity.</p><p>The aim of the project was to investigate and increase the ability of LignoBoost kraft lignins to bind metals in aqueous solutions.</p><p>The metal binding property of kraft lignins was evaluated using copper (II) ions. The metal binding capacities were 1.76 mg Cu²⁺/g LignoBoost softwood kraft lignin, 0.96 mg Cu²⁺/g LignoBoost hardwood kraft lignin and 1.12 mg Cu²⁺/g condensed softwood kraft lignin. The metal binding capacities of the softwood and hardwood kraft lignins from LignoBoost were lower than expected, when compared to the metal binding capacities of other lignins found in literature. The highest copper binding capacity of a kraft lignin found in literature was almost 50 times greater than that of the LignoBoost softwood kraft lignin.</p><p> </p><p>The Mannich reaction was used to increase the nitrogen content in softwood lignin, and thereby increase its electron-donating capacity. An increase in electron-donating capacity should promote its metal binding capacity.</p><p> </p><p>The Mannich reaction occurs in the vacant ortho position of the phenolic groups of lignin, introducing an aminomethyl group at that position. The only vacant ortho position in the phenol unit for reaction is in the guaicyl unit. Softwood lignin underwent a Mannich reaction, since softwood contains a greater number of guaiacyl units than hardwoods.</p><p> </p><p>A screening of the products from this Mannich reaction on LignoBoost softwood kraft lignin was performed to optimise the reaction conditions. The reaction time, temperature, amount of formaldehyde and dimethylamine were varied. The Mannich products were evaluated by elemental analysis. The conditions giving the highest nitrogen content in the product were used further in a Mannich reaction of condensed softwood kraft lignin. The condensed softwood kraft lignin (7 g) was treated with dimethylamine (0.35 mol) and formaldehyde (0.35 mol) at 80°C for 24 hours.</p><p> </p><p>The metal binding experiment could not be carried out with Mannich-modified condensed softwood kraft lignin since the lignin dissolved in the copper solution.</p><p> </p><p>When introducing nitrogen functionalities into lignin the electron-donating capacity should increase. An increase in donor groups should promote the metal binding capacity of the lignin. A problem that occurred when introducing aminomethyl groups was an increase in solubility of the lignin. Water solubility of the lignin derivative is undesirable in the envisaged utilization area, metal binding in, for example mine deposits, from where contaminated water may be a concentrated source of heavy metals.</p>

<p>The aim of this project is to investigate the possibilities of minimizing the sulphur content in Kraft lignin. Kraft lignin contains about 1.5 to 3% sulphur. The sulphur is believed to be present in lignin as inorganic sulphur, as elemental sulphur, as adsorbed polysulphide and/or as organically bound sulphur. For the determination of these different types of sulphur components, different approaches and methods were used. For the determination of inorganic sulphur, lignin was washed with water at pH 6 and pH 2 and the wash waters were analysed with ion chromatography (IC). For the determination of total sulphur content in the lignin, two methods were used; Schöniger combustion followed by ion chromatography (IC) and wet digestion followed by inductively coupled plasma (ICP). The elemental sulphur content in water-extracted lignin was determined after n-pentane extraction. ICP analysis was performed on the washed lignin.</p><p>Calcium present in the lignin may bind polysulphides and thus be a source of the observed sulphur. The lignin was thus ion-exchanged to remove any calcium. To further investigate how the sulphur content in lignin can be decreased, two different types of reactions were performed on lignin; oxidation and reduction. The oxidation reactions were made in sodium hydroxide with oxygen at different temperatures and time on both original and water-extracted lignin. The reduction reactions were made on water-extracted lignin with Raney nickel in three different solvent systems: methanol: water, acetone: water and sodium hydroxide.</p><p> </p><p>The original lignin contained 2.6% sulphur as determined by ICP. Washing lowered the content to 1.85% sulphur. By n-pentane extraction the elemental sulphur was lowered to a level of 1.82% sulphur, which was considered to be organically bound sulphur. Neither the ion exchange nor the oxidation lowered the sulphur content significantly.</p><p> </p><p>The reduction reactions successfully the organically bound sulphur from 1.82% to a level of 0.54%.</p><p> </p><p>The relative distribution of the sulphur content in the studied softwood lignin was as follows: about 29% as inorganic sulphur, about 1% as elemental sulphur and approximately 70% as organically bound sulphur, of which 49% could be removed by Raney nickel.</p>

No description available.