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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Schwefelfreies IDE-Zellstoffherstellungsverfahren Entwicklung eines Konzeptes zur Online-Prozessüberwachung mittels Infrarot-Spektroskopie und Vergasung der Ablaugen zur Energie- und Stoffrückgewinnung /

Gong, Jian. January 1900 (has links) (PDF)
München, Techn. Universiẗat, Diss., 2003.
2

Prétraitement du miscanthus x giganteus : vers une valorisation optimale de la biomasse lignocellulosique / Pretreatment of Miscanthus x giganticus : towards an optimal valorization of lignocellulosic biomass

El Hage, Roland 29 October 2010 (has links)
Le miscanthus x Giganteus (MxG) constitue, du fait de sa composition, une source renouvelable de matière lignocellulosique pouvant être d'un grand intérêt pour la production de molécules à haute valeur ajoutée. Le MxG ayant servi à ce travail provient du lycée agricole à Courcelles-Chaussy, Metz-France. Sa teneur élevée en hémicelluloses (26 %), en lignine (26 %) et en cellulose (36 %) en fait une bonne source de polymères et de carburant renouvelable. L'étude que nous avons réalisée a été menée dans le but de caractériser la paille de MxG et d'optimiser le processus de délignification en une seule étape (1) par un traitement organosolv à l'éthanol et en deux étapes (2) par un prétraitement consistant en une autohydrolyse à l'eau/organosolv. Le procédé éthanol organosolv a permis un bon fractionnement des trois constituants de la biomasse (la lignine, la cellulose et les hémicelluloses). Le procédé de traitement en deux étapes, impliquant une autohydrolyse à l'eau (en présence et en l'absence du 2-naphtol), préalable au traitement organosolv, a permis de faciliter l'étape ultérieure de délignification en déstructurant la lignine. Une investigation portant sur la structure physico-chimique a été réalisée sur de la lignine de bois broyé et de la lignine organosolv de MxG extraite à différentes sévérités de traitement. Nous nous sommes ensuite intéressés à utiliser la lignine organosolv pour la formulation d'un adhésif pour le bois dans laquelle un aldéhyde non toxique et peu volatile (le glyoxal) est employé en remplacement du formaldéhyde. Une formulation, composée à 100 % de résines naturelles (60 % de tannins de mimosa et 40 % de lignine glyoxalée) a été utilisée pour la conception d'un panneau de particules et a donné des résultats prometteurs avec une force de liaison interne de 0,41 MPa, supérieure à la valeur de la norme européenne en vigueur. Enfin, une étude des propriétés antioxydantes a été faite sur les lignines extraites. Les résultats obtenus ont montré une corrélation entre l'activité antioxydante et les conditions opératoires du traitement organosolv, la masse moléculaire moyenne, l'indice de polydispersité et les groupements hydroxyles phénoliques des lignines. / Miscanthus x giganteus (MxG) is, because of its composition, a source of renewable lignocellulosic material that can be of great interest for the production of high added value molecules. MxG used in this work comes from the agricultural high school of Courcelles-Chaussy, Metz-France. Its high content of hemicelluloses (26 %), lignin (26 %) and cellulose (36 %) makes it a good source of polymers and renewable fuel. In the present study we have characterized the straw of MxG and optimized the process of delignification in a single step (1) by an ethanol organosolv treatment and in a two steps (2) including an autohydrolysis pretreatment with water / organosolv. The ethanol organosolv process permits a good separation of the three constituents of our biomass (lignin, cellulose and hemicelluloses). The two steps treatment process, involving an autohydrolysis with water (in the presence or absence of 2-naphthol) before the pretreatment organosolv has facilitated the later stage of delignification in destructurizing the lignin. An investigation of the physico-chemical properties was performed on the structure of the milled wood lignin and organosolv lignin of MxG extracted with different treatment severities. A way of valorization for the organosolv lignin has been proposed by their incorporation in the formulation of an adhesive for wood in which a non volatile and low toxic aldehyde (glyoxal) is used instead of formaldehyde. A formulation consisting in 100 % of natural resins (60 % tannins of mimosa and 40 % of glyoxalated lignin) was used for the production of particle board and gave promising results with internal bond strength of 0.41 MPa, higher than the value of the current European standard. Finally, a study was conducted on the antioxidant properties of organosolv lignin extracted at different severities. The results have shown a correlation between the antioxidant activity and the operating conditions of treatment organosolv, the average molecular weight, the polydispersity index and the phenolic hydroxyl groups of lignin
3

Comparison of Miscanthus grass lignin with spruce lignin from organosolv process for nanoparticles production / En jämförelse mellan organosolvlignin från Miscanthusgräs och gran för nanopartikeltillverkning

la Placa, Antonia January 2020 (has links)
There is a growing global energy demand and the society is forced to shift towards renewable energy sources due to the depletion of fossil fuels. Lignocellulosic biomass is a renewable resource available in vast amounts and could therefore have the potential to become a primary source for fuel production. Lignin, as a substantial part of the biomass, is underutilized due to its complex structure which can limit the potential of applying lignin towards value- adding products. However, one way to promote lignin valorization is to produce lignin nanoparticles (LNPs) that are considered valuable in the biomedical field. The aim of this report was to investigate if different botanical origins will affect the properties of LNPs, such as size, polydispersity index, 𝜁-potential and morphology. LNPs from Miscanthus sinensis grass lignin, obtained by the organosolv process, was successfully produced via solvent exchange and compared with LNPs from spruce organosolv lignin. The experimental part resulted in Miscanthus LNPs ranging from 133.7 to 377.4 nm, where a higher initial concentration yielded larger particles, and the average ζ- potential was -38.7 mV. This work has shown that the botanical origin will affect both size and shape of LNPs produced with the same method. Miscanthus LNPs were larger in size and ellipsoidal in shape compared to the spherical spruce LNPs. The lignin concentration influenced the particle size for both origins and the difference in LNP size became more significant as the concentration increased. However, to only explore two different types of plant origins is not sufficient enough to reach a general conclusion. Also, there are many influential steps from plant origin to LNP and to reach a more generalized conclusion, it is arguable that there is a necessity to explore and determine both the applied pulping method, the process to isolate the lignin and the method used to produce the LNPs. / Det globala energibehovet ökar och samhället tvingas därmed att växla till förnybara resurser eftersom de fossila bränslena kan ta slut. Biomassa är en förnybar resurs som finns tillgänglig i stora mängder och kan därför bli en potentiell primär energikälla. Lignin, som är en väsentlig del av biomassan, används inte i lika stor utsträckning på grund av dess komplexa struktur. Komplexiteten begränsar därför användandet av lignin i värdeskapande produkter. Men en väg för att ta tillvara på lignins värdefulla egenskaper kan vara framställandet av nanopartiklar (NP), vilket öppnar upp för användning av lignin inom det biomedicinska fältet. Syftet med den här rapporten är att undersöka om lignin från olika botaniska ursprung påverkar nanopartiklarnas egenskaper, som exempelvis storlek, polydispersitet, 𝜁-potential och morfologi. NP av lignin från gräsarten Miscanthus sinensis framställdes genom solvent exchange och jämfördes sedan med NP från granlignin. Både miscanthus- och granligninet var isolerat genom organosolvprocessen. Den experimentella delen av arbetet visade att NP from miscanthuslignin gav partiklar inom intervallet 133.7 to 377.4 nm, där högre koncentration gav större partiklar, och medelvärdet för 𝜁-potentialen var -38.7 mV. Resultatet från arbetet visade att det botaniskt ursprunget påverkar både storleken och formen på NP av lignin som framställts med samma metod. NP från miscanthuslignin var större och hade en mer elliptisk form, i jämförelse med de mer sfäriska partiklarna från granlignin. Ligninkoncentrationen påverkade partikelstorleken för båda typerna av lignin, dessutom blev skillnaden i partikelstorlek större när koncentrationen ökade. Däremot var det svårt att dra någon generell slutsats genom att bara undersöka två olika ursprung. Eftersom det finns flera steg i processen från växters ursprung till NP av lignin som kan påverka partiklarnas egenskaper kan det vara nödvändigt att utforska både den tillämpade massaprocessen, isoleringsmetoden och metoden som används för att framställa NP av lignin.
4

Effect of Organosolv Lignin and Extractable Lignin on Enzymatic Hydrolysis of Lignocelluloses

Tan, Xin January 2020 (has links)
No description available.
5

\"Utilização de fluidos no estado sub/supercritico na polpação de Eucalyptus grandis e Pinus taeda\" / Utilization of sub/supercritical fluids in Eucalyptus grandis e Pinus taeda

Pimenta, Maria Teresa Borges 19 December 2005 (has links)
A utilização de dióxido de carbono em condições sub e supercríticas (em associação com co-solventes) em processos de deslignificação/polpação já se encontra descrito na literatura especializada. Esta técnica se beneficia da elevada difusibilidade apresentada por fluidos no estado sub/supercrítico. Quando aplicada em processos de polpação, a utilização destes fluidos nestas condições pode proporcionar vantagens nas etapas de impregnação e de processamento dos efluentes gerados no processo. Visando aplicar o potencial da elevada difusibilidade apresentada pelo dióxido de carbono supercrítico, realizou-se o estudo comparativo do desempenho dos processos kraft, organossolve convencional e supercrítico frente à deslignificação de diferentes espécies (Eucalyptus grandis e Pinus taeda), empregando-se amostras de diferentes dimensões. O processo kraft se mostrou mais eficiente com o emprego de cavacos, enquanto que a utilização de dióxido de carbono supercrítico, com o uso de co-solvente etanol/água (processo SFE), foi mais eficiente com amostras de maiores dimensões (cubos de 3,5 x 3,5 x 4,0cm). Dentro dos intervalos considerados para as variáveis utilizadas nos diferentes processos de polpação, as polpas obtidas pelo processo SFE a partir de amostras de seção quadrada 3,5 x 3,5cm apresentaram maior conteúdo de holocelulose e maior alvura, evidenciando um elevado rendimento livre de lignina. Estudou-se também o uso de acetona/água e de dioxano/água como co-solventes em processos realizados com dióxido de carbono no estado supercrítico. Os resultados obtidos foram comparados com estudos anteriores realizados com álcoois alifáticos e indicaram a maior efetividade do uso de dioxano/água e 1-propanol/água. Foram realizados também estudos empregando amônia como fluido supercrítico no tratamento de cavacos de Pinus taeda, com o intuito de verificar a capacidade nucleofílica da amônia frente às reações de deslignificação. As reações foram realizadas com o uso exclusivo de amônia e na presença de etanol, água e misturas etanol/água como cosolventes. A análise dos resultados obtidos evidenciou a ocorrência pouco significativa de remoção de lignina, com migração desta para a periferia dos cavacos. As ligninas obtidas nos diferentes estudos foram caracterizadas por diferentes técnicas analíticas e não apresentaram diferenças significativas entre as amostras obtidas nos diferentes processos estudados. / The utilization of carbon dioxide under sub/supercritical conditions (in association with co-solvents) in delignification/pulping reactions has already been reported in the literature. This technique takes advantage of the high diffusivity presented by fluids at the supercritical state. When applied to pulping processes the utilization of these fluids can lead to advantages mainly in the impregnation and effluent treatment steps. In an attempt to apply the high diffusivity exhibited by supercritical carbon dioxide, this work presents the results obtained in the comparative study of the performance of the kraft, organosolv and supercritical processes in the delignification of different species (Eucalyptus grandis and Pinus taeda), employing samples with different dimensions. The kraft process presented a higher efficiency in the treatment of wood chips while the supercritical carbon dioxide, with ethanol/water as co-solvent, (SFE process) was more efficient in the treatment of high dimension samples (3.5 x 3.5 x 4.0 cm). In the experimental conditions applied in this study, the pulps obtained in the SFE treatment of samples with square section 3.5 x 3.5 cm showed higher holocellulose content and higher brightness which corresponds to high free of lignin pulp yield. It was also studied the utilization of acetone/water and dioxane/water as co-solvents in the carbon dioxide supercritical pulping process. The results were compared with previous studies performed with aliphatic alcohols and indicated a higher efficiency of the dioxane/water and 1-propanol/water mixtures. The utilization of supercritical ammonia in the treatment of Pinus taeda wood chips was also studied in order to verify the nucleophilic capability of this fluid in the delignification reactions. The reactions were performed with ammonia, exclusively, and in the presence of different co-solvents (ethanol, water and ethanol/water mixtures). The results of the delignifications showed the occurrence of low amount of lignin removal, with migration of lignin to the periphery of the wood chips. The lignins isolated from the reactions performed in this work were characterized by different analytical techniques. The results indicated no significant differences among the samples obtained in the different delignification processes.
6

\"Utilização de fluidos no estado sub/supercritico na polpação de Eucalyptus grandis e Pinus taeda\" / Utilization of sub/supercritical fluids in Eucalyptus grandis e Pinus taeda

Maria Teresa Borges Pimenta 19 December 2005 (has links)
A utilização de dióxido de carbono em condições sub e supercríticas (em associação com co-solventes) em processos de deslignificação/polpação já se encontra descrito na literatura especializada. Esta técnica se beneficia da elevada difusibilidade apresentada por fluidos no estado sub/supercrítico. Quando aplicada em processos de polpação, a utilização destes fluidos nestas condições pode proporcionar vantagens nas etapas de impregnação e de processamento dos efluentes gerados no processo. Visando aplicar o potencial da elevada difusibilidade apresentada pelo dióxido de carbono supercrítico, realizou-se o estudo comparativo do desempenho dos processos kraft, organossolve convencional e supercrítico frente à deslignificação de diferentes espécies (Eucalyptus grandis e Pinus taeda), empregando-se amostras de diferentes dimensões. O processo kraft se mostrou mais eficiente com o emprego de cavacos, enquanto que a utilização de dióxido de carbono supercrítico, com o uso de co-solvente etanol/água (processo SFE), foi mais eficiente com amostras de maiores dimensões (cubos de 3,5 x 3,5 x 4,0cm). Dentro dos intervalos considerados para as variáveis utilizadas nos diferentes processos de polpação, as polpas obtidas pelo processo SFE a partir de amostras de seção quadrada 3,5 x 3,5cm apresentaram maior conteúdo de holocelulose e maior alvura, evidenciando um elevado rendimento livre de lignina. Estudou-se também o uso de acetona/água e de dioxano/água como co-solventes em processos realizados com dióxido de carbono no estado supercrítico. Os resultados obtidos foram comparados com estudos anteriores realizados com álcoois alifáticos e indicaram a maior efetividade do uso de dioxano/água e 1-propanol/água. Foram realizados também estudos empregando amônia como fluido supercrítico no tratamento de cavacos de Pinus taeda, com o intuito de verificar a capacidade nucleofílica da amônia frente às reações de deslignificação. As reações foram realizadas com o uso exclusivo de amônia e na presença de etanol, água e misturas etanol/água como cosolventes. A análise dos resultados obtidos evidenciou a ocorrência pouco significativa de remoção de lignina, com migração desta para a periferia dos cavacos. As ligninas obtidas nos diferentes estudos foram caracterizadas por diferentes técnicas analíticas e não apresentaram diferenças significativas entre as amostras obtidas nos diferentes processos estudados. / The utilization of carbon dioxide under sub/supercritical conditions (in association with co-solvents) in delignification/pulping reactions has already been reported in the literature. This technique takes advantage of the high diffusivity presented by fluids at the supercritical state. When applied to pulping processes the utilization of these fluids can lead to advantages mainly in the impregnation and effluent treatment steps. In an attempt to apply the high diffusivity exhibited by supercritical carbon dioxide, this work presents the results obtained in the comparative study of the performance of the kraft, organosolv and supercritical processes in the delignification of different species (Eucalyptus grandis and Pinus taeda), employing samples with different dimensions. The kraft process presented a higher efficiency in the treatment of wood chips while the supercritical carbon dioxide, with ethanol/water as co-solvent, (SFE process) was more efficient in the treatment of high dimension samples (3.5 x 3.5 x 4.0 cm). In the experimental conditions applied in this study, the pulps obtained in the SFE treatment of samples with square section 3.5 x 3.5 cm showed higher holocellulose content and higher brightness which corresponds to high free of lignin pulp yield. It was also studied the utilization of acetone/water and dioxane/water as co-solvents in the carbon dioxide supercritical pulping process. The results were compared with previous studies performed with aliphatic alcohols and indicated a higher efficiency of the dioxane/water and 1-propanol/water mixtures. The utilization of supercritical ammonia in the treatment of Pinus taeda wood chips was also studied in order to verify the nucleophilic capability of this fluid in the delignification reactions. The reactions were performed with ammonia, exclusively, and in the presence of different co-solvents (ethanol, water and ethanol/water mixtures). The results of the delignifications showed the occurrence of low amount of lignin removal, with migration of lignin to the periphery of the wood chips. The lignins isolated from the reactions performed in this work were characterized by different analytical techniques. The results indicated no significant differences among the samples obtained in the different delignification processes.
7

De l'extraction de la lignine à sa valorisation / From lignin extraction to its valorization

Constant, Sandra 27 September 2012 (has links)
L'objectif de ce travail de thèse vise à étudier la conversion de la lignine dans des conditions oxydantes hydrothermales, par catalyse hétérogène. La lignine est l'une des principales constituantes des matériaux ligno-cellulosiques. Considérée comme déchet des procédés de valorisation de la cellulose, elle est majoritairement brûlée pour produire de l'énergie. De par sa structure de polymère phénolique, la lignine peut être considérée comme la principale source de noyaux aromatiques. Une méthodologie analytique complexe a, dans un premier temps, été mise en place pour permettre une caractérisation poussée des lignines et produits d'oxydation. Les lignines étudiées ont été extraites à partir de la paille par un procédé organosolv. Le procédé d'extraction influe sur les rendements mais aussi sur les structures et propriétés des différents produits. Les catalyseurs d'oxydation sont des oxydes divisés des métaux de transition, synthétisés par voie alginate. L'oxydation de la vanilline, composé modèle de la lignine, met en évidence des phénomènes d'oligomérisation des produits formés. Lors de l'oxydation des lignines, l'utilisation d'un catalyseur augmente les rendements et modifie les équilibres de dépolymérisation – oligomérisation. / The objective of this thesis is to study the conversion of lignin in oxidizing hydrothermal conditions, by heterogeneous catalysis. Lignin is among the main constituents of lignocellulose materials. Being considered like a waste of the cellulose valorization procedures, it is mostly burned to produce the energy. Taking into account its phenolic polymer structure, lignin can be considered as the main source of aromatic rings. Complex analytical methodology has initially been set up to allow a thorough characterization of lignins and oxidation products. Lignins were extracted from the straw by the organosolv procedure. The extraction process affects not only yields but also the structures and properties of products. The oxidation catalysts are transition metal oxides, synthesized by an alginate route. The oxidation of vanillin (lignin's model compound) shows the oligomerization phenomena of obtained products. In the oxidation of lignin, the use of a catalyst increases the yield and modifies the equilibrium of depolymerization - oligomerization.
8

Étude de faisabilité de la valorisation en bioraffinerie de biomasses issues de phytotechnologies : cas d’une plante hyperaccumulatrice (noccaea caerulescens) et d’un ligneux (salix viminalis) / Study of the feasibility of converting biomass from phytotechnology into biorefinery : Case of a hyperaccumulator plant (Noccaea caerulescens) and a woody plant (Salix viminalis)

Menana, Zahra 21 December 2018 (has links)
La phytoremédiation est un concept pour la dépollution et de réhabilitation des sols et/ou de friches industrielles contaminés par des éléments traces métalliques (ETMs), utilisant les végétaux pour absorber ou immobiliser les contaminants en présence des organismes microbiens de la rhizosphère. Cette technique a pour conséquence une production de biomasse plus ou moins contaminée qu’il est nécessaire de traiter et également de valoriser. Cependant, la présence d’ETMs peut être problématique dans une approche de conversion en bioraffinerie. Pour répondre à cette question, deux espèces ont été étudiées : une plante herbacée hyperaccumulatrice (Noccaea caerulescens) et un ligneux (Salix viminalis). Deux prétraitements ont été sélectionnés pour cette étude : les prétraitements par explosion vapeur et organosolv, en appliquant différentes conditions opératoires, afin (1) de suivre la distribution des ETMs au cours du traitement, (2) de purifier la matière lignocellulosique et (3) d’évaluer l’effet des ETMs sur les étapes ultérieures d’hydrolyse enzymatique et de fermentation. Pour le prétraitement organosolv la majeure partie des ETMs est récupérée dans le résidu solide cellulosique alors que par explosion à la vapeur, les ETMs sont extraits en grande partie dans les effluents aqueux du traitement. La présence d’ETMs dans les pâtes cellulosiques et les hydrolysats ne montre pas d’effet significatif sur la cinétique d’hydrolyse enzymatique et de fermentation. Concernant spécifiquement Noccaea caerulescens des teneurs relativement importantes en pectines ont été observées, ce qui ouvre des perspectives intéressantes pour la valorisation de cette plante par la production d’un biopolymère d’intérêt industriel. Finalement, les résultats obtenus montrent qu’il serait possible de combiner réhabilitation des sols et valorisation en bioraffinerie de biomasses issues de phytotechnologies soit pour la production du bioéthanol ou la production de molécules plateforme / Phytoremediation is a concept for the depollution and rehabilitation of soils and/or industrial wastelands contaminated by metal trace elements (MTEs), using plants to absorb or immobilize contaminants in the presence of microbial organisms in the rhizosphere. This technique results in a more or less contaminated biomass production that must be treated and also recovered. However, the presence of MTEs can be an issue in a biorefinery conversion approach. To address this question, two species were studied: an hyperaccumulator herbaceous plant (Noccaea caerulescens) and a woody plant (Salix viminalis). Two pre-treatments were selected for this study: steam explosion and organosolv pre-treatments, applying different operating conditions, in order to (1) monitor the distribution of MTEs during the process, (2) purify lignocellulosic material and (3) evaluate the effect of MTEs on subsequent enzymatic hydrolysis and fermentation steps. For organosolv pretreatment, most of the MTEs are recovered in the solid cellulosic residue while by steam explosion, MTEs are mostly extracted in the aqueous effluents of the treatment. The presence of MTEs in cellulosic pastes and hydrolysates does not show a significant effect on the kinetics of enzymatic hydrolysis and fermentation. Concerning specifically Noccaea caerulescens, the plant contains relatively high levels of pectins, which opens up interesting prospects for the valorization of this plant through the production of a biopolymer of industrial interest. Finally, the results obtained show that it would be possible to combine soil rehabilitation and biorefinery valorization of biomasses from phytotechnologies for either bioethanol production or the production of platform molecules
9

Determinação da relação dos parâmetros de solubilidade de Hansen de solventes orgânicos com a deslignificação organossolve de bagaço de cana-de-açúcar / Determination of the relation between the Hansen solubility parameters of the organic solvents with the organosolv delignification of sugarcane bagasse

Novo, Lísias Pereira 13 March 2012 (has links)
O uso do bagaço de cana-de-açúcar, um subproduto da produção sucroalcooleira, ainda está hoje atrelado diretamente à produção de energia com sua queima nas usinas, um uso que é pouco nobre, considerando-se a grande diversidade de compostos químicos presentes neste tipo de material. A possibilidade de valorização desta matéria-prima lignocelulósica está ligada a realização de etapas de separação das principais frações de compostos, a celulose, as hemiceluloses e a lignina. Neste contexto, as deslignificações organossolve, etapa de remoção da lignina através da solubilização da mesma em soluções orgânicas, tem grande potencial de uso, visto que nestas pode-se recuperar tanto a polpa como o licor de polpação para posterior uso. Assim, verifica-se que a solubilidade da lignina é o fator que diferencia a utilização de um dado solvente orgânico em uma deslignificação organossolve. Desta maneira, pode-se utilizar o conceito de parâmetros de solubilidade para a escolha de um melhor solvente para o processo. Neste trabalho, verificou-se a relação entre a deslignificação organossolve e a distância e afinidade de um solvente com a esfera de solubilidade de Hansen para a lignina de bagaço de cana-de-açúcar. Verificou-se que os parâmetros de solubilidade de Hansen para a lignina verificados na literatura não apresentam boa correlação com os dados de deslignificação, porém, uma nova esfera de solubilidade foi desenvolvida, na qual verificou-se um coeficiente de determinação de 0,93856, em detrimento de um de 0,72074 para a esfera de solubilidade verificada na literatura. Concluiu-se que o modelo desenvolvido possuía como principal diferença com relação ao modelo obtido por Hansen e Björkman para a lignina, um parâmetro de solubilidade para interações intermoleculares polares (δp) inferior e um parâmetro de solubilidade para a capacidade de realização de ligações de hidrogênio (δh) bem superior, porém mantendo o mesmo parâmetro de solubilidade total (δ). Confirmou-se a relação entre a deslignificação e os valores de distância e de afinidade obtidos neste trabalho, com a realização de deslignificações usando misturas ternárias e quaternárias com solventes de baixo custo e/ou excedentes no mercado (etanol, glicerol e 2-butanol, além de água). Concluiu-se que apesar da esfera de solubilidade desenvolvida permitir melhor ajuste dos dados, não se pode afirmar que esta é com certeza a esfera real para a lignina. / The use of sugarcane bagasse, a by-product of sugar and ethanol production, is still linked today directly to energy production with its burning in power plants, a use which is not very noble, considering the great diversity of chemical compounds present in the lignocellulosic matrix. The possibility of better use of lignocellulosic feedstock is linked to steps of separation of their main fractions, cellulose, hemicelluloses and lignin. In this context, organosolv delignification, in which lignin is removed by the solubilization in organic solutions have great potential, since both pulps and the pulping liquor can be recovered for later use. Thus, since the solubility of lignin is the factor that differentiates the use of a given organic solvent in an organosolv delignification, the concept of solubility parameters can be used for the selection of the organic solvent. In this dissertation the relationship between the distance and the affinity of a solvent with the Hansen sphere of solubility for lignin from bagasse cane sugar and organosolv delignification were studied. It was found that the Hansen solubility parameters for lignin found in the literature do not present a good correlation with delignification data. Thus a new sphere of solubility was developed, with a determination coefficient of 0.93856, over a determination coefficient of 0.72074 for the sphere of solubility found in the literature. It was concluded that the main differences between the developed model and the model obtained by Hansen and Björkman for lignin were a lower solubility parameter for polar intermolecular interactions (δp) and a higher solubility parameter for hydrogen bonds (δh), however keeping the same total solubility parameter (δ). The relationship between delignification and the values of the distance and affinity obtained in this work were confirmed with the attainment of organosolv delignification using tertiary and quaternary mixtures of solvents with low cost and/or availability in the market (ethanol, glycerol and 2-butanol, in addition to water). It was concluded that although the developed solubility sphere allowed a better fit of the data, it cannot be stated with certainty that this is the real sphere for lignin.
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Produção e caracterização de polpa organossolve de bambu para reforço de matrizes cimentícias / Production and characterization of bamboo organosolv pulp for reinforcement cementitious matrices

Correia, Viviane da Costa 17 March 2011 (has links)
A utilização de fibras vegetais como reforço de matrizes frágeis de cimento é justificada pelo baixo custo, alta disponibilidade, principalmente em países como o Brasil, que possui agricultura desenvolvida, boas condições edafo-climáticas e grandes áreas para cultivo. No entanto, em razão da alta alcalinidade do cimento a matriz reforçada tem a durabilidade comprometida pela degradação das fibras. Uma medida para minimizar esse ataque alcalino é a dissolução da lignina e da hemicelulose das fibras, menos resistentes em condições de pH elevado, através da polpação química, processo que individualiza as fibras celulósicas, que podem ser utilizadas como reforço de compósitos cimentícios em substituição parcial às fibras sintéticas. As polpas aplicadas para este fim são comumente produzidas pelo processo Kraft. Uma alternativa mais limpa a este processo é a polpação organossolve que usa reagentes orgânicos durante o cozimento e proporciona facilidade para recuperação do solvente no final do processo. O bambu possui fibras de elevada resistência mecânica, portanto sua utilização como matéria-prima para produção de polpas celulósicas é justificada por ser um material viável, de fácil aplicação, rápido crescimento e pronta disponibilidade. A proposta deste trabalho foi a produção de polpa de bambu pelo processo organossolve utilizando as variáveis tempo x temperatura com a finalidade de encontrar a condição ótima para o processo, de forma que houvesse melhor rendimento e que as características químicas, físicas e morfológicas da polpa fossem compatíveis às exigidas para utilização como reforço de matrizes cimentícias. A melhor condição foi o cozimento a temperatura de 190ºC durante 2 h. O tempo de 1 h de cozimento foi insuficiente para a solubilização da lignina e o período de 3 h é inviável devido a degradação da cadeia de celulose. Foram produzidos pelo método de sucção a pressão negativa, compósitos com matriz de cimento com substituição parcial de metacaulim e testados os teores de 6, 8, 10 e 12% de polpa de bambu como reforço. O teor de polpa definido como ideal foi 8%, o mesmo encontrado na literatura para polpa Kraft de bambu. Produziram-se placas com duas composições. Uma com substituição parcial de 25% do cimento por metacaulim e a segunda com substituição de 25% do cimento por calcário moído. Os compósitos contendo metacaulim foram submetidos a envelhecimento acelerado por meio de 50, 100 e 200 ciclos de imersão e secagem para avaliação da durabilidade. As propriedades físicas foram melhoradas com os ciclos de envelhecimento, ocasionando diminuição na porosidade aparente pela migração dos produtos da hidratação do cimento para a zona em torno das fibras, e, em consequência, melhorias nas propriedades mecânicas de módulo de ruptura (MOR), limite de proporcionalidade (LOP) e módulo de elasticidade (MOE), tanto para a substituição parcial do cimento por metacaulim como para calcário. Houve diminuição na energia específica (EE) com os ciclos de imersão e secagem, justificada pela maior aderência entre fibra-matriz. Observados os parâmetros de polpação organossolve adotados para o bambu, essa polpa apresenta-se viável para reforço de matrizes inorgânicas a base de cimento Portland. / The use of natural fibers as reinforcement for brittle cement matrices is justified by the its low cost, high availability, especially in countries like Brazil, which has developed agriculture, good soil and climatic conditions and large areas for cultivation. However, due to the high alkalinity of cement the reinforced matrix has it durability compromised by the fiber degradation. One measure to minimize this alkaline attack is the dissolution of lignin and hemicellulose fibers, that are less resistant under conditions of high pH, by chemical pulping, that is a process that individualizes the cellulosic fibers, which can be used as reinforcement of cementitious composites in partial replacement synthetic fibers. The pulps applied for this purpose are commonly produced by the kraft pulping process. A cleaner alternative to this process is the organosolv pulping that use organic reagents during cooking and provides facility for solvent recovery at the end of the process.The bamboo fibers have high mechanical strength, therefore their use as raw materials for production of cellulose pulps is justified because it is a viable material, easily applied, rapid growth and ready availability. The purpose of this study was the production of bamboo pulp by the organosolv process using the variables time vs temperature in order to find the optimum condition for the process, so that there was a better yield and that the chemical, physical and morphological characteristics of the pulp were compatible to those required for use as reinforcement in cementitious matrices. The best condition was the cooking temperature of 190ºC for 2 h. The time of 1 h of cooking was insufficient to solubilize the lignin and the time of 3 h is infeasible due to degradation of the cellulose chain. The composites with matrix of cement and with partial replacement of metakaolin were produced by the method of negative pressure suction and tested the levels of 6, 8, 10 and 12% bamboo pulp as reinforcement. The pulp content was defined as an ideal 8%, as found in the literature for bamboo Kraft pulp. The plates were produced with two compositions. One with partial substitution of cement by 25% of metakaolin and the second with 25% replacement of cement by limestone. The composites containing metakaolin were subjected to accelerated ageing through 50, 100 and 200 wet and dry cycles for durability evaluation. The physical properties were improved with the ageing cycles, decreasing the porosity by migration of the cement hydration products to the zone around the fibers and, consequently, improvements in mechanical properties of modulus of rupture (MOR), limit proportionality (LOP) and modulus of elasticity (MOE) for both the partial replacement of cement by metakaolin as for limestone. The decreased of the specific energy (EE) with the wet and dry cycles was due to the higher adhesion between fiber-matrix. With the observation of the parameters adopted for bamboo organosolv pulping, this pulp has to be feasible for reinforcement of inorganic matrices based in Portland cement.

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