Caracterização de ligninas de Eucalyptus spp. pela técnica de pirólise associada à cromatografia gasosa e à espectrometria de massas
Autor(a) principal: | |
---|---|
Data de Publicação: | 2006 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | LOCUS Repositório Institucional da UFV |
Texto Completo: | http://locus.ufv.br/handle/123456789/2174 |
Resumo: | Lignin is one of the main wood components as well as the cellulose and hemicellulose. It is known that the composition of lignin relative to the amounts of unit syringyl (S) and guaiacyl (G) can affect the efficiency of the kraft pulping. Thus, this work was carried out to develop a methodology for the determination of the S/G relationship in the Eucalyptus spp. wood, by using the pyrolysis coupled to the gas chromatography and mass spectrometry (Pi-CG/EM), in order to selecting eucalyptus clones for kraft pulping. Some analyses were accomplished for Pi-CG/EM of the wood, extractive-free wood, acetone extractive and lignin (MWL) of the Eucalyptus grandis and Eucalyptus urograndis species at the temperatures of 300, 350, 400, 450, 500, 550 and 600 °C. When analyzing the pyrograms of the wood under several temperatures, The presence of many phenolic monomers from the lignin and several furanic and pyranic compounds originating from either dehydration and the carbohydrate rearrangements were observed, when analyzing the wood pyrograms. At 600 oC temperature, the relative abundance of the compounds from the carbohydrates overcame that of the compounds originating from lignin. The S/G relationship largely varied as a function of the temperature, and the maximum S/G relationship in both species of Eucalyptus were obtained at 300 °C. Besides the temperature, the amount of the sample to be pyrolised was observed to interfere into S/G relationship. The analyzed pyrograms of the extractive-free woods showed a similar behavior to that of the wood with extractive. When analyzing the pyrograms of the acetone extractives, the following presence were observed: several fatty acids, hydrocarbons, alcohols, aromatic compounds and fatty ester. In the analyses of the lignin pyrograms (MWL), however, the S/G relationship was very similar to that of the wood with extractive at 550 °C temperature. At the lowest temperatures, only few compounds were volatilized, whereas at 600 °C many compounds were degraded, therefore composing lignin-modified derivatives, such as 3-methoxycatechol. The accomplished studies showed the uses of the Pi-CG/EM to be a powerful tool for the characterization of the S/G relationship because its high sensibility. The temperature at 550 °C showed to be most appropriate for the pyrolysis of the wood. In the pyrolysis of the extractiveless wood, acetone extractives and lignin (MWL), it was noticed that the extractives have just few influence on the determination of the S/G relationship, and the carbohydrates more than the extractives. The methodology developed in this work showed to be effective for determination of the S/G relationship in both wood with and without extractives, since the use of those eight marker compounds for lignin derivatives (guaiacol, 4-methylguaiacol, 4-vinylguaiacol and trans-isoeugenol, syringol, 4-methylsyringol, 4-vinylsyringol and trans-propenylsyringol) at 550 °C temperature were satisfactory in determining the S/G relationship. This result will be useful to the industries, as making possible the determination of the S/G relationship in Eucalyptus species on a faster way than by the nitrobenzene oxidation. |
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Silva, Vanessa Lopeshttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4702816E9Maltha, Célia Regina álvareshttp://lattes.cnpq.br/7346715444030145Colodette, Jorge Luizhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4721443U9Barbosa, Luiz Claudio de Almeidahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4781106J2Ventorim, Gustavohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4723799D8Reis, Efraim Lázarohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788214H72015-03-26T13:00:40Z2006-12-052015-03-26T13:00:40Z2006-08-28SILVA, Vanessa Lopes. Characterizing the lignins of Eucalyptus spp. by the pyrolysis technique associated to both gas chromatography and mass spectrometry. 2006. 85 f. Dissertação (Mestrado em Agroquímica analítica; Agroquímica inorgânica e Físico-química; Agroquímica orgânica) - Universidade Federal de Viçosa, Viçosa, 2006.http://locus.ufv.br/handle/123456789/2174Lignin is one of the main wood components as well as the cellulose and hemicellulose. It is known that the composition of lignin relative to the amounts of unit syringyl (S) and guaiacyl (G) can affect the efficiency of the kraft pulping. Thus, this work was carried out to develop a methodology for the determination of the S/G relationship in the Eucalyptus spp. wood, by using the pyrolysis coupled to the gas chromatography and mass spectrometry (Pi-CG/EM), in order to selecting eucalyptus clones for kraft pulping. Some analyses were accomplished for Pi-CG/EM of the wood, extractive-free wood, acetone extractive and lignin (MWL) of the Eucalyptus grandis and Eucalyptus urograndis species at the temperatures of 300, 350, 400, 450, 500, 550 and 600 °C. When analyzing the pyrograms of the wood under several temperatures, The presence of many phenolic monomers from the lignin and several furanic and pyranic compounds originating from either dehydration and the carbohydrate rearrangements were observed, when analyzing the wood pyrograms. At 600 oC temperature, the relative abundance of the compounds from the carbohydrates overcame that of the compounds originating from lignin. The S/G relationship largely varied as a function of the temperature, and the maximum S/G relationship in both species of Eucalyptus were obtained at 300 °C. Besides the temperature, the amount of the sample to be pyrolised was observed to interfere into S/G relationship. The analyzed pyrograms of the extractive-free woods showed a similar behavior to that of the wood with extractive. When analyzing the pyrograms of the acetone extractives, the following presence were observed: several fatty acids, hydrocarbons, alcohols, aromatic compounds and fatty ester. In the analyses of the lignin pyrograms (MWL), however, the S/G relationship was very similar to that of the wood with extractive at 550 °C temperature. At the lowest temperatures, only few compounds were volatilized, whereas at 600 °C many compounds were degraded, therefore composing lignin-modified derivatives, such as 3-methoxycatechol. The accomplished studies showed the uses of the Pi-CG/EM to be a powerful tool for the characterization of the S/G relationship because its high sensibility. The temperature at 550 °C showed to be most appropriate for the pyrolysis of the wood. In the pyrolysis of the extractiveless wood, acetone extractives and lignin (MWL), it was noticed that the extractives have just few influence on the determination of the S/G relationship, and the carbohydrates more than the extractives. The methodology developed in this work showed to be effective for determination of the S/G relationship in both wood with and without extractives, since the use of those eight marker compounds for lignin derivatives (guaiacol, 4-methylguaiacol, 4-vinylguaiacol and trans-isoeugenol, syringol, 4-methylsyringol, 4-vinylsyringol and trans-propenylsyringol) at 550 °C temperature were satisfactory in determining the S/G relationship. This result will be useful to the industries, as making possible the determination of the S/G relationship in Eucalyptus species on a faster way than by the nitrobenzene oxidation.A lignina é um dos principais componentes da madeira, assim como a celulose e a hemicelulose. Sabe-se que a composição da lignina em relação às quantidades de unidades siringila (S) e guaiacila (G) pode afetar a eficiência da polpação kraft. Portanto, este trabalho foi realizado com o objetivo de desenvolver uma metodologia para a determinação da relação S/G em madeiras de Eucalyptus spp., utilizando-se a pirólise acoplada à cromatografia gasosa e espectrometria de massas (Pi-CG/EM), com vistas à seleção de clones de eucalipto para a polpação kraft. Foram realizadas análises de Pi-CG/EM da serragem, da serragem livre de extrativos, do extrativo em acetona e da lignina (MWL) das espécies de Eucalyptus grandis e Eucalyptus urograndis, nas temperaturas de 300, 350, 400, 450, 500, 550 e 600 °C. Na análise dos pirogramas da serragem sob as várias temperaturas, notou-se a presença de muitos monômeros fenólicos derivados da lignina e diversos compostos furânicos e pirânicos oriundos da desidratação e rearranjo dos carboidratos. Na temperatura de 600 °C foi observado que a abundância relativa de compostos derivados dos carboidratos superava a de compostos originários da lignina. A relação S/G variou muito em função da temperatura, sendo que a 300 °C foi obtida a máxima relação S/G em ambas as espécies de Eucalyptus. Observou-se, durante os experimentos, que a quantidade de amostra a ser pirolisada também interfere na relação S/G, além da temperatura. As análises dos pirogramas das serragens livres de extrativos mostraram comportamento semelhante ao da serragem com extrativo. Na análise dos pirogramas dos extrativos em acetona, notou-se a presença de vários ácidos graxos, hidrocarbonetos, álcoois, compostos aromáticos e éster graxo. Já nas análises dos pirogramas das ligninas (MWL) ficou evidenciado que a relação S/G foi muito parecida com a da madeira com extrativo na temperatura de 550 °C. Nas temperaturas mais baixas, somente alguns compostos foram volatilizados, enquanto a 600 °C muitos compostos foram degradados, formando derivados modificados da lignina, por exemplo o 3-metoxicatecol. Os estudos realizados demonstraram que a utilização da Pi-CG/EM é ferramenta poderosa para a caracterização da relação S/G, devido a sua alta sensibilidade. A temperatura de 550 °C indicou ser a mais adequada para a pirólise da serragem. Na pirólise da serragem sem extrativo, dos extrativos em acetona e da lignina (MWL), notou-se que os extrativos influenciam pouco a determinação da relação S/G, já os carboidratos, mais do que os extrativos. A metodologia desenvolvida neste trabalho mostrou-se eficaz na determinação da relação S/G na serragem com extrativo e sem extrativo, visto que a utilização dos oito compostos marcadores dos derivados de lignina (guaiacol, 4-etilguaiacol, 4-vinilguaiacol e trans-isoeugenol, siringol, 4-metilsiringol, 4-inilsiringol e trans-propenilsiringol) na temperatura de 550 °C foi satisfatória na determinação da relação S/G. Isso possibilitará às indústrias determinarem a relação S/G em espécies de Eucalyptus de maneira mais rápida do que pela oxidação por nitrobenzeno.Conselho Nacional de Desenvolvimento Científico e Tecnológicoapplication/pdfporUniversidade Federal de ViçosaMestrado em AgroquímicaUFVBRAgroquímica analítica; Agroquímica inorgânica e Físico-química; Agroquímica orgânicaLigninaPiróliseEspectrometria de massasCromatografia gasosaLigninPyrolysisMass spectrometryGas chromatographyCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICACaracterização de ligninas de Eucalyptus spp. pela técnica de pirólise associada à cromatografia gasosa e à espectrometria de massasCharacterizing the lignins of Eucalyptus spp. by the pyrolysis technique associated to both gas chromatography and mass spectrometryinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisinfo:eu-repo/semantics/openAccessreponame:LOCUS Repositório Institucional da UFVinstname:Universidade Federal de Viçosa (UFV)instacron:UFVORIGINALtexto completo.pdfapplication/pdf500259https://locus.ufv.br//bitstream/123456789/2174/1/texto%20completo.pdf730e3d449a962f323be6b0ee030dc49aMD51TEXTtexto completo.pdf.txttexto completo.pdf.txtExtracted texttext/plain117545https://locus.ufv.br//bitstream/123456789/2174/2/texto%20completo.pdf.txt8e2bb025090e1db8d581fe89b43da5f5MD52THUMBNAILtexto completo.pdf.jpgtexto completo.pdf.jpgIM Thumbnailimage/jpeg3727https://locus.ufv.br//bitstream/123456789/2174/3/texto%20completo.pdf.jpgeed87e7cf3e1cf724a16b992c0a98e0eMD53123456789/21742016-04-08 23:01:40.05oai:locus.ufv.br:123456789/2174Repositório InstitucionalPUBhttps://www.locus.ufv.br/oai/requestfabiojreis@ufv.bropendoar:21452016-04-09T02:01:40LOCUS Repositório Institucional da UFV - Universidade Federal de Viçosa (UFV)false |
dc.title.por.fl_str_mv |
Caracterização de ligninas de Eucalyptus spp. pela técnica de pirólise associada à cromatografia gasosa e à espectrometria de massas |
dc.title.alternative.eng.fl_str_mv |
Characterizing the lignins of Eucalyptus spp. by the pyrolysis technique associated to both gas chromatography and mass spectrometry |
title |
Caracterização de ligninas de Eucalyptus spp. pela técnica de pirólise associada à cromatografia gasosa e à espectrometria de massas |
spellingShingle |
Caracterização de ligninas de Eucalyptus spp. pela técnica de pirólise associada à cromatografia gasosa e à espectrometria de massas Silva, Vanessa Lopes Lignina Pirólise Espectrometria de massas Cromatografia gasosa Lignin Pyrolysis Mass spectrometry Gas chromatography CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA |
title_short |
Caracterização de ligninas de Eucalyptus spp. pela técnica de pirólise associada à cromatografia gasosa e à espectrometria de massas |
title_full |
Caracterização de ligninas de Eucalyptus spp. pela técnica de pirólise associada à cromatografia gasosa e à espectrometria de massas |
title_fullStr |
Caracterização de ligninas de Eucalyptus spp. pela técnica de pirólise associada à cromatografia gasosa e à espectrometria de massas |
title_full_unstemmed |
Caracterização de ligninas de Eucalyptus spp. pela técnica de pirólise associada à cromatografia gasosa e à espectrometria de massas |
title_sort |
Caracterização de ligninas de Eucalyptus spp. pela técnica de pirólise associada à cromatografia gasosa e à espectrometria de massas |
author |
Silva, Vanessa Lopes |
author_facet |
Silva, Vanessa Lopes |
author_role |
author |
dc.contributor.authorLattes.por.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4702816E9 |
dc.contributor.author.fl_str_mv |
Silva, Vanessa Lopes |
dc.contributor.advisor-co1.fl_str_mv |
Maltha, Célia Regina álvares |
dc.contributor.advisor-co1Lattes.fl_str_mv |
http://lattes.cnpq.br/7346715444030145 |
dc.contributor.advisor-co2.fl_str_mv |
Colodette, Jorge Luiz |
dc.contributor.advisor-co2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4721443U9 |
dc.contributor.advisor1.fl_str_mv |
Barbosa, Luiz Claudio de Almeida |
dc.contributor.advisor1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4781106J2 |
dc.contributor.referee1.fl_str_mv |
Ventorim, Gustavo |
dc.contributor.referee1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4723799D8 |
dc.contributor.referee2.fl_str_mv |
Reis, Efraim Lázaro |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788214H7 |
contributor_str_mv |
Maltha, Célia Regina álvares Colodette, Jorge Luiz Barbosa, Luiz Claudio de Almeida Ventorim, Gustavo Reis, Efraim Lázaro |
dc.subject.por.fl_str_mv |
Lignina Pirólise Espectrometria de massas Cromatografia gasosa |
topic |
Lignina Pirólise Espectrometria de massas Cromatografia gasosa Lignin Pyrolysis Mass spectrometry Gas chromatography CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA |
dc.subject.eng.fl_str_mv |
Lignin Pyrolysis Mass spectrometry Gas chromatography |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA |
description |
Lignin is one of the main wood components as well as the cellulose and hemicellulose. It is known that the composition of lignin relative to the amounts of unit syringyl (S) and guaiacyl (G) can affect the efficiency of the kraft pulping. Thus, this work was carried out to develop a methodology for the determination of the S/G relationship in the Eucalyptus spp. wood, by using the pyrolysis coupled to the gas chromatography and mass spectrometry (Pi-CG/EM), in order to selecting eucalyptus clones for kraft pulping. Some analyses were accomplished for Pi-CG/EM of the wood, extractive-free wood, acetone extractive and lignin (MWL) of the Eucalyptus grandis and Eucalyptus urograndis species at the temperatures of 300, 350, 400, 450, 500, 550 and 600 °C. When analyzing the pyrograms of the wood under several temperatures, The presence of many phenolic monomers from the lignin and several furanic and pyranic compounds originating from either dehydration and the carbohydrate rearrangements were observed, when analyzing the wood pyrograms. At 600 oC temperature, the relative abundance of the compounds from the carbohydrates overcame that of the compounds originating from lignin. The S/G relationship largely varied as a function of the temperature, and the maximum S/G relationship in both species of Eucalyptus were obtained at 300 °C. Besides the temperature, the amount of the sample to be pyrolised was observed to interfere into S/G relationship. The analyzed pyrograms of the extractive-free woods showed a similar behavior to that of the wood with extractive. When analyzing the pyrograms of the acetone extractives, the following presence were observed: several fatty acids, hydrocarbons, alcohols, aromatic compounds and fatty ester. In the analyses of the lignin pyrograms (MWL), however, the S/G relationship was very similar to that of the wood with extractive at 550 °C temperature. At the lowest temperatures, only few compounds were volatilized, whereas at 600 °C many compounds were degraded, therefore composing lignin-modified derivatives, such as 3-methoxycatechol. The accomplished studies showed the uses of the Pi-CG/EM to be a powerful tool for the characterization of the S/G relationship because its high sensibility. The temperature at 550 °C showed to be most appropriate for the pyrolysis of the wood. In the pyrolysis of the extractiveless wood, acetone extractives and lignin (MWL), it was noticed that the extractives have just few influence on the determination of the S/G relationship, and the carbohydrates more than the extractives. The methodology developed in this work showed to be effective for determination of the S/G relationship in both wood with and without extractives, since the use of those eight marker compounds for lignin derivatives (guaiacol, 4-methylguaiacol, 4-vinylguaiacol and trans-isoeugenol, syringol, 4-methylsyringol, 4-vinylsyringol and trans-propenylsyringol) at 550 °C temperature were satisfactory in determining the S/G relationship. This result will be useful to the industries, as making possible the determination of the S/G relationship in Eucalyptus species on a faster way than by the nitrobenzene oxidation. |
publishDate |
2006 |
dc.date.available.fl_str_mv |
2006-12-05 2015-03-26T13:00:40Z |
dc.date.issued.fl_str_mv |
2006-08-28 |
dc.date.accessioned.fl_str_mv |
2015-03-26T13:00:40Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
format |
masterThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
SILVA, Vanessa Lopes. Characterizing the lignins of Eucalyptus spp. by the pyrolysis technique associated to both gas chromatography and mass spectrometry. 2006. 85 f. Dissertação (Mestrado em Agroquímica analítica; Agroquímica inorgânica e Físico-química; Agroquímica orgânica) - Universidade Federal de Viçosa, Viçosa, 2006. |
dc.identifier.uri.fl_str_mv |
http://locus.ufv.br/handle/123456789/2174 |
identifier_str_mv |
SILVA, Vanessa Lopes. Characterizing the lignins of Eucalyptus spp. by the pyrolysis technique associated to both gas chromatography and mass spectrometry. 2006. 85 f. Dissertação (Mestrado em Agroquímica analítica; Agroquímica inorgânica e Físico-química; Agroquímica orgânica) - Universidade Federal de Viçosa, Viçosa, 2006. |
url |
http://locus.ufv.br/handle/123456789/2174 |
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por |
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Universidade Federal de Viçosa |
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UFV |
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Agroquímica analítica; Agroquímica inorgânica e Físico-química; Agroquímica orgânica |
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Universidade Federal de Viçosa |
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