Lactic acid production from hydrothermal conversion of glycerol using homogeneous and heterogeneous catalysis

Detalhes bibliográficos
Autor(a) principal: Anne Kerolaine de Oliveira Rodrigues
Data de Publicação: 2016
Tipo de documento: Tese
Idioma: por
Título da fonte: Biblioteca Digital de Teses e Dissertações da UFC
Texto Completo: http://www.teses.ufc.br/tde_busca/arquivo.php?codArquivo=16779
Resumo: The use of alternative energy sources is a of the major current priorities, that appears to circumvent the serious problems caused by technological development. Accordingly, biodiesel arises as an alternative fuel to petroleum. However, high biodiesel production generates a large quantity of glycerin (10 wt%) which is considered an unwanted byproduct. To increase the market values of the biodiesel byproduct, it is necessary to convert glycerin into other chemicals, such as in lactic acid, which is becoming increasingly important due to their promising polymers applications - eg.: poly(lactic acid) (PLA) - as an alternative to replace petrochemical plastics. In the present study the hydrothermal process was used for lactic acid production, replacing the fermentation process that is currently used to obtain this product. For hydrothermal conversion of glycerol into lactic acid by homogeneous catalysis, NaOH and KOH catalysts were used. And for hydrothermal glycerol lactic acid by heterogeneous catalysis, Cu/SiO2 catalyst was used. Initial glycerol concentration (0.51-17.1 M), temperature (160-280 ÂC), pressure (2-43 bar), water/glycerol volumetric ratio (0.8 to 31), catalyst/glycerol molar ratio (0.01 to 1.02) and total reaction time (3-4 hours) were the variables studied with temperature and water/glycerol volumetric ratio having the major influence. In addition, a first-order kinetic model for glycerol concentration versus time was developed and verified experimentally under conditions with different temperatures. Comparing the results obtained from hydrothermal conversion by homogeneous and heterogeneous catalysis, it was observed that KOH was catalyst with the best performance. The highest yield obtained was 87.5% at 220 ÂC and 28.8 bar, after 3 h, from a solution water/glycerol volumetric ratio equal to 0.8 and KOH/glycerol molar ratio equal to 0.03. From this result, hydrothermal process can be seen as a promising method to add value to glycerol.
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spelling info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisLactic acid production from hydrothermal conversion of glycerol using homogeneous and heterogeneous catalysisProduÃÃo de Ãcido lÃtico a partir da conversÃo hidrotÃrmica do glicerol via catÃlise homogÃnea e heterogÃnea2016-01-29Fabiano Andrà Narciso Fernandes26059059856http://lattes.cnpq.br/9978219072711522Luciana Rocha Barros GonÃalves56400969187http://buscatextual.cnpq.br/buscatextual/visualizacv.jsp?id=K4798113A3Samuel Jorge Marques Cartaxo54515939572Ivanildo Josà da Silva Junior97038962434http://lattes.cnpq.br/8628710115274949Maria Alexsandra de Sousa Rios49214756368http://lattes.cnpq.br/687291673129961700429987358http://lattes.cnpq.br/8773450319320064Anne Kerolaine de Oliveira RodriguesUniversidade Federal do CearÃPrograma de PÃs-GraduaÃÃo em Engenharia QuÃmicaUFCBRÃcido lÃtico ConversÃo hidrotÃrmica CatalisadoresLactic acid Glycerol Hydrothermal conversion CatalystENGENHARIA QUIMICAThe use of alternative energy sources is a of the major current priorities, that appears to circumvent the serious problems caused by technological development. Accordingly, biodiesel arises as an alternative fuel to petroleum. However, high biodiesel production generates a large quantity of glycerin (10 wt%) which is considered an unwanted byproduct. To increase the market values of the biodiesel byproduct, it is necessary to convert glycerin into other chemicals, such as in lactic acid, which is becoming increasingly important due to their promising polymers applications - eg.: poly(lactic acid) (PLA) - as an alternative to replace petrochemical plastics. In the present study the hydrothermal process was used for lactic acid production, replacing the fermentation process that is currently used to obtain this product. For hydrothermal conversion of glycerol into lactic acid by homogeneous catalysis, NaOH and KOH catalysts were used. And for hydrothermal glycerol lactic acid by heterogeneous catalysis, Cu/SiO2 catalyst was used. Initial glycerol concentration (0.51-17.1 M), temperature (160-280 ÂC), pressure (2-43 bar), water/glycerol volumetric ratio (0.8 to 31), catalyst/glycerol molar ratio (0.01 to 1.02) and total reaction time (3-4 hours) were the variables studied with temperature and water/glycerol volumetric ratio having the major influence. In addition, a first-order kinetic model for glycerol concentration versus time was developed and verified experimentally under conditions with different temperatures. Comparing the results obtained from hydrothermal conversion by homogeneous and heterogeneous catalysis, it was observed that KOH was catalyst with the best performance. The highest yield obtained was 87.5% at 220 ÂC and 28.8 bar, after 3 h, from a solution water/glycerol volumetric ratio equal to 0.8 and KOH/glycerol molar ratio equal to 0.03. From this result, hydrothermal process can be seen as a promising method to add value to glycerol.A utilizaÃÃo de fontes alternativas de energia à uma das grandes prioridades atuais, que surge para contornar os graves problemas ocasionados pelo desenvolvimento tecnolÃgico. Neste sentido, o biodiesel surge como um combustÃvel alternativo ao petrÃleo. No entanto, a elevada produÃÃo de biodiesel gera uma grande quantidade de glicerina (10% em massa) que à considerada um coproduto. Para aumentar o valor de mercado da glicerina, faz-se necessÃrio convertÃ-la em outros produtos quÃmicos, como por exemplo, em Ãcido lÃtico, que està se tornando cada vez mais importante, devido a aplicaÃÃes promissoras de seus polÃmeros â ex.: poli(Ãcido lÃtico) (PLA) â como uma alternativa para substituir os plÃsticos petroquÃmicos. O presente estudo teve como objetivo utilizar o processo hidrotÃrmico para a produÃÃo de Ãcido lÃtico, em substituiÃÃo ao processo fermentativo que Ã, atualmente, utilizado para a obtenÃÃo deste produto. Para conversÃo hidrotÃrmica do glicerol em Ãcido lÃtico, via catÃlise homogÃnea, NaOH e KOH foram os catalisadores utilizados. E para a conversÃo hidrotÃrmica do glicerol em Ãcido lÃtico, via catÃlise heterogÃnea, Cu/SiO2 foi o catalisador usado. ConcentraÃÃo inicial de glicerol (0,51-17,1 M), temperatura (160-280 ÂC), pressÃo (2-43 bar), razÃo volumÃtrica de Ãgua/glicerol (0,8-31), razÃo molar catalisador/glicerol (0,01-1,02) e tempo total de reaÃÃo (3-4 horas) foram as variÃveis estudadas. A temperatura e a razÃo volumÃtrica de Ãgua/glicerol foram as variÃveis de maior influÃncia. AlÃm disso, um modelo cinÃtico de primeira ordem para determinaÃÃo da concentraÃÃo de glicerol em funÃÃo do tempo foi desenvolvido e verificado experimentalmente em diferentes temperaturas. Comparando os resultados obtidos a partir das conversÃes hidrotÃrmicas, via catÃlise homogÃnea e heterogÃnea, foi possÃvel observar que o KOH foi o catalisador com o melhor desempenho. O maior rendimento obtido foi de 87,5%, a 220 ÂC e a 28,8 bar, em um tempo total de reaÃÃo de 3 h, a partir de uma soluÃÃo de razÃo volumÃtrica Ãgua/glicerina igual a 0,8 e razÃo molar KOH/glicerol igual a 0,03. A partir deste resultado, processo hidrotÃrmico pode ser visto como sendo um processo promissor para agregar valor ao glicerol.CoordenaÃÃo de AperfeÃoamento de Pessoal de NÃvel Superior http://www.teses.ufc.br/tde_busca/arquivo.php?codArquivo=16779application/pdfinfo:eu-repo/semantics/openAccessporreponame:Biblioteca Digital de Teses e Dissertações da UFCinstname:Universidade Federal do Cearáinstacron:UFC2019-01-21T11:30:11Zmail@mail.com -
dc.title.en.fl_str_mv Lactic acid production from hydrothermal conversion of glycerol using homogeneous and heterogeneous catalysis
dc.title.alternative.pt.fl_str_mv ProduÃÃo de Ãcido lÃtico a partir da conversÃo hidrotÃrmica do glicerol via catÃlise homogÃnea e heterogÃnea
title Lactic acid production from hydrothermal conversion of glycerol using homogeneous and heterogeneous catalysis
spellingShingle Lactic acid production from hydrothermal conversion of glycerol using homogeneous and heterogeneous catalysis
Anne Kerolaine de Oliveira Rodrigues
Ãcido lÃtico
ConversÃo hidrotÃrmica
Catalisadores
Lactic acid
Glycerol
Hydrothermal conversion
Catalyst
ENGENHARIA QUIMICA
title_short Lactic acid production from hydrothermal conversion of glycerol using homogeneous and heterogeneous catalysis
title_full Lactic acid production from hydrothermal conversion of glycerol using homogeneous and heterogeneous catalysis
title_fullStr Lactic acid production from hydrothermal conversion of glycerol using homogeneous and heterogeneous catalysis
title_full_unstemmed Lactic acid production from hydrothermal conversion of glycerol using homogeneous and heterogeneous catalysis
title_sort Lactic acid production from hydrothermal conversion of glycerol using homogeneous and heterogeneous catalysis
author Anne Kerolaine de Oliveira Rodrigues
author_facet Anne Kerolaine de Oliveira Rodrigues
author_role author
dc.contributor.advisor1.fl_str_mv Fabiano Andrà Narciso Fernandes
dc.contributor.advisor1ID.fl_str_mv 26059059856
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/9978219072711522
dc.contributor.referee1.fl_str_mv Luciana Rocha Barros GonÃalves
dc.contributor.referee1ID.fl_str_mv 56400969187
dc.contributor.referee1Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.jsp?id=K4798113A3
dc.contributor.referee2.fl_str_mv Samuel Jorge Marques Cartaxo
dc.contributor.referee2ID.fl_str_mv 54515939572
dc.contributor.referee3.fl_str_mv Ivanildo Josà da Silva Junior
dc.contributor.referee3ID.fl_str_mv 97038962434
dc.contributor.referee3Lattes.fl_str_mv http://lattes.cnpq.br/8628710115274949
dc.contributor.referee4.fl_str_mv Maria Alexsandra de Sousa Rios
dc.contributor.referee4ID.fl_str_mv 49214756368
dc.contributor.referee4Lattes.fl_str_mv http://lattes.cnpq.br/6872916731299617
dc.contributor.authorID.fl_str_mv 00429987358
dc.contributor.authorLattes.fl_str_mv http://lattes.cnpq.br/8773450319320064
dc.contributor.author.fl_str_mv Anne Kerolaine de Oliveira Rodrigues
contributor_str_mv Fabiano Andrà Narciso Fernandes
Luciana Rocha Barros GonÃalves
Samuel Jorge Marques Cartaxo
Ivanildo Josà da Silva Junior
Maria Alexsandra de Sousa Rios
dc.subject.por.fl_str_mv Ãcido lÃtico
ConversÃo hidrotÃrmica
Catalisadores
topic Ãcido lÃtico
ConversÃo hidrotÃrmica
Catalisadores
Lactic acid
Glycerol
Hydrothermal conversion
Catalyst
ENGENHARIA QUIMICA
dc.subject.eng.fl_str_mv Lactic acid
Glycerol
Hydrothermal conversion
Catalyst
dc.subject.cnpq.fl_str_mv ENGENHARIA QUIMICA
dc.description.sponsorship.fl_txt_mv CoordenaÃÃo de AperfeÃoamento de Pessoal de NÃvel Superior
dc.description.abstract.por.fl_txt_mv The use of alternative energy sources is a of the major current priorities, that appears to circumvent the serious problems caused by technological development. Accordingly, biodiesel arises as an alternative fuel to petroleum. However, high biodiesel production generates a large quantity of glycerin (10 wt%) which is considered an unwanted byproduct. To increase the market values of the biodiesel byproduct, it is necessary to convert glycerin into other chemicals, such as in lactic acid, which is becoming increasingly important due to their promising polymers applications - eg.: poly(lactic acid) (PLA) - as an alternative to replace petrochemical plastics. In the present study the hydrothermal process was used for lactic acid production, replacing the fermentation process that is currently used to obtain this product. For hydrothermal conversion of glycerol into lactic acid by homogeneous catalysis, NaOH and KOH catalysts were used. And for hydrothermal glycerol lactic acid by heterogeneous catalysis, Cu/SiO2 catalyst was used. Initial glycerol concentration (0.51-17.1 M), temperature (160-280 ÂC), pressure (2-43 bar), water/glycerol volumetric ratio (0.8 to 31), catalyst/glycerol molar ratio (0.01 to 1.02) and total reaction time (3-4 hours) were the variables studied with temperature and water/glycerol volumetric ratio having the major influence. In addition, a first-order kinetic model for glycerol concentration versus time was developed and verified experimentally under conditions with different temperatures. Comparing the results obtained from hydrothermal conversion by homogeneous and heterogeneous catalysis, it was observed that KOH was catalyst with the best performance. The highest yield obtained was 87.5% at 220 ÂC and 28.8 bar, after 3 h, from a solution water/glycerol volumetric ratio equal to 0.8 and KOH/glycerol molar ratio equal to 0.03. From this result, hydrothermal process can be seen as a promising method to add value to glycerol.
A utilizaÃÃo de fontes alternativas de energia à uma das grandes prioridades atuais, que surge para contornar os graves problemas ocasionados pelo desenvolvimento tecnolÃgico. Neste sentido, o biodiesel surge como um combustÃvel alternativo ao petrÃleo. No entanto, a elevada produÃÃo de biodiesel gera uma grande quantidade de glicerina (10% em massa) que à considerada um coproduto. Para aumentar o valor de mercado da glicerina, faz-se necessÃrio convertÃ-la em outros produtos quÃmicos, como por exemplo, em Ãcido lÃtico, que està se tornando cada vez mais importante, devido a aplicaÃÃes promissoras de seus polÃmeros â ex.: poli(Ãcido lÃtico) (PLA) â como uma alternativa para substituir os plÃsticos petroquÃmicos. O presente estudo teve como objetivo utilizar o processo hidrotÃrmico para a produÃÃo de Ãcido lÃtico, em substituiÃÃo ao processo fermentativo que Ã, atualmente, utilizado para a obtenÃÃo deste produto. Para conversÃo hidrotÃrmica do glicerol em Ãcido lÃtico, via catÃlise homogÃnea, NaOH e KOH foram os catalisadores utilizados. E para a conversÃo hidrotÃrmica do glicerol em Ãcido lÃtico, via catÃlise heterogÃnea, Cu/SiO2 foi o catalisador usado. ConcentraÃÃo inicial de glicerol (0,51-17,1 M), temperatura (160-280 ÂC), pressÃo (2-43 bar), razÃo volumÃtrica de Ãgua/glicerol (0,8-31), razÃo molar catalisador/glicerol (0,01-1,02) e tempo total de reaÃÃo (3-4 horas) foram as variÃveis estudadas. A temperatura e a razÃo volumÃtrica de Ãgua/glicerol foram as variÃveis de maior influÃncia. AlÃm disso, um modelo cinÃtico de primeira ordem para determinaÃÃo da concentraÃÃo de glicerol em funÃÃo do tempo foi desenvolvido e verificado experimentalmente em diferentes temperaturas. Comparando os resultados obtidos a partir das conversÃes hidrotÃrmicas, via catÃlise homogÃnea e heterogÃnea, foi possÃvel observar que o KOH foi o catalisador com o melhor desempenho. O maior rendimento obtido foi de 87,5%, a 220 ÂC e a 28,8 bar, em um tempo total de reaÃÃo de 3 h, a partir de uma soluÃÃo de razÃo volumÃtrica Ãgua/glicerina igual a 0,8 e razÃo molar KOH/glicerol igual a 0,03. A partir deste resultado, processo hidrotÃrmico pode ser visto como sendo um processo promissor para agregar valor ao glicerol.
description The use of alternative energy sources is a of the major current priorities, that appears to circumvent the serious problems caused by technological development. Accordingly, biodiesel arises as an alternative fuel to petroleum. However, high biodiesel production generates a large quantity of glycerin (10 wt%) which is considered an unwanted byproduct. To increase the market values of the biodiesel byproduct, it is necessary to convert glycerin into other chemicals, such as in lactic acid, which is becoming increasingly important due to their promising polymers applications - eg.: poly(lactic acid) (PLA) - as an alternative to replace petrochemical plastics. In the present study the hydrothermal process was used for lactic acid production, replacing the fermentation process that is currently used to obtain this product. For hydrothermal conversion of glycerol into lactic acid by homogeneous catalysis, NaOH and KOH catalysts were used. And for hydrothermal glycerol lactic acid by heterogeneous catalysis, Cu/SiO2 catalyst was used. Initial glycerol concentration (0.51-17.1 M), temperature (160-280 ÂC), pressure (2-43 bar), water/glycerol volumetric ratio (0.8 to 31), catalyst/glycerol molar ratio (0.01 to 1.02) and total reaction time (3-4 hours) were the variables studied with temperature and water/glycerol volumetric ratio having the major influence. In addition, a first-order kinetic model for glycerol concentration versus time was developed and verified experimentally under conditions with different temperatures. Comparing the results obtained from hydrothermal conversion by homogeneous and heterogeneous catalysis, it was observed that KOH was catalyst with the best performance. The highest yield obtained was 87.5% at 220 ÂC and 28.8 bar, after 3 h, from a solution water/glycerol volumetric ratio equal to 0.8 and KOH/glycerol molar ratio equal to 0.03. From this result, hydrothermal process can be seen as a promising method to add value to glycerol.
publishDate 2016
dc.date.issued.fl_str_mv 2016-01-29
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
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status_str publishedVersion
format doctoralThesis
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dc.publisher.program.fl_str_mv Programa de PÃs-GraduaÃÃo em Engenharia QuÃmica
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dc.publisher.country.fl_str_mv BR
publisher.none.fl_str_mv Universidade Federal do CearÃ
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