Controle de qualidade de biodieseis de macaúba e algodão e suas misturas com o diesel usando espectrometria no infravermelho médio e cartas de controle multivariadas

Detalhes bibliográficos
Autor(a) principal: Guimarães, Eloiza
Data de Publicação: 2018
Tipo de documento: Tese
Idioma: por
Título da fonte: Repositório Institucional da UFU
Texto Completo: https://repositorio.ufu.br/handle/123456789/21006
http://dx.doi.org/10.14393/ufu.di.2018.258
Resumo: The Law No. 13.033/2014 establishes the addition of 7 ± 0.5% (v/v) of biodiesel to the diesel used in the road system and prohibits the addition of vegetable oils or any solvents to this mixture. However, there are cases of irregular addition of vegetable and/or waste oils in diesel, mainly due to the low cost of these raw materials when compared to the final or contaminated product during transportation and storage. Thus, analyzes are necessary to provide immediate and efficient responses in order to ensure the quality of the marketed fuels. In this sense, the present study proposed the quality monitoring of biodiesel/diesel blends (7% biodiesel and 93% diesel) through the use of the Medium Infrared Spectrometry associated with Multivariate Control Charts based on the liquid analytical signal (NAS). Biodiesel was produced from macaúba (acrocomia aculeate) and cotton oils using methanol and ethanol. For each model, three charts were developed: the NAS Chart, which corresponds to the analyte of interest (in this case biodiesel); the interfering chart, related to the contributions of other components in the sample (diesel); and the waste chart, corresponding to non-systematic variation in spectra (instrumental noise). A total of 1508 samples were used for the calibration and validation of the six models (ethyl and cotton biodiesel, macaúba almond (acrocomia aculeate) methyl biodiesel, macaúba mesocarp (acrocomia aculeate) methyl and biodiesel, and also commercial B7 biodiesel). At the calibration stage, 103 samples were used within the quality specifications, these samples were used to establish the statistical limits for each chart. The validation step was carried out with samples within and out of the quality specifications (1405 samples). The validation with non-standard quality samples was carried out in two ways: in relation to the biodiesel content in diesel and the presence of adulterants in biodiesel, diesel and blend. The presence of adulterants was due to the partial replacement of biodiesel by soybean, corn and residual oils; the partial replacement of diesel by lubricating oil, kerosene and gasoline; and by direct addition of the adulterants mentioned in the biodiesel/diesel blend (B7) in the range of 3.5 to 43.5% (v/v) corresponding to an adulteration range of 0.2 to 30% (v/v) in the blend. Thus, it was possible to separate the conforming and non-conforming samples, both regarding the biodiesel content in diesel and the presence of adulterants, since the samples within the specifications were within the established limits, and the samples out of the specifications have exceeded the limit in least one of the charts. Thus, the results have showed that the method described in this study is a viable, efficient and fast alternative to the biofuel quality control.
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spelling Controle de qualidade de biodieseis de macaúba e algodão e suas misturas com o diesel usando espectrometria no infravermelho médio e cartas de controle multivariadasQuality control of macaúba and cotton biodiesels and their diesel blends usind MID Spectrometry and Multivariate Control ChartsEspectrometria MIRB7DieselMIR SpectrometryMultivariate Control ChartsChemometricsCartas de Controle MultivariadasQuimiometriaCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAThe Law No. 13.033/2014 establishes the addition of 7 ± 0.5% (v/v) of biodiesel to the diesel used in the road system and prohibits the addition of vegetable oils or any solvents to this mixture. However, there are cases of irregular addition of vegetable and/or waste oils in diesel, mainly due to the low cost of these raw materials when compared to the final or contaminated product during transportation and storage. Thus, analyzes are necessary to provide immediate and efficient responses in order to ensure the quality of the marketed fuels. In this sense, the present study proposed the quality monitoring of biodiesel/diesel blends (7% biodiesel and 93% diesel) through the use of the Medium Infrared Spectrometry associated with Multivariate Control Charts based on the liquid analytical signal (NAS). Biodiesel was produced from macaúba (acrocomia aculeate) and cotton oils using methanol and ethanol. For each model, three charts were developed: the NAS Chart, which corresponds to the analyte of interest (in this case biodiesel); the interfering chart, related to the contributions of other components in the sample (diesel); and the waste chart, corresponding to non-systematic variation in spectra (instrumental noise). A total of 1508 samples were used for the calibration and validation of the six models (ethyl and cotton biodiesel, macaúba almond (acrocomia aculeate) methyl biodiesel, macaúba mesocarp (acrocomia aculeate) methyl and biodiesel, and also commercial B7 biodiesel). At the calibration stage, 103 samples were used within the quality specifications, these samples were used to establish the statistical limits for each chart. The validation step was carried out with samples within and out of the quality specifications (1405 samples). The validation with non-standard quality samples was carried out in two ways: in relation to the biodiesel content in diesel and the presence of adulterants in biodiesel, diesel and blend. The presence of adulterants was due to the partial replacement of biodiesel by soybean, corn and residual oils; the partial replacement of diesel by lubricating oil, kerosene and gasoline; and by direct addition of the adulterants mentioned in the biodiesel/diesel blend (B7) in the range of 3.5 to 43.5% (v/v) corresponding to an adulteration range of 0.2 to 30% (v/v) in the blend. Thus, it was possible to separate the conforming and non-conforming samples, both regarding the biodiesel content in diesel and the presence of adulterants, since the samples within the specifications were within the established limits, and the samples out of the specifications have exceeded the limit in least one of the charts. Thus, the results have showed that the method described in this study is a viable, efficient and fast alternative to the biofuel quality control.CNPq - Conselho Nacional de Desenvolvimento Científico e TecnológicoTese (Doutorado)A Lei nº 13.033/2014 estabelece a adição de 7 ± 0,5% (v/v) de biodiesel ao óleo diesel utilizado no sistema viário e proíbe a adição de óleos vegetais ou quaisquer solventes nesta mistura. No entanto, há casos de adição irregular de óleos vegetais e/ou residuais no diesel devido, principalmente, ao baixo custo destas matérias-primas em comparação com o produto final ou contaminado durante seu transporte e armazenamento. Assim, são necessárias análises que forneçam respostas imediatas e eficientes para garantir a qualidade dos combustíveis comercializados. Nesse sentido, o presente trabalho propõe o monitoramento da qualidade das misturas biodiesel/diesel (7% de biodiesel e 93% de diesel) usando a Espectrometria no Infravermelho Médio associada a Cartas de Controle Multivariadas baseadas no sinal analítico líquido (NAS). Os biodieseis foram produzidos a partir de óleos de macaúba e algodão usando metanol e etanol. Para cada modelo, foram desenvolvidas três cartas (gráficos): a Carta NAS, que corresponde ao analito de interesse (nesse caso o biodiesel), a carta interferente, relacionadas às contribuições de outros componentes na amostra (diesel), e a carta resíduo correspondendo à variação não sistemática nos espectros (ruído instrumental). Foram analisadas 1508 amostras utilizadas na calibração e validação de seis modelos (biodieseis etílicos e metílicos de algodão, biodieseis metílicos da amêndoa da macaúba, biodieseis metílicos e etílicos do mesocarpo da macaúba, e também de B7 comercial). Na etapa de calibração foram usadas 103 amostras dentro das especificações de qualidade, amostras estas usadas para estabelecerem os limites estatísticos para cada carta. A etapa de validação se deu com amostras dentro e fora das especificações de qualidade (1405 amostras). A validação com amostras fora dos padrões de qualidade foi feita de duas maneiras: em relação ao teor de biodiesel no diesel e à presença de adulterantes no biodiesel, no diesel e na mistura. A presença de adulterantes se deu por substituição parcial do biodiesel por óleos de soja, milho e residual, substituição parcial do diesel por óleo lubrificante, querosene e gasolina e por adição direta dos adulterantes citados na mistura biodiesel/diesel (B7) na faixa de 3,5 a 43,5% (v/v) correspondendo a uma faixa de adulteração de 0,2 a 30% (v/v) na mistura. Assim, foi possível separar as amostras conformes e não conformes tanto em relação ao teor de biodiesel no diesel quanto à presença de adulterantes, uma vez que as amostras dentro das especificações ficaram dentro dos limites estabelecidos e as amostras fora das especificações saíram do limite em pelo menos uma das cartas. Desta maneira, os resultados mostraram que o método descrito neste trabalho é uma alternativa viável, eficiente e rápida no controle de qualidade de biocombustível.Universidade Federal de UberlândiaBrasilPrograma de Pós-graduação em QuímicaBorges Neto, WaldomiroEiras, Sebastião de Paula,Pinto, Frederico GarciaTrovó, Alam Gustavo,Pereira, Luciano de AlmeidaGuimarães, Eloiza2018-03-28T12:25:28Z2018-03-28T12:25:28Z2018-02-23info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfGUIMARÃES, Eloiza. Controle de qualidade de biodieseis de macaúba e algodão e suas misturas com o diesel usando espectrometria no infravermelho médio e cartas de controle multivariadas. 2018. 95 f. Tese (Doutorado em Química) - Universidade Federal de Uberlândia, Uberlândia, 2018.https://repositorio.ufu.br/handle/123456789/21006http://dx.doi.org/10.14393/ufu.di.2018.258porinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFUinstname:Universidade Federal de Uberlândia (UFU)instacron:UFU2021-09-14T19:55:08Zoai:repositorio.ufu.br:123456789/21006Repositório InstitucionalONGhttp://repositorio.ufu.br/oai/requestdiinf@dirbi.ufu.bropendoar:2021-09-14T19:55:08Repositório Institucional da UFU - Universidade Federal de Uberlândia (UFU)false
dc.title.none.fl_str_mv Controle de qualidade de biodieseis de macaúba e algodão e suas misturas com o diesel usando espectrometria no infravermelho médio e cartas de controle multivariadas
Quality control of macaúba and cotton biodiesels and their diesel blends usind MID Spectrometry and Multivariate Control Charts
title Controle de qualidade de biodieseis de macaúba e algodão e suas misturas com o diesel usando espectrometria no infravermelho médio e cartas de controle multivariadas
spellingShingle Controle de qualidade de biodieseis de macaúba e algodão e suas misturas com o diesel usando espectrometria no infravermelho médio e cartas de controle multivariadas
Guimarães, Eloiza
Espectrometria MIR
B7
Diesel
MIR Spectrometry
Multivariate Control Charts
Chemometrics
Cartas de Controle Multivariadas
Quimiometria
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
title_short Controle de qualidade de biodieseis de macaúba e algodão e suas misturas com o diesel usando espectrometria no infravermelho médio e cartas de controle multivariadas
title_full Controle de qualidade de biodieseis de macaúba e algodão e suas misturas com o diesel usando espectrometria no infravermelho médio e cartas de controle multivariadas
title_fullStr Controle de qualidade de biodieseis de macaúba e algodão e suas misturas com o diesel usando espectrometria no infravermelho médio e cartas de controle multivariadas
title_full_unstemmed Controle de qualidade de biodieseis de macaúba e algodão e suas misturas com o diesel usando espectrometria no infravermelho médio e cartas de controle multivariadas
title_sort Controle de qualidade de biodieseis de macaúba e algodão e suas misturas com o diesel usando espectrometria no infravermelho médio e cartas de controle multivariadas
author Guimarães, Eloiza
author_facet Guimarães, Eloiza
author_role author
dc.contributor.none.fl_str_mv Borges Neto, Waldomiro
Eiras, Sebastião de Paula,
Pinto, Frederico Garcia
Trovó, Alam Gustavo,
Pereira, Luciano de Almeida
dc.contributor.author.fl_str_mv Guimarães, Eloiza
dc.subject.por.fl_str_mv Espectrometria MIR
B7
Diesel
MIR Spectrometry
Multivariate Control Charts
Chemometrics
Cartas de Controle Multivariadas
Quimiometria
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
topic Espectrometria MIR
B7
Diesel
MIR Spectrometry
Multivariate Control Charts
Chemometrics
Cartas de Controle Multivariadas
Quimiometria
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
description The Law No. 13.033/2014 establishes the addition of 7 ± 0.5% (v/v) of biodiesel to the diesel used in the road system and prohibits the addition of vegetable oils or any solvents to this mixture. However, there are cases of irregular addition of vegetable and/or waste oils in diesel, mainly due to the low cost of these raw materials when compared to the final or contaminated product during transportation and storage. Thus, analyzes are necessary to provide immediate and efficient responses in order to ensure the quality of the marketed fuels. In this sense, the present study proposed the quality monitoring of biodiesel/diesel blends (7% biodiesel and 93% diesel) through the use of the Medium Infrared Spectrometry associated with Multivariate Control Charts based on the liquid analytical signal (NAS). Biodiesel was produced from macaúba (acrocomia aculeate) and cotton oils using methanol and ethanol. For each model, three charts were developed: the NAS Chart, which corresponds to the analyte of interest (in this case biodiesel); the interfering chart, related to the contributions of other components in the sample (diesel); and the waste chart, corresponding to non-systematic variation in spectra (instrumental noise). A total of 1508 samples were used for the calibration and validation of the six models (ethyl and cotton biodiesel, macaúba almond (acrocomia aculeate) methyl biodiesel, macaúba mesocarp (acrocomia aculeate) methyl and biodiesel, and also commercial B7 biodiesel). At the calibration stage, 103 samples were used within the quality specifications, these samples were used to establish the statistical limits for each chart. The validation step was carried out with samples within and out of the quality specifications (1405 samples). The validation with non-standard quality samples was carried out in two ways: in relation to the biodiesel content in diesel and the presence of adulterants in biodiesel, diesel and blend. The presence of adulterants was due to the partial replacement of biodiesel by soybean, corn and residual oils; the partial replacement of diesel by lubricating oil, kerosene and gasoline; and by direct addition of the adulterants mentioned in the biodiesel/diesel blend (B7) in the range of 3.5 to 43.5% (v/v) corresponding to an adulteration range of 0.2 to 30% (v/v) in the blend. Thus, it was possible to separate the conforming and non-conforming samples, both regarding the biodiesel content in diesel and the presence of adulterants, since the samples within the specifications were within the established limits, and the samples out of the specifications have exceeded the limit in least one of the charts. Thus, the results have showed that the method described in this study is a viable, efficient and fast alternative to the biofuel quality control.
publishDate 2018
dc.date.none.fl_str_mv 2018-03-28T12:25:28Z
2018-03-28T12:25:28Z
2018-02-23
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/doctoralThesis
format doctoralThesis
status_str publishedVersion
dc.identifier.uri.fl_str_mv GUIMARÃES, Eloiza. Controle de qualidade de biodieseis de macaúba e algodão e suas misturas com o diesel usando espectrometria no infravermelho médio e cartas de controle multivariadas. 2018. 95 f. Tese (Doutorado em Química) - Universidade Federal de Uberlândia, Uberlândia, 2018.
https://repositorio.ufu.br/handle/123456789/21006
http://dx.doi.org/10.14393/ufu.di.2018.258
identifier_str_mv GUIMARÃES, Eloiza. Controle de qualidade de biodieseis de macaúba e algodão e suas misturas com o diesel usando espectrometria no infravermelho médio e cartas de controle multivariadas. 2018. 95 f. Tese (Doutorado em Química) - Universidade Federal de Uberlândia, Uberlândia, 2018.
url https://repositorio.ufu.br/handle/123456789/21006
http://dx.doi.org/10.14393/ufu.di.2018.258
dc.language.iso.fl_str_mv por
language por
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Universidade Federal de Uberlândia
Brasil
Programa de Pós-graduação em Química
publisher.none.fl_str_mv Universidade Federal de Uberlândia
Brasil
Programa de Pós-graduação em Química
dc.source.none.fl_str_mv reponame:Repositório Institucional da UFU
instname:Universidade Federal de Uberlândia (UFU)
instacron:UFU
instname_str Universidade Federal de Uberlândia (UFU)
instacron_str UFU
institution UFU
reponame_str Repositório Institucional da UFU
collection Repositório Institucional da UFU
repository.name.fl_str_mv Repositório Institucional da UFU - Universidade Federal de Uberlândia (UFU)
repository.mail.fl_str_mv diinf@dirbi.ufu.br
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