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
Autor(a) principal: | |
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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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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 |
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por |
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info:eu-repo/semantics/openAccess |
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openAccess |
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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 |
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Universidade Federal de Uberlândia (UFU) |
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UFU |
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UFU |
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Repositório Institucional da UFU |
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Repositório Institucional da UFU |
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Repositório Institucional da UFU - Universidade Federal de Uberlândia (UFU) |
repository.mail.fl_str_mv |
diinf@dirbi.ufu.br |
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1813711308801966080 |