Desenvolvimento de um fotômetro multi LED NIR para determinação de metano em gás natural
Autor(a) principal: | |
---|---|
Data de Publicação: | 2019 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Biblioteca Digital de Teses e Dissertações da UFPB |
Texto Completo: | https://repositorio.ufpb.br/jspui/handle/123456789/19299 |
Resumo: | Natural gas (NG) is a fossil fuel considered clean due to the lower emission of polluting gases when compared to coal or petroleum. NG can be used as an input or raw material, being well known for its versatility and efficiency. As it is present in residences, commercial establishments, industries and in the transportation, the necessity and the demand for the quality control of this type of fuel grows, mainly with respect to its composition, since, as influences occur in its calorific power. The composition of NG marketed in Brazil follows a standard of compliance determined by the Agência National de Petróleo, Gás Natural e Biodiesel (ANP), guaranteeing the energy efficiency of this fuel. Thus, this work proposes the development of a multi LED NIR photometer that indicates the composition of the natural gas with respect to its major component (methane). Therefore, an automatic system was used for the preparation of gas mixtures and evaluation of the NIR region, by means of the multivariate calibration associated with a bench and a miniaturized NIR spectrophotometer. In the first step, using the bench equipment, the iPLS, PLS and GA - MLR models obtained RMSEP values of 2.08, 1.45 and 1.00 % mol mol-1 and correlation coefficient (r) equal to 0.97, 0.90 and 0.88, for determination of methane, ethane and propane, respectively. In the second part, a miniaturized NIR spectrophotometer was evaluated for the same purpose in natural gas samples and in a biogas sample. For methane, ethane and propane, the metrics SW - MLR, GA - MLR and iPLS, provided RMSEP values of 3.38, 3.05 and 1.58 % mol mol-1 with r values of 0.97, respectively. Therefore, the construction of the photometer in the NIR region converged to LEDs at wavelengths in 2020, 2140, 2200 and 2350 nm. The detector used was the PbS and the control of the photometer was performed via Arduino board with a program written in Matlab.The LED with the highest intensity and sensitivity to hydrocarbons was 2350 nm, and this one was used to determination of methane in gas mixtures with ethane and propane. The photometer presented linearity in the absorbances obtained as a function of the methane concentration in the gaseous mixtures with the other hydrocarbons, with R2 equal to 0.9852, in the calibration range of 50-100 % mol mol-1 .The ANOVA results showed significance in the regression without lack of fit with LOD and LOQ values of 2.92 and 8.84 % mol mol-1 , respectively. In certified and commercial samples prediction, the methodology did not present statistically significant differences with the reference methodology (GC), obtaining a confidence limit of ± 2.85 % mol mol-1 .The methodology with the photometer was also validated by means of a recovery test, in which a mean and standard deviation of 100.2 ± 0.9 were obtained for tests involving certified and commercial samples. |
id |
UFPB_d338b5bca93a470e258040bc9c835391 |
---|---|
oai_identifier_str |
oai:repositorio.ufpb.br:123456789/19299 |
network_acronym_str |
UFPB |
network_name_str |
Biblioteca Digital de Teses e Dissertações da UFPB |
repository_id_str |
|
spelling |
Desenvolvimento de um fotômetro multi LED NIR para determinação de metano em gás naturalGás naturalSistema automático para preparação de misturasEspectrometria NIRCalibração multivariadaFotômetro à base de LEDsNatural gasAutomatic system for preparation of gas mixturesNIR spectrometryMultivariate calibrationPhotometer based on LEDsCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICANatural gas (NG) is a fossil fuel considered clean due to the lower emission of polluting gases when compared to coal or petroleum. NG can be used as an input or raw material, being well known for its versatility and efficiency. As it is present in residences, commercial establishments, industries and in the transportation, the necessity and the demand for the quality control of this type of fuel grows, mainly with respect to its composition, since, as influences occur in its calorific power. The composition of NG marketed in Brazil follows a standard of compliance determined by the Agência National de Petróleo, Gás Natural e Biodiesel (ANP), guaranteeing the energy efficiency of this fuel. Thus, this work proposes the development of a multi LED NIR photometer that indicates the composition of the natural gas with respect to its major component (methane). Therefore, an automatic system was used for the preparation of gas mixtures and evaluation of the NIR region, by means of the multivariate calibration associated with a bench and a miniaturized NIR spectrophotometer. In the first step, using the bench equipment, the iPLS, PLS and GA - MLR models obtained RMSEP values of 2.08, 1.45 and 1.00 % mol mol-1 and correlation coefficient (r) equal to 0.97, 0.90 and 0.88, for determination of methane, ethane and propane, respectively. In the second part, a miniaturized NIR spectrophotometer was evaluated for the same purpose in natural gas samples and in a biogas sample. For methane, ethane and propane, the metrics SW - MLR, GA - MLR and iPLS, provided RMSEP values of 3.38, 3.05 and 1.58 % mol mol-1 with r values of 0.97, respectively. Therefore, the construction of the photometer in the NIR region converged to LEDs at wavelengths in 2020, 2140, 2200 and 2350 nm. The detector used was the PbS and the control of the photometer was performed via Arduino board with a program written in Matlab.The LED with the highest intensity and sensitivity to hydrocarbons was 2350 nm, and this one was used to determination of methane in gas mixtures with ethane and propane. The photometer presented linearity in the absorbances obtained as a function of the methane concentration in the gaseous mixtures with the other hydrocarbons, with R2 equal to 0.9852, in the calibration range of 50-100 % mol mol-1 .The ANOVA results showed significance in the regression without lack of fit with LOD and LOQ values of 2.92 and 8.84 % mol mol-1 , respectively. In certified and commercial samples prediction, the methodology did not present statistically significant differences with the reference methodology (GC), obtaining a confidence limit of ± 2.85 % mol mol-1 .The methodology with the photometer was also validated by means of a recovery test, in which a mean and standard deviation of 100.2 ± 0.9 were obtained for tests involving certified and commercial samples.Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqO gás natural (GN) é um combustível fóssil considerado limpo devido a menor emissão de gases poluentes quando comparado ao carvão ou petróleo. O GN pode ser usado como insumo ou matéria-prima, sendo bastante conhecido por sua versatilidade e eficiência. Como está presente em residências, estabelecimentos comerciais, indústrias e nos transportes, cresce a necessidade e a demanda pelo controle da qualidade desse tipo de combustível, principalmente no que diz respeito a sua composição, visto que, ocorrem influências em seu poder calorífico. A composição do GN comercializado no Brasil segue um padrão de conformidade determinado pela Agência Nacional do Petróleo, Gás Natural e Biocombustíveis (ANP), garantindo a eficiência energética desse combustível. Dessa forma, este trabalho propõe o desenvolvimento de um fotômetro multi LED NIR que indique a composição do gás natural no que diz respeito ao seu componente majoritário (metano). Sendo assim, utilizou-se um sistema automático para a preparação de misturas gasosas e avaliação da região NIR, por meio da calibração multivariada associada a um espectrofotômetro NIR de bancada e um miniaturizado. Na primeira etapa, utilizando o equipamento de bancada, os modelos iPLS, PLS e GA – MLR obtiveram valores de RMSEP 2,08, 1,45 e 1,00 % mol mol-1 e de coeficiente de correlação (r) iguais a 0,97, 0,90 e 0,88, para determinação de metano, etano e propano, respectivamente. Na segunda parte, um espectrofotômetro NIR miniaturizado foi avaliado para mesma finalidade em amostras de gás natural e em uma amostra de biogás. Para metano, etano e propano, as métricas SW – MLR, GA – MLR e iPLS, forneceram valores de RMSEP de 3,38, 3,05 e 1,58 % mol mol-1 com r iguais a 0,97, respectivamente. Por conseguinte, a construção do fotômetro na região NIR convergiu para LEDs nos comprimentos de onda em 2020, 2140, 2200 e 2350 nm. O detector usado foi o PbS e o controle do fotômetro foi realizado via placa Arduino com um programa escrito em Matlab. O LED com maior intensidade e sensibilidade aos hidrocarbonetos foi o de 2350 nm, e este foi usado para determinação de metano em misturas gasosas com etano e propano. O fotômetro apresentou linearidade nas absorbâncias obtidas em função da concentração de metano nas misturas gasosas com os demais hidrocarbonetos, com R2 igual a 0,9852, na faixa de calibração de 50-100 % mol mol-1 . Os resultados da ANOVA mostraram significância na regressão sem falta de ajuste com valores de LOD e LOQ de 2,92 e 8,84 % mol mol-1 , respectivamente. Na predição em amostras certificadas e comerciais a metodologia não apresentou diferenças estatisticamente siginificativas com a metodologia de referência (GC), obtendo limite de confiança de ± 2,85 % mol mol-1 . A metodologia com o fotômetro também foi validada também por meio de um teste de recuperação, em que foi obtido média e desvio padrão igual a 100,2 ± 0,9, para ensaios envolvendo amostras certificadas e comerciais.Universidade Federal da ParaíbaBrasilQuímicaPrograma de Pós-Graduação em QuímicaUFPBAraújo, Mário César Ugulino dehttp://lattes.cnpq.br/7281739070942782Soares, Sófacles Figueredo Carreirohttp://lattes.cnpq.br/7653207334385666Barbosa, Mayara Ferreira2021-02-07T20:31:56Z2020-04-102021-02-07T20:31:56Z2019-04-10info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesishttps://repositorio.ufpb.br/jspui/handle/123456789/19299porhttp://creativecommons.org/licenses/by-nd/3.0/br/info:eu-repo/semantics/embargoedAccessreponame:Biblioteca Digital de Teses e Dissertações da UFPBinstname:Universidade Federal da Paraíba (UFPB)instacron:UFPB2021-08-16T14:36:19Zoai:repositorio.ufpb.br:123456789/19299Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufpb.br/PUBhttp://tede.biblioteca.ufpb.br:8080/oai/requestdiretoria@ufpb.br|| diretoria@ufpb.bropendoar:2021-08-16T14:36:19Biblioteca Digital de Teses e Dissertações da UFPB - Universidade Federal da Paraíba (UFPB)false |
dc.title.none.fl_str_mv |
Desenvolvimento de um fotômetro multi LED NIR para determinação de metano em gás natural |
title |
Desenvolvimento de um fotômetro multi LED NIR para determinação de metano em gás natural |
spellingShingle |
Desenvolvimento de um fotômetro multi LED NIR para determinação de metano em gás natural Barbosa, Mayara Ferreira Gás natural Sistema automático para preparação de misturas Espectrometria NIR Calibração multivariada Fotômetro à base de LEDs Natural gas Automatic system for preparation of gas mixtures NIR spectrometry Multivariate calibration Photometer based on LEDs CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Desenvolvimento de um fotômetro multi LED NIR para determinação de metano em gás natural |
title_full |
Desenvolvimento de um fotômetro multi LED NIR para determinação de metano em gás natural |
title_fullStr |
Desenvolvimento de um fotômetro multi LED NIR para determinação de metano em gás natural |
title_full_unstemmed |
Desenvolvimento de um fotômetro multi LED NIR para determinação de metano em gás natural |
title_sort |
Desenvolvimento de um fotômetro multi LED NIR para determinação de metano em gás natural |
author |
Barbosa, Mayara Ferreira |
author_facet |
Barbosa, Mayara Ferreira |
author_role |
author |
dc.contributor.none.fl_str_mv |
Araújo, Mário César Ugulino de http://lattes.cnpq.br/7281739070942782 Soares, Sófacles Figueredo Carreiro http://lattes.cnpq.br/7653207334385666 |
dc.contributor.author.fl_str_mv |
Barbosa, Mayara Ferreira |
dc.subject.por.fl_str_mv |
Gás natural Sistema automático para preparação de misturas Espectrometria NIR Calibração multivariada Fotômetro à base de LEDs Natural gas Automatic system for preparation of gas mixtures NIR spectrometry Multivariate calibration Photometer based on LEDs CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
Gás natural Sistema automático para preparação de misturas Espectrometria NIR Calibração multivariada Fotômetro à base de LEDs Natural gas Automatic system for preparation of gas mixtures NIR spectrometry Multivariate calibration Photometer based on LEDs CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
Natural gas (NG) is a fossil fuel considered clean due to the lower emission of polluting gases when compared to coal or petroleum. NG can be used as an input or raw material, being well known for its versatility and efficiency. As it is present in residences, commercial establishments, industries and in the transportation, the necessity and the demand for the quality control of this type of fuel grows, mainly with respect to its composition, since, as influences occur in its calorific power. The composition of NG marketed in Brazil follows a standard of compliance determined by the Agência National de Petróleo, Gás Natural e Biodiesel (ANP), guaranteeing the energy efficiency of this fuel. Thus, this work proposes the development of a multi LED NIR photometer that indicates the composition of the natural gas with respect to its major component (methane). Therefore, an automatic system was used for the preparation of gas mixtures and evaluation of the NIR region, by means of the multivariate calibration associated with a bench and a miniaturized NIR spectrophotometer. In the first step, using the bench equipment, the iPLS, PLS and GA - MLR models obtained RMSEP values of 2.08, 1.45 and 1.00 % mol mol-1 and correlation coefficient (r) equal to 0.97, 0.90 and 0.88, for determination of methane, ethane and propane, respectively. In the second part, a miniaturized NIR spectrophotometer was evaluated for the same purpose in natural gas samples and in a biogas sample. For methane, ethane and propane, the metrics SW - MLR, GA - MLR and iPLS, provided RMSEP values of 3.38, 3.05 and 1.58 % mol mol-1 with r values of 0.97, respectively. Therefore, the construction of the photometer in the NIR region converged to LEDs at wavelengths in 2020, 2140, 2200 and 2350 nm. The detector used was the PbS and the control of the photometer was performed via Arduino board with a program written in Matlab.The LED with the highest intensity and sensitivity to hydrocarbons was 2350 nm, and this one was used to determination of methane in gas mixtures with ethane and propane. The photometer presented linearity in the absorbances obtained as a function of the methane concentration in the gaseous mixtures with the other hydrocarbons, with R2 equal to 0.9852, in the calibration range of 50-100 % mol mol-1 .The ANOVA results showed significance in the regression without lack of fit with LOD and LOQ values of 2.92 and 8.84 % mol mol-1 , respectively. In certified and commercial samples prediction, the methodology did not present statistically significant differences with the reference methodology (GC), obtaining a confidence limit of ± 2.85 % mol mol-1 .The methodology with the photometer was also validated by means of a recovery test, in which a mean and standard deviation of 100.2 ± 0.9 were obtained for tests involving certified and commercial samples. |
publishDate |
2019 |
dc.date.none.fl_str_mv |
2019-04-10 2020-04-10 2021-02-07T20:31:56Z 2021-02-07T20:31:56Z |
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 |
https://repositorio.ufpb.br/jspui/handle/123456789/19299 |
url |
https://repositorio.ufpb.br/jspui/handle/123456789/19299 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.rights.driver.fl_str_mv |
http://creativecommons.org/licenses/by-nd/3.0/br/ info:eu-repo/semantics/embargoedAccess |
rights_invalid_str_mv |
http://creativecommons.org/licenses/by-nd/3.0/br/ |
eu_rights_str_mv |
embargoedAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal da Paraíba Brasil Química Programa de Pós-Graduação em Química UFPB |
publisher.none.fl_str_mv |
Universidade Federal da Paraíba Brasil Química Programa de Pós-Graduação em Química UFPB |
dc.source.none.fl_str_mv |
reponame:Biblioteca Digital de Teses e Dissertações da UFPB instname:Universidade Federal da Paraíba (UFPB) instacron:UFPB |
instname_str |
Universidade Federal da Paraíba (UFPB) |
instacron_str |
UFPB |
institution |
UFPB |
reponame_str |
Biblioteca Digital de Teses e Dissertações da UFPB |
collection |
Biblioteca Digital de Teses e Dissertações da UFPB |
repository.name.fl_str_mv |
Biblioteca Digital de Teses e Dissertações da UFPB - Universidade Federal da Paraíba (UFPB) |
repository.mail.fl_str_mv |
diretoria@ufpb.br|| diretoria@ufpb.br |
_version_ |
1801843024900128768 |