Pirólise térmica e catalítica de polímeros pós-consumo sobre catalisadores tipo AIMCM-4

Detalhes bibliográficos
Ano de defesa: 2015
Autor(a) principal: Santos, Tiago Gomes dos
Orientador(a): Souza, Marcelo José Barros de
Banca de defesa: Não Informado pela instituição
Tipo de documento: Dissertação
Tipo de acesso: Acesso aberto
Idioma: por
Instituição de defesa: Não Informado pela instituição
Programa de Pós-Graduação: Pós-Graduação em Engenharia Química
Departamento: Não Informado pela instituição
País: Não Informado pela instituição
Palavras-chave em Português:
Palavras-chave em Inglês:
Área do conhecimento CNPq:
Link de acesso: http://ri.ufs.br/jspui/handle/riufs/17052
Resumo: Due to the increase in the production of post-consumer plastic waste, the improper disposal and long-term degradation of this material, Brazil has faced serious environmental impacts. In order to avoid a worsening situation, the catalytic pyrolysis has become a very attractive process within the chemical treatment of post-consumer polymers, reducing the operating limitations of thermal pyrolysis, thus promoting processes with lower energy expenditure and selectively generating product high added value. Thus, in the present work were synthesized by hydrothermal method, a series of acids with heterogeneous catalysts mesoporous AlMCM-48 type cubic structure containing different ratios of Si/Al (50, 100, 150) for application to the pyrolysis reaction. The syntheses were performed over a period of three days with the pH between 11-13 and a highly polymerized silica source, ie, the ratio CTMABr/TEOS 0.59. The catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), thermal analysis via TG/DTG and nitrogen adsorption. Through these characterization techniques it was observed that it was possible to develop a series of catalysts with high cubic mesoporous ordering equivalent and thermally stable thermogravimetric profile, surface area and size relatively high pore volume and had agglomerated spherical morphology. The thermal and catalytic pyrolysis reactions were performed using high density polyethylene (HDPE) and polypropylene (PP), where a comparative analysis of the thermal and catalytic pyrolysis catalysts on different AlMCM-48 type was performed. Through the conversion curves it was possible to observe and compare the operating conditions to obtain a given conversion as a function of the temperature correlated with the results obtained by kinetic Isoconversional methods proposed by Flynn-Wall-Ozawa (FWO) and Vyazovkin, may analyze the influence of AlMCM-48 on the activation energy (Ea) of pyrolysis reactions. The results showed a remarkable effect of the catalyst to accelerate the process of pyrolysis. In the catalytic pyrolysis of HDPE that the catalyst was more efficiently presented the Si/Al = 50 ratio, with a yield of 77.31 %, and the PP to the most efficient catalyst was the Si/Al = 100 ratio, who presented a yield of 75.84 %. As for the kinetics, both methods have been effective isoconversão to determine Ea HDPE and PP. The method Vyazovkin exhibited lower activation energies, an average difference 87.220 kJ.mol-1 for HDPE and 111.811 kJ.mol-1 to PP compared with the FWO method. The Ea determined by both methods showed the same behavior on the dependence of conversion and Ea(HDPE) < Ea(PP). In this work, efficient kinetic results were obtained, compared to pyrolysis reactions involving the HDPE and PP over AlMCM-48 catalysts, providing a basis for the potential benefit of the chemical recycling of post-consumer polymers, potentially leading to an efficient process in terms of energy costs.
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spelling Santos, Tiago Gomes dosSouza, Marcelo José Barros deAraujo, Antonio Souza de2023-02-03T23:07:23Z2023-02-03T23:07:23Z2015-07-15SANTOS, Tiago Gomes dos. Pirólise térmica e catalítica de polímeros pós-consumo sobre catalisadores tipo AIMCM-4. 2015. 86 f. Dissertação (Mestrado em Engenharia Química) - Universidade Federal de Sergipe, São Cristóvão, 2015.http://ri.ufs.br/jspui/handle/riufs/17052Due to the increase in the production of post-consumer plastic waste, the improper disposal and long-term degradation of this material, Brazil has faced serious environmental impacts. In order to avoid a worsening situation, the catalytic pyrolysis has become a very attractive process within the chemical treatment of post-consumer polymers, reducing the operating limitations of thermal pyrolysis, thus promoting processes with lower energy expenditure and selectively generating product high added value. Thus, in the present work were synthesized by hydrothermal method, a series of acids with heterogeneous catalysts mesoporous AlMCM-48 type cubic structure containing different ratios of Si/Al (50, 100, 150) for application to the pyrolysis reaction. The syntheses were performed over a period of three days with the pH between 11-13 and a highly polymerized silica source, ie, the ratio CTMABr/TEOS 0.59. The catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), thermal analysis via TG/DTG and nitrogen adsorption. Through these characterization techniques it was observed that it was possible to develop a series of catalysts with high cubic mesoporous ordering equivalent and thermally stable thermogravimetric profile, surface area and size relatively high pore volume and had agglomerated spherical morphology. The thermal and catalytic pyrolysis reactions were performed using high density polyethylene (HDPE) and polypropylene (PP), where a comparative analysis of the thermal and catalytic pyrolysis catalysts on different AlMCM-48 type was performed. Through the conversion curves it was possible to observe and compare the operating conditions to obtain a given conversion as a function of the temperature correlated with the results obtained by kinetic Isoconversional methods proposed by Flynn-Wall-Ozawa (FWO) and Vyazovkin, may analyze the influence of AlMCM-48 on the activation energy (Ea) of pyrolysis reactions. The results showed a remarkable effect of the catalyst to accelerate the process of pyrolysis. In the catalytic pyrolysis of HDPE that the catalyst was more efficiently presented the Si/Al = 50 ratio, with a yield of 77.31 %, and the PP to the most efficient catalyst was the Si/Al = 100 ratio, who presented a yield of 75.84 %. As for the kinetics, both methods have been effective isoconversão to determine Ea HDPE and PP. The method Vyazovkin exhibited lower activation energies, an average difference 87.220 kJ.mol-1 for HDPE and 111.811 kJ.mol-1 to PP compared with the FWO method. The Ea determined by both methods showed the same behavior on the dependence of conversion and Ea(HDPE) < Ea(PP). In this work, efficient kinetic results were obtained, compared to pyrolysis reactions involving the HDPE and PP over AlMCM-48 catalysts, providing a basis for the potential benefit of the chemical recycling of post-consumer polymers, potentially leading to an efficient process in terms of energy costs.Devido ao aumento na produção de resíduos plásticos pós-consumo, no descarte inadequado e no longo período de degradação deste material, o Brasil tem enfrentado sérios impactos ambientais. A fim de evitar uma situação de agravamento, a pirólise catalítica tornou-se um processo bastante atrativo no âmbito do tratamento químico de polímeros pós-consumo, atenuando as limitações operacionais da pirólise térmica, promovendo assim processos com menores gastos energéticos e gerando seletivamente produtos de alto valor agregado. Assim, no presente trabalho de pesquisa foram sintetizados, pelo método hidrotérmico, uma série de catalisadores heterogêneos mesoporosos ácidos com estrutura cúbica tipo AlMCM-48 contendo diferentes razões de Si/Al (50, 100, 150) para aplicação na reação de pirólise. As sínteses foram realizadas durante um período de três dias com o pH entre 11-13 e uma fonte de sílica altamente polimerizada, ou seja, a razão CTMABr/TEOS de 0,59. Os catalisadores obtidos foram caracterizados por difração de raios-X (DRX), microscopia eletrônica de varredura (MEV), análise térmica via TG/DTG e adsorção de nitrogênio. Através destas técnicas de caracterização observou-se que foi possível desenvolver uma série de catalisadores com alto grau de ordenação cúbica mesoporosa, perfil termogravimétrico equivalente e termicamente estável, tamanhos de área superficial e volume de poros relativamente altos e apresentaram morfologia esférica e aglomerada. As reações de pirólise térmica e catalítica foram realizadas utilizando polietileno de alta densidade (PEAD) e polipropileno (PP), onde uma análise comparativa da pirólise térmica e catalítica sobre os diferentes catalisadores tipo AlMCM-48 foi realizada. Através das curvas de conversão foi possível observar e comparar as condições operacionais para se obter uma determinada conversão em função da temperatura, sendo os resultados obtidos correlacionados pelos métodos cinéticos de isoconversão propostos por Flynn-Wall-Ozawa (FWO) e Vyazovkin, podendo-se analisar a influência do AlMCM-48 na energia de ativação (Ea) das reações de pirólise. Os resultados obtidos mostraram um efeito notável do catalisador para acelerar os processos da pirólise. Na pirólise catalítica do PEAD o catalisador que apresentou mais eficiência foi o de razão Si/Al = 50, com um rendimento de 77,31 %, e quanto ao PP o catalisador mais eficiente foi o de razão Si/Al = 100, que apresentou um rendimento de 75,84 %. Quanto ao comportamento cinético, ambos os métodos de isoconversão se mostraram eficientes para determinar as Ea do PEAD e do PP. O método de Vyazovkin exibiu energias de ativação mais baixas, numa diferença média de 87,220 kJ.mol -1 para o PEAD e 111,811 kJ.mol1 para o PP, quando comparado com o método de FWO. As Ea determinadas por ambos os métodos mostraram o mesmo comportamento sobre a dependência da conversão e Ea(PEAD) < Ea(PP). Neste trabalho, foram obtidos resultados cinéticos eficientes, frente às reações de pirólise que envolveram o PEAD e o PP sobre os catalisadores AlMCM-48, fornecendo uma base para o benefício potencial da reciclagem química de polímeros pós-consumo, levando potencialmente a um processo eficaz, em termos de gastos de energia.Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqSão CristóvãoporEngenharia químicaProcessos químicosPirólisePolímerosCatalisadoresSíntese hidrotérmicaAlMCM-48Polímeros pós-consumoPirólise catalíticaMétodos de isoconversãoHydrothermal synthesisPost-consumer polymersCatalytic pyrolysisIsoconversional methodsENGENHARIAS::ENGENHARIA QUIMICAPirólise térmica e catalítica de polímeros pós-consumo sobre catalisadores tipo AIMCM-4Pyrolysis thermal and catalytic of post-consumer polymer over catalysts type AlMCM-48info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisPós-Graduação em Engenharia QuímicaUniversidade Federal de Sergipereponame:Repositório Institucional da UFSinstname:Universidade Federal de Sergipe (UFS)instacron:UFSinfo:eu-repo/semantics/openAccessLICENSElicense.txtlicense.txttext/plain; charset=utf-81475https://ri.ufs.br/jspui/bitstream/riufs/17052/1/license.txt098cbbf65c2c15e1fb2e49c5d306a44cMD51ORIGINALTIAGO_GOMES_SANTOS.pdfTIAGO_GOMES_SANTOS.pdfapplication/pdf6773655https://ri.ufs.br/jspui/bitstream/riufs/17052/2/TIAGO_GOMES_SANTOS.pdfab69db9ddacc24fa729b4254b8e1e07cMD52TEXTTIAGO_GOMES_SANTOS.pdf.txtTIAGO_GOMES_SANTOS.pdf.txtExtracted texttext/plain145366https://ri.ufs.br/jspui/bitstream/riufs/17052/3/TIAGO_GOMES_SANTOS.pdf.txt2eb3f12f8951af522a272ded36ba4592MD53THUMBNAILTIAGO_GOMES_SANTOS.pdf.jpgTIAGO_GOMES_SANTOS.pdf.jpgGenerated Thumbnailimage/jpeg1232https://ri.ufs.br/jspui/bitstream/riufs/17052/4/TIAGO_GOMES_SANTOS.pdf.jpg8c9951784e6bbdf0fc82ac1e839467e8MD54riufs/170522023-02-03 20:07:23.308oai:ufs.br:riufs/17052TElDRU7Dh0EgREUgRElTVFJJQlVJw4fDg08gTsODTy1FWENMVVNJVkEKCkNvbSBhIGFwcmVzZW50YcOnw6NvIGRlc3RhIGxpY2Vuw6dhLCB2b2PDqiAobyBhdXRvcihlcykgb3UgbyB0aXR1bGFyIGRvcyBkaXJlaXRvcyBkZSBhdXRvcikgY29uY2VkZSDDoCBVbml2ZXJzaWRhZGUgRmVkZXJhbCBkZSBTZXJnaXBlIG8gZGlyZWl0byBuw6NvLWV4Y2x1c2l2byBkZSByZXByb2R1emlyIHNldSB0cmFiYWxobyBubyBmb3JtYXRvIGVsZXRyw7RuaWNvLCBpbmNsdWluZG8gb3MgZm9ybWF0b3Mgw6F1ZGlvIG91IHbDrWRlby4KClZvY8OqIGNvbmNvcmRhIHF1ZSBhIFVuaXZlcnNpZGFkZSBGZWRlcmFsIGRlIFNlcmdpcGUgcG9kZSwgc2VtIGFsdGVyYXIgbyBjb250ZcO6ZG8sIHRyYW5zcG9yIHNldSB0cmFiYWxobyBwYXJhIHF1YWxxdWVyIG1laW8gb3UgZm9ybWF0byBwYXJhIGZpbnMgZGUgcHJlc2VydmHDp8Ojby4KClZvY8OqIHRhbWLDqW0gY29uY29yZGEgcXVlIGEgVW5pdmVyc2lkYWRlIEZlZGVyYWwgZGUgU2VyZ2lwZSBwb2RlIG1hbnRlciBtYWlzIGRlIHVtYSBjw7NwaWEgZGUgc2V1IHRyYWJhbGhvIHBhcmEgZmlucyBkZSBzZWd1cmFuw6dhLCBiYWNrLXVwIGUgcHJlc2VydmHDp8Ojby4KClZvY8OqIGRlY2xhcmEgcXVlIHNldSB0cmFiYWxobyDDqSBvcmlnaW5hbCBlIHF1ZSB2b2PDqiB0ZW0gbyBwb2RlciBkZSBjb25jZWRlciBvcyBkaXJlaXRvcyBjb250aWRvcyBuZXN0YSBsaWNlbsOnYS4gVm9jw6ogdGFtYsOpbSBkZWNsYXJhIHF1ZSBvIGRlcMOzc2l0bywgcXVlIHNlamEgZGUgc2V1IGNvbmhlY2ltZW50bywgbsOjbyBpbmZyaW5nZSBkaXJlaXRvcyBhdXRvcmFpcyBkZSBuaW5ndcOpbS4KCkNhc28gbyB0cmFiYWxobyBjb250ZW5oYSBtYXRlcmlhbCBxdWUgdm9jw6ogbsOjbyBwb3NzdWkgYSB0aXR1bGFyaWRhZGUgZG9zIGRpcmVpdG9zIGF1dG9yYWlzLCB2b2PDqiBkZWNsYXJhIHF1ZSBvYnRldmUgYSBwZXJtaXNzw6NvIGlycmVzdHJpdGEgZG8gZGV0ZW50b3IgZG9zIGRpcmVpdG9zIGF1dG9yYWlzIHBhcmEgY29uY2VkZXIgw6AgVW5pdmVyc2lkYWRlIEZlZGVyYWwgZGUgU2VyZ2lwZSBvcyBkaXJlaXRvcyBhcHJlc2VudGFkb3MgbmVzdGEgbGljZW7Dp2EsIGUgcXVlIGVzc2UgbWF0ZXJpYWwgZGUgcHJvcHJpZWRhZGUgZGUgdGVyY2Vpcm9zIGVzdMOhIGNsYXJhbWVudGUgaWRlbnRpZmljYWRvIGUgcmVjb25oZWNpZG8gbm8gdGV4dG8gb3Ugbm8gY29udGXDumRvLgoKQSBVbml2ZXJzaWRhZGUgRmVkZXJhbCBkZSBTZXJnaXBlIHNlIGNvbXByb21ldGUgYSBpZGVudGlmaWNhciBjbGFyYW1lbnRlIG8gc2V1IG5vbWUocykgb3UgbyhzKSBub21lKHMpIGRvKHMpIApkZXRlbnRvcihlcykgZG9zIGRpcmVpdG9zIGF1dG9yYWlzIGRvIHRyYWJhbGhvLCBlIG7Do28gZmFyw6EgcXVhbHF1ZXIgYWx0ZXJhw6fDo28sIGFsw6ltIGRhcXVlbGFzIGNvbmNlZGlkYXMgcG9yIGVzdGEgbGljZW7Dp2EuIAo=Repositório InstitucionalPUBhttps://ri.ufs.br/oai/requestrepositorio@academico.ufs.bropendoar:2023-02-03T23:07:23Repositório Institucional da UFS - Universidade Federal de Sergipe (UFS)false
dc.title.pt_BR.fl_str_mv Pirólise térmica e catalítica de polímeros pós-consumo sobre catalisadores tipo AIMCM-4
dc.title.alternative.eng.fl_str_mv Pyrolysis thermal and catalytic of post-consumer polymer over catalysts type AlMCM-48
title Pirólise térmica e catalítica de polímeros pós-consumo sobre catalisadores tipo AIMCM-4
spellingShingle Pirólise térmica e catalítica de polímeros pós-consumo sobre catalisadores tipo AIMCM-4
Santos, Tiago Gomes dos
Engenharia química
Processos químicos
Pirólise
Polímeros
Catalisadores
Síntese hidrotérmica
AlMCM-48
Polímeros pós-consumo
Pirólise catalítica
Métodos de isoconversão
Hydrothermal synthesis
Post-consumer polymers
Catalytic pyrolysis
Isoconversional methods
ENGENHARIAS::ENGENHARIA QUIMICA
title_short Pirólise térmica e catalítica de polímeros pós-consumo sobre catalisadores tipo AIMCM-4
title_full Pirólise térmica e catalítica de polímeros pós-consumo sobre catalisadores tipo AIMCM-4
title_fullStr Pirólise térmica e catalítica de polímeros pós-consumo sobre catalisadores tipo AIMCM-4
title_full_unstemmed Pirólise térmica e catalítica de polímeros pós-consumo sobre catalisadores tipo AIMCM-4
title_sort Pirólise térmica e catalítica de polímeros pós-consumo sobre catalisadores tipo AIMCM-4
author Santos, Tiago Gomes dos
author_facet Santos, Tiago Gomes dos
author_role author
dc.contributor.author.fl_str_mv Santos, Tiago Gomes dos
dc.contributor.advisor1.fl_str_mv Souza, Marcelo José Barros de
dc.contributor.advisor-co1.fl_str_mv Araujo, Antonio Souza de
contributor_str_mv Souza, Marcelo José Barros de
Araujo, Antonio Souza de
dc.subject.por.fl_str_mv Engenharia química
Processos químicos
Pirólise
Polímeros
Catalisadores
Síntese hidrotérmica
AlMCM-48
Polímeros pós-consumo
Pirólise catalítica
Métodos de isoconversão
topic Engenharia química
Processos químicos
Pirólise
Polímeros
Catalisadores
Síntese hidrotérmica
AlMCM-48
Polímeros pós-consumo
Pirólise catalítica
Métodos de isoconversão
Hydrothermal synthesis
Post-consumer polymers
Catalytic pyrolysis
Isoconversional methods
ENGENHARIAS::ENGENHARIA QUIMICA
dc.subject.eng.fl_str_mv Hydrothermal synthesis
Post-consumer polymers
Catalytic pyrolysis
Isoconversional methods
dc.subject.cnpq.fl_str_mv ENGENHARIAS::ENGENHARIA QUIMICA
description Due to the increase in the production of post-consumer plastic waste, the improper disposal and long-term degradation of this material, Brazil has faced serious environmental impacts. In order to avoid a worsening situation, the catalytic pyrolysis has become a very attractive process within the chemical treatment of post-consumer polymers, reducing the operating limitations of thermal pyrolysis, thus promoting processes with lower energy expenditure and selectively generating product high added value. Thus, in the present work were synthesized by hydrothermal method, a series of acids with heterogeneous catalysts mesoporous AlMCM-48 type cubic structure containing different ratios of Si/Al (50, 100, 150) for application to the pyrolysis reaction. The syntheses were performed over a period of three days with the pH between 11-13 and a highly polymerized silica source, ie, the ratio CTMABr/TEOS 0.59. The catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), thermal analysis via TG/DTG and nitrogen adsorption. Through these characterization techniques it was observed that it was possible to develop a series of catalysts with high cubic mesoporous ordering equivalent and thermally stable thermogravimetric profile, surface area and size relatively high pore volume and had agglomerated spherical morphology. The thermal and catalytic pyrolysis reactions were performed using high density polyethylene (HDPE) and polypropylene (PP), where a comparative analysis of the thermal and catalytic pyrolysis catalysts on different AlMCM-48 type was performed. Through the conversion curves it was possible to observe and compare the operating conditions to obtain a given conversion as a function of the temperature correlated with the results obtained by kinetic Isoconversional methods proposed by Flynn-Wall-Ozawa (FWO) and Vyazovkin, may analyze the influence of AlMCM-48 on the activation energy (Ea) of pyrolysis reactions. The results showed a remarkable effect of the catalyst to accelerate the process of pyrolysis. In the catalytic pyrolysis of HDPE that the catalyst was more efficiently presented the Si/Al = 50 ratio, with a yield of 77.31 %, and the PP to the most efficient catalyst was the Si/Al = 100 ratio, who presented a yield of 75.84 %. As for the kinetics, both methods have been effective isoconversão to determine Ea HDPE and PP. The method Vyazovkin exhibited lower activation energies, an average difference 87.220 kJ.mol-1 for HDPE and 111.811 kJ.mol-1 to PP compared with the FWO method. The Ea determined by both methods showed the same behavior on the dependence of conversion and Ea(HDPE) < Ea(PP). In this work, efficient kinetic results were obtained, compared to pyrolysis reactions involving the HDPE and PP over AlMCM-48 catalysts, providing a basis for the potential benefit of the chemical recycling of post-consumer polymers, potentially leading to an efficient process in terms of energy costs.
publishDate 2015
dc.date.issued.fl_str_mv 2015-07-15
dc.date.accessioned.fl_str_mv 2023-02-03T23:07:23Z
dc.date.available.fl_str_mv 2023-02-03T23:07:23Z
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dc.identifier.citation.fl_str_mv SANTOS, Tiago Gomes dos. Pirólise térmica e catalítica de polímeros pós-consumo sobre catalisadores tipo AIMCM-4. 2015. 86 f. Dissertação (Mestrado em Engenharia Química) - Universidade Federal de Sergipe, São Cristóvão, 2015.
dc.identifier.uri.fl_str_mv http://ri.ufs.br/jspui/handle/riufs/17052
identifier_str_mv SANTOS, Tiago Gomes dos. Pirólise térmica e catalítica de polímeros pós-consumo sobre catalisadores tipo AIMCM-4. 2015. 86 f. Dissertação (Mestrado em Engenharia Química) - Universidade Federal de Sergipe, São Cristóvão, 2015.
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