Produção de olefinas leves a partir de etanol em ZSM-5 sintetizada sem direcionador nitrogenado

Detalhes bibliográficos
Ano de defesa: 2015
Autor(a) principal: Albiero, Jalusa Konzen lattes
Orientador(a): Castilhos, Fernanda de lattes
Banca de defesa: Schwaab, Marcio lattes, Egues, Silvia Maria da Silva lattes
Tipo de documento: Dissertação
Tipo de acesso: Acesso aberto
Idioma: por
Instituição de defesa: Universidade Federal de Santa Maria
Programa de Pós-Graduação: Programa de Pós-Graduação em Engenharia de Processos
Departamento: Engenharia de Processos
País: BR
Palavras-chave em Português:
Palavras-chave em Inglês:
Área do conhecimento CNPq:
Link de acesso: http://repositorio.ufsm.br/handle/1/7987
Resumo: The petrochemical industry is currently strongly based on the production of light olefins ethylene and propylene, which are mainly produced by hydrocarbons from oil. Due to the environmental appeal and unstable oil market scenario, alternative routes to the production of these olefins are being developed, meanly regarding the use of alcohol as raw material. In this context, ethanol is highlighted with Ethanol to Olefins Process (ETO), in which there is catalytic conversion via reactions of dehydration, oligomerization, cracking, isomerization, among others. This work aims to obtain ethylene and propylene from ethanol using ZSM-5 zeolite as catalyst in its acid form. The synthesis of this material was performed using non-conventional sources of silicon and aluminum, kaolin and silica extracted from rice husk ash, and in the absence of nitrogenous templates. The use of seeds was employed together with ethanol, which acts as cotemplate of the zeolitic structure, in different quantities, and in different silica/alumina ratios and crystallisation times. The influence of each of these variables was evaluated with the support of a full factorial experimental design on the final characteristics of the synthesized samples, such as relative crystallinity, chemical composition and textural properties. All samples presented the characteristic crystal structure of ZSM-5 as verified by both X-ray diffractograms and infrared spectra. However, samples with small amounts of seed and ethanol added to short periods of crystallization presented lower crystallinities and specific areas in comparison to other samples. On the other hand, the use of high quantities of seed can lead to the formation of quartz when the crystallization time is extended. With the catalytic tests of ethanol conversion into olefins it was possible to evaluate the influence of synthesis variables, the residence time and the concentration of ethanol in feed, proving the importance of all synthesis variables in the distribution of the reaction products The total conversion of ethanol was observed in all tests made, evidencing the high activity of hZSM-5 in the dehydration of ethanol to ethylene, being the propylene yield strongly influenced by the reaction temperature and characteristics of the catalitic material, with a maximum yield of 27% at 500 °C. The HZSM-5 presented high stability under reaction conditions while maintaining the production of ethylene for more than 40 hours of reaction, whereas the coke formation drastically reduces the production of propylene still in the early hours of reaction.
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spelling 2015-06-222015-06-222015-03-05ALBIERO, Jalusa Konzen. LIGHT OLEFINS PRODUCTION FROM ETHANOL IN ZSM-5 SYNTHESIZED WITHOUT NITROGENOUS TEMPLATE. 2015. 124 f. Dissertação (Mestrado em Engenharia) - Universidade Federal de Santa Maria, Santa Maria, 2015.http://repositorio.ufsm.br/handle/1/7987The petrochemical industry is currently strongly based on the production of light olefins ethylene and propylene, which are mainly produced by hydrocarbons from oil. Due to the environmental appeal and unstable oil market scenario, alternative routes to the production of these olefins are being developed, meanly regarding the use of alcohol as raw material. In this context, ethanol is highlighted with Ethanol to Olefins Process (ETO), in which there is catalytic conversion via reactions of dehydration, oligomerization, cracking, isomerization, among others. This work aims to obtain ethylene and propylene from ethanol using ZSM-5 zeolite as catalyst in its acid form. The synthesis of this material was performed using non-conventional sources of silicon and aluminum, kaolin and silica extracted from rice husk ash, and in the absence of nitrogenous templates. The use of seeds was employed together with ethanol, which acts as cotemplate of the zeolitic structure, in different quantities, and in different silica/alumina ratios and crystallisation times. The influence of each of these variables was evaluated with the support of a full factorial experimental design on the final characteristics of the synthesized samples, such as relative crystallinity, chemical composition and textural properties. All samples presented the characteristic crystal structure of ZSM-5 as verified by both X-ray diffractograms and infrared spectra. However, samples with small amounts of seed and ethanol added to short periods of crystallization presented lower crystallinities and specific areas in comparison to other samples. On the other hand, the use of high quantities of seed can lead to the formation of quartz when the crystallization time is extended. With the catalytic tests of ethanol conversion into olefins it was possible to evaluate the influence of synthesis variables, the residence time and the concentration of ethanol in feed, proving the importance of all synthesis variables in the distribution of the reaction products The total conversion of ethanol was observed in all tests made, evidencing the high activity of hZSM-5 in the dehydration of ethanol to ethylene, being the propylene yield strongly influenced by the reaction temperature and characteristics of the catalitic material, with a maximum yield of 27% at 500 °C. The HZSM-5 presented high stability under reaction conditions while maintaining the production of ethylene for more than 40 hours of reaction, whereas the coke formation drastically reduces the production of propylene still in the early hours of reaction.A indústria petroquímica atualmente está fortemente baseada na produção das olefinas leves eteno e propeno, que são principalmente produzidas através de hidrocarbonetos oriundos do petróleo. Em virtude do apelo ambiental e do instável cenário do mercado de petróleo, rotas alternativas para a produção destas olefinas estão sendo desenvolvidas, principalmente no que tange a utilização de álcoois como matéria-prima. Neste contexto, o etanol ganha destaque com o processo Ethanol to Olefins (ETO), no qual se tem conversão catalítica via reações de desidratação, oligomerização, craqueamento, isomerização, entre outras. O presente trabalho tem por objetivo a obtenção de eteno e propeno através de etanol empregando como catalisador a zeólita do tipo ZSM-5 na forma ácida. A síntese deste material foi realizada utilizando fontes não convencionais de silício e alumínio, o caulim e a sílica extraída da cinza da casca de arroz, e na ausência de direcionadores de estrutura nitrogenados. O emprego de sementes foi adotado juntamente com etanol, que atua como codirecionador da estrutura zeolítica, em diferentes quantidades, assim como em diferentes razões sílica/alumina e tempos de cristalização. A influência de cada uma destas variáveis foi avaliada com o auxílio do planejamento experimental fatorial completo nas características finais das amostras sintetizadas, como cristalinidade relativa, composição química e propriedades texturais. Todas as amostras obtidas apresentaram estrutura cristalina característica da ZSM-5, comprovada tanto nos difratogramas de Raios-X como nos espectros de absorção na região do Infravermelho. Entretanto, as amostras com pequenas quantidades de sementes e de etanol somadas a curtos períodos de cristalização apresentaram cristalinidades e áreas específicas reduzidas em relação às demais amostras. Em contrapartida, o emprego de elevadas quantidades de sementes pode levar a formação de quartzo quando o tempo de cristalização é prolongado. Com os testes catalíticos de conversão de etanol em olefinas foi possível avaliar a influência das variáveis de síntese, do tempo de residência e a concentração de etanol na alimentação, comprovando a importância de todas as variáveis de síntese na distribuição dos produtos da reação. A conversão total de etanol foi observada em todos os testes realizados, evidenciando a elevada atividade da HZSM-5 na desidratação de etanol a eteno, sendo o rendimento a propeno fortemente influenciado pela temperatura de reação e características do material catalítico, com máximo rendimento igual a 27% na temperatura de 500°C. A HZSM-5 apresentou elevada estabilidade nas condições de reação, mantendo a produção de eteno por mais de 40 horas de reação, enquanto que a formação de coque reduz drasticamente a produção de propeno ainda nas primeiras horas de reação.Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em Engenharia de ProcessosUFSMBREngenharia de ProcessosOlefinas LevesEtanolZeólita ZSM-5SementesCatáliseLight olefinsEthanolZSM-5 zeoliteSeedsCatalysisCNPQ::ENGENHARIAS::ENGENHARIA DE PRODUCAOProdução de olefinas leves a partir de etanol em ZSM-5 sintetizada sem direcionador nitrogenadoLight olefins production from ethanol in ZSM-5 synthesized without nitrogenous templateinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisCastilhos, Fernanda dehttp://lattes.cnpq.br/4590978604104577Coutinho, Elisa Barbosahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4767971T6Schwaab, Marciohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4706157Z4Egues, Silvia Maria da Silvahttp://lattes.cnpq.br/8029656203911141http://lattes.cnpq.br/3605054496028093Albiero, Jalusa Konzen300800000005400300300300300300340e815f-99e3-423d-b9d8-4333d082cb0f81c3c09f-a4b9-42c1-95a6-341bc1f5b4c2fe5e7a55-7991-46a7-aa57-ea2250b2e84c3be0e558-76e8-42e9-ab3e-85288d2a5e0c3b33401d-f4ab-47a0-9d85-d834337edc1ainfo:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALALBIERO, JALUSA KONZEN.pdfapplication/pdf3020066http://repositorio.ufsm.br/bitstream/1/7987/1/ALBIERO%2c%20JALUSA%20KONZEN.pdf7d9cf89ff430dce1e1037da4d074eb35MD51TEXTALBIERO, JALUSA KONZEN.pdf.txtALBIERO, JALUSA KONZEN.pdf.txtExtracted texttext/plain223958http://repositorio.ufsm.br/bitstream/1/7987/2/ALBIERO%2c%20JALUSA%20KONZEN.pdf.txt1c1ef6947ea582704a44c459201670d5MD52THUMBNAILALBIERO, JALUSA KONZEN.pdf.jpgALBIERO, JALUSA KONZEN.pdf.jpgIM Thumbnailimage/jpeg5168http://repositorio.ufsm.br/bitstream/1/7987/3/ALBIERO%2c%20JALUSA%20KONZEN.pdf.jpg0bc0461e575e18a7e6591e188b35d308MD531/79872021-03-30 08:22:18.322oai:repositorio.ufsm.br:1/7987Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestopendoar:39132021-03-30T11:22:18Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false
dc.title.por.fl_str_mv Produção de olefinas leves a partir de etanol em ZSM-5 sintetizada sem direcionador nitrogenado
dc.title.alternative.eng.fl_str_mv Light olefins production from ethanol in ZSM-5 synthesized without nitrogenous template
title Produção de olefinas leves a partir de etanol em ZSM-5 sintetizada sem direcionador nitrogenado
spellingShingle Produção de olefinas leves a partir de etanol em ZSM-5 sintetizada sem direcionador nitrogenado
Albiero, Jalusa Konzen
Olefinas Leves
Etanol
Zeólita ZSM-5
Sementes
Catálise
Light olefins
Ethanol
ZSM-5 zeolite
Seeds
Catalysis
CNPQ::ENGENHARIAS::ENGENHARIA DE PRODUCAO
title_short Produção de olefinas leves a partir de etanol em ZSM-5 sintetizada sem direcionador nitrogenado
title_full Produção de olefinas leves a partir de etanol em ZSM-5 sintetizada sem direcionador nitrogenado
title_fullStr Produção de olefinas leves a partir de etanol em ZSM-5 sintetizada sem direcionador nitrogenado
title_full_unstemmed Produção de olefinas leves a partir de etanol em ZSM-5 sintetizada sem direcionador nitrogenado
title_sort Produção de olefinas leves a partir de etanol em ZSM-5 sintetizada sem direcionador nitrogenado
author Albiero, Jalusa Konzen
author_facet Albiero, Jalusa Konzen
author_role author
dc.contributor.advisor1.fl_str_mv Castilhos, Fernanda de
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/4590978604104577
dc.contributor.advisor-co1.fl_str_mv Coutinho, Elisa Barbosa
dc.contributor.advisor-co1Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4767971T6
dc.contributor.referee1.fl_str_mv Schwaab, Marcio
dc.contributor.referee1Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4706157Z4
dc.contributor.referee2.fl_str_mv Egues, Silvia Maria da Silva
dc.contributor.referee2Lattes.fl_str_mv http://lattes.cnpq.br/8029656203911141
dc.contributor.authorLattes.fl_str_mv http://lattes.cnpq.br/3605054496028093
dc.contributor.author.fl_str_mv Albiero, Jalusa Konzen
contributor_str_mv Castilhos, Fernanda de
Coutinho, Elisa Barbosa
Schwaab, Marcio
Egues, Silvia Maria da Silva
dc.subject.por.fl_str_mv Olefinas Leves
Etanol
Zeólita ZSM-5
Sementes
Catálise
topic Olefinas Leves
Etanol
Zeólita ZSM-5
Sementes
Catálise
Light olefins
Ethanol
ZSM-5 zeolite
Seeds
Catalysis
CNPQ::ENGENHARIAS::ENGENHARIA DE PRODUCAO
dc.subject.eng.fl_str_mv Light olefins
Ethanol
ZSM-5 zeolite
Seeds
Catalysis
dc.subject.cnpq.fl_str_mv CNPQ::ENGENHARIAS::ENGENHARIA DE PRODUCAO
description The petrochemical industry is currently strongly based on the production of light olefins ethylene and propylene, which are mainly produced by hydrocarbons from oil. Due to the environmental appeal and unstable oil market scenario, alternative routes to the production of these olefins are being developed, meanly regarding the use of alcohol as raw material. In this context, ethanol is highlighted with Ethanol to Olefins Process (ETO), in which there is catalytic conversion via reactions of dehydration, oligomerization, cracking, isomerization, among others. This work aims to obtain ethylene and propylene from ethanol using ZSM-5 zeolite as catalyst in its acid form. The synthesis of this material was performed using non-conventional sources of silicon and aluminum, kaolin and silica extracted from rice husk ash, and in the absence of nitrogenous templates. The use of seeds was employed together with ethanol, which acts as cotemplate of the zeolitic structure, in different quantities, and in different silica/alumina ratios and crystallisation times. The influence of each of these variables was evaluated with the support of a full factorial experimental design on the final characteristics of the synthesized samples, such as relative crystallinity, chemical composition and textural properties. All samples presented the characteristic crystal structure of ZSM-5 as verified by both X-ray diffractograms and infrared spectra. However, samples with small amounts of seed and ethanol added to short periods of crystallization presented lower crystallinities and specific areas in comparison to other samples. On the other hand, the use of high quantities of seed can lead to the formation of quartz when the crystallization time is extended. With the catalytic tests of ethanol conversion into olefins it was possible to evaluate the influence of synthesis variables, the residence time and the concentration of ethanol in feed, proving the importance of all synthesis variables in the distribution of the reaction products The total conversion of ethanol was observed in all tests made, evidencing the high activity of hZSM-5 in the dehydration of ethanol to ethylene, being the propylene yield strongly influenced by the reaction temperature and characteristics of the catalitic material, with a maximum yield of 27% at 500 °C. The HZSM-5 presented high stability under reaction conditions while maintaining the production of ethylene for more than 40 hours of reaction, whereas the coke formation drastically reduces the production of propylene still in the early hours of reaction.
publishDate 2015
dc.date.accessioned.fl_str_mv 2015-06-22
dc.date.available.fl_str_mv 2015-06-22
dc.date.issued.fl_str_mv 2015-03-05
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identifier_str_mv ALBIERO, Jalusa Konzen. LIGHT OLEFINS PRODUCTION FROM ETHANOL IN ZSM-5 SYNTHESIZED WITHOUT NITROGENOUS TEMPLATE. 2015. 124 f. Dissertação (Mestrado em Engenharia) - Universidade Federal de Santa Maria, Santa Maria, 2015.
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