Conversão térmica de casca de arroz à baixa temperatura: produção de bioóleo e resíduo sílico-carbonoso adsorvente
Autor(a) principal: | |
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Data de Publicação: | 2005 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Manancial - Repositório Digital da UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/4152 |
Resumo: | The exploitation of rice husks through thermal conversion at low temperature, adding economical value through its pyrolysis products, may represent a solution to the current environmental problem of discharging this agricultural residue. Dry, ground and granulometrically classified rice husks were submitted to pyrolysis at bench scale, in a fixed bed reactor, at a maximum temperature of 440 oC. The thermal conversion was made in an inert atmosphere (N2) that also served as a dragging gas, determining the time of permanence of the gases inside the system. The products, after cooling in the reactor exit, were collected and separated in fractions, to evaluate yields related to the previous established parameters. Gaseous products (gases of mean heat value), liquids (aqueous and bio-oil) and solids (silicon-carbonous residues) were obtained. The solid and liquid products were submitted to many characterization tests. The bio-oil samples were analyzed by techniques of Nuclear Magnetic Resonance (NMR) of 1H and 13C; Gas Chromatography coupled to Mass Spectrometry (GC-MS); Infrared (IR) and Ultraviolet (UV) Spectrophotometry; Fluorescence Spectrophotometry (FS) and Electronic Paramagnetic Resonance (EPR). Elemental analysis was done and the High Heating Value (HHV) was determined. Bio-oil and aqueous fraction were also submitted to tests of biodegradability and toxicity with the aid of test animals (mice and lizards). The silica-carbonous residue was submitted to adsorption tests (acetic acid, textile dyes and carbohydrates) and characterization (iodine-methylen blue- and phenazone-number); BET analysis; Blaine test; IR Spectrophotometry; X-Ray Diffraction (XRD); Scanning Electronic Microscopy (SEM); High Resolution Spectroscopy of Solid-State Nuclear Magnetic Resonance of 13C and 29Si (HR/SSNMR) and High Heating Value (HHV). The silica, resultant from calcination of silica-carbonous residue was also submitted to adsorption tests (textile dyes and carbohydrates) and characterization (methylen blue-number); X-ray Diffraction (XRD); Scanning Electronic Microscopy (SEM); High Resolution Spectroscopy of Solid-State Nuclear Magnetic Resonance in the of 29Si (HR/SSNMR) and Blaine test. In the pyrolysis study it was observed that, with the rising of the process temperature, the yield of the gases formed also increases. The aqueous fraction formation rises with the temperature up to 440 oC; above such a temperature, there is a reduction on the aqueous fraction. Yet the bio-oil production rises up to the temperature of 420 oC, higher temperatures than this reduce the bio-oil production. The yield on silica-carbonous residue decreases continually as the process temperature increases. The silicon-carbonous residue and the silica has adsorbent properties. It was determined that in the liquid oily fraction oxygenated compounds predominate, mainly phenols, highliting the presence of mixed function showing ethers, esters, ketones, aldehydes, alcohols, among others. The presence of such compounds in its constitution allows the use of bio-oil in the production of resins, replacement of the petrochemical phenol, as a substitute for fuel oil and as an additive for diesel oil. The high number of compounds present in the bio-oil makes the identification and determination of chemical species a task beyond the objective of this paper. The bio-oil obtained (distilled or not distilled) presented low text of humidity. Analytical tests had shown that the distillation of the liquid fraction modifies the composition of the bio-oil. The necessary heating for the distillation generates free radicals, reduces the carbon text and the hydrogen and, consequently it rises the oxygen text. The bio-oil, separated for distillation, was presented highly viscous and reactive, polymerizing easily in contact with atmospheric air. |
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2017-05-182017-05-182005-07-29DINIZ, Juraci. Thermal conversion of rice husks at low temperature: production of bio-oil and residual silica-carbonous adsorbent. 2005. 185 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2005.http://repositorio.ufsm.br/handle/1/4152The exploitation of rice husks through thermal conversion at low temperature, adding economical value through its pyrolysis products, may represent a solution to the current environmental problem of discharging this agricultural residue. Dry, ground and granulometrically classified rice husks were submitted to pyrolysis at bench scale, in a fixed bed reactor, at a maximum temperature of 440 oC. The thermal conversion was made in an inert atmosphere (N2) that also served as a dragging gas, determining the time of permanence of the gases inside the system. The products, after cooling in the reactor exit, were collected and separated in fractions, to evaluate yields related to the previous established parameters. Gaseous products (gases of mean heat value), liquids (aqueous and bio-oil) and solids (silicon-carbonous residues) were obtained. The solid and liquid products were submitted to many characterization tests. The bio-oil samples were analyzed by techniques of Nuclear Magnetic Resonance (NMR) of 1H and 13C; Gas Chromatography coupled to Mass Spectrometry (GC-MS); Infrared (IR) and Ultraviolet (UV) Spectrophotometry; Fluorescence Spectrophotometry (FS) and Electronic Paramagnetic Resonance (EPR). Elemental analysis was done and the High Heating Value (HHV) was determined. Bio-oil and aqueous fraction were also submitted to tests of biodegradability and toxicity with the aid of test animals (mice and lizards). The silica-carbonous residue was submitted to adsorption tests (acetic acid, textile dyes and carbohydrates) and characterization (iodine-methylen blue- and phenazone-number); BET analysis; Blaine test; IR Spectrophotometry; X-Ray Diffraction (XRD); Scanning Electronic Microscopy (SEM); High Resolution Spectroscopy of Solid-State Nuclear Magnetic Resonance of 13C and 29Si (HR/SSNMR) and High Heating Value (HHV). The silica, resultant from calcination of silica-carbonous residue was also submitted to adsorption tests (textile dyes and carbohydrates) and characterization (methylen blue-number); X-ray Diffraction (XRD); Scanning Electronic Microscopy (SEM); High Resolution Spectroscopy of Solid-State Nuclear Magnetic Resonance in the of 29Si (HR/SSNMR) and Blaine test. In the pyrolysis study it was observed that, with the rising of the process temperature, the yield of the gases formed also increases. The aqueous fraction formation rises with the temperature up to 440 oC; above such a temperature, there is a reduction on the aqueous fraction. Yet the bio-oil production rises up to the temperature of 420 oC, higher temperatures than this reduce the bio-oil production. The yield on silica-carbonous residue decreases continually as the process temperature increases. The silicon-carbonous residue and the silica has adsorbent properties. It was determined that in the liquid oily fraction oxygenated compounds predominate, mainly phenols, highliting the presence of mixed function showing ethers, esters, ketones, aldehydes, alcohols, among others. The presence of such compounds in its constitution allows the use of bio-oil in the production of resins, replacement of the petrochemical phenol, as a substitute for fuel oil and as an additive for diesel oil. The high number of compounds present in the bio-oil makes the identification and determination of chemical species a task beyond the objective of this paper. The bio-oil obtained (distilled or not distilled) presented low text of humidity. Analytical tests had shown that the distillation of the liquid fraction modifies the composition of the bio-oil. The necessary heating for the distillation generates free radicals, reduces the carbon text and the hydrogen and, consequently it rises the oxygen text. The bio-oil, separated for distillation, was presented highly viscous and reactive, polymerizing easily in contact with atmospheric air.O aproveitamento da casca de arroz por meio da conversão térmica à baixa temperatura, agregando-lhe valor econômico através de seus produtos de pirólise, pode representar uma solução para o atual problema ambiental de descarte deste resíduo agrícola. Casca de arroz seca, triturada e classificada granulometricamente foi submetida à pirólise sob temperatura máxima de 440 oC, em reator em batelada, de leito fixo e em escala de bancada. A conversão térmica foi feita em atmosfera inerte (N2), que também serviu como gás de arraste e determinante do tempo de permanência dos gases dentro do sistema. Os produtos, após resfriamento na saída do reator, foram coletados e separados em frações para avaliar rendimentos, relacionando-os com os parâmetros previamente estabelecidos. Obtiveram-se produtos gasosos (gases de médio poder calorífico), líquidos (aquoso e bioóleo) e sólidos (resíduo silico-carbonoso e sílica). Os produtos líquidos e sólidos foram submetidos a vários testes de caracterização. O bioóleo foi analisado pelas técnicas de ressonância magnética nuclear (NMR) de 1H e 13C; cromatografia gasosa capilar acoplada a espectrometria de massa (GC-MS); espectrofotometria de infravermelho (IR) e ultravioleta (UV); espectrofotometria de fluorescência (FS) e ressonância paramagnética eletrônica (EPR). Foi realizada análise elementar e determinado o poder calorífico superior (HHV) do bioóleo. Amostras de bioóleo e de fração aquosa foram submetidas, também, a testes de biodegradabilidade e toxicidade, com auxílio de cobaias (lagartas e ratos). O resíduo silico-carbonoso foi submetido a testes de adsorção (ácido acético, corantes têxteis e carboidratos) e de caracterização (número de iodo, de azul de metileno e de fenazona); medida de área (teste BET de Brunauer, Emmet e Teller; teste Blaine); espectrofotometria de infravermelho (IR); difração de raios X (XRD); microscopia eletrônica por varredura (SEM); espectroscopia de alta resolução por ressonância magnética nuclear no estado sólido de 13C e de 29Si (HR/SSNMR) e poder calorífico superior (HHV). A sílica, resultante da calcinação do resíduo sílico-carbonoso foi submetida a testes de adsorção (corantes têxteis e carboidratos) e de caracterização (número de azul de metileno); difração de raios X (XRD); microscopia eletrônica por varredura (SEM); espectroscopia de alta resolução por ressonância magnética nuclear no estado sólido de 29Si (HR/SSNMR) e teste Blaine. No estudo da pirólise observou-se que, ao aumentar-se a temperatura do processo, o rendimento em formação de gases também aumenta. A formação de fração aquosa aumenta até temperaturas de processo da ordem de 440 oC; acima desta temperatura, há redução do rendimento em fração aquosa, por outro lado, o rendimento de bioóleo cresce até temperaturas de processo de cerca de 420 oC; temperaturas mais elevadas reduzem a produção de bioóleo. O rendimento em resíduo silico-carbonoso diminui continuamente à medida que a temperatura do processo aumenta. O resíduo silico-carbonoso e a sílica nele contida, mesmo sem tratamento de ativação, possuem propriedades adsorventes. Verificou-se que, na fração líquida oleosa, predominam compostos oxigenados, principalmente fenóis, destacando-se a presença de funções mistas tais como éteres, ésteres, cetonas, aldeídos, álcoois, entre outros. A presença de tais compostos em sua constituição torna possível a utilização de bioóleo na produção de resinas, em substituição ao fenol petroquímico, como substituto de óleo combustível e como aditivo para o óleo diesel. O elevado número de compostos presentes no bioóleo dificulta a completa identificação e determinação das espécies químicas que o compõem. O bioóleo obtido (destilado ou não destilado) apresentou baixo teor de umidade. Testes analíticos mostraram que a destilação da fração líquida altera a composição do bioóleo. O aquecimento necessário para a destilação gera radicais livres, reduz o teor de carbono e de hidrogênio e, conseqüentemente eleva o teor de oxigênio. O bioóleo, separado por destilação, apresentou-se altamente viscoso e reativo, polimerizando facilmente em contato com o ar atmosférico.application/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaCasca de arrozPiroliseBiooleoRice rindPiroliseBiooleoCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAConversão térmica de casca de arroz à baixa temperatura: produção de bioóleo e resíduo sílico-carbonoso adsorventeThermal conversion of rice husks at low temperature: production of bio-oil and residual silica-carbonous adsorbentinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisMartins, Ayrton Figueiredohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4787438A0Piazza, José Luizhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4781127U0Paniz, José Neri Gottfriedhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4701043Z3Dressler, Valderi Luizhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4723641Z7Mortari, Sergio Robertohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4721640J6http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4760176H6Diniz, Juraci100600000000400300300300300300300ade6000d-a348-4d49-a531-6500a65a153ac933d1ff-9994-4a71-a28e-686b089f8e5c354252bb-d1ef-4aa9-973c-a542aae1a40496786b4b-a5d5-4cd8-a0bb-d7af0080745aa9ee5e70-810a-4fbb-8a1f-0e0aaf8d83f3ebb296a1-1569-43d1-8946-7cc7e3bec814info:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALTese Juraci1.pdfapplication/pdf2193746http://repositorio.ufsm.br/bitstream/1/4152/1/Tese%20Juraci1.pdf0563e303abbb18f4b82eb1214dbb18abMD51TEXTTese Juraci1.pdf.txtTese Juraci1.pdf.txtExtracted texttext/plain319079http://repositorio.ufsm.br/bitstream/1/4152/2/Tese%20Juraci1.pdf.txt27603edc1a89218a5db48e7ee794fb5cMD52THUMBNAILTese Juraci1.pdf.jpgTese Juraci1.pdf.jpgIM Thumbnailimage/jpeg5629http://repositorio.ufsm.br/bitstream/1/4152/3/Tese%20Juraci1.pdf.jpg8bdcbe8f8db0aeceaf4e910432806186MD531/41522017-07-25 11:05:06.232oai:repositorio.ufsm.br:1/4152Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestopendoar:39132017-07-25T14:05:06Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Conversão térmica de casca de arroz à baixa temperatura: produção de bioóleo e resíduo sílico-carbonoso adsorvente |
dc.title.alternative.eng.fl_str_mv |
Thermal conversion of rice husks at low temperature: production of bio-oil and residual silica-carbonous adsorbent |
title |
Conversão térmica de casca de arroz à baixa temperatura: produção de bioóleo e resíduo sílico-carbonoso adsorvente |
spellingShingle |
Conversão térmica de casca de arroz à baixa temperatura: produção de bioóleo e resíduo sílico-carbonoso adsorvente Diniz, Juraci Casca de arroz Pirolise Biooleo Rice rind Pirolise Biooleo CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Conversão térmica de casca de arroz à baixa temperatura: produção de bioóleo e resíduo sílico-carbonoso adsorvente |
title_full |
Conversão térmica de casca de arroz à baixa temperatura: produção de bioóleo e resíduo sílico-carbonoso adsorvente |
title_fullStr |
Conversão térmica de casca de arroz à baixa temperatura: produção de bioóleo e resíduo sílico-carbonoso adsorvente |
title_full_unstemmed |
Conversão térmica de casca de arroz à baixa temperatura: produção de bioóleo e resíduo sílico-carbonoso adsorvente |
title_sort |
Conversão térmica de casca de arroz à baixa temperatura: produção de bioóleo e resíduo sílico-carbonoso adsorvente |
author |
Diniz, Juraci |
author_facet |
Diniz, Juraci |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Martins, Ayrton Figueiredo |
dc.contributor.advisor1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4787438A0 |
dc.contributor.referee1.fl_str_mv |
Piazza, José Luiz |
dc.contributor.referee1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4781127U0 |
dc.contributor.referee2.fl_str_mv |
Paniz, José Neri Gottfried |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4701043Z3 |
dc.contributor.referee3.fl_str_mv |
Dressler, Valderi Luiz |
dc.contributor.referee3Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4723641Z7 |
dc.contributor.referee4.fl_str_mv |
Mortari, Sergio Roberto |
dc.contributor.referee4Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4721640J6 |
dc.contributor.authorLattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4760176H6 |
dc.contributor.author.fl_str_mv |
Diniz, Juraci |
contributor_str_mv |
Martins, Ayrton Figueiredo Piazza, José Luiz Paniz, José Neri Gottfried Dressler, Valderi Luiz Mortari, Sergio Roberto |
dc.subject.por.fl_str_mv |
Casca de arroz Pirolise Biooleo |
topic |
Casca de arroz Pirolise Biooleo Rice rind Pirolise Biooleo CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Rice rind Pirolise Biooleo |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The exploitation of rice husks through thermal conversion at low temperature, adding economical value through its pyrolysis products, may represent a solution to the current environmental problem of discharging this agricultural residue. Dry, ground and granulometrically classified rice husks were submitted to pyrolysis at bench scale, in a fixed bed reactor, at a maximum temperature of 440 oC. The thermal conversion was made in an inert atmosphere (N2) that also served as a dragging gas, determining the time of permanence of the gases inside the system. The products, after cooling in the reactor exit, were collected and separated in fractions, to evaluate yields related to the previous established parameters. Gaseous products (gases of mean heat value), liquids (aqueous and bio-oil) and solids (silicon-carbonous residues) were obtained. The solid and liquid products were submitted to many characterization tests. The bio-oil samples were analyzed by techniques of Nuclear Magnetic Resonance (NMR) of 1H and 13C; Gas Chromatography coupled to Mass Spectrometry (GC-MS); Infrared (IR) and Ultraviolet (UV) Spectrophotometry; Fluorescence Spectrophotometry (FS) and Electronic Paramagnetic Resonance (EPR). Elemental analysis was done and the High Heating Value (HHV) was determined. Bio-oil and aqueous fraction were also submitted to tests of biodegradability and toxicity with the aid of test animals (mice and lizards). The silica-carbonous residue was submitted to adsorption tests (acetic acid, textile dyes and carbohydrates) and characterization (iodine-methylen blue- and phenazone-number); BET analysis; Blaine test; IR Spectrophotometry; X-Ray Diffraction (XRD); Scanning Electronic Microscopy (SEM); High Resolution Spectroscopy of Solid-State Nuclear Magnetic Resonance of 13C and 29Si (HR/SSNMR) and High Heating Value (HHV). The silica, resultant from calcination of silica-carbonous residue was also submitted to adsorption tests (textile dyes and carbohydrates) and characterization (methylen blue-number); X-ray Diffraction (XRD); Scanning Electronic Microscopy (SEM); High Resolution Spectroscopy of Solid-State Nuclear Magnetic Resonance in the of 29Si (HR/SSNMR) and Blaine test. In the pyrolysis study it was observed that, with the rising of the process temperature, the yield of the gases formed also increases. The aqueous fraction formation rises with the temperature up to 440 oC; above such a temperature, there is a reduction on the aqueous fraction. Yet the bio-oil production rises up to the temperature of 420 oC, higher temperatures than this reduce the bio-oil production. The yield on silica-carbonous residue decreases continually as the process temperature increases. The silicon-carbonous residue and the silica has adsorbent properties. It was determined that in the liquid oily fraction oxygenated compounds predominate, mainly phenols, highliting the presence of mixed function showing ethers, esters, ketones, aldehydes, alcohols, among others. The presence of such compounds in its constitution allows the use of bio-oil in the production of resins, replacement of the petrochemical phenol, as a substitute for fuel oil and as an additive for diesel oil. The high number of compounds present in the bio-oil makes the identification and determination of chemical species a task beyond the objective of this paper. The bio-oil obtained (distilled or not distilled) presented low text of humidity. Analytical tests had shown that the distillation of the liquid fraction modifies the composition of the bio-oil. The necessary heating for the distillation generates free radicals, reduces the carbon text and the hydrogen and, consequently it rises the oxygen text. The bio-oil, separated for distillation, was presented highly viscous and reactive, polymerizing easily in contact with atmospheric air. |
publishDate |
2005 |
dc.date.issued.fl_str_mv |
2005-07-29 |
dc.date.accessioned.fl_str_mv |
2017-05-18 |
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2017-05-18 |
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info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
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doctoralThesis |
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publishedVersion |
dc.identifier.citation.fl_str_mv |
DINIZ, Juraci. Thermal conversion of rice husks at low temperature: production of bio-oil and residual silica-carbonous adsorbent. 2005. 185 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2005. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/4152 |
identifier_str_mv |
DINIZ, Juraci. Thermal conversion of rice husks at low temperature: production of bio-oil and residual silica-carbonous adsorbent. 2005. 185 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2005. |
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http://repositorio.ufsm.br/handle/1/4152 |
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