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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
11

Poli (l?quidos i?nicos) celul?sicos aplicados como catalisadores heterog?neos para transforma??o qu?mica do CO2 em carbonatos c?clicos

Rodrigues, Daniela Maffi 27 July 2018 (has links)
Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2018-12-03T15:52:09Z No. of bitstreams: 1 Dissertacao DANIELA MAFFI RODRIGUES.pdf: 1641622 bytes, checksum: 7201a3a551a602c84d3776d0f02f7399 (MD5) / Approved for entry into archive by Sheila Dias (sheila.dias@pucrs.br) on 2018-12-05T13:35:48Z (GMT) No. of bitstreams: 1 Dissertacao DANIELA MAFFI RODRIGUES.pdf: 1641622 bytes, checksum: 7201a3a551a602c84d3776d0f02f7399 (MD5) / Made available in DSpace on 2018-12-05T13:50:46Z (GMT). No. of bitstreams: 1 Dissertacao DANIELA MAFFI RODRIGUES.pdf: 1641622 bytes, checksum: 7201a3a551a602c84d3776d0f02f7399 (MD5) Previous issue date: 2018-07-27 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / Carbon capture and storage (CCS) and carbon capture and utilisation(CCU) technologies has been pointed out as possibilities to mitigate the effects caused by the massiverelease of CO2 into the atmosphere. The use of CO2 in cycloaddition reactions toepoxides obtaining cyclic carbonates is an interesting possibility to reduce CO2emission. Cyclic carbonates are products of great applicability as solvents in the chemical industry and are used as raw material for a wide range of products. Meanwhile, the use of CO2 for a cycloaddition reaction requires a large amount of energy being necessary the use of catalysts in order to optimize such reactions. Poly (ionic liquids) (PIL) are alternative catalysts due its selective, recyclability and conversion. In this work, cellulosic poly(ionic liquids) (CPIL) obtained from rice husk were testedas heterogeneous catalyst. Cellulose extraction was carried out by chemical method. A chemical modification of the cellulose fibers was carried out by the treatment with citric acid and functionalization with 3 mmol of the ionic liquids BMIM Cl, TBAB, TBPB and BMPYRR to form CPIL-BMIM, CPIL-TBA, CPIL-TBP and CPIL-BMPYRR), without addition of solvents. Cyclo addition reactions were carried out with propylene and styrene oxides with different CO2 pressures(25, 30 and 40 bar) and temperatures (90, 110 and 120 ?C) for 6 h. The obtained product was characterized by gas chromatography (GC), Fourier Transform Infrared Spectroscopy(FTIR)and Nuclear Magnetic Resonance (1H NMR). The results showed better yields for CPIL-TBP and CPIL-TBA, whose values were 53.2% and 39% respectively for propylene carbonate and 67.3% for styrene carbonate using CPIL-TBP. When the ZnBr2 cocatalyst was used, there was an increase in the catalytic activity of these catalysts. For CPIL-TBP the yields were 71.4% for propylene carbonate and 78.7% for styrene carbonate. For CPIL-TBA the increase in propylene carbonate yield was 67.7%. / O uso das tecnologias de captura e armazenamento de carbono (CCS) e de captura utiliza??o do carbono (CCU) v?m sendo apontadas como possibilidades para mitigar os efeitos causados pela libera??o deliberada de elevadas concentra??es de CO2 na atmosfera. A utiliza??o do CO2 em rea??es de cicloadi??o em ep?xidos para obter carbonatos c?clicos vem se mostrando uma possibilidade interessante para reduzir a emiss?o de CO2 na atmosfera. Os carbonatos c?clicos s?o produtos de grande aplicabilidade como solventes na ind?stria qu?mica e s?o utilizados como mat?ria prima para uma vasta gama de produtos. Entretanto, o CO2 apresenta baixa reatividade tornando-se necess?rio o uso de catalisadores para otimizar tais rea??es. Os poli(l?quidos i?nicos) (PILs) v?m se mostrando como poss?veis catalisadores alternativos, demonstrando-se seletivos, recicl?veis e gerando consider?vel convers?o. Neste trabalho foram testados poli(l?quidos i?nicos) celul?sicos (CPIL), obtidos a partir da casca do arroz, como catalisador heterog?neo. A extra??o da celulose foi realizada por um m?todo qu?mico. A modifica??o qu?mica das fibras de celulose foi realizada a partir do tratamento com ?cido c?trico e a funcionaliza??o desta com 3 mmol dos l?quidos i?nicos BMIM Cl, TBAB, TBPB e BMPYRR formando CPIL-BMIM, CPIL-TBA, CPIL-TBP e CPIL-BMPYRR. As rea??es de cicloadi??o foram realizadas com os ?xidos de propileno e estireno com diferentes press?es de CO2 (15, 25, 30 e 40 bar) e temperaturas (90, 110, 120 e 130?C) durante (3, 6 e 9h), todas as rea??es foram realizadas sem a utiliza??o de solventes. O produto obtido foi caracterizado por cromatografia gasosa (CG) , espectroscopia de infravermelho com transformada de Fourier (FTIR) e Resson?ncia Magn?tica Nuclear (1H RMN). Os resultados demonstraram melhores rendimentos para CPIL-TBP e CPIL-TBA, cujos valores foram de 53,2% e 39% respectivamente para o carbonato de propileno e de 67,3% para o carbonato de estireno utilizando o CPIL-TBP. Quando o cocatalisador ZnBr2 foi utilizado, houve um aumento na a atividade catal?tica destes catalisadores, para o CPIL-TBP os rendimentos foram de 71,4 % para o carbonato de propileno e 78,7% para o carbonato de estireno. Para o CPIL-TBA o aumento no rendimento de carbonato de propileno foi de 67,7%.

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