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Previous issue date: 2014-09-25 / Este trabalho descreve a s?ntese e aplica??o de catalisadores de ferro homog?neos e heterogeneizados
na rea??o de alquila??o do tolueno com propeno, empregando planejamento de
experimentos. O complexo homog?neo foi obtido atrav?s da s?ntese do ligante org?nico
seguida da complexa??o de cloreto de ferro(II). Quanto aos complexos heterogeneizados,
inicialmente foram sintetizados suportes inorg?nicos (SBA-15, MCM-41 e Al-MCM41).
Em seguida sintetizou-se novamente o ligante org?nico, que atrav?s de funcionaliza??o com
o cloropropiltrimetoxisilano (CPTMS), foi ancorado ao suporte previamente calcinado.
A estes ligantes ancorados, foi complexado cloreto de ferro(II), previamente solubilizado
em tetrahidrofurano (THF). A caracteriza??o do ligante org?nico foi realizada atrav?s
de resson?ncia magn?tica nuclear (RMN) e espectroscopia na regi?o do infravermelho
(IV). Os suportes foram caracterizados por difra??o de raios-x (DRX), an?lises texturais
por adsor??o/dessor??o de nitrog?nio (antes e depois do ancoramento), an?lise de
termogravimetria (TG) e espectroscopia na regi?o do infravermelho (IV). A quantidade
de metal foi quantificado atrav?s de espectrofotometria de absor??o at?mica (AAS). Os
complexos foram testados em rea??es catal?ticas empregando-se sesquicloreto de etilalum?-
nio (EASC) como co-catalisador, respons?vel pela ativa??o do complexo catal?tico, em
reator de a?o, sob agita??o mec?nica. As condi??es reacionais variaram entre 4 e 36 ?C,
para diversas raz?es alum?nio/ferro, sempre sob 6 atmosferas de press?o de propeno e
com 30 minutos de tempo reacional. Os produtos das rea??es catal?ticas foram analisados
atrav?s de cromatografia gasosa (CG). Os catalisadores se mostraram ativos tanto em
meio homog?neo como heterogeneizados nos suportes. O complexo catal?tico homog?neo
apresentou frequ?ncia de rota??o (FR) de at? 8,63 ?103
? h
?1
, enquanto que, em algumas
condi??es, os complexos ancorados apresentaram melhores resultados, com FR de at?
8,08 ?103
? h
?1
. Adicionalmente, foi poss?vel determinar uma equa??o, para o sistema
homog?neo, que relaciona a quantidade de produto em fun??o da temperatura reacional e
da raz?o alum?nio/ferro. / This work describes the synthesis and aplication of homogeneous and heterogenized iron
catalysts in the alkylation reaction of toluene with propene, empolying experimental design.
The homogenous complex was obtained trough the synthesis of the organic ligand folowed
by the complexation of the iron(II) chloride. As to the heterogenized complexes, first were
synthetized the inorganic supports (SBA-15, MCM-41 and Al-MCM-41). Then, it was
synthetized the ligand again, that through funcionalization with chloropropyltrimethoxysilane
(CPTMS), was anchored on the support previously calcinated. To these anchored
ligands, was complexed the iron(II) chloride, previously solubilizated in tetrahydrofuran
(THF). The organic ligand characterization was accomplished trough nuclear magnetic
resonance (NMR) and Infrared spectroscopy (IV). The supports were characterized with
x-ray diffraction (DRX), texture analysis with nitrogen adsorption/desorption (before
and after the anchoring), termogravimetric analysis (TG) and infrared (IV). The metalic
content was quantified trough the atomic absorption spectrophotometry (AAS). The complexes
were tested in catalytic reactions emolying ethylaluminium sesquichloride (EASC)
as co-catalyst in steel reactor, under mecanic stirring. The reaction conditions ranged from
4 to 36 ?C, with many aluminum/iron ratios. The catalysts were actives in homogeneous
and heterogenized ways. The homogenous catalytic complex showed a maximum turnover
frequency (TOF) of 8.63 ?103
? h
?1
, while, in some conditions, the anchored complexes
showed better results, with TOF of until 8.08 ?103
? h
?1
. Aditionally, it was possible to
determine an equation, to the homogenous catalyst, that describes the product quantity
in function of reacional temperature and aluminum/iron ratio.
| Identifer | oai:union.ndltd.org:IBICT/oai:repositorio.ufrn.br:123456789/19826 |
| Date | 25 September 2014 |
| Creators | Pinheiro, Carlos Ant?nio de Albuquerque |
| Contributors | 50942611004, http://lattes.cnpq.br/5249001430287414, Gasparotto, Luiz Henrique da Silva, 21859095844, http://lattes.cnpq.br/2649423643904707, Braga, Tiago Pinheiro, 00880643366, http://lattes.cnpq.br/9170391410490804, Santos, Eduardo Nicolau dos, 10210721847, http://lattes.cnpq.br/9246600674685393, Gusm?o, Katia Bernardo, Pergher, Sibele Berenice Castella |
| Publisher | Universidade Federal do Rio Grande do Norte, PROGRAMA DE P?S-GRADUA??O EM QU?MICA, UFRN, Brasil |
| Source Sets | IBICT Brazilian ETDs |
| Language | Portuguese |
| Detected Language | English |
| Type | info:eu-repo/semantics/publishedVersion, info:eu-repo/semantics/masterThesis |
| Source | reponame:Repositório Institucional da UFRN, instname:Universidade Federal do Rio Grande do Norte, instacron:UFRN |
| Rights | info:eu-repo/semantics/openAccess |
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