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Fluoroacrylate copolymer-grafted rho...

Flores Velazquez, Roberto.

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Fluoroacrylate copolymer-grafted rhodium catalysts for hydrogenation reactions in supercritical fluids.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Fluoroacrylate copolymer-grafted rhodium catalysts for hydrogenation reactions in supercritical fluids./
作者:	Flores Velazquez, Roberto.
面頁冊數:	165 p.
附註:	Source: Dissertation Abstracts International, Volume: 64-04, Section: B, page: 1820.
Contained By:	Dissertation Abstracts International64-04B.
標題:	Engineering, Chemical. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3088138
ISBN:	9780496359004

Fluoroacrylate copolymer-grafted rhodium catalysts for hydrogenation reactions in supercritical fluids.
Flores Velazquez, Roberto.

Fluoroacrylate copolymer-grafted rhodium catalysts for hydrogenation reactions in supercritical fluids. - 165 p.

Source: Dissertation Abstracts International, Volume: 64-04, Section: B, page: 1820.

Thesis (Ph.D.)--Texas A&M University, 2003.

Organometallic catalysts in homogeneous media offer high reactivity, selectivity, and tunability. Nevertheless, most solvents used in organic synthesis have a negative effect on the environment due to their toxicity. Supercritical carbon dioxide (scCO2) has shown significant potential for replacing the common toxic organic solvents as reaction media because of its unique properties, which near the critical region are easily tunable by small variation in pressure and/or temperature allowing the possibility of engineering the reaction environment to improve the reactivity and selectivity. Limitations of scCO2 as solvent are associated with its weak solvent strength. Efforts have been directed to the design of catalyst ligands that are soluble in scCO2 under mild conditions. Particularly, flouroacrylate copolymers and silicones have been found to be moderately soluble in scCO2. Based on that, a novel catalyst soluble in scCO2 was synthesized by grafting rhodium ligands to a fluroacrylate copolymer. To determine the performance of the novel catalyst, hydrogenation of 1-octene and cyclohexene were used as model reactions. The main objective of this research was to evaluate the catalytic activity of the novel catalyst for hydrogenation reactions in scCO2. The effect of catalyst composition, operating conditions, hydrogen concentration, and substrate to catalyst molar ratio on the reactivity and selectivity were analyzed. It was found that 1-octene was not only hydrogenated to n-octane, but also it was isomerized to (E)2-octene and (Z)2-octene. Also, no hydrogenation of the 2-octene isomers was observed in the presence of 1-octene. On the other hand, cyclohexene was only hydrogenated to cyclohexane, and no side products were detected. Moreover, deactivation of the catalyst was observed during the reaction time. Catalyst composition only affected the reactivity of the catalyst, but no effect was observed on the selectivity. The same trend was observed when analyzing the effect of pressure and temperature. Finally, a kinetic model that represents the hydrogenation and isomerization processes with the new catalyst was developed and its parameters determined from experimental data.

ISBN: 9780496359004Subjects--Topical Terms:

1018531
Engineering, Chemical.

Fluoroacrylate copolymer-grafted rhodium catalysts for hydrogenation reactions in supercritical fluids.
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