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Hydroformylation of 1-octene using rhodium-phosphite catalyst in a thermomorphic solvent system

Shaharun , M.S. and Dutta, B.K and Mukhtar , H. (2010) Hydroformylation of 1-octene using rhodium-phosphite catalyst in a thermomorphic solvent system. Chemical Engineering Science , 65 (1). pp. 273-281. ISSN 00092509

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Abstract

The use of a liquid-liquid biphasic thermomorphic or temperature-dependent multicomponent solvent (TMS) system, in which the catalyst accumulates in one of the liquid phases and the product goes preferably to the other liquid phase, can be an enabling strategy of commercial hydroformylation processes with high selectivity, efficiency and ease of product separation and catalyst recovery. This paper describes the synthesis of n-nonanal, a commercially important fine chemical, by the hydroformylation reaction of 1-octene using a homogeneous catalyst consisting of HRh(PPh<sub>3</sub>)<sub>3</sub>(CO) and P(OPh)<sub>3</sub> in a TMS-system consisting of propylene carbonate (PC), dodecane and 1,4-dioxane. At a reaction temperature of 363 K, syngas pressure of 1.5 MPa and 0.68 mM concentration of the catalyst, HRh(CO)(PPh<sub>3</sub>)<sub>3</sub>, the conversion of 1-octene and the yield of total aldehyde were 97% and 95%, respectively. With a reaction time of 2 h and a selectivity of 89.3%, this catalytic system can be considered as highly reactive and selective compared to conventional ones. The resulting total turnover number was 600, while the turnover frequency was 400 h<sup>-1</sup>. The effects of increasing the concentration of 1-octene, catalyst loading, partial pressure of CO and H<sub>2</sub> and temperature on the rate of reaction have been studied at 353, 363 and 373 K. The rate was found to be first order with respect to concentrations of the catalyst and 1-octene, and the partial pressure of H<sub>2</sub>. The dependence of the reaction rate on the partial pressure of CO showed typical substrate inhibited kinetics. The kinetic behavior differs significantly from the kinetics of conventional systems employing HRh(CO)(PPh<sub>3</sub>)<sub>3</sub> in organic solvents. Most notable are the lack of olefin inhibition and the absence of a critical catalyst concentration. A mechanistic rate equation has been proposed and the kinetic parameters evaluated with an average error of 5.5%. The activation energy was found to be 69.8 kJ/mol. © 2009 Elsevier Ltd. All rights reserved.

Item Type:Article
Impact Factor:cited By (since 1996) 0
Uncontrolled Keywords:1-octene; Average errors; Biphasic; Catalyst concentration; Catalyst loadings; Catalyst recovery; Catalytic system; Concentration of; Conventional systems; Dodecane; Fine Chemicals; First order; High selectivity; Homogeneous catalyst; Hydroformylation process; Kinetic behavior; Liquid Phase; Liquid phasis; Liquid-liquids; Multi-component solvents; Product separation; Propylene carbonate; Rate equations; Rate of reaction; Reaction temperature; Reaction time; Rhodium catalysts; Syn-gas; Temperature dependent; Thermomorphic solvent systems; Total turnover; Turnover frequency, Activation energy; Aldehydes; Catalysis; Concentration (process); Ethers; Functional electric stimulation; Hydroformylation; Hydroxylation; Liquids; Organic solvents; Propylene; Reaction rates; Rhodium, Catalyst selectivity
Subjects:T Technology > TP Chemical technology
Departments / MOR / COE:Departments > Chemical Engineering
ID Code:1201
Deposited By: Assoc Prof Dr Hilmi Mukhtar
Deposited On:14 Jun 2011 12:34
Last Modified:01 Apr 2014 11:20

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