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Kinetics of the hydroformylation of soybean oil by ligand‐modified homogeneous rhodium catalysis
Author(s) -
Kandanarachchi Pramod,
Guo Andrew,
Demydov Dmytro,
Petrovic Zoran
Publication year - 2002
Publication title -
journal of the american oil chemists' society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.512
H-Index - 117
eISSN - 1558-9331
pISSN - 0003-021X
DOI - 10.1007/s11746-002-0631-2
Subject(s) - hydroformylation , rhodium , chemistry , olefin fiber , catalysis , ligand (biochemistry) , kinetics , soybean oil , triphenylphosphine , medicinal chemistry , homogeneous catalysis , reaction rate , chemical kinetics , polymer chemistry , organic chemistry , biochemistry , physics , receptor , food science , quantum mechanics
The kinetics and mechanism of the hydroformylation of soybean oil by homogeneous ligand‐modified rhodium catalysts were investigated at 70–130°C and 4000–11,000 kPa. The effects of reaction rates on systematic variations in reaction parameters were evaluated in order to develop an industrial process to convert vegetable oils to polyaldehydes. The activation energies in the presence of triphenylphosphine (Ph 3 P) (61.1±0.8 kJ/mol) (mean±SD) and triphenyl phosphite [(PhO) 3 P] (77.4±5.0 kJ/mol) were determined. The catalyst was deactivated at temperatures higher than 100°C. An evaluation of the effects of the reaction parameters on initial rates yielded the rate laws for Ph 3 P {rate= k [olefin][Rh(CO) 2 Acac] 1.1 [Ph 3 P] −0.5 (pH 2 +pCO) 1.4 , where Rh(CO) 2 Acac is (acetylacetonato)dicarbonylrhodium (I)} and (PhO) 3 P {rate=[olefin] [Rh(CO) 2 Acac] 1.2 [(PhO) 3 P] −0.8 (pH 2 +pCO) 0.9 at total pressures lower than 7000 kPa, and rate =[olefin] [Rh(CO) 2 Acac] 1.2 [(PhO) 3 P] −0.8 (pH 2 +pCO) 1.7 at total pressures higher than 7000 kPa}.