Ethylene oligomerisation with zirconium arylalkyls and alkenyls

Attridge, C. J.; Jackson, R F W; Maddock, Susan J.; Thompson, David

doi:10.1039/c39730000132

Cited by 18 publications

(5 citation statements)

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“…Rhodium Rhodium chloride is active in the dimerization of ethylene at 30-50 °C.155 Cramer162 has made a detailed study of the dimerization of ethylene under the influence of rhodium chloride in alcoholic hydrochloric acid solutions and proposed the mechanism as shown in Scheme XVIII. Activation of catalyst occurs by the reaction between RhCl3 and ethylene with formation of a complex anion (20) of univalent rhodium with two ethylene ligands.…”

Section: Rutheniummentioning

confidence: 99%

“…1.125 g/ (L-min) (20) Ti(OC4H9)4-Al(C2H6)3 heptane, 4 atm, Al/Ti = 10 0.243 g/min (20) rates in other Ti(OC4H9)4-Al(C2H5)3 heptane, 10 atm, Al-Ti = 7.5 0.25 g/min (20) solvents given Ti(OC4H<,)4-Al(CH3)3 heptane, 10 atm, Al/Ti -7.5 0.18 g/min (20) Ti(OC4H9)4-Al(i-Pr)3 heptane, 10 atm, Al/Ti = 7.5 0.09 g/min (20) Ti(0-n-C4H9)4-Al(C2H5)3 toluene, 10 atm, Al/Ti = 10 0.77 g/min (20) rates for other Ti(OC4H9)4-Ai(C2H5)3 heptane, 460 torr, Al/Ti = 10 3.5 g/(L-min) (22) alkoxides given Ti(OC2H5)4-Al(C2Hs);i n-decane, 2.7 atm, 2 h 1.83 g/(L-min) (20) 222 Ti (OC4H9) 4-Al (C 2H5) 3-n-heptane, 3 atm, 280 min 1.57 g/ (L-min) (20) 222 m-phenylenediamine Ti(OC4H9)4-Al(j-Bu)2H diethyl ether, 9.3 atm, 109 min 6.5 g/(L-min) (60) 222 WCI6 2,6-dimethylaniline-benzene, 1 h, 27 atm 0.85 mol/(L*min) (40) Al/M = 3.8, 7.12 atm 0.17 g/(L-min) (90) CrCl2(NO)2(Ph3PO)2-(C2H5)AlCl2 chlorobenzene, 500 psig, 1 h 7.6 g/(L-min) (50) CrCl2(4-Etpy )2-(C2H5)AlCl2 chlorobenzene, 500 psig, 1 h 7.5 g/(L-min) (50) CrCl2(NO)2(4-Etpy)2-(C2Hs)AlCl2 chlorobenzene, 500 psig 1 h 7.9 g/(L-min) (50) chlorobenzene, 750 psig 1 h, Al/Cr = 5…”

Section: -Butenementioning

confidence: 99%

“…6.8 g/(L-min) (50) CrCl3(Bu3P)2-(C2H5)AlCI2 chlorobenzene, 500 psig, 1 h, Al/Cr = 5 7.5 g/(L-min) (50) RhCl3-3H20 EtOH-HCl, 4 atm 3.2 X 10 " g/min (33) E" = 13.6 kcal/mol [RhCf(C2H4)2]2 EtOH-HCl, 4 atm 1.01 X 10-* g/min (20) E" = 14.7 kcal/mol…”

Section: -Butenementioning

confidence: 99%

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Dimerization of ethylene and propylene catalyzed by transition-metal complexes

Pillai¹,

Ravindranathan²,

Sivaram³

1986

Chem. Rev.

192

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Section: Rutheniummentioning

confidence: 99%

Section: -Butenementioning

confidence: 99%

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Dimerization of ethylene and propylene catalyzed by transition-metal complexes

Pillai¹,

Ravindranathan²,

Sivaram³

1986

Chem. Rev.

192

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“…Complexes of titanium and nickel are the most often used catalysts for ethylene oligomerization [47,49,58]. Zirconium complexes have also been found to be very active catalyst in this reaction [5,33,34,42]. The use of other transition metal complexes in ethylene oligomerization is uncommon.…”

Section: Introductionmentioning

confidence: 99%

“…4 Rate constant of attachment in the chain propagation reaction k - 4 Rate constant of detachment in the chain propagation reaction k ? 5 Rate constant of attachment in the chain transfer reaction k - 5 Rate constant of detachment in the chain transfer reaction k c…”

mentioning

confidence: 99%

A kinetic model for ethylene oligomerization using zirconium/aluminum- and nickel/zinc-based catalyst systems in a batch reactor

et al. 2014

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The aim of this work is to develop a kinetic model of the oligomerization of ethylene to linear alpha olefins (LAOs) for zirconium/aluminum and nickel/zinc catalyst systems. The development of such model helps in the study of the behavior of industrial LAOs reactors as well as in the optimization of their operation. The kinetic model was developed based on a four-step mechanism: site activation, initiation and propagation, chain transfer and site deactivation. A novel stochastic optimization algorithm, Intelligent Firefly Algorithm, was used to obtain the kinetic model parameters that best fit the available experimental data that were obtained from published sources. The values of the kinetic parameters were obtained for the developed kinetic models for two catalyst systems. The performance of the model with the estimated parameters was tested against the experimental data. The proposed kinetic model predicts the product distribution for the zirconium/aluminum catalyst system with suitable accuracy. The model can also predict the product distribution for the nickel/zinc catalyst system with good accuracy for all products. As expected, the accuracy of the model to predict the concentration of the higher carbon products decreases with the carbon number. Keywords Ethylene Á Oligomerization Á Modeling Á Zirconium/aluminum catalyst Á Nickel/zinc catalyst Abbreviation Notation A Pre-exponential factor C CAT Catalyst concentration, mol/l C CAT k Active catalyst concentration, mol/l C CAT k ÁM Complex active catalyst/ethylene concentration, mol/l C decy Moles of deactivated catalysts, mol C M Concentration of ethylene monomer, mol/l C M k Concentration of active ethylene monomer, mol/l C M k ÁTEA Concentration of complex active ethylene monomer/co-catalyst, mol/l C P 0 Concentration of active site, mol/l C P i Concentration of living polymers, mol/l C P k i Concentration of active living polymers, mol/l C P k i ÁTEA Concentration of complex active living polymers/co-catalyst, mol/l C TEA Co-catalyst concentration, mol/l C TEA k Active co-catalyst concentration, mol/l C TEA k ÁCAT Complex active co-catalyst/catalyst concentration, mol/l C TEA k 1 ÁCAT Complex active co-catalyst/catalyst concentration-catalyst, mol/l D Moles of dead oligomer, mol E Activation energy, cal/mol k 1 Rate constant of active site k 2 Rate constant of chain initiation k 3 Rate constant of chain propagation k 4 Rate constant of chain transfer k 5 Rate constant of deactivation k ?1 Rate constant of attachment of the catalyst in the site activation k-1 Rate constant of detachment of the catalyst in the site activation

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