Ethylene oligomerization in the presence of catalyst systems based on mixed-ligand β-diketonatozirconium chlorides

Khanmetov, A. A.; Azizov, A. G.; Piraliev, A. G.

doi:10.1134/s0965544106050069

Cited by 3 publications

(3 citation statements)

References 2 publications

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“…For this purpose, several zirconium complexes based on β-diketonate ligands containing various electron donating and withdrawing groups were synthesized and then evaluated in the ethylene oligomerization. [45] The results showed that the increase of electron acceptor ability in the β-diketonate ligands caused an increase in the quantity of 1-butene in the product composition as same as activity of catalysts. When Zr (AcAc) 3 Cl was applied as a component of the catalyst at 70 C and P et = 4 MPa in toluene medium the activity was determined to be 3486.6 g oligomer/g Zr h −1 , whereas, the activity of the catalysts based on Zr (trifluoroAcAc) 3 Cl and Zr (hexafluoroAcAc) 4 were 11419.1 and 14311.2 g oligomer/g Zr h −1 , respectively.…”

Section: Catalysts Based On Zirconium Alkoxide and Phenolic Compoundsmentioning

confidence: 94%

“…For this purpose, several zirconium complexes based on β‐diketonate ligands containing various electron donating and withdrawing groups were synthesized and then evaluated in the ethylene oligomerization . The results showed that the increase of electron acceptor ability in the β‐diketonate ligands caused an increase in the quantity of 1‐butene in the product composition as same as activity of catalysts.…”

Section: Catalysts Based On Zirconium β‐Diketonate and β‐Aminoketonatesmentioning

confidence: 99%

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Zirconium Catalyzed Ethylene Oligomerization

Khamiyev

Khanmetov

Vakhshouri

et al. 2020

Applied Organom Chemis

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A review of the scientific and patent literature on oligomerization of ethylene to linear olefins in the presence of homogenous or heterogeneous zirconium complexes and various aluminum organic compounds has been fulfilled for last twenty‐five years. Over these years, a wide range of studies had been conducted for selective oligomerization of ethylene into a narrow fraction of linear α‐olefins such as C4‐C8 and C6‐C10 fractions. During the discussion of these catalytic systems, exceptional attention is also paid to feature works such as the activity of the catalysts and the acquisition of clear liquid product without any trace of polymer, all of which play important roles in the selection of the best technology.

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Section: Catalysts Based On Zirconium Alkoxide and Phenolic Compoundsmentioning

confidence: 94%

Section: Catalysts Based On Zirconium β‐Diketonate and β‐Aminoketonatesmentioning

confidence: 99%

Zirconium Catalyzed Ethylene Oligomerization

Khamiyev

Khanmetov

Vakhshouri

et al. 2020

Applied Organom Chemis

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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%

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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