Catalysis
Mohammad Javad Sharifi; Alireza Fazlali; Seyed Hamed Mahdaviani; Davood soudbar
Abstract
The performance of the catalyst system [chromium(III)/pyrrole/co-catalyst/halide] on the trimerization of ethylene has been studied using the combined experimental and response surface method (RSM). The chromium(III) tris(2-ethylhexanoate) was synthesized and characterized by FTIR, 1HNMR and 13CNMR, ...
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The performance of the catalyst system [chromium(III)/pyrrole/co-catalyst/halide] on the trimerization of ethylene has been studied using the combined experimental and response surface method (RSM). The chromium(III) tris(2-ethylhexanoate) was synthesized and characterized by FTIR, 1HNMR and 13CNMR, to study chemical properties and identify molecular structures. The effect of four variables Al/Cr molar ratio, halide/Cr molar ratio, reaction temperature and catalyst dosage have been considered on catalyst activity, 1-hexene selectivity and polymer content. The central composite design (CCD) model with three main parameters in three response levels for each factor was applied to analyze the effects of the parameters. The comparative studies showed that carbon-tetra-chloride (CCl4) and tri-n-octyl-aluminum (TNOA) were the best candidates for this catalyst system, demonstrating high selectivity of 1-hexene formation, higher catalytic activity and lower polymer content. Based on the RSM results, the best trimerization condition for ethylene at 25 bar and 91.2°C was obtained at the catalytic system [Cr(2-EH)3/2,5-DMP/CCl4/TNOA] molar ratio of 1:6:10.8:201.5, which showed the activity of 105328 (g 1-C6/(g Cr.hr)), 99.21% selectivity for 1-hexene and no polymer was formed. The predicted process parameters were also verified by actual experiments at the optimized conditions.
Olefin oligomerization
Ahad Hanifpour; Mahdi Hashemzadeh Gargari; Mohammad Reza Rostami Darounkola; Zahra Kalantari; Naeimeh Bahri-Laleh
Abstract
Herein a quenched-flow kinetic technique was applied to calculate the rate constants of 1-hexene and 1-octene oligomerization catalyzed by the Cp2ZrCl2 and Cp2HfCl2/MAO catalyst systems, and subsequently a mechanism for the higher α-olefin oligomerization reaction was proposed. The oligomerization ...
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Herein a quenched-flow kinetic technique was applied to calculate the rate constants of 1-hexene and 1-octene oligomerization catalyzed by the Cp2ZrCl2 and Cp2HfCl2/MAO catalyst systems, and subsequently a mechanism for the higher α-olefin oligomerization reaction was proposed. The oligomerization results showed that Zr-based catalyst in the oligomerization of 1-octene had the highest activity of 17 in comparison to Hfbased one with an activity value of 15 g oligomer/(mmolCat.h)). According to the obtained results, increasing monomer length led to a shift in molecular weight and polydispersity index value (Mw/Mn) to lower values. Furthermore, the microstructure-viscosity relationship was followed by the calculation of branching ratio and short-chain branching percentage. The obtained results revealed that, the oligomers synthesized by the Cp2HfCl2 catalyst had lower short chain branching ratio value and short-chain branching percentages. According to the kinetic results, the initiation rate constant (ki) of Zr-based catalyst was higher than that of Hf-based catalyst, and the order of calculated propagation rate constants was Zr>Hf for both the 1-hexene and 1-octene-based oligomerizations.
Olefin oligomerization
Tanja H. Ritter; Helmut G. Alt
Abstract
Nine different bis(arylimino)pyridine complexes of Fe(III) with different halide substituents (F, Cl, Br, I) at different positions of the iminophenyl group of the ligand have been synthesized, characterized and applied for homogeneous 1-pentene and 1-hexene oligomerization and co-oligomerization reactions ...
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Nine different bis(arylimino)pyridine complexes of Fe(III) with different halide substituents (F, Cl, Br, I) at different positions of the iminophenyl group of the ligand have been synthesized, characterized and applied for homogeneous 1-pentene and 1-hexene oligomerization and co-oligomerization reactions after activation with methylaluminoxane (MAO). The best activity in 1-hexene oligomerization (152 kg/mol.h) was observed for 4/ MAO with an iodine substituent in para position of the iminophenyl group. Fluorine substituents in the meta position of the iminophenyl group proved as disadvantageous (1 kg/mol.h) in homo-oligomerization reactions but advantageous in co-oligomerization reactions of 1-pentene and 1-hexene. Obviously, tiny electronic or steric differences at the active sites of the corresponding catalysts are responsible for this result (structure-property relationship). The product distributions of the co-dimerization reactions of 1-pentene and 1-hexene reflected a binominal behaviour with dominating co-products. The ratio of dimers is 1:2:1 (C10:C11:C12) while the trimers (pentadecenes up to octadecenes) show proportions of 1:3:3:1.
Olefin oligomerization
Tanja H. Ritter; Helmut G. Alt
Abstract
1-Pentene, respectively 1-hexene, were reacted with 13 homogeneous metallocene catalysts to give linear oligomerization products, predominantly dimers, with selectivities above 90%. The product distributions of the codimerization reactions of 1-pentene with 1-hexene reflected a binomial behaviour. Therefore, ...
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1-Pentene, respectively 1-hexene, were reacted with 13 homogeneous metallocene catalysts to give linear oligomerization products, predominantly dimers, with selectivities above 90%. The product distributions of the codimerization reactions of 1-pentene with 1-hexene reflected a binomial behaviour. Therefore, the ratio for dimers is 1:2:1 (C10:C11:C12) while the trimers (pentadecenes up to octadecenes) show a proportion of 1:3:3:1. By changing the ratio of the 1-pentene/1-hexene mixture, the binomial distribution switched to the side of products of the higher concentrated monomer. Even when using methyl branched olefins, the binomial product distribution could be observed. Alkenes with an internal double bond could not be dimerized under these conditions. The reactions with olefins containing a methyl group in β-position, a tert-butyl group or a neopentyl group failed. Addition of appropriate additives like tributylphosphine or aluminum powder raised both the activities and the selectivities for dimers, which means that the fraction of undecenes obtained from the codimerization reactions of 1-pentene and 1-hexene increased.
Olefin oligomerization
Mohammad Rostamizadeh; Fereydoon Yaripour; Hossein Hazrati
Abstract
Highly siliceous ZSM-5 nanocatalysts can dehydrate methanol to a wide range of hydrocarbons. In this study, the development of hierarchical H-ZSM-5 nanocatalysts (Si/Al=200) were reported for the methanol-toolefins (MTO) reaction. The nanocatalysts were prepared through a hydrothermal technique and treated ...
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Highly siliceous ZSM-5 nanocatalysts can dehydrate methanol to a wide range of hydrocarbons. In this study, the development of hierarchical H-ZSM-5 nanocatalysts (Si/Al=200) were reported for the methanol-toolefins (MTO) reaction. The nanocatalysts were prepared through a hydrothermal technique and treated by NaOH desilication. The parent and desilicated nanocatalysts were characterized using FE-SEM, XRD, FTIR, NH3-TPD and N2 adsorption-desorption techniques. The mesoporosity increased five times without significant collapse of the crystalline framework as a result of the appropriate desilication of H-ZSM-5 nanocatalyst. For the nanocatalyst, a high surface area of 189.5 m2 g-1, mesopore volume of 0.35 cm3 g-1 and well-adjusted strong acidity of 0.16 mmol NH3 g-1 resulted in a high methanol conversion of 100%, high propylene selectivity of 43% and low light paraffins selectivity of <8% in the MTO reaction. A broad mesopore size of 2-10 nm suppressed coke deposition and provided a long catalytic life time of 75 h. The developed high silica nanocatalyst showed a high potential for industrial applications due to its stable performance.
Reaction engineering
Mohsen Najafi; Mahmoud Parvazinia; Mir Hamid Reza Ghoreishy
Abstract
A two-dimensional single particle finite element model was used to examine the effects of particle fragmental pattern on the average molecular weights, polymerization rate and particle overheating in heterogeneous Ziegler-Natta olefin polymerization. A two-site catalyst kinetic mechanism was employed ...
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A two-dimensional single particle finite element model was used to examine the effects of particle fragmental pattern on the average molecular weights, polymerization rate and particle overheating in heterogeneous Ziegler-Natta olefin polymerization. A two-site catalyst kinetic mechanism was employed together with a dynamic two-dimensional molecular species in diffusion-reaction equation. The initial catalyst active sites distribution was assumed to be uniform, while the monomer diffusion coefficient was considered to be different inside the fragments and cracks. In other words, the cracks were distinguished from fragments with higher monomer diffusion coefficient. To model the particle temperature a lumped heat transfer model was used. The fragmentation pattern was considered to remain unchanged during the polymerization. A Galerkin finite element method was used to solve the resulting two-dimensional (2-D) moving boundary value, diffusion-reaction problem. A two-dimensional polymeric flow model (PFM) was implemented on the finite element meshes. The simulation results showed that the fragmentation pattern had effects on the molecular properties, reaction rate and the particle temperature at early stages of polymerization.
