Mechanisms and Kinetics of Ethylene Oligomerization Over Nickel-based Heterogeneous Catalysts PDF Download

Author: Gabriel Viana Sueth Seufitelli
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Languages : en
Pages : 202

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Book Description
The present research describes the kinetics and mechanisms of the ethylene oligomerization over nickel-based solid catalysts at subcritical and supercritical ethylene conditions. The Ni-H-Beta catalyst was used due to its high activity for the conversion of ethylene into higher alkenes. Initially, the role of nickel and Brønsted sites on the ethylene oligomerization over Ni-H-Beta catalysts is investigated. According to the catalyst characterization results, nickel is present on the catalyst surface as Ni2+, from the free NiO phase and highly dispersed Ni2+ interacting with the catalyst’s lattice oxygen. Ethylene sorption results indicate that ethylene dissociates over two active sites upon adsorption over the Ni-H-Beta. Further characterization via pyridine sorption suggests that the presence of non-coordinated Ni2+ or Brønsted sites decreases the probability for the formation of the active sites on the catalyst surface. Then, the kinetics of ethylene oligomerization over the Ni-H-Beta are discussed. A kinetic model was developed for temperatures varying between 50 and 100°C and pressures varying between 5 and 28 atm. The results indicate the butene and hexene are formed via a series of ethylene coordination-insertion steps and the formation of octene follows the co-oligomerization of ethylene and desorbed butene. In the present study, we refer to the pathway involving co-oligomerization of butene and hexene as "cascade co-oligomerization". A detailed reaction network is proposed and modeled based on the Langmuir-Hinshelwood-Hougen-Watson kinetics. After studying the mechanisms and kinetics of the ethylene oligomerization under subcritical conditions, the solubility of coke in supercritical ethylene is discussed. The solubility of coke in ethylene was investigated at 30, 50, and 75°C and pressures ranging from 1 to 68 bar; conditions previously screened by our research group for ethylene oligomerization. The approach uses n-decane as a model compound to simulate coke formed during the catalytic process. A detailed thermodynamic model is developed for the solubility of n-decane in subcritical and supercritical ethylene. Beyond the ethylene critical point (P = 50.3 bar and T = 9.4°C) the solubility of n-decane in ethylene at 30°C reaches a maximum value of 3.0%; close to the value observed at 50 and 75°C, under the same pressure. Comparison of kinetic and solubility data show that the transport of products from the catalyst to the bulk of the supercritical fluid is a function of the reaction temperature. At low temperatures (30°C), coke dissolution rates are higher than apparent coke production rates. However, at high temperatures (60 and 90°C), coke dissolution rates are not able to outcompete the high rates of coke formation. The last step of the study with the Ni-H-Beta catalyst involves a kinetic model under supercritical ethylene conditions. The kinetic data under supercritical conditions are modeled based on the Langmuir-Hinshelwood-Hougen-Watson kinetics. Three different reaction limiting steps are compared: adsorption, chain-growth, and desorption. The model that assumes desorption of products as the reaction limiting step provides the best fitting of the kinetic data among the models proposed in the present work. Therefore, the slow desorption of products from the catalyst surface to the bulk of supercritical ethylene limits the reaction. This result is consistent with the result obtained in the solubility study.Based on the previous solubility and kinetic studies, a novel catalyst is designed for the oligomerization of supercritical ethylene. This catalyst is composed of nickel supported on mesoporous SIRAL support. We report the production of liquid products at 50, 100, and 200°C and 40 and 65 bar operating at both single and dual reactor configurations. The novel Ni-SIRAL catalyst is able to oligomerize ethylene at supercritical conditions without experiencing deactivation. The liquid product is composed of linear alkenes and a substantial fraction of cycloalkanes (8.5 wt. %). A high yield for liquid hydrocarbons of 60.8 wt. % is reported at 200oC and 65 bar.