Kinetics of ethylene oligomerization over Ni-H-Beta catalysts

Seufitelli, Gabriel V.S.; Park, Jason J.W.; Tran, Phuong N.; Dichiara, Anthony B.; Resende, Fernando L.P.; Gustafson, Rick

doi:10.1016/j.jcat.2021.07.008

Cited by 11 publications

(26 citation statements)

References 29 publications

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“…Therefore, termination is much more consistent with the Ni-oligomerization model of Seufitelli et al, which reports a butene formation activation energy of 10.5 kcal mol −1 . 48 Likewise, many of the acid site parameters are close in magnitude to those found by Vernuccio et al in the kinetic modeling of propylene oligomerization in H-ZSM-5. The differences in pre-exponential factors and intrinsic energy barriers likely come from a combination of different framework structures, Ni-exchange effects, range of valid operating conditions, and lumping rescaling.…”

Section: Table 1 Summary Of Catalyst Properties and Experimental Reac...supporting

confidence: 76%

“…80 Seufitelli et al do explore octene production via a solely ethene coordination against octene production via readsorption of butene, which is referred to as "cascade cooligomerization". 48 Yet, both models were able to describe the trends in experimental rates. Moreover, Seufitelli et al does not include the possibility of octene production via acid-catalyzed oligomerization.…”

Section: Table 1 Summary Of Catalyst Properties and Experimental Reac...mentioning

confidence: 99%

“…Recently, Seufitelli et al published a model of ethene oligomerization over Ni−H-β; however, this model only considered Ni sites in the production of butene, hexene, and octene, and acid site chemistry was not considered. 48 In this work, Toch et al's Ni−H-β model was recreated and expanded upon to capture the experimental results of Toch et al, 32 Martı ́nez et al, 21 and Joshi et al, 2020 all of which are previously published experimental investigations on Ni−H-β zeolites using different space times, temperatures, and catalyst properties. To reach higher conversions and olefin size, postnetwork generation isomer lumping techniques were used to assume equilibrium between similar isomers and hence reduce computational demand and model stiffness.…”

Section: ■ Introductionmentioning

confidence: 99%

“…However, Toch et al made simplifying kinetic assumptions, matched a single experimental data set that reached a maximum of 15% conversion, and extrapolated up to 99% conversion, which are aspects addressed and improved upon in our Ni−β model. Recently, Seufitelli et al published a model of ethene oligomerization over Ni–H-β; however, this model only considered Ni sites in the production of butene, hexene, and octene, and acid site chemistry was not considered …”

Section: Introductionmentioning

confidence: 99%

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Kinetic Modeling of Ethene Oligomerization on Bifunctional Nickel and Acid β Zeolites

Koninckx

Gounder

Thybaut

et al. 2022

Ind. Eng. Chem. Res.

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Bifunctional catalysts are challenging to model because there are two active sites capable of unique intermediates and reaction types. Nevertheless, they are versatile catalysts because the relative number of both active sites can be tuned to alter rate and selectivity in response to variation in feed compositions. In this work, a microkinetic model of ethene oligomerization on a Ni−H-β zeolite catalyst was developed based on nickel and Brønsted acid reaction families, with kinetic parameters estimated using transition-state theory, Evans− Polanyi relationships, and thermodynamic data. Species lumping allowed for the formation of products of high molecular weight at high conversion to be captured in the model while avoiding network truncation effects. The reaction mechanism culminated in a complex model describing the formation of C2−C12 products that accurately predicted three published experimental investigations using Ni−H-β (10 unique experiments) up to about 30% conversion. The agreement between the experiment and model predictions demonstrates the model's broad applicability and robustness. Ni sites produce linear alkenes of even carbon number, while Brønsted acid sites catalyze further oligomerization, cracking, and isomerization to broaden the product distribution. The model was used to probe potential experimental conditions and catalyst properties, without extrapolation, allowing for a better understanding of the effect of common experimental parameters (space time, temperature, pressure, Ni wt %) on reaction flux and selectivity to desired products, demonstrating the model as a powerful tool in catalyst and process design.

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Section: Table 1 Summary Of Catalyst Properties and Experimental Reac...supporting

confidence: 76%

Section: Table 1 Summary Of Catalyst Properties and Experimental Reac...mentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Kinetic Modeling of Ethene Oligomerization on Bifunctional Nickel and Acid β Zeolites

Koninckx

Gounder

Thybaut

et al. 2022

Ind. Eng. Chem. Res.

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“…As the partial pressure of the olefin is increased, the Ni sites are occupied by more adsorbed surface species which results in the first order dependency on propylene partial pressure (Table S2 †). 60,76,77 Cho et al reported similar reaction rate order dependency on ethylene partial pressure for butene production while investigating ethylene oligomerization. With a 1 wt% Ni-POM-WD loading on SBA-15 at 0.62 MPa, the authors found the butene production reaction rate followed a second order dependence, whereas at 2 MPa the observed reaction rate followed a first order dependence.…”

Section: Measurement Of Kinetic Parameters Of Ni-pom-wdmentioning

confidence: 86%

Single-site, Ni-modified Wells–Dawson-type polyoxometalate for propylene dimerization

Magazova

Cho

Muhlenkamp

et al. 2022

Catal. Sci. Technol.

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Ethylene Oligomerization: Unraveling the Roles of Ni Sites, Acid Sites, and Zeolite Pore Topology through Continuous and Pulsed Reactions

Abed,

Mohamed,

Hita

et al. 2023

ChemCatChem

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Herein, four catalysts, consisting of either MFI or BEA as the zeolite framework in the presence or absence of Ni, are compared to explore the individual and collective adsorptive and catalytic contributions of pore topology, Ni sites, and acid sites. Both continuous and pulsed chemisorption/reaction experiments are used to obtain a complete picture of the time‐dependent adsorption‐desorption behavior, reaction mechanisms, and deactivation steps. The methodology highlights the effect of acid sites, especially during the initial stages of reaction and in the BEA‐based catalysts, which have higher acidity at a given Si/Al ratio. In addition, Ni accelerates the reaction and improves the selectivity towards intermediate oligomers. However, the tendency for the most active Ni and acid sites to saturate and deactivate more rapidly than the less active ones may lead to misinterpretation when using the continuous reactor alone. Hence, the dominant mechanisms over the different catalyst sites and reaction times are discussed based on the combined steady and dynamic experiments.

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Kinetics of ethylene oligomerization over Ni-H-Beta catalysts

Cited by 11 publications

References 29 publications

Kinetic Modeling of Ethene Oligomerization on Bifunctional Nickel and Acid β Zeolites

Kinetic Modeling of Ethene Oligomerization on Bifunctional Nickel and Acid β Zeolites

Single-site, Ni-modified Wells–Dawson-type polyoxometalate for propylene dimerization

Ethylene Oligomerization: Unraveling the Roles of Ni Sites, Acid Sites, and Zeolite Pore Topology through Continuous and Pulsed Reactions

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