Oligomerization of supercritical ethylene over nickel-based silica-alumina catalysts

Jan, Oliver; Song, Kunlin; Dichiara, Anthony B.; Resende, Fernando L.P.

doi:10.1016/j.ces.2018.12.018

Cited by 17 publications

(15 citation statements)

References 26 publications

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“…The specific oligomerization activity, which corresponds to the numbers of mmoles of ethylene converted per gram of a catalyst and per hour, increases from 13 to 20 mmol g −1 h −1 when increasing pressure from 1 to 20 bar. Such results are consistent with other studies [21,23], that might be due to the decreasing of ethylene gas velocity at higher pressure, which is leading to higher residence times. Ethylene molecules could be further adsorbed to active sites, allowing higher conversions and activities.…”

Section: Effect Of Pressuresupporting

confidence: 94%

“…No peak corresponding to NiO in the profile of Ni-AlSBA-15 is observed. This is consistent with the result reported by Jan et al [21]; in which Ni is ionexchanged with the support and might be presented at level lower than the detection limit of XRD.…”

Section: Ethylene Oligomerizationsupporting

confidence: 93%

“…Liquid hydrocarbons yield was defined by amount of the obtained liquid product compared to the total ethylene fed. Ethylene conversion, product selectivity, liquid hydrocarbon yield, and deactivation rate were calculated based on previous researches [14,21] by the following equations: . Such a pattern implies the existence of the well-ordered two-dimensional hexagonal structure in SBA-15 [22].…”

Section: Ethylene Oligomerizationmentioning

confidence: 99%

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Jet fuel range hydrocarbon synthesis through ethylene oligomerization over platelet Ni-AlSBA-15 catalyst

et al. 2020

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Converting ethylene to biojet fuel range hydrocarbons via oligomerization is an important step in biojet production from ethanol. The present study investigates the catalytic ethylene oligomerization over platelet Ni-AlSBA-15 mesoporous catalysts. The catalysts are synthesized and characterized using nitrogen adsorption-desorption isotherms, X-ray fluorescence and X-ray diffraction techniques. The catalytic performances are then evaluated in a continuous flow fixed-bed reactor under various conditions of reaction weight hourly space velocities (0.56-4.5 h −1), temperatures (150-350 °C) and pressures (1-20 bar). Experimental results demonstrate that platelet Ni-AlSBA-15 is a promising catalyst for the ethylene oligomerization to produce biojet fuel range hydrocarbons. It performs a good catalytic activity, yielding 98-99 mol% ethylene conversion and 34-42 wt% C 8+ selectivity at 0.56 h −1 , 275-300 °C and 20 bar. The obtained products contain mainly C 4-C 10 olefins with low aromatic compounds. Moreover, the catalyst exhibits good stability of the activity during long periods of operation.

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Section: Effect Of Pressuresupporting

confidence: 94%

Section: Ethylene Oligomerizationsupporting

confidence: 93%

Section: Ethylene Oligomerizationmentioning

confidence: 99%

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Jet fuel range hydrocarbon synthesis through ethylene oligomerization over platelet Ni-AlSBA-15 catalyst

et al. 2020

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“…Alkene oligomerization carried out under near‐supercritical conditions has been proposed to attenuate deactivation via the solvation of carbonaceous species that serve as coke precursors, [11–15] reminiscent of regeneration treatments using supercritical alkane phases to remove coke from zeolite catalysts during hydrocarbon processing [16–20] . Mitigated deactivation was reported during ethene oligomerization on Ni−H‐Beta and Ni−Al‐SBA‐15 under supercritical conditions by Jan et al., [13] and during heavier alkene (e. g., 1‐butene, 1‐hexene) oligomerization on H‐FER, H‐MFI, and H‐FAU under near‐supercritical conditions [12,14] . The use of high pressures and low temperatures can also lead to capillary condensation of reactant alkenes within mesoporous voids, at temperatures and reduced pressures that can be predicted by the Kelvin equation [21,22] .…”

Section: Figurementioning

confidence: 99%

Effects of Ethene Pressure on the Deactivation of Ni‐Zeolites During Ethene Oligomerization at Sub‐ambient Temperatures

et al. 2021

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Ni cation sites exchanged onto microporous materials catalyze ethene oligomerization to butenes and heavier oligomers but also undergo rapid deactivation. The use of mesoporous supports has been reported previously to alleviate deactivation in regimes of high ethene pressures and low temperatures that cause capillary condensation of ethene within mesoporous voids. Here, we reproduce these prior findings on mesoporous Ni‐MCM‐41 and report that, in sharp contrast, reaction conditions that nominally correspond to ethene capillary condensation in microporous Ni‐Beta or Ni‐FAU zeolites do not mitigate deactivation, likely because confinement within microporous voids restricts the formation of condensed phases of ethene that are effective at solvating and desorbing heavier intermediates that are precursors to deactivation. Deactivation rates are found to transition from a first‐order to a second‐order dependence on Ni site density in Ni‐FAU zeolites with increasing ethene pressure, suggesting a transition in the dominant deactivation mechanism involving a single Ni site to one involving two Ni sites, reminiscent of the effects of increasing H2 pressure on changing the kinetic order of deactivation in our prior work on Ni‐Beta zeolites.

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“…Research at the University of Washington has extensively studied the oligomerization of ethylene over nickel-based solid catalysts. − We reported the production of liquid products over the Ni–H-β and provided visual evidence that supercritical ethylene promotes coke dissolution during the reaction. , High pressures are required for supercritical ethylene oligomerization because of the high ethylene critical pressure, 50.4 bar. Most of the liquid obtained under supercritical conditions comprised C 10 + alkenes with a small fraction of cycloalkanes (less than 1.0 wt %).…”

Section: Introductionmentioning

confidence: 99%

Novel Ni-SIRAL Catalyst for Heterogeneous Ethylene Oligomerization

Seufitelli

Gustafson

2022

Ind. Eng. Chem. Res.

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We describe a novel route for producing alkenes and cycloalkanes via the oligomerization of ethylene with a novel Ni-SIRAL catalyst. We report the production of liquid products (ambient conditions) at 50, 100, and 200 °C with subcritical and supercritical ethylene using Ni-SIRAL catalysts with nickel loadings varying from 0.4 to 6.9 wt %, operating at both single-and dualreactor configurations. The highest liquid yield, 43 wt %, with a single reactor, was obtained at supercritical conditions (65 bar), at 200 °C, with a nickel loading of 2.8%. Under supercritical conditions, at 200 °C, the liquid yield increased from 43 to 80 wt % after the addition of a second oligomerization reactor using the Ni-SIRAL catalyst with 2.8 wt % nickel. The ethylene oligomerization under subcritical conditions (40 bar) led to a much lower yield for liquid products than the yield obtained at supercritical conditions at both reactor configurations (single and dual). The dual-reactor configuration proved to be the better configuration for the production of cycloalkanes, with a yield of 7 wt % at subcritical conditions and 10 wt % at supercritical conditions. We proposed a reaction pathway consistent with the experimental data.

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Oligomerization of supercritical ethylene over nickel-based silica-alumina catalysts

Cited by 17 publications

References 26 publications

Jet fuel range hydrocarbon synthesis through ethylene oligomerization over platelet Ni-AlSBA-15 catalyst

Jet fuel range hydrocarbon synthesis through ethylene oligomerization over platelet Ni-AlSBA-15 catalyst

Effects of Ethene Pressure on the Deactivation of Ni‐Zeolites During Ethene Oligomerization at Sub‐ambient Temperatures

Novel Ni-SIRAL Catalyst for Heterogeneous Ethylene Oligomerization

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