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Nickel-Exchanged Zincosilicate Catalysts for the Oligomerization of Propylene

Deimund, Mark A. and Labinger, Jay and Davis, Mark E. (2014) Nickel-Exchanged Zincosilicate Catalysts for the Oligomerization of Propylene. ACS Catalysis, 4 (11). pp. 4189-4195. ISSN 2155-5435. doi:10.1021/cs501313z.

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Two nickel-containing zincosilicates (Ni-CIT-6 and Ni–Zn-MCM-41) and two nickel-containing aluminosilicates (Ni-HiAl-BEA and Ni-USY) are synthesized and used as catalysts to oligomerize propylene into C_(3n) (C_6 and C_9) products. Both Ni-CIT-6 and Ni-HiAl-BEA have the *BEA topology and are investigated to assess the effects of framework zinc versus aluminum because the former gives two framework charges per atom, whereas the latter, only one. Ni-CIT-6 and Ni–Zn-MCM-41 enable the comparison of a microporous to a mesoporous zincosilicate. Ni^2+ ion-exchanged into zeolite Y has been previously reported to oligomerize propylene and is used here for comparison. Reaction data are obtained at 180 and 250 °C, atmospheric pressure, and WHSV = 1.0 h^–1 in a feed stream of 85 mol % propylene (in inert). At these conditions, all catalysts are capable of oligomerizing propylene with steady-state conversions ranging from 3 to 16%. With the exception of Ni-HiAl-BEA, all catalysts have higher propylene conversions at 250 °C than at 180 °C. Both *BEA materials exhibit similar propylene conversions at each temperature, but Ni-HiAl-BEA is not as selective to C_3n products as Ni-CIT-6. Zincosilicates demonstrate higher average selectivities to C_3n products than the aluminosilicates at both reaction temperatures tested. Hexene products other than those expected by simple oligomerization are present, likely formed by double-bond isomerization catalyzed at acid sites. Additionally, both of the aluminosilicate materials catalyzed cracking reactions, forming non-C_3n products. The reduced acidity of the zincosilicates relative to the aluminosilicates likely accounts for higher C_(3n) product selectivity of the zincosilicates. Zincosilicates also exhibited higher linear-to-branched hexene isomer ratios (typically 1.0–1.5) when compared with the aluminosilicates, which had ratios on the order of 0.3. The mesoporous zincosilicate shows the best reaction behavior (including C_(3n) product selectivity: ∼99% at both temperatures for Ni–Zn-MCM-41) of the catalytic materials tested here.

Item Type:Article
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URLURL TypeDescription Information
Labinger, Jay0000-0002-1942-9232
Davis, Mark E.0000-0001-8294-1477
Additional Information:© 2014 American Chemical Society. Received: September 2, 2014; Revised: October 14, 2014; Published: October 14, 2014. The authors thank BP for financial support of this work through the XC2 program.
Subject Keywords:propylene; oligomerization; nickel; zincosilicate
Issue or Number:11
Record Number:CaltechAUTHORS:20141027-132313969
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Official Citation:Nickel-Exchanged Zincosilicate Catalysts for the Oligomerization of Propylene Mark A. Deimund, Jay Labinger, and Mark E. Davis ACS Catalysis 2014 4 (11), 4189-4195
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:50863
Deposited By: Jason Perez
Deposited On:27 Oct 2014 22:25
Last Modified:10 Nov 2021 19:02

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