Impact of Alkali and Alkali‐Earth Cations on Ni‐Catalyzed Dimerization of Butene

Ehrmaier, Andreas; Löbbert, Laura; Sanchez‐Sanchez, Maricruz; Bermejo‐Deval, Ricardo; Lercher, Johannes

doi:10.1002/cctc.202000349

Title: Impact of Alkali and Alkali‐Earth Cations on Ni‐Catalyzed Dimerization of Butene

Abstract

Abstract The presence of alkali (Na ⁺ or Li ⁺ ) or alkali‐earth (Ca ²⁺ or Mg ²⁺ ) cations adjusting the acid‐base properties on amorphous silica‐alumina influences markedly the catalytic properties of supported Ni for 1‐butene dimerization. The low concentration of Brønsted acid sites on these catalysts reduces the double bond isomerization of butene and inhibits the formation of dimethylhexene as primary product. While the alkali and alkali‐earth cations act as weak Lewis acid sites, only Ni ²⁺ sites are catalytically active for dimerization of 1‐butene. n ‐Octene and methylheptene are formed selectively as primary products; dimethylhexene is a secondary product. The open environment of the Ni ²⁺ sites does not induce different reaction pathways compared to Ni ²⁺ in the pores of zeolites.

Authors:

Ehrmaier, Andreas ^[1]; Löbbert, Laura ^[1]; Sanchez‐Sanchez, Maricruz ^[1]; Bermejo‐Deval, Ricardo ^[1];

^[2]

Lehrstuhl für Technische Chemie II TU München 85748 Garching Germany
Lehrstuhl für Technische Chemie II TU München 85748 Garching Germany, Institute for Integrated Catalysis Pacific Northwest National Laboratory P.O. Box 999 Richland WA 99352 USA

Publication Date:: Wed Jun 03 00:00:00 EDT 2020

Research Org.:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1631785

Alternate Identifier(s):: OSTI ID: 1631788; OSTI ID: 1643786

Report Number(s):: PNNL-SA-154839
Journal ID: ISSN 1867-3880

Grant/Contract Number:: FWP 47319; AC05-76RL01830

Resource Type:: Published Article

Journal Name:: ChemCatChem

Additional Journal Information:: Journal Name: ChemCatChem Journal Volume: 12 Journal Issue: 14; Journal ID: ISSN 1867-3880

Publisher:: Wiley Blackwell (John Wiley & Sons)

Country of Publication:: Germany

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Ehrmaier, Andreas, Löbbert, Laura, Sanchez‐Sanchez, Maricruz, Bermejo‐Deval, Ricardo, and Lercher, Johannes. Impact of Alkali and Alkali‐Earth Cations on Ni‐Catalyzed Dimerization of Butene.  Germany: N. p., 2020. 
Web.  doi:10.1002/cctc.202000349.

Copy to clipboard


                    Ehrmaier, Andreas, Löbbert, Laura, Sanchez‐Sanchez, Maricruz, Bermejo‐Deval, Ricardo, & Lercher, Johannes. Impact of Alkali and Alkali‐Earth Cations on Ni‐Catalyzed Dimerization of Butene.  Germany.  https://doi.org/10.1002/cctc.202000349

Copy to clipboard


                    Ehrmaier, Andreas, Löbbert, Laura, Sanchez‐Sanchez, Maricruz, Bermejo‐Deval, Ricardo, and Lercher, Johannes. Wed .  
"Impact of Alkali and Alkali‐Earth Cations on Ni‐Catalyzed Dimerization of Butene".  Germany.  https://doi.org/10.1002/cctc.202000349.

Copy to clipboard


                    
@article{osti_1631785,

  title        = {Impact of Alkali and Alkali‐Earth Cations on Ni‐Catalyzed Dimerization of Butene},

  author       = {Ehrmaier, Andreas and Löbbert, Laura and Sanchez‐Sanchez, Maricruz and Bermejo‐Deval, Ricardo and Lercher, Johannes},

  abstractNote = {Abstract The presence of alkali (Na + or Li + ) or alkali‐earth (Ca 2+ or Mg 2+ ) cations adjusting the acid‐base properties on amorphous silica‐alumina influences markedly the catalytic properties of supported Ni for 1‐butene dimerization. The low concentration of Brønsted acid sites on these catalysts reduces the double bond isomerization of butene and inhibits the formation of dimethylhexene as primary product. While the alkali and alkali‐earth cations act as weak Lewis acid sites, only Ni 2+ sites are catalytically active for dimerization of 1‐butene. n ‐Octene and methylheptene are formed selectively as primary products; dimethylhexene is a secondary product. The open environment of the Ni 2+ sites does not induce different reaction pathways compared to Ni 2+ in the pores of zeolites.},

  doi          = {10.1002/cctc.202000349},

  journal      = {ChemCatChem},

  number       = 14,

  volume       = 12,

  place        = {Germany},

  year         = {Wed Jun 03 00:00:00 EDT 2020},

  month        = {Wed Jun 03 00:00:00 EDT 2020}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Publisher's Version of Record
https://doi.org/10.1002/cctc.202000349

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 7 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Oligomerisierung von n-Butenen
journal, June 2005

Albrecht, S.; Kießling, D.; Wendt, G.
Chemie Ingenieur Technik, Vol. 77, Issue 6
DOI: 10.1002/cite.200407090

Dimerization of 1-butene in liquid phase reaction: Influence of structure, pore size and acidity of Beta zeolite and MCM-41 mesoporous material
journal, January 2012

Kumar, N.; Mäki-Arvela, P.; Yläsalmi, T.
Microporous and Mesoporous Materials, Vol. 147, Issue 1
DOI: 10.1016/j.micromeso.2011.05.032

Handbook of Heterogeneous Catalysis
book, March 2008

,
DOI: 10.1002/9783527610044

The Vibrational Spectrum of Pyridine and the Thermodynamic Properties of Pyridine Vapors
journal, July 1944

Kline, Charles H.; Turkevich, John
The Journal of Chemical Physics, Vol. 12, Issue 7
DOI: 10.1063/1.1723943

Über das Adsorptionsverhalten von Aluminiumoxid
journal, December 1971

Knözinger, H.; Stolz, H.
Fortschrittsberichte über Kolloide und Polymere, Vol. 55, Issue 1
DOI: 10.1007/BF02826259

Experimental and theoretical investigation of heterogeneous catalyzed oligomerization of a mixed C4 stream over modified amorphous aluminosilicates
journal, November 2018

Nadolny, Fabian; Hannebauer, Bernd; Alscher, Felix
Journal of Catalysis, Vol. 367
DOI: 10.1016/j.jcat.2018.08.014

The ion-exchange properties of zeolites. II. Ion exchange in the synthetic zeolite Linde 4A
journal, April 1967

Sherry, Howard S.; Walton, Harold F.
The Journal of Physical Chemistry, Vol. 71, Issue 5
DOI: 10.1021/j100864a042

Catalysis on solid acids: Mechanism and catalyst descriptors in oligomerization reactions of light alkenes
journal, December 2016

Sarazen, Michele L.; Doskocil, Eric; Iglesia, Enrique
Journal of Catalysis, Vol. 344
DOI: 10.1016/j.jcat.2016.10.010

The Effect of Noncatalytic Cations on the Activity and Selectivity of Nickel-Exchanged X Zeolites for Propene Oligomerization
journal, June 2013

Mlinar, Anton N.; Ho, Otto C.; Bong, Gerry G.
ChemCatChem, Vol. 5, Issue 10
DOI: 10.1002/cctc.201300232

Oligomerization of 1-butene with a homogeneous catalyst system based on allylic nickel complexes
journal, January 2015

Behr, A.; Bayrak, Z.; Peitz, S.
RSC Advances, Vol. 5, Issue 52
DOI: 10.1039/C5RA05202E

Propene Oligomerization using Alkali Metal- and Nickel-Exchanged Mesoporous Aluminosilicate Catalysts
journal, December 2013

Mlinar, Anton N.; Shylesh, Sankaranarayanapillai; Ho, Otto C.
ACS Catalysis, Vol. 4, Issue 1
DOI: 10.1021/cs4007809

Tracing Active Sites in Supported Ni Catalysts during Butene Oligomerization by Operando Spectroscopy under Pressure
journal, November 2016

Rabeah, Jabor; Radnik, Jörg; Briois, Valérie
ACS Catalysis, Vol. 6, Issue 12
DOI: 10.1021/acscatal.6b02331

Adsorption properties of alumina: VI. An IR-investigation of the adsorption of pyridine
journal, January 1971

Stolz, H.; Knözinger, H.
Kolloid-Zeitschrift & Zeitschrift für Polymere, Vol. 243, Issue 1
DOI: 10.1007/BF01500618

Das Mülheimer Normaldruck-Polyäthylen-Verfahren
journal, October 1955

Ziegler, Karl; Holzkamp, E.; Breil, H.
Angewandte Chemie, Vol. 67, Issue 19-20
DOI: 10.1002/ange.19550671902

Ziegler-Natta catalysis II. Surface structure of layer-lattice transition metal chlorides
journal, February 1964

Arlman, E.
Journal of Catalysis, Vol. 3, Issue 1
DOI: 10.1016/0021-9517(64)90096-X

Dimerization of 1-butene over nickel zeolitic catalysts: A search for linear dimers
journal, March 1994

Beltrame, Paolo; Forni, Lucio; Talamini, Antonello
Applied Catalysis A: General, Vol. 110, Issue 1
DOI: 10.1016/0926-860X(94)80103-7

Stability of bound species during alkene reactions on solid acids
journal, May 2017

Sarazen, Michele L.; Iglesia, Enrique
Proceedings of the National Academy of Sciences, Vol. 114, Issue 20
DOI: 10.1073/pnas.1619557114

A case study: surface chemistry and surface structure of catalytic aluminas, as studied by vibrational spectroscopy of adsorbed species
journal, February 1996

Morterra, Claudio; Magnacca, Giuliana
Catalysis Today, Vol. 27, Issue 3-4
DOI: 10.1016/0920-5861(95)00163-8

Principles of electronegativity Part I. General nature
journal, February 1988

Sanderson, R. T.
Journal of Chemical Education, Vol. 65, Issue 2
DOI: 10.1021/ed065p112

On the role of co-cations in nickel exchanged LTA zeolite for butene dimerization
journal, August 2019

Ehrmaier, Andreas; Peitz, Stephan; Sanchez-Sanchez, Maricruz
Microporous and Mesoporous Materials, Vol. 284
DOI: 10.1016/j.micromeso.2019.03.047

Dimerization of Linear Butenes on Zeolite-Supported Ni ²⁺
journal, November 2018

Ehrmaier, Andreas; Liu, Yue; Peitz, Stephan
ACS Catalysis, Vol. 9, Issue 1
DOI: 10.1021/acscatal.8b03095

Textural damage of cation-exchanged LTA zeolites studied by gas adsorption
journal, January 1994

Amari, Djilali; Ginoux, Jean-Louis; Bonnetain, Lucien
Zeolites, Vol. 14, Issue 1
DOI: 10.1016/0144-2449(94)90054-X

Steaming of Zeolite BEA and Its Effect on Acidity: A Comparative NMR and IR Spectroscopic Study
journal, April 2011

Maier, Sarah M.; Jentys, Andreas; Lercher, Johannes A.
The Journal of Physical Chemistry C, Vol. 115, Issue 16
DOI: 10.1021/jp108338g

The oligomerization of butenes with partially alkali exchanged NiNaY zeolite catalysts
journal, September 1997

Nkosi, B.; Ng, F. T. T.; Rempel, G. L.
Applied Catalysis A: General, Vol. 158, Issue 1-2
DOI: 10.1016/S0926-860X(96)00420-6

Ziegler-Natta catalysis I. Mechanism of polymerization of $alpha;-olefins with Ziegler-Natta catalysts*1
journal, February 1964

Cossee, P.
Journal of Catalysis, Vol. 3, Issue 1
DOI: 10.1016/0021-9517(64)90095-8

The role of different Ni sites in supported nickel catalysts for butene dimerization under industry-like conditions
journal, August 2009

Brückner, A.; Bentrup, U.; Zanthoff, H.
Journal of Catalysis, Vol. 266, Issue 1
DOI: 10.1016/j.jcat.2009.05.021

Similar Records in DOE PAGES and OSTI.GOV collections:

Dimerization of Linear Butenes on Zeolite-Supported Ni ²⁺

Journal Article Ehrmaier, Andreas ; Liu, Yue ; Peitz, Stephan ; ... - ACS Catalysis

Nickel- and alkali-earth-modified LTA based zeolites catalyze the dimerization of 1-butene in the absence of Bronsted acid sites. The catalyst reaches over 95% selectivity to n-octenes and methylheptenes. The ratio of these two dimers is markedly influenced by the parallel isomerization of 1-butene to 2-butene, shifting the methylheptene/octene ratio from 0.7 to 1.4 as the conversion increases to 35%. At this conversion, the thermodynamic equilibrium of 90% cis- and trans-2-butenes is reached. Conversion of 2-butene results in methylheptene and dimethylhexene with rates that are 1 order of magnitude lower than those with 1-butene. The catalyst is deactivated rapidly by stronglymore »« less
https://doi.org/10.1021/acscatal.8b03095
Propene Oligomerization using Alkali Metal- and Nickel-Exchanged Mesoporous Aluminosilicate Catalysts

Journal Article Mlinar, Anton N. ; Shylesh, Sankaranarayanapillai ; Ho, Otto C. ; ... - ACS Catalysis

A series of alkali metal- and nickel-exchanged Al-MCM-41 catalysts were prepared via aqueous ion exchange and then investigated for gas-phase oligomerization of propene at 453 K and near ambient pressures. All catalysts were active and produced oligomers with >98% selectivity. The highest activities per Ni²⁺ cation were observed when the cations were highly dispersed as a consequence of either lowering the Ni loading for a fixed MCM-41 Si/Al ratio or by decreasing the concentration of exchangeable sites within the material by increasing the MCM-41 Si/Al ratio at a fixed Ni loading. The identity of the alkali metal cation had nomore »« less
https://doi.org/10.1021/cs4007809
Rapid atom-efficient polyolefin plastics hydrogenolysis mediated by a well-defined single-site electrophilic/cationic organo-zirconium catalyst

Journal Article Mason, Alexander H. ; Motta, Alessandro ; Das, Anusheela ; ... - Nature Communications

Abstract Polyolefins comprise a major fraction of single-use plastics, yet their catalytic deconstruction/recycling has proven challenging due to their inert saturated hydrocarbon connectivities. Here a very electrophilic, formally cationic earth-abundant single-site organozirconium catalyst chemisorbed on a highly Brønsted acidic sulfated alumina support and characterized by a broad array of experimental and theoretical techniques, is shown to mediate the rapid hydrogenolytic cleavage of molecular and macromolecular saturated hydrocarbons under mild conditions, with catalytic onset as low as 90 °C/0.5 atm H ₂ with 0.02 mol% catalyst loading. For polyethylene, quantitative hydrogenolysis to light hydrocarbons proceeds within 48 min with an activity of > 4000 mol(CH ₂more »« less
https://doi.org/10.1038/s41467-022-34707-6
Zeolite-Catalyzed Formaldehyde-Propylene Prins Condensation

Journal Article Vasiliadou, Efterpi S. ; Gould, Nicholas S. ; Lobo, Raul F. - ChemCatChem

Abstract Prins condensation of formaldehyde with propylene to form 3‐buten‐1‐ol is investigated using microporous solid acid catalysts. Zn/H‐beta shows high conversion but leads to a broad product distribution composed primarily of pyrans. Mechanistic studies revealed that 3‐buten‐1‐ol reacts via Prins cyclization or dehydrate to 1,3‐butadiene that further reacts with formaldehyde via a hetero‐Diels–Alder reaction. These secondary reactions are suppressed over ZSM‐5 catalysts: 3‐buten‐1‐ol is the predominant product over H‐ZSM‐5 zeolite under all conditions investigated. 3‐Buten‐1‐ol selectivity of up to 75 % is achieved. In a second step 3‐buten‐1‐ol dehydrates at temperatures as low as 423 K, forming 1,3‐butadiene. Although Brønsted acid sitesmore »« less
Cited by 19
https://doi.org/10.1002/cctc.201701315

Full Text Available
Metal-organic framework supported single-site nickel catalysts for butene dimerization

Journal Article Zheng, Jian ; Löbbert, Laura ; Chheda, Saumil ; ... - Journal of Catalysis

Homotopic sites in a well-controlled environment are not only ideal systems for mechanistic studies, but also allow optimal control of catalytic transformations. Sites having only a single metal cation and sites consisting of metal oxo complexes with few nickel (Ni) cations supported on the nodes of UiO-66 metal-organic framework (Ni-UiO-66) are studied for 1-butene dimerization. Monomeric Ni sites, which bind to the Zr₆ node via two Zr-OH(µ3) linkages, are active and selective for the dimerization of 1-butene to linear and mono-branched C₈ isomers. Ni oxo complexes with few Ni cations show lower activity and promote the oligomerization of transiently formedmore »« less
https://doi.org/10.1016/j.jcat.2022.06.019

Full Text Available

Similar Records

Title: Impact of Alkali and Alkali‐Earth Cations on Ni‐Catalyzed Dimerization of Butene

Abstract

Citation Formats

Oligomerisierung von n-Butenen journal, June 2005

Dimerization of 1-butene in liquid phase reaction: Influence of structure, pore size and acidity of Beta zeolite and MCM-41 mesoporous material journal, January 2012

Handbook of Heterogeneous Catalysis book, March 2008

The Vibrational Spectrum of Pyridine and the Thermodynamic Properties of Pyridine Vapors journal, July 1944

Über das Adsorptionsverhalten von Aluminiumoxid journal, December 1971

Experimental and theoretical investigation of heterogeneous catalyzed oligomerization of a mixed C4 stream over modified amorphous aluminosilicates journal, November 2018

The ion-exchange properties of zeolites. II. Ion exchange in the synthetic zeolite Linde 4A journal, April 1967

Catalysis on solid acids: Mechanism and catalyst descriptors in oligomerization reactions of light alkenes journal, December 2016

The Effect of Noncatalytic Cations on the Activity and Selectivity of Nickel-Exchanged X Zeolites for Propene Oligomerization journal, June 2013

Oligomerization of 1-butene with a homogeneous catalyst system based on allylic nickel complexes journal, January 2015

Propene Oligomerization using Alkali Metal- and Nickel-Exchanged Mesoporous Aluminosilicate Catalysts journal, December 2013

Tracing Active Sites in Supported Ni Catalysts during Butene Oligomerization by Operando Spectroscopy under Pressure journal, November 2016

Adsorption properties of alumina: VI. An IR-investigation of the adsorption of pyridine journal, January 1971

Das Mülheimer Normaldruck-Polyäthylen-Verfahren journal, October 1955

Ziegler-Natta catalysis II. Surface structure of layer-lattice transition metal chlorides journal, February 1964

Dimerization of 1-butene over nickel zeolitic catalysts: A search for linear dimers journal, March 1994

Stability of bound species during alkene reactions on solid acids journal, May 2017

A case study: surface chemistry and surface structure of catalytic aluminas, as studied by vibrational spectroscopy of adsorbed species journal, February 1996

Principles of electronegativity Part I. General nature journal, February 1988

On the role of co-cations in nickel exchanged LTA zeolite for butene dimerization journal, August 2019

Dimerization of Linear Butenes on Zeolite-Supported Ni 2+ journal, November 2018

Textural damage of cation-exchanged LTA zeolites studied by gas adsorption journal, January 1994

Steaming of Zeolite BEA and Its Effect on Acidity: A Comparative NMR and IR Spectroscopic Study journal, April 2011

The oligomerization of butenes with partially alkali exchanged NiNaY zeolite catalysts journal, September 1997

Ziegler-Natta catalysis I. Mechanism of polymerization of $alpha;-olefins with Ziegler-Natta catalysts*1 journal, February 1964

The role of different Ni sites in supported nickel catalysts for butene dimerization under industry-like conditions journal, August 2009

Oligomerisierung von n-Butenen
journal, June 2005

Dimerization of 1-butene in liquid phase reaction: Influence of structure, pore size and acidity of Beta zeolite and MCM-41 mesoporous material
journal, January 2012

Handbook of Heterogeneous Catalysis
book, March 2008

The Vibrational Spectrum of Pyridine and the Thermodynamic Properties of Pyridine Vapors
journal, July 1944

Über das Adsorptionsverhalten von Aluminiumoxid
journal, December 1971

Experimental and theoretical investigation of heterogeneous catalyzed oligomerization of a mixed C4 stream over modified amorphous aluminosilicates
journal, November 2018

The ion-exchange properties of zeolites. II. Ion exchange in the synthetic zeolite Linde 4A
journal, April 1967

Catalysis on solid acids: Mechanism and catalyst descriptors in oligomerization reactions of light alkenes
journal, December 2016

The Effect of Noncatalytic Cations on the Activity and Selectivity of Nickel-Exchanged X Zeolites for Propene Oligomerization
journal, June 2013

Oligomerization of 1-butene with a homogeneous catalyst system based on allylic nickel complexes
journal, January 2015

Propene Oligomerization using Alkali Metal- and Nickel-Exchanged Mesoporous Aluminosilicate Catalysts
journal, December 2013

Tracing Active Sites in Supported Ni Catalysts during Butene Oligomerization by Operando Spectroscopy under Pressure
journal, November 2016

Adsorption properties of alumina: VI. An IR-investigation of the adsorption of pyridine
journal, January 1971

Das Mülheimer Normaldruck-Polyäthylen-Verfahren
journal, October 1955

Ziegler-Natta catalysis II. Surface structure of layer-lattice transition metal chlorides
journal, February 1964

Dimerization of 1-butene over nickel zeolitic catalysts: A search for linear dimers
journal, March 1994

Stability of bound species during alkene reactions on solid acids
journal, May 2017

A case study: surface chemistry and surface structure of catalytic aluminas, as studied by vibrational spectroscopy of adsorbed species
journal, February 1996

Principles of electronegativity Part I. General nature
journal, February 1988

On the role of co-cations in nickel exchanged LTA zeolite for butene dimerization
journal, August 2019

Dimerization of Linear Butenes on Zeolite-Supported Ni ²⁺
journal, November 2018

Textural damage of cation-exchanged LTA zeolites studied by gas adsorption
journal, January 1994

Steaming of Zeolite BEA and Its Effect on Acidity: A Comparative NMR and IR Spectroscopic Study
journal, April 2011

The oligomerization of butenes with partially alkali exchanged NiNaY zeolite catalysts
journal, September 1997

Ziegler-Natta catalysis I. Mechanism of polymerization of $alpha;-olefins with Ziegler-Natta catalysts*1
journal, February 1964

The role of different Ni sites in supported nickel catalysts for butene dimerization under industry-like conditions
journal, August 2009