Olefin dimerization over cobalt-oxide-on-carbon catalysts I. Propylene dimerization

Schultz, Robert G.; Schuck, James M.; Wildi, Bernard S.

doi:10.1016/0021-9517(66)90164-3

Cited by 19 publications

(10 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The doubly ammoniated cobalt oxide on carbon catalyst (2A-CoOx/N-C) was reported to exhibit high linear C8 olefin selectivity (70–85%). This linear oligomer selectivity is almost two times as high as that of other heterogeneous catalysts including solid acid catalysts, , supported nickel oxide, and cobalt oxide on other supports. , The low linear selectivity (less than 30%) of solid acid catalysts is due to the existence of Brønsted acid sites that create tertiary and secondary carbocations. Our postulated mechanism for 1-butene oligomerization by our cobalt oxide on N-doped carbon catalyst is a Cossee–Arlman insertion mechanism (Figure ).…”

Section: Introductionmentioning

confidence: 82%

Cobalt Oxide on N-Doped Carbon for 1-Butene Oligomerization to Produce Linear Octenes

Zhao

Chada

et al. 2017

ACS Catal.

View full text Add to dashboard Cite

Cobalt oxide supported on N-doped carbon catalysts were investigated for 1-butene oligomerization. The materials were synthesized by treating activated carbon with nitric acid and subsequently with NH 3 at 200, 400, 600, and 800 °C, followed by impregnation with cobalt. The 1-butene oligomerization selectivity increased with ammonia treatment temperature of the carbon support. The oligomerization selectivity of cobalt oxide on N-doped carbon synthesized at 800 °C (800A-CoOx/N-C) is 2.6 times higher than previously reported cobalt oxide on N-doped carbon synthesized with NH 4 OH (2A-CoOx/N-C). Over 70% of the butene dimers were linear C8 olefins for all catalysts. The oligomerization selectivity increased with 1-butene conversion. The catalysts were characterized by elemental analysis, N 2 adsorption, X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy (XPS). The nitrogen content of the catalysts increases with ammonia treatment temperature as confirmed by elemental analysis. The surface content of pyridinic nitrogen with a binding energy of 398.4 ± 0.1 eV increased with ammonia treatment temperature as evidenced by deconvolution of N 1s XPS spectra.

show abstract

Section: Introductionmentioning

confidence: 82%

Cobalt Oxide on N-Doped Carbon for 1-Butene Oligomerization to Produce Linear Octenes

Zhao

Chada

et al. 2017

ACS Catal.

View full text Add to dashboard Cite

show abstract

“…The 13 wt % cobalt on carbon catalyst was synthesized based on a wetness impregnation method previously described in the literature. , The catalyst is denoted as CoO X /N–C. The chromium-promoted cobalt on carbon catalyst was synthesized as follows: 2.00 g of sieved activated carbon (Norit, Darco MRXm-1721; BET surface area 600–800 m 2 /g; 250–600 μm particle size) was first treated with 1.8 mL of 30% NH 4 OH solution at room temperature.…”

Section: Methodsmentioning

confidence: 99%

“…Schultz et al have used cobalt oxide supported on ammonia-treated carbon for the dimerization of light olefins. − Ort et al improved the activity of this catalyst by approximately 2-fold by adding ZnO into the cobalt oxide on carbon catalyst. Addy et al have reported that the incorporation of nickel, chromium, and copper into the cobalt oxide supported on carbon catalyst was able to show improved activity for olefin oligomerization.…”

Section: Introductionmentioning

confidence: 99%

Ethylene Dimerization and Oligomerization to 1-Butene and Higher Olefins with Chromium-Promoted Cobalt on Carbon Catalyst

Xu¹,

Chada²,

Xu³

et al. 2018

ACS Catal.

View full text Add to dashboard Cite

Industrial dimerization of ethylene to 1-butene is achieved with catalysts bearing ligand structures and activated by a co-catalyst. Here, we report that a Cr-promoted cobalt oxide on carbon catalyst was able to produce 1-butene with 53.5− 82.4% total selectivity at ethylene conversions between 8.9 and 31.5% without the use of a co-catalyst. The Cr-promoted catalyst showed enhanced activity and stability compared to the nonpromoted catalyst. The characterization results revealed that the incorporation of Cr into the cobalt oxide on carbon catalyst was able to decrease the cobalt oxide particle size. Charge transfer from Cr to Co was also observed in the Cr-promoted catalyst compared to monometallic Co and Cr on carbon. The kinetic model built to rationalize the experimental observations predicted a 50% increase in active site dispersion in the Crpromoted catalyst, which explained the 1.6× apparent reaction rate increase compared to the nonpromoted catalyst.

show abstract

“…[2] The value of a long olefin depends on its skeletal structure; linear olefins are the most valuable. [5][6] The development of a solid cobalt catalyst for olefin-oligomerization is, however, not straightforward. Homogeneous cobalt catalysts show better selectivity for linear oligomers than nickel catalysts and are more resistant to poisons, such as thiols, thiophenes, and dihydrogensulfide impurities that are contained in industrial feedstocks.…”

mentioning

confidence: 99%

“…In industrial olefin-oligomerization processes, dissolved nickel complexes and supported-nickel catalysts are used to produce semi-linear oligomers. [2][3][4][5][6] By building on the knowledge of the placement of transition-metal-and alkaline-earth-metal cations in zeolites and by exploiting the concept of framework-stabilization, we designed the first zeolite-based cobalt catalyst for olefin-oligomerization and demonstrated its excellent selectivity for the synthesis of quasi-linear octene from butenes. [3] Solid catalysts allow reactions to be performed in fixed-bed reactors.…”

mentioning

confidence: 99%

Design of a Cobalt–Zeolite Catalyst for Semi‐Linear Higher‐Olefin Synthesis

Franken¹,

Kirschhock²,

Mathys³

et al. 2012

ChemCatChem

View full text Add to dashboard Cite

Olefins that contain 6-16 carbon atoms are important chemical intermediates in the synthesis of plasticizers and surfactants. [1] They are produced on an industrial scale in oligomerization processes, mainly starting from ethylene, propylene, and butenes. [2] The value of a long olefin depends on its skeletal structure; linear olefins are the most valuable. In industrial olefin-oligomerization processes, dissolved nickel complexes and supported-nickel catalysts are used to produce semi-linear oligomers. Homogeneous cobalt catalysts show better selectivity for linear oligomers than nickel catalysts and are more resistant to poisons, such as thiols, thiophenes, and dihydrogensulfide impurities that are contained in industrial feedstocks. [3] Solid catalysts allow reactions to be performed in fixed-bed reactors. Heterogeneous cobalt catalysts have been reported in the literature dating back to the 1960s. [5][6] The development of a solid cobalt catalyst for olefin-oligomerization is, however, not straightforward. [2][3][4][5][6] By building on the knowledge of the placement of transition-metal-and alkaline-earth-metal cations in zeolites and by exploiting the concept of framework-stabilization, we designed the first zeolite-based cobalt catalyst for olefin-oligomerization and demonstrated its excellent selectivity for the synthesis of quasi-linear octene from butenes. The active site, in which alkyl chains are attached to the cobalt atom, was uniquely visualized by X-ray diffraction and structure-refinement.Zeolite catalysts have shown great potential in the olefin-oligomerization reaction. ZSM-57 zeolite in its acid form is an excellent butene-dimerization catalyst; [7] the octene products are mainly comprised of dimethylhexenes and the number of chain branches (NCB) of the dimer fraction is around 2. ZSM-22 zeolite, with its narrow tubular pores, has shown the ability to reduce the NCB of propene oligomers, but it is less active in the conversion of butenes. [8] Oligomers with low degrees of branching can be obtained by using a heterogeneous nickel catalyst in a process called OCTOL. [9] Here, the NCB of the octene-product fraction out of n-butenes is about 1.1. The mechanism of coordinative oligomerization by nickel on homogeneous as well as heterogeneous catalysts involves Ni I species and can be divided into three steps: [10][11] 1) the formation of a p-complex between the olefin and the transition-metal ion followed by transformation into a s-bonded metalÀ alkyl complex; 2) insertion of olefin molecules, in which a pbonded olefin is inserted into the metalÀcarbon bond of the metalÀalkyl complex; and 3) the termination of chain-growth by b-H-transfer or b-elimination. Starting from terminal alkenes, this mechanism leads to linear and monobranched dimerization products. On the targeted heterogeneous cobalt catalyst, on analogy with nickel, a similar reaction mechanism could be followed provided that Co I atoms with free coordination sites can be generated at the surface of a solid support.The synthetic faujasite...

show abstract

Olefin dimerization over cobalt-oxide-on-carbon catalysts I. Propylene dimerization

Cited by 19 publications

References 2 publications

Cobalt Oxide on N-Doped Carbon for 1-Butene Oligomerization to Produce Linear Octenes

Cobalt Oxide on N-Doped Carbon for 1-Butene Oligomerization to Produce Linear Octenes

Ethylene Dimerization and Oligomerization to 1-Butene and Higher Olefins with Chromium-Promoted Cobalt on Carbon Catalyst

Design of a Cobalt–Zeolite Catalyst for Semi‐Linear Higher‐Olefin Synthesis

Contact Info

Product

Resources

About