Novel Ni-SIRAL Catalyst for Heterogeneous Ethylene Oligomerization

Abstract

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.

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

“…61 Recently, Seufitelli and Gustafson reported ethylene oligomerization with a Ni-SIRAL catalyst with rates of 11.1 × 10 −5 mol g cat −1 s −1 at supercritical conditions (200 °C and 65 bar). 62 The observed ethylene dimers over Ni-POM-WD/SBA-15 were exclusively linear butenes, which was expected for transition metal-catalyzed olefin oligomerization proceeding through the Cossee–Arlman pathway. 13 The measured kinetic parameters were consistent with Ni 2+ exchanged on zeolites, the apparent activation energy was averaged at 41 kJ mol −1 and reaction rate order was estimated as 1.9.…”

Techno-economic analysis of an integrated biorefinery to convert poplar into jet fuel, xylitol, and formic acid

“…The present design employs a trifluoromethanesulfonic acid silica-based catalyst at 200 °C and 1 atm [45] for ethanol dehydration into ethylene, with an overall yield of 98% and excellent selectivity (> 99%) to production of ethylene as reported in the literature [45]. In the present design, a nickel-based heterogeneous catalyst (Ni-H-Beta, Ni-SBA15, or Ni-Siral) was used for ethylene oligomerization based on previous studies at the University of Washington [46][47][48][49][50][51][52]. Conversions and selectivities have been reported in [46][47][48][49][50][51] for ethylene oligomerization.…”

Impacts of Ni-Loading Method on the Structure and the Catalytic Activity of NiO/SiO2-Al2O3 for Ethylene Oligomerization

“…With the gradual maturation of technologies for producing ethylene using resources other than petroleum (e.g., dehydrogenation of ethane derived from shale gas, bioethanol conversion to ethylene by catalytic dehydration, and the zeolite-catalyzed methanol-toolefin (MTO) process), the production of chemicals and liquid fuels from ethylene has attracted renewed attention [1][2][3]. Oligomerization of ethylene into long-chain olefins is one of the important reactions required for ethylene conversion and has been applied in the production of chemical intermediates, base materials, and liquid fuels [1,[4][5][6]. Currently, several million tons of linear α-olefins are produced by homogeneously-catalyzed ethylene oligomerization (EO), which comprises transition metal complexes, alkylaluminum cocatalysts, and organic solvents.…”

“…Ni-containing catalysts, microporous and mesoporous catalysts, and solid acid catalysts have been extensively studied as heterogeneous catalysts for EO; examples of such catalysts include the following: nickel ion-exchanged zeolites (e.g., Y [6,9,10], beta [11][12][13][14], ZSM-5 [15,16], MCM-22 [17,18], MCM-36 [17,18]); nickel-loaded amorphous silica-alumina (ASA) [5,[19][20][21][22][23][24][25][26][27]; Ni-exchanged cationic clay [28]; Ni-containing ordered mesoporous silicaalumina (e.g., Al-MCM-41 [29][30][31][32], Al-SBA-15 [33][34][35][36], Al-KIT-6 [37,38]); nickel sulfate (NiSO 4 ) supported on Al 2 O 3 [39][40][41][42], ASA [43], ZrO 2 [44] or TiO 2 [44]; and nickel phosphide (Ni 2 P) supported on ASA [45] or SiO 2 [46]. These catalysts are easy to handle and recycle, and they do not need any promoters or solvents (except for Ni 2 P catalysts).…”