Enhanced Catalytic Performance by Zirconium Phosphate‐Modified SiO₂‐Supported RuCo Catalyst for Fischer–Tropsch Synthesis

Abstract

Our zirconium phosphate (ZrP)‐promoted Ru/Co/ZrP/SiO2 catalyst reveals a high catalytic activity and stability during Fischer–Tropsch synthesis. Surface modification with ZrP on SiO2 support with an appropriate amount of phosphorous component prevents cobalt particle aggregation and enhances its stability. These positive effects of ZrP are mainly induced by the spatial confinement of cobalt particles in a thermally stable ZrP matrix, and the catalytic performance was greatly improved when the P/(Zr+P) molar ratio was 0.134 on the CoZrP(0.5) catalyst.

Zirconium Phosphate Catalysts in the XXI Century: State of the Art from 2010 to Date

“…Cr(III) immobilized on m-ZrP Oxidation of allylic and benzylic compounds [39] Conversion of fructose into HMF [40] Fe(III) immobilized on window-type organic zirconium phosphonate Formaldehyde decomposition [41] Fe(Salen) and Cu(Salen) complexes supported on microcystalline ZrP Cyclohexene oxidation [42,43] Rh(III) and Ir(III) complexes intercalated into ZrP Visible light driven H 2 production [44] ClRh(PPh 3 ) 3 immobilized on ethoxysilane-modified ZrP Olefin hydrogenation [45] Co-Ru immobilized on ZrP/SiO 2 Fischer-Tropsch reaction [46] Pd NPs supported on ZrP Synthesis of 1,6-hexanediol from HMF [47] Heck reaction [48] Pd NPs supported on zirconium phosphonates Suzuki-Miyaura coupling reaction [49] Pd fluorinated complexes intercalated into microcrystalline ZrP Sonogashira and Heck reactions [50] TiO 2 pillared ZrP Degradation of methyl orange [51] TiO 2−x clusters grafted on ZrP nanosheets Degradation of methylene blue [52] Ag@AgCl/nanosized ZrP Degradation of Rhodamine B [53] Vanadium phosphorus oxide supported on ZrP dehydration of glycerol [54] 1-butyl-3-methylimidazolium chloride intercalated into layered θ-ZrP synthesis of propylene carbonate from CO 2 and propylene oxide [55] Mo et al immobilized Fe(III) ions on a new window-type porous organic zirconium phosphonate hybrid material having the formula Zr 5 (HPO 4 ) 6 [O 3 PCH 2 N(CH 2 CH 2 COOH)CH 2 PO 3 ] (ZrNCP), based on b-alanine-N,N-dimethylidenephosphonate groups bonded to adjacent inorganic layers, thus creating windows and, therefore, porosity [41]. Moreover, the presence of both nitrogen atoms and carbonyl groups in the organic chains allowed the coordination of metal ions with the wall of pores by ion exchange.…”

“…Co-based catalysts supported on oxides generally exhibit high catalytic activity and selectivity to linear paraffinic hydrocarbons with a low activity for the water-gas shift reaction [46,[57][58][59][60]. They are used in combination with promoters such as Ru, Zr, Ti, and La which have different roles, including tuning the metal-support interaction and reducibility [46].…”

“…Co-based catalysts supported on oxides generally exhibit high catalytic activity and selectivity to linear paraffinic hydrocarbons with a low activity for the water-gas shift reaction [46,[57][58][59][60]. They are used in combination with promoters such as Ru, Zr, Ti, and La which have different roles, including tuning the metal-support interaction and reducibility [46]. The composite Co/ZrP/SiO 2 catalyst was also impregnated with a Ru precursor, since ruthenium acts as a promoter, and finally calcined at 400 • C so that the final catalyst had the following composition: 0.5 wt % Ru/16.6 wt % Co/7.5 wt % ZrP/75.4 wt % SiO 2 , with a different wt % P (x) on ZrP/SiO 2 , ranging from 0 to 2.…”

Ruthenium Modification on Mn and Zr-Modified Co/SiO2 Catalysts for Slurry-Phase Fischer-Tropsch Synthesis

“…It is generally accepted that the activity of Co catalysts for FT synthesis depends OPEN ACCESS on the presence of surface-exposed Co metal atoms [5,6], and therefore Co species should be both highly dispersed and reduced on the catalyst surface. For this reason, Co is generally deposited on high surface area supports such as SiO2 [7][8][9][10][11], Al2O3 [12,13] and TiO2 [14,15], in order to increase the quantity of active Co metal species. However, strong interactions between Co atoms and the support material can decrease both the reducibility and the activity of a Co catalyst [7,8].…”

“…Our group is focused on the use of SiO2 as a catalyst support and has investigated the modification of this support using both metals and oxide additives. It is well known that the addition of Zr to a Co/SiO2 catalyst (Zr/Co/SiO2) increases the FT synthesis activity of the catalyst [9][10][11]. Furthermore, the addition of Mn to Zr/Co/SiO2 enhances the catalyst stability during the FT synthesis reaction [16].…”