172 research outputs found
Mössbauer emission study on 57Co doped carbon-supported Ni and Ni-Mo sulfide hydrotreating catalysts : the influence of phosphorus on the structure
In the present study it is demonstrated that Mössbauer emission spectroscopy (MES) can generate information on the various Ni phases present in sulfided Ni containing catalysts when a small amount of 57Co is used as a probe for Ni.Application of MES to 57Co:Ni(4.5)Mo(8.0)/C and 57Co:Ni(5.6)/C revealed the formation of a so-called "Ni-Mo-S" phase in the former and a bulk sulfide in the latter catalyst. After addition of phosphorus a "Ni-(thio)phosphate" phase is found to be formed in both catalysts.The relation between the structure of these catalysts and their activity for thiophene HDS and quinoline HDN is discussed
Sulfidation and activity of Co/C catalysts having extremely low cobalt-loading: A Moessbauer emission spectroscopy and thiophene hydrodesulfurization study
Up to a sulfiding temp. of 473 K, the behavior of Co/C catalysts with extremely low cobalt loadings (ppm range) agrees with the trend obsd. before in the Moessbauer emission spectroscopy (MES) spectra of Co/C catalysts with much higher cobalt loadings (0.04-43. wt.%). Sulfiding at 573 K results in a rather well-defined very highly dispersed (most likely monatomically) Co sulfide species which shows a doublet with the extremely large value Q.S. = 4.11 mm/s. In this species the cobalt atoms may be four-fold (square-planar) or five-fold (square-pyramid) coordinated by sulfur. Sulfiding at 673 K results in the disappearance of this highly dispersed Co sulfide species and the newly formed species are again similar to the one previously found for Co/C catalysts with higher cobalt loadings. This finally formed Co sulfide species does not exhibit the Co-Mo-S MES spectrum (Q.S. between 1.0 and 1.3 mm/s) whereas its intrinsic thiophene hydrodesulfurization (HDS) activity equals that of cobalt in the Co-Mo-S phase. Thus, there is no general relation between the thiophene HDS activity (measured at atm. pressure) and the amt. of cobalt exhibiting a Co-Mo-S MES spectrum. [on SciFinder (R)
Behavior of the resonant absorption area of a 57Fe-doped Ni/C catalyst during sulfidation
In-situ Moessbauer spectroscopy measurements down to 4.2 K were performed on a 57Fe-doped Ni/C catalyst after various successive sulfidation treatments. After exposure of the catalysts to the H2S/H2 gas mixt. at room temp., part of the 57Fe becomes sulfidic. The rest is present as a sulfate-like intermediate species. The interaction between this intermediate species and the carbon support material is influenced by water. A
An EXAFS study on the so-called "Co-Mo-S" phase in Co/C and CoMo/c, compared with a Mössbauer emission spectroscopy study
EXAFS measurements were performed on four sulfided catalysts with the same compn. as their 57Co-contg. counterparts which were previously characterized by Moessbauer emission spectroscopy. The Co species in Co/C catalysts with a Co-Mo-S-like Moessbauer emission spectrum after sulfidation at 373 K is similar to the species with the Co-Mo-S spectrum in CoMo/C catalysts. In both cases the Co atoms are present in a very highly dispersed Co species. In the catalyst without Mo this sulfidic Co species strongly sinters during sulfidation at 673 K, resulting in a Co9S8-type phase. In the CoMo/C catalyst, the Mo hinders sintering of the Co species. [on SciFinder (R)
An EXAFS study on the so-called "Co-Mo-S" phase in Co/C and CoMo/c, compared with a Mössbauer emission spectroscopy study
EXAFS measurements were performed on four sulfided catalysts with the same compn. as their 57Co-contg. counterparts which were previously characterized by Moessbauer emission spectroscopy. The Co species in Co/C catalysts with a Co-Mo-S-like Moessbauer emission spectrum after sulfidation at 373 K is similar to the species with the Co-Mo-S spectrum in CoMo/C catalysts. In both cases the Co atoms are present in a very highly dispersed Co species. In the catalyst without Mo this sulfidic Co species strongly sinters during sulfidation at 673 K, resulting in a Co9S8-type phase. In the CoMo/C catalyst, the Mo hinders sintering of the Co species. [on SciFinder (R)
Sulfidation of carbon-supported iron-molybdemum oxide catalysts
Carbon-supported iron-molybdenum sulphide catalysts were characterized by means of Mössbauer spectroscopy at temperatures down to 4.2 K. Thiophene hydrodesulphurization (HDS) activity measurements were performed at 673 K in a flow microreactor operating at atmospheric pressure. The molybdenum content was 9.5 wt.-% whereas the iron content varied from 0.6 to 9.0 wt.-%. Sequential deposition (Molybdenum first) by pore-volume impregnation was employed to prepare oxidic catalyst precursors. The oxidic catalyst precursors were dried at 293 K in an air flow, followed by an additional hydrogen treatment up to 393 K. The type and relative particle sizes of the iron compounds present in the oxidic precursors and in the sulphided and reoxidized catalysts were determined by Mössbauer spectroscopy. It was demonstrated that after sulphidation for 4 h at 623 K, the composition of the sulphide catalyst depends on the iron content. Sulphided Fe-Mo/C catalysts contain a mixed "FeMoS" phase and "Fe-sulphide". The former is responsible for the observed promoting effect toward thiophene HDS. From the temperature dependence of the resonant absorption areas, it was concluded that the iron atoms in the "FeMoS" phase are located at the surface of MoS2 microcrystals. The amount of "Fe-sulphide" present in the catalyst was found to increase with increasing iron content. This "Fe-sulphide" might partly cover the "FeMoS" phase, thus causing a decrease in the promoting effect
Sulfidation of carbon-supported iron-molybdemum oxide catalysts
Carbon-supported iron-molybdenum sulphide catalysts were characterized by means of Mössbauer spectroscopy at temperatures down to 4.2 K. Thiophene hydrodesulphurization (HDS) activity measurements were performed at 673 K in a flow microreactor operating at atmospheric pressure. The molybdenum content was 9.5 wt.-% whereas the iron content varied from 0.6 to 9.0 wt.-%. Sequential deposition (Molybdenum first) by pore-volume impregnation was employed to prepare oxidic catalyst precursors. The oxidic catalyst precursors were dried at 293 K in an air flow, followed by an additional hydrogen treatment up to 393 K. The type and relative particle sizes of the iron compounds present in the oxidic precursors and in the sulphided and reoxidized catalysts were determined by Mössbauer spectroscopy. It was demonstrated that after sulphidation for 4 h at 623 K, the composition of the sulphide catalyst depends on the iron content. Sulphided Fe-Mo/C catalysts contain a mixed "FeMoS" phase and "Fe-sulphide". The former is responsible for the observed promoting effect toward thiophene HDS. From the temperature dependence of the resonant absorption areas, it was concluded that the iron atoms in the "FeMoS" phase are located at the surface of MoS2 microcrystals. The amount of "Fe-sulphide" present in the catalyst was found to increase with increasing iron content. This "Fe-sulphide" might partly cover the "FeMoS" phase, thus causing a decrease in the promoting effect
So-called "Co-Mo-S" phase observed in carbon-supported cobalt sulfide catalyst by Mössbauer emission spectroscopy
No abstract
Hydrodesulfurization catalysis by small metal sulfide particles
Monometallic (Mo, Co and Ni) sulfide particles dispersed in the micropores of zeolites can have a very high initial activity for the hydrodesulfurization of thiophene. Catalyst characterization, using Xe-129 NMR, HREM and Mossbauer Emission Spectroscopy (MES), shows that the location (in- or outside the zeolite pores) and size of the sulfide particles depends strongly on catalyst preparation conditions. The kinetics of thiophene HDS has been studied on metal (Mo, Co, Ph and Pt) sulfides dispersed on a carbon support. The order of thiophene in the HDS reaction appears to be a strong function of metal sulfide and temperature. The catalysts show a large compensation effec
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