Effects of Weak Surface Modification on Co/SiO2 Catalyst for Fischer-Tropsch Reaction.
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ABSTRACT:
SUBMITTER: Ning W
PROVIDER: S-EPMC4418669 | biostudies-literature | 2015
REPOSITORIES: biostudies-literature
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Project description:The way in which the triple bond in CO dissociates, a key reaction step in the Fischer-Tropsch (FT) reaction, is a subject of intense debate. Direct CO dissociation on a Co catalyst was probed by 12C16O/13C18O scrambling in the absence and presence of H2. The initial scrambling rate without H2 was significantly higher than the rate of CO consumption under CO hydrogenation conditions, which indicated that the surface contained sites sufficiently reactive to dissociate CO without the assistance of H atoms. Only a small fraction of the surface was involved in CO scrambling. The minor influence of CO scrambling and CO residence time on the partial pressure of H2 showed that CO dissociation was not affected by the presence of H2. The positive H2 reaction order was correlated to the fact that the hydrogenation of adsorbed C and O atoms was slower than CO dissociation. Temperature-programmed in?situ IR spectroscopy underpinned the conclusion that CO dissociation does not require H atoms.
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Project description:Fischer-Tropsch (FT) synthesis is one of the most complex catalyzed chemical reactions in which the chain-growth mechanism that leads to formation of long-chain hydrocarbons is not well understood yet. The present work provides deeper insight into the relation between the kinetics of the FT reaction on a silica-supported cobalt catalyst and the composition of the surface adsorbed layer. Cofeeding experiments of 12C3H6 with 13CO/H2 evidence that CH x surface intermediates are involved in chain growth and that chain growth is highly reversible. We present a model-based approach of steady-state isotopic transient kinetic analysis measurements at FT conditions involving hydrocarbon products containing up to five carbon atoms. Our data show that the rates of chain growth and chain decoupling are much higher than the rates of monomer formation and chain termination. An important corollary of the microkinetic model is that the fraction of free sites, which is mainly determined by CO pressure, has opposing effects on CO consumption rate and chain-growth probability. Lower CO pressure and more free sites leads to increased CO consumption rate but decreased chain-growth probability because of an increasing ratio of chain decoupling over chain growth. The preferred FT condition involves high CO pressure in which chain-growth probability is increased at the expense of the CO consumption rate.
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Project description:A study was done on the effect of temperature and catalyst pre-treatment on CO hydrogenation over plasma-synthesized catalysts during the Fischer?Tropsch synthesis (FTS). Nanometric Co/C, Fe/C, and 50%Co-50%Fe/C catalysts with BET specific surface area of ~80 m² g?1 were tested at a 2 MPa pressure and a gas hourly space velocity (GHSV) of 2000 cm³ h-1 g-1 of a catalyst (at STP) in hydrogen-rich FTS feed gas (H?:CO = 2.2). After pre-treatment in both H? and CO, transmission electron microscopy (TEM) showed that the used catalysts shifted from a mono-modal particle-size distribution (mean ~11 nm) to a multi-modal distribution with a substantial increase in the smaller nanoparticles (~5 nm), which was statistically significant. Further characterization was conducted by scanning electron microscopy (SEM with EDX elemental mapping), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The average CO conversion at 500 K was 18% (Co/C), 17% (Fe/C), and 16% (Co-Fe/C); 46%, 37%, and 57% at 520 K; and 85%, 86% and 71% at 540 K respectively. The selectivity of Co/C for C5+ was ~98% with 8% gasoline, 61%, diesel and 28% wax (fractions) at 500 K; 22% gasoline, 50% diesel, and 19% wax at 520 K; and 24% gasoline, 34% diesel, and 11% wax at 540 K, besides CO? and CH? as by-products. Fe-containing catalysts manifested similar trends, with a poor conformity to the Anderson?Schulz?Flory (ASF) product distribution.
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Project description:In recent years, rising environmental concerns have led to the focus on some of the innovative alternative technologies to produce clean burning fuels. Fischer-Tropsch (FT) synthesis is one of the alternative chemical processes to produce synthetic fuels, which has a current research focus on reactor and catalyst improvements. In this work, a cobalt nanofilm (~4.5 nm), deposited by the atomic layer deposition (ALD) technique in a silicon microchannel microreactor (2.4 cm long × 50 µm wide × 100 µm deep), was used as a catalyst for atmospheric Fischer-Tropsch (FT) synthesis. The catalyst film was characterized by XPS, TEM-EDX, and AFM studies. The data from AFM and TEM clearly showed the presence of polygranular cobalt species on the silicon wafer. The XPS studies of as-deposited and reduced cobalt nanofilm in silicon microchannels showed a shift on the binding energies of Co 2p spin splits and confirmed the presence of cobalt in the Co0 chemical state for FT synthesis. The FT studies using the microchannel microreactor were carried out at two different temperatures, 240 °C and 220 °C, with a syngas (H2:CO) molar ratio of 2:1. The highest CO conversion of 74% was observed at 220 °C with the distribution of C1-C4 hydrocarbons. The results showed no significant selectivity towards butane at the higher temperature, 240 °C. The deactivation studies were performed at 220 °C for 60 h. The catalyst exhibited long-term stability, with only ~13% drop in the CO conversion at the end of 60 h. The deactivated cobalt film in the microchannels was investigated by XPS, showing a weak carbon peak in the XPS spectra.
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Project description:The development of efficient catalysts for Fischer-Tropsch (FT) synthesis, a core reaction in the utilization of non-petroleum carbon resources to supply energy and chemicals, has attracted much recent attention. ε-Iron carbide (ε-Fe2C) was proposed as the most active iron phase for FT synthesis, but this phase is generally unstable under realistic FT reaction conditions (> 523 K). Here, we succeed in stabilizing pure-phase ε-Fe2C nanocrystals by confining them into graphene layers and obtain an iron-time yield of 1258 μmolCO gFe-1s-1 under realistic FT synthesis conditions, one order of magnitude higher than that of the conventional carbon-supported Fe catalyst. The ε-Fe2C@graphene catalyst is stable at least for 400 h under high-temperature conditions. Density functional theory (DFT) calculations reveal the feasible formation of ε-Fe2C by carburization of α-Fe precursor through interfacial interactions of ε-Fe2C@graphene. This work provides a promising strategy to design highly active and stable Fe-based FT catalysts.
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Project description:In order to examine fundamental processes connected with the use of an unpromoted iron based Fischer-Tropsch synthesis (FTS) catalyst, model studies examining the temporal formation of hydrocarbonaceous species that form over the catalyst are undertaken using a combination of temperature-programmed oxidation, powder X-ray diffraction, Raman scattering, transmission electron microscopy and inelastic neutron scattering (INS). Catalyst samples were exposed to ambient pressure CO hydrogenation at 623 K for defined periods of time-on-stream (3, 6, 12 and 24 h) prior to analysis. INS reveals a progressive retention of hydrogenous species that is associated with the evolution of a hydrocarbonaceous overlayer, as evidenced by the presence of sp2 and sp3 hybridized C-H vibrational modes. Correlations between the formation of aliphatic and olefinic/aromatic moieties with post-reaction characterization leads to the proposal of a number of chemical transformations that, collectively, define the conditioning phase of the catalyst under the specified set of reaction conditions. A comparison between the inelastic neutron scattering spectra of the 24 h sample with that of an iron catalyst extracted from a commercial grade Fischer-Tropsch reactor validates the relevance of the experimental approach adopted.
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Project description:In situ TEM gas-cell imaging and spectroscopy with in situ XRD have been applied to reveal morphological changes in NiFe2O4@Co3O4 core-shell nanoparticles in hydrogen. The core-shell structure is retained upon reduction under mild conditions (180 °C for 1 h), resulting in a partially reduced shell. The core-shell structure was retained after exposing these reduced NiFe2O4@Co3O4 core-shell nanoparticles to Fischer-Tropsch conditions at 230 °C and 20 bar. Slightly harsher reduction (230 °C, 2 h) resulted in restructuring of the NiFe2O4@Co3O4 core-shell nanoparticles to form cobalt islands in addition to partially reduced NiFe2O4. NiFe2O4 underwent further transformation upon exposure to Fischer-Tropsch conditions, resulting in the formation of iron carbide and nickel/iron-nickel alloy. The turnover frequency in the Fischer-Tropsch synthesis over NiFe2O4@Co3O4 core-shell nanoparticles reduced in hydrogen at 180 °C for 1 h was estimated to be less than 0.02 s-1 (cobalt-time yield of 8.40 μmol.g-1.s-1) with a C5+ selectivity of 38 C-%. The low turnover frequency under these conditions in relation to the turnover frequency obtained with unsupported cobalt is attributed to the strain in the catalytically active cobalt.
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Project description:Renewable liquid fuels production from landfill waste provides a promising alternative to conventional carbon-intensive waste management methods and has the potential to contribute to the transition toward low-carbon fuel pathways. In this work, we investigated the life cycle greenhouse gas (GHG) emissions of producing Fischer-Tropsch diesel from landfill gas (LFG) using the TriFTS catalytic conversion process and compared it to fossil-based petroleum diesel. A life cycle-based comparison was made between TriFTS diesel and other LFG waste management pathways, LFG-to-Electricity and LFG-to-Compressed renewable natural gas (RNG), on a per kilogram of feedstock basis as well as on a per MJ of energy basis, which also included the LFG-to-Direct Combustion pathway. The study considered flaring of LFG as the common underlying counterfactual scenario for all of the waste-to-energy product pathways. We estimated the life cycle GHG emissions for TriFTS diesel to be -36.4 carbon dioxide equivalent (grams CO2e)/MJ which is significantly lower than its fossil fuel counterpart which was estimated to be 90.5 g CO2e/MJ on a cradle-to-grave basis. The life cycle emission results from both perspectives (per kg feedstock and per MJ energy output) show that TriFTS diesel is a viable alternative energy pathway from LFG when compared to other pathways, primarily due to the main product being a renewable fuel that can serve as a drop-in fuel for diesel-based uses, within both the waste industry as well as the larger market. Further sensitivity analysis was performed based on the production of TriFTS diesel with the counterfactual waste management scenario of LFG-to-Flaring as well as the alternative LFG-to-Electricity waste management pathway. The sensitivity of the carbon intensity for TriFTS diesel to flaring efficiency and the carbon intensity of the electricity grid were also investigated. The study highlights the potential for the TriFTS conversion process technology to contribute to the waste industry's closed loop and decarbonization initiatives and to provide low carbon fuel for transportation.
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Project description:The effectiveness of Mg as a promoter of Co-Ru/γ-Al2O3 Fischer-Tropsch catalysts depends on how and when the Mg is added. When the Mg is impregnated into the support before the Co and Ru addition, some Mg is incorporated into the support in the form of MgxAl2O3+x if the material is calcined at 550°C or 800°C after the impregnation, while the remainder is present as amorphous MgO/MgCO3 phases. After subsequent Co-Ru impregnation MgxCo3-xO4 is formed which decomposes on reduction, leading to Co(0) particles intimately mixed with Mg, as shown by high-resolution transmission electron microscopy. The process of impregnating Co into an Mg-modified support results in dissolution of the amorphous Mg, and it is this Mg which is then incorporated into MgxCo3-xO4. Acid washing or higher temperature calcination after Mg impregnation can remove most of this amorphous Mg, resulting in lower values of x in MgxCo3-xO4. Catalytic testing of these materials reveals that Mg incorporation into the Co oxide phase is severely detrimental to the site-time yield, while Mg incorporation into the support may provide some enhancement of activity at high temperature.
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Project description:Electro-fuels are seen as a promising alternative to curb carbon emissions in the transport sector due to their appealing properties, similar to those of their fossil counterparts, allowing them to use current infrastructure and state-of-the-art automotive technologies. However, their broad implications beyond climate change remain unclear as previous studies mainly focused on analyzing their carbon footprint. To fill this gap, here, we evaluated the environmental and economic impact of Fischer-Tropsch electro-diesel (FT e-diesel) synthesized from electrolytic H2 and captured CO2. We consider various power (wind, solar, nuclear, or the current mix) and carbon sources (capture from the air (DAC) or a coal power plant) while covering a range of impacts on human health, ecosystems, and resources. Applying process simulation and life cycle assessment (LCA), we found that producing e-diesel from wind and nuclear H2 combined with DAC CO2 could reduce the carbon footprint relative to fossil diesel, leading to burden-shifting in human health and ecosystems. Also, it would incur prohibitive costs, even when considering externalities (i.e., indirect costs of environmental impacts). Overall, this work highlights the need to embrace environmental impacts beyond climate change in the analysis of alternative fuels and raises concerns about the environmental appeal of electro-fuels.
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