Effect of Support on Stability and Coke Resistance of Ni-Based Catalyst in Combined Steam and CO2 Reforming of CH4
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ABSTRACT:
SUBMITTER: Hong Phuong P
PROVIDER: S-EPMC9202042 | biostudies-literature | 2022 Jun
REPOSITORIES: biostudies-literature
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Project description:Methane steam reforming (MSR) plays a key role in the production of syngas and hydrogen from natural gas. The increasing interest in the use of hydrogen for fuel cell applications demands development of catalysts with high activity at reduced operating temperatures. Ni-based catalysts are promising systems because of their high activity and low cost, but coke formation generally poses a severe problem. Studies of ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) indicate that CH4/H2O gas mixtures react with Ni/CeO2(111) surfaces to form OH, CH x , and CH x O at 300 K. All of these species are easy to form and desorb at temperatures below 700 K when the rate of the MSR process is accelerated. Density functional theory (DFT) modeling of the reaction over ceria-supported small Ni nanoparticles predicts relatively low activation barriers between 0.3 and 0.7 eV for complete dehydrogenation of methane to carbon and the barrierless activation of water at interfacial Ni sites. Hydroxyls resulting from water activation allow for CO formation via a COH intermediate with a barrier of about 0.9 eV, which is much lower than that through a pathway involving lattice oxygen from ceria. Neither methane nor water activation is a rate-determining step, and the OH-assisted CO formation through the COH intermediate constitutes a low-barrier pathway that prevents carbon accumulation. The interactions between Ni and the ceria support and the low metal loading are crucial for the reaction to proceed in a coke-free and efficient way. These results pave the way for further advances in the design of stable and highly active Ni-based catalysts for hydrogen production.
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Project description:A highly active and stable nano structured Pt/Mg1-xNixO catalysts was developed by a simple co-precipitation method. The obtained Pt/Mg1-xNixO catalyst exhibited cubic structure nanocatalyst with a size of 50-80 nm and realized CH4 and CO2 conversions as high as 98% at 900°C with excellent stability in the dry reforming of methane. The characterization of catalyst was performed using various kinds of analytical techniques including XRD, BET, XRF, TPR-H2, TGA, TEM, FESEM, FT-IR, and XPS analyses. Characterization of spent catalyst further confirms that Pt/Mg1-xNixO catalyst has high coke-resistance for dry reforming. Thus, the catalyst demonstrated in this study, offers a promising catalyst for resolving the dilemma between dispersion and reducibility of supported metal, as well as activity and stability during high temperature reactions.
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Project description:Reforming CH4 into syngas using CO2 remains a fundamental challenge due to carbon deposition and nanocatalyst instability. We, for the first time, demonstrate highly efficient electrochemical reforming of CH4/CO2 to produce syngas in a solid oxide electrolyser with CO2 electrolysis in the cathode and CH4 oxidation in the anode. In situ exsolution of an anchored metal/oxide interface on perovskite electrode delivers remarkably enhanced coking resistance and catalyst stability. In situ Fourier transform infrared characterizations combined with first principle calculations disclose the interface activation of CO2 at a transition state between a CO2 molecule and a carbonate ion. Carbon removal at the interfaces is highly favorable with electrochemically provided oxygen species, even in the presence of H2 or H2O. This novel strategy provides optimal performance with no obvious degradation after 300 hours of high-temperature operation and 10 redox cycles, suggesting a reliable process for conversion of CH4 into syngas using CO2.
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Project description:Dry reforming of methane (DRM) is an efficient process to transform methane and carbon dioxide to syngas. Nickel could show good catalytic activity for DRM, whereas the deactivation of nickel surfaces by the formation of inert carbon structures is inevitable. In this study, we carry out a detailed investigation of the evolution and catalytic performance of the carbon-covered surface structure on Ni(100) with a combined density functional theory and microkinetic modeling approach. The results suggest that the pristine Ni(100) surface is prone to carbon deposition and accumulation under reaction conditions. Further studies show that over this carbon-covered reconstructed Ni(100) surface, a carbon-based Mars-van-Krevelen mechanism would be favored, and the activity and coke resistance is promoted. This surface state and reaction mechanism were rarely reported before and would provide more insights into the DRM process under real reaction conditions and would help design more stable Ni catalysts.
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Project description:In the present study, Ni/Ce-Sm-xCu (x = 5, 7, 10 at.%) catalysts were prepared using microwave radiation coupled with sol-gel and followed by wetness impregnation method for the Ni incorporation. Highly dispersed nanocrystallites of CuO and NiO on the Ce-Sm-Cu support were found. Increase of Cu content seems to facilitate the reducibility of the catalyst according to the H₂ temperature-programmed reduction (H₂-TPR). All the catalysts had a variety of weak, medium and strong acid/basic sites that regulate the reaction products. All the catalysts had very high XC3H8O3 for the entire temperature (400⁻750 °C) range; from ≈84% at 400 °C to ≈94% at 750 °C. Ni/Ce-Sm-10Cu catalyst showed the lowest XC3H8O3-gas implying the Cu content has a detrimental effect on performance, especially between 450⁻650 °C. In terms of H₂ selectivity (SH2) and H₂ yield (YH2), both appeared to vary in the following order: Ni/Ce-Sm-10Cu > Ni/Ce-Sm-7Cu > Ni/Ce-Sm-5Cu, demonstrating the high impact of Cu content. Following stability tests, all the catalysts accumulated high amounts of carbon, following the order Ni/Ce-Sm-5Cu < Ni/Ce-Sm-7Cu < Ni/Ce-Sm-10Cu (52, 65 and 79 wt.%, respectively) based on the thermogravimetric analysis (TGA) studies. Raman studies showed that the incorporation of Cu in the support matrix controls the extent of carbon graphitization deposited during the reaction at hand.
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Project description:This study investigates the influence of the phosphorus-to-nickel (P:Ni) ratio on methanol steam reforming (MSR) over nickel phosphide catalysts using density functional theory (DFT) calculations. The catalytic behavior of Ni(111) and Ni12P5(001) surfaces was explored and contrasted to our previous results from research on Ni2P(001). The DFT-predicted barriers reveal that Ni(111) predominantly favors the methanol decomposition route, where methanol is converted into carbon monoxide through a stepwise pathway involving CH3OH* → CH3O* → CH2O* → CHO* → CO*. On the other hand, Ni12P5 with a P:Ni atomic ratio of 0.42 (5:12) exhibits a substantial increase in selectivity towards methanol steam reforming (MSR) relative to methanol decomposition. In this pathway, formaldehyde is transformed into CO2 through a sequence of reactions involving CH2O*→ H2COOH* → HCOOH* → HCOO* → CO2. The introduction of phosphorus into the catalyst alters the surface morphology and electronic structure, favoring the MSR pathway. However, with a further increase in the P:Ni atomic ratio to 0.5 (1:2) on Ni2P catalysts, the selectivity towards MSR decreases, resulting in a more balanced competition between methanol decomposition and MSR. These results highlight the significance of tuning the P:Ni atomic ratio in designing efficient catalysts for the selective production of CO2 through the MSR route, offering valuable insights into optimizing nickel phosphide catalysts for desired chemical transformations.
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Project description:In this work; a response surface methodology (RSM) was implemented to investigate the process variables in a hydrogen production system. The effects of five independent variables; namely the temperature (X₁); the flow rate (X₂); the catalyst weight (X₃); the catalyst loading (X₄) and the glycerol-water molar ratio (X₅) on the H₂ yield (Y₁) and the conversion of glycerol to gaseous products (Y₂) were explored. Using multiple regression analysis; the experimental results of the H₂ yield and the glycerol conversion to gases were fit to quadratic polynomial models. The proposed mathematical models have correlated the dependent factors well within the limits that were being examined. The best values of the process variables were a temperature of approximately 600 °C; a feed flow rate of 0.05 mL/min; a catalyst weight of 0.2 g; a catalyst loading of 20% and a glycerol-water molar ratio of approximately 12; where the H₂ yield was predicted to be 57.6% and the conversion of glycerol was predicted to be 75%. To validate the proposed models; statistical analysis using a two-sample t-test was performed; and the results showed that the models could predict the responses satisfactorily within the limits of the variables that were studied.
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Project description:The suppression of methane and coke formation over Ni-based catalysts for low temperature ethanol steam reforming remains challenging. This paper describes the structural evolution of Fe-modified Ni/MgAl2O4 catalysts and the influence of iron species on methane and coke suppression for low temperature ethanol steam reforming. Ni-Fe alloy catalysts are gradually oxidized by water to generate Ni-rich alloy and γ-Fe2O3 species at steam-to-carbon ratio of 4. The electron transfer from iron to nickel within Ni-Fe alloy weakens the CO adsorption and effectively alleviates the CO/CO2 methanation. The oxidation capacity of γ-Fe2O3 species promotes the transformation of ethoxy to acetate groups to avoid methane formation and the elimination of carbon deposits for anticoking. Ni10Fe10/MgAl2O4 shows a superior performance with a highest H2 yield of 4.6 mol/mol ethanol at 400 °C for 15 h. This research could potentially provide instructions for the design of Ni-based catalysts for low-temperature ethanol steam reforming.
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Project description:A series of Cu catalysts supported on SiO2, Al2O3-SiO2, TiO2 rutile, and Cu/TiO2 anatase metal oxides has been studied for methanol reforming in the vapor phase. The highest activity was obtained on Cu/SiO2 catalysts (5493 ?mol H2 min-1·gcat -1) followed by Cu/TiO2 rutile, Cu/Al2O3-SiO2, and anatase. XRD and HRTEM characterization after reaction revealed that on Cu/SiO2 significant sintering occurred during reaction. In contrast, the particle size growth on Cu/TiO2 rutile and anatase was less pronounced, which could be associated with the interaction between Cu clusters and TiO2. Characterization by TGA showed that on Cu/Al2O3-SiO2 the main cause of deactivation was coke deposition.
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