Ordered mesoporous Fe-Al2O3 based-catalysts synthesized via a direct "one-pot" method for the dry reforming of a model biogas mixture

Biogas plays a vital role in the emerging renewable energy sector and its efficient utilization is attracting significant attention as an alternative energy carrier to non-renewable fossil fuel resources. Since biogas consists mainly of CH₄ and CO₂, dry reforming of methane arises as an appropriate process enabling its chemical conversion to high-quality synthesis gas (syngas: H₂ and CO mixtures). In this study, we synthesized via a direct "one-pot" method following an evaporation-induced self-assembly approach, ordered mesoporous Fe_10%, Ni_5% and Fe_x%Ni_(1-x) (x: 2.5, 5 or 7.5%) in Al₂O₃ as catalysts for syngas production via dry reforming of a model biogas mixture (CH₄/CO₂ = 1.8, at a temperature of 700 °C). Monometallic Fe_10%Al₂O₃ catalyst presented lower reactivity levels and slightly deactivated during catalysis compared to stable Ni_5%Al₂O₃. According to physico-chemical characterization techniques, the incomplete reduction of Fe₂O₃ into Fe₃O₄ rather than Fe⁰ nanoparticles (catalytically active) coupled with the segregation of Fe₃O₄ oxides were the main factors leading to the low performance of mesoporous Fe_10%Al₂O₃. These drawbacks were overcome upon the partial substitution of Fe by Ni (another transition metal) forming specifically bimetallic Fe_5%Ni_5%Al₂O₃ displaying reactivity levels close to thermodynamic expected ones. The formation of Fe-Ni alloys stabilized iron inside alumina matrix and protected it from segregation. Along with the confinement effect, spent catalyst characterizations showed high resistance towards coke deposition.     

Iron incorporated Ni–ZrO2 catalysts for electric power generation from methane

On the purpose to perform as functional layer of SOFCs operating on methane fuel, NiFe–ZrO₂ alloy catalysts have been synthesized and investigated for methane partial oxidation reactions. Ni₄Fe₁–ZrO₂ shows catalytic activity comparable to that of Ni–ZrO₂ and superior to other Fe-containing catalysts. In addition, O₂-TPO analysis indicates iron is also prone to coke formation; as a result, most of NiFe–ZrO₂ catalysts do not show improved coking resistance than Ni–ZrO₂. Anyway, Ni₄Fe₁–ZrO₂ (Ni:Fe = 4:1 by weight) prepared by glycine-nitrate process shows somewhat less carbon deposition than the others. However, Raman spectroscopy demonstrates that the addition of Fe does reduce the graphitization degree of the deposited carbon, suggesting the easier elimination of carbon once it is deposited over the catalyst. Ni₄Fe₁–ZrO₂ has an excellent long-term stability for partial oxidation of methane reaction at 850 °C. A solid oxide fuel cell with conventional nickel cermet anode and Ni₄Fe₁–ZrO₂ functional layer is operated on CH₄–O₂ gas mixture to yield a peak power density of 1038 mW cm⁻² at 850 °C, which is comparable to that of hydrogen fuel. In summary, the Ni₄Fe₁–ZrO₂ catalyst is potential catalyst as functional layer for solid-oxide fuel cells operating on methane fuel.     

Thermochemical methane reforming using WO3 as an oxidant below 1173 K by a solar furnace simulator

Thermochemical methane reforming by a reactive redox system of WO₃ was demonstrated under direct irradiation of the metal oxide by a concentrated, solar-simulated Xe-lamp beam below 1173 K, for the purpose of converting solar high-temperature heat to chemical fuels. In the proposed cycling redox process, the metal oxide is expected to react with methane as an oxidant to produce syngas with a H₂/CO ratio of two, which is suitable for the production of methanol, and the reduced metal oxide which is oxidized back with steam in a separate step to generate hydrogen uncontaminated with carbon oxide. The ZrO₂-supported WO₃ gave about 45% of CO yield and 55% of H₂ yield with a H₂/CO ratio of about 2.4 in a temperature range of 1080–1160 K at a W/F ratio of 0.167 g min Ncm⁻³ (W is the weight of WO₃ phase and F is the flow rate of CH₄). The activity data under the solar simulation were compared to those for the WO₃/ZrO₂ heated by irradiation of an infrared light. This comparison indicated that the CO selectivity was much improved to 76–85% in the solar-simulated methane reforming, probably by photochemical effect due to WO₃ phase. The main solid product of WO₂ in the reduced WO₃/ZrO₂ was reoxidized to WO₃ with steam to generate hydrogen below 1173 K.     

Effect of CaO–ZrO2 addition to Ni supported on γ-Al2O3 by sequential impregnation in steam methane reforming

Ni catalysts supported on (CaO–ZrO₂)-modified γ-Al₂O₃ were prepared by sequential impregnation. The effects of varied CaO to ZrO₂ mole ratios at 0, 0.20, 0.35, 0.45, and 0.55 on the activity and stability of the modified Ni catalysts were studied. As a result of using CaO–ZrO₂ as a promoter, each catalyst contained CaO–ZrO₂ at only 5%. γ-Al₂O₃ used as support was modified by CaO–ZrO₂ before the deposition of nickel oxide. The addition of CaO–ZrO₂ at an optimum ratio was expected to improve the stability of Ni catalysts due to the decrease of carbon formation resulting from carbon gasification. All the fresh catalysts were characterized by ICP, XRD, BET surface area, TGA in H₂, and TPR before catalytic testing in steam methane reforming at 600 °C. The spent catalysts were examined by TEM and TGA to observe the catalysts deactivation. The identification of CaO–ZrO₂ phases indicated that CaO and ZrO₂ reacted with each other to be monoclinic solid solution ZrO₂, CaZr₄O₉, CaZrO₃, and CaO corresponding to the phase diagram of CaO–ZrO₂. The existence of CaZrO₃ for 0.55 mol ratio of CaO/ZrO₂ enhanced activity in steam methane reforming because oxygen vacancies in CaZrO₃ greatly preferred the water adsorption creating the favorable conditions for carbon gasification and, then, water gas shift. The prominence and continued existence of these two reactions on the Ni catalysts leads to the particular increase of H₂ yield. Moreover, the increasing amount of CaZrO₃ in the Ni catalysts significantly improved carbon gasification. However, the Ni catalysts with CaZrO₃ showed whisker carbon after catalytic testing; this carbon specie has not been tolerated in steam methane reforming. Therefore, these results significantly differed from the hypothesis.     

Thermodynamic and experimental study of combined dry and steam reforming of methane on Ru/ ZrO2-La2O3 catalyst at low temperature

Analysis of the effect of adding small amounts of steam to the methane dry reforming feed on activity and products distribution was performed from thermodynamic equilibrium calculations of the system based on the Gibbs free energy minimization method. This analysis is supported by new insights from the direct experimental investigation of the influence of co-feeding with H₂O over a Ru/ZrO₂-La₂O₃ catalyst. Activity measurements were carried out in a fixed-bed reactor but using the operating conditions applicable in a Pd membrane reactor, that is, at maximum reaction temperature below 550 °C. Experimental results were in good agreement with thermodynamics predictions. It was observed that the addition of H₂O into the dry reforming feed strongly affects activity and products distribution. The co-feeding of steam resulted in increasing methane conversion and hydrogen yield but decreasing carbon dioxide conversion and carbon monoxide yield. At a given temperature, syngas composition (H₂/CO ratio) can be tuned by changing the amount of H₂O co-fed. Interestingly the stability of the Ru/ZrO₂-La₂O₃ catalyst was improved by adding steam to the dry reforming reactant mixtures.     

The structure-reactivity relationships of using three-dimensionally ordered macroporous LaFe1−xNixO3 perovskites for chemical-looping steam methane reforming

Chemical-looping steam methane reforming (CL-SMR) is a novel technology for syngas and hydrogen production without purification process. A series of three-dimensionally ordered macroporous (3DOM) LaFe_1?xNi_xO₃ (x = 0.05, 0.1, 0.15, 0.2, 0.25, 0.3) perovskite-type oxides were synthesized using the polystyrene colloidal crystal templating method. The structural and physico-chemical properties of the obtained oxides were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Brunauere-Emmette-Teller (BET) surface area technologies. The structure-reactivity relationships and effects of Ni-substitution on the improvement of reactivity and resistance to carbon formation were investigated in a thermo-gravimetric analyzer and a fixed-bed reactor. It was found that the as-prepared oxides obtained standard perovskite structures and the well-ordered skeleton was surrounded with uniform close-packed macroporous windows. Ni-substitution improved the ability for oxygen supply but simultaneously enhanced the methane dissociation. While the openness channel and large surface area of 3DOM perovskite allowed low mass-transfer resistances and provided high active sites for reaction. Complicated factors synergistically affected the reactivity and an optimal value for Ni-substitution is confirmed with x = 0.1 by comprehensively considering from the points of reactivity, resistance to carbon formation, as well as hydrogen generation capacity. During the following successive redox reactions, 3DOM LaFe_0.9Ni_0.1O₃ exhibited good regenerability and thermo-stability probably converting 90% of CH₄ into syngas in methane reforming stage and generating ～210–220 ml hydrogen in steam splitting stage.     

Ce–Fe oxygen carriers for chemical-looping steam methane reforming

Chemical-looping steam methane reforming (CL-SMR) is a novel process for the co-production of pure hydrogen and syngas (synthesis gas) without purification processes. Ce_1−xFe_xO_2−δ oxides (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 1) prepared by chemical precipitation were characterized by X-ray powder diffraction, BET, Raman spectra, temperature-programmed reduction technologies and used as oxygen carrier for the CL-SMR process. The methane conversion/water splitting redox properties of samples were evaluated at the different temperatures (800, 850, and 900 °C). With the combination of CeO₂ and Fe₂O₃, Fe₂O₃ particles were well dispersed on ceria surface and a small amount of iron ions was incorporated into the CeO₂ lattice to form a Ce–Fe–O solid solution. It was found that reducibility of CeO₂ was enhanced by the added Fe₂O₃. These results therefore led to the conclusion of the strong Ce–Fe interaction in CeO₂–Fe₂O₃ mixed oxides. As a result, the redox activity of CL-SMR was significantly improved, and increased in desired product yield. The redox performance was also affected by the redox temperatures, and the desired product yield was obviously enhanced at the higher temperatures. It was found that Ce_0.5Fe_0.5O_2−δ oxygen carrier showed the highest performance for the co-production of syngas and hydrogen.     

Enhancement of the quality of syngas from catalytic steam gasification of biomass by the addition of methane/model biogas

In this study, methane and model biogas were added during the catalytic steam gasification of pine to regulate the syngas composition and improve the quality of syngas. The effects of Ni/γ-Al₂O₃ catalyst, steam and methane/model biogas on H₂/CO ratio, syngas yield, carbon conversion rate and tar yield were explored. The results indicated that the addition of methane/model biogas during biomass steam gasification could increase the H₂/CO ratio to about 2. Methane/model biogas, steam and Ni/γ-Al₂O₃ catalyst significantly affected the quality of syngas. High H₂ content syngas with H₂/CO ratio of about 2, biomass carbon conversion >85% and low tar yield was achieved under the optimum condition: S/C = 1.5, α = 0.2 and using Ni/γ-Al₂O₃ catalyst. According to ANOVA, methane and catalyst were the key influencing factors of the H₂/CO ratio and syngas yield, and the tar yield mainly depended on the Ni/γ-Al₂O₃ catalyst. Biogas, as a more environmentally friendly material than methane, can also regulate the composition of syngas co-feeding with biomass.     

Nanocomposite Ni/ZrO2: Highly active and stable catalyst for H2 production via cyclic stepwise methane reforming reactions

This work investigates the catalytic performance of nanocomposite Ni/ZrO₂-AN catalyst consisting of comparably sized Ni (10–15 nm) and ZrO₂ (15–25 nm) particles for hydrogen production from the cyclic stepwise methane reforming reaction with either steam (H₂O) or CO₂ at 500–650 °C, in comparison with a conventional Ni/ZrO₂-CP catalyst featuring Ni particles supported by large and widely sized ZrO₂ particles (20–400 nm). Though both catalysts exhibited similar activity and stability during the reactions at 500 and 550 °C, they showed remarkably different catalytic stabilities at higher temperatures. The Ni/ZrO₂-CP catalyst featured a significant deactivation even during the methane decomposition step in the first cycle of the reactions at ≥600 °C, but the Ni/ZrO₂-AN catalyst showed a very stable activity during at least 17 consecutive cycles in the cyclic reaction with steam. Changes in the catalyst beds at varying stages of the reactions were characterized with TEM, XRD and TPO–DTG and were correlated with the amount and nature of the carbon deposits. The Ni particles in Ni/ZrO₂-AN became stabilized at the sizes of around 20 nm but those in Ni/ZrO₂-CP kept on growing in the methane decomposition steps of the cyclic reaction. The small and narrowly sized Ni particles in the nanocomposite Ni/ZrO₂-AN catalyst led to a selective formation of filamentous carbons whereas the larger Ni particles in the Ni/ZrO₂-CP catalyst a preferred formation of graphitic encapsulating carbons. The filamentous carbons were favorably volatilized in the steam treatment step but the CO₂ treatment selectively volatilized the encapsulating carbons. These results identify that the nature but not the amount of carbon deposits is the key to the stability of Ni/ZrO₂ catalyst and that the nanocomposite Ni/ZrO₂-AN would be a promising catalyst for hydrogen production via cyclic stepwise methane reforming reactions.     

Reduction characteristics of CuFe2O4 and Fe3O4 by methane; CuFe2O4 as an oxidant for two-step thermochemical methane reforming

The reduction characteristics of CuFe₂O₄ and Fe₃O₄ by methane at 600–900 °C were determined in a thermogravimetric analyzer for the purpose of using CuFe₂O₄ as an oxidant of two-step thermochemical methane reforming. It was found that the addition of Cu to Fe₃O₄ largely affected the reduction kinetics and carbon formation in methane reduction. In the case of CuFe₂O₄, the reduction kinetics was found to be faster than that of Fe₃O₄. Furthermore, carbon deposition and carbide formation from methane decomposition were effectively inhibited. In case of Fe₃O₄, Fe metal formed from Fe₃O₄ decomposed methane catalytically, that lead to the formation of graphite and Fe₃C phases. It is deduced that Cu in CuFe₂O₄ enhanced reduction kinetics, decreased reduction temperature and prevented carbide and graphite formation. Additionally, methane conversion and CO selectivity in the syngas production step with CuFe₂O₄ were in the range of 33.5–55.6% and 54.9–59.6%, respectively.     

Hydrogen production from steam reforming of coke oven gas and its utility for indirect reduction of iron oxides in blast furnace

Hydrogen and synthesis gas (syngas) can be produced from steam reforming (SR) of coke oven gas (COG). When the reforming gas is used for indirect reduction (IR) of iron oxides in blast furnaces (BFs), carbon dioxide emissions can be lessened. Motivated from utilizing hydrogen and mitigating greenhouse gas emissions in ironmaking, the reaction phenomena of SR of COG are investigated thermodynamically. Low-temperature and high-temperature IR of iron oxides using reforming gas as a feedstock is also analyzed. With appropriate operating conditions, the maximum H₂ and syngas yields are 3.5 and 4.2 mol (mol fuel)⁻¹, respectively. Two different reforming gases are employed to reduce iron oxides. When the reforming gas/hematite (R/H) molar ratio is no less than 1, Fe₂O₃ conversion is always higher than 98.5%, whether low-temperature or high-temperature IR is carried out. This reveals that COG possesses the potential as a reducing agent in BFs. The reactions of IR from the two reforming gases are almost identical, implying that the operation of SR from COG for producing hydrogen or syngas and reducing iron oxides in BFs is flexible.     

Redox cycling of CuFe2O4 supported on ZrO2 and CeO2 for two-step methane reforming/water splitting

CuFe₂O₄ supported on ZrO₂ and CeO₂ for two-step methane reforming was evaluated to determine if it could enhance the reactivity, CO selectivity and thermal stability of CuFe₂O₄. Two-step methane reforming consists of a syngas production step and a water splitting step. CuFe₂O₄ supported on ZrO₂ and CeO₂ was prepared using an aerial oxidation method. Non-isothermal methane reduction was carried out on TGA to compare the reactivity of CuFe₂O₄/ZrO₂ and CuFe₂O₄/CeO₂. In addition, a syngas production step was performed at 900 °C and water splitting was conducted at 800 °C alternatively five times to compare the methane conversion, CO selectivity, cycle ability and hydrogen production by water splitting in a fixed bed reactor. If the 1st syngas production step results are excluded due to over-oxidation, CuFe₂O₄/ZrO₂ and CuFe₂O₄/CeO₂ showed approximately 74.0–82.8% and 60.3–87.5% methane conversion, respectively, and 44.0–47.8% and 65.2–81.5% CO selectivity, respectively. Using CeO₂ and ZrO₂ as supports effectively improved the reactivity and methane conversion compared to CuFe₂O₄. CuFe₂O₄/ZrO₂ showed high methane conversion due to the high phase stability and thermal stability of ZrO₂ but the selectivity was not improved. After 5 successive cycles, the CeFeO₃ phase was found on CuFe₂O₄/CeO₂. Furthermore, methane conversion, CO selectivity and the amounts of hydrogen production of CuFe₂O4/CeO₂ increased with increasing number of cycles. Additional test up to the 11th cycle on CuFe₂O₄/CeO₂ revealed that CeO₂ is a better support that ZnO₂ in terms of the reactivity and CO selectivity.     

A direct synthesis of nickel nanoclusters embedded on multicomponent mesoporous metal oxides and their catalytic properties for glycerol steam reforming to hydrogen

Nickel nanoclusters embedded in multicomponent mesoporous metal oxides (Ni–MMOs) are obtained at various support compositions by a single-step synthesis of Ni ion incorporated mesoporous metal oxides (NiO–MMOs) followed by selective reduction of the NiO to Ni metal clusters. The resultant Ni–MMOs catalysts displayed enhanced Ni dispersion with well-developed mesopore structures at various support composition, exhibiting superior catalytic properties when compared to a siliceous SBA-16-supported Ni catalyst prepared by a conventional impregnation method. Glycerol steam reforming conducted at 873 K on 1Ni–2Al₂O₂–2ZrO₂ and 1Ni–2SiO₂–2ZrO₂ catalysts exhibited considerably higher glycerol conversions over the 10 wt%-Ni/SBA-16 catalyst with similar Ni loading amount. This was primarily due to the enhanced Ni dispersion resulting from the direct synthesis process. The multicomponent mesoporous supports also significantly affect product selectivity, favoring higher hydrogen concentration in the product stream. The water–gas shift reaction appears to be positively affected by the 2Al₂O₂–2ZrO₂ and 2SiO₂–2ZrO₂ multicomponent metal oxide matrices, which facilitated the conversion of the CO produced by the glycerol reforming further to additional hydrogen. Direct single-step synthesis of Ni–MMO catalysts was effective in enhancing the dispersion of Ni nanoclusters, as well as variation of the support components of the mesoporous catalyst systems.     

The role of aluminum in the formation of Ni–Al–Co-containing porous ceramic converters with high activity in dry and steam reforming of methane and ethanol

The role of aluminum in the formation of Ni–Al–Co-containing porous ceramic membrane-catalytic converters (MCC) obtained by SHS method, which are high-active in dry and steam reforming of methane, ethanol and fusel alcohols into synthesis gas, was discovered. It was shown that the aluminum introduced into the charge through mechanical alloying leads to a significant increase in the catalytic activity of the converter in the studied processes, as compared to aluminum introduced by mechanical mixing. In this case, the addition of 5% aluminum to the initial nickel charge allows achieving of maximum productivity for syngas against other studied concentrations of Al. The Al content increase above the optimum leads to a significant formation of the catalytically inactive phase of Ni₃Al intermetallide. TEM and X-ray diffraction methods show that due to oxidation-reduction phase transformations involving aluminum there occurs the formation of metal oxides on the basis of γ-Al₂O₃ with the structure of spinel having nanosized Ni–Co alloy particles formed on its surface during the reductive activation stage.     

Catalytic reforming of biomass primary tar from pyrolysis over waste steel slag based catalysts

Steel slag (SS) contains high amounts of metal oxides and could be applied as the catalyst or support material for the reforming of biomass derived tar. In this research, steel slag supported nickel catalysts were prepared by impregnation of a small amount of nickel (0–10 wt%) and calcination at 900 °C, and then tested for the catalytic reforming of biomass primary tar from pine sawdust pyrolysis. The steel slag after calcination was mainly composed of Fe₂O₃ and MgFe₂O₄, and granular NiO particles was formed and highly dispersed on the surface of nickel loaded steel slag which lead to a porous structure of the catalysts. The steel slag showed good activity on converting biomass primary tar into syngas, and its performance can be further enhanced by the loading of nickel. The yield of H₂ increased significantly with the increase of nickel loading amount, while excessive nickel loading resulted in the decrease in CO and CH₄ yields and significant increase in CO₂ yield. The presence of steam contributed to enhancing the tar steam reforming as well as reactions between steam and produced gases, while decrease the contact probability between the reactants and the active sites of catalysts, leading to a little decrease in tar conversion efficiency but significant increase in syngas yield. The iron and nickel oxides were reduced by the syngas (CO and H₂) from the biomass pyrolysis, and stable and porous structure was formed on the surface of the nickel loaded catalysts during tar reforming.     

Characterization and activity test of commercial Ni/Al2O3, Cu/ZnO/Al2O3 and prepared Ni–Cu/Al2O3 catalysts for hydrogen production from methane and methanol fuels

In this study, methane and methanol steam reforming reactions over commercial Ni/Al₂O₃, commercial Cu/ZnO/Al₂O₃ and prepared Ni–Cu/Al₂O₃ catalysts were investigated. Methane and methanol steam reforming reactions catalysts were characterized using various techniques. The results of characterization showed that Cu particles increase the active particle size of Ni (19.3 nm) in Ni–Cu/Al₂O₃ catalyst with respect to the commercial Ni/Al₂O₃ (17.9). On the other hand, Ni improves Cu dispersion in the same catalyst (1.74%) in comparison with commercial Cu/ZnO/Al₂O₃ (0.21%). A comprehensive comparison between these two fuels is established in terms of reaction conditions, fuel conversion, H₂ selectivity, CO₂ and CO selectivity. The prepared catalyst showed low selectivity for CO in both fuels and it was more selective to H₂, with H₂ selectivities of 99% in methane and 89% in methanol reforming reactions. A significant objective is to develop catalysts which can operate at lower temperatures and resist deactivation. Methanol steam reforming is carried out at a much lower temperature than methane steam reforming in prepared and commercial catalyst (275–325 °C). However, methane steam reforming can be carried out at a relatively low temperature on Ni–Cu catalyst (600–650 °C) and at higher temperature in commercial methane reforming catalyst (700–800 °C). Commercial Ni/Al₂O₃ catalyst resulted in high coke formation (28.3% loss in mass) compared to prepared Ni–Cu/Al₂O₃ (8.9%) and commercial Cu/ZnO/Al₂O₃ catalysts (3.5%).     

Catalytic performance of Ni catalysts for steam reforming of methane at high space velocity

Three Ni-based catalysts, namely Ni/ZrO₂/Al₂O₃, Ni/La-Ca/Al₂O₃ and Ni_0.5Mg_2.5AlO₉ catalysts were prepared, tested and characterized for steam reforming of methane (SRM), especially at high space velocities. Experimental results demonstrated that Ni_0.5Mg_2.5AlO₉ catalysts showed excellent catalytic activity, e.g., the high reaction performance (i.e., activity and stability) at a very short residence time of 20 ms. For the accompanied water gas shift (WGS) reaction with the SRM at the steam to methane ratio of 3:1, the overall hydrogen yield depended on both the CH₄ conversion and the CO₂ selectivity. The results showed that CO₂ selectivity had opposite trend compared with CH₄ conversion in such a short-contact process. Catalyst characterizations by XRD, SEM-EDS, TEM and TGA suggested that the good performance of nickel catalysts was closely related with the good dispersion of the active component. The nano-sized nickel particles in strong interaction with the supports would lead to the good dispersion, thereafter having a slight tendency to sintering, and then to coking.     

Thermochemical two-step water splitting by ZrO2-supported NixFe3−xO4 for solar hydrogen production

A thermochemical two-step water-splitting cycle using a redox metal oxide was examined for Ni(II) ferrites or Ni_xFe_3−xO₄ (0  x  1) for the purpose of converting solar high-temperature heat to hydrogen. The Ni(II) ferrite was decomposed to Ni-doped wustite (Ni_yFe_1−yO) at 1400 °C under an inert atmosphere in the first thermal-reduction step of the cycle; it was then reoxidized with steam to generate hydrogen at 1000 °C in the second water-decomposition step. Although nondoped Fe₃O₄ powders formed a nonporous, dense mass of iron oxide by the fusion of FeO and its subsequent solidification after the thermal-reduction step, Ni(II)–ferrite powders were converted into a porous, soft mass after the step. This was probably because Ni doping in the FeO phase raised the melting point of wustite above 1400 °C. Supporting the Ni(II) ferrites on m-ZrO₂ (monoclinic zirconia) alleviated the high-temperature sintering of iron oxide; as a result, the supported ferrites exhibited greater reactivity and assisted the repeatability of the cyclic water splitting process as compared to the unsupported ferrites. The reactivity increased with the doping value x, and was maximum at x = 1.0 in the Ni_xFe_3−xO₄/m-ZrO₂ system.     

Stability improvements of Ni/α-Al2O3 catalysts to obtain hydrogen from methane reforming

Ni catalysts supported on commercial α-Al₂O₃ modified by addition of CeO₂ and/or ZrO₂ were prepared in the present work. Since the principal objective was to evaluate the behavior of these systems and the support effect on the stability, methane reforming reactions were studied with steam, carbon dioxide, partial oxidation and mixed reforming. Results show that catalysts supported on Ce–Zr–α-Al₂O₃ composites present better reforming activity and stability noticeably higher than in the case of the reference support. With respect to composites, the presence of mixed oxides of Ce_xZr_1−xO₂ type facilitates the formation of active phases with higher interaction. This fact reduces the deactivation by sintering conferring to the system a higher contribution of adsorbed oxygen species, favoring the deposited carbon elimination. These improvements resulted in being dependent on the Ce:Zr ratio of the composite, thus obtaining more stable catalysts for Ce:Zr = 4:1 ratios.     

CO2 reforming of methane combined with steam reforming or partial oxidation of methane to syngas over NdCoO3 perovskite-type mixed metal-oxide catalyst

CO₂ reforming with simultaneous steam reforming or partial oxidation of methane to syngas over NdCoO₃ perovskite-type mixed metal oxide catalyst (prereduced by H₂) at different process conditions has been investigated. In the simultaneous CO₂ and steam reforming, the conversion of methane and H₂O and also the H₂/CO product ratio are strongly influenced by the CO₂/H₂O feed-ratio. In the simultaneous CO₂ reforming and partial oxidation of methane, the conversion of methane and CO₂, H₂ selectivity and the net heat of reaction are strongly influenced by the process parameters (viz. temperature, space velocity and relative concentration of O₂ in the feed). In both cases, no carbon deposition on the catalyst was observed. The reduced NdCoO₃ perovskite-type mixed-oxide catalyst (Co dispersed on Nd₂O₃) is a highly promising catalyst for carbon-free CO₂ reforming combined with steam reforming or partial oxidation of methane to syngas.