A comparative study of dry reforming of methane over nickel catalysts supported on perovskite-type LaAlO3 and commercial α-Al2O3

A systematic and comparative study was made to determine the influence of perovskite-type LaAlO₃ and commercial α-Al₂O₃ on the performance of nickel-based catalysts in dry reforming of methane (DRM). The perovskite-type LaAlO₃ was selected due to its characteristics of solid state semiconductor with oxygen vacancies and high structural stability. The catalysts were characterized by X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), N₂ adsorption-desorption, temperature programmed reduction (TPR-H₂), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The catalyst performance was evaluated based on activity tests (600–800 °C) and short- and long-term stability (10 and 20 h) at 700 °C at a GHSV (Gas Hourly Space Velocity) of 18 and 72 L g^?1 h^?1. The TPR-H₂ profiles indicate that the oxygen vacancies on the perovskite surface exerted a strong effect on the reduction temperature and reducibility of the NiO nanoparticles, resulting in weak Ni⁰/support interaction. The results of the tests after 10 h under GHSV of 18 L g^?1 h^?1 indicate that the Ni/LaAlO₃ catalyst is 7.8 and 11.5% more stable than Ni/α-Al₂O₃ in the conversions of CH₄ and CO₂, respectively. The higher stability and activity of Ni/LaAlO₃ is directly ascribed to the presence of NiO (3.38 wt%) after activation, which promoted the formation of carbon nanotubes (CNT) and increased the dispersion of the metallic phase. Even under severe conditions of activation and reaction (high GHSV), as in the long-term test, the Ni/LaAlO₃ catalyst showed a 37.2% higher H₂ yield than the Ni/α-Al₂O₃. Analyses by TEM indicate that the Ni/α-Al₂O₃ catalyst exhibited deactivation problems associated with sintering effects. Thus, the presence of structural defects and surfaces rich in oxygen vacancies makes LaAlO₃ perovskite a potential support for application in methane catalytic reforming processes.     

Hydrogen production from methane autothermal reforming over CaTiO3, BaTiO3 and SrTiO3 supported nickel catalysts

Nickel supported on perovskite supports were investigated in the autothermal reforming of methane. The catalysts were prepared by incipient wetness impregnation and characterized by energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), N₂ physisorption, H₂ temperature programmed reduction (H₂-TPR), H₂ chemisorption, dehydrogenation of cyclohexane model reaction and Raman spectroscopy. The alumina supported catalyst exhibited highest initial conversion and selectivity to H₂, however it deactivated. All catalysts with perovskite support were very stable, with Ni/CaTiO₃ and Ni/BaTiO₃ converting over 70% of the methane. Due to carbon formation, Ni/SrTiO₃ conversion was only 50%. Turnover frequency was higher on perovskite supported catalysts. Deactivated Ni/Al₂O₃ favored total oxidation of methane instead of methane reforming, however the selectivity of catalysts supported on perovskites remained stable.     

Steam reforming of gasoline promoted by partial oxidation reaction on novel bimetallic Ni-based catalysts to generate hydrogen for fuel cell-powered automobile applications

Steam reforming of gasoline fuels combined with partial oxidation reaction on ZSM-5-supported Ni-based bimetallic catalysts and Al₂O₃-supported Ni-Re bimetallic catalysts with different Ni/Re ratios for hydrogen generation at a relatively lower reaction temperature was studied. The ZSM-5-supported Ni-Ce and Ni-Mo bimetallic catalysts exhibited a higher activity than the Ni/ZSM-5 catalyst for the oxidative reforming of gasoline. Steam reforming of gasoline to produce hydrogen was remarkably promoted by partial oxidation reaction by addition of molecular oxygen to the reaction system on ZSM-5-supported Ni-Ce catalyst. Al₂O₃-supported Ni-Re catalyst with suitable Ni/Re ratios exhibits unique high activity and sulfur tolerance because of the alloying of Ni with Re to form a new active sites for oxidative steam reforming of gasoline to generate hydrogen. The crystal structure of Al₂O₃-supported bimetallic Ni-Re catalyst and monometallic catalysts of Ni and Re were characterized by XRD method. Structured changes resulting from the alloying of Ni with Re were found.     

Preparation of nickel catalysts supported on CaO.2Al2O3 for methane reforming with carbon dioxide

Nanocrystalline calcium aluminate (CaO.2Al₂O₃) was prepared by a simple co-precipitation method using Poly (ethylene glycol)-block-poly(propylene glycol)-block poly(ethylene glycol) (PEG-PPG-PEG, MW:5800) as surfactant and employed as catalyst support for nickel catalysts in methane reforming with carbon dioxide. The prepared samples were characterized by X-ray diffraction (XRD), N₂ adsorption (BET), Temperature programmed reduction and oxidation (TPR-TPO) and Scanning electron microscopy (SEM) techniques. The results showed that the prepared support has a high potential as support for nickel catalysts in methane reforming with carbon dioxide. The results showed high catalytic activity and stability for the prepared catalysts. Among the prepared catalysts 15% Ni/CaO.2Al₂O₃ was the most active catalyst and showed the highest affinity for carbon formation. In addition, 7% Ni/CaO.2Al₂O₃ possessed high catalytic stability during 50 h time on stream. The TPO analysis revealed that increasing in nickel content increased the amount of deposited carbon over the spent catalysts. SEM results detected only whisker type of carbon for all spent catalysts.     

Hydrogen production by steam reforming of ethanol over mesoporous Ni–Al2O3–ZrO2 aerogel catalyst

A mesoporous Ni–Al₂O₃–ZrO₂ aerogel (Ni–AZ) catalyst was prepared by a single-step epoxide-driven sol–gel method and a subsequent supercritical CO₂ drying method. For comparison, a mesoporous Al₂O₃–ZrO₂ aerogel (AZ) support was prepared by a single-step epoxide-driven sol–gel method, and subsequently, a mesoporous Ni/Al₂O₃–ZrO₂ aerogel (Ni/AZ) catalyst was prepared by an incipient wetness impregnation method. The effect of preparation method on the physicochemical properties and catalytic activities of Ni–AZ and Ni/AZ catalysts was investigated. Although both catalysts retained a mesoporous structure, Ni/AZ catalyst showed lower surface area than Ni–AZ catalyst. From TPR, XRD, and H₂–TPD results, it was revealed that Ni–AZ catalyst retained higher reducibility and higher nickel dispersion than Ni/AZ catalyst. In the hydrogen production by steam reforming of ethanol, both catalysts showed a stable catalytic performance with complete conversion of ethanol. However, Ni–AZ catalyst showed higher hydrogen yield than Ni/AZ catalyst. Superior textural properties, high reducibility, and high nickel surface area of Ni–AZ catalyst were responsible for its enhanced catalytic performance in the steam reforming of ethanol.     

Oxidation resistance of Ni/La0.7Sr0.3AlO3−δ catalyst for steam reforming of model aromatic hydrocarbon

Oxidative resistance of Ni catalysts supported on various oxides La_0.7Sr_0.3AlO_3−δ, LaAlO₃, and α-Al₂O₃ were investigated for hydrogen production by steam reforming of model aromatic hydrocarbons. Ni/α-Al₂O₃ lost its steam reforming activity by oxidation treatment. In contrast, Ni/La_0.7Sr_0.3AlO_3−δ and Ni/LaAlO₃ catalysts showed steam reforming activity even after the oxidation treatment. The XANES (X-ray absorption near-edge structure) spectra at Ni K-edge for Ni/La_0.7Sr_0.3AlO_3−δ and Ni/α-Al₂O₃ after oxidation treatment revealed that the supported Ni on La_0.7Sr_0.3AlO_3−δ and α-Al₂O₃ were oxidized completely. Although the mean particle size of Ni on Ni/α-Al₂O₃ increased by oxidation treatment or reduction treatment, Ni particles on Ni/La_0.7Sr_0.3AlO_3−δ retained the fine structure after oxidation treatment or reduction treatment. Moreover, TPR (temperature programmed reduction) and XPS (X-ray photoelectron spectroscopy) measurements for elucidating the reducibility of Ni/La_0.7Sr_0.3AlO_3−δ showed that the supported Ni on La_0.7Sr_0.3AlO_3−δ was easily reduced even after the oxidation treatment.     

Current advances in syngas (CO + H2) production through bi-reforming of methane using various catalysts: A review

Today, bi - reforming of methane is considered as an emerging replacement for the generation of high-grade synthesis gas (H₂:CO = 2.0), and also as an encouraging renewable energy substitute for fossil fuel resources. For achieving high conversion levels of CH₄, H₂O, and CO₂ in this process, appropriate operation variables such as pressure, temperature and molar feed constitution are prerequisites for the high yield of synthesis gas. One of the biggest stumbling blocks for the methane reforming reaction is the sudden deactivation of catalysts, which is attributed to the sintering and coke formation on active sites. Consequently, it is worthwhile to choose promising catalysts that demonstrate excellent stability, high activity and selectivity during the production of syngas. This review describes the characterisation and synthesis of various catalysts used in the bi-reforming process, such as Ni-based catalysts with MgO, MgO–Al₂O₃, ZrO_2, CeO₂, SiO₂ as catalytic supports. In summary, the addition of a Ni/SBA-15 catalyst showed greater catalytic reactivity than nickel celites; however, both samples deactivated strongly on stream. Ce-promoted catalysts were more found to more favourable than Ni/MgAl₂O₄ catalyst alone in the bi-reforming reaction due to their inherent capability of removing amorphous coke from the catalyst surface. Also, Lanthanum promoted catalysts exhibited greater nickel dispersion than Ni/MgAl₂O₄ catalyst due to enhanced interaction between the metal and support. Furthermore, La₂O₃ addition was found to improve the selectivity, activity, sintering and coking resistance of Ni implanted within SiO₂. Non-noble metal-based carbide catalysts were considered to be active and stable catalysts for bi-reforming reactions. Interestingly, a five-fold increase in the coking resistance of the nickel catalyst with Al₂O₃ support was observed with incorporation of Cr, La₂O₃ and Ba for a continuous reaction time of 140 h. Bi-reforming for 200 h with Ni-γAl₂O₃ catalyst promoted 98.3% conversion of CH₄ and CO₂ conversion of around 82.4%. Addition of MgO to the Ni catalyst formed stable MgAl₂O₄ spinel phase at high temperatures and was quite effective in preventing coke formation due to enhancement in the basicity on the surface of catalyst. Additionally, the distribution of perovskite oxides over 20 wt % silicon carbide-modified with aluminium oxide supports promoted catalytic activity. NdCOO₃ catalysts were found to be promising candidates for longer bi-reforming operations.     

Biohydrogen production by gas phase reforming of glycerine and ethanol mixtures

In this paper the steam reforming of bioalcohols over Ni and Pt catalysts supported on bare Al₂O₃ and La₂O₃ and CeO₂-modified Al₂O₃ to produce H₂ was studied. Catalytic activity results showed that the glycerine and the intermediate liquid products may hinder the ethanol adsorption on metal active sites of the catalysts, especially at temperatures below 773 K. In fact, ethanol conversion was lower than glycerine conversion in the steam reforming reaction at low temperatures. H₂ chemisorption revealed that La₂O₃ doping of the Ni/Al₂O₃ catalyst improved the metal dispersion providing a better behaviour to the Ni/Al₂O₃-O2 catalyst towards H₂ production. In the case of Pt catalysts, the good reducibility and the H₂ spillover effect provided to the Pt/Al₂O₃-O1 catalyst the capacity to produce higher H₂ yields.     

Investigation of Ba doping in A-site deficient perovskite Ni-exsolved catalysts for biogas dry reforming

This work presents the development of an A-site deficient La_0.9−xBa_xAl_0.85Ni_0.15O₃ (x = 0, 0.02, 0.04, and 0.06) perovskite oxide catalyst for dry reforming of model biogas. The catalysts are prepared using a citrate sol-gel method and used for biogas dry reforming at 800 °C for feed ratios (CH₄/CO₂) of 1.5 and 2.0. The fresh and spent catalysts are analyzed using XRD, FTIR, TPD, XPS, FESEM, TEM, TPR, TGA-DTA, and Raman analysis. The XRD analysis exhibits the host perovskite oxide structure and the exsolved Ni phase for all prepared catalysts. The partial doping of Ba improves the metal support interaction and oxygen vacancies that enhance catalytic activity and stability, as revealed by the TPR and XPS analysis. The stability experiment on La_0.9−xBa_xAl_0.85Ni_0.15O₃, for x = 0 catalyst resulted in reduced activity due to the catalyst deactivation by sintering, as confirmed by XRD and FE-SEM. Among all the catalysts studied, La_0.84Ba_0.06Al_0.85Ni_0.15O₃ (LB6AN-15) exhibited the highest catalytic stability with CH₄, and CO₂ conversions are 60% and 93%, respectively, for 40 h time-on-stream due to the strong metal support interactions, high oxygen vacancies, and anti-sintering of exsolved Ni nanoparticles in biogas dry 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%).     

CO2 reforming of methane over Pt-Ni/Al2O3 catalysts: Effects of catalyst composition, and water and oxygen addition to the feed

A series of Pt-Ni bimetallic catalysts supported on δ-Al₂O₃ to be used in carbon dioxide reforming of methane was prepared and tested with the objective of optimizing the Ni/Pt metal composition to obtain high activity and stability. Selected catalyst samples, before and after reaction, were characterized by XRD, XPS, TGA/DTA and SEM-EDS. The activity results showed that the catalytic performance of bimetallic Pt-Ni samples strongly depended on the metal loadings and Ni/Pt loading ratio. Among all the catalysts, 0.3%Pt-10%Ni/Al₂O₃, which has the lowest Ni/Pt ratio, exhibited the highest catalytic activity and stability. The combined characterization and catalyst performance tests results reveal that low Ni/Pt molar loading ratio of 0.3%Pt-10%Ni/Al₂O₃ sample led to a relatively easy reduction of nickel oxide species and smaller nano-sized nickel particles having better dispersion caused by the intimate interaction between Pt and Ni sites in the closed vicinity. The changes in the catalysts’ activity and stability under the presence of an additional oxygen source were determined through addition of small amounts of either oxygen or water vapor to the feed stream. The results of the combined dry reforming and partial oxidation tests strongly indicated a change in surface reaction mechanism depending on the Pt load and Ni/Pt ratio of the catalysts. 0.3Pt-10Ni was capable of operating under a variety of feed conditions without significant deactivation suggesting that the catalyst is very promising for synthesis gas production for gas-to-liquid technology.     

Catalytic steam reforming of complex gasified biomass tar model toward hydrogen over dolomite promoted nickel catalysts

The complex mixture of gasified tar model (phenol, toluene, naphthalene, and pyrene) was steam reformed for hydrogen production over 10 wt% nickel based catalysts. The catalysts were prepared by co-impregnation method with dolomite promoter and various oxide supports (Al₂O₃, La₂O₃, CeO₂, and ZrO₂). Steam reforming was carried out at 700 °C at atmospheric pressure with steam to carbon molar ratio of 1 and gas hourly space velocity of 20 L/h·g_cat. The catalysts were characterised for reducibility, basicity, crystalline, and total surface area properties. Dolomite promoter strengthened the metal-support interaction and basicity of catalyst. The Ni/dolomite/La₂O₃ (NiDLa) catalyst with mesoporous structure (26.42mn), high reducibility (104.42%), and strong basicity (5.56 mmol/g) showed superior catalytic performance in terms of carbon conversion to gas (77.7%), H₂ yield (66.2%) and H₂/CO molar ratio (1.6). In addition, the lowest amount of filamentous coke was deposited on the spent NiDLa after 5 h.     

A comparative study of catalytic behaviors of Mn,Fe, Co,Ni, Cu and Zn–Based catalysts in steam reforming of methanol,acetic acid and acetone

This study investigated the distinct catalytic behaviors of mono Mn, Fe, Co, Ni, Cu and Zn catalysts in the reforming of the small organics including methanol, acetic acid and acetone. The results showed that Mn, Fe or Zn-based catalysts showed almost no activity for steam reforming of either methanol, acetic acid or acetone, due to their low capacity to break the chemical bonds of the organics or to activate steam. Co and Cu-based catalysts were generally active for steam reforming of methanol. Nevertheless, Co-based catalysts promoted methanol decomposition to form a substantial amount of CO. Alumina as a support remarkably influenced catalytic stability of the catalyst. The unsupported Cu catalyst showed a much lower stability than Cu/Al₂O₃. Nevertheless, the unsupported Ni was more stable than Ni/Al₂O₃ catalyst, due to its high resistivity towards coking. The unsupported Co, however, was prone to coking. The C/H ratios in the coke formed over the unsupported and alumina-supported Ni or Co catalysts were distinct, indicating the involvement of alumina in the coking process. In addition, Ni and Co catalysts behaved differently. Ni/Al₂O₃ showed a superior stability than Co/Al₂O₃ in steam reforming of acetone. The coke formed on Ni/Al₂O₃ was more aromatic than that over Co/Al₂O₃ catalysts while morphologies of coke (nanotubes over Ni/Al₂O₃ versus fibrous coke over Co/Al₂O₃) were also different.     

Ce promoting effect on the activity and coke formation of Ni catalysts supported on mesoporous nanocrystalline γ-Al2O3 in autothermal reforming of methane

In this study methane autothermal reforming (ATR) was investigated over Ni/Al₂O₃ and Ni/Al₂O₃–CeO₂ catalysts. The catalyst carriers were prepared through a facile one-step method, which produced mesoporous nanocrystalline carriers for Ni catalysts. The samples were characterized by XRD, TPR, BET, TPO and SEM characterization techniques and the catalytic activity and stability were also studied at different conditions (GHSV and feed ratio) in methane ATR. It was found that the nickel catalyst supported on 3 wt.% Ce–Al₂O₃ exhibited higher activity compared to the catalysts supported on the Al₂O₃ and promoted Al₂O₃ with 1 and 6 wt.% Ce. The results also showed that the nickel catalyst supported on 3 wt.% Ce–Al₂O₃ possessed the highest resistance against carbon deposition in ATR reaction.     

Combination of CO2 reforming and partial oxidation of methane to produce syngas over Ni/SiO2 and Ni–Al2O3/SiO2 catalysts with different precursors

Ni/SiO₂ and Ni–Al₂O₃/SiO₂ catalysts were prepared by incipient wetness impregnation using citrate and nitrate precursors and tested with a reaction of combination of CO₂ reforming and partial oxidation of methane to produce syngas (H₂/CO). The catalytic activity of Ni/SiO₂ and Ni–Al₂O₃/SiO₂ greatly depended on interaction between NiO and support. NiO strongly interacted with support formed small nickel particles (about 4 nm for NiSC which is abbreviation of Ni/SiO₂ prepared with Nickel citrate precursor) after reduction. The small nickel particles over NiSC catalysts exhibited a good catalytic performance.     

Improved catalytic stability and anti-coking ability of Ni/La2O3–Al2O3 catalyst by doping alkaline earth metals for n-decane reforming

In this paper, a series of alkaline earth metals oxides doped Ni/La₂O₃–Al₂O₃ catalysts were synthesized by the coprecipitation method combined with two step impregnation methods. n-decane reforming was used to investigate these catalysts, in order to develop an excellent catalyst with better hydrogen selectivity, activity, stability, as well as lower carbon deposition. Deactivation by carbon deposition, the catalyst regenerability and stability tests were also used to weigh the selected catalyst. These catalysts are characterized by N₂ adsorption-desorption, XRD, NH₃-TPD, Raman, and TEM. The introduction of alkaline earth metals modifiers enhances the activity, stability and anti-coking ability, meanwhile the SrO modified Ni/La₂O₃–Al₂O₃ shows the best catalytic activity. Moreover, the hydrogen selectivity and conversion over regenerative Ni/La₂O₃–Al₂O₃/SrO catalysts were quite close to the results of fresh ones. The enhancements of M oxides doped catalysts (especially Sr) can be due to the improved textural properties, basicity, metal-support interaction and anti-coking ability. As a consequence, loading different metals in different ways helps to gradually improve the stability, activity and coking inhibition of catalysts is an effective approach to obtain a multi-function catalyst.     

CO2 dry-reforming of methane over La0.8Sr0.2Ni0.8M0.2O3 perovskite (M = Bi,Co, Cr,Cu, Fe): Roles of lattice oxygen on C–H activation and carbon suppression

La_0.8Sr_0.2Ni_0.8M_0.2O₃ (LSNMO) (where M = Bi, Co, Cr, Cu and Fe) perovskite catalyst precursors have been successfully developed for CO₂ dry-reforming of methane (DRM). Among all the catalysts, Cu-substituted Ni catalyst precursor showed the highest initial catalytic activity due to the highest amount of accessible Ni and the presence of mobile lattice oxygen species which can activate C–H bond, resulting in a significant improvement of catalytic activity even at the initial stage of reaction. However, these Ni particles can agglomerate to form bigger Ni particle size, thereby causing lower catalytic stability. As compared to Cu-substituted Ni catalyst, Fe-substituted Ni catalyst has low initial activity due to the lower reducibility of Ni–Fe and the less mobility of lattice oxygen species. However, Fe-substituted Ni catalyst showed the highest catalytic stability due to: (1) strong metal–support interaction which hinders thermal agglomeration of the Ni particles; and (2) the presence of the abundant lattice oxygen species which are not very active for C–H bond activation but active to react with CO₂ to form La₂O₂CO₃, hence minimizing carbon formation by reacting with surface carbon to form CO.     

Evaluation of Ni/Y2O3/Al2O3 catalysts for hydrogen production by autothermal reforming of methane

Ni/xY₂O₃–Al₂O₃ (x = 5, 10, 15, 20 wt%) catalysts were prepared by sequential impregnation synthesis. The catalytic performance for the autothermal reforming of methane was evaluated and compared with Ni/γ-Al₂O₃ catalyst. The physicochemical properties of catalysts were characterized by X-ray diffraction (XRD), Transmission electron microscope (TEM), X-Ray Photoelectron Spectrometer (XPS), Thermo Gravimetric Analyzer (TGA) and H₂-temperature programmed reduction techniques (TPR). The decrease of nickel particle size and the change of reducibility were found with Y modification. The CH₄ conversion increased with elevating levels of Y₂O₃ from 5% to 10%, then decreased with Y content from 10% to 20%. Ni/xY₂O₃–Al₂O₃ catalysts maintained high activity after 24 h on stream, while Ni/Al₂O₃ had a significant deactivation. The characterization of spent catalysts indicated that the addition of Y retarded Ni sintering and decreased the amount of coke.     

Effect of transition metal on stability and activity of La-Ca-M-(Al)-O (M = Co,Cr, Fe and Mn) perovskite oxides during partial oxidation of methane

Perovskite oxides of the type of La_xCa_1-xM_yAl_1-yO_3-δ (M = Co, Cr, Fe, Mn; x = 0.5; y = 0.7–1.0) were prepared using the polymerization methods and evaluated via N₂ adsorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy dispersive X-ray (EDX) spectroscopy, temperature-programmed reduction by hydrogen (TPR-H₂) and temperature-programmed oxidation by oxygen (TPO-O₂). Catalytic behaviour of the perovskite oxides during methane oxidation was studied using a tubular fixed-bed reactor. In a partial oxidation, which proceeded in two steps, there was total oxidation in the first step and CO₂ and H₂O were formed; in the second step, the total oxidation products oxidized methane by (dry and wet) reforming reactions to yield CO and H₂. Total oxidation and the two reforming reactions proceeded on two types of an active centre formed by transition metal ions, oxygen vacancies and oxide ions. The catalytic system La-Ca-Co-Al-O which contained aluminium, decomposed in partial oxidation of methane (POM) into a composite that contained firmly bonded cobalt nanoparticles in the surface of a substrate made up of La₂O₃, CaO and Al₂O₃ which catalysed POM with a high methane conversion and hydrogen selectivity.     

Numerical investigation of hydrogen production via autothermal reforming of steam and methane over Ni/Al2O3 and Pt/Al2O3 patterned catalytic layers

In this study a numerical analysis of hydrogen production via an autothermal reforming reactor is presented. The endothermic reaction of steam methane reforming and the exothermic combustion of methane were activated with patterned Ni/Al₂O₃ catalytic layer and patterned Pt/Al₂O₃ catalytic layer, respectively. Aiming to achieve a more compacted process, a novel design of a reactor was proposed in which the reforming and the combustion catalysts were modeled as patterned thin layers. This configuration is analyzed and compared with two configurations. In the first configuration, the catalysts are modeled as continuous thin layers in parallel, while, in the second configuration the catalysts are modeled as continuous thin layers in series (conventional catalytic autothermal reactor). The results show that the pattern of the catalyst layers improves slightly the hydrogen yield, i.e. 3.6%. Furthermore, for the same concentration of hydrogen produced, the activated zone length can be decreased by 38% and 15% compared to the conventional catalytic autothermal reforming and the configuration where the catalysts are fitted in parallel, respectively. Besides, the oxygen consumption is lowered by 5%. The decrement of the catalyst amount and the oxygen feedstock in the novel studied design lead to lower costs and compact process.