Plasma-reduced Ni/γ–Al2O3 and CeO2–Ni/γ–Al2O3 catalysts for improving dry reforming of propane

Pristine Ni/γ–Al₂O₃ and CeO₂–Ni/γ–Al₂O₃ catalysts were prepared by co-impregnation technique for dry reforming of propane. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) were used to examine the structure and morphology of the catalysts before and after the reforming reactions. The excellent interaction between catalyst active phases was observed in both CeO₂–Ni/γ–Al₂O₃ and Ni/γ–Al₂O₃ stabilized with polyethelene glycol (Ni/γ–Al₂O₃–PEG). Towards C₃H₈ and CO₂ conversion, the CeO₂–Ni/γ–Al₂O₃ and Ni/γ–Al₂O₃–PEG showed improved catalytic activity when compared to the pristine Ni/γ–Al₂O₃ catalyst. Interestingly, high H₂ concentration was achieved with the CeO₂–Ni/γ–Al₂O₃ and high CO concentration with the Ni/γ–Al₂O₃–PEG, which is due to the nanoconfinement of nickel particles within the support and favorable metal-support interaction as a result of plasma reduction. The CeO₂–Ni/γ–Al₂O₃ catalyst exhibited better stability for anti-sintering and coke resistance, thus exhibiting high reactivity and durability in the 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%).     

Thermocatalytic decomposition of methane over mesoporous Ni/xMgO·Al2O3 nanocatalysts

This paper describes a facile method to produce mesoporous nanostructure Ni/Al₂O₃, Ni/MgO, and Ni/xMgO.Al₂O₃ (x: MgO/Al₂O₃ molar ratio) catalysts prepared by “one-pot” evaporation-induced self-assembly (EISA) method with some modifications for investigating in the thermocatalytic decomposition of methane. Detailed characterizations of the material were performed with X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and N₂ adsorption/desorption, hydrogen temperature-programmed reduction (H₂-TPR), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and temperature-programmed oxidation (TPO). The characterizations demonstrated that the synthesized catalysts with various MgO/Al₂O₃ molar ratios possessed mesoporous structure with the high BET area in the range of 216.79 to 31.74 m² g^?1. The effect of different surfactants and calcination temperatures on the characterizations and catalytic activity of the catalysts were also examined in details. The experimental results showed that the catalysts exhibited high catalytic potential in this process and the 55 wt.% Ni/2 MgO·Al₂O₃ catalyst calcined at 600^οC possessed an acceptable methane conversion (～60%) under the harsh reaction conditions (GHSV = 48000 (mL h^?1 g_cat^?1)).     

Catalysts of Ni/α-Al2O3 and Ni/La2O3-αAl2O3 for hydrogen production by steam reforming of bio-oil aqueous fraction with pyrolytic lignin retention

This paper reports on the steam reforming, in continuous regime, of the aqueous fraction of bio-oil obtained by flash pyrolysis of lignocellulosic biomass (sawdust). The reaction system is provided with two steps in series: i) thermal step at 200 °C, for the pyrolytic lignin retention, and ii) reforming in-line of the treated bio-oil in a fluidized bed reactor, in the range 600–800 °C, with space-time between 0.10 and 0.45 g_catalyst h (g_bio-oil)⁻¹. The benefits of incorporating La₂O₃ to the Ni/α-Al₂O₃ catalyst on the kinetic behavior (bio-oil conversion, yield and selectivity of hydrogen) and deactivation were determined. The significant role of temperature in gasifying coke precursors was also analyzed. Complete conversion of bio-oil is achieved with the Ni/La₂O₃-αAl₂O₃ catalyst, at 700 °C and space-time of 0.22 g_catalyst h (g_bio-oil)⁻¹. The catalyst deactivation is low and the hydrogen yield and selectivity achieved are 96% and 70%, respectively.     

Oxidative steam reforming of ethanol over Ni/Al2O3 catalysts promoted by CeO2, ZrO2 and CeO2–ZrO2

Oxidative steam reforming of ethanol at low oxygen to ethanol ratios was investigated over nickel catalysts on Al₂O₃ supports that were either unpromoted or promoted with CeO₂, ZrO₂ and CeO₂–ZrO₂. The promoted catalysts showed greater activity and a higher hydrogen yield than the unpromoted catalyst. The characterization of the Ni-based catalysts promoted with CeO₂ and/or ZrO₂ showed that the variations induced in the Al₂O₃ by the addition of CeO₂ and/or ZrO₂ alter the catalyst's properties by enhancing Ni dispersion and reducing Ni particle size. The promoters, especially CeO₂–ZrO₂, improved catalytic activity by increasing the H₂ yield and the CO₂/CO and the H₂/CO values while decreasing coke formation. This results from the addition of ZrO₂ into CeO₂. This promoter highlights the advantages of oxygen storage capacity and of mobile oxygen vacancies that increase the number of surface oxygen species. The addition of oxygen facilitates the reaction by regenerating the surface oxygenation of the promoters and by oxidizing surface carbon species and carbon-containing products.     

Hydrogen production from CH4 dry reforming over bimetallic Ni–Co/Al2O3 catalyst

Bimetallic 5%Ni–10%Co/Al₂O₃ catalyst was synthesized using impregnation method and evaluated for methane dry reforming reaction at different reaction temperatures. NiO, Co₃O₄ and spinal metal aluminates, namely, CoAl₂O₄ and NiAl₂O₄ phases were formed on γ-Al₂O₃ support surface during calcination process. 5%Ni–10%Co/Al₂O₃ catalyst exhibited reasonable surface area of 86.93 m² g^?1 with small crystallite dimension of less than 10 nm suggesting that both Co₃O₄ and NiO phases were finely dispersed on the surface of support in agreement with results from scanning electron microscopy (SEM) measurement. Temperature-programmed calcination measurement indicates the complete thermal decomposition and oxidation of metal precursors, viz. Ni(NO₃)₂ and Co(NO₃)₂ to metal oxides and metal aluminates at below 700 K. Both CH₄ and CO₂ conversions were stable over a period of 4 h on-stream and attained an optimum at about 67% and 71%, respectively at 973 K whilst H₂ selectivity and yield were higher than 49%. The ratio of H₂/CO was always less than unity for all runs indicating the presence of reverse water–gas shift reaction. The activation energy for CH₄ and CO₂ consumption was computed as 55.60 and 40.25 kJ mol^?1, correspondingly. SEM micrograph of spent catalyst detected the formation of whisker-like carbon on catalyst surface whilst D and G bands characteristic for the appearance of amorphous and graphitic carbons in this order were observed on surface of used catalyst by Raman spectroscopy analysis. Additionally, the percentage of filamentous carbon was greater than that of graphitic carbon.     

Effects of Y2O3-modification to Ni/γ-Al2O3 catalysts on autothermal reforming of methane with CO2 to syngas

The effects of Y₂O₃-modification to Ni/γ-Al₂O₃ catalysts on autothermal reforming of methane to syngas were investigated. It was found that the introduction of Y₂O₃ (5%, 8%, 10%) lead to significant improvement in catalytic activity and stability, and the H₂/CO ratio could be adjusted via controlling the O₂/CO₂ ratio of the feed gas. According to the characterization results of catalysts before and after reaction, it was found that the Y₂O₃·γ-Al₂O₃ supported Ni catalysts had higher NiO reducibility, smaller Ni particle size, higher Ni dispersion and stronger basicity than those of the Ni/γ-Al₂O₃ catalysts. The analysis of catalysts after reaction showed that the addition of Y₂O₃ inhibited the Ni sintering, changed the type of coke and decreased the amount of coke on the catalysts. All the experimental results indicated that the introduction of Y₂O₃ to Ni/γ-Al₂O₃ resulted in excellent catalytic performances in autothermal reforming of methane, and Y₂O₃ played important roles in preventing metal sintering and coke deposition via controlling NiO reducibility, Ni particle size and dispersion, and basicity of catalysts.     

Power-law type rate equation for propane ATR over Pt–Ni/Al2O3 catalyst

Kinetics of autothermal reforming (ATR) of propane on bimetallic Pt–Ni catalyst supported over δ-Al₂O₃ is investigated at 673 K with the purpose of obtaining an easy-to-implement power-law type rate equation. The rate expression is proposed for conditions extending up to 20% propane conversion and has reaction orders of 1.64, 2.44 and −0.59 in propane, oxygen and steam partial pressures, respectively. Parameters estimated by non-linear regression analysis in the MATLAB™ environment can be reliably used for propane ATR in the steam-to-carbon ratio range of 2.0–3.0 and carbon-to-oxygen ratio range of 3.0–5.4. The apparent activation energy is calculated as 46 ± 4 kJ mol⁻¹ in the 653–693 K interval.     

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.     

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.     

Autothermal syngas production from model gasoline over Ni,Rh and Ni–Rh/Al2O3 monolithic catalysts

On-board reforming of liquid fuels is attractive for fuel cell-powered auxiliary power units in vehicles. In this work, monometallic Ni/Al₂O₃/cordierite, Rh/Al₂O₃/cordierite and bimetallic Ni–Rh/Al₂O₃/cordierite monolithic catalysts were prepared, characterized and tested in ATR of isooctane for syngas production. Compared to monometallic formulations, the bimetallic Ni–Rh/Al₂O₃ catalyst was active for ATR at lower temperature and H₂ production already reached the equilibrium composition in 400–550 °C temperature range. The Ni–Rh/Al₂O₃ catalyst exhibited stable performances for 140 h in ATR of isooctane at 700 °C, and was unaffected by oxidizing conditions at 700 °C. Thermoneutral reactions conditions at H₂O/C = 2 were obtained with O/C = 0.66. Carbon deposition was marginal during ATR of isooctane and no carbons whiskers were detected. Post-reaction characterizations showed that the Ni particles were small enough to prevent filamentous carbon formation, while Rh also prevented carbon film deposition by improving the gasification of adsorbed C with steam.     

The ReSER-COG process for hydrogen production on a Ni–CaO/Al2O3 complex catalyst

The reactive sorption-enhanced reforming process of simulated coke oven gas (ReSER-COG) was investigated in a laboratory-scale fixed-bed reactor with Ni–CaO/Al₂O₃ complex catalyst. Simulated coke oven gases that are free of or contain C2+ hydrocarbons (C₂H₄, C₂H₆, C₃H₆, C₃H₈) have been studied as feed materials of the ReSER process for hydrogen production. The effects of temperature, steam to methane molar ratio (S/CH₄) and carbon space velocity on the characteristics of ReSER-COG were studied. The results showed that the hydrogen concentration reaches up to 95.8% at a reaction temperature of 600 °C and a S/CH₄ of 5.8 under normal atmospheric pressure conditions. This reaction temperature was approximately 200 °C lower than that of the coke oven gas steam reforming (COGSR) processes used for the hydrogen production. The amount of H₂ generated by ReSER-COG was approximately 4.4 times more than that produced by the pressure-swing adsorption (PSA) method per unit volume of COG. The reaction temperature was 50 °C lower when simulated COG with C2+ was used, as opposed to when COG without C2+ was used. The complex catalyst has a better resistance of coking during the ReSER-COG process when C2+ gas is present.     

Thermophysical properties and devitrification of SrO–La2O3–Al2O3–B2O3–SiO2-based glass sealant for solid oxide fuel/electrolyzer cells

Thermal behaviors and stability of glass/glass–ceramic-based sealant materials are critical issues for high temperature solid oxide fuel/electrolyzer cells. To understand the thermophysical properties and devitrification behavior of SrO–La₂O₃–Al₂O₃–B₂O₃–SiO₂ system, glasses were synthesized by quenching (25 − X)SrO–20La₂O₃–(7 + X)Al₂O₃–40B₂O₃–8SiO₂ oxides, where X was varied from 0.0 mol% to 10.0 mol% at 2.5 mol% interval. Thermal properties were characterized by dilatometry and differential scanning calorimetry (DSC). Microstructural studies were performed by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). All the compositions have a glass transition temperature greater than 620 °C and a crystallization temperature greater than 826 °C. Also, all the glasses have a coefficient of thermal expansion (CTE) between 9.0 × 10⁻⁶ K⁻¹ and 14.5 × 10⁶ K⁻¹ after the first thermal cycle. La₂O₃ and B₂O₃ contribute to glass devitrification by forming crystalline LaBO₃. Al₂O₃ stabilizes the glasses by suppressing devitrification. Significant improvement in devitrification resistance is observed as X increases from 0.0 mol% to 10.0 mol%.     

CO2 reforming of CH4 by combination of cold plasma jet and Ni/γ-Al2O3 catalyst

CO₂ reforming of CH₄ to synthesis gas was investigated by cold plasma jet (CPJ) only and combination of cold plasma jet with Ni/γ-Al₂O₃ catalyst at atmospheric pressure. The higher selectivity of H₂ and CO, and higher energy efficiency was obtained by this novel process. The optimum experimental conditions are: CH₄ = 3.33 Nl/min, CO₂ = 5.00 Nl/min, N₂ = 8.33 Nl/min, and the input power at 770 W. The results showed that, for the plasma only, the conversions of CH₄ and CO₂ were 46% and 34%, the selectivities of CO and H₂ were 85% and 78%, the energy efficiency was 2.9 mmol/kJ, respectively; for the combination of cold plasma jet with Ni/γ-Al₂O₃ catalyst, the conversions of CH₄ and CO₂ were increased by 14% and 6%, the yield of H₂ and CO increased by 18% and 11%, the energy efficiency reached at 3.7 mmol/kJ, respectively. And the catalyst hasn't accessorial heating. The CPJ method has the advantage of simple processing and is easy to be industrialized.     

A study on electrical conductivity of chemosynthetic Al2O3–2SiO2 geoploymer materials

Al₂O₃–2SiO₂ amorphous powders are synthesized by sol–gel method with tetraethoxysilane (TEOS) and aluminum nitrate (ANN) as the starting materials. The microstructure and phase structure of the powders are investigated by SEM and XRD analysis. Geopolymer materials samples are prepared by mechanically mixing stoichiometric amounts of calcined Al₂O₃–2SiO₂ powders and sodium silicate solutions to allow a mass ratio of Na₂O/Al₂O₃ = 0.4, 0.375, 0.35, 0.325, 0.288, 0.26, 0.23 or 0.2 separately, and finally to form a homogenous slurry at a fixed H₂O/Na₂O mole ratio = 11.7. The results show that the synthetic Al₂O₃–2SiO₂ powders have polycondensed property and their compressive strengthes are similar to that of nature metakaolin geopolymer materials. The results also show that the water consumption is not the main influencing factor on electrical conductivity of harden geopolymer materials but it can intensively affect the microstructure of geopolymer materials. In addition, the electrical conductivity of harden geopolymer sample is investigated, and the results show that the geopolymer materials have a high ionic electrical conductivity of about 1.5 × 10⁻⁶ S cm⁻¹ in air at room temperature.     

Ag/Al2O3(Li2O)/g-C3N4光催化乙醇制取环氧乙烷

本文制备了一系列Ag/Al₂O₃(Li₂O)/g-C₃N₄复合催化剂,考察了其可见光催化乙醇制取环氧乙烷的性能。Li₂O可调变Al₂O₃表面的酸性,从而降低了主要副产物乙醛的选择性。Ag/Al₂O₃(Li₂O) 在g-C₃N₄上的负载量对产物环氧乙烷的选择性有较大影响,当Ag/Al₂O₃(Li₂O) 负载量为5wt%时,乙醇具有较高的转换率,且环氧乙烷的选择性高达100%。     

The surfactant-assisted Ni–Al2O3 catalyst prepared by a homogeneous precipitation method for CH4 steam reforming

The surfactant-assisted Ni–Al₂O₃ catalysts are prepared by the homogeneous precipitation method with a surfactant/Al molar ratio ranging from 0.0 to 2.0. It has been investigated the effects of the surfactant on the physicochemical properties and the catalytic activities of the Ni–Al₂O₃ catalysts. The BET surface area of the catalysts decreases with increasing the surfactant content. The pore volume and pore size of the catalysts increase with increasing the surfactant content. XRD results indicate that all of the catalysts exhibit strong diffraction peaks corresponding to NiO and weak peaks corresponding to NiAl₂O₄. In the TPR results, the reduction peaks which indicates that the Ni particles strongly interacted with the support are present at between 668 and 688 °C. The activities of the prepared catalysts for methane steam reforming increase with increasing surfactant content in fresh and poisoned state due to an increase of pore volume and pore size.     

Production of hydrogen via steam reforming of biofuels on Ni/CeO2–Al2O3 catalysts promoted by noble metals

The catalytic activity of Ni/CeO₂–Al₂O₃ catalysts modified with noble metals (Pt, Ir, Pd and Ru) was investigated for the steam reform of ethanol and glycerol. The catalysts were characterized by the following techniques: Energy-dispersive X-ray, BET, X-ray diffraction, temperature-programmed reduction, UV–vis diffuse reflectance spectroscopy and X-ray absorption near edge structure (XANES). The results showed that the formation of inactive nickel aluminate was prevented by the presence of CeO₂ dispersed on alumina. The promoting effect of noble metals included a decrease in the reduction temperatures of NiO species interacting with the support, due to the hydrogen spillover effect. It was seen that the addition of noble metal stabilized the Ni sites in the reduced state along the reforming reaction, increasing the ethanol and glycerol conversions and decreasing the coke formation. The higher catalytic performance for the ethanol steam reforming at 600 °C and glycerol steam reforming was obtained for the NiPd and NiPt catalysts, respectively, which presented an effluent gaseous mixture with the highest H₂ yield with reasonably low amounts of CO.     

Production of hydrogen by methane catalytic decomposition over Ni–Cu–Fe/Al2O3 catalyst

Catalysts with high nickel concentrations 75%Ni–12%Cu/Al₂O₃, 70%Ni–10%Cu–10%Fe/Al₂O₃ were prepared by mechanochemical activation and their catalytic properties were studied in methane decomposition. It was shown that modification of the 75%Ni–12%Cu/Al₂O₃ catalyst with iron made it possible to increase optimal operating temperatures to 700–750 °C while maintaining excellent catalyst stability. The formation of finely dispersed Ni–Cu–Fe alloy particles makes the catalysts stable and capable of operating at 700–750 °C in methane decomposition to hydrogen and carbon nanofibers. The yield of carbon nanofibers on the modified 70%Ni–10%Cu–10%Fe/Al₂O₃ catalyst at 700–750 °C was 150–160 g/g. The developed hydrogen production method is also efficient when natural gas is used as the feedstock. An installation with a rotating reactor was developed for production of hydrogen and carbon nanofibers from natural gas. It was shown that the 70%Ni–10%Cu–10%Fe/Al₂O₃ catalyst could operate in this installation for a prolonged period of time. The hydrogen concentration at the reactor outlet exceeded 70 mol%.     

CO2 reforming of methane on Ni/γ-Al2O3 catalyst prepared by dielectric barrier discharge hydrogen plasma

Ni/γ-Al₂O₃ catalyst was prepared by direct treatment of Ni(NO₃)₂/γ-Al₂O₃ precursor with dielectric barrier discharge (DBD) hydrogen plasma at different input powers, characterized by XRD, H₂-TPR, CO₂-TPD, N₂ adsorption and TEM, respectively, and used as the catalyst for CO₂ reforming of methane (CRM). The results showed that the input power obviously affected the reduction degree and catalytic performances of catalysts. Low input power under 40 W mainly resulted in the decomposition of nickel nitrate into Ni oxides. The reduction degree, catalytic activity and stability increase with the input power. Similar catalytic performances in CRM reaction can be obtained when the power exceeds 80 W. Compared with the Ni/Al₂O₃ catalyst prepared by traditional method, Ni/γ-Al₂O₃ samples prepared by H₂ DBD plasma exhibit better activities, stability and anti-carbon deposit performances. It is mainly ascribed to smaller Ni particle size, more basic sites and weaker basicity. The increase of Ni particle sizes due to the sintering at high temperature results in the decrease of catalytic activities and coke formation.