Hydrogen production by low-temperature reforming of organic compounds in bio-oil over a CNT-promoting Ni catalyst

Present study reports on high catalytic activity of CNTs-supported Ni catalyst (x% Ni-CNTs) synthesized by the homogeneous deposition–precipitation method, which was successfully applied for low-temperature reforming of organic compounds in bio-oil. The optimal Ni-loading content was about 15 wt%. The H₂ yield over the 15 wt% Ni-CNTs catalyst reached about 92.5% at 550 °C. The influences of the reforming temperature (T), the molar ratio of steam to carbon fed (S/C) and the current (I) passing through the catalyst, on the reforming process of the bio-oil over the Ni-CNTs' catalysts were investigated using the stream as the carrier gas in the reforming reactor. The features of the Ni-CNTs' catalysts with different loading contents of Ni were investigated via XRD, XPS, TEM, ICP/AES, H₂-TPD and the N₂ adsorption–desorption isotherms. From these analyses, it was found that the uniform and narrow distribution with smaller Ni particle size as well as higher Ni dispersion was realized for the CNTs-supported Ni catalyst, leading to excellent low-temperature reforming of oxygenated organic compounds in bio-oil.     

Hydrogen production by steam reforming of liquefied natural gas (LNG) over Ni/Al2O3–ZrO2 xerogel catalysts: Effect of calcination temperature of Al2O3–ZrO2 xerogel supports

Al₂O₃–ZrO₂ (AZ) xerogel supports prepared by a sol-gel method were calcined at various temperatures. Ni/Al₂O₃–ZrO₂ (Ni/AZ) catalysts were then prepared by an impregnation method for use in hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of calcination temperature of AZ supports on the catalytic performance of Ni/AZ catalysts in the steam reforming of LNG was investigated. Crystalline phase of AZ supports was transformed in the sequence of amorphous γ-Al₂O₃ and amorphous ZrO₂ → θ-Al₂O₃ and tetragonal ZrO₂ → (θ + α)-Al₂O₃ and (tetragonal + monoclinic) ZrO₂ → α-Al₂O₃ and (tetragonal + monoclinic) ZrO₂ with increasing calcination temperature from 700 to 1300 °C. Nickel oxide species were strongly bound to γ-Al₂O₃ and θ-Al₂O₃ in the Ni/AZ catalysts through the formation of solid solution. In the steam reforming of LNG, both LNG conversion and hydrogen composition in dry gas showed volcano-shaped curves with respect to calcination temperature of AZ supports. Nickel surface area of Ni/AZ catalysts was well correlated with catalytic performance of the catalysts. Among the catalysts tested, Ni/AZ1000 (nickel catalyst supported on AZ support that had been calcined at 1000 °C) with the highest nickel surface area showed the best catalytic performance. Well-developed and pure tetragonal phase of ZrO₂ in the AZ1000 support played an important role in the adsorption of steam and the subsequent spillover of steam from the support to the active nickel.     

Oxidative steam reforming of ethanol on mesoporous silica supported PtNi/CeO2 catalysts

In order to assure good catalyst stability and low carbon deposition rate, in the present work three catalysts having different CeO₂ loadings (CeO₂/SiO₂ ratio ranging between 25 and 40%) were prepared by depositing Pt and Ni over a CeO₂/SiO₂ mixed support and tested for oxidative steam reforming of ethanol. All the catalysts exhibited total ethanol conversion between 350 and 600 °C; however, the CeO₂/SiO₂ ratio strongly affected catalyst stability at 500 °C: despite the similar hydrogen yields (almost 40%), the best sample, which displayed the lowest carbon formation rate (1.2 × 10⁻⁶ g_coke/(g_cat*g_carbon,fed*h)) and stable behaviour for 135 h, was the 3wt%Pt-10wt%Ni/30CeO₂/SiO₂. The lower dimension for Ni crystallites was measured over the latter exhausts catalyst and the dependence of carbon formation rate form such parameter was identified. Anyway, the carbon selectivities measured over all the investigated samples were significantly lower than the values reported in the recent literature.     

Hydrogen production from steam and autothermal reforming of LPG over high surface area ceria

Steam and autothermal reforming reactions of LPG (propane/butane) over high surface area CeO₂ (CeO₂ (HSA)) synthesized by a surfactant-assisted approach were studied under solid oxide fuel cell (SOFC) operating conditions. The catalyst provides significantly higher reforming reactivity and excellent resistance toward carbon deposition compared to the conventional Ni/Al₂O₃. These benefits of CeO₂ are due to the redox property of this material. During the reforming process, the gas–solid reactions between the hydrocarbons present in the system (i.e. C₄H₁₀, C₃H₈, C₂H₆, C₂H₄, and CH₄) and the lattice oxygen (O_O^x) take place on the ceria surface. The reactions of these adsorbed surface hydrocarbons with the lattice oxygen (C_nH_m + O_O^x → nCO + m/2(H₂) + V_O + 2e′) can produce synthesis gas (CO and H₂) and also prevent the formation of carbon species from hydrocarbons decomposition reactions (C_nH_m ⇔ nC + 2mH₂). Afterwards, the lattice oxygen (O_O^x) can be regenerated by reaction with the steam present in the system (H₂O + V_O + 2e′ ⇔ O_O^x + H₂). It should be noted that V_O denotes as an oxygen vacancy with an effective charge 2⁺.At 900 °C, the main products from steam reforming over CeO₂ (HSA) were H₂, CO, CO₂, and CH₄ with a small amount of C₂H₄. The addition of oxygen in autothermal reforming was found to reduce the degree of carbon deposition and improve product selectivities by completely eliminating C₂H₄ formation. The major consideration in the autothermal reforming operation is the O₂/LPG (O/C molar ratio) ratio, as the presence of a too high oxygen concentration could oxidize the hydrogen and carbon monoxide produced from the steam reforming. A suitable O/C molar ratio for autothermal reforming of CeO₂ (HSA) was 0.6.     

Role of CeO2/ZrO2 mole ratio and nickel loading for steam reforming of n-butanol using Ni–CeO2–ZrO2–SiO2 composite catalysts: A reaction mechanism

This study presents steam reforming of n-butanol to synthesis gas using high surface area mesoporous Ni–CeO₂–ZrO₂–SiO₂ composite catalysts. The reaction proceeds through a combination of dehydrogenation, dehydration, and cracking reactions with propanal, butanal, and C₂–C₄ hydrocarbons as intermediate compounds. The ceria forms a solid solution with zirconia, promotes dispersion of nickel, and enhances oxygen storage/release capacity. The carbon conversion to synthesis gas (CCSG) and hydrogen yield are thus enhanced with increasing CeO₂/ZrO₂ mole ratio up to 1:2 and decreased slightly for higher mole ratios. The CCSG and hydrogen yield are also boosted by increasing the amount of nickel in the catalyst up to 20 wt%. 1:2 CeO₂/ZrO₂ mole ratio and 20 wt% nickel content are thus deliberated as optimum. The optimum catalyst exhibits stable catalytic performance for about 30 h time-on-stream. The study further presents the effect of temperature and steam/carbon mole ratio on n-butanol steam reforming.     

Methane autothermal reforming with CO2 and O2 to synthesis gas at the boundary between Ni and ZrO2

A series of different amount ZrO₂-promoted SiO₂ supported Ni catalysts were prepared and used for methane autothermal reforming with CO₂ and O₂ [MATR] to synthesis gas in a fluidized bed reactor. Pulse-injected surface reactions and in situ XRD characterizations disclosed that CO₂ dissociated exclusively at the boundary between Ni and ZrO₂. O species derived from CO₂ dissociation overflowed to metallic Ni and accelerated the activation of methane. Ni/5ZrO₂–SiO₂ catalyst with larger Ni–ZrO₂ boundary exhibited the best activity and stability for MATR even at an extremely space velocity 90,000 h^?1.     

Hydrogen production from catalytic steam reforming of bio-oil aqueous fraction over Ni/CeO2–ZrO2 catalysts

A series of composite catalysts Ni/CeO₂–ZrO₂ were prepared via impregnation method with Ni as the active metal. A laboratory-scale fixed-bed reactor was employed to investigate the catalyst performance during hydrogen production by steam reforming bio-oil aqueous fraction. Effects of water-to-bio-oil ratio (W/B), reaction temperature, and the loaded weight of Ni and Ce on the hydrogen production performance of Ni/CeO₂–ZrO₂ catalysts were examined. The obtained results were compared with commercial nickel-based catalysts (Z417). The best performance of Ni/CeO₂–ZrO₂ catalyst was observed when the Ni and Ce loaded weight were 12% and 7.5% respectively. At W/B = 4.9, T = 800 °C, H₂ yield reaches the highest of 69.7% and H₂ content of 61.8% were obtained. Under the same condition, H₂ yield and H₂ content were higher than commercial nickel-based catalysts (Z417).     

Steam reforming of methane over unsupported nickel catalysts

This paper describes a study of steam reforming of methane using unsupported nickel powder catalysts. The reaction yields were measured and the unsupported nickel powder surface was studied to explore its potential as a catalyst in internal or external reforming solid oxide fuel cells. The unsupported nickel catalyst used and presented in this paper is a pure micrometric nickel powder with an open filamentary structure, irregular ‘fractal-like’ surface and high external/internal surface ratio. CH₄ conversion increases and coke deposition decreases significantly with the decrease of CH₄:H₂O ratio. At a CH₄:H₂O ratio of 1:2 thermodynamic equilibrium is achieved, even with methane residence times of only ∼0.5 s. The CH₄ conversion is 98 ± 2% at 700 °C and no coke is generated during steam reforming which compares favorably with supported Ni catalyst systems. This ratio was used in further investigations to measure the hydrogen production, the CH₄ conversion, the H₂ yield and the selectivity of the CO, and CO₂ formation. Methane-rich fuel ratios cause significant deviations of the experimental results from the theoretical model, which has been partially correlated to the adsorption of carbon on the surface according to TEM, XPS and elemental analysis. At the fuel: water ratio of 1:2, the unsupported Ni catalyst exhibited high catalytic activity and stability during the steam reforming of methane at low-medium temperature range.     

Ultrasonic-assisted synthesis of highly active catalyst Au/MnOx–CeO2 used for the preferential oxidation of CO in H2-rich stream

A series of nano-gold catalysts supported on binary oxides MO_x–CeO₂ (atomic ratio M/Ce = 1:1, M = Mn, Fe, Co, Ni) are prepared by deposition–precipitation (DP). An innovative and rather convenient ultrasonic pretreatment of the support is employed for Au/MnO_x–CeO₂ preparation. It is found that for preferential CO oxidation Au/MnO_x–CeO₂ is more active than Au/CeO₂. Ultrasonic pretreatment of MnO_x–CeO₂ further promotes the performance of Au/MnO_x–CeO₂, with CO conversion increased by 24 % at 120 °C. Meanwhile, the selectivity of oxygen to CO₂ is promoted in the whole temperature range, especially in 80–120 °C, the selectivity is increased by 15–21%. HR-TEM and XRD results indicate that ultrasonic pretreatment is favorable to the formation of much smaller gold nanoparticles (<5 nm). The characterization of XPS, UV–vis DRS, H₂-TPR and CO-TPR confirms that the strong interaction between Au and the support effectively inhibits the dissociation and oxidation of H₂ over the ultrasonically pretreated catalyst Au/MnO_x–CeO₂, making it highly selective to CO oxidation.     

Zirconia supported nickel catalysts for glycerol steam reforming: Effect of zirconia structure on the catalytic performance

The effect of the zirconia structure in Ni/ZrO₂ catalysts on the glycerol steam reforming (GSR) reaction was studied. A tetragonal zirconia support was synthesized via a hydrolysis technique and loaded with 5 wt% Ni via a wet-impregnation method. Similarly, a commercial monoclinic zirconia support was also impregnated with 5 wt% Ni. Following calcination at 600 °C, physico-chemical properties of the prepared catalysts were investigated by X-Ray Diffraction (XRD), H₂-Temperature Programmed Reduction (H₂-TPR) and CO₂-Temperature Programmed Desorption (CO₂-TPD) techniques. The catalysts were then tested in the GSR reaction in the 400–700 °C range with a steam to glycerol molar ratio of 9:1 and a flow rate of 0.025 mL/min. The monoclinic catalyst exhibited a better performance giving higher hydrogen yields and glycerol conversions. This was attributed to an improved reducibility of Ni in this catalyst. Stability tests at 600 °C revealed the deactivation of the tetragonal catalyst during 6 h as a result of the formation of encapsulating coke which blocked active Ni metal sites. The monoclinic catalyst, exhibiting the formation of only filamentous coke, remained relatively stable for 24 h.     

Carbon deposition on Ni/ZrO2–CeO2 catalyst during steam reforming of acetic acid

Steam reforming of acetic acid, one model compounds of bio-oil, was studied on the Ni/ZrO₂–CeO₂ catalysts which were prepared by the impregnation method. The results showed that high acetic acid conversion and hydrogen yield were obtained in the temperature range of 650–750 °C when H₂O/HAC ratio was 3. Nevertheless, the catalyst deactivation was caused by carbon deposition eventually with time-on-stream. In order to discuss the behavior of the carbon deposition on the Ni/ZrO₂–CeO₂ catalyst during steam reforming of bio-oil, the structure and morphology of carbon deposition were investigated by BET, XRD, TG/DTA, TPR, SEM and EDX techniques. All the experimental results showed acetone and CO were the important carbon precursors of acetic acid reforming and the graphitic-like carbon was the main type of carbon deposition on the surface of the deactivated 12%Ni/CeO₂–ZrO₂ catalyst.     

Ethanol oxidative steam reforming over Ni-based catalysts

Oxidative steam reforming of ethanol for hydrogen production in order to feed a solid polymer fuel cell (SPFC) has been studied over several catalysts at on board conditions (a molar ratio of H₂O/EtOH and of O₂/EtOH equal to 1.6 and 0.68 respectively) and a reforming temperature between 923 and 1073 K. Two Ni (11 and 20 wt.%)/Al₂O₃ catalysts and five bimetallic catalysts, all of them supported on Al₂O₃, were tested. The bimetallic catalysts were Ni (approximately 20 wt.%) based catalysts doped with Cr (0.65 wt.%), Fe (0.6 wt.%), Zn (0.7 wt.%) or Cu (0.6 and 3.1 wt.%). The results in terms of H₂ production and CO₂/CO_x ratio obtained over Ni-based catalysts supported on Al₂O₃ are compared with those obtained over Ni–Cu/SiO₂ and Rh/Al₂O₃ catalysts reported in our previous works. Tendencies of the product selectivities are analyzed in the light of the reaction network proposed.     

Effects of synthesis route on the performance of mesoporous ceria-alumina and ceria-zirconia-alumina supported nickel catalysts in steam and autothermal reforming of diesel

Decline in catalyst performance due to coke deposition is the main problem in diesel steam (SR) and autothermal reforming (ATR) reactions. Good redox potential and strong interaction of CeO₂ with nickel increase activity and coke resistivity of Ni/Al₂O₃ catalysts. In this study, mesoporous Al₂O₃, CeO₂/Al₂O₃, and CeO₂/ZrO₂/Al₂O₃ supported nickel catalysts were successfully synthesized. The highest hydrogen yield, 97.7%, and almost no coke deposition were observed with CeO₂/ZrO₂/Al₂O₃ catalyst (Ni@8CeO₂-2ZrO₂-Al₂O₃-EISA) in SR reaction. The second highest hydrogen yield, 91.4%, was obtained with CeO₂/Al₂O₃ catalyst (Ni@10CeO₂-Al₂O₃-EISA) with 0.3 wt% coke deposition. Presence of ZrO₂ prevented the transformation of cubic CeO₂ into CeAlO₃, which enhanced water gas shift reaction (WGSR) activity. Ni@10CeO₂-Al₂O₃-EISA did not show any decline in activity in a long-term performance test. Higher CeO₂ incorporation (20 wt%) caused lower steam reforming activity. Change of synthesis route from one-pot to impregnation for the CeO₂ incorporation decreased the number of acid sites, limiting cracking reactions and causing a significant drop in hydrogen production.     

Cu,Mg and Co effect on nickel-ceria supported catalysts for ethanol steam reforming reaction

Ethanol steam reforming is a promising reaction which produces hydrogen from bio and synthetic ethanol. In this study, the nano-structured Ni-based bimetallic supported catalysts containing Cu, Co and Mg were synthesized through impregnation method and characterized by XRD, BET, SEM, TPR and TPD analysis. The prepared catalysts were tested in steam reforming of ethanol in the S/C = 6, GHSV of 20,000 mL/(g_cat h) at the temperature range of 450–600 °C. Among the xNi/CeO₂ (x = 10, 13, 15 wt%) catalyst, the sample containing 13 wt% Ni with surface area of 64 m²/g showed the best performance with 89% ethanol conversion and 71% H₂ selectivity as well as low CO selectivity of 8% at 600 °C and The addition of Cu, Mg, and Co to catalyst structure were evaluated and it was found that the nature of second metal has a strong influence on the catalyst selectivity for H₂ production. Considering to results of TPR analysis, the 13Ni–4Cu/CeO₂ catalyst showed proper reduction which caused in better activity. On the other side based on TPD analysis, the more basic property of 13Ni–4Mg/CeO₂ bimetallic catalyst provided a better condition to methane steam reforming, leading to lower CH₄ selectivity and consequently more H₂ production. The 13Ni–4Cu/CeO₂ exhibited the highest activity and lowest selectivity towards ethanol conversion and CO production about 99% and 4%, while the 13Ni–4Mg/CeO₂ catalyst possessed the highest H₂ selectivity and lowest CH₄ selectivity about 74% and 1% respectively at 600 °C. The Ni–Cu and Ni–Mg bimetallic catalysts shows good stability with time on stream.     

Biohydrogen synthesis from catalytic steam gasification of furniture waste using nickel catalysts supported on modified CeO2

Present study evaluated the catalytic steam gasification of furniture waste to enhance the biohydrogen production. To do this, 10 wt% nickel loaded catalysts on the variety of supports (Al₂O₃, CeO₂, CeO₂-La₂O₃, and CeO₂–ZrO₂) were prepared by the novel solvent deficient method. The hydrogen selectivity (vol%) order of the catalysts was achieved as Ni/CeO₂–ZrO₂>Ni/CeO₂>Ni/Al₂O₃?Ni/CeO₂-La₂O₃. The best catalytic activity of Ni/CeO₂–ZrO₂ catalyst (~82 vol % H₂ at 800 °C) was ascribed to the smaller size of nickel crystals, finely dispersed Ni on the catalyst surface, and Ce_1-xZr_xO_2-δ solid solution. The role of Ce_1-xZr_xO_2-δ solid solution in Ni/CeO₂–ZrO₂ catalyst was observed as bi-functional; acceleration of water-gas-shift and oxidation of carbon reaction. The high resistance of Ni/CeO₂–ZrO₂ towards the coke formation showed its potential to establish a cost-effective commercial-scale biomass steam gasification process. This study is expected to provide a promising solution for the disposal of furniture wastes for production of clean energy (biohydrogen).     

Hydrogen production for fuel cells through methane reforming at low temperatures

Hydrogen production for fuel cells through methane (CH₄) reforming at low temperatures has been investigated both thermodynamically and experimentally. From the thermodynamic equilibrium analysis, it is concluded that steam reforming of CH₄ (SRM) at low pressure and a high steam-to-CH₄ ratio can be achieved without significant loss of hydrogen yield at a low temperature such as 550 °C. A scheme for the production of hydrogen for fuel cells at low temperatures by burning the unconverted CH₄ to supply the heat for SRM is proposed and the calculated value of the heat-balanced temperature is 548 °C. SRM with and/or without the presence of oxygen at low temperatures is experimentally investigated over a Ni/Ce–ZrO₂/θ-Al₂O₃ catalyst. The catalyst shows high activity and stability towards SRM at temperatures from 400 to 650 °C. The effects of O₂:CH₄ and H₂O:CH₄ ratios on the conversion of CH₄, the hydrogen yield, the selectivity for carbon monoxide, and the H₂:CO ratio are investigated at 650 °C with a constant CH₄ space velocity. Results indicate that CH₄ conversion increases significantly with increasing O₂:CH₄ or H₂O:CH₄ ratio, and the hydrogen content in dry tail gas increases with the H₂O:CH₄ ratio.     

Achievement of hydrogen production from autothermal steam reforming of methanol over Cu-loaded mesoporous CeO2 and Cu-loaded mesoporous CeO2–ZrO2 catalysts

Hydrogen production by oxidative steam reforming of methanol (OSRM) or autothermal steam reforming of methanol (ASRM) was investigated over Cu-loaded mesoporous CeO₂ and Cu-loaded mesoporous CeO₂–ZrO₂ catalysts, synthesized via a nanocasting process using MCM-48 as a hard template, followed by a deposition–precipitation technique. Various Cu contents were loaded on the mesoporous CeO₂ and CeO₂–ZrO₂ supports. The fresh and spent catalysts were characterized by N₂ adsorption–desorption, X-ray diffraction, temperature-programmed oxidation, and X-ray photoelectron spectroscopy. The ASRM results showed that 9 wt% Cu loading onto mesoporous CeO₂ and CeO₂–ZrO₂ provided the best catalytic performance with 100% methanol conversion and 60% H₂ yield at 350° and 300 °C, respectively. Furthermore, the time-on-stream stability testing of the 9 wt% Cu loading catalyst was at 168 h, and the CO selectivity of these two catalysts indicated that the addition of ZrO₂ into the catalyst reduced the CO selectivity during the ASRM process.     

Production of CO-rich hydrogen gas from glycerol dry reforming over La-promoted Ni/Al2O3 catalyst

Dry reforming of glycerol has been carried out over alumina-supported Ni catalyst promoted with lanthanum. The catalysts were characterized using EDX, liquid N₂ adsorption, XRD technique as well as temperature-programmed reduction. Significantly, catalytic glycerol dry reforming under atmospheric pressure and at reaction temperature of 1023 K employing 3 wt%La–Ni/Al₂O₃ catalyst yielded H₂, CO and CH₄ as main gaseous products with H₂:CO < 2.0. Post-reaction, XRD analysis of used catalysts showed carbon deposition during glycerol dry reforming. Consequently, BET surface area measurement for used catalysts yielded 10–21% area reduction. Temperature-programmed gasification studies with O₂ as a gasification agent has revealed that La promotion managed to reduce carbon laydown (up to 20% improvement). In comparison, the unpromoted Ni/Al₂O₃ catalyst exhibited the highest carbon deposition (circa 33.0 wt%).     

Catalytic steam reforming of glycerol over Ni–La2O3–CeO2/SBA-15 catalyst for stable hydrogen-rich gas production

Ni-based catalysts (Ni, Ni–La₂O₃, and Ni–La₂O₃–CeO₂) on mesoporous silica supports (SBA-15 and KIT-6) were prepared by an incipient wetness impregnation and tested in glycerol steam reforming (GSR) for hydrogen-rich gas production. The catalysts were characterized by the N₂-physisorption, TPD, X-ray diffraction (XRD), SEM-EDS, and TEM techniques. N₂-physisorption results of calcined catalysts highlight that adding of La₂O₃ increased surface area of the catalyst by preventing pore mouth plugging in SBA-15, which was frequently observed due to the growth of NiO crystals. A set of GSR experiments over the catalysts were performed in an up-flow continuous packed-bed reactor at 650 °C and atmospheric pressure. The highest hydrogen concentration of 62 mol% was observed with a 10%Ni–5%La₂O₃ –5%CeO₂/SBA-15 catalyst at a LHSV of 5.8 h⁻¹. Adding of CeO₂ to the catalyst appeared to increase catalytic stability by facilitating the oxidative gasification of carbon formed on/near nickel active sites of Ni–La₂O₃–CeO₂/SBA-15 and Ni–La₂O₃–CeO₂/KIT-6 catalyst during the glycerol steam reforming reaction.     

Study of Ni/CeO2–ZnO catalysts in the production of H2 from acetone steam reforming

This paper reports the study of new Ni/ZnO-based catalysts for hydrogen production from substoichiometric acetone steam reforming (ASR). The effect of CeO₂ introduction is analyzed regarding the catalytic behavior and carbon deposits formation. ASR was studied at 600 °C using a steam/carbon ratio S/C = 1. Ni/xCeZnO (x = 10, 20, 30 CeO₂ wt %) catalysts showed a better performance than the bare Ni/ZnO. Ni/xCeZnO generated a lower amount and less ordered carbon deposits than Ni/ZnO. The higher the CeO₂ content in Ni/xCeZnO, the lower the amount of carbon deposits in the post-reaction catalyst. The highest H₂ production under ASR at the experimental conditions used was achieved for the Ni/xCeZnO catalysts. In-situ DRIFTS-MS experiments under ESR conditions showed different reaction pathways over Ni/20CeZnO and Ni/ZnO catalysts.