The evaluation of autothermal methane reforming for hydrogen production over Ni/CeO2 catalysts

Nanocrystalline Ni/CeO₂ catalysts with various loadings of Ni (10, 15, 20, and 25%) were synthesised by a facile solvent deficient precipitation method for methane autothermal reforming process. The characterisation techniques such as XRD, BET, TPH, H₂-TPR were carried out on fresh and spent samples to investigate the catalytic properties of the Ni/CeO₂. On the basis of characterisation results, the 20% Ni/CeO₂ performs the best activity among the catalysts with different Ni contents. The optimal reaction conditions for autothermal methane reforming has been investigated by evaluating the effect of reaction parameters including the reactivity temperature, the gas hourly space velocity (GHSV) and H₂O/CH₄ (S/C) and O₂/CH₄ (O/C) molar ratios. The stability of 20 wt% Ni/CeO₂ catalyst at 700 °C is examined for 20 h on-stream reaction. It reveals that the methane conversion starts a graduate decrease trend from the second 10 h, which is found to be because of the sintering of Ni nanoparticles by TPH and BET analysis.     

Dry reforming over mesoporous nanocrystalline 5% Ni/M-MgAl2O4 (M: CeO2, ZrO2, La2O3) catalysts

In this article mesoporous nanocrystalline 5 wt%M-95 wt%MgAl₂O₄ (M: CeO₂, ZrO₂, La₂O₃) powders were prepared by a novel on-step sol-gel process and employed as a support for the synthesis of 5 wt%Ni catalysts for synthesis gas production via dry reforming. The magnesium aluminate spinel prepared with this sol-gel method possessed a high BET area of 264 m² g⁻¹ with a high pore volume of 0.436 cm³ g⁻¹. The results indicated that the addition of promoters (CeO₂, ZrO₂, La₂O₃) to magnesium aluminate improved the BET area and pore volume and also decreased the crystallite size. Among the prepared powders and catalysts, 5 wt%La₂O₃-95 wt%MgAl₂O₄ and 5 wt%Ni/5 wt%CeO₂-95 wt%MgAl₂O₄ exhibited the highest BET area of 306 m² g⁻¹ and 263 m² g⁻¹, respectively. The catalytic results indicated that the 5 wt%Ni/5 wt%CeO₂-95 wt%MgAl₂O₄ catalyst exhibited the highest activity and the lowest carbon formation among the prepared catalysts with the same content of the promoter. The influence of the CeO₂ content on the textural and catalytic performance was also investigated and the results illustrated that the increment in CeO₂ content improved the methane conversion and reduced the amount of deposited carbon, which could be related to the redox properties of the catalyst support.     

Effect of Co,Fe and Rh addition on coke deposition over Ni/Ce0.5Zr0.5O2 catalysts for steam reforming of ethanol

Ni-based monometallic and bimetallic catalysts (Ni, NiRh, NiCo and NiFe) supported on Ce_0.5Zr_0.5O₂ support were evaluated on the steam reforming of ethanol (SRE) performance. The supports of Ce_0.5Zr_0.5O₂ composite oxide was prepared by co-precipitation method with Na₂CO₃ precipitant and assigned as CeZr(N). The monometallic catalyst was prepared by incipient wetness impregnation method and assigned as Ni/CeZr(N). The bimetallic catalysts were prepared by co-impregnation method to disperse the metals on the CeZr(N) support and assigned as NiM/CeZr(N). All samples were characterized by using XRD, TPR, BET, EA and TEM techniques at various stages of the catalyst. The results indicated that the facile reduction and smaller particle size of Ni/CeZr(N) (T₉₉ = 300 °C) and NiRh/CeZr(N) (T₉₉ = 250 °C) catalysts were preferential than the NiFe/CeZr(N) (T₉₉ = 325 °C) and NiCo/CeZr(N) (T₉₉ = 375 °C) catalysts. Also, both the Ni/CeZr(N) and NiRh/CeZr(N) catalysts displayed better durability among these catalysts over 100 h and 400 h, respectively. Since the serious coke formation for the NiCo/CeZr(N) catalyst, the activity only maintained around 6 h, the durability on the NiFe/CeZr(N) catalyst approached 50 h.     

Hydrogen production from carbon dioxide reforming of methane over Ni-Co/MgO-ZrO2 catalyst: Process optimization

Greenhouse gases, carbon dioxide and methane are utilized in the production of hydrogen through carbon dioxide reforming of methane catalyzed by Ni-Co/MgO-ZrO₂ catalyst. Design of Experiments (DOE) was used to study the effects of process variables such as, carbon dioxide to methane ratios (1-5), gas hourly space velocity (8400-200,000 mL/g/h), oxygen concentration in the feed (3-8 mol%) and reaction temperature (700-800 °C) over methane conversion and yield of hydrogen. The ANOVA analysis indicated that the effect of each process variable was significant to its respective responses in the proposed quadratic model. The response surface methodology (RSM) was used to find the optimum value of the process variables by maximizing the hydrogen yield in the process model. The optimum space velocity as 145,190 mL/g/h at reaction temperature 749 °C with carbon dioxide to methane ratio of 3 and 7 mol% of oxygen in the feed gave 88 mol% of CH₄ conversion and 86 mol% of hydrogen yield, respectively. The experiments were run at the optimum condition gave 87.7 mol% methane conversion and 85.5 mol% of hydrogen yield, which were in good agreement with the simulated values obtained from the model. The catalyst stability and its regeneration characteristics were studied at the optimum condition by monitoring methane conversion and hydrogen yield with time on stream.     

Effect of boron doping and preparation method of Ni/Ce0.5Zr0.5O2 catalysts on the performance for steam reforming of ethanol

Ce_0.5Zr_0.5O₂ supported Ni-based catalysts with a Ni loading of 10 wt% and a B loading of 0.5 wt% were prepared by co-precipitation (assigned as NiCeZr(C) and BNiCeZr(C), respectively) and impregnation (assigned as NiCeZr(I) and BNiCeZr(I), respectively) procedures to evaluate the effects of fabrication methods and B-doped on the catalytic performance for steam reforming of ethanol (SRE). These catalysts were characterized with XRD, TPR, TPO, TEM, BET, TG and EA. The well dispersed active species that can be obtained through co-precipitation and formation of a NiB alloy come from a B-doped catalyst, which can promote catalysis performance and reaction pathway. Further, it can improve the selectivity of hydrogen for a SRE reaction. Also, the B-doped catalysts possess a high oxygen storage capacity (OSC) via formation of CeBO₃ under SRE ambience, which is the factor for removal of the carbonaceous species. TG and EA analyses demonstrate that there are fewer carbon deposits for the B-doped catalysts. The performance of the BNiCeZr(C) catalyst was preferential among these catalysts.     

Methane tri-reforming for synthesis gas production using Ni/CeZrO2/MgAl2O4 catalysts: Effect of Zr/Ce molar ratio

Three Ni/CeZrO₂/MgAl₂O₄ catalysts synthesized using different Zr/Ce molar ratios (0.25, 1, and 4) were studied for methane tri-reforming. The catalysts were characterized using XRD, ²⁷Al-NMR, H₂-TPR, CO₂-TPD, XPS, and in situ techniques (XPD and XANES). The addition of CeZrO₂ at Zr/Ce = 0.25 on the MgAl₂O₄ spinel support considerably reduced the amount of carbon deposits, because the methane decomposition reaction was attenuated by the presence of less agglomerated Ni⁰ species produced after the reduction process. The highest CO₂ adsorption capacity (basicity) was associated with the participation of medium-strength basic sites, which facilitated coke gasification and led to higher CO₂ conversions. A syngas with quality (H₂/CO ratio) of 1.8 was produced, suitable for use in Fischer-Tropsch reactions.     

Hydrogen production by ethanol steam reforming over M-Ni/sepiolite (M = La,Mg or Ca) catalysts

Ethanol steam reforming (ESR) is a technology of great promise for hydrogen production but designing highly efficient, green and inexpensive Ni-based catalysts for inhibiting metal sinter and carbon deposition and increasing catalyst activity and stability is still a key challenge. In this paper, the M-Ni/Sepiolite catalysts (M-Ni/SEP, M = La, Mg or Ca) were synthesized using a hydrothermal-assisted impregnation method. The results from characterizations such as N₂ adsorption-desorption, XRD, H₂-TPR, XPS, HRTEM and NH₃/CO₂-TPD showed that La, Mg and Ca promoters can facilitate the dispersion and exposure of Ni⁰ active sites, enhance the metal-support interaction and modify surface acid/alkaline sites. Furthermore, the results of catalyst activity tests in ESR demonstrated that the Ca–Ni/SEP catalyst exhibited the highest carbon conversion of 95% and hydrogen yield of 65%, attributed to the small mean Ni particle size, strong metal-support interaction, abundant surface Ni⁰ active sites and modified surface alkaline/acid sites. According to the carbon deposition analyses, it was observed in Ca–Ni/SEP that the carbon deposition amount was evidently decreased, and the graphitic degree of coke was increased due to the increased metal site amount.     

Powder and structured Pt/Ce0.75Zr0.25O2-based catalysts: Water gas shift performance and quasi in situ XPS studies

The data on the performance in water gas shift reaction of a powder 5 wt% Pt/Ce_0.75Zr_0.25O₂ and a structured 0.33 wt% Pt/Ce_0.75Zr_0.25O₂/θ-Al₂O₃/FeCrAl catalysts are reported in this work. For the powder one the lowest outlet CO concentrations were shown to be 0.5, 0.9 and 1.5 vol% corresponding to the initial ones of 5, 10 and 15 vol%, respectively; the temperature required to reach these values did not exceed 310 °C. The quasi in situ XPS data have shown that doping CeO₂ with Zr enhances the reducibility of the oxide allowing Ce³⁺ formation without any treatment. Additionally, it was found that there are 20–30% of nonmetallic Pt atoms on the surface even after a treatment in CO at 300 °C. For the structured catalyst the downward temperature gradient along the monolith was observed with a dispersion of 50–60 °C. The lowest CO concentrations were observed at the temperatures at the catalyst's back point of 280 °C–3.9 and 4.3 vol% CO in the dry gas for 15,700 and 31,400 cm³·g_cat⁻¹·h⁻¹, respectively, for 10 vol% CO in the feed gas.     

Hydrogen production from glycerol steam reforming over Co-based catalysts supported on La2O3, AlZnOx and AlLaOx

A comparative study of 10 wt% Co-based catalysts supported on La₂O₃, AlZnO_x and AlLaO_x was performed for glycerol steam reforming (GSR). The catalysts physicochemical characterization was done through several techniques. All catalysts were screened in terms of catalytic activity and time-on-stream stability for GSR. The catalytic activity experiments aimed to assess the effect of temperature (400–700 °C) on the glycerol conversion and yield of gaseous products (H₂, CO₂, CO and CH₄). Additionally, catalytic stability experiments were conducted at 625 °C to investigate deactivation of the catalysts, in which a drop in the activity was observed, especially for Co/La₂O₃. The glycerol conversion into gaseous products as a function of the time-on-stream was more affected for all catalysts in comparison to total glycerol conversion, being this effect assigned to the increase in the formation of liquid products and to the formation of coke. CoAlLaO_x was observed to be more carbon-resistant, followed by CoAlZnO_x, through the measurement of the quantity of carbonaceous species formed during the GSR experiments. A NiAlLaO_x catalyst was also prepared and assessed in terms of catalytic stability for GSR; a stable behavior was observed throughout all experiment in relation to glycerol conversion into gaseous products and H₂ yield.     

Effects of catalyst preparation route and promoters (Ce and Zr) on catalytic activity of CuZn/CNTs catalysts for hydrogen production from methanol steam reforming

Ce or Zr promoted CuZn/CNTs (carbon nanotubes) catalysts were synthesized by microwave-assisted polyol, co-precipitation and impregnation methods and were used to generate hydrogen by methanol steam reforming (MSR) process. The physico-chemical properties of the prepared catalysts were analyzed by BET, XRD, FT-IR, TEM, FE-SEM, EDX-dot mapping and H₂-TPR methods. The effect of various operating parameters on methanol conversion and selectivity of gaseous products was investigated. The results indicated that the addition of 2 wt% CeO₂ promoter on CuZn/CNTs catalyst synthesized by impregnation route (CuZn/CNTs (Imp)) increased its methanol conversion from 81.3 to 85.2%, and decreased its CO selectivity from 6.2 to 3.8% at 300 °C, WHSV of 7.5 h^?1 and S/C molar ratio of 2. In addition, the CeCuZn/CNTs catalyst prepared via the microwave-assisted polyol route (CeCuZn/CNTs (Pol)) exhibited the best catalytic activity with 98.2% hydrogen selectivity, 2.6% CO selectivity and 94.2% methanol conversion at 300 °C. Furthermore, a 48 h continuous MSR reaction at 300 °C, identified CeCuZn/CNTs (Pol) as the most stable catalyst due to its higher metal particle dispersion and better interaction between the active phase and the CNTs support.     

Fibrous spherical Ni-M/ZSM-5 (M: Mg,Ca, Ta,Ga) catalysts for methane dry reforming: The interplay between surface acidity-basicity and coking resistance

A highly active and robust fibrous spherical ZSM-5-supported nickel catalyst with different promoters (Mg, Ca, Ta, Ga) have been synthesised by microemulsion method for dry reforming of methane (DRM). The structural framework provided by the unique fibrous spherical ZSM-5 aided confinement of Ni particles. Catalytic activity was improved by homogenous distribution of surface acid-basic sites, thereby reducing the propensity of coke deposition. Bimetallic Ni-Ta catalyst produced the highest CH₄ and CO₂ conversions at 93% and 98%, respectively, with H₂/CO ratio closer to unity (0.97). The nature of acid sites and bimetallic Ni-Ta synergism amplified interaction of catalyst components, resulting in improved interaction with the reactants, thus impeding metal sintering and coke deposition. Consequently, the Ni-Ta/FZSM-5 catalyst shows long-term activity (80 hours) for the DRM reaction at 800°C.     

MxOy (M = Mg,Zr, La,Ce) modified Ni/CaO dual functional materials for combined CO2 capture and hydrogenation

The integrated CO₂ capture and utilization has recently attracted attention as a promising approach to reduce CO₂ emissions as well as produce value-added chemicals and fuels. Herein, metal oxides (M_xO_y, M = Mg, Zr, La, and Ce) modified Ni/CaO dual functional materials (M-Ni/Ca DFMs) were synthesized and applied to the combined CO₂ capture and hydrogenation using a single reactor at one temperature. The La–Ni/Ca showed the highest CO₂ adsorption capacity (13.8 mmol/g), CO₂ conversion (64.3%) and CO yield (8.7 mmol/g). Results indicated that the addition of metal oxides increased the number of basic sites which played important role in efficient CO₂ capture. The high activities of M-Ni/Ca were attributed to the formation of highly dispersed small-sized Ni particles. Furthermore, the La–Ni/Ca exhibited excellent cyclic stability after 20 cycles due to the La₂O₃ as a physical barrier and a support for inhibiting the growth and sintering of CaO and Ni particles.     

Hydrogen production via CO2 reforming of CH4 over low-cost Ni/SBA-15 from silica-rich palm oil fuel ash (POFA) waste

H₂ was produced via CO₂ reforming of CH₄ (CRM) using low-cost Ni/SBA-15 synthesized from palm oil fuel ash (POFA) waste as silica precursor. A series of Ni/SBA-15 were synthesized by employing different Na₂SiO₃-POFA/P123 mass ratios (2.0, 2.9 and 4.0) and were compared with Ni/SBA-15 prepared from commercial Na₂SiO₃ (Ni/SBA-15(Comm.)). Na₂SiO₃-POFA/P123 = 2.9 was found to be the optimal synthesis ratio, which produces a well-defined hexagonal framework, smaller NiO particles, stronger Ni-support interaction, homogeneous metal distribution and higher amount of basic sites. The catalytic performance complied with the trend of Ni/SBA-15(R4.0) < Ni/SBA-15(R2.0) < Ni/SBA-15(R2.9) ≈ Ni/SBA-15(Comm.), indicating the excellent catalytic activity of Ni/SBA-15(R2.9) (H₂ selectivity = 87.6%). The favorable physicochemical properties of Ni/SBA-15(R2.9) ameliorated the active Ni metals stabilization over SBA-15 and boosted the catalyst's virtues towards an outstanding catalytic performance. Hence, it is affirmed that POFA with an optimal Na₂SiO₃-POFA/P123 ratio of 2.9 can be served as silica substitution of Ni/SBA-15 for efficient H₂ production via CRM.     

Hydrogen production via steam reforming of methanol over Cu/(Ce,Gd)O2−x catalysts

Hydrogen production via steam reforming of methanol is carried out over Cu/(Ce,Gd)O_2−x catalysts at 210–600 °C. The CO content in reformate is about 1% at 210–270 °C, which are the typical temperature for hydrogen production via steam reforming of methanol. Largest H₂ yield and CO₂ selectivity and smallest CO content are obtained at 240 °C. The formation rate of CO increases with increasing temperature. The average formation rate of CO becomes larger than that of CO₂ at about 450 °C. The H₂ yield, the CO₂ selectivity and the CO content become constant at about 550 °C. At 240 °C, the smallest CO content is obtained with a catalyst weight of 0.5 g and a Cu content of 3 wt%. The H₂ yield, defined as H₂/(CO + CO₂) in formation rates, at 240 °C is always 3 and not affected by the variations of either the catalyst weight or the Cu content.     

Preparation of nanocrystalline Zr,La and Mg-promoted 10% Ni/Ce0.95Mn0.05O2 catalysts for syngas production via dry reforming reaction

The influence of the various promoters (Zr, La and Mg) on the physicochemical and catalytic characteristics of the 10% Ni/Ce_0.95Mn_0.05O₂ solid solution catalyst were investigated in methane dry reforming at atmospheric pressure. The co-precipitation method was employed for the synthesis of the catalyst carrier. The catalysts were characterized by BET, XRD, H₂-TPR and TPO analyses. The obtained results revealed that the addition of the promoters increased the BET surface area and the highest BET surface area was related to the catalyst promoted by La (58.99 m²/gr). The results of the TPR analysis showed that the broad peak related to the reduction of NiO species was shifted to the higher temperature, indicating the enhancement of the interaction between NiO particles and the support due to the addition of the promoter. The obtained results indicated that the addition of Mg improved the activity (CH₄ conversion (%) = 67 at 700 °C) and stability and reduced the amount of deposited carbon. Furthermore smaller Ni crystalline size was related to the catalyst promoted by Mg (10.0 nm). The highest and the lowest amount of carbon deposition was observed on the 10Ni/Ce_0.95Mn₀.₀₅O₂ and 10Ni/Ce_0.85Zr_0.10Mn_0.05O₂ catalysts, respectively.     

Effect of Ca,Ce or K oxide addition on the activity of Ni/SiO2 catalysts for the methane decomposition reaction

To increase the activity and stability of Ni/SiO₂ catalysts, a series of Ni–Ca, Ni–K and Ni–Ce promoted catalysts were prepared by successive impregnations. The textural properties, reducibility and catalytic performance in the methane decomposition reaction were investigated. The catalyst containing 30 wt.% Ni and 30 wt.% cerium oxide greatly increased the conversion of methane (90% of equilibrium value) and improved the stability, whereas the Ni–K and Ni–Ca were less active and stable than the Ni/SiO₂ catalyst. The results suggest that Ce addition prevents the sintering of nickel particles during reduction process maintaining a random distribution between the silica and cerium oxide improving the distribution and migration of deposited carbon.     

A comparative study of ZrO2, Y2O3 and Sm2O3 promoted Ni/SBA-15 catalysts for evaluation of CO2/methane reforming performance

Ni-based/SBA-15 catalysts, were promoted by 3wt % of samaria (Sm₂O₃), Yttria (Y₂O₃) and Zirconia (ZrO₂), by two-solvent impregnation method. The catalysts characterization was performed by N2 adsorption–desorption, X-ray Diffraction (XRD), X-ray Fluorescence (XRF), High Resolution Transmission Electron Microscopy (HRTEM), Field Emission Electron Scanning Microscopy (FESEM), Temperature Programmed Oxidation/Reduction (TPO/TPR) and NH₃-Temperature Programmed Desorption (NH₃-TPD) techniques. Then, evaluated by CO₂/methane reforming.The CO₂/methane reforming outcomes revealed that samaria-promoted catalyst showed excellent activity, stability and cock resistance, while yttria-promoted catalyst just illustrated good activity at high temperature and zirconia-promoted catalyst didn't show any modification in catalytic performance in comparison to Ni-based catalyst with no promoter. Samaria-promoted TEM and TPR analysis, indicated adding samaria improved the NiO particles interaction with SBA-15 support pores wall and NiO dispersion. The TPO analysis displayed that coke deposition in samaria-promoted sample after 12 h reaction is less than yttria-promoted during stream of 5 h. Also, it is suggested that for samaria containing catalyst, cock deposition occurred on the support. Therefore, nickel active sites were preserved for time on stream of 12 h, which is the main reason for samaria-promoted catalyst superior stability than other's.     

Hydrogen production by steam reforming of model bio-oil using structured Ni/Al2O3 catalysts

This study focuses on hydrogen production from the steam reforming of model bio-oil over Ni/Al₂O₃ catalysts prepared in two different geometries (monolith and pellet) using the dip-coating and wet impregnation methods and characterized using Powder X-Ray diffraction, Temperature Programmed Reduction, Scanning Electron Microscopy (SEM) and BET Surface area analysis. The effects of the catalyst geometry and reforming temperatures were studied by carrying out experiments at the optimal conditions of T = (823, 923, 1023) K and S/C ratio = 13 determined from the thermodynamic analysis of the process prior to the experiments using the process simulator PRO-II. The experimental results showed high steady state H₂ yield corresponding to 2.58 and 1.73 mol (out of 5.13 mol) using monolithic and the pelletized catalysts respectively. The product distribution achieved with the monolithic catalyst was closer to the thermodynamic results suggesting a higher selectivity to hydrogen production.     

Synthesis gas production in the combined CO2 reforming with partial oxidation of methane over Ce-promoted Ni/SiO2 catalysts

A series of nickel-based catalyst supported on silica (Ni/SiO₂) with different loading of Ce/Ni (molar ratio ranging from 0.17 to 0.84) were prepared using conventional co-impregnation method and were applied to synthesis gas production in the combination of CO₂ reforming with partial oxidation of methane. Among the cerium-containing catalysts, the cerium-rich ones exhibited the higher activity and stability than the cerium-low ones. The temperature-programmed reduction (TPR) and UV–vis diffuse reflectance spectroscopy (UV–vis DRS) analysis revealed that the addition of CeO₂ reduced the chemical interaction between Ni and support, resulting in an increase in reducibility and dispersion of Ni. Over NiCe-x/SiO₂ (x = 0.17, 0.50, 0.67, 0.84) catalysts, the reduction peak in TPR profiles shifted to the higher temperature with increasing Ce/Ni molar ratio, which was attributed to the smaller metallic nickel size of the reduced catalysts. The transmission electron microscopy (TEM) and X-ray diffraction (XRD) for the post-reaction catalysts confirmed that the promoter retained the metallic nickel species and prevented the metal particle growth at high reaction temperature. The NiCe-0.84/SiO₂ catalyst with small Ni particle size exhibited the stable activity with the constant H₂/CO molar ratio of 1.2 during 6-h reaction in the combination of CO₂ reforming with partial oxidation of methane at 850 °C and atmospheric pressure.