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.     

Hydrogen and syngas production by methane dry reforming on SBA-15 supported nickel catalysts: On the effect of promotion by Ce0.75Zr0.25O2 mixed oxide

In this work, the effects of doping Ni-based SBA-15 catalysts with Ceria–Zirconia mixed oxide (CZ) on the activity and stability of these catalysts during syngas production by methane dry reforming (MDR) were investigated and compared with the activity and stability of unmodified Ni/SBA-15. The above catalysts were prepared by incipient wetness impregnation (IWI) with different impregnation strategy. The samples were characterized by nitrogen physisorption, X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), temperature programmed reduction (TPR) and H₂ chemisorption. The results indicated that the unmodified Ni/SBA-15 showed clear deactivation especially in the first period of the stability test and between 600 °C and 630 °C during the activity test whereas the CZ modified samples had better stability.     

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.     

Aqueous-phase reforming of n-BuOH over Ni/Al2O3 and Ni/CeO2 catalysts

The aqueous-phase reforming (APR) of n-butanol (n-BuOH) over Ni(20 wt%) loaded Al₂O₃ and CeO₂ catalysts has been studied in this paper. Over 100 h of run time, the Ni/Al₂O₃ catalyst showed significant deactivation compared to the Ni/CeO₂ catalyst, both in terms of production rates and the selectivity to H₂ and CO₂. The Ni/CeO₂ catalyst demonstrated higher selectivity for H₂ and CO₂, lower selectivity to alkanes, and a lower amount of C in the liquid phase compared to the Ni/Al₂O₃ sample. For the Ni/Al₂O₃ catalyst, the selectivity to CO increased with temperature, while the Ni/CeO₂ catalyst produced no CO. For the Ni/CeO₂ catalyst, the activation energies for H₂ and CO₂ production were 146 and 169 kJ mol⁻¹, while for the Ni/Al₂O₃ catalyst these activation energies were 158 and 175 kJ mol⁻¹, respectively. The difference of the active metal dispersion on Al₂O₃ and CeO₂ supports, as measured from H₂-pulse chemisorption was not significant. This indicates deposition of carbon on the catalyst as a likely cause of lower activity of the Ni/Al₂O₃ catalyst. It is unlikely that carbon would build up on the Ni/CeO₂ catalyst due to higher oxygen mobility in the Ni doped non-stoichiometric CeO₂ lattice. Based on the products formed, the proposed primary reaction pathway is the dehydrogenation of n-BuOH to butaldehyde followed by decarbonylation to propane. The propane then partially breaks down to hydrogen and carbon monoxide through steam reforming, while CO converts to CO₂ mostly through water gas shift. Ethane and methane are formed via Fischer-Tropsch reactions of CO/CO₂ with H₂.     

Syngas production via dry reforming of methane over CeO2 modified Ni/Al2O3 catalysts

Syngas production via dry reforming of methane (DRM) was experimentally investigated using Ni-based catalyst. Ni/Al₂O₃ modification with CeO₂ addition and O₂ addition in the reactant were employed in this study to suppress carbon deposition and to enhance catalyst activity. It was found that DRM performance can be enhanced using CeO₂ modified Ni/Al₂O₃ catalyst due to CeAlO₃ formation. However, an optimum amount of CeO₂ loading exists to obtain the best DRM performance due to the decrease in specific surface area as the CeO₂ loading increases. Without O₂ addition, the reverse water-gas shift reaction plays an important role in DRM. It was found that CH₄ conversion and CO yield were enhanced while CO₂ conversion and H₂ yield are decreased as the CO₂ amount in feedstock increased in DRM. With O₂ addition in the fed reactant, it was found that the methane oxidation reaction plays an important role in DRM. CH₄ conversion can be enhanced by O₂ addition. However, decreases in CO₂ conversion and H₂ and CO yields occurred due to greater H₂O and CO₂ productions from the methane oxidation reaction. The thermogravimetric analysis (TGA) results showed that CeO₂ modified Ni/Al₂O₃ catalyst would have the lowest amount of carbon deposition when O₂ is introduced into the reaction.     

Catalytic performance of Samaria-promoted Ni and Co/SBA-15 catalysts for dry reforming of methane

Methane reforming with CO₂ over Samaria-promoted Ni and Co/SBA-15 was comparatively investigated. The Co, Ni (10%wt) and Sm (0.5, 1 and 1.5%wt) ions were introduced by two-solvent impregnation method. The Ni and Co catalysts with/without promoter, were examined by N2 adsorption-desorption, x-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), temperature programmed reduction (TPR) and thermogravimetric analysis (TGA) methods, and then evaluated in CO₂ reforming of methane. The XRD and TEM results indicated that Ni and Co/SBA-15 promoted by 1%wt of Samaria, had the smallest NiO and Co₃O₄ particles size and the highest dispersion; as a result, they would rather studying dry reforming of methane test. Catalytic results indicated that Samaria promoted Ni/SBA-15 had the highest conversion (CH₄ conversion～58% at 700 °C), while a remarkable decrease of catalytic activity was observed over Samaria-promoted Co/SBA-15 (CH₄ conversion～25% at 700 °C). The positive effect of Samaria on Ni/SBA-15 catalyst activity is probably due to smaller NiO particles, higher NiO dispersion and lower trend to carbon deposition. On the contrary, the negative effect of Samaria on Co/SBA-15 catalyst activity is maybe due to Co oxidation to inactive phase and sintering of Co particles in high temperatures.     

Hydrogen production via CO2 dry reforming of glycerol over ReNi/CaO catalysts

The present work investigates the performance of Re-promoted Nickel-based catalyst supported on calcium oxide for glycerol dry reforming reaction. The catalysts were prepared using wet impregnation method and their catalytic performance was tested in a packed bed reactor with CO₂ to glycerol ratio (CGR) of 1–5, reaction temperature of 600–900 °C and gas hourly specific velocity (GHSV) of 1.44 × 10⁴–7.20 × 10⁴ ml g_cat⁻¹ s⁻¹. The optimum operating temperature for both Ni/CaO and ReNi/CaO is 800 °C, with the GHSV of 3.6 × 10⁴ mL g_cat⁻¹s⁻¹. The optimum CGR for Ni/CaO and ReNi/CaO is 1.0 and 3.0, respectively. At this condition, hydrogen gas is directly produced from glycerol decomposition and indirectly from water-gas-shift reaction. After 2 h at the optimum conditions, 5% ReNi/CaO gives optimal glycerol conversion and hydrogen yield of approximately 61% and 56%, respectively, while in comparison to 15% Ni/CaO, the conversion and yield are 35 and 30%, respectively. Characterization of the spent catalysts showed the existence of whisker carbon from the CO₂ hydrogenation and methanation processes. By comparing to 15% Ni/CaO, the addition of Re increases the acidic sites of the catalyst and enhanced the surface adsorption of OH group of the glycerol. The adsorbed glycerol on the catalyst surface would further react with the adsorbed CO₂ to yield gases products. Thus, the catalytic activity improved significantly.     

Design of Ni/La2O3 catalysts for dry reforming of methane: Understanding the impact of synthesis methods

Fine-tuning of materials properties, particularly the catalytic properties, through innovative synthesis procedures has gained an increased research interest in the last decades. It is well known that synthesis procedures have considerable impact on the physio-chemical properties of the synthesized materials even if the chemical composition is maintained. Herein, we investigated the impact of selected synthesis methods on the catalytic performance of Ni/La₂O₃ for the dry reforming of methane (DRM), a challenging reaction known for severe coking. Although this catalyst has been frequently studied for DRM, however, tuning the structure-activity relationship by varying the synthesis routes has not been reported. Herein, the chosen synthesis techniques; for example the solution combustion synthesis (Ni/La-SC), sol-gel (Ni/La-SG), homogeneous precipitation (Ni/La-HP), solvothermal (Ni/La-ST), and modified oleylamine-assisted synthesis (Ni/La-ME); considerably affected the morphology, metal support interaction (MSI), and surface area of Ni/La₂O₃ catalysts leading to variation in their performance for DRM. The investigated catalysts were thoroughly characterized by using SEM-EDX, TEM, N₂-physisorption, XRD, XPS, and H₂-TPR to understand the structural properties. Their catalytic performance towards the DRM was evaluated by varying the temperature between 550 and 800 °C. DRM experiments demonstrated that among the studied catalysts, Ni/La-SC showed the best performance for DRM with a high catalytic activity and coking resistance. For instance, Ni/La-SC revealed the highest CO₂ and CH₄ conversions i.e. 97.9 ± 1.5% and 96.6 ± 1.8%, respectively at 800 °C. The same sample revealed the highest hydrogen yield i.e. 71.9% and the highest H₂/CO ratio i.e. 1.03 ± 0.013 at the same temperature. The results revealed that Ni/La-SC demonstrated the lowest increment (20.9%) in the Ni crystallite size after DRM reaction, highest durability, and the lowest rate of coke formation (42 ± 5.2 mg C/g_catalyst) over an operating period of 100 h at 800 °C. The outstanding performance of Ni/La-SC catalyst was credited to the small crystallite size of Ni, high Ni⁰/Ni²⁺ ratio, high BET area, and a good dispersion of nickel sites over the La₂O₃ support. The obtained results may open new frontiers for size and shape-controlled synthesis of nanostructured metals/metal oxides catalysts with controllable morphologies and dispersion that can lead to desirable catalytic properties.     

Enhanced dry reforming toward hydrogen production over Ni/CeO2SiO2 via different catalyst synthesis routes

Dry reforming of methane to produce hydrogen-rich syngas is widely studied, where the productivity of the reaction is greatly dependent on the activity and stability of the catalyst. In this investigation, a binary catalyst support consisting of a SiO₂CeO₂ combination was developed to produce an efficient catalyst support with high resistance to carbon deposition during the reaction. Four different preparation methods (deposition-precipitation, DP; impregnation, IMP; sol-gel, SG; and ball milling, BM) were used to synthesize SiO₂CeO₂ supports, and 5 wt % nickel was added to the support via wet impregnation. The catalyst performance was recorded in the order: Ni/CS-DP ˃ Ni/CS-IMP ˃ Ni/CS-BM ˃ Ni/CS-SG at 800 °C for 10 h reaction with a CH₄/CO₂ feed-gas composition ratio of 1:1. Ni/CS-DP was seen to be the most promising catalyst, exhibiting H₂ and CO selectivities of ∼95% and ∼73%, respectively, with a H₂/CO ratio of >1:1, and maintaining 97% CH₄ conversion up to 10 h of reaction with very low coke deposition. The superior catalytic performance of Ni/CS-DP was achieved as a result of the synergistic effects of high basicity and low reducibility, which was achieved via direct alteration during the preparation of the support.     

Preparation and characterization of Ni catalysts supported on pillared nanoporous bentonite powders for dry reforming reaction

The Ni/pillared-bentonite catalysts with high BET area were synthesized and used in dry reforming reaction. The effects of different parameters such as calcination temperature, OH⁻/Al³⁺ ratio, temperature and time of pillaring process and the content of nickel on the textural and catalytic properties of the synthesized catalysts were studied. The results indicated that the 15 wt% Ni catalyst supported on pillared bentonite prepared under specified conditions (OH⁻/Al³⁺ = 2.2, pillaring temperature of 40 °C and pillaring time of 3 h) possessed the highest BET area (90.80 m²/g). Also, this catalyst possessed higher catalytic activity and stability with lower amount of deposited carbon in comparison to other prepared catalysts in methane reforming with CO₂.     

Syngas production via the biogas dry reforming reaction over Ni supported on zirconia modified with CeO2 or La2O3 catalysts

The catalytic efficiency and bench scale time on steam stability of Ni dispersed on three commercially available catalytic supports (ZrO₂, La₂O₃–ZrO₂ and CeO₂–ZrO₂) has been studied for the dry reforming of methane (DRM) in the temperature range of 500–800 °C and a CH₄/CO₂ ratio equal to 1.5, simulating typical biogas quality. Ni supported on LaZr and CeZr carriers that obeyed enhanced basicity and oxygen ion lability values than Zr, exhibited superior catalytic efficiency and stability. A variety of techniques, namely N₂ physisorption-desorption (BET method), powder X-ray diffraction (XRD), hydrogen temperature programmed reduction (H₂-TPR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, potentiometric titration and inductively coupled plasma emission spectroscopy (ICP), were applied for the characterization of particles morphology, textural, structural and other physical properties of the materials, as well as the type of carbon deposited on the catalytic surface after exposure to DRM reaction conditions. Post-reaction analysis of the deposited carbon on the catalysts surfaces showed that the prominent trend of the carbon deposits on the Ni/Zr and Ni/LaZr samples was to have a filamentous tube like morphology (graphite-2H). In contrast, on the Ni/CeZr used catalyst, the formation of small amount of carbon tube-like architectures was detected. The enhanced basicity and Ni dispersion of the Ni/LaZr and Ni/CeZr samples as well as the high oxygen ion lability of the lattice oxygen in the latter, were considered to be the major factors involved in the superior efficiency and durability of these samples in comparison to Ni/Zr sample.     

Hydrogen production by auto-thermal reforming of ethanol over Ni catalysts supported on ZrO2: Effect of preparation method of ZrO2 support

Zirconia supports were prepared by a sol–gel method (S-ZrO₂) and by a templating sol–gel method (M-ZrO₂). Nickel catalysts supported on zirconia were then prepared by an incipient wetness impregnation method for use in hydrogen production by auto-thermal reforming of ethanol. For comparison, a commercial zirconia (C-ZrO₂) was also employed as a support for nickel catalyst. The effect of preparation method of zirconia on the catalytic property and catalytic performance of supported nickel catalysts (Ni/C-ZrO₂, Ni/S-ZrO₂, and Ni/M-ZrO₂) was investigated. The crystalline and physical property of zirconia supports and the catalytic performance of supported nickel catalysts were strongly affected by the preparation method of zirconia. BET surface area and pore volume were decreased in the order of M-ZrO₂ > S-ZrO₂ > C-ZrO₂. Both M-ZrO₂ and S-ZrO₂ supports showed only tetragonal phase of ZrO₂, while C-ZrO₂ support exhibited tetragonal and monoclinic phases of ZrO₂. Crystalline size of nickel species in the Ni/ZrO₂ catalysts decreased with increasing surface area and pore volume of ZrO₂ supports. All the Ni/ZrO₂ catalysts exhibited 100% conversion of ethanol at 500 °C, while product distributions over the Ni/ZrO₂ catalysts were different depending on the preparation method of zirconia. Among the catalysts tested, the Ni/M-ZrO₂ catalyst showed the best catalytic performance in hydrogen production by auto-thermal reforming of ethanol. Well developed mesopore, high surface area, and pure tetragonal phase of ZrO₂ were responsible for fine nickel dispersion and high catalytic performance of Ni/M-ZrO₂. C–C bond cleavage reaction and methane steam reforming reaction were also accelerated over the Ni/M-ZrO₂ catalyst.     

CNT-based catalysts for H2 production by ethanol reforming

Hydrogen production by steam reforming of ethanol (SRE) was studied using steam-to-ethanol ratio of 3:1, between the temperature range of 150–450 °C over metal and metal oxide nanoparticle catalysts (Ni, Co, Pt and Rh) supported on carbon nanotubes (CNTs) and compared to a commercial catalyst (Ni/Al₂O₃). The aim was to find out the suitability of CNTs supports with metal nanoparticles for the SRE reactions at low temperatures. The idea to develop CNT-based catalysts that have high selectivity for H₂ is one of the driving forces for this study. The catalytic performance was evaluated in terms of ethanol conversion, product gas composition, hydrogen yield and selectivity to hydrogen. The Co/CNT and Ni/CNT catalysts were found to have the highest activity and selectivity towards hydrogen formation among the catalysts studied. Almost complete ethanol conversion is achieved over the Ni/CNT catalyst at 400 °C. The highest hydrogen yield of 2.5 is, however, obtained over the Co/CNT catalyst at 450 °C. The formation of CO and CH₄ was very low over the Co/CNT catalyst compared to all the other tested catalysts. The Pt and Rh CNT-based catalysts were found to have low activity and selectivity in the SRE reaction. Hydrogen production via steam reforming of ethanol at low temperatures using especially Co/CNT catalyst has thus potential in the future in e.g. the fuel cell applications.     

Carbon dioxide methanation over Ni-M/Al2O3 (M: Fe,CO, Zr,La and Cu) catalysts synthesized using the one-pot sol-gel synthesis method

In this paper, a series of mesoporous supported nickel based catalysts on nanocrystalline alumina carrier promoted with various metals (Fe, CO, Zr, La and Cu) were prepared and employed in carbon dioxide methanation reaction. The samples were characterized by XRD, BET, TPR and SEM techniques. The BET results showed that the incorporation of promoters into nickel based catalysts decreased the surface area. The results showed that among the prepared catalysts, 30 wt.%Ni-5 wt.%La/Al₂O₃ and 30 wt.%Ni-5 wt.%Fe/Al₂O₃ possessed the highest surface area and the largest pore volume, respectively. Likewise, there was a slight decrease in the pore volume and the average pore diameters of the promoted samples. The TPR results depicted that the incorporation of the promoters enhanced the reducibility of the catalysts and shifted the reduction of NiO species to a lower reduction temperature. The CO₂ conversions of all promoted catalysts except Cu-promoted sample were higher peculiarly at low temperatures compared to those attained for the unpromoted catalyst. 30 wt.%Ni-5 wt.%Fe/Al₂O₃ catalyst exhibited the best catalytic performance (70.63% CO₂ conversion and 98.87% CH₄ selectivity at 350 °C), high stability and desirable resistance against sintering.     

Preparation of mesoporous nanostructure NiO–MgO–SiO2 catalysts for syngas production via propane steam reforming

In this research, the propane steam reforming (PSR) as a promising alternative route over a mesoporous NiO–MgO–SiO₂ catalyst to produce syngas (SG) was undertaken. This catalyst was prepared using a co-precipitation method followed by hydrothermal treatment. The influence of such catalyst preparation factors as the hydrothermal time and temperature, pH and calcination temperature on the physicochemical characteristics of the prepared samples were examined. Next, these materials were characterized through the BET-BJH, XRD, TPR, and FTIR analyses. The thermal stability of this catalyst was tested through the TGA and DTA techniques. Furthermore, the deactivation of the calcined catalysts at different temperatures was investigated via the TPO analysis. The utilized synthesis method led to preparation of a species with a mesoporous structure possessing a rather high surface area of 741 m²g^-1. The catalyst performance at a reaction temperature of 550 °C revealed that, the increment in calcination temperature from 500 to 800 °C led to lowering of the propane conversion as well as the hydrogen yield from 65 to 37.4% and 39.4 to 22.6%, respectively. Meanwhile, the extent of the deposited coke upon the catalyst surface was reduced when implementing the higher calcination temperature. This was attributed to high amounts of the NiO, which was included in the solid solution containing the MgO–SiO₂ support. In other words, the isolation of Ni²⁺ with Mg²⁺ species and strong interaction between NiO and MgO decreased the NiO particle size hence, its reducibility. These in turn led to the formation of smaller active sites possessing higher deactivation resistance against sintering and coke deposition. Thus, a highly active and stable catalyst was developed.     

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.     

Mesoporous nanostructured Ni/MgAl2O4 catalysts: Highly active and stable catalysts for syngas production in combined dry reforming and partial oxidation

In this paper, the combination of dry reforming and partial oxidation of methane on nickel catalysts supported on mesoporous MgAl₂O₄ was investigated. The support was prepared by a facile sol-gel route using propylene oxide as a gelation agent. The characterizations of the catalysts were performed by BET, XRD, TPR, TPO, TPH, UV–vis, CO-dispersion, SEM and TEM techniques. In addition, the effects of nickel content, reaction and reduction temperatures, feed ratio and the GHSV value on the physicochemical and catalytic properties were studied. The results revealed that the nickel content had an optimum value of 7.5 wt% and the catalyst with this content of nickel exhibited the highest activity. Furthermore, the results demonstrated that the increase in reaction temperature enhanced the rate of the dry reforming reaction and led to obtain a H₂/CO ratio around unity. The 7.5 wt% nickel catalyst showed a 5% decline in activity within 15 h in combined reforming. The TPO analysis showed that there was no deposited carbon on the catalyst surface in combined reforming and the SEM analysis confirmed the results of TPO analysis.     

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%).     

Syngas production from glycerol-dry(CO2) reforming over La-promoted Ni/Al2O3 catalyst

A 3 wt% La-promoted Ni/Al₂O₃ catalyst was prepared via wet co-impregnation technique and physicochemically-characterized. Lanthanum was responsible for better metal dispersion; hence higher BET specific surface area (96.0 m² g⁻¹) as compared to the unpromoted Ni/Al₂O₃ catalyst (85.0 m² g⁻¹). In addition, the La-promoted catalyst possessed finer crystallite size (9.1 nm) whilst the unpromoted catalyst measured 12.8 nm. Subsequently, glycerol dry reforming was performed at atmospheric pressure and temperatures ranging from 923 to 1123 K employing CO₂-to-glycerol ratio from zero to five. Significantly, the reaction results have yielded syngas as main gaseous products with H₂:CO ratios always below than 2.0 with concomitant maximum 96% glycerol conversion obtained at the CO₂-to-glycerol ratio of 1.67. In addition, the glycerol consumption rate can be adequately captured using power law modelling with the order of reactions equal 0.72 and 0.14 with respect to glycerol and CO₂ whilst the activation energy was 35.0 kJ mol⁻¹. A 72 h longevity run moreover revealed that the catalyst gave a stable catalytic performance.     

Determination of the operating range of CO2 conversion and syngas production in dry auto-thermal reforming

A porous medium-catalyst hybrid reformer for CO₂ conversion by dry auto-thermal reforming (DATR) was investigated in this study, and its operating range was discovered. The hybrid design was used to enhance the oxidative heat release by internal heat recirculation during exothermic reaction conditions, thereby increasing the CO₂ conversion efficiency. The experimental results show that the CO₂ conversion could be enhanced with higher catalyst inlet temperatures. The examination of the operating range of DATR showed that the CO₂ conversion efficiency increased at higher reaction temperatures and CO₂/CH₄ ratios (≧1). Moreover, DATR in high temperature conditions must be carried out with high O₂/CH₄ ratios. Under these conditions of high oxygen content, CO₂ generation and reduction reactions occur simultaneously. Overall, optimal CO₂ conversion can be obtained with an O₂/CO₂ ratio of approximately 0.5. At these conditions, CO₂ conversion efficiency can reach approximately 13% without external heat addition.