Combined dry reforming and partial oxidation of methane to synthesis gas on noble metal catalysts

In this paper CO₂ reforming of methane combined with partial oxidation of methane to syngas over noble metal catalysts (Rh, Ru, Pt, Pd, Ir) supported on alumina-stabilized magnesia has been studied. The catalysts were characterized by using BET, XRD, SEM, TEM, TPR, TPH and H₂S chemisorption techniques. The H₂S chemisorption analysis showed an active metal crystallite size in the range of 1.8-4.24 nm for the prepared catalysts. The obtained results revealed that the Rh and Ru catalysts showed the highest activity in combined reforming and both the dry reforming and partial oxidation of methane. The obtained results also showed a high catalytic stability without any decrease in methane conversion up to 50 h of reaction. In addition, the H₂/CO ratio was around 2 and 0.7 over different catalysts for catalytic partial oxidation and dry reforming, respectively.     

Optimized mixed reforming of biogas with O2 addition in spark-discharge plasma

Adding O₂ into biogas to achieve partial oxidation and CO₂ mixed reforming can not only increase H₂ + CO concentration, but also reduce energy cost for H₂ production. In this study, optimized mixed reforming of biogas with O₂ addition in spark-discharge plasma was pursued in combination with thermodynamic-equilibrium calculation. With respect to mixed reforming of biogas with O₂ addition in spark-discharge plasma, combination coefficients of independent reactions were given to quantitatively evaluate the mixed extent at various O₂/(CH₄–CO₂) ratios. Compared thermodynamic-equilibrium with experimental results, it can be concluded that the optimal O₂/(CH₄–CO₂) ratio for optimized mixed reforming of biogas in spark-discharge plasma was about 0.7. When total-carbon conversion was relatively high (>75%), H₂ + CO concentration on wet basis was the highest and energy cost for H₂ production was the lowest at O₂/(CH₄–CO₂) = 0.7, and their experimental results were closest to their thermodynamic-equilibrium values.     

Study of partial oxidation reforming of methane to syngas over self-sustained electrochemical promotion catalyst

A self-sustained electrochemical promotion (SSEP) catalyst is synthesized for partial oxidation reforming (POXR) of CH₄ to produce syngas (H₂ and CO) at a relatively low temperature ranging from 350 to 650 °C. The SSEP catalyst is comprised of 4 components: microscopic Ni/Cu/CeO₂ anode, La_0.9Sr_0.1MnO₃ cathode, copper as electron conductor, and yttria-stabilized-zirconia as oxygen ion conductor, which form microscopic electrochemical cells to enable the self-sustained electrochemical promotion for the POXR process. The SSEP catalyst exhibited much better catalytic performance in POXR of CH₄ than a Ni–Cu–CeO₂ catalyst and a commercial Pt–CeO₂ catalyst. The CH₄ conversion over the SSEP catalyst is 29.4% at 350 °C and reaches 100% at 550 °C and the maximum selectivity to H₂ is on the level of 90% at 450–650 °C under a GHSV of 42,000 h⁻¹. The mechanism of the SSEP is discussed.     

Exergy analysis of hydrogen production via biogas dry reforming

Among the alternative pathways for hydrogen production, the use of biogas from organic waste via dry reforming of methane (DRM), water gas shift reaction and pressure swing adsorption (PSA) is often seen as an interesting option. In this work, the thermodynamic performance of this type of biohydrogen energy system –additionally including a combined-cycle scheme that satisfies the electricity and steam requirements of the process– is evaluated through exergy analysis. The main data needed for the analysis are acquired from a predictive simulation model implemented in Aspen Plus^®. The system shows an exergetic efficiency of 55%, with the DRM and the power generation subsystems arising as the main sources of irreversibility. Furthermore, given the significant influence found for the PSA off-gas on the thermodynamic performance of the system, two alternative process configurations based on the use of this stream are evaluated. In this regard, full recirculation of the PSA off-gas to the DRM reactor is found to improve the system's exergetic performance.     

Pt supported on doped CeO2/Al2O3 as catalyst for dry reforming of methane

This work investigated the effect of the nature of dopant (Pr, Nb and Zr) on the performance of Pt supported on cerium-based oxides deposited on alumina for dry reforming of methane. in situ XRD and XANES analyses showed that the sample doped with Pr exhibited the highest redutibility of ceria (23%). Furthermore, the cyclohexane dehydrogenation reaction revealed that the addition of Pr improved the resistance to metal sintering during the dry reforming reaction. In the absence of doped-ceria oxide, a strong deactivation took place on Pt/Al₂O₃ catalyst during reaction, which was due to the absence of support reducibility and the highest Pt sintering. Among the doped-ceria samples, Pt/CePr/Al₂O₃ exhibited the highest activity and stability. These results were attributed to: (i) the oxygen mobility of the supports containing ceria, mainly for the sample doped with Pr, which favors the carbon removal mechanism; and (ii) the absence of Pt sintering during the reaction.     

Parametric study of catalytic dry reforming of methane for syngas production at elevated pressures

This study examined and elucidated the catalytic dry reforming of methane (DRM) for synthesis gas (syngas) production. The DRM performance was characterized using CH₄ and CO₂ conversions and product yields under various operating conditions and reactant compositions. A fixed-bed tubular reactor was used as the physical model and axisymmetric non-isothermal governing equations for the gas flow, energy transfer and species transport were solved numerically. The reactant inlet temperature was used as the primary parameter. Good agreement between the numerically predicted and experimentally measured data was obtained as the carbon formation reactions were included. A carbon-free reaction was obtained from the numerical model at high temperature which agreed with the thermodynamic equilibrium analysis. It was found that the DRM performance was degraded as the reaction pressure and reactant flow rate were increased. Under these conditions, carbon yield increases with the increase in pressure and reactant flow rate. It was also found that DRM performance can be enhanced by introducing excessive CO₂ into the reaction system. Carbon formation was suppressed by the excessive CO₂ supply. The numerical results also indicated that decreases in CO₂ and CH₄ partial pressures led to enhance the DRM performance. The addition of H₂ as one of the reactants suppresses CH₄ conversion and inhibited carbon formation while the addition of CO resulted in suppressing CO₂ conversion and enhancing carbon formation.     

Simulative optimization of catalyst configuration for biogas dry reforming

Biogas dry reforming is a promising technology for converting biomass into high-value products and reducing greenhouse gas emissions. Recent improvements to biogas reforming have mainly focused on the preparation of functional catalysts; however, little attention has been paid to the effects of catalyst configuration in plug flow reactors. In this study, a Ni/MgO catalyst for biogas reforming was synthesized via the wet impregnation method. Parameters were optimized using an experimental rig and then simulations were performed using an Aspen HYSYS reaction simulator. We simulated loading the same amount of catalyst into 1, 2, 3, or 10 zones inside the reactor and compared performance parameters, including H₂ yield, CO yield, CH₄ conversion, and CO₂ conversion. The results of simulations showed that a 2-zone configuration with a catalyst ratio of 1:4 was optimal, with 88.2% H₂ yield, 83.5% CO yield, 96.4% CH₄ conversion, and 91.7% CO₂ conversion. Catalyst zone number, catalyst distribution, and catalyst zone position all had significant effects on catalytic behavior. The findings of this study provide new insights into the processes of biogas reforming and other heterogeneous catalysis reactions.     

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.     

Syngas production from methane dry reforming over SmCoO3 perovskite catalyst: Kinetics and mechanistic studies

The kinetics of the methane dry (CO₂) reforming over the SmCoO₃ was investigated in the temperature ranged 973–1073 K by varying the CH₄ and CO₂ partial pressures. Based on detailed study of the reaction mechanism, a mechanistic model is proposed from which a kinetic model is derived. The mechanistic pattern assumes adsorption of CH₄ on reduced Co, followed by methane cracking and carbon deposition. CO₂ reacts with Sm₂O₃ to form Sm₂O₂CO₃ and the oxycarbonates react with carbon to produce CO. The power law and Langmuir–Hinshelwood kinetic model which is established on this mechanism were able to forecast the kinetic results.     

Hydrogen production from glycerol dry reforming over Ag-promoted Ni/Al2O3

In recent times, glycerol has been employed as feedstock for the production of syngas (H₂ and CO) with H₂ as its main constituent. This study centers on dry reforming of glycerol over Ag-promoted Ni/Al₂O₃ catalysts. Prior to characterization, the catalysts were synthesized using the wet impregnation method. The reforming process was carried out using a fixed bed reactor at reactor operating conditions; 873–1173 K, carbon dioxide to glycerol ratio of 0.5 and gas hourly space velocity (WHSV) in the range of 14.4 ≤ 72 L g_cat⁻¹ h⁻¹). Ag (3)-Ni/Al₂O₃ gave highest glycerol conversion and hydrogen yield of 40.7% and 32%, respectively. The optimum conditions which gave highest H₂ production, minimized methane production and carbon deposition were reaction temperature of 1073 K and carbon dioxide to glycerol ratio of 1:1. This result can attributed to the small metal crystallite size characteristics possessed by Ag (3)–Ni/Al₂O₃, which enhanced metal dispersion in the catalyst matrix. Characterization of the spent catalyst revealed the formation of two types of carbon species; encapsulating and filamentous carbon which can be oxidized by O₂.     

Influence of promoting Ni-based catalysts with ruthenium in the dry reforming of polypropylene plastics for syngas production

The catalytic dry reforming of plastic waste is conducted in two-stage fixed bed reactors. The pyrolysis of polypropylene plastics occurs in the first reactor, and the pyrolyzed gases undergo a reforming reaction with carbon dioxide over a catalyst in the second reactor. The wet impregnation method is used to synthesize Ru–Ni/Al₂O₃ catalysts, which are then calcined and reduced at 800 °C. The results show that as the nickel loading increases, the syngas production increases. Promoting the catalyst with a small quantity of ruthenium significantly improves the plastic conversion into syngas. The dry reforming of polypropylene over 1Ru15Ni/Al₂O₃ catalyst resulted in the maximum syngas yield (159 mmol_syngas/g_PP) at a 2:1 plastic to catalyst ratio. The catalytic dry reforming of plastics is promising for the production of synthesis gas.     

Ni/MgAl2O4 catalyst for low-temperature oxidative dry methane reforming with CO2

Oxidative dry reforming of methane has been performed for 100 h on stream using Ni supported on MgAl₂O₄ spinel at different loadings at 500–700 °C, CO₂/CH₄ molar ratio of 0.76, and variable O₂/CH₄ molar ratio (0.12–0.47). Syngas with an H₂/CO ratio of 1.5–2.1 has been produced by manipulating reforming feed composition and temperature. The developed oxidative dry reforming process allowed high CH₄ conversion at all conditions, while CO₂ conversion decreased significantly with the lowering of the reforming temperature and increasing O₂ concentration. When considering both greenhouse gas conversions and H₂/CO ratio enhancement, the optimal reforming condition should be assigned to 550 °C and O₂/CH₄ molar ratio of 0.47, which delivered syngas with H₂/CO ratio of 1.5. Coke-free operation was also achieved, due to the combustion of surface carbon species by oxygen. The 3.4 wt% Ni/MgAl₂O₄ catalyst with a mean Ni nanoparticle diameter of 9.8 nm showed stable performance during oxidative dry reforming for 100 h on stream without deactivation by sintering or coke deposition. The superior activity and stability of MgAl₂O₄ supported Ni catalyst shown during reaction trials is consistent with characterization results from XRD, TPR, STEM, HR-STEM, XPS, and CHNS analysis.     

Study on hydrogen-rich syngas production by dry autothermal reforming from biomass derived gas

In this study, the H₂-rich syngas (H₂ + CO) production from biomass derived gas (BDG) by dry autothermal reforming (DATR) is investigated. Methane and carbon dioxide is the major composition of biomass derived gas. DATR reaction combined benefits of partial oxidation (POX) and dry reforming (DR) reaction was carried out in this study. The reforming parameters on the conversion of methane and syngas selectivity were explored. The reforming parameters included the fuel feeding rate, CO₂/CH₄ and O₂/CH₄ molar ratios. The experimental results demonstrated that it not only supplied the energy required for self-sustained reaction, but also avoided the coke formation by dry autothermal reforming. It has a wide operation region to maintain the moderate production of the syngas. During the reforming process, the reformate gas temperature was between 650 and 900 °C, and energy loss percentage in reforming process was between 15 and 30%. Further, high CO₂ concentration in the reactant had a considerable influence on the heat release of oxidation, and thereby decreased the reformate gas temperature. It caused the reduction of synthesis gas concentration and assisting/impeding combustion composition (A/I) ratio. However, it was favorable to CO selectivity because of the reverse water-gas shifting reaction. The H₂/CO molar ratio between 1 and 2 was achieved by varying CO₂/CH₄ molar ratio. However, the syngas concentrations were affected by CO₂/CH₄ and O₂/CH₄ molar ratio.     

Physico-chemical properties and syngas production via dry reforming of methane over NiAl2O4 catalyst

Nano-particles of NiAl₂O₄ were prepared by co-precipitation and their bulk and surface were characterized by XRD, Raman spectroscopy, N₂-adsorption-desorption analysis, SEM-EDS and XPS. The reducibility was studied by TPR and HTXRD techniques under H₂ atmosphere. The synthetized catalyst was made of NiAl₂O₄ spinel oxide as main phase and of NiO (10%) free oxide. Interestingly, it was shown that the surface was richer in Al species. The catalytic performances in methane dry reforming were evaluated without H₂-pretreatment of catalyst. A very high activity was observed with conversion of methane and CO₂ at 750 °C of 84 and 90 mol%, respectively and high H₂/CO ratio. The amount of coke deposited during the reaction on this spinel was ～3.6%. The physico-chemical properties of the catalyst on their behavior in the dry reforming of methane are discussed.     

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.     

Preparation and improvement of the mesoporous nanostructured nickel catalysts supported on magnesium aluminate for syngas production by glycerol dry reforming

Dry reforming of glycerol is an interesting method for syngas production due to its H₂/CO ≈ 1 that is suitable for FT synthesis. In this study, the performance of the Ni/MgO.Al₂O₃ catalysts with different nickel contents was investigated in glycerol dry reforming. The MgO.Al₂O₃ carrier was prepared by a simple sol-gel method and the nickel-based catalysts were synthesized by the wet impregnation method. The prepared catalysts possessed high BET surface area and pore volume. The TPR analysis showed a strong interaction between Ni and the catalyst support. The results demonstrated that the glycerol conversion decreased by increasing in CO₂/glycerol (GRR) molar ratio. All the prepared samples showed high stability in glycerol dry reforming during 25 h of reaction, indicating the high resistance of the catalysts against carbon formation. Also, 10 wt%Ni/MgO.Al₂O₃ catalysts possessed the highest catalytic performance (52% of glycerol conversion at 750 °C) due to the high dispersion of nickel on the prepared carrier.     

Theoretical study of ethanol partial oxidation for syngas production under cold plasma conditions

In this work, pathways of partial oxidation of ethanol under cold plasma conditions have been studied by density functional theory (DFT) method. The calculation results show that the energy barrier of ethanol conversion is reduced and the conversion from ethanol to H₂ and CO is promoted with the presence of O₂ under cold plasma conditions. The formation of syngas is through a multi-step pathway via the methoxy radical conversion and dissociation of formaldehyde, while the recombination of H generated extra H₂. The present DFT study also demonstrates that the plasma synthesis will normally lead to a formation of a mixture of syngas, hydrocarbons, and oxygenates.     

Influence of the operating parameters over dry reforming of methane to syngas

The influence of operating parameters over dry reforming of methane reaction was evaluated using a Ni-based catalyst obtained after calcination of a hydrotalcite-like precursor. The studied variables were mass to flow ratio (W/F), reaction temperature and CO₂/CH₄ ratio. Maximum methane and carbon dioxide conversions were achieved at W/F ratios above 0.21 g h L⁻¹. The higher the W/F ratio was, the lower amount of water was formed, which led to a higher H₂/CO ratio. The increase in reaction temperature produced an increase in conversions. Water concentration in the outlet stream showed a maximum at 600 °C. At this temperature, reverse water–gas-shift reaction (RWGS) was favoured because it is endothermic. However, steam reforming and carbon gasification were also favoured and they consumed great part of the water produced. CO₂/CH₄ ratios above 1 led to a higher CH₄ conversion but selectivity to hydrogen decreased because RWGS reaction was favoured. When CO₂/CH₄ was below unity, CH₄ conversion decreased but less amount of water was produced so a higher H₂ selectivity was achieved. The catalyst exhibited good stability over dry reforming of methane under all the tested conditions, which may be ascribed to its high basicity. This property improved CO₂ adsorption and then RWGS reaction and carbon gasification.     

Biogas reforming over La-promoted Ni/SBA-16 catalyst for syngas production: Catalytic structure and process activity investigation

Biogas, a mixture of CO₂/CH₄, is reasonable for conversion to syngas (H₂/CO) by dry methane reforming (DMR) reaction. The modification of Ni/SBA-16 with a lanthanum promoter using the co-impregnation technique is investigated in this study. The temperature of reaction (600–750 °C), La loading (3.85–11.56 wt%), and Ni loading (10–30 wt%) are the parameters that are varied for maximizing reaction conversions. The synthesized catalysts and SBA-16 supporting material were characterized by several methods before and after reaction. According to the analysis, the existence of La₂O₃ particles on the catalyst's surface has decreased the particle sizes, as well as enhanced their dispersion. Therefore, the maximum CH₄ conversion of 94.21%, CO₂ conversion of 90.12%, H₂ yield of 90.53%, and H₂/CO molar ratio of 2.03 are achieved using 20Ni-5.78La/SBA16 at 700 °C. Besides, this catalyst showed lower deposited coke and higher stability compared with other synthesized catalysts.     

Pressurization effect on dry reforming of biogas in kilohertz spark-discharge plasma

To produce high-concentration syngas (CO + H₂) from biogas, the effect of pressurization on dry reforming of biogas (CH₄/CO₂ = 60%/40%) in kilohertz spark-discharge plasma was reported for the first time by elevating the pressure from 1 bar to 2 bar. It was found that elevating the pressure could not only increase the reactant conversions, but also reduce energy cost and increase fuel-production efficiency at the same specific energy input (SEI). In particular, pressurization exhibited a significantly positive effect on increasing CO₂ conversion and decreasing energy cost for converting CO₂. Syngas concentration as high as 83% (H₂/CO = 1.4) was achieved with a ratio of the flow rates of product gas (dry basis) to feeding gas, 1.7, at 2 bar and SEI = 753 kJ/mol. The by-product, H₂O, was produced with only about 5% of hydrogen-based selectivity in this work. At 2 bar, the effect of SEI was investigated by varying the power and flow rate, respectively. Compared with those at 1 bar, with the increase in SEI, reactants conversion increased fast, energy cost rose slowly and fuel-production efficiency decreased slowly at 2 bar.