Search Results (239)

The energetic valorization of digestate obtained from anaerobic digestion (AD) of the organic fraction of municipal solid waste (OFMSW) was investigated via pyrolysis in a bench-scale rotary kiln. The mass rate of dried digestate to the rotary kiln pyrolyzer was fixed at 500 gr/h. The effect of the pyrolysis temperature was investigated at 600, 700, and 800 °C. The pyrolysis products, char, oil, and gas, were quantified and chemically analyzed. It was observed that with the increase in the temperature from 600 to 800 °C, the char decreased from 60.3% to 52.2% and the gas increased from 26.5% to 35.3%. With the aim of increasing the methane production and methane concentration in syngas, the effect of CaO addition to the pyrolysis process was investigated at the same temperature, too. The mass ratio CaO/dried digestate was set at 0.2. The addition of CaO sorbent has a clear effect on the yield and composition of pyrolysis products. Under the experimental conditions, CaO was observed to act both as a CO₂ sorbent and as a catalyst, promoting cracking and reforming reactions of volatile compounds. In more detail, at the investigated temperatures, a net reduction in CO₂ concentration was observed in syngas, accompanied by an increase in CH₄ concentration. The gas yield decreased with the CaO addition because of CO₂ chemisorption. The oil yield decreased as well, probably because of the cracking and reforming effect of the CaO on the volatiles. A very promising performance of the CaO sorbent was observed at 600 °C; at this temperature, the CO₂ concentration decreased from 32.2 to 13.9 mol %, and the methane concentration increased from 16.1 to 29.4 mol %. At the same temperature, the methane production increased from 34 to 63 g/kg_digestate. Full article

The mixed oxides of Ni/ZrO₂, Ni-Ca/ZrO₂, Ni-Ba/ZrO₂, and Ni-Ba-Ca/ZrO₂ were prepared using the co-precipitation method at a pH of precisely 8.3. The catalytic mixed oxides of Ni/ZrO₂, Ni-Ca/ZrO₂, Ni-Ba/ZrO₂, and Ni-Ba-Ca/ZrO₂ were characterized using x-ray diffraction XRD, Brunauer Emmett Teller (BET), scanning electron microscopy (SEM), and metal dispersion for the screening of phase purity, surface area, and morphology. The mixed oxides are subjected to CO₂-TPD to quantify the basicity of every composition. The mixed oxide catalysts of Ni/ZrO₂, Ni-Ca/ZrO₂, Ni-Ba/ZrO₂, and Ni-Ba-Ca/ZrO₂ were screened for oxythermal reforming of CH₄ with CO₂ in a fixed bed tubular reactor at 800 °C. Among all catalysts, the Ba- and Ca- loaded Ni-Ba-Ca/ZrO₂ showed high conversion by the decomposition of methane and CO₂ disproportionation throughout the time on stream of 29 h. The high activity with stability led to less coke formation over Ni-Ba-Ca/ZrO₂ over the surface. The stable syngas production with an active catalyst bed contributed to the improved bimetallic synergy. The high surface basicity of Ni-Ba-Ca/ZrO₂ may keep actively gasifying the formed soot and allow for further stable reforming reactions. Full article

This study examines the surface chemistry of platinum, palladium, rhodium, and ruthenium-substituted lanthanum strontium cobaltate perovskite catalysts in the context of the dry reforming of methane (DRM). The catalysts were synthesized by the solution combustion method and characterized by using a series of techniques. To explore the effect of noble metal ion substitution on the DRM, surface reaction was probed by CH₄/CO₂ TPSR using mass spectroscopy. It was recognized that La_1−xSr_xCo_1−yPd_yO₃ show the best activities for the reaction in terms of the temperature but became deactivated over time. CH₄/CO₂ temperature-programmed surface reactions (TPSRs) were set up to unravel the details of the surface phenomena responsible for the deactivation of the DRM activity on the LSPdCO. The CH₄/CO₂ TPSR analysis conclusively demonstrated the importance of lattice oxygen in the removal of carbon, which is responsible for the stability of the catalysts on the synthesized perovskites upon noble metal ion substitution. Full article

The dry reforming of methane (DRM) and the combined steam–CO₂ reforming of methane (CSCRM) are promising routes for syngas production while simultaneously utilizing two major greenhouse gases—CO₂ and CH₄. In this study, a series of Ni/MgO-Al₂O₃ catalysts with varying Mg/Al molar ratios (Ni/MgAl(x), x = 0.5–0.9), along with Ni/MgO and Ni/Al₂O₃, were synthesized, characterized, and evaluated in both the DRM and CSCRM. Ni/MgO and Ni/Al₂O₃ exhibited a lower activity due to fewer active sites and a poor CH₄/CO₂ activation balance. In contrast, Ni/MgAl(0.6), Ni/MgAl(0.7), and Ni/MgAl(0.8) showed an enhanced activity, attributed to more abundant active sites and a more balanced activation of CH₄ and CO₂. Ni/MgAl(0.7) delivered the best DRM performance, whereas Ni/MgAl(0.8) was optimal for the CSCRM, likely due to its greater number of strong basic sites promoting CO₂ and H₂O adsorption. At 750 °C and 0.1 MPa over 100 h, Ni/MgAl(0.7) maintained a stable DRM performance (77% CH₄ and 86% CO₂ conversion; H₂/CO = 0.9) at 120 L/(g_cat·h), while Ni/MgAl(0.8) achieved a stable CSCRM performance (80% CH₄ and 62% CO₂ conversion; H₂/CO = 2.1) at 132 L/(g_cat·h). This study provides valuable insights into designing efficient Ni/MgO-Al₂O₃ catalysts for targeted syngas production. Full article

The use of CH₄ and CO₂ as fuels in direct internal reforming solid oxide fuel cells (DIR-SOFCs) is a promising strategy for efficient power generation with reduced greenhouse gas emissions. In this study, Ni catalysts supported on Ce–Pr mixed oxides with varying Pr contents (0–80 mol%) were synthesized, calcined at 1200 °C, and tested for dry reforming of methane (DRM), aiming at their application as catalytic layers in SOFC anodes. Physicochemical characterization (XRD, TPR, TEM) showed that increasing Pr loading enhances catalyst reducibility and promotes the formation of the Pr₂NiO₄ phase, which contributes to the generation of smaller Ni⁰ particles after reduction. Catalytic tests revealed that all samples exhibited low-carbon deposition, attributed to the large Ni crystallites. The catalyst with 80 mol% Pr showed the best performance, achieving the highest CH₄ conversion (72%), a H₂/CO molar ratio of 0.89, and improved stability. These findings suggest that Ni/Ce_0.2Pr_0.8 could be a promising candidate for use as a catalyst layer of anodes in DIR-SOFC anodes. Although electrochemical data are not yet available, future work will evaluate the catalyst’s performance and durability under SOFC-relevant conditions. Full article

The Ni/SiO₂ and the ceria-promoted Ni-CeO₂/SiO₂ were prepared by the impregnation method and co-impregnation method, respectively. The performance of the carbon dioxide reforming of methane (CDR) over Ni/SiO₂ and Ni-CeO₂/SiO₂ was investigated under the conditions of CH₄/CO₂ = 1.0, T = 800 °C, and GHSV = 60,000 mL·g⁻¹·h⁻¹. As a result, a high CDR performance, especially stability, was obtained over Ni-CeO₂/SiO₂, in which the conversion of CH₄ was very similar to that of the thermodynamic equilibrium (88%), and a negligible decrease in CH₄ conversion was observed after 50 h of the CDR reaction. Ni/SiO₂ and Ni-CeO₂/SiO₂ before and after the CDR reaction were subjected to structural characterization by XRD, TEM, TG–DSC, and physical adsorption. It was found that the addition of CeO₂ into Ni/SiO₂ significantly affected its surface area, the size and dispersion of Ni, the reduction behavior, and the coking properties. Moreover, the redox property of Ce³⁺-Ce⁴⁺, which accelerates the gasification of the coke, made Ni-CeO₂/SiO₂ successfully operate for 50 h without observable deactivation. Thus, the developed catalyst is very promising for the CDR. Full article

The potential of dry reforming methane (DRM) to convert two greenhouse gases concurrently is drawing interest from around the world. This research focused on developing supported nickel catalysts for the DRM, utilizing stabilized zirconia (SZ31107), which contains 5% SiO₂, as the support material. To promote the catalysts with a 5 wt.% Ni concentration, we used varying gallium loadings, specifically 0.1, 0.25, 0.5, 0.75, and 1 wt.%. After a detailed analysis, characterization was performed using X-ray diffraction, N₂-physorption, temperature-programmed reduction/desorption techniques, thermogravimetry, and Raman spectroscopy. The optimal DRM performance, achieved at 700 °C with a 1:1 CH₄:CO₂ feed, was recorded for the catalyst that has 0.25 wt.% Ga. The catalyst demonstrated remarkable average conversion rates of 56% for CH₄ and 66% for CO₂ after 300 min at 700 °C, with an H₂:CO ratio of 0.84. Activity was further enhanced by raising the temperature to 800 °C, which resulted in an 87% CO₂ conversion and an 80% CH₄ conversion. Studies on the catalyst’s long-term stability revealed a slow deactivation. With computed activation energies of 28,009 J/mol for CH₄ conversion and 21,875 J/mol for CO₂ conversion, temperature-programmed reaction tests conducted over the best catalyst demonstrated the DRM reaction’s endothermic character. Small additions of Ga encouraged the creation of more graphitic carbon structures, according to Raman spectroscopy of spent catalysts; the ideal catalyst had the lowest I_D/I_G ratio. These results suggest that the 5Ni+0.25Ga/SZ31107 catalyst is a promising candidate for large-scale syngas and hydrogen production. Full article

Solid oxide fuel cells (SOFCs) represent a pivotal technology in renewable energy due to their clean and efficient power generation capabilities. Their role in potential carbon mitigation enhances their viability. SOFCs can operate via a variety of alternative fuels, including hydrocarbons, alcohols, solid carbon, and ammonia. However, several solutions have been proposed to overcome various technical issues and to allow for stable operation in dry methane, without coking in the anode layer. To avoid coke formation thermodynamically, methane is typically reformed, contributing to an increased degradation rate through the addition of oxygen-containing gases into the fuel gas to increase the O/C ratio. The performance achieved by reforming catalytic materials, comprising active sites, supports, and electrochemical testing, significantly influences catalyst performance, showing relatively high open-circuit voltages and coking-resistance of the CH₄ reforming catalysts. In the next step, the operating principles and thermodynamics of methane reforming are explored, including their traditional catalyst materials and their accompanying challenges. This work explores the components and functions of SOFCs, particularly focusing on anode materials such as perovskites, Ruddlesden–Popper oxides, and spinels, along with their structure–property relationships, including their ionic and electronic conductivity, thermal expansion coefficients, and acidity/basicity. Mechanistic and kinetic studies of common reforming processes, including steam reforming, partial oxidation, CO₂ reforming, and the mixed steam and dry reforming of methane, are analyzed. Furthermore, this review examines catalyst deactivation mechanisms, specifically carbon and metal sulfide formation, and the performance of methane reforming and partial oxidation catalysts in SOFCs. Single-cell performance, including that of various perovskite and related oxides, activity/stability enhancement by infiltration, and the simulation and modeling of electrochemical performance, is discussed. This review also addresses research challenges in regards to methane reforming and partial oxidation within SOFCs, such as gas composition changes and large thermal gradients in stack systems. Finally, this review investigates the modeling of catalytic and non-catalytic processes using different dimension and segment simulations of steam methane reforming, presenting new engineering designs, material developments, and the latest knowledge to guide the development of and the driving force behind an oxygen concentration gradient through the external circuit to the cathode. Full article

In this work, Aspen Plus was used to simulate a sorption-enhanced steam methane reforming (SE-SMR) process in a fluidized bed reformer using a Ni-based catalyst and CaO as a sorbent for CO₂ removal from the reaction environment. The performances of the process in terms of the outlet gas hydrogen purity (y_H2), methane conversion (X_CH4), and hydrogen yield (η_H2) were investigated. The process was simulated by varying the following different reformer operating parameters: pressure, temperature, steam/methane (S/C) feed ratio, and CaO/CH₄ feed ratio. A clear sorption-enhanced effect occurred, where CaO was fed to the reformer, compared with traditional SMR, resulting in improvements of y_H2, X_CH4, and η_H2. This effect, in percentage terms, was more relevant, as expected, in conditions where the traditional process was unfavorable at higher pressures. The presence of CaO could only partially balance the negative effect of a pressure increase. This partial compensation of the negative pressure effect demonstrated that the intensification process has the potential to produce blue hydrogen while allowing for less severe operating conditions. Indeed, when moving traditional SMR from 1 to 10 bar, an average decrease of y_H2, X, and η by −16%, −44%, and −41%, respectively, was recorded, while when moving from 1 bar SMR to 10 bar SE-SMR, y_H2 showed an increase of +20%, while X_CH4 and η_H2 still showed a decrease of −14% and −4%. Full article

The dry reforming of methane (DRM) converts two greenhouse gases, CH₄ and CO₂, into H₂ and CO, offering a crucial technological pathway for reducing greenhouse gas emissions and producing clean energy. However, the reaction faces two main challenges: high activation energy barriers require high temperatures to drive the reaction, while sintering and carbon deactivation at high temperatures are common with conventional nickel-based catalysts, which severely limit the further development of the methane dry reforming reaction. In this study, a nitrogen-doped carbon nanotube-loaded nickel catalytic system (Ni/NCNT) was developed to overcome the challenges caused by limited active sites while maintaining the stable structure of the Ni/CNT system. Ni/NCNT catalysts were prepared using different nitrogen precursors, and the impact of the mixing method on catalytic performance was examined. Characterization using H₂-TPR, XPS, and TEM revealed that nitrogen doping enhanced the metal–support interaction (MSI). Additionally, pyridine nitrogen species synergistically interact with nickel particles, modulating the electronic environment on the carbon nanotube surface and increasing catalyst active site density. The Ni/NCNT-IU catalyst, prepared with impregnated urea, exhibited excellent stability, with methane conversion decreasing from 85.0% to 82.9% over 24 h of continuous reaction. This study supports the use of non-precious-metal carbon-based catalysts in high-temperature catalytic systems, which is strategically important for the industrialization of DRM and the development of decarbonized energy conversion. Full article

Among biomass gasification syngas cleaning methods, non-catalytic reforming emerges as a sustainable and high-efficiency alternative. This study employed integrated experimental analysis and kinetic modeling to examine non-catalytic reforming processes of biomass-derived producer gas utilizing a synthetic tar mixture containing representative model compounds: naphthalene (C₁₀H₈), toluene (C₇H₈), benzene (C₆H₆), and phenol (C₆H₅OH). The experiments were conducted using a high-temperature fixed-bed reactor under varying temperatures (1100–1500 °C) and equivalence ratios (ERs, 0.10–0.30). The results obtained from the experiment, namely the measured mole concentration of H₂, CO, CH₄, CO₂, H₂O, soot, and tar suggested that both reactor temperature and O₂ content had an important effect. Increasing the temperature significantly promotes the formation of H₂ and CO. At 1500 °C and a residence time of 0.01 s, the product gas achieved CO and H₂ concentrations of 28.02% and 34.35%, respectively, while CH₄, tar, and soot were almost entirely converted. Conversely, the addition of O₂ reduces the concentrations of H₂ and CO. Increasing ER from 0.10 to 0.20 could reduce CO from 22.25% to 16.11%, and H₂ from 13.81% to 10.54%, respectively. Experimental results were used to derive a kinetic model to accurately describe the non-catalytic reforming of producer gas. Furthermore, the maximum of the Root Mean Square Error (RMSE) and the Relative Root Mean Square Error (RRMSE) between the model predictions and experimental data are 2.42% and 11.01%, respectively. In particular, according to the kinetic model, the temperature increases predominantly accelerated endothermic reactions, including the Boudouard reaction, water gas reaction, and CH₄ steam reforming, thereby significantly enhancing CO and H₂ production. Simultaneously, O₂ content primarily influenced carbon monoxide oxidation, hydrogen oxidation, and partial carbon oxidation. Full article

The CO₂ (Dry) Reforming of Methane (DRM) is a key process for reducing CO₂ and CH₄ emissions while producing syngas with an H₂/CO ratio of 1, ideal for Fischer–Tropsch synthesis. This study explores DRM and the Reverse Water Gas Shift (RWGS) reaction under mild conditions using Ru-based catalysts supported on CeO₂, YSZ, TiO₂, and SiO₂, with three reactant ratios: (i) stoichiometric, PCO₂ = 1 kPa, PCH₄ = 1 kPa, (ii) oxidizing, PCO₂ = 2 kPa, PCH₄ = 1 kPa, and (iii) reducing, PCO₂ = 1 kPa, PCH₄ = 4 kPa. The results highlight the importance of redox support for catalyst stability, with mobile lattice oxygen aiding carbon gasification. While Ru/CeO₂ is stable at high temperatures, it rapidly deactivates at low temperatures, emphasizing the need for precise metal particle size control. This work demonstrates the necessity of fine-tuning catalyst properties for more sustainable DRM, offering insights for next-generation CO₂ utilization catalysts. Full article

This study investigates the effect of potassium (K) promotion on Pt/m-ZrO₂ catalysts in methanol steam reforming (MSR), revealing critical insights into reaction pathways and catalyst performance. While increasing K loading reduces catalytic activity, it selectively enhances the hydrogen-producing formate dehydrogenation and de-carboxylation pathway. Structural analyses using HR-TEM and DRIFTS show that higher K concentrations block Pt sites and promote agglomeration, reshaping catalytic behavior. Notably, the 3.1% K-promoted catalyst achieves high stability at 358 °C, with a CO₂ selectivity exceeding 80% and minimal methane formation, outperforming the unpromoted catalyst in terms of CO and CH₄ selectivity. Temperature studies further demonstrate reduced CO selectivity at higher temperatures, highlighting distinct advantages of K-doped catalysts. These findings underscore the role of K in enhancing surface basicity and its impact on formate interaction, offering valuable insights for optimizing MSR catalysts and advancing hydrogen production technologies. Full article

This study proposes a novel system integrating a molten carbonate fuel cell (MCFC) with a dry reforming process (DR-MCFC) and develops a corresponding simulation model. In a DR-MCFC, the reacting gases from the dry reforming of methane (DRM) process are fed into a molten carbonate fuel cell. CH₄ and CO₂ were used as the reaction gases, while N₂ was employed as the carrier gas and introduced into the DRM. Following the DRM, the reformed gases were humidified and injected into the anode of the MCFC. A simulation model combining the dry reforming process and the MCFC was developed using COMSOL Multiphysics to evaluate the system’s performance and feasibility. The mole fraction of H₂ after the DRM ranged from 0.181 to 0.214 under five different gas conditions. The average current density of the fuel cell varied between 1321.5 and 1444.9 A·m⁻² at a cell voltage of 0.8 V, which was up to 27.07% lower than that of a conventional MCFC operating at 923 K due to the lower hydrogen concentration in the anode. Based on these results, the integration of dry reforming with the MCFC’s operation did not cause any operational issues, demonstrating the feasibility of the proposed DR-MCFC system. Full article

Biogas (primarily biomethane), as a carbon-neutral renewable energy source, holds great potential to replace fossil fuels for sustainable hydrogen production. Conventional biogas reforming systems adopt strategies similar to industrial natural gas reforming, posing challenges such as high temperatures, high energy consumption, and high system complexity. In this study, we propose a novel multi-product sequential separation-enhanced reforming method for biogas-derived hydrogen production, which achieves high H₂ yield and CO₂ capture under mid-temperature conditions. The effects of reaction temperature, steam-to-methane ratio, and CO₂/CH₄ molar ratio on key performance metrics including biomethane conversion and hydrogen production are investigated. At a moderate reforming temperature of 425 °C and pressure of 0.1 MPa, the conversion rate of CH₄ in biogas reaches 97.1%, the high-purity hydrogen production attains 2.15 mol-H₂/mol-feed, and the hydrogen yield is 90.1%. Additionally, the first-law energy conversion efficiency from biogas to hydrogen reaches 65.6%, which is 11 percentage points higher than that of conventional biogas reforming methods. The yield of captured CO₂ reaches 1.88 kg-CO₂/m³-feed, effectively achieving near-complete recovery of green CO₂ from biogas. The mild reaction conditions allow for a flexible integration with industrial waste heat or a wide selection of other renewable energy sources (e.g., solar heat), facilitating distributed and carbon-negative hydrogen production. Full article