Search Results (35)

Ni (20 wt.%) catalysts supported on CeO₂ were synthesized using the incipient wetness impregnation method and promoted with varying amounts of CaO (0, 5, 10, 15, 20 wt.%). The catalysts were evaluated in dry reforming of methane (DRM) at 650 °C for 24 h. Fresh catalysts were characterized by XRD, WD-XRF, H₂-TPR, N₂ physisorption, HDP, SEM, and FT-IR spectroscopy (DRIFT and ATR), while spent catalysts were characterized by XRD, Raman spectroscopy, and SEM. The incorporation of 5–15 wt.% CaO on CeO₂ significantly improved its catalytic performance. FT-IR analysis confirmed the presence of CaCO₃ bands, indicating carbonate formation. The Ni/CeO₂ catalyst with 15 wt.% CaO exhibited the highest catalytic activity. The promoted catalysts demonstrated high stability, attributed to strong interactions between CeO₂, CaO, and CaCO₃. However, when CaO promotion reached 20 wt.%, catalytic activity decreased. Despite large carbon formations, the catalysts maintained their stability with no significant deactivation due to sintering or coke accumulation. Full article

Forest degradation is a major issue in ecosystem monitoring, and to take reformative measures, it is important to detect, map, and quantify the losses of forests. Synthetic Aperture Radar (SAR) time-series data have the potential to detect forest loss. However, its sensitivity is influenced by the ecoregion, forest type, and site conditions. In this work, we assessed the accuracy of open-source C-band time-series data from Sentinel-1 SAR for detecting deforestation across forests in Africa, South Asia, and Southeast Asia. The statistical Cumulative Sums of Change (CuSUM) algorithm was applied to determine the point of change in the time-series data. The algorithm’s robustness was assessed for different forest site conditions, SAR polarizations, resolutions, and under varying moisture conditions. We observed that the change detection algorithm was affected by the site- and forest-management activities, and also by the precipitation. The forest type and eco-region affected the detection performance, which varied for the co- and cross-pol backscattering components. The cross-pol channel showed better deforested region delineation with less spurious detection. The results for Kalimantan showed a better accuracy at a 100 m spatial resolution, with a 25.1% increase in the average Kappa coefficient for the VH polarization channel in comparison with a 25 m spatial resolution. To avoid false detection due to the high impact of soil moisture in the case of Haldwani, a seasonal analysis was carried out based on dry and wet seasons. For the seasonal analysis, the cross-pol channel showed good accuracy, with an average Kappa coefficient of 0.85 at the 25 m spatial resolution. This work was carried out in support of the upcoming NISAR mission. The datasets were repackaged to the NISAR-like HDF5 format and processing was carried out with methods similar to NISAR ATBDs. Full article

Among the countless routes for renewable hydrogen (H₂) production, Biogas Dry Reforming (DR) has been highlighted as one of the most promising for the circular bio-economy sector. However, DR requires high operating temperatures (700 °C–900 °C), and, for greater efficiency, a thermally stable catalyst is necessary, being, above all, resistant to coke formation, sintering, and sulfur poisoning. Mesoporous metallic catalysts, such as nickel (Ni) supported on silica, stand out due to their high catalytic activity concerning such characteristics. In this regard, the presented work evaluated the influences of the nickel addition stage during the synthesis of mesoporous catalyst type Si-MCM-41. Two different catalysts were prepared: catalyst A (Ni/Si-MCM-41_A), synthesized through the in situ addition of the precursor salt of nickel (Ni(Ni(NO₃)₂·6H₂O) before the addition of TEOS (Tetraethyl orthosilicate) and after the addition of the directing agent; and catalyst B (Ni/Si-MCM-41_B), resulting from the addition of the precursor salt after the TEOS, following the conventional methodology, by wet impregnation in situ. The results evidenced that the metal addition stage has a direct influence on the mesoporous structure. However, no significant influence was observed on the efficiency concerning BDR, and the conversions into H₂ were 97% and 96% for the Ni/SiMCM-41_A and Ni/Si-MCM-41_B catalysts, respectively. Full article

In this study, the surface and textural properties as well as the catalytic performance of Ni/CeO₂ and NiIn/CeO₂ catalysts prepared by wet impregnation (WI) and deposition–precipitation (DP) are investigated. The addition of Ni (3.0 wt.%) resulted in a decrease in the specific surface area and pore volume in the case of the WI method, possibly due to a blockage of mesopores. A minimal addition of In (0.25 wt.%) caused a further decrease in the surface area in both cases. XRD analysis showed that Ni deposited on CeO₂ by DP resulted in some lattice incorporation, affecting the crystallinity of the support. The H₂-TPR profiles altered depending on the different ways of Ni and In introduction. STEM-EDS-derived elemental maps indicated that the Ni and NiIn particles deposited on CeO₂ using the DP method were somewhat smaller than in the WI synthesis. A comprehensive CO-DRIFTS analysis proved a direct Ni-In interaction in bimetallic samples, leading to the formation of a surface NiIn alloy. Ni/CeO₂ catalysts showed a higher activity in the process of dry reforming of methane (DRM) than the bimetallic counterparts at 650 °C, with the Ni_DP sample performing slightly better. However, the Ni_DP catalyst showed significant coking, which was drastically reduced by the addition of In. The agglomeration of Ni and/or NiIn particles during the 6 h DRM reaction somewhat impaired the catalyst performance. Overall, this study highlights the intricate relationship between the catalyst preparation, surface properties and catalytic performance in the DRM reaction and emphasizes the beneficial role of In addition in reducing the coking of the monometallic catalyst and the critical location and surface morphology of nickel nanoparticles decorated with indium and in contact with ceria. Full article

In this study, vermiculite was explored as a support material for nickel catalysts in two key processes in syngas production: dry reforming of methane with CO₂ and steam reforming of ethanol. The vermiculite underwent acid or base treatment, followed by the preparation of Ni catalysts through incipient wetness impregnation. Characterization was conducted using various techniques, including X-ray diffraction (XRD), SEM–EDS, FTIR, and temperature-programmed reduction (H₂-TPR). TG-TD analyses were performed to assess the formation of carbon deposits on spent catalysts. The Ni-based catalysts were used in reaction tests without a reduction pre-treatment. Initially, raw vermiculite-supported nickel showed limited catalytic activity in the dry reforming of methane. After acid (Ni/VTA) or base (Ni/VTB) treatment, vermiculite proved to be an effective support for nickel catalysts that displayed outstanding performance, achieving high methane conversion and hydrogen yield. The acidic treatment improved the reduction of nickel species and reduced carbon deposition, outperforming the Ni over alkali treated support. The prepared catalysts were also evaluated in ethanol steam reforming under various conditions including temperature, water/ethanol ratio, and space velocity, with acid-treated catalysts confirming the best performance. Full article

Waste carbon fibre-reinforced plastics were recycled by pyrolysis followed by a thermo-catalytic treatment in order to achieve both fibre and resin recovery. The conventional pyrolysis of this waste produced unusable gas and hazardous liquid streams, which made necessary the treatment of the pyrolysis vapours. In this work, the vapours generated from pyrolysis were valorised thermochemically. The thermal treatment of the pyrolysis vapours was performed at 700 °C, 800 °C and 900 °C, and the catalytic treatment was tested at 700 °C and 800 °C with two Ni-based catalysts, one commercial and one homemade over a non-conventional olivine support. The catalysts were deeply characterised, and both had low surface area (99 m²/g and 4 m²/g, respectively) with low metal dispersion. The thermal treatment of the pyrolysis vapours at 900 °C produced high gas quantity (6.8 wt%) and quality (95.5 vol% syngas) along with lower liquid quantity (13.3 wt%) and low hazardous liquid (92.1 area% water). The Ni–olivine catalyst at the lowest temperature, 700 °C, allowed us to obtain good gas results (100% syngas), but the liquid was not as good (only 58.4 area% was water). On the other hand, the Ni commercial catalyst at 800 °C improved both the gas and liquid phases, producing 6.4 wt% of gas with 93 vol% of syngas and 13.6 wt% of liquid phase with a 97.5 area% of water. The main reaction mechanisms observed in the treatment of pyrolysis vapours were cracking, dry and wet reforming and the Boudouard reaction. Full article

This study investigated the production of hydrogen-rich syngas from renewable sources using durable and efficient catalysts. Specifically, the research focused on steam methane reforming (SRM) and dry methane reforming (DRM) of simulated producer gas from biomass steam gasification in a fluidized bed reactor. The catalysts tested are ZSM-5-supported nickel-iron-cobalt-based trimetallic catalysts in different ratios, which were prepared via the wet impregnation method. Synthesized catalysts were characterized using XRD, BET, H₂-TPR, and SEM techniques. The results of the SRM with the simulated producer gas showed that the 20%Ni-20%Fe-10%Co/ZSM-5 trimetallic catalyst, at a gas hourly space velocity (GHSV) of 12 L·h⁻¹·g⁻¹ and reaction temperature of 800 °C, achieved the highest CH₄ conversion (74.8%) and highest H₂ yield (65.59%) with CO₂ conversion (36.05%). Comparing the performance of the SRM and DRM of the simulated producer gas with the 20%Ni-20%Fe-10%Co/ZSM5 at a GHSV of 36 L·h⁻¹·g⁻¹ and 800 °C, they achieved a CH₄ conversion of 67.18% and 64.43%, a CO₂ conversion of 43.01% and 52.1%, and a H₂ yield of 55.49% and 42.02%, respectively. This trimetallic catalyst demonstrated effective inhibition of carbon formation and sintering, with only 2.6 wt.% carbon deposition observed from the thermo-gravimetric analysis of the used catalyst from the SRM of the simulated producer gas, thus promoting the potential of the ZSM-5-supported trimetallic catalysts in methane reforming. Full article

The design of economical and robust catalysts is a substantial challenge for the dry reforming of methane (DRM). Monometallic nickel-based catalysts used for DRM reactions had comparable activity to noble metals. However, they turned out to be less stable during the reactions. As a continuation of the interest in synthesizing catalysts for DRM, this paper evaluates the catalytic performance of bimetallic Co–Ni catalysts regarding their synergy effect, with graphene oxide (GO) as support for the first time. The synthesized bimetallic catalysts prepared via the wet-impregnation method were characterized using N₂ physisorption analysis, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and X-ray diffraction (XRD). The catalytic test was performed in a stainless-steel tubular reactor in atmospheric conditions with a reaction temperature of 800 °C, time-on-stream (TOS) of 300 min and CH₄: CO₂ being fed with a ratio of 1:1. The bimetallic 10 wt%Co–10 wt%Ni/GO and 20 wt%Co–10 wt%Ni/GO catalysts had a similar BET specific surface area in N₂ physisorption analysis. The XRD pattern displayed a homogeneous distribution of the Co and Ni on the GO support, which was further validated through SEM–EDX. The conversion of CO₂, CH₄, and H₂ yield decreased with reaction time due to the massive occurrence of side reactions. High conversions for CO₂ and CH₄ were 94.26% and 95.24%, respectively, attained by the bimetallic 20 wt%Co–10 wt%Ni/GO catalyst after 300 min TOS, meaning it displayed the best performance in terms of activity among all the tested catalysts. Full article

Citric acid, one of the representative chelate compounds, has been widely used as an additive to achieve the highly dispersed metal-supported catalysts. This study aimed to investigate the effect of citric acid concentration on the preparation of the highly dispersed Ni catalysts on mesoporous silica (SBA-15) for the dry reforming of methane. A series of Ni/SBA-15 catalysts with citric acid were prepared using the acid-assisted incipient wetness impregnation method, and the Ni/SBA-15 catalyst as a reference was synthesized via the impregnation method. First of all, the citric acid addition during the catalyst synthesis step regardless of its concentration resulted in highly dispersed Ni particles of ~4–7 nm in size in Ni/SBA-15 catalysts, which had a superior and stable catalytic performance in the dry reforming of methane (93% of CO₂ conversion and 86% of CH₄ conversion). In addition, the amount of coke formation was much lower in a series of Ni/SBA-15 catalysts with citric acid (~2–5 mg_coke g_cat⁻¹ h⁻¹) compared to pristine Ni/SBA-15 catalysts (~22 mg_coke g_cat⁻¹ h⁻¹). However, when the concentration of citric acid became higher, the more free NiO species that formed on the SBA-15 support, leading to large Ni particles after the stability test. The addition of citric acid is a very clear strategy for making highly dispersed catalysts, but its concentration needs to be carefully controlled. Full article

The effects of operating parameters such as reaction temperature, space velocity, and feed gas composition on the performance of the methane dry-reforming reaction (DRM) over the Ni/Al₂O₃ catalyst are systemically investigated. The Ni/Al₂O₃ catalyst, which is synthesized by conventional wet impregnation, showed well-developed mesoporosity with well-dispersed Ni nanoparticles. CH₄ and CO₂ conversions over the Ni/Al₂O₃ catalyst are dramatically increased as both the reaction temperature is increased, and space velocity is decreased. The feed gas composition, especially the CO₂/CH₄ ratio, significantly influences the DRM performance, catalyst deactivation and the reaction behavior of side reactions. When the CO₂-rich gas composition (CO₂/CH₄ > 1) was used, a reverse water gas shift (RWGS) reaction significantly occurred, leading to the consumption of hydrogen produced from DRM. The CH₄-rich gas composition (CO₂/CH₄ < 1) induces severe carbon depositions followed by a reverse Boudouard reaction, resulting in catalytic activity drastically decreasing at the beginning followed by a stable conversion. The catalyst after the DRM reaction with a different feed ratio was analyzed to investigate the amount and structure of carbon deposited on the catalyst. In this study, we suggested that the optimal DRM reaction conditions can achieve stable performances in terms of conversion, hydrogen production and long-term stability. Full article

This study focuses on the synthetic approach influence in morphostructural features and catalytic performances for Ni/CeO₂ catalysts. Incipient wetness impregnation, coprecipitation and nitrate combustion were studied as catalyst preparation approaches, and the materials were then tested at 700 °C for methane dry reforming (MDR). The morphostructural properties of the materials were deeply studied using several techniques, such as temperature programmed reduction (TPR), to investigate reducibility and support-metal interaction, N₂ physisorption to evaluate the porosity and the surface area, scanning electron microscopy (SEM) and X-ray diffraction (XRD) to estimate Ni dispersion, and temperature programmed oxidation (TPO) to identify the type and amount of coke formed on catalysts’ surface after reaction. From the data obtained, coprecipitation turned out to be the most suitable technique for this application because this catalyst was able to reach 70% of CO₂ conversion and 30% methane conversion, with an H₂ yield of 15% and 30% yield of CO at the end of the 30 h test. Moreover, it was also the catalyst with the highest metal dispersion, the strongest interaction with the support, and the lowest coke deposition. Full article

Dry reforming of methane (DRM), to produce synthesis gas, is one of the most important chemical reactions used for the industrial production of hydrogen and leads to the synthesis of hydrocarbons (liquid fuels) and other valuable products. A cost-effective alternative to active and stable noble metal DRM catalysts, with comparable catalytic performance, can be composite materials based on nickel, cobalt and transition metal carbides. In this line, the present work proposes a non-standard way to obtain dry reforming catalysts of Ni, Co and Ni-Co-modified tungsten carbide (WC) produced by an electric arc method. Different amounts of nickel, cobalt and their mixtures were deposited on tungsten carbide by deposition-precipitation with NaOH (DP) and incipient wetness impregnation (IWI) methods. The resulting materials were characterized by N₂ adsorption-desorption, transmission electron microscopy, energy dispersive spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy, and their performance was evaluated in DRM. The composition and preparation method of catalysts predetermined their structural, textural and electronic properties, playing a decisive role in their activity for DRM. DP-prepared 20%Ni/WC material remained resistant to oxidation, both that of the active metal (nickel) and of the tungsten carbide, as well as to coking during DRM. This sample proved to be the most active and stable among all studied materials. Possibly, the resistance to oxidation and coking was due to a more efficient implementation of the oxidation/(re)carbonization cycle on the surface of this catalyst. Full article

The study presents the results of research on using fixed-bed, activated carbon (AC) adsorbers in the cleaning of heavily tar-laden producer gas from the gasification of biomass. The efficiency of removal of organic compounds as well as the remaining adsorption capacity of the bed were determined using a spectrum of commonly applied diagnostic methods, including qualitative and quantitative analyses of the adsorbed compounds and changes in the pore volume of the bed material (IN, MN). The authors compare these lab quantifications with a simple technique which is based on the analysis of the changes in the position of temperature front in the bed. The main benefit of the latter is the possibility of performing the diagnostics of the bed “online” and using low-cost temperature measurements. The test was performed using a commercially available AC Desotec AIRPEL 10-3 and real producer gas obtained through the gasification of alder chips. For tar, VOC and C₂–C₅ compounds, the removal efficiencies reached respectively 74.5%-wt., 52.8%-wt., and 85.5%-wt. Obtained results indicate that depending on the final application of the gas, the use of dry adsorption systems is an interesting alternative to the well-established but complicated, cumbersome, and costly wet scrubbers. Moreover, a concept for in situ regeneration of the adsorbent, coupled with direct reforming of the tars, is presented and discussed. Full article

A series of ultra-clean, unsupported Cu-doped and Pd-doped Ni model catalysts was investigated to develop the fundamental concept of metal doping impact on the carbon tolerance and catalytic activity in the dry reforming of methane (DRM). Wet etching with concentrated HNO₃ and a subsequent single sputter–anneal cycle resulted in the full removal of an already existing oxidic passivation layer and segregated and/or ambient-deposited surface and bulk impurities to yield ultra-clean Ni substrates. Carbon solubility, support effects, segregation processes, cyclic operation temperatures, and electronic and ensemble effects were all found to play a crucial role in the catalytic activity and stability of these systems, as verified by X-ray photoelectron spectroscopy (XPS) surface and bulk characterization. Minor Cu promotion showed the almost complete suppression of coking with a moderate reduction in catalytic activity, while high Cu loadings facilitated carbon growth alongside severe catalytic deactivation. The improved carbon resistance stems from an increased CH₄ dissociation barrier, decreased carbon solubility in the bulk, good prevailing CO₂ activation properties and enhanced CO desorption. Cyclic DRM operation on surfaces with Cu content that is too high leads to impaired carbon oxidation kinetics by CO₂ and causes irreversible carbon deposition. Thus, an optimal and stable NiCu composition was found in the region of 70–90 atomic % Ni, which allows an appropriate high syngas production rate to be retained alongside a total coking suppression during DRM. In contrast, the more Cu-rich NiCu systems showed a limited stability under reaction conditions, leading to undesired surface and bulk segregation processes of Cu. The much higher carbon deposition rate and solubility of unsupported NiPd and Pd model catalysts results in severe carbon deposition and catalytic deactivation. To achieve enhanced carbon conversion and de-coking, an active metal oxide boundary is required, allowing for the increased clean-off of re-segregated carbon via the inverse Boudouard reaction. The carbon bulk diffusion on the investigated systems depends strongly on the composition and decreases in the following order: Pd > NiPd > Ni > NiCu > Cu. Full article

For the work presented herein nickel catalysts supported on γ-alumina extrudates (Ni/Al) with an egg-shell structure were prepared, using a modified Equilibrium Deposition Filtration (EDF) technique. Their performance was compared, for the biogas dry reforming reaction, with corresponding Ni/Al catalysts with a uniform structure, synthesized via the conventional wet impregnation method. The bulk and surface physicochemical characteristics of all final catalysts were determined using ICP-AES, N₂ adsorption-desorption isotherms, XRD, SEM, and TEM. A theoretical model describing the impregnation process for the EDF extrudates, based on the Lee and Aris model, was also developed. It was concluded that following specific impregnation conditions, the egg-shell macro-distributions can be successfully predicted, in agreement with the experimental results. It was shown that the Ni/Al catalysts with an egg-shell structure had a higher H₂ yield in comparison with the ones with a uniform structure. The difference in catalytic performance was attributed to the improved surface and structural properties of the egg-shell catalysts, resulting from the modified EDF technique used for their preparation. Full article