Solid-state synthesis method for the preparation of cobalt doped Ni–Al2O3 mesoporous catalysts for CO2 methanation

In this study, a simple solid-state synthesis method was employed for the preparation of the Ni–Co–Al₂O₃ catalysts with various Co loadings, and the prepared catalysts were used in CO₂ methanation reaction. The results demonstrated that the incorporation of cobalt in nickel-based catalysts enhanced the activity of the catalyst. The results showed that the 15 wt%Ni-12.5 wt%Co–Al₂O₃ sample with a specific surface area of 129.96 m²/g possessed the highest catalytic performance in CO₂ methanation (76.2% CO₂ conversion and 96.39% CH₄ selectivity at 400 °C) and this catalyst presented high stability over 10 h time-on-stream. Also, CO methanation was investigated and the results showed a complete CO conversion at 300 °C.     

Ni/Al2O3 catalysts for CO2 methanation: Effect of silica and nickel loading

Samples containing from 1 to 33 wt.% of NiO on silica and alumina doped with silica (1 and 20 wt.% silica in the support) have been prepared and characterized by BET, XRD, FT-IR, UV–vis–NIR, FE-SEM, EDXS, and TPR techniques. Catalysts have been pre-reduced in situ before catalytic experiments and data have been compared with Ni/Al₂O₃ reference sample. Characterization results showed that SiO₂ support has a low Ni dispersion ability mainly producing segregated NiO particles and a small amount of dispersed Ni²⁺ in exchange sites. Instead, for the Si-doped alumina a “surface spinel monolayer phase” is formed by increasing Ni loading and, only when the support surface is completely covered by this layer, NiO is formed. Moreover, H₂-TPR results indicated that NiO particles are more easily reduced compared to Ni species. Low loading Ni/SiO₂ catalysts show high selectivity and moderate activity for RWGS (reverse Water Gas Shift) reaction, likely mainly due to nickel species dispersed in silica exchange sites, as evidenced by visible spectroscopy. High loading Ni/SiO₂ catalysts show both methanation and RWGS but evident short-term deactivation for methanation, attributed to large, segregated Ni metal particles, covered by a carbon veil. Ni on alumina -rich carriers, where nickel disperses forming a surface spinel phase, show high activity and selectivity for methanation, and short-term catalyst stability as well. This activity is attributed to small nickel clusters or metal particles interacting with alumina, formed upon reaction. The addition of SiO₂ in Al₂O₃ support decreases the activity of Ni catalysts in CO₂ methanation, because it reduces the ability of the support to disperse nickel in form of the surface spinel phase, thus reducing the amount of Ni clusters in the reduced catalysts.     

Production of H2- and CO-rich syngas from the CO2 gasification of cow manure over (Sr/Mg)-promoted-Ni/Al2O3 catalysts

The valorization of cow manure (CM), as bio-waste, under a CO₂ atmosphere could be an attractive strategy for tackling the environmental problems related to waste management and CO₂ emission and producing valuable syngas. For this purpose, highly loaded Ni–Al₂O₃ catalysts with alkaline-earth metals (Mg and Sr) were synthesized and applied to the gasification of CM under CO₂. The lowest yields of bio-oil (16.98 wt %) and coke (0.34 wt %) and the highest yield of syngas (55.09 wt %) were obtained from the catalytic decomposition of hydrocarbons when Sr was incorporated into Ni/Al₂O₃ (SN-AO). The highest selectivity for H₂ (34.23 vol %) and CO (37.16 vol %) were obtained applying SN-AO followed by Mg-promoted Ni/Al₂O₃ (MN-AO) and Ni/Al₂O₃ (N-AO) catalysts. With increasing gasification temperature from 750 °C to 850 °C, the syngas yield (from 55.09 to 70.17 wt %) and H₂ concentration (from 34.23 to 38.03 vol %) increased considerably because of the endothermic gasification process. The yield and selectivity of syngas (H₂ and CO) increased under CO₂ compared to those obtained under N₂, indicating the high potential of CO₂ for the thermal decomposition and dehydrogenation of the volatile matter.     

Current advances in syngas (CO + H2) production through bi-reforming of methane using various catalysts: A review

Today, bi - reforming of methane is considered as an emerging replacement for the generation of high-grade synthesis gas (H₂:CO = 2.0), and also as an encouraging renewable energy substitute for fossil fuel resources. For achieving high conversion levels of CH₄, H₂O, and CO₂ in this process, appropriate operation variables such as pressure, temperature and molar feed constitution are prerequisites for the high yield of synthesis gas. One of the biggest stumbling blocks for the methane reforming reaction is the sudden deactivation of catalysts, which is attributed to the sintering and coke formation on active sites. Consequently, it is worthwhile to choose promising catalysts that demonstrate excellent stability, high activity and selectivity during the production of syngas. This review describes the characterisation and synthesis of various catalysts used in the bi-reforming process, such as Ni-based catalysts with MgO, MgO–Al₂O₃, ZrO_2, CeO₂, SiO₂ as catalytic supports. In summary, the addition of a Ni/SBA-15 catalyst showed greater catalytic reactivity than nickel celites; however, both samples deactivated strongly on stream. Ce-promoted catalysts were more found to more favourable than Ni/MgAl₂O₄ catalyst alone in the bi-reforming reaction due to their inherent capability of removing amorphous coke from the catalyst surface. Also, Lanthanum promoted catalysts exhibited greater nickel dispersion than Ni/MgAl₂O₄ catalyst due to enhanced interaction between the metal and support. Furthermore, La₂O₃ addition was found to improve the selectivity, activity, sintering and coking resistance of Ni implanted within SiO₂. Non-noble metal-based carbide catalysts were considered to be active and stable catalysts for bi-reforming reactions. Interestingly, a five-fold increase in the coking resistance of the nickel catalyst with Al₂O₃ support was observed with incorporation of Cr, La₂O₃ and Ba for a continuous reaction time of 140 h. Bi-reforming for 200 h with Ni-γAl₂O₃ catalyst promoted 98.3% conversion of CH₄ and CO₂ conversion of around 82.4%. Addition of MgO to the Ni catalyst formed stable MgAl₂O₄ spinel phase at high temperatures and was quite effective in preventing coke formation due to enhancement in the basicity on the surface of catalyst. Additionally, the distribution of perovskite oxides over 20 wt % silicon carbide-modified with aluminium oxide supports promoted catalytic activity. NdCOO₃ catalysts were found to be promising candidates for longer bi-reforming operations.     

CO2 methanation over CoNi bimetal-doped ordered mesoporous Al2O3 catalysts with enhanced low-temperature activities

The Ni based catalysts have been considered as potential candidates for the CO₂ methanation owing to the low cost. However, the poor low-temperature catalytic activities limit their large-scale industrial application. In order to address this challenge, a series of CoNi bimetal doped ordered mesoporous Al₂O₃ materials have been designed and fabricated via the one-pot evaporation induced self-assembly strategy and employed as the catalysts for CO₂ methanation. It is found that the large specific surface areas (up to 260.0 m^2/g), big pore volumes (up to 0.59 cm³/g), and narrow pore size distributions of these catalysts have been successfully retained after 700 °C calcination. The Co and Ni species are homogenously distributed among the Al₂O₃ matrix due to the unique advantage of the one-pot synthesis strategy. The strong interaction between metal and mesoporous framework have been formed and the severely thermal sintering of the metallic CoNi active centers can be successfully inhibited during the processes of catalyst reduction and 50 h CO₂ methanation reaction. More importantly, the synergistic effect between Co and Ni can greatly enhance the low-temperature catalytic activity by coordinating the activation of H₂ and CO₂, prominently decreasing the activation energy toward CO₂ methanation. As a result, their low-temperature activities are evidently promoted. Furthermore, the effect of the Co/(Co + Ni) molar percentage ratio on the catalytic property has been also systematically investigated over these catalysts. It is found that only the catalyst with appropriate ratio (20.0%) behaves the optimum catalytic performances. Therefore, the current CoNi based ordered mesoporous materials promise potential catalysts for CO₂ methanation.     

Hydrogen production by biomass gasification in supercritical water with bimetallic Ni-M/γAl2O3 catalysts (M = Cu, Co and Sn)

Supercritical water gasification (SCWG) of wet biomass is a very promising technology for hydrogen energy and the utilization of biomass resources. Ni-based catalysts are effective in catalyzing SCWG of original biomass and organic compounds for hydrogen production. In this paper, hydrogen production by SCWG of glucose over alumina-supported nickel catalysts modified with Cu, Co and Sn was studied. The bimetallic Ni-M (M = Cu, Co and Sn) catalysts were prepared by a co-impregnation method and tested in an autoclave reactor at 673 K with a feedstock concentration of 9.09 wt.%. XRD, XRF, N₂ adsorption/desorption, SEM and TGA were adopted to investigate the changes of chemical properties between Ni and Ni-M catalysts and the deactivation mechanism of catalysts. According to the experimental results, the hydrogen yield followed this order: Ni-Cu/γAl₂O₃ > Ni/γAl₂O₃ > Ni-Co/γAl₂O₃ > Ni-Sn/γAl₂O₃. The results show that Cu could improve the catalytic activity of Ni catalyst in reforming reaction of methane to produce hydrogen in SCWG. In addition, Cu can mitigate the sintering of alumina detected by SEM. Co was found to be an excellent promoter of Ni-based catalyst in relation to hydrogen selectivity.     

Modulating Fischer-Tropsch synthesis performance on the Co3O4@SixAly catalysts by tuning metal-support interaction and acidity

ZIF-67 derived catalysts for Fischer-Tropsch synthesis have attracted much attention in recent years, while there is still a potential to improve their activity and selectivity. In this work, we prepared Si/Al co-immobilized Co₃O₄@Si_xAl_y catalysts by in-situ doping tetraethylorthosilicate and aluminum nitrate during the synthesis of ZIF-67. The effects of different Si/Al ratios on the metal-support interaction, acidity and FTS performance were explored. Results indicated that the Co₃O₄@Si₀Al₄ catalyst exhibited the best FTS performance with the CO conversion as high as 79.9% and CTY (cobalt time yield) value of 19.5 × 10^?5 mol_CO·g_Co^?1·s^?1, which was ascribed to the moderate metal-support interaction and the most active Co sites. Meanwhile, the Co₃O₄@Si₃Al₁ and Co₃O₄@Si₂Al₂ catalysts exhibited higher iso-paraffin and olefin selectivity due to more acidic sites.     

Methanation of CO2 over alumina supported nickel or cobalt catalysts: Effects of the coordination between metal and support on formation of the reaction intermediates

This study focused on the potential coordination between nickel or cobalt and alumina in Ni/Al₂O₃ and Co/Al₂O₃ catalysts and the impacts on their catalytic performances in methanation of CO₂. The results exhibited that Co/Al₂O₃ catalyst was far more active than Ni/Al₂O₃ catalyst, due to the varied reaction intermediates formed in methanation. The DRIFTS results of methanation of CO₂ exhibited that, over bare alumina, bicarbonate, formate and carbonate were the main intermediate species, which could be formed at even 80 °C. Over unsupported Ni catalyst, the formaldehyde species (H₂CO*) and CO* species were dominated. Over the Ni/Al₂O₃ catalyst, however, the reaction intermediates formed were determined by alumina and accumulated on surface of the catalysts. The coordination effects between nickel and alumina in Ni/Al₂O₃ were thus not remarkable in terms of enhancing catalytic activity when compared to that in Co/Al₂O₃ catalyst. Over unsupported Co catalyst and the bare alumina, the reaction intermediates formed were roughly similar. Nevertheless, the combination of Co and alumina in Co/Al₂O₃ catalyst could effectively facilitate the conversion of bicarbonate, formate and carbonate species. CO₂ could be activated over metallic cobalt sites, which could migrate and integrate with the hydroxyl group in alumina to form bicarbonate and further to formate and CO* species, and be further hydrogenated over cobalt sites to CH₄. Such a coordination between alumina and cobalt species promoted the catalytic performances.     

Characterization and activity test of commercial Ni/Al2O3, Cu/ZnO/Al2O3 and prepared Ni–Cu/Al2O3 catalysts for hydrogen production from methane and methanol fuels

In this study, methane and methanol steam reforming reactions over commercial Ni/Al₂O₃, commercial Cu/ZnO/Al₂O₃ and prepared Ni–Cu/Al₂O₃ catalysts were investigated. Methane and methanol steam reforming reactions catalysts were characterized using various techniques. The results of characterization showed that Cu particles increase the active particle size of Ni (19.3 nm) in Ni–Cu/Al₂O₃ catalyst with respect to the commercial Ni/Al₂O₃ (17.9). On the other hand, Ni improves Cu dispersion in the same catalyst (1.74%) in comparison with commercial Cu/ZnO/Al₂O₃ (0.21%). A comprehensive comparison between these two fuels is established in terms of reaction conditions, fuel conversion, H₂ selectivity, CO₂ and CO selectivity. The prepared catalyst showed low selectivity for CO in both fuels and it was more selective to H₂, with H₂ selectivities of 99% in methane and 89% in methanol reforming reactions. A significant objective is to develop catalysts which can operate at lower temperatures and resist deactivation. Methanol steam reforming is carried out at a much lower temperature than methane steam reforming in prepared and commercial catalyst (275–325 °C). However, methane steam reforming can be carried out at a relatively low temperature on Ni–Cu catalyst (600–650 °C) and at higher temperature in commercial methane reforming catalyst (700–800 °C). Commercial Ni/Al₂O₃ catalyst resulted in high coke formation (28.3% loss in mass) compared to prepared Ni–Cu/Al₂O₃ (8.9%) and commercial Cu/ZnO/Al₂O₃ catalysts (3.5%).     

Effect of the Rare Earth Metals (Tb,Nd, Dy) addition for the modification of nickel catalysts supported on alumina in CO2 Methanation

In the current research, a group of rare-earth metals functionalized mesoporous Ni-M/Al₂O₃ (M = Tb, Dy, Nd) composite oxides were prepared by the one-pot sonochemical pathway and applied in the CO₂ methanation procedure. Promoters can partially influence the textural and catalytic characteristics of Ni–Al₂O₃ catalysts. Physicochemical characteristics of the as-fabricated catalysts were identified utilizing X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Energy-dispersive X-ray spectroscopy (EDS), Temperature Programmed Reduction (H₂-TPR), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), and Brunauer-Emmett-Teller (BET) analyses. Among the specimens, the catalyst modified by Terbium (Tb) manifested better catalytic performance and CH₄ selectivity, particularly at low temperatures (350–400 °C). The influence of reaction temperature (200–500 °C) was scrutinized below space velocity (GHSV) of 25,000 ml/g_cath, atmospheric pressure, and stoichiometric ratio of CO₂ to H₂ (1: 4). The impact of the desired content of nickel and terbium was examined. The 25Ni–5Tb–Al₂O₃ operates the best function for CO₂ methanation, which can attain the highest CO₂ conversion of 66.93% at 400 °C at atmospheric pressure. The superior catalytic performance of 25Ni–5Tb–Al₂O₃ could be assigned to the appropriate fabrication method and the promotion effect of Terbium. The synthesis effect could be assigned to its large surface area, obtaining by the hot spot mechanism. The addition of Terbium promotes the Ni distribution on the supports as well as accelerates the positive reaction due to the oxygen vacancies of Terbium. Besides, these outcomes could be defined with the maximum distribution of active nickel sites on the catalyst and improvement in the catalyst reduction ability at low temperatures.     

Promoted Ni–Co–Al2O3 nanostructured catalysts for CO2 methanation

15 wt.%Ni-12.5 wt.%Co–Al₂O₃ catalysts promoted with Fe, Mn, Cu, Zr, La, Ce, and Ba were prepared by a novel solid-state synthesis method and employed in CO₂ methanation reaction. BET, XRD, EDS, SEM, TPR, TGA, and FTIR analyses were conducted to identify the chemicophysical characteristics of the prepared samples. The addition of Fe, Mn, La, Ce, and Ba was effective to improve the catalytic performance of the 15 wt%Ni-12.5 wt%Co–Al₂O₃ due to the higher CO₂ adsorption capacity of the promoted catalysts. Among the studied promoters, the Fe-promoted catalyst possessed the highest catalytic activity (X_CO2 = 61.2% and S_CH4 = 98.87% at 300 °C). Also, the effect of calcination temperature, feed composition, and GHSV on the performance of the 15 wt%Ni-12.5 wt%Co-5wt%Fe–Al₂O₃ catalyst in CO₂ methanation reaction was assessed. The outcomes confirmed that the 15 wt%Ni-12.5 wt%Co-5wt%Fe–Al₂O₃ catalyst with the BET area of 122.4 m²/g and the highest pore volume and largest pore diameter had the highest catalytic activity. Also, the catalytic performance in the methanation of carbon monoxide was studied, and 100% conversion of carbon monoxide was observed at 250 °C.     

A highly reactive and stable Ru/Co6−xMgxAl2 catalyst for hydrogen production via methane steam reforming

Hydrogen production by methane steam reforming is an important yet challenging process. A performing catalyst will favor the thermodynamic equilibrium while ensuring good hydrogen selectivity. We hereby report the synthesis of a ruthenium based catalyst on a cobalt, magnesium, and aluminum mixed oxides supports. An interaction between cobalt and ruthenium favors the formation of smaller, well dispersed cobalt/ruthenium oxide species. The Ru/Co₆Al₂ catalyst outmatches the widely used industrial Ru/Al₂O₃ catalyst. The catalyst is stable for 100 h on stream. After test characterization shows the formation of carbon and coke deposits at trace levels. However, this does not affect the catalytic performance of the catalysts making it good candidates for industrial applications.     

Promotional Effect of ZrO2 on supported FeCoK Catalysts for Ethylene Synthesis from catalytic CO2 hydrogenation

This study is to convert renewable H₂ and increasingly concerned CO₂ to ethylene or C₂H₄ over Fe_3.33Co_1.67K₅/ZrO₂ and Fe_3.33Co_1.67K₅/Al₂O₃ catalysts. The ZrO₂ support provides amounts of surface oxygen vacancies (OVs) as well as stable and rich surface hydroxyl groups (-OH), which promotes the Fe_3.33Co_1.67K₅/ZrO₂ catalysts with 5% Fe and Co loadings to achieve C₂H₄ space time yield (STY) of 0.064 mmol_C2H4∙m⁻²_cat∙h⁻¹ at 290 °C and 2.0 MPa, while the Fe_3.33Co_1.67K₅/Al₂O₃ catalysts only reach C₂H₄ STY of 0.009 mmol_C2H4∙m⁻²_cat∙h⁻¹ at 330 °C and 2 MPa Fe_3.33Co_1.67K₅/ZrO₂ catalysts are very promising for converting the captured CO₂ and renewable H₂ to highly demanded C₂H₄. This work not only provides a guideline for developing efficient catalysts but also advances the mechanistic understanding of catalytic CO₂ hydrogenation.     

Effect of surface properties controlled by Ce addition on CO2 methanation over Ni/Ce/Al2O3 catalyst

Ce-promoted Ni/Al₂O₃ catalysts with Ce contents of 0, 5, 10, 15, and 20 wt% were investigated for CO₂ methanation. Ni/15Ce/Al₂O₃ showed good selectivity and catalytic performance in CO₂ methanation and remained stable at 350 °C for 80 h with minor fluctuations. Interactions between Ni and the Ce/Al₂O₃ support was characterized using X-ray diffraction, temperature-programmed reduction of H₂, temperature-programmed desorption of CO₂, X-ray photoelectron spectroscopy, Raman spectroscopy, and thermogravimetric analysis. Addition of Ce did not increase the catalytic surface area, which can significantly enhance the heterogeneous catalytic activity. However, XPS analysis showed that the Ce on the Ni/Al₂O₃ catalyst changed the surface electron states of Ni, Ce, and O. Additionally, CO₂ adsorption/desorption was confirmed to be related to the amount of Ce present on Ni/Al₂O₃ by TGA and CO₂-TPD. The Ce addition thus played an important role in determining the CO₂ adsorption, desorption, and conversion.     

The effects of bimetallic Co–Ru nanoparticles on Co/RuO2/Al2O3 catalysts for the water gas shift and methanation

The effects of Co on RuO₂/Al₂O₃'s activities for water gas shift (WGS) and methanation were studied. Catalysts were characterized with BET, XRD, SEM/EDS, H₂-TPR and CO-TPR. The effects of various parameters, such as calcination temperature, Ru–Co loading, Ru/Co ratio, inlet CO concentration and H₂O/CO ratio on the activities of catalysts were investigated. There existed Co_I (strongly interact with RuO₂) and Co_II (weakly interact with RuO₂). For Co/RuO₂/Al₂O₃ (Ru/Co = 1, AT = 350), only Co_I existed as bimetallic Co–Ru nanoparticles. This unique structure led this catalyst to achieve the highest CO conversion of 98.6% exceeding WGS's theoretical thermodynamic equilibrium limit due to the co-occurrence of methanation. Co/RuO₂/Al₂O₃ was more favorable to catalyze CO methanation than CO₂ methanation. The apparent activation energies of forward and reverse WGS catalyzed by Co/RuO₂/Al₂O₃ were 37.8 and 74.6 kJ mol⁻¹, respectively. The difference was corresponding well to the enthalpy change (−41.1 kJ mol⁻¹) of WGS.     

Insight into the role of Fe on catalytic performance over the hydrotalcite-derived Ni-based catalysts for CO2 methanation reaction

A series of Fe modified hydrotalcite-derived Ni-based catalysts (Ni₃Fe_x-calc) were synthesized to evaluate the effect of Fe on CO₂ methanation performance over Ni₃-calc catalyst. The results showed that Ni₃–Fe_0.5-calc had superior catalytic activity with 78% CO₂ conversion rate at 200 °C. The addition of moderate amount of Fe can effectively improve the reducibility, enrich the medium basic sites of Ni₃-calc catalyst, and further facilitate the adsorption and activation of CO₂. This resulted in the outstanding low-temperature CO₂ methanation activity, as well as the enhanced resistance of carbon deposition. In-situ DRIFTS results indicated that the CO₂ methanation reaction mechanism involved a progressive hydrogenation of carbonate and formate species to methane route. The formate species was the main intermediates during CO₂ methanation. The introduction of Fe could significantly accelerate the hydrogenation rate of carbonates and formate species.     

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.     

Experimental optimization analysis on operating conditions of CO removal process from hydrogen-rich reformate

The catalytic effects of CO preferential oxidation and methanation catalysts for deep CO removal under different operating conditions (temperature, space velocity, water content, etc.) are systematically studied from the aspects of CO content, CO selectivity, and hydrogen loss index. Results indicate that the 3 wt% Ru/Al₂O₃ preferential oxidation catalysts reduce CO content to below 10 ppm with a high hydrogen consumption of 11.6–15.7%. And methanation catalysts with 0.7 wt% Ru/Al₂O₃ also exhibit excellent CO removal performance at 220–240 °C without hydrogen loss. Besides, NiCl_x/CeO₂ methanation catalysts possess the characteristics of high space velocity, high activity, and high water-gas resistance, and can maintain the CO content at close to 20 ppm. Based on these experimental results, the coupling scheme of combining NiCl_x/CeO₂ methanation catalysts (low cost and high reaction space velocity) with 0.7 wt% Ru/Al₂O₃ methanation catalysts (high activity) to reduce CO content to below10 ppm is proposed.     

Mesoporous zirconia-modified clays supported nickel catalysts for CO and CO2 methanation

The Ni catalysts supported on a new structure with zirconia nanoparticles highly dispersed on the partly damaged clay layers has been prepared by the incipient wetness impregnation method and the new structure of the support has been prepared in one pot by the hydrothermal treatment of the mixture of the clay suspension and the ZrO(NO₃)₂ solution. The catalytic performances for the CO and CO₂ methanation on the catalysts have been investigated at a temperature range from 300 °C to 500 °C at atmospheric pressure. The catalysts and supports have been characterized by X-ray diffraction (XRD), transmittance electron microscopy (TEM), H₂ temperature-programmed reduction (H₂-TPR), nitrogen adsorption–desorption, and thermogravimetry and differential thermal analysis (TG-DTA). It is found that the zirconia-modified clays have the typical bimodal pore size distribution. Most of the pores with the sizes smaller than 10 nm are resulted from the zirconia pillared clays and the mesopores with the sizes larger than 10 nm and the macropores with the sizes larger than 50 nm are resulted from the partly damaged clay layers. The bimodal pore structure is beneficial to the dispersion of Ni on the layers of the zirconia-modified clays and the increase in Ni loading. The zirconia nanoparticles are highly dispersed on the partly damaged clay layers. Nickel oxide in cubic phase is the only Ni species that can be detected by XRD. The nickel oxide nanoparticles with the sizes of 12 nanometers or more are well dispersed on the zirconia-modified clay layers, which are observed to be buried in the stack layers of zirconia. The presence of nickel oxide in six different forms could be perceived on the new structure. Five of them except the Ni species that forms the spinel phase with Al in clays can be reduced to the active Ni species for the CO and CO₂ methanation. But the activity of the Ni species is different, which is associated with the chemical environment at which the Ni species is located. The catalyst with the higher zirconia content, which also has the larger specific surface area and pore volume, exhibits the better catalytic performance for the CO or CO₂ methanation. Zirconia in the catalyst is responsible for the dispersion of the Ni species, and it prevents the metallic Ni nanoparticles from sintering during the process of the reaction. In addition, it is also responsible for the reduction of the inactive carbon deposition. The catalyst with 15 wt.% zirconia content has the highest CO conversion of about 100% and the highest methane selectivity of about 93% at 450 °C for CO methanation, and the catalyst with 20% zirconia content has the CO₂ conversion of about 80% and the highest methane selectivity of about 99% for CO₂ methanation at 350 °C. The catalyst with 15 wt.% zirconia possesses promising stability and no distinct deactivation could be perceived after reaction for 40 h. This new catalyst has great potential to be used in the conversion of the blast furnace gas (BFG) and the coke oven gas (COG) to methane.     

Enhanced activity of CO2 methanation over mesoporous nanocrystalline Ni–Al2O3 catalysts prepared by ultrasound-assisted co-precipitation method

The ultrasound-assisted co-precipitation method was employed for the synthesis of the Ni–Al₂O₃ catalysts with different metal loadings for the CO₂ methanation reaction. This study indicated that increasing the Ni loading up to 25 wt.% enhanced the surface area, decreased the crystallinity and improved the reducibility of the catalysts, while further raise in Ni loading adversely influenced the surface area. Improvements in catalytic performance were obtained with the raise in Ni content because of enhancing the BET area. The results confirmed that the 25Ni–Al₂O₃ catalyst with the highest BET area (188 m² g^?1) and dispersion of Ni has the highest catalytic activity in CO₂ methanation and reached to 74% CO₂ conversion and 99% CH₄ selectivity at 350 °C. In addition, this catalyst exhibited a great stability after 10 h time-on-stream.