Enhanced performance and selectivity of CO2 methanation over g-C3N4 assisted synthesis of NiCeO2 catalyst: Kinetics and DRIFTS studies

The hydrogenation of CO₂ on CeNi catalyst modified with g-C₃N₄ (CeNiCN) as a sacrificial and protective template was studied by in-situ DRIFTS and Kinetics experiments to investigate the influence of modification on the catalytic activity and selectivity to gain mechanistic insight. After modification, the catalyst showed higher catalytic activity and selectivity. H₂-TPR, CO₂-TPD, TEM and XPS confirmed that this modification could enhance the interaction of nickel and ceria and decrease the particle size of nickel, which is in favor of the dissociation of H₂ and adsorption of CO₂. The in-situ DRIFTS experiments demonstrated that CO₂ is adsorbed on ceria sites, forming carboxylate (CO₂^δ?), unidentate carbonate and bicarbonates, which, in turn, react with adsorbed and dissociated H on Ni to produce formate species. Furthermore, adsorbed methoxy species were observed, which are recognized to be intermediates in the methanation process. In-situ transient DRIFTS confirm that the adsorbed CO is not a reaction intermediate, but a by-product, which originates from the decomposition of weak-binding formate species on Ce³⁺ sites. The unmodified catalyst has more weak-binding formate species, which are more inclined to decompose into CO accounting for the low selectivity. Furthermore, the adsorbed CO on Ce³⁺ sites cannot react with the adsorbed hydrogen to produce methane. Kinetics studies are consistent with a Langmuir-Hinshelwood type mechanism in which the formation of bicarbonate is the rate-determining step (RDS).     

Influence of the supports ZrO2 on selective methanation of CO over the nickel supported catalysts

It is attempted to optimize preparation of ZrO₂ as support of the nickel catalysts for selective methanation of CO in H₂-rich gas (CO-SMET). Therefore, the supports ZrO₂ were prepared at first by thermal decomposition method from zirconium oxynitrate and zirconium oxychloride at the calcination temperature of 400 °C and 800 °C, respectively. It is illustrated that the salt kind and calcination temperature affected phase state (tetragonal, monoclinic), crystallite size and specific surface area (SSA) of the supports. The difference in property of the supports influenced catalytic performance of the catalysts Ni/ZrO₂ for CO-SMET reaction. Especially, the chlorine ion residues in the support ZrO₂ prepared from zirconium oxychloride was beneficial for CO removal selectively. Furthermore, a precipitation method was adopted to prepare ZrO₂ for comparison with the thermal decomposition method with use of the zirconium oxychloride as starting material. It is found that the supports ZrO₂ prepared by the precipitation method induced a better dispersion of metallic Ni on its surface. The catalyst Ni/ZrO₂ with use of the support ZrO₂ prepared by the precipitation method and calcination at 400 °C exhibited a good performance at the reaction temperature of 220 °C in the 100 h durability test, where CO outlet concentration was kept below 10 ppm and the selectivity remained constant at 100%. Relation of Ni crystallite size and chlorine ion residues with the catalytic performance was discussed.     

TiO2 and ZrO2 supported Ru catalysts for CO mitigation following the water-gas shift reaction

CO oxidation and methanation over Ru-TiO₂ and Ru-ZrO₂ catalysts were investigated for CO removal for applications in proton exchange membrane fuel cells. The catalysts were synthesised by the deposition precipitation method at a pH of 7–7.5 for better interactions between the support and the active Ru metal. Various characterization experiments such as TPR, XPS, FTIR-CO, CO chemisorption and HRTEM were conducted to better understand the physio-chemical properties of Ru on the supports. Both catalysts showed excellent activity for the total oxidation of CO, however, with the addition of H₂, the catalysts activity to CO oxidation decreased significantly. Higher temperatures for the preferential oxidation reaction indicated that the Ru catalysts not only oxidize CO, but hydrogenate it as well. Furthermore, H₂ oxidation was favoured over the catalysts. Hydrogenation of CO over these catalysts gave high CO conversion and selectivity towards CH₄. Both the catalysts showed similar activity across the temperature range screened and gave maximum CO conversions of 99.9% from 240 °C onwards, with 99.9% selectivity towards CH₄. The catalysts also showed good stability in the reaction and the similarities in the catalytic activity of these were attributed to the well-dispersed Ru metal over the supports. The Ru catalysts effectively reduced CO concentrations in the reformate gas to less than 10 ppm, as is required for practical applications.     

Impact of mesoporous structure of acid-treated clay on nickel dispersion and carbon deposition for CO methanation

Nickel catalysts supported on different acid-treated clays were prepared by the impregnation method in order to investigate the effect of the pore structures of supports on the dispersion and the chemical states of nickel species, and thus on the carbon depositions resulted from the dissociation of the CO molecules adsorbed on different active nickel sites. The catalysts and supports were characterized by the X-ray diffraction (XRD), the transmittance electron microscopy (TEM), the H₂ temperature-programmed reduction (H₂-TPR), the nitrogen adsorption–desorption, and the thermogravimetry and differential thermal analysis (TG-DTA). The CO methanation performance of the catalyst was investigated at a temperature range from 300 °C to 500 °C. The results indicated that the dispersion and the states of the nickel species on the support were influenced strongly by the pore structures of the acid-treated clays, and only the mesopores composed by partly damaged clay layers were conducive to forming the active nickel species, and thus reducing the deposition of the inactive carbon and improving the stability of the catalyst. The carbon species deposited on different active sites was slightly different in the oxidative properties when it was oxidized in air. A fraction of aluminum in the clays was leached out by acid, which decreased the possibility of forming the spinel phase of nickel aluminate in the catalyst. The highly dispersed nickel species showed little relevance to the high activity of the catalyst, but it exhibited a strong relation to the nickel sites from the bulk nickel species.     

Highly efficient MOF-templated Ni catalyst towards CO selective methanation in hydrogen-rich reformate gases

Highly efficient and non-noble metal-based Ni/ZrO₂ catalyst templated with Ni/UiO-66 precursor was successfully prepared and applied to CO selective methanation in H₂-rich gases. This catalyst showed excellent activity and selectivity in an extremely wide temperature window of 215–350 °C, and it also had high stability with no deactivation during a long-term stability test (120 h). The increased specific surface area, smaller crystallite size (3.5 nm) and higher dispersion (15.3%) of Ni nanoparticles, and the enhanced chemisorption capability for CO might contribute to its excellent performance.     

W-doped ordered mesoporous Ni–Al2O3 catalyst for methanation of carbon monoxide

In order to simultaneously inhibit the Ni sintering and coke formation as well as investigate the effects of WO₃ promoter on catalytic performance, the ordered mesoporous Ni–WO₃/Al₂O₃ catalysts were synthesized by a facile one-pot evaporation-induced self-assembly method for CO methanation reaction to produce synthetic natural gas. Addition of WO₃ species could significantly promote the catalytic activity due to the enhancement of the Ni reducibility and the increase of active centers, and the optimal N10W5/OMA catalyst with NiO of 10 wt% and WO₃ of 5 wt% achieved the maximum CH₄ yield 80% at 425 °C, 0.1 MPa and a weight hourly space velocity of 60000 mL g⁻¹ h⁻¹. Besides, the reference catalyst N10W5/OMA-Im prepared by the conventional co-impregnation method was also evaluated. Compared with N10W5/OMA, N10W5/OMA-Im showed lower catalytic activity due to the partial block of channels by Ni and WO₃ nanoparticles, which reduced active centers and restrict the mass transfer during the reaction. In addition, the N10W5/OMA catalyst showed superior anti-sintering and anti-coking properties in a 425^oC-100 h-lifetime test, mainly because of confinement effect of ordered mesoporous structure to anchor the Ni particle in the alumina matrix.     

A strategy to regenerate coked and sintered Ni/Al2O3 catalyst for methanation reaction

Supported Ni/Al₂O₃ catalysts are widely used in chemical industries. Regeneration of the deactivated Ni catalysts caused by sintering of Ni nanoparticles and carbon deposition after long-term operation is significant but still very challenging. In this work, a feasible strategy via solid-phase reaction between NiO and Al₂O₃ followed by a controlled reduction is developed which can burn out the deposited carbon and re-disperse the Ni nanoparticles well, thus regenerating the deactivated Ni catalysts. To demonstrate the feasibility of this method, Ni catalyst supported on α-Al₂O₃ (Ni/Al₂O₃) for CO methanation reaction was selected as a model system. The structure and composition of the fresh, deactivated and regenerated Ni/Al₂O₃ catalysts were comprehensively characterized by various techniques. The reduction and redistribution of Ni species as well as the interfacial interaction between Ni nanoparticles and Al₂O₃ support were investigated in detail. It is found that calcining the deactivated Ni/Al₂O₃ in air at high temperature can burn out the coke, while the sintered Ni species can combine with superficial Al₂O₃ to form a surface NiAl₂O₄ spinel phase through the solid-phase reaction. After the controlled reduction of the NiAl₂O₄ spinel, highly dispersed Ni nanoparticles on Al₂O₃ support are re-generated, thus achieving the regeneration of the deactivated Ni/Al₂O₃. Interestingly, compared with the fresh Ni/Al₂O₃ catalyst, the sizes of Ni nanoparticles became even smaller in the regenerated ones. The regenerated Ni/Al₂O₃ showed much enhanced catalytic activity in CO methanation and became more resistant to carbon deposition, due to the better dispersed Ni nanoparticles and strengthened interaction between Ni and Al₂O₃ support. Our work not only addresses the long existing catalyst regeneration issue, but also provides effective and renewable Ni-based catalysts for CO methanation.     

An in situ FTIR-DRIFTS study on CDRM over Co–Ce/ZrO2: Active surfaces and mechanistic features

CDRM (Carbon Dioxide Reforming of Methane) is an effective route to utilize the most abundant greenhouse gases, CH₄ and CO₂, to produce synthesis gas. This study aims to define the CDRM features, including both surface characteristics and mechanistic properties, of Co–Ce/ZrO₂ catalysts via FTIR-DRIFTS (Diffuse Reflectance Infrared Fourier Transform Spectroscopy). In this manner, CO adsorption, CDRM reaction and cyclic experiments are applied to Co–Ce/ZrO₂ system under different operating conditions. Accordingly, it is verified that Co sites are responsible for CH₄ activation. Ceria has a strong interaction with oxygen related groups, due to its enhanced oxygen transfer ability. Co/Ce ratio dominantly affects surface properties of the catalysts and causes variations on type and amount of surface intermediates during the reaction. CO₂ activation occurs at ZrO₂ sites, especially at their oxygen vacancies. The CH₄/CO₂ feed ratio is crucial in maintaining C–O balance in the reaction medium. Finally, a possible reaction route, valid for all tested catalysts, is discussed.     

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.     

Three-dimensional porous Mn–Ni/Al2O3 microspheres for enhanced low temperature CO hydrogenation to produce methane

CO methanation has attracted much attention because it transforms CO in syngas and coke oven gas into CH₄. Here, porous Al₂O₃ microspheres were successfully used as catalyst supports meanwhile the Mn was used as a promoter of Ni/Al₂O₃ catalysts. The as-obtained Ni/Al₂O₃ and Mn–Ni/Al₂O₃ samples display a micro-spherical morphology with a center diameter near 10 μm. Versus the Ni/Al₂O₃ catalyst, the 10Mn–Ni/Al₂O₃ catalyst exhibits a high specific surface area of 92.5 m²/g with an average pore size of 7.0 nm. The 10Mn–Ni/Al₂O₃ catalyst has the best performance along with can achieve a CO conversion of 100% and a CH₄ selectivity of 90.7% at 300 °C. Even at 130 °C, the 10Mn–Ni/Al₂O₃ catalyst shows a CO conversion of 44.0% and a CH₄ selectivity of 84.1%. The higher low-temperature catalytic activity may be since the catalyst surface contains more CO adsorption sites and thus has a stronger adsorption performance for CO. Density functional theory (DFT) calculations confirm that the Mn additive enhances the adsorption of CO, especially for the 10Mn–Ni/Al₂O₃ catalyst with the strongest adsorption energy.     

煤制天然气过程催化甲烷化的数值模拟

两步法煤制天然气的第一步反应主要生产粗煤气CO和 H2,调整CO与 H2的比值后进行甲烷化反应。在计算软件HSC中分别控制反应温度、压力和CO与H2比例,计算了甲烷化产物变化规律,得到第二步甲烷化反应最适条件是1．8 M Pa、700℃;通过在计算软件FL U EN T 中进行一步对催化甲烷化反应的模拟,0．1 M Pa、720℃时的催化甲烷化即可达到无催化高压条件的甲烷摩尔产率,甲烷化产率最高时对应的n（H2）∶ n（C O ）比值为1．8。