Carbon resistance of xNi/HTASAO5 catalyst for the production of H2 via CO2 reforming of methane

xNi/HTASAO5 catalysts (x = 2.5, 3.3, 4.4, 5.8, 8.2) were prepared for CO₂ reforming of methane. No crystalline nickel species formed on the catalysts with lower nickel content (≤4.4%), and large Ni⁰ crystallite formed on 5.8% (10 nm) and 8.2 wt%Ni/HTASAO5 (17 nm), whereas the surface concentration of Ce³⁺ decreased with Ni loading. The initial conversion of CH₄ increased from 29.5% to 46.9% with Ni loading. The xNi/HTASAO5 (x ≤ 4.4%) performed stably in the reaction due to the presence of dispersed Ni species and high surface Ce³⁺ content without coke formation, however, 5.8% and 8.2 wt%Ni/HTASAO5 exhibited decreased activity with time on stream, because of the formation of large Ni particles with lower surface Ce³⁺, leading to carbon accumulation. Thus, CH₄ conversion stabilized at about 43% and no carbon formed on 4.4 wt%Ni/HTASAO5 with optimum Ni loading.     

Production of hydrogen from methanol steam reforming using CuPd/ZrO2 catalysts – Influence of the catalytic surface on methanol conversion and CO selectivity

Electricity generation for mobile applications by proton exchange membrane fuel cells (PEMFCs) is typically hindered by the low volumetric energy density of hydrogen. Nevertheless, nearly pure hydrogen can be generated in-situ from methanol steam reforming (MSR), with Cu-based catalysts being the most common MSR catalysts. Cu-based catalysts display high catalytic performance, even at low temperatures (ca. 250 °C), but are easily deactivated. On the other hand, Pd-based catalysts are very stable but show poor MSR selectivity, producing high concentrations of CO as by-product. This work studies bimetallic catalysts where Cu was added as a promoter to increase MSR selectivity of Pd. Specifically, the surface composition was tuned by different sequences of Cu and Pd impregnation on a monoclinic ZrO₂ support. Both methanol conversion and MSR selectivity were higher for the catalyst with a CuPd-rich surface compared to the catalyst with a Pd-rich surface. Characterization analysis indicate that the higher MSR selectivity results from a strong interaction between the two metals when Pd is impregnated first (likely an alloy). This sequence also resulted in better metallic dispersion on the support, leading to higher methanol conversion. A H₂ production rate of 86.3 mmol h^?1 g^?1 was achieved at low temperature (220 °C) for the best performing catalyst.     

Barium promoted manganese oxide catalysts in low-temperature methane catalytic combustion

In this study, a series of BaO-MnO_x mixed oxide catalysts were synthesized by the mechanochemical method and employed in lean methane catalytic combustion (MCC) at low temperatures. The synthesized catalysts were characterized by XRD, BET, TGA, FT-IR, H₂-TPR, O₂-TPD, and FESEM analyses. The results indicated that the 10 wt% BaO-MnO_x catalyst with a BET surface area of 25 m² g^?1 possessed the best catalytic performance. The higher activity of the 10 wt% BaO-MnO_x catalyst was due to the higher ability to supply oxygen through the components during the MCC process. The light-off temperature corresponding to 50% of the methane conversion was about 330 °C, which was about 50 °C lower than the pure MnO_x. Moreover, for the BaO(10)-MnO_x catalyst, the 10 and 90% of methane conversion temperatures were about 305 and 427 °C, respectively. Also, the 10 wt% BaO-MnO_x catalyst exhibited high catalytic stability under dry feed condition at 450 °C for 50 h. Furthermore, the influence of various parameters such as calcination temperature, feed ratio, GHSV, pretreatment condition, and presence of water vapor in the feedstock was studied on the catalytic performance.     

Comparative study of the effect of TiO2 support composition and Pt loading on the performance of Pt/TiO2 photocatalysts for catalytic photoreforming of cellulose

Herein, catalytic aqueous phase photoreforming of cellulose was carried out over Pt/m-TiO₂ (i.e., mixed phase of anatase and rutile) and Pt/anatase catalysts to investigate the effect of the TiO₂ support structure and Pt loading on the production of H₂. The effect of the TiO₂ support on the properties of the resulting Pt/TiO₂ catalysts (such as actual Pt loading and BET surface area) was not significant. At low Pt loading of 0.16 wt.%, the TiO₂ supports affected the sub-nanometre Pt structures which was confirmed by the diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) characterisation (using CO as the probe). Conversely, the effect of TiO₂ supports on larger Pt particles (on 1 wt.% catalysts) was insignificant possibly due to the reduced effect of restructuration of bigger Pt particles on the TiO₂ supports. With an increase in Pt loading from 0.16 wt% to 1.00 wt.%, the normalised H₂ production rate (with respect to the actual supported Pt amount and specific surface area of the catalysts) showed a decreasing trend over the two types of the catalysts, i.e., from 10.6 to 1.4 μmol h⁻¹ m⁻² mg_Pt⁻¹ for Pt/m-TiO₂, and from 8.5 to 1.2 μmol h⁻¹ m⁻² mg_Pt⁻¹ for Pt/anatase. Specifically, large Pt particle sizes reduced the CO₂/H₂ production from cellulose photoreforming over both Pt/m-TiO₂ and Pt/anatase catalysts, indicting an important role played by Pt particle size in photoreforming. Interestingly, in this study, the m-TiO₂ supported catalysts only showed the benefits of enhanced charge separation across the phase junction in producing H₂ with small Pt particles (at sub-nanometre), whilst, when large Pt particles (at around 1–2 nm) were supported, such a benefit was not significant in cellulose photoreforming. The promoting effect of small, sub-nm particles is attributed to the better capture of photoelectrons from bulk TiO₂ and better activity of H⁺ coupling on small Pt particle. Further fundamental study on such guest-host interactions is devised to optimise Pt/TiO₂ catalysts for improving H₂ production from photoreforming reactions.     

Enhanced hydrogen-assisted cracking of 1,3,5-triisopropylbenzene over fibrous silica ZSM-5: Influence of co-surfactant during synthesis

In this study, unique fibrous silica ZSM-5 was successfully synthesized by using three type of alcohol possessing different alkyl-chain length as the co-surfactant. The effect of diverse co-surfactant was observed in the changes of physical properties, such as crystallinity, inter-dendrimer distances and pore properties. According to the IR and temperature programmed desorption of ammonia (NH₃-TPD) analyses, all catalysts exhibited different acid strengths which could be triggered by the different amount of additional silica species. All catalysts exhibited high catalytic performance in the hydrocracking of 1,3,5-triisopropylbenzene due to the absence of diffusion limitation. However, FZSM5C3 exhibited the highest catalytic activity which corresponded to its high number of Brønsted acid sites. It was observed that different length of co-surfactant alkyl-chain has resulted in different degree of oil penetration into the microemulsion system which subsequently triggered in various inter-dendrimer distances and amount of incorporated silica species. Hence, the altered physicochemical properties led to the difference in catalytic performance due to the presence of different number of Brønsted acid sites.     

Assessing the cyclic-variability of spark-ignition engine running on methane-hydrogen blends with high hydrogen contents of up to 50%

The cyclic variability in a spark-ignition (SI) engine is examined fueled with methane/hydrogen blends with the use of an in-house computational fluid dynamics (CFD) code. A recent methodology is followed, which has been developed with the main aim at providing accurate predictions of the coefficient of variation (COV) of the indicated mean effective pressure (IMEP) in a fraction of time. Instead of simulating several tens of engine cycles, the methodology is based on the numerical results obtained from just 5 cycles, which are then processed for developing suitable fitted correlations of the main parameters as a function of a normalized distance. The latter expresses the distance of the spheres of the initial flame within the computational cell at the spark-plug region with the local turbulent eddy, and provides a smooth transition from the laminar burning regime to the fully turbulent one. This sub-model is included in the ignition numerical approach and is applied here in a SI engine with 3 different hydrogen contents, 10%, 30% and 50%, and three equivalence ratios, 1, 0.8 and 0.7, showing that the COV of IMEP is well predicted compared to the available measured data. Other parameters of engine cycle variations are also examined, such as the distribution of the IMEP. The variability of NO (nitric oxide) emissions is also examined, showing that for the stoichiometric cases it follows a distribution similar to a normal (Gaussian) one, while for lower ratios it is positively skewed. Overall, the methodology seems to provide reliable results for the whole range of the operating conditions examined, while the next steps of this activity will focus on similar cases for engine with variable speed and load, with the final goal to include additional mechanisms that contribute to the engine cycle variations.     

Lower temperature hydrothermal pretreatment improves the anaerobic digestion performance of spent cow bedding

The anaerobic digestion (AD) performance of spent cow bedding was investigated with different hydrothermal pretreatment (HP) conditions. Spent cow bedding was pretreated with low temperatures (50, 70, and 90℃) and different pretreatment times (2-72 h) with ammonia and without ammonia. The results showed that spent cow bedding was a good raw material for AD. After pretreatment, the concentration of volatile fatty acids (VFAs) in the group of hydrothermal pretreatments with ammonia (HPA) was higher than that in the HP group at the same pretreatment temperature and time. The optimal pretreatment condition was achieved with an HPA of 50℃ holding for 72 h. At the optimal condition, the highest concentration of VFAs was 1.58-10.85 times higher than that of the other pretreated groups. The highest hemicellulose and lignin removal rates were 58.07% and 10.32%, respectively. The highest methane yield was 163.0 ml·(g VS)^-1, which was 48.9% higher than that of the untreated group. The VFAs, pH, and reducing sugars showed positive relationships with the methane yield. Therefore, HP at low temperature can enhance the AD performance of spent cow bedding.     

A generalized CFD model for evaluating catalytic separation process in structured porous materials

A hybrid multiphase model is developed to simulate the simultaneous momentum, heat and mass transfer and heterogeneous catalyzed reaction in structured catalytic porous materials. The approach relies on the combination of the volume of fluid (VOF) and Eulerian–Eulerian models, and several plug-in field functions. The VOF method is used to capture the gas–liquid interface motion, and the Eulerian–Eulerian framework solves the temperature and chemical species concentration equations for each phase. The self-defined field functions utilize a single-domain approach to overcome convergence difficulty when applying the hybrid multiphase for a multi-domain problem. The method is then applied to investigate selective removal of specific species in multicomponent reactive evaporation process. The results show that the coupling of catalytic reaction and interface species mass transfer at the phase interface is conditional, and the coupling of catalytic reaction and momentum transfer across fluid–porous interface significantly affects the conversion rate of reactants. Based on the numerical results, a strategy is proposed for matching solid catalyst with operating condition in catalytic distillation application.     

The impact of hydrogen addition to natural gas on flame stability

Injecting hydrogen into existing natural gas networks is a promising step to mitigate global warming. However there is little evidence showing that how much degree of hydrogen admixture can be accepted. Experiments on populations of gas appliances are not available at present, thus a unified estimation method is required. First, a single-port burner was experimentally evaluated using methane-hydrogen mixtures (hydrogen percentage: 0–50%vol, unburned mixture temperature:373–573K, equivalence ratio:0.8–2). Mathematical formulae of the critical boundary velocity gradient, which quantitatively depict the relationships between flashback, lifting and hydrogen percentage, temperature were provided. A multi-ports burner was subsequently assessed, and the results of the two burners showed good agreement. An analysis method for changes in the flame stability region and gas source replacement decision was proposed based on curves of the flashback and lifting limits. This work provides an important basis for introducing hydrogen into gas networks and the design and adjustment of gas appliances.     

Design and analysis of a new solar hydrogen plant for power,methane, ammonia and urea generation

In this paper, a solar power-based combined plant for power, hydrogen, methane, ammonia and urea production is proposed. A parabolic trough collector is utilized for the system prime mover. Moreover, steam Rankine cycle, organic Rankine cycle, hydrogen production and compression subsystem, ammonia, methane and urea production units, single-effect absorption cooling unit, and freshwater production plant are integrated together to develop the present system for better system performance and cost-effectiveness and reduced environmental impact. In order to analyze and evaluate the proposed multigeneration plant, thermodynamic, parametric and economic studies are performed. According to the assessment results, it is found that energetic and exergetic efficiencies of the present multigeneration plant are 66.12% and 61.56%, respectively. The comparisons of the subsystem and overall plant efficiencies show that the highest energetic and energetic efficiencies belong to freshwater production plant by 79.24% and 75.62%, respectively. In addition, the present parametric analysis indicates that an increase in the reference temperature, solar radiation intensity and working pressure of the solar process has a positive effect on the plant's performance. The cost analysis reveals that as the solar radiation intensity and the working pressure of the solar process increase, the hydrogen generation cost decreases. Furthermore, the hydrogen generation cost is achieved to be 1.94 $/kgH₂ at 650 W/m² of the solar radiation intensity, with other parameters remaining constant.