A comparison of the emission and impingement heat transfer of LPG–H2 and CH4–H2 premixed flames

Experiments were performed to add hydrogen to liquefied petroleum gas (LPG) and methane (CH₄) to compare the emission and impingement heat transfer behaviors of the resultant LPG–H₂–air and CH₄–H₂–air flames. Results show that as the mole fraction of hydrogen in the fuel mixture was increased from 0% to 50% at equivalence ratio of 1 and Reynolds number of 1500 for both flames, there is an increase in the laminar burning speed, flame temperature and NO_x emission as well as a decrease in the CO emission. Also, as a result of the hydrogen addition and increased flame temperature, impingement heat transfer is enhanced. Comparison shows a more significant change in the laminar burning speed, temperature and CO/NO_x emissions in the CH₄ flames, indicating a stronger effect of hydrogen addition on a lighter hydrocarbon fuel. Comparison also shows that the CH₄ flame at α = 0% has even better heat transfer than the LPG flame at α = 50%, because the longer CH₄ flame configures a wider wall jet layer, which significantly increases the integrated heat transfer rate.     

Synthesis and characterization of bimetallic Cu–Ni/ZrO2 nanocatalysts: H2 production by oxidative steam reforming of methanol

Cu/ZrO₂, Ni/ZrO₂ and bimetallic Cu–Ni/ZrO₂ catalysts were prepared by deposition–precipitation method to produce hydrogen by oxidative steam reforming of methanol (OSRM) reaction in the range of 250–360 °C. TPR analysis of the Cu–Ni/ZrO₂ catalyst showed that the presence of Cu facilitates the reduction of the Ni at lower temperatures. In addition, this sample showed two reduction peaks, the former peak was attributed to the reduction of the adjacent Cu and Ni atoms which could be forming a bimetallic Cu-rich phase, and the second was assigned to the remaining Ni atoms forming bimetallic Ni-rich nanoparticles. Transmission Electron Microscopy revealed Cu or Ni nanoparticles on the monometallic samples, while bimetallic nanoparticles were identified on the Cu–Ni/ZrO₂ catalyst. On the other hand, Cu–Ni/ZrO₂ catalyst exhibited better catalytic activity than the monometallic samples. The difference between them was related to the Cu–Ni nanoparticles present on the former catalyst, as well as the bifunctional role of the bimetallic phase and the support that improve the catalytic activity. All the catalysts showed the same selectivity toward H₂ at the maximum reaction temperature and it was ∼60%. The high selectivity toward CO is associated to the presence of the bimetallic Ni-rich nanoparticles, as evidenced by TEM–EDX analysis, since this behavior is similar to the one showed by the monometallic Ni-catalyst.     

Preferential oxidation of CO in H2 stream on Au/ZnO–TiO2 catalysts

A series of gold catalysts supported on ZnO–TiO₂ with various ZnO contents were prepared. ZnO–TiO₂ was prepared by incipient-wetness impregnation using aqueous solution of Zn(NO₃)₂ onto TiO₂. Gold catalysts with nominal gold loading of 1 wt. % were prepared by deposition-precipitation (DP) method. Various preparation parameters, such as pH value and Zn/Ti ratio on the characteristics of the catalysts were investigated. The catalysts were characterized by inductively-coupled plasma–mass spectrometry, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and high-resolution transmission electron microscopy. The preferential oxidation of CO in H₂ stream (PROX) on these catalysts was carried out in a fixed bed micro-reactor with a feed of CO: O₂: H₂: He = 1: 1: 49: 49 (volume ratios) and a space velocity of 30,000 ml/g h. Limited amount of oxygen was used in the feed. A high gold dispersion and narrow gold particle size distribution was obtained. Au/ZnO–TiO₂ with Zn/Ti atomic ratio of 5/95 showed the highest CO conversion at room temperature. The conversion increased with increasing temperature even in the presence of limited amount of oxygen, showing suppression in H₂ oxidation. Au/ZnO–TiO₂ prepared at pH 6 had a higher CO conversion and higher selectivity of CO oxidation than those prepared at other pH values. The addition of ZnO on TiO₂ resulted in higher dispersion of gold particles and narrow particle size distribution. The stronger the Au–Zn(OH)₂ interaction, the finer the supported Au nanoparticles, and the better the catalytic performance of the catalyst for PROX reaction. Part of Au was in Au⁺ state due to the interaction with Zn(OH)₂ and nano Au size. The oxidation state of gold species played an important role in determining its CO conversion and selectivity of CO oxidation in hydrogen stream. The catalysts were stable at 80 °C for more than 80 h.     

Enhanced photoelectrochemical performance of anatase TiO2 by metal-assisted S–O coupling for water splitting

In this study, hybrid density functional theory calculations have been used to investigate the electronic structures of (Mg, S), (2Al, S), (Ca, S), and (2Ga, S) codoped anatase TiO₂, aiming at improving their photoelectochemical performance for water splitting. It is found that the acceptor metals (Mg, Al, Ca, and Ga), assisting the coupling of the incorporated S with the neighboring O in TiO₂, lead to the fully occupied energy levels in the forbidden band of TiO₂, which is driven by the antibonding state π* of the S–O bond. It is also found that the metal-assisted S–O coupling can prevent the recombination of the photo-generated electron–hole pairs and effectively reduce the band gap of TiO₂. Among these systems, the (Mg, S) codoped anatase TiO₂ has the narrowest band gap of 2.206 eV, and its band edges match well with the redox potentials of water. We propose that this metal-assisted S–O coupling could improve the visible light photoelectrochemical activity of anatase TiO₂.     

Catalytic partial oxidation of CH4–H2 mixtures over Ni foams modified with Rh and Pt

The catalytic partial oxidation (CPO) of methane–hydrogen mixtures in air, intended for the first stage of hybrid radiant catalytic burners, was investigated under self-sustained short contact time conditions on commercial Ni foam catalysts eventually modified with Rh and Pt. The modified catalysts were prepared by a simple novel method based on the spontaneous deposition of noble metals via metal exchange reactions onto those Ni foam substrates. SEM-EDS, electrochemical methods and H₂-TPR analysis were integrated to characterize morphology, surface area of metal deposits and reducibility of foam catalysts before and after exposure to severe conditions in the CPO reactor. In particular Rh forms finely dispersed deposits that retain their high specific surface area at temperatures up ca. 1100 °C. Modification with noble metals enhances stability and reducibility of the Ni foam whereas the overall CPO performance is not significantly improved. Safe operation of the CPO reactor with up to 70% vol. H₂ in the fuel mixture has been achieved by properly increasing the feed equivalence ratio to avoid catalyst overheating, while guaranteeing high methane conversions and a persistent net hydrogen production.     

A novel catalyst–sorbent system for an efficient H2 production with in-situ CO2 capture

This paper presents an experimental investigation for an improved process of sorption-enhanced steam reforming of methane in an admixture fixed bed reactor. A highly active Rh/Ce_αZr_1−αO₂ catalyst and K₂CO₃-promoted hydrotalcite are utilized as novel catalyst/sorbent materials for an efficient H₂ production with in situ CO₂ capture at low temperature (450–500 °C). The process performance is demonstrated in response to temperature (400–500 °C), pressure (1.5–6.0 bar), and steam/carbon ratio (3–6). Thus, direct production of high H₂ purity and fuel conversion >99% is achieved with low level of carbon oxides impurities (<100 ppm). A maximum enhancement of 162% in CH₄ conversion is obtained at a temperature of 450 °C and a pressure of 6 bar using a steam/carbon molar ratio of 4. The high catalyst activity of Rh yields an enhanced CH₄ conversion using much lower catalyst/sorbent bed composition and much smaller reactor size than Ni-based sorption enhanced processes at low temperature. The cyclic stability of the process is demonstrated over a series of 30 sorption/desorption cycles. The sorbent exhibited a stable performance in terms of the CO₂ working sorption capacity and the corresponding CH₄ conversion obtained in the sorption enhanced process. The process showed a good thermal stability in the temperature range of 400–500 °C. The effects of the sorbent regeneration time and the purge stream humidity on the achieved CH₄ conversion are also studied. Using steam purge is beneficial for high degree of CO₂ recovery from the sorbent.     

The retardation kinetics of magnetite reduction using H2 and H2–H2O mixtures

Cylindrical compacts of magnetite were isothermally reduced at 773–1273 K with pure H₂ or H₂–H₂O mixtures. The initial reduction rates increased with temperature and partial pressures of H₂ in the H₂–H₂O mixtures. However, with progressing reduction, a dense iron layer formed around the wüstite grains and the rate significantly reduced. In this regime, solid state oxygen diffusion through the dense iron layer was rate limiting. This retardation of reduction occurred at degrees of reduction of 51–89%, depending on the temperature and H₂ partial pressure, which has a linear relationship with the dimensionless kinetic parameter, k₁^mixed/k₂^mixed, (k₁^mixed, k₂^mixed: contribution of gaseous mass transport (GMT) and interfacial chemical reaction (ICR) to the reduction rate, respectively) in the reaction-regime controlled by a combination of both mechanisms. However, under certain conditions (H₂, H₂–10%H₂O, 773 K//H₂–10, 20%H₂O, 873 K//H₂–20%H₂O, 973 K) the retardation was absent because of the formation of a microporous iron layer product.     

Adiabatic burning velocity of H2–O2 mixtures diluted with CO2/N2/Ar

Global warming due to CO₂ emissions has led to the projection of hydrogen as an important fuel for future. A lot of research has been going on to design combustion appliances for hydrogen as fuel. This has necessitated fundamental research on combustion characteristics of hydrogen fuel. In this work, a combination of experiments and computational simulations was employed to study the effects of diluents (CO₂, N₂, and Ar) on the laminar burning velocity of premixed hydrogen/oxygen flames using the heat flux method. The experiments were conducted to measure laminar burning velocity for a range of equivalence ratios at atmospheric pressure and temperature (300 K) with reactant mixtures containing varying concentrations of CO₂, N₂, and Ar as diluents. Measured burning velocities were compared with computed results obtained from one-dimensional laminar premixed flame code PREMIX with detailed chemical kinetics and good agreement was obtained. The effectiveness of diluents in reduction of laminar burning velocity for a given diluent concentration is in the increasing order of argon, nitrogen, carbon dioxide. This may be due to increased capabilities either to quench the reaction zone by increased specific heat or due to reduced transport rates. The lean and stoichiometric H₂/O₂/CO₂ flames with 65% CO₂ dilution exhibited cellular flame structures. Detailed three-dimensional simulation was performed to understand lean H₂/O₂/CO₂ cellular flame structure and cell count from computed flame matched well with the experimental cellular flame.     

H2 production by γ and He ions water radiolysis, effect of presence TiO2 nanoparticles

The effect of TiO₂ particles on the yield of H₂ formation under water radiolysis is measured. Irradiations were performed using a ⁶⁰Co γ−ray source as well as with He ions particles (4He2⁺) generated by a cyclotron with an external beam energy of 6 MeV. The resulting hydrogen as a stable product of radiolysis was measured by mass spectrometry. G(H₂) obtained for water radiolysis by He ions−irradiation in aerated and argon water are found to be 1.91 × 10⁻⁷ and 1.35 × 10⁻⁷ mol J⁻¹, respectively. In the presence of titanium oxide anatase−type dispersed in water, under He ions−irradiation, G(H₂) is found to increase slightly from 1.04 × 10⁻⁷ to 1.35 × 10⁻⁷ mol J⁻¹ by increasing the specific surface from 8 to 253 m²/g, respectively. Under γ-irradiation, G(H₂) is found to be 0.41 × 10⁻⁷ mol J⁻¹ close to primary yield of hydrogen in presence of OH. Radical scavenger. In addition, radiolysis of water adsorbed in the titanium oxide with low water content, which corresponds to a few layers of water sorbed onto the solid surface gives a huge values of the G(H₂). For the same amount of water, with using the dose absorbed by TiO₂ particles, for He ions-irradiation, G(H₂) increases from 14.5 × 10⁻⁷ to 35 × 10⁻⁷ mol J^-1 by increasing the surface area of TiO₂ nanoparticles from 4 to 52 m²/g, respectively. For γ−irradiation G(H₂) is found to be 5.25 × 10⁻⁷ mol J^-1 for the sample with 8 m²/g specific surface area.     

Effects of Fe substitutions by Ni in La–Ni–O perovskite-type oxides in reforming of methane with CO2 and O2

LaNiO₃ and LaNi_1−xFe_xO₃ (x = 0.2, 0.4, 0.6, 0.8 and 1) perovskites were prepared by the citrate sol–gel method. The prepared compounds were characterized by using thermogravimetric analysis (TGA) and X-ray diffraction (XRD), temperature programmed reduction (TPR), and inductively coupled plasma (ICP) techniques. Specific surface area of the samples was measured by BET method. Morphology study of the prepared catalysts was performed using scanning and transmission electron microscopy (SEM and TEM, respectively). The XRD patterns of fresh catalysts indicated the formation of well-crystallized perovskite structure as the main phase present in the prepared samples. The results showed that the highly homogeneous and pure solids with particle sizes in the range of nanometers were obtained through this synthesis method. TPR analysis revealed that by increasing the degree of substitution (x) the reduction of the prepared samples became difficult. The effects of the partial substitution of Ni by Fe and reaction temperatures at atmospheric pressure were investigated in the combined reforming of methane with CO₂ and O₂ (CRM), after reduction of the samples under hydrogen. LaNiO₃ exhibited high activity and selectivity without coke formation between all of the studied perovskites. Among Fe-substituted catalysts, the following order of activity was observed: LaNiO₃>LaNi_0.4Fe_0.6O₃>LaNi_0.6Fe_0.4O₃ > LaNi_0.8Fe_0.2O₃ > LaNi_0.2Fe_0.8O₃ > LaFeO₃.     

Anatase/rutile-TiO2 hollow hierarchical architecture modified by SnO2 toward efficient lithium storage

Hierarchical architecture of anatase/rutile-mixed phases TiO₂ with hollow interior was successfully fabricated via a Topotactic synthetic method, including the synthesis of CaTiO₃ precursors and transforming them into TiO₂ through ion-exchange process. The as-synthesized TiO₂ hierarchical architectures as the anode materials were used as lithium-ion batteries (LIBs). Compared with TiO₂ samples, the TiO₂@SnO₂-5% shows the improved lithium storage capacity, cycling performance and rate properties. The impedance of the TiO₂ electrode decreases evidently after adding few amount of SnO₂. The hollow hierarchical structure with different compositions provide much more active sites, and well connect interface among anatase, rutile, and SnO₂, facilitating the electron and ion transport quickly and efficiently. Addition appropriate number of SnO₂ not only well kept the hierarchical architecture but also enhanced the capacity and conductivity of the TiO₂ sample. As a result, TiO₂@SnO₂-5% exhibited excellent lithium storage performance.     

Combustion characteristics of an SI engine fueled with H2–CO blended fuel and diluted by CO2

This paper presents further results of the study on fundamental combustion characteristics of gaseous fuels simulated for a biogas produced through a biomass gasification process with a catalyzer. The main work focuses on combustion characteristics of H₂–CO blended fuel and the effect of CO₂ dilution on it in a spark-ignition engine under the condition of WOT, MBT and a constant speed of 1500 rpm. Equivalence ratio were limited to lower than 0.8 in order to avoid excessive high combustion temperature to damage the engine, and lean conditions were maintained during the experiment to get acceptable economy and emissions. The results show that the BMEP decreases with an increase in dilution rate. The COV of IMEP is lower than 10% under most conditions, while H₂ and CO₂ have the opposite influence on brake thermal efficiency. CO₂ dilution combustion could induce to remarkable decreasing in NO_x emission with little decrease in brake thermal efficiency, which benefits for biomass gaseous fuel application. If 500 ppm of NO_x emission and 26% of brake thermal efficiency could be viewed as accepted level, the accepted operation range of H₂–CO mixture have been obtained.     

IrO2/Nb–TiO2 electrocatalyst for oxygen evolution reaction in acidic medium

A corrosion-resistant Nb_0.05Ti_0.95O₂ material with high surface area was prepared by a sol–gel process. IrO₂ nanoparticles (about 16–33 wt%) were successfully loaded on Nb_0.05Ti_0.95O₂ powders as the electrocatalyst for oxygen evolution reaction (OER) in acidic medium. The IrO₂/Nb_0.05Ti_0.95O₂ catalyst with the IrO₂ loading of 26 wt% exhibits the best mass normalized cyclic voltammetry charge and mass normalized activity among all the IrO₂/Nb_0.05Ti_0.95O₂ catalysts because IrO₂ nanoparticles were uniformly supported on the surface of Nb_0.05Ti_0.95O₂ providing conductive channels to reduce the grain boundary resistance. Due to the anchoring effect of carrier on the catalyst, the stability of the supported IrO₂ was significantly improved as compared to the unsupported one. The IrO₂/Nb_0.05Ti_0.95O₂ catalyst with 26 wt% IrO₂ loading demonstrates the best effectiveness of the OER activity and cost.     

Combustion,performance and emissions of a diesel engine with H2, CH4 and H2–CH4 addition

Experiments were conducted to investigate the combustion and emission characteristics of a diesel engine with addition of hydrogen or methane for dual-fuel operation, and mixtures of hydrogen–methane for tri-fuel operation. The in-cylinder pressure and heat release rate change slightly at low to medium loads but increase dramatically at high load owing to the high combustion temperature and high quantity of pilot diesel fuel which contribute to better combustion of the gaseous fuels. The performance of the engine with tri-fuel operation at 30% load improves with the increase of hydrogen fraction in methane and is always higher than that with dual-fuel operations. Compared with ULSD–CH₄ operation, hydrogen addition in methane contributes to a reduction of CO/CO₂/HC emissions without penalty on NO_x emission. Dual-fuel and tri-fuel operations suppress particle emission to the similar extent. All the gaseous fuels reduce the geometry mean diameter and total number concentration of diesel particulate. Tri-fuel operation with 30% hydrogen addition in methane is observed to be the best fuel in reducing particulate and NO_x emissions at 70 and 90% loads.     

Development of Fe2O3–TiO2 mixed oxide incorporated Ni–P coating for electrocatalytic hydrogen evolution reaction

Considering the electronic parameters and chemical characteristics, a synergistic catalytic effect of Fe₂O₃ along with TiO₂ could be achieved for electrochemical reactions if both the oxides are produced in a mixed oxide form. The present study explored the mixed oxide composite viz; Fe₂O₃–TiO₂, synthesized via thermal decomposition method, to increase the catalytic efficiency of Ni–P electrodes, the well known catalytic electrodes for hydrogen evolution reaction in alkaline medium. The incorporation of the Fe₂O₃–TiO₂ mixed oxide into Ni–P matrix substantially reduced overpotential during hydrogen evolution reaction (HER) in 32% NaOH solution. A significant improvement on the electrochemical activity of the Ni–P coated electrodes was achieved as evidenced from the results of Tafel and impedance studies. The incorporation of Fe₂O₃–TiO₂ mixed oxide composite into the Ni–P matrix has improved both metallurgical and electrochemical characteristics and hence its amount of incorporation should be optimum. The electrodes exhibited high stability under dynamic experimental conditions. The role of the composite and the possible mechanism are discussed in this paper.     

In situ thermal desorption of H2 from LiNH2–2LiH monitored by environmental SEM

This article describes in situ heating and observation of a LiNH₂–2LiH mixture in an environmental scanning electron microscope (ESEM). The LiNH₂–2LiH mixture showed extensive morphological changes with heating and attendant hydrogen desorption. Static images and real-time movies were obtained during the dehydrogenation process. H₂ evolution commences at ∼150 °C (LiNH₂ + 2LiH → Li₂NH + H₂ + LiH), and continues until ∼410 °C. Dramatic morphological changes are observed at 220 and 410 °C (Li₂NH + LiH → Li₃N + H₂). The material converts to a microcrystalline phase at higher temperatures (>500 °C). The observed H₂ desorption and morphological changes occur at temperatures in good agreement with those measured by complementary analytical methods. This is the first time the major structural and morphological changes attendant on H₂ loss from this system have been observed in situ and in real time.     

Laminar burning velocities and flame characteristics of CO–H2–CO2–O2 mixtures

Laminar burning velocities of CO–H₂–CO₂–O₂ flames were measured by using the outwardly spherical propagating flame method. The effect of large fraction of hydrogen and CO₂ on flame radiation, chemical reaction, and intrinsic flame instability were investigated. Results show that the laminar burning velocities of CO–H₂–CO₂–O₂ mixtures increase with the increase of hydrogen fraction and decrease with the increase of CO₂ fraction. The effect of hydrogen fraction on laminar burning velocity is weakened with the increase of CO₂ fraction. The Davis et al. syngas mechanism can be used to calculate the syngas oxyfuel combustion at low hydrogen and CO₂ fraction but needs to be revised and validated by additional experimental data for the high hydrogen and CO₂ fraction. The radiation of syngas oxyfuel flame is much stronger than that of syngas–air and hydrocarbons–air flame due to the existence of large amount of CO₂ in the flame. The CO₂ acts as an inhibitor in the reaction process of syngas oxyfuel combustion due to the competition of the reactions of H + O₂ = O + OH, CO + OH = CO₂ + H and H + O₂(+M) = HO₂(+M) on H radical. Flame cellular structure is promoted with the increase of hydrogen fraction and is suppressed with the increase of CO₂ fraction due to the combination effect of hydrodynamic and thermal-diffusive instability.     

Rehydrogenation performance of an MgH2–Nb2O5 system modified by heptane and acetone

An MgH₂ + 1 mol% Nb₂O₅ system was modified by heptane and acetone through a high-energy ball milling process, and their rehydrogenation performances were investigated. XRD results indicated that except MgH₂ and Nb₂O₅ phases Mg and MgO phases existed after ball milling. The rehydrogenation results showed that after modification by heptane the capacity increased from 3.0 wt% and 4.2 wt% to 5.0 wt% and 5.5 wt% within 110 s at 523 K and 573 K, respectively. The hydriding rate increased from 0.08 wt%/s after 20 s to 0.22 wt%/s after 10 s at 523 K. However, after modification by acetone it only absorbed 1.8 wt% and 2.0 wt% of hydrogen even within 8000 s at 523 K and 573 K, respectively. Rietveld refinement results indicated that after modification by the heptane the content of MgO was reduced from 6.8 wt% to 4.2 wt%, while after the modification by the acetone the content of MgO was significantly increased from 6.8 wt% to 23.8 wt%. The difference in the rehydrogenation performance was believed to be attributed to the different contents of the MgO phase, which led to the difference in the contents of the MgH₂ phase. It implied that the heptane acted as a solvent without oxygen element in it to prevent the MgH₂ + Nb₂O₅ system from aggregation, crystallization and oxidation. It suggested heptane was suitable for the improvement of the rehydrogenation performance of MgH₂ system.     

Photoelectrochemical application of mesoporous TiO2/WO3 nanohoneycomb prepared by sol–gel method

A mesoporous TiO₂/WO₃ nanohoneycomb at a molar ratio of 3:1 was prepared by sol–gel method for photoelectrochemical splitting of water. In order to create a highly porous structure, the composite TiO₂/WO₃ with a block copolymer internal template was deposited on the substrate covered with polystyrene (PS) nanospheres. A mesoporous TiO₂/WO₃ composite nanohoneycomb was obtained after removing the PS spheres and copolymer by thermal treatment. It exhibited a lower band gap energy than TiO₂ so that the optical absorption edge was shifted toward the visible light region. It also showed a better photoelectrochemical efficiency of water splitting and higher production of hydrogen due to lower energy gap, higher reactive surface area, and better charge separation efficiency.     

Comparative analysis of performance and techno-economics for a H2O–NH3–H2 absorption refrigerator driven by different energy sources

The objectives of the present work are of two-folds. First, it evaluates the transient temperature performance of the H₂O–NH₃–H₂ absorption cooling machine system’s components under two types of energy sources, i.e. the conventional electric energy from grid (electric) and fuel energy from liquid petroleum gas (LPG). Results obtained have shown that performance of various components under different type of energy sources is almost coherent. For the evaporator, the system with electric supply has shorter starting time, around 6 min earlier than the system run with LPG. Meanwhile, the system powered by LPG produced a lower cooling temperature around −9 °C, compared to the system run with electric which produced temperature at around −7 °C. Economical study had been carried out subsequently, for three different energy sources, i.e. electric, LPG and solar energy (photovoltaic). From the techno-economical analyzes, it was found that the conventional electric from grid is still the best form of energy source for short-term application, as far as the present location and conditions are concerned. LPG is the next attractive energy source, especially at locations with constant LPG supply; the photovoltaic energy from solar is attractive for long term consideration since it has zero fuel cost and environmentally-friendly, but with the highest initial cost.