Can refillable alkaline methanol–air systems replace metal–air cells?

A new start in development of the alkaline methanol/air system was made at the Graz University of Technology. A comparison between the metal/air system and the methanol/air system, some new work on the electrodes for the methanol/air system and silver as catalyst for oxygen reduction is given in this paper.     

Direct methanol–air fuel cells with membranes plus circulating electrolyte

A new approach for direct methanol–air fuel cells (DMFC), with the advantage of reduced methanol crossover is discussed in this paper. Methanol traces in the circulated electrolyte are recovered and CO₂ bubbles in the cells are removed due to the forced methanol–electrolyte stream through the cell.Degradation of the catalyst is reduced since fuel cell electrodes degrade on activated stand without load to a higher extent than under load because high voltage on open circuit promotes carbon oxidation, catalyst changes, etc. Therefore, life expectancy increases with circulating electrolyte by removing the electrolyte from the cells between operating periods.     

Measurements of laminar burning velocities and flame stability analysis for dissociated methanol–air–diluent mixtures at elevated temperatures and pressures

The laminar burning velocities and Markstein lengths for the dissociated methanol–air–diluent mixtures were measured at different equivalence ratios, initial temperatures and pressures, diluents (N₂ and CO₂) and dilution ratios by using the spherically outward expanding flame. The influences of these parameters on the laminar burning velocity and Markstein length were analyzed. The results show that the laminar burning velocity of dissociated methanol–air mixture increases with an increase in initial temperature and decreases with an increase in initial pressure. The peak laminar burning velocity occurs at equivalence ratio of 1.8. The Markstein length decreases with an increase in initial temperature and initial pressure. Cellular flame structures are presented at early flame propagation stage with the decrease of equivalence ratio or dilution ratio. The transition positions can be observed in the curve of flame propagation speed to stretch rate, indicating the occurrence of cellular structure at flame fronts. Mixture diluents (N₂ and CO₂) will decrease the laminar burning velocities of mixtures and increase the sensitivity of flame front to flame stretch rate. Markstein length increases with an increase in dilution ratio except for very lean mixture (equivalence ratio less than 0.8). CO₂ dilution has a greater impact on laminar flame speed and flame front stability compared to N₂. It is also demonstrated that the normalized unstretched laminar burning velocity is only related to dilution ratio and is not influenced by equivalence ratio.     

Laminar-burning velocities of hydrogen–air and hydrogen–methane–air mixtures: An experimental study

The laminar burning velocities of hydrogen–air and hydrogen–methane–air mixtures are very important in designing and predicting the progress of combustion and performance of combustion systems where hydrogen is used as fuel. In this work, laminar flame velocities of hydrogen–air and different composition of hydrogen–methane–air mixtures (from 100% hydrogen to 100% methane) have been measured at ambient temperatures for variable equivalence ratios (ER=0.8–3.2$\mathrm{ER}=0.8–3.2$). A modified test rig has been developed from the former Cardiff University ‘Cloud Chamber’ for this experimental study. The rig comprises of a 250 mm length cylindrical stainless steel explosion bomb enclosed at one end with a stainless steel plug which houses an internal stirrer to allow mixing. The other end is sealed with a 120 mm diameter round quartz window. Optical access for filming flame propagation is afforded via two diametrically opposed quartz windows in both sides. Flame speeds are determined within the bomb using a high-speed Schlieren photographic technique. This method is an accurate way to determine the flame–speed and the burning velocities were then derived using a CHEMKIN computer model to provide the expansion ratio. The design of the test facility ensures the flame is laminar which results in a spherical flame which is not affected by buoyancy. The experimental study demonstrated that increasing the hydrogen percentage in the hydrogen–methane mixture brought about an increase in the resultant burning velocity and caused a widening of the flammability limits. This experiments also suggest that a hydrogen–methane mixture (i.e. 30% hydrogen+70% methane) could be a competitive alternative fuel for existing combustion plants.     

The effect of hydrogen addition on premixed laminar acetylene–hydrogen–air and ethanol–hydrogen–air flames

In the present work, the laminar premixed acetylene–hydrogen–air and ethanol–hydrogen–air flames were investigated numerically. Laminar flame speeds, the adiabatic flame temperatures were obtained utilizing CHEMKIN PREMIX and EQUI codes, respectively. Sensitivity analysis was performed and flame structure was analyzed. The results show that for acetylene–hydrogen–air flames, combustion is promoted by H and O radicals. The highest flame speed (247 cm/s) was obtained in mixture with 95% H₂–5% C₂H₂ at λ = 1.0. The region between 0.95 < X_H2 < 1.0 was referred to as the acetylene-accelerating hydrogen combustion since the flame speed increases with increase the acetylene fraction in the mixture. Further increase in the acetylene fraction decreases the H radicals in the flame front. In ethanol–hydrogen–air mixtures, the mixture reactivity is determined by H, OH and O radicals. For X_H2 < 0.6, the flame speed in this regime increases linearly with increasing the hydrogen fraction. For X_H2 > 0.8, the hydrogen chemistry control the combustion and ethanol addition inhibits the reactivity and reduces linearly the laminar flame speed. For 0.6 < X_H2 < 0.8, the laminar flame speed increases exponentially with the increase of hydrogen fraction.     

Performance and combustion characteristics of biodiesel–diesel–methanol blend fuelled engine

An experimental investigation was conducted to evaluate the effects of using methanol as additive to biodiesel–diesel blends on the engine performance, emissions and combustion characteristics of a direct injection diesel engine under variable operating conditions. BD50 (50% biodiesel and 50% diesel in vol.) was prepared as the baseline fuel. Methanol was added to BD50 as an additive by volume percent of 5% and 10% (denoted as BDM5 and BDM10). The results indicate that the combustion starts later for BDM5 and BDM10 than for BD50 at low engine load, but is almost identical at high engine load. At low engine load of 1500 r/min, BDM5 and BDM10 show the similar peak cylinder pressure and peak of pressure rise rate to BD50, and higher peak of heat release rate than that of BD50. At low engine load of 1800 r/min, the peak cylinder pressure and the peak of pressure rise rate of BDM5 and BDM10 are lower than those of BD50, and the peak of heat release rate is similar to that of BD50. The crank angles at which the peak values occur are later for BDM5 and BDM10 than for BD50. At high engine load, the peak cylinder pressure, the peak of pressure rise rate and peak of heat release rate of BDM5 and BDM10 are higher than those of BD50, and the crank angle of peak values for all tested fuels are almost same. The power and torque outputs of BDM5 and BDM10 are slightly lower than those of BD50. BDM5 and BDM10 show dramatic reduction of smoke emissions. CO emissions are slightly lower, and NO_x and HC emissions are almost similar to those of BD50 at speed characteristic of full engine load.     

Binary Pt–Pd and ternary Pt–Pd–Ru nanoelectrocatalysts for direct methanol fuel cells

Nano-sized binary and ternary alloys are synthesized by polyol process on Vulcan XC72-R support. Nanostructured binary Pt–Pd/C catalysts are prepared either by co-deposition or by depositing on each other. Ternary Pt–Pd–Ru/C catalysts are prepared by co-deposition. The structural characteristics of the nanocatalysts are examined by TEM and XRD. Their electrocatalytic activity toward methanol oxidation and CO stripping curves were measured by electrochemical measurements and compared with that of commercial Pt/C catalyst. The results show that the binary nanocatalyst prepared by depositing the Pt precursor colloids on Pd-Vulcan XC-72R are more active toward methanol oxidation than that of the co-deposited binary alloy nanocatalyst. The co-deposited ternary Pt–Pd–Ru/C nanocatalyst based membrane electrodes assembly shows higher power density compared to the binary nanocatalysts as well as commercial Pt/C catalyst in direct methanol fuel cell. Significantly higher catalytic activity of the nanocatalysts toward methanol oxidation compared to that of the commercial Pt/C is believed to be due to lower level of catalyst poisoning.     

Ni–P and Ni–Cu–P modified carbon catalysts for methanol electro-oxidation in KOH solution

The electrocatalytic oxidation of methanol was studied on Ni–P and Ni–Cu–P supported over commercial carbon electrodes in 0.1 M KOH solution. Cyclic voltammetry and chronoamperometry techniques were employed. Electroless deposition technique was adopted for the preparation of these catalysts. The effect of the electroless deposition parameters on the catalytic activity of the formed samples was examined. They involve the variation of the deposition time, pH and temperature. The scanning electron micrography showed a compact Ni–P surface with a smooth and low porous structure. A decreased amount of nickel and phosphorus was detected by EDX analysis in the formed catalyst after adding copper to the deposition solution. However, an improvement in the catalytic performance of Ni–Cu–P/C samples was noticed. This is attributed to the presence of copper hydroxide/nickel oxyhydroxide species. It suppresses the formation of γ-NiOOH phase and stabilizes β-NiOOH form. Linear dependence of the oxidation current density on the square root of the scan rate reveals the diffusion controlled behaviour.     

Explosion characteristics of hydrogen–nitrogen–air mixtures at elevated pressures and temperatures

An experimental study on the combustion characteristics of nitrogen diluted hydrogen was conducted in a constant volume combustion vessel over a wide range of equivalence ratios and dilution ratios at elevated pressures and temperatures. The explosion characteristics such as the explosion pressure, the combustion duration, the maximum rate of pressure rise, the deflagration index and the normalized mass burning rate were derived. The result shows that a short combustion duration and higher normalized mass burning rate were presented with the increase of equivalence ratio. With the increase of initial temperature, the explosion pressure, the maximum rate of pressure rise and the deflagration index were decreased, and a shorter combustion duration and higher normalized mass burning rate were presented. With the increase of initial pressure, the explosion pressure, the maximum rate of pressure rise and the deflagration index increase, a shorter combustion duration and higher normalized mass burning rate were presented. Nitrogen dilution significantly reduces the normalized mass burning rate and the deflagration index and thus the potential of explosion hazards.     

Detonation wave propagation in semi-confined layers of hydrogen–air and hydrogen–oxygen mixtures

This paper presents results of an experimental investigation on detonation wave propagation in semi-confined geometries. Large scale experiments were performed in layers up to 0.6 m filled with uniform and non-uniform hydrogen–air mixtures in a rectangular channel (width 3 m; length 9 m) which is open from below. A semi confined driver section is used to accelerate hydrogen flames from weak ignition to detonation. The detonation propagation was observed in a 7 m long unobstructed part of the channel. Pressure measurements, ionization probes, soot-records and high speed imaging were used to observe the detonation propagation. Critical conditions for detonation propagation in different layer thicknesses are presented for uniform H₂/air-mixtures, as well as experiments with uniform H₂/O₂ mixtures in a down scaled transparent channel. Finally detail investigations on the detonation wave propagation in H₂/air-mixtures with concentration gradients are shown.     

A study on methane–air premixed flames interacting with syngas–air premixed flames

Numerical study on the interaction between methane–air and syngas–air premixed flames is conducted according to equivalence ratio and global strain rate in detailed chemistry. This study targets at understanding of an interacting combustion system as an alternative retrofit concept where one can modify the existing facilities minimally in industrial and power plant burners in order to reduce the emission of carbon dioxide. It is seen that methane premixed flame interacting with syngas premixed flame can be sustained even over the rich flammable limit of single methane premixed flame. The inspection of detailed flame structure such as the distributions of major species and chain carrier radicals, flame separation distance, spatial flow velocity, and spatial distribution of the rate of production and consumption of CH₄, H₂, and CO is also conducted to depict the flame interactions. The importance of global strain rate and thus the flame separation distance in the enhanced burning of methane premixed flame is also stressed through the inspection of the consumption rates of H₂, CO, and CH₄. Anomalous phenomena such as the migration of premixed flame cross the stagnation plane and the nearly constant flame separation distance are also discussed.     

Experimental and numerical study on laminar burning characteristics of premixed methane–hydrogen–air flames

An experimental and numerical study on laminar burning characteristics of the premixed methane–hydrogen–air flames was conducted at room temperature and atmospheric pressure. The unstretched laminar burning velocity and the Markstein length were obtained over a wide range of equivalence ratios and hydrogen fractions. Moreover, for further understanding of the effect of hydrogen addition on the laminar burning velocity, the sensitivity analysis and flame structure were performed. The results show that the unstretched laminar burning velocity is increased, and the peak value of the unstretched laminar burning velocity shifts to the richer mixture side with the increase of hydrogen fraction. Three regimes are identified depending on the hydrogen fraction in the fuel blend. They are: the methane-dominated combustion regime where hydrogen fraction is less than 60%; the transition regime where hydrogen fraction is between 60% and 80%; and the methane-inhibited hydrogen combustion regime where hydrogen fraction is larger than 80%. In both the methane-dominated combustion regime and the methane-inhibited hydrogen combustion regime, the laminar burning velocity increases linearly with the increase of hydrogen fraction. However, in the transition regime, the laminar burning velocity increases exponentially with the increase of hydrogen fraction in the fuel blends. The Markstein length is increased with the increase of equivalence ratio and is decreased with the increase of hydrogen fraction. Enhancement of chemical reaction with hydrogen addition is regarded as the increase of H, O and OH radical mole fractions in the flame. Strong correlation is found between the burning velocity and the maximum radical concentrations of H and OH in the reaction zone of the premixed flames.     

Experimental investigation on the effect of intake air temperature and air–fuel ratio on cycle-to-cycle variations of HCCI combustion and performance parameters

Combustion in HCCI engines is a controlled auto ignition of well-mixed fuel, air and residual gas. Since onset of HCCI combustion depends on the auto ignition of fuel/air mixture, there is no direct control on the start of combustion process. Therefore, HCCI combustion becomes unstable rather easily, especially at lower and higher engine loads. In this study, cycle-to-cycle variations of a HCCI combustion engine fuelled with ethanol were investigated on a modified two-cylinder engine. Port injection technique is used for preparing homogeneous charge for HCCI combustion. The experiments were conducted at varying intake air temperatures and air–fuel ratios at constant engine speed of 1500 rpm and P-θ diagram of 100 consecutive combustion cycles for each test conditions at steady state operation were recorded. Consequently, cycle-to-cycle variations of the main combustion parameters and performance parameters were analyzed. To evaluate the cycle-to-cycle variations of HCCI combustion parameters, coefficient of variation (COV) of every parameter were calculated for every engine operating condition. The critical optimum parameters that can be used to define HCCI operating ranges are ‘maximum rate of pressure rise’ and ‘COV of indicated mean effective pressure (IMEP)’.     

Porous medium based burner for efficient and clean combustion of ammonia–hydrogen–air systems

Due to its high hydrogen density and extensive experience base, ammonia (NH₃) has been gaining special attention as a potential green energy carrier. This study focuses on premixed ammonia–hydrogen–air flames under standard temperature and pressure conditions using an inert silicon-carbide (SiC) porous block as a practical and effective medium for flame stabilization. Combustion experiments conducted using a lab scale burner resulted in stable combustion and high combustion efficiencies at very high ammonia concentration levels over a wide range of equivalence ratios. Noticeable power output densities have also been achieved. Preliminary results of NO_x emission measurements indicate NO_x concentrations as low as 35 ppm under rich conditions. The remarkable capability of this specific burner to operate efficiently and cleanly at high ammonia concentration levels, which can easily be achieved by partial cracking of NH₃, is believed to be a key accomplishment in the development of ammonia fired power generation systems.     

Electrodeposition of Pt–Ru and Pt–Ru–Ni nanoclusters on multi-walled carbon nanotubes for direct methanol fuel cell

A full-electrochemical method is developed to deposit three dimension structure (3D) flowerlike platinum-ruthenium (PtRu) and platinum-ruthenium-nickel (PtRuNi) alloy nanoparticle clusters on multi-walled carbon nanotubes (MWCNTs) through a three-step process. The structure and elemental composition of the PtRu/MWCNTs and PtRuNi/MWCNTs catalysts are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray polycrystalline diffraction (XRD), IRIS advantage inductively coupled plasma atomic emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS). The presence of Pt(0), Ru(0), Ni(0), Ni(OH)₂, NiOOH, RuO₂ and NiO is deduced from XPS data. Electrocatalytic properties of the resulting PtRu/MWCNTs and PtRuNi/MWCNTs nanocomposites for oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) are investigated. Compared with the Pt/MWCNTs, PtNi/MWCNTs and PtRu/MWCNTs electrodes, an enhanced electrocatalytic activity and an appreciably improved resistance to CO poisoning are observed for the PtRuNi/MWCNTs electrode, which are attributed to the synergetic effect of bifunctional catalysis, three dimension structure, and oxygen functional groups which generated after electrochemical activation treatment on MWCNTs surface. The effect of electrodeposition conditions for the metal complexes on the composition and performance of the alloy nanoparticle clusters is also investigated. The optimized ratios for PtRu and PtRuNi alloy nanoparticle clusters are 8:2 and 8:1:1, respectively, in this experiment condition. The PtRuNi catalyst thus prepared exhibits excellent performance in the direct methanol fuel cells (DMFCs). The enhanced activity of the catalyst is surely throwing some light on the research and development of effective DMFCs catalysts.     

Influence of initial pressure and temperature on flammability limits of hydrogen–air

This paper presents data on the lower and upper flammability limits of hydrogen–air mixtures at elevated temperature and pressure. A 5-L explosion vessel, an ignition system, and a transient pressure measurement sub-system were used in this study. Through a series of experiments carried out, the lower and upper flammability limits of hydrogen–air mixtures at different initial pressures and temperatures have been studied and the influence of initial temperature and pressure on the lower and upper flammability limits of hydrogen–air mixtures has been analysed and discussed. It was found that the decrement of the LFLs of hydrogen–air with the initial temperature from 21 to 90 °C at the initial pressure of 0.1 MPa is less than 1%, the decrement of the LFLs with the initial temperature from 21 to 90 °C at 0.2 MPa is less than 1%, the decrement of the LFLs with the initial temperature from 21 to 90°Cat 0.3 MPa is less than 0.66%, and the decrement of the LFLs with the initial temperature from 21 to 90 °C at 0.4 MPa is less than 0.25%. The lower flammability limits of hydrogen–air mixtures at the pressures of 0.1 and 0.4 MPa are 4 and 1.25%(V/V), respectively. The upper flammability limits of the hydrogen–air mixtures increase with the initial pressure and temperature. The upper flammability limit of the hydrogen–air mixtures at 90 °C and 0.4 MPa reaches 93%(V/V) which is much higher than that (76%(V/V)) at 21 °C and 0.1 MPa.     

A novel Rh–Ir electrocatalyst for the oxygen reduction reaction and the hydrogen and methanol oxidation reactions

A novel Rh–Ir based material was synthesized by pyrolysis of an Ir₄(CO)₁₂/Rh₆(CO)₁₆ mixture in a reductive (H₂) atmosphere. The material was characterized by FTIR spectroscopy, X-ray diffraction, energy dispersive spectroscopy and scanning electron microscopy, and was evaluated as electrocatalyst for oxygen reduction and hydrogen and methanol oxidation by rotating disk electrode measurements. The bimetallic material shows a high catalytic activity for the oxygen reduction reaction and is also capable to carry out the hydrogen oxidation reaction even in the presence of carbon monoxide in different concentrations (100 ppm and 0.5%), in contrast with commercial platinum catalysts, which become easily deactivated by CO. The activity of the catalyst for methanol oxidation is acceptable but still low in comparison with Pt–Ru. The results show that the new bimetallic catalyst is a potential candidate to be evaluated as both cathode and anode in a reforming hydrogen PEMFC, and as an anode in a direct methanol fuel cell.