Characteristics of methane reforming using gliding arc reactor

A gliding arc reformer was proposed to produce hydrogen-rich gas. The reformer has two reactors including a plasma reactor and a catalyst reactor.     

Oxidative pyrolysis reforming of methanol in warm plasma for an on-board hydrogen production

To achieve on-board hydrogen production with high energy efficiency and low energy cost, the oxidative pyrolysis reforming (OPR) of methanol using air as an oxidant in a heat-insulated gliding arc plasma reactor is explored. Effects of dioxygen/methanol (O₂/C) ratio, steam/methanol (S/C) ratio and specific energy input (SEI) on the OPR are investigated. The reaction rate ratio (α) of pyrolysis reforming to oxidative reforming in the OPR is deduced. The OPR of methanol strongly depends on the O₂/C ratio, with which methanol conversion increases rapidly. In the OPR, methanol conversions occur mainly by the oxidative reforming (partial oxidation) at the O₂/C ratios below 0.20, but by the oxidative reforming and the promoted pyrolysis reforming at the O₂/C ratios above 0.20, which is confirmed by the enthalpy change for the overall reaction of OPR. Higher O₂/C ratio results in higher energy efficiency and lower energy cost, however, higher S/C ratio or larger SEI leads to lower energy efficiency and higher energy cost. Under conditions of O₂/C = 0.30, S/C = 0.5, SEI = 24 kJ/mol, energy efficiency of 74% and energy cost of 0.45 kWh/Nm³ with methanol conversion of 88% are achieved.     

Plasma reforming for hydrogen production: Pathways,reactors and storage

Hydrogen is an energy carrier with a very high energy density (>119 MJ/kg). Pure hydrogen is barely available; thus, it requires extraction from its compounds. Steam reforming and water electrolysis are commercially viable technologies for hydrogen production from water, alcohols, methane, and other hydrocarbons; however, both processes are energy-intensive. Current study aims at understanding the methane and ethanol-water mixture pathway to generate hydrogen molecules. The various intermediate species (like CH_X, CH₂O, CH₃CHO) are generated before decomposing methane/ethanol into hydrogen radicals, which later combine to form hydrogen molecules. The study further discusses the various operating parameters involved in plasma reforming reactors. All the reactors work on the same principle, generating plasma to excite electrons for collision. The dielectric barrier discharge reactor can be operated with or without a catalyst; however, feed flow rate and discharge power are the most influencing parameters. In a pulsed plasma reactor, feed flow rate, electrode velocity, and gap are the main factors that can raise methane conversion (40–60%). While the gliding arc plasma reactor can generate up to 50% hydrogen yield at optimized values of oxygen/carbon ratio and residence time, the hydrogen yield in the microwave plasma reactor is affected by flow rate and feed concentration. Therefore, all the reactors have the potential to generate hydrogen at lower energy demand.     

A comparative study of non-thermal plasma assisted reforming technologies

On board hydrogen production out of hydrocarbons (reforming) for fuel cells feed is subject to problems when used with traditional catalysts. High device weight, a relatively long transient time and poisoning problems make the integration onboard a vehicle complex. In response to these challenges, hydrocarbons reforming processes assisted by non-thermal plasmas for hydrogen production have been implemented over recent years. This paper aims to provide an overview of the setting up, feasibility and efficiency of the existing technologies here investigated. This state-of-the-art technology review explains the key characteristics of plasma reforming through various original approaches. The performances of some of the systems are then compared against each other and discussed.     

Plasma dry reforming of methane in an atmospheric pressure AC gliding arc discharge: Co-generation of syngas and carbon nanomaterials

An alternating-current (AC) gliding arc reactor has been developed offering a new route for the co-generation of syngas and value-added carbon nanomaterials by plasma dry reforming of methane. Different carbon nanostructures including spherical carbon nanoparticles, multi-wall carbon nanotubes and amorphous carbon have been obtained as by-products of syngas generation in the plasma system. Optical emission spectra of the discharge demonstrate the formation of different reactive species (Al, CO, CH, C₂, H_α, H_β and O) in the plasma dry reforming reaction. The effect of different operating parameters (feed flow rate, input power and CH₄/CO₂ molar ratio) on the performance of the plasma process has been evaluated in terms of the conversion of feed gas, product selectivity and energy conversion efficiency. It is interesting to note that gliding arc plasma can be used to generate much cleaner gas products of which syngas is the main one. The results also show that the energy efficiency of dry reforming using gliding arc plasma is an order of magnitude higher than that for processing using dielectric barrier or corona discharges. Both of these can be attributed to the higher electron density in the order of 10²³ m⁻³ generated in the gliding arc plasma.     

Experimental study of hydrogen production from reforming of methane and ammonia assisted by Laval nozzle arc discharge

The production of hydrogen from hydrogen compounds for fuel cell or internal combustion engine applications is a potential method for responding to the energy crisis and environmental problems. In this work carbon dioxide reforming of methane and decomposition of ammonia using a Laval nozzle arc discharge (LNAD) reactor has been exploited at atmospheric pressure without external heating or catalysts. CH₄ (or NH₃) conversion and H₂ selectivity were observed to be negatively correlated with the concentration of CH₄ (or NH₃) and the flux of CO₂ (N₂) and positively correlated with voltage and the Laval nozzle throat radius. Power consumption increased with the concentration of methane at the same CO₂ flow rate, and the conversion of methane gradually increased with the content of water vapor in the gas mixture. A high conversion rate and fair H₂ selectivity were achieved, 51% and 37.5%, respectively, when the methane and carbon dioxide flow rates were 4 L/min and 14 L/min, respectively, and the minimum distance between the two electrodes was 2.5 mm. The LNAD reactor used in this study exhibited a good conversion rate and low energy consumption, which should be suitable for the industrial scale-up of the system.     

Experimental investigation of hydrogen production by CH4–CO2 reforming using rotating gliding arc discharge plasma

Hydrogen produced from CH₄–CO₂ reforming by an optimized rotating gliding arc discharge plasma reactor is investigated in this study. The effect of CH₄/CO₂ ratio (mole ratio), total input flow rate, discharge gap, voltage, and discharge frequency are analyzed. The results show that H₂ yield increases with the increase of CH₄/CO₂ ratio. Arc can be stretched effectively by increasing total input flow rate, then the discharge region is enlarged. Increasing discharge gap can enlarge the discharge region, but the reaction of the gas mixture would be suppressed if the discharge region was excessively large. The discharge region decreases with the increased discharge frequency to a certain degree. Based on the experimental results, the optimal experimental condition is concluded as applied voltage 60 V, discharge frequency 20 kHz, and minimum discharge gap 3 mm. It is anticipated that the results would serve as a good guideline to the application of hydrogen production from hydrocarbon fuels by plasma reforming onboard.     

Production of hydrogen via methane reforming using atmospheric pressure microwave plasma

In this paper, results of hydrogen production via methane reforming in the atmospheric pressure microwave plasma are presented. A waveguide-based nozzleless cylinder-type microwave plasma source (MPS) was used to convert methane into hydrogen. Important advantages of the presented waveguide-based nozzleless cylinder-type MPS are: stable operation in various gases (including air) at high flow rates, no need for a cooling system, and impedance matching. The plasma generation was stabilized by an additional swirled nitrogen flow (50 or 100 l min⁻¹). The methane flow rate was up to 175 l min⁻¹. The absorbed microwave power could be changed from 3000 to 5000 W. The hydrogen production rate and the corresponding energy efficiency in the presented methane reforming by the waveguide-based nozzleless cylinder-type MPS were up to 255 g[H₂] h⁻¹ and 85 g[H₂] kWh⁻¹, respectively. These parameters are better than those typical of the conventional methods of hydrogen production (steam reforming of methane and water electrolysis).     

Oxidative steam reforming of ethanol over a Pt/Al2O3 catalyst in a Pd-based membrane reactor

In this study, the ability of a Pd-Ag membrane reactor of producing ultrapure hydrogen via oxidative steam reforming of ethanol has been evaluated. A self supported Pd-Ag tube of wall thickness 60 μm has been filled with a commercial Pt-based catalyst and assembled into a membrane module in a finger-like configuration. In order to evaluate the hydrogen yield behavior under different operating conditions, experimental tests have been performed at temperatures of 400 and 450 °C and pressures of 150 and 200 kPa. The oxidative steam reforming of ethanol has been carried out by feeding the membrane reactor with a gas stream containing a dilute water-ethanol mixture and air. Different water/ethanol feed flow rates (5, 10, 15 g h⁻¹), several water/ethanol (4, 10, 13) and oxygen/ethanol (0.3, 0.5, 0.7) feed molar ratios have been tested. The results pointed out that the highest hydrogen yield (moles of permeated hydrogen per mole of ethanol fed) corresponding to almost 4.1 has been attained at 450 °C and 200 kPa of lumen pressure by using a water/ethanol/oxygen feed molar ratio of 10/1/0.5.The results of these tests have been compared with those reported for the ethanol steam reforming in a Pd-Ag membrane reactor filled with the same Pt-based catalyst. This comparison has shown a positive effect on the hydrogen yield of small oxygen addition in the feed stream.     

Reaction mechanism of naphtha steam reforming on nickel-based catalysts,and FTIR spectroscopy with CO adsorption to elucidate real active sites

To improve the understanding of the hydrocarbon steam reforming reaction mechanism and the nature of the active sites, different nickel-based catalysts have been synthesized and studied under several reaction conditions. Catalysts from hydrotalcite precursors show better activity and higher coking resistance than traditionally prepared samples. Furthermore, introducing additives (Ce, Li or Co) in the hydrotalcite structure produces no blockage of the nickel active sites. Different structural and physical–chemical properties have been analyzed by XRD, TPR, BET and elemental analysis. FTIR spectroscopy with CO adsorption reveals interesting catalyst structure–catalytic behavior relationships; oxygen release through the catalyst surface is key parameter to improve steam reforming activity and coking resistance; and, highly unsaturated Ni surface atoms located on the metal–support interphase are relevant structures to the catalysis and most active sites for the steam reforming reaction. Steam reforming reaction proposed sequence involves: 1) hydrocarbon preferably activation on active Ni surface sites and steam preferred activation on basic support surface sites, 2) oxygen spill-over from the support to the metal phase, and 3) reaction between carbon and oxygen species occurring on the metal–support interphase.     

滑动弧等离子体协助甲烷蒸汽重整制氢

采用甲烷为主要原料,在常温和常压条件下,利用滑动弧等离子体放电技术,进行了甲烷与空气、水蒸气重整反应的试验。试验研究了过量空气系数、反应气流量和水蒸气含量等参数对甲烷与空气、水蒸气重整反应的影响,并对重整副产物进行了分析。试验表明,当过量空气系数为0.8时,氢气选择性最高可达到45.9%;反应气流量达到14L/min时,单位氢气生产成本最低;在反应气中加入一定量的水蒸气,有利于重整反应的进行。     

Hydrogen production via catalytic pulsed plasma conversion of methane: Effect of Ni–K2O/Al2O3 loading,applied voltage,and argon flow rate

Despite industrial application of methane as an energy source and raw material for chemical manufacturing, it is a potent heat absorber and a strong greenhouse gas. Evidently reduction of methane emission especially in the natural gas sector is essential. Methane to hydrogen conversion through non-thermal plasma technologies has received increasing attention. In this paper, catalytic methane conversion into hydrogen is experimentally studied via nano-second pulsed DBD plasma reactor. The effect of carrier gas flow, applied voltage, and commercial Ni–K₂O/Al₂O₃ catalyst loading on methane conversion, hydrogen production, hydrogen selectivity, discharge power, and energy efficiency are studied. The results showed that in the plasma alone system, the highest methane conversion and hydrogen production occurs at argon flow rate of 70 mL/min. Increase in the applied voltage increases the methane conversion and hydrogen production while it decreases the energy efficiency. Presence of 1 g Ni–K₂O/Al₂O₃ catalyst shifts the optimum voltage for methane conversion and hydrogen production to 8 kV, reduces the required power, and increases the energy efficiency of the process. Finally in the catalytic plasma mode the optimum process condition occurs at the argon flow rate of 70 mL/min, applied voltage of 8 kV, and catalyst loading of 6 g. Compared with the optimum condition in the absence of catalyst, presence of 6 g Ni–K₂O/Al₂O₃ catalyst increased the methane conversion, hydrogen production, hydrogen selectivity and energy efficiency by 15.7, 22.5, 7.1, and 40% respectively.     

Thermodynamic equilibrium composition analysis of methanol autothermal reforming for proton exchanger membrane fuel cell based on FLUENT Software

Methanol autothermal reforming was thermodynamically analyzed using FLUENT software. The calculation methodology using this software is simple and convenient, and its validity was confirmed by comparing the obtained data with previous studies. As a function of the effects of temperature, pressure, molar steam-to-carbon ratio (S/C), and molar oxygen-to-carbon ratio (O/C) on the objective products, favorable operational parameters were evaluated, under which H₂ yield maximizes, the CO molar fraction minimizes and carbon deposition can be eliminated. The equilibrium constants of the possible reactions involved in oxidative methanol steam reforming, coupled with the reaction mechanism for the entire investigated temperature range, were elucidated and discussed. On the basis of the concluded possible mechanisms, three areas are inferred. In each individual area, H₂ or CO yield reached a maximum, or solid C was efficiently suppressed. Therein, a favorable operational range is proposed to assure the most optimized product yield.