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).     

Atmospheric pressure microwave plasma source for hydrogen production

Nowadays hydrogen is considered as a clean energy carrier and fuel of the future. That is why the interest in production and storage of hydrogen is still increasing. One of the promising technology is using microwave plasma for hydrogen production. In this study we propose two types of an atmospheric pressure microwave plasma source (MPS) for hydrogen production via methane conversion. The first one was a nozzleless waveguide-supplied coaxial-line-based. The second one was a nozzleless waveguide-supplied metal-cylinder-based. They can be operated with microwave frequency of 2.45 GHz and power up to a few kW with a high gas flow rates (up to several thousands l/h). We present experimental results concerning electrical properties of the MPS, plasma visualization, spectroscopic diagnostics and hydrogen production. The experiment was carried out with methane flow rate up to 12,000 l/h. An additional nitrogen or carbon dioxide swirl flow was used. The absorbed microwave power was up to 5000 W. Our experiments show that MPSs presented in this paper have a high potential for hydrogen production via hydrocarbon conversion.     

Characteristics of methane wet reforming driven by microwave plasma in liquid phase for hydrogen production

Discharge plasma reforming of methane to produce hydrogen has been a hotspot in recent years. At present, there is no report on liquid-phase discharge for methane reforming. In this paper, directly coupled liquid-phase microwave discharge plasma (LPMDP) is used for the first time to realize liquid-phase methane wet reforming to produce hydrogen. When methane gas is injected into the water in the reactor, plasma is generated in the water by microwave discharge. The type and relative intensity of active radicals produced during discharge are detected by emission spectroscopy. Methane gas is introduced into the reactor through two electrode structures. When the microwave power was 900 W, the optimal methane conversion rate reached 94.3%, and the highest concentration of hydrogen reached 74.0%. In addition, through the optimization of the electrode structure, while improving the stability of the plasma system, the higher yield of hydrogen and energy efficiency of hydrogen production were obtained, and the highest energy efficiency of hydrogen production was approximately 0.92 mmol/kJ. This investigation provides a new method for hydrogen production by liquid-phase plasma methane wet reforming.     

An experimental investigation of reverse vortex flow plasma reforming of methane

This paper focuses on the reforming of methane into hydrogen rich gas by means of gliding arc plasma stabilized in a reverse vortex flow. Parametric tests utilizing a 42 mm diameter reactor investigated the effects of electrode gap distance, reaction chamber exit diameter, steam input, methane input (fuel to oxygen ratio), and power input. Over the range of conditions tested, reactor performance was most sensitive to methane input. Decreasing the diameter of the reaction chamber exit impeded the performance of the reformer. A set of factorial tests determined the optimal operating conditions of the system to be at flow rates of 2 slpm nitrogen, 0.56 slpm oxygen, 1.25 slpm methane, an electrode gap distance of 34.5 mm, an outlet diameter of 12.65 mm, and a power input of 260 W. At these conditions the system yielded 83.3% hydrogen selectivity, 79.8% methane conversion and efficiency of 43.5%. Physical operating boundaries of the system defined by soot production and arc extinction were identified.     

Technoeconomic analysis of hydrogen production via hydrogen sulfide methane reformation

Feasibility analysis of methane reforming by hydrogen sulfide for hydrogen production from technical and economical viewpoints was made. An improved Hydrogen Sulfide Methane Reformation (H₂SMR) process flowsheet was proposed in order to compare its production costs with those of Steam Methane Reformation (SMR) conventional process. Major findings were: high production of hydrogen, a partial self-sustainability process since some of the hydrogen produced could be used as an energy source, no greenhouse gases generated, common sizes of main equipment for a typical H₂ production and the possibility of eliminating Claus plants. Aspen Plus^® V8.4 simulation software was used. Results showed H₂SMR is a more economical source of H₂ production than SMR conventional process, with an estimated cost of 1.41 $/kg.     

Pyrolysis of methane via thermal steam plasma for the production of hydrogen and carbon black

Methane pyrolysis for the production of hydrogen and solid carbon was studied in plasma reactor PlasGas equipped with a DC plasma torch with the arc stabilized by a water vortex. Steam plasma is produced by direct contact of electric arc discharge with water surrounding the arc column in a cylindrical torch chamber. The composition of the gas produced was compared with the results of the equilibrium calculations for different flow rates of input methane. We have found that for the net plasma power 52 kW the optimal flow rate of the input methane was between 200 slm and 300 slm, for which high methane conversions of 75% and 80% are achieved. For the flow rate of 500 slm, the methane conversion is only 60%; however, the output still consists of a mixture of hydrogen, methane and solid carbon, without other unwanted components. For the flow rate of 100 slm, the methane conversion is 88%. For 100 and 200 slm of input methane the energy excess for the reaction with respect to the calculated value is 16 kW and 4 kW. On the other hand, for 300 and 500 slm of input methane we have the energy lack of 10 kW and 38 kW. The solid carbon produced was composed of well-defined spherical particles of the size about 1 μm. Comparison with the steam and dry reforming of methane in the same system shows that the presence of oxygen increases the methane conversion, despite lower available energy produced.     

Thermodynamic analysis of autothermal reforming of methane via entropy maximization: Hydrogen production

In this work a thermodynamic analysis of the autothermal reforming (ATR) of methane was performed. Equilibrium calculations employing entropy maximization were performed in a wide range of oxygen to methane mole ratio (O/M), steam to methane ratio (S/M), inlet temperature (IT), and system pressure (P). The main calculated parameters were hydrogen yield, carbon monoxide formation, methane conversion, coke formation, and equilibrium temperature. Further, the optimum operating oxygen to methane feed ratio that maximizes hydrogen production, at P = 1 bar, has been calculated. The nonlinear programming problem applied to the simultaneous chemical and phase equilibrium calculation was implemented in GAMS^®, using CONOPT2 solver. The maximum amount of hydrogen obtained was in the order of 3 moles of hydrogen per mole of fed methane at IT = 1000 °C, P = 1 bar, S/M = 5, and O/M = 0.18. Experimental literature data are in good agreement with calculation results obtained through proposed methodology.     

Hydrogen production from methanol reforming in microwave “tornado”-type plasma

A microwave (2.45 GHz) “tornado”-type plasma with a high-speed tangential gas injection (swirl) at atmospheric pressure conditions has been applied for methanol reforming. The vortex gas flow “detaches” the hot plasma core from the wall and stable operation of the plasma source has been achieved. The hydrogen production rate dependence on the partial methanol flux has been investigated both in Ar and Ar + water plasma environments. Hydrogen, carbon oxide and carbon dioxide are the main decomposition products. Mass and FT-IR spectroscopy have been used to detect the species in the outlet gas stream. It has been found that the hydrogen production rate increases by nearly a factor of 1.5 when water is added into the plasma. Higher energetic hydrogen mass yield is achieved when compared with the results obtained under laminar gas flow conditions. Practically 100% methanol conversion rate has been achieved. Moreover, optical emission spectroscopy has been applied to determine the gas temperature, the electron density and the radiative species present in the plasma. A theoretical model based on a set of equations describing the chemical kinetics and the gas thermal balance equation has been developed. The theoretical results on the decomposition products agree well with the experimental ones and confirm that microwave plasma decomposition of methanol is a temperature dependent process. The results clearly show that this type of plasma is an efficient tool for hydrogen production.     

Effect of gas temperature on partial oxidation of methane in plasma reforming

Plasma-reforming process has been widely studied for over a decade, with a focus on diverse fuels and plasma parameters for finding the optimum conditions. This study evaluates the effect of thermal activation on the chemistry and energy efficiency of the methane-reforming process. Based on the empirical evaluation, a correlation was found among the methane conversion rate, reaction composition, reactant temperature, and plasma power. Moreover, the plasma chemistry did not change with the reactant temperature within the temperature range evaluated. In addition, it was found that the ratio of the plasma power to the heating input power was an important parameter for enhancing the efficiency of the partial oxidation of methane.     

Hydrogen and syngas production from glycerol through microwave plasma gasification

Glycerol which is a byproduct of biodiesel production is considered as a potential feedstock for syngas production with the increase of biodiesel demand. In this study, the characteristics of glycerol gasification under a microwave plasma torch with varying oxygen and steam supply conditions were investigated. The experimental results demonstrated that the gasification efficiency and syngas heating value increased with the supplied microwave power while the increase of oxygen and steam led to a lower gasification performance. In order to achieve high carbon conversion and cold gas efficiency in the microwave plasma gasification of glycerol, the O₂/fuel ratio should be maintained at 0–0.4. It was revealed that the fuel droplet size and the mixing effect and retention time inside the plasma flames are critical factors that influence the product gas yield and gasification efficiency. This study verified that syngas with a high content of H₂ and CO could be effectively produced from glycerol through microwave plasma gasification.     

Application of atmospheric pressure microwave plasma source for hydrogen production from ethanol

In contrast to conventional technologies of hydrogen production like water electrolysis or coal gasification we propose a method based on the atmospheric pressure microwave plasma. In this paper we present results of the experimental investigations of the hydrogen production from ethanol in the atmospheric pressure plasma generated in waveguide-supplied cylindrical type nozzleless microwave (915 MHz and 2.45 GHz) plasma source (MPS). Argon, nitrogen and carbon dioxide were used as a working gas. All experimental tests were performed with the working gas flow rate Q ranged from 1500 to 3900 NL/h and absorbed microwave power P_A up to 6 kW. Ethanol was introduced into the plasma as vapours carried with the working gas. The process resulted in the ethanol conversion rate greater than 99%. The hydrogen production rate was up to 210 NL[H₂]/h and the energy efficiency was 77 NL[H₂] per kWh of absorbed microwave energy.     

Effect of microwave plasma torch on the pyrolysis fuel oil in the presence of methane and ethane to increase hydrogen production

Pyrolysis fuel oil (PFO) processing by microwave plasma torch was developed for the production of hydrogen. The PFO cracking process was performed at atmospheric pressure in the absence of catalyst and effect of plasma gas on the production rate of hydrogen and light hydrocarbons (C₂–C₄) was evaluated. In the first step, effect of the applied power and the working gas flow rate was investigated. In the second step, the applied power and working gas rate were set to 650 W and 4000 sccm, respectively, which were provided by combining methane or ethane as 0%, 2.5%, 7.5%, and 20% with argon. By increasing the percentage of the existing methane in argon, production rate of the sum of the light hydrocarbons was increased and that of hydrogen was reduced, but it was more than the case when argon was applied alone. By increasing ethane percentage, hydrogen production and light hydrocarbon rate were increased. The best conditions of the plasma gas for producing hydrogen at the power of 650 W were obtained as 5CC PFO feed, 2500 sccm (80%) argon, and 500 sccm (20%). The hydrogen production rate in optimized conditions was 2343.16SCCM with selectivity of 84.41%. Sum of the obtained hydrocarbons in this test was 434.25 sccm. Another parameter in the present study was the feed volume processed by plasma. In this case, 5 cc, 3 cc, and 1 cc of the feed were tested when the plasma gas was 3000 sccm argon with the power of 650 W. The results showed that, by increasing the feed, the products were increased. In the processing of 5 cc feed with plasma, 896.41 sccm hydrogen and 61 sccm light hydrocarbon were produced.     

An energy-efficient plasma methane pyrolysis process for high yields of carbon black and hydrogen

A novel thermal plasma process was developed, which enables economically viable commercial-scale hydrogen and carbon black production. Key aspects of this process are detailed in this work. Selectivity and yield of both solid, high-value carbon and gaseous hydrogen are given particular attention. For the first time, technical viability is demonstrated through lab scale reactor data which indicate methane feedstock conversions of >99%, hydrogen selectivity of >95%, solid recovery of >90%, and the ability to produce carbon particles of varying crystallinity having the potential to replace traditional furnace carbon black. The energy intensity of this process was established based on real-time operation data from the first commercial plant utilizing this process. In its current stage, this technology uses around 25 kWh per kg of H2 produced, much less than water electrolysis which requires approximately 60 kWh per kg of H2 produced. This energy intensity is expected to be reduced to 18–20 kWh per kg of hydrogen with improved heat recovery and energy optimization.     

Hydrogen production by radio frequency plasma stimulation in methane hydrate at atmospheric pressure

Methane hydrate, formed by injecting methane into 100 g of shaved ice at a pressure of 7 MPa and reactor temperature of 0 °C, was decomposed by applying 27.12 MHz radio frequency plasma in order to produce hydrogen. The process involved the stimulation of plasma in the methane hydrate with a variable input power at atmospheric pressure. It was observed that production of CH₄ is optimal at a slow rate of CH₄ release from the methane hydrate, as analyzed by in light of the steam methane reforming (SMR) and the methane cracking reaction (MCR) processes in accordance with the content of gas production. In comparison with the steam methane reforming (SMR), it was found that methane-cracking reaction (MCR) was dominant in conversion of CH₄ into hydrogen. An H₂ content of 55% in gas production was obtained from conversion of 40% of CH₄ at an input power of 150 W. The results clearly show that hydrogen can be directly produced from methane hydrate by the in-liquid plasma method.     

Improved configuration of supported nickel catalysts in a steam reformer for effective hydrogen production from methane

The heat and mass transfer characteristics in a steam reformer are investigated via experimental and numerical approaches and a new configuration of packed catalysts is proposed for effective hydrogen production. Prior to the numerical investigation, parametric studies are carried for the furnace temperature, steam-to-carbon (S:C) ratio, and gas flow rate. After validation of the developed code, numerical work is undertaken to determine the relationship of the operating parameters. Based on the experimental and numerical results, and with the goal of obtaining optimum heat transfer characteristics and an efficient catalyst array, a new configuration for the packed bed is proposed and numerically investigated taking into account the endothermicity of the steam reforming reaction. A bed packed repeatedly with inert and active catalysts is found to be an efficient means to obtain the same, or better, hydrogen production with small amounts of the active catalysts compared with a typical steam reformer.     

Design of an annular microchannel reactor (AMR) for hydrogen and/or syngas production via methane steam reforming

A bench-scale annular microchannel reactor (AMR) prototype with microchannel width of 0.3 mm and total catalyst length of 9.53 × 10⁻² m active for the endothermic steam reforming of methane is presented. Experimental results at a steam to methane feed molar ratio of 3.3:1, reactor temperature of 1023 K, and pressure of 11 bar confirm catalyst power densities upwards of 1380 W per cm³ of catalyst at hydrogen yields >98% of thermodynamic equilibrium. A two-dimensional steady-state computational fluid dynamic model of the AMR prototype was validated using experimental data and subsequently employed to identify suitable operating conditions for an envisioned mass-production AMR design with 0.3 mm annular channel width and a single catalyst length of 254 mm. Thermal efficiencies, defined based upon methane and product hydrogen higher heating values (HHVs), of 72.7–57.7% were obtained from simulations for methane capacities of 0.5–2S LPM (space velocities of 195,000–782,000 h⁻¹) at hydrogen yields corresponding to 99%–75% of equilibrium values. Under these conditions, analysis of local composition, temperature and pressure indicated that catalyst deactivation via coke formation or Nickel oxidation is not thermodynamically favorable. Lastly, initial analysis of an envisioned 10 kW autothermal reformer combining 19 parallel AMRs within a single methane-air combustion chamber, based upon existing manufacturing capabilities within Power & Energy, Inc., is presented.     

Hydrogen-rich syngas production through coal and charcoal gasification using microwave steam and air plasma torch

In the present study, microwave plasma gasification of two kinds of coal and one kind of charcoal was performed with various O₂/fuel ratios of 0–0.544. Plasma-forming gases used under 5 kW microwave plasma power were steam and air. The changes in the syngas composition and gasification efficiency in relation to the location of the coal supply to the reactor were also compared. As the O₂/fuel ratio was increased, the H₂ and CH₄ contents in the syngas decreased, and CO and CO₂ increased. When steam plasma was used to gasify the fuel with the O₂/fuel ratio being zero, it was possible to produce syngas with a high content of hydrogen in excess of 60% with an H₂/CO ratio greater than 3. Depending on the O₂/fuel ratio, the composition of the syngas varied widely, and the H₂/CO ratio necessary for using the syngas to produce synthetic fuel could be adjusted by changing the O₂/fuel ratio alone. Carbon conversion increased as the O₂/fuel ratio was increased, and cold gas efficiency was maximized when the O₂/fuel ratio was 0.272. Charcoal with high carbon and fixed carbon content had a lower carbon conversion and cold gas efficiency than the coals used in this study.     

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.     

New low cost mesoporous silica (MSN) as a promising support of Ni-catalysts for high-hydrogen generation via dry reforming of methane (DRM)

In this study, a new nano-sized mesoporous silica (MSN) as support for Ni-based catalysts was produced from natural resources and tested in the dry reforming of methane between 823 and 1023 K. The fresh and spent catalysts Ni-x/MSN (x = 5, 10 and 20 wt.%) were characterized by various techniques. All catalysts are selective for hydrogen production and exhibited long-term stability with low coke formation predominantly as carbon nanotubes, for Ni loadings less than 10% at 973 K. The catalytic results were correlated with the in situ generation of Ni nanoparticles which are highly dispersed on the MSN surface due to strong metal-support interactions thus preventing the sintering process. No significant deactivation was recorded along 25 h on stream meaning that the textural properties of the catalysts have not been altered by the coke deposition or reaction temperature. The prepared MSN is a potential support to be utilized for hydrogen generation.     

A model of steam reforming of iso-octane: The effect of thermal boundary conditions on hydrogen production and reactor temperature

Steam reforming of iso-octane in a monolithic type reactor was simulated by a three-dimensional computational fluid dynamics model. The variations of hydrogen production and reactor temperature along the length of the reactor were calculated at isothermal, adiabatic and constant heat flux conditions. The reaction rate expressions based on steam reforming of methane in the Langmuir-Hinshelwood format were used to model steam reforming of iso-octane. The difference between the simulated results and experimental data on hydrogen produced was less than 18%. The results indicated that a large drop in temperature was in the first one-tenth of the reactor under adiabatic conditions with inlet temperatures of 600–900 °C. To achieve the same mole fraction of hydrogen (0.27, dry basis) at the exit of the reactor, the maximum temperature difference across the reactor was much smaller at certain heat flux conditions than that at adiabatic conditions. Further, rate of hydrogen production may be evenly distributed in the reactor under certain conditions of constant heat flux.