Hydrogen production from methane hydrate with sequestering of carbon dioxide

Methane hydrate exists in large amounts in certain locations, in sea sediments and the geological structures below them and below artic regions permafrost, at low temperature and high pressure. It has recently been shown that there are suitable methods for producing methane, perhaps on a floating platform. There it could be reformed in an endothermic process to produce hydrogen and carbon dioxide. Some of the methane could be used to provide heat energy for a power plant on the platform to provide all needed power and support for the reforming process. After separation, hydrogen is the valuable and transportable product. All carbon dioxide produced on the platform could be separated from other gases and then sequestered, in one of several possible forms. In this way, hydrogen could be made available without the release of carbon dioxide to the atmosphere and the hydrogen could be an enabling step toward a world hydrogen economy, free of particles and carbon dioxide pollution.     

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).     

Reforming of methane and carbon dioxide by DC water plasma at atmospheric pressure

An experimental plasma chemical reactor, equipped with a novel water plasma torch, was used for reforming methane and carbon dioxide mixture to produce synthesis gas (syngas). Water plasma is generated by the torch at atmospheric pressure, in the absence of carrier gases, water cooling system and special steam supply system. The influence of the ratio of CO₂ to CH₄ and total feed gas rate on syngas production, composition and energy conversion efficiency were investigated. Compared to other plasma technologies, the higher reaction performance was obtained by the novel water plasma process. The results show that, under optimum experimental conditions, the energy conversion efficiency reaches up to maximum value of 1.87 mmol/kJ and the highest energy efficiency of 74.63% is achieved, which is higher than that of other plasma processes. Furthermore, the obtained syngas with high mole ratio of H₂ to CO (close to 2) is suitable for the direct industrial application.     

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.     

Hydrogen production by coupled catalytic partial oxidation and steam methane reforming at elevated pressure and temperature

Hydrogen production by coupled catalytic partial oxidation (CPO) and steam methane reforming of methane (OSMR) at industrial conditions (high temperatures and pressures) have been studied over supported 1 wt.% NiB catalysts. Mixture of air/CH₄/H₂O was applied as the feed. The effects of O₂:CH₄ ratio, H₂O:CH₄ ratio and the gas hourly space velocity (GHSV) on oxy-steam reforming (OSRM) were also studied. Results indicate that CH₄ conversion increases significantly with increasing O₂:CH₄ or H₂O:CH₄ ratio. However, the hydrogen mole fraction goes through a maximum, depending on reaction conditions, e.g., pressure, temperature and the feed gases ratios. Carbon deposition on the catalysts has been greatly decreased after steam addition. The supported 1 wt.% NiB catalysts exhibit high stability with 85% methane conversion at 15 bar and 800 °C during 70 h time-on-stream reaction (CH₄:O₂:H₂O:N₂ = 1:0.5:1:1.887). The thermal efficiency was increased from 35.8% by CPO (without steam) to 55.6%. The presented data would be useful references for further design of enlarged scale hydrogen production system.     

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.     

Hydrogen production by methane decomposition using bimetallic Ni–Fe catalysts

The catalytic methane decomposition is the leading method for CO_x-free hydrogen and carbon nanomaterial production. In the present study, calcium-silicate based bimetallic Ni–Fe catalysts have been prepared and used to decompose the methane content of the ‘product gas’ obtained in the biomass gasification process for increasing total hydrogen production. Al₂O₃ was used as secondary support on calcium silicate based support material where Ni or Ni–Fe were doped by co-impregnation technique. The activity of catalysts was examined for diluted 6% methane-nitrogen mixture in a tubular reactor at different temperatures between 600 °C and 800 °C under atmospheric pressure, and data were collected using a quadrupole mass spectrometer. Catalysts were characterized by XRD, SEM/EDS, TEM, XPS, ICP-MS, BET, TPR, and TGA techniques. The relation between structural and textural properties of catalysts and their catalytic activity has been investigated. Even though the crystal structure of catalysts had a significant effect on the activity, a direct relation between the BET surface area and the activity was not observed. The methane conversion increased by increasing temperature up to 700 °C. The highest methane conversion has been obtained as 69% at 700 °C with F3 catalyst which has the highest Fe addition, and the addition of Fe improved the stability of catalysts. Moreover, carbon nanotubes with different diameter were formed during methane decomposition reaction, and the addition of Fe increased the formation tendency.     

Ni-based catalysts with coke resistance enhance by radio frequency discharge plasma for CH4/CO2 reforming

Coke deposition has been considered to be one of the most important reasons hindering the stability of the catalyst during CH₄/CO₂ reforming. In this study, after the addition of P123 (PEG-PPG-PEG triblock copolymer), Ni²⁺ can be well-dispersed on the mesoporous molecular sieve MCM-41. And then, the catalysts were prepared by using N₂ radio frequency (RF) discharge plasma for different treatment times to reduce the size of Ni particles, improve the anti-coking performance, and thereby improve the stability of the catalyst. The results showed that the catalyst NM-P123-PN2h exhibits superior catalytic properties in the CH₄/CO₂ reforming. The initial conversions of CH₄ and CO₂ were 90.80% and 89.60% at 750 °C, respectively. The catalyst NM-P123-PN2h showed highly coke resistance with less carbon deposition (1.12%) at 750 °C after 10 h of continuous reaction, while the carbon deposition of the catalyst NM-C was 37.32%. Compared with the traditional calcination method, the catalyst prepared by plasma treatment has a smaller particle size and better dispersibility of nickel. In particular, the nickel particle size of the catalyst NM-C was 8.37 nm, however, that of the catalyst NM-P123-PN2h was only 1.70 nm, and the nickel particle size was reduced by 5 times. Therefore, it can be concluded that the catalyst prepared under the combined action of P123 and RF plasma-treated can effectively improve the coke resistance of the catalyst and the stability of the CH₄/CO₂ 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.     

Hydrogen production by low-temperature plasma decomposition of liquids

The paper shows, that a low-temperature plasma initiated in liquid media in interelectrode discharge gap is able to decompose hydrogen containing organic molecules resulting in obtaining gaseous products with volume part of hydrogen higher than 90% (up to gas chromatography data). Tentative assessments of energy efficiency, calculated with regard for hydrogen and feedstock heating value and energy consumption, have shown efficiency factor of 60–70%, depending on the source mixture composition. Theoretical model calculations of discharge current and voltage have been performed; the values are in good accordance with experimental data.     

Hydrogen production by methane decomposition: A review

Methane decomposition can be utilized to produce CO_X-free hydrogen for PEM fuel cells, oil refineries, ammonia and methanol production. Recent research has focused on enhancing the production of hydrogen by the direct thermocatalytic decomposition of methane to form elemental carbon and hydrogen as an attractive alternative to the conventional steam-reforming process. In this context, we review a comprehensive body of work focused on the development of metal or carbonaceous catalysts for enhanced methane conversion and on the improvement of long-term catalyst stability. This review also evaluates the roles played by various parameters, such as temperature and flow rate, on the rate of hydrogen production and the characteristics of the carbon produced. The heating source, type of reactor, operating conditions, catalyst type and its preparation, deactivation and regeneration and the formation and utilization of the carbon by-product are discussed and classified in this paper. While other hydrogen production methods, economic aspects and thermal methane decomposition methods using alternative heating sources such as solar and plasma are briefly presented in this work where relevant, the review focuses mainly on the thermocatalytic decomposition of methane using metal and carbonaceous catalysts.     

Hydrogen production by methane cracking using Ni-supported catalysts in a fluidized bed

Nickel, supported on porous alumina (γAl₂O₃), non-porous alumina (αAl₂O₃), and porous silica, was used to catalyze methane cracking in a fluidized bed reactor for hydrogen production. The effects of temperature, PCH₄${\text{P}}_{{\text{CH}}_4}$, and particle diameter, and their interactions, on methane conversion were studied with each catalyst. Temperature was the dominant parameter affecting the hydrogen production rate for all catalysts and particle diameter had the strongest effect on the total amount of carbon deposited. Maximum methane conversion as a function of support type followed the order Ni/SiO₂ > Ni/αAl₂O₃ > Ni/γAl₂O₃. Nonetheless, better fluidization quality was obtained with Ni/γAl₂O₃. Methane conversion was increased by increasing temperature and particle size from 108 to 275 μm due to better fluidization achieved with 275 μm particles. Increasing the flow rate and methane partial pressure (PCH₄${\text{P}}_{{\text{CH}}_4}$) caused a drop in methane conversion. Tests were also run in a fixed bed reactor, and at constant weight hourly space velocity (WHSV), higher conversion was achieved in the fixed bed, but at the same time faster deactivation occurred since a higher methane conversion led to increase in carbon filament and encapsulating carbon formation rates. A critical problem with the fixed bed was the pressure build-up inside the reactor due to carbon accumulation. Finally, a series of cracking/regeneration cycle experiments were carried out in the fluidized bed reactor. The regeneration was performed through product carbon gasification in air. Ni/αAl₂O₃ and Ni/γAl₂O₃ activity decreased significantly with the first regeneration, which is attributed to Ni sintering during exothermic regeneration/carbon oxidation. However, Ni/SiO₂ was thermally stable over at least three cracking/regeneration cycles, but mechanical attrition was observed.     

Hydrogen production by catalytic methane decomposition over yttria doped nickel based catalysts

Catalytic methane decomposition can become a green process for hydrogen production. In the present study, yttria doped nickel based catalysts were investigated for catalytic thermal decomposition of methane. All catalysts were prepared by sol-gel citrate method and structurally characterized with X-ray powder diffraction (XRD), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and Brunauer, Emmet and Teller (BET) surface analysis techniques. Activity tests of synthesized catalysts were performed in a tubular reactor at 500 ml/min total flow rate and in a temperature range between 390 °C and 845 °C. In the non-catalytic reaction, decomposition of methane did not start until 880 °C was reached. In the presence of the catalyst with higher nickel content, methane conversion of 14% was achieved at the temperature of 500 °C. Increasing the reaction temperature led to higher coke formation. Lower nickel content in the catalyst reduced the carbon formation. Consequently, with this type of catalyst methane conversion of 50% has been realized at the temperature of 800 °C.     

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.     

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.     

Hydrogen addition effect on NO formation in methane/air lean-premixed flames at elevated pressure

The present study investigates freely propagating methane/hydrogen lean-premixed laminar flames at elevated pressures to understand the hydrogen addition effect of natural gas on the NO formation under the conditions of industrial gas turbine combustors. The detailed chemical kinetic model which was used in the previous study on the NO formation in high pressure methane/air premixed flames was adopted for the present study to analyze NO formation of methane/hydrogen premixed flames. The present mechanism shows good agreement with experimental data for methane/hydrogen mixtures, including ignition delay times, laminar burning velocities, and NO concentration in premixed flames. Hydrogen addition to methane/air mixtures with maintaining methane content leads to the increase of NO concentration in laminar premixed flames due to the higher flame temperature. Methane/hydrogen/argon/air premixed flames are simulated to avoid the flame temperature effect on NO formation over a pressure range of 1–20atm and equivalence ratio of 0.55. Kinetic analyses shows that the N₂O mechanism is important on NO formation for lean flames between the reaction zone and postflame region, and thermal NO is dominant in the postflame zone. The hydrogen addition leads to the increase of NO formation from prompt NO and NNH mechanisms, while NO formation from thermal and N₂O mechanisms are decreased. Additionally, the NO formation in the postflame zone has positive pressure dependencies for thermal NO with an exponent of 0.5. Sensitivity analysis results identify that the initiation reaction step for the thermal NO and the N₂O mechanism related reactions are sensitive to NO formation near the reaction zone.     

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.     

Hydrogen and methane production from lipid-extracted microalgal biomass residues

A two-stage process to produce hydrogen and methane from lipid-extracted microalgal biomass residues (LMBRs) was developed. The biogas production and energy efficiency were compared between one- and two-stage processes. The two-stage process generated 46 ± 2.4 mL H₂/g-volatile solid (VS), and 393.6 ± 19.5 mL CH₄/g-VS. The methane yield was 22% higher than the one in the one-stage process. Energy efficiency increased from 51% in the one-stage process to 65% in the two-stage process. Additionally, it was found that repeated batch cultivation was a useful method to cultivate the cultures to improve the methane production rate and reduce the fermentation time. In the repeated batch cultivation, the methane yield slightly decreased if the ammonia levels rose, suggesting that the accumulation of ammonia could affect methane production.     

H2 production from methane decomposition by fullerene at low temperature

Carbon materials have previously been reported to work as catalysts for hydrogen (H₂) production from hydrocarbons. Mechanisms of the catalytic behavior of graphite and carbon black (CB) have often been discussed in literature. Graphite and CB is constructed from mainly 6-membered rings with sp² bonds. To understand the catalytic behavior of carbon materials for H₂ production by methane (CH₄) decomposition, the catalytic behavior of fullerenes with 6-membered rings and also those comprising 5- and 7-membered rings with sp² bonds and their associated mechanisms should be investigated. In this study, the fullerene catalyst activity has been investigated using gas chromatography and the electronic states and nanoscale structures have been analyzed.H₂ production started at 400 °C and the H₂ production rate gradually increased with time, and the activation energy of the fullerene for H₂ production by CH₄ decomposition was found to be 166 kJ/mol. Moreover, in situ heating X-ray photon spectroscopy (XPS) measurements showed that the π-π1 transition signal becomes stronger with increasing temperature above the threshold of 300 °C. The transition of the π electrons to π1 orbitals upon heating is expected to decompose CH₄ absorbed on fullerene. Moreover, transmission electron microscopy (TEM) analysis revealed that the generated carbon atoms from the CH₄ decomposition were deposited onto the surfaces of the fullerenes, forming amorphous and layered concentric sphere carbon. Amorphous carbon is reported to not work as a catalyst for CH₄ decomposition at around 400 °C. From XPS analysis and TEM observations of these two structures, it is anticipated that the ring structures without 6-membered rings in carbon materials with sp² bonding contribute to this catalytic behavior for CH₄ decomposition at a low temperature of 400 °C.