Production of Hydrogen-Rich Syngas from Biogas Reforming with Partial Oxidation Using a Multi-Stage AC Gliding Arc System

The aim of this research work was to evaluate the possibility of upgrading the simulated biogas (70?% CH₄ and 30?% CO₂) for hydrogen-rich syngas production using a multi-stage AC gliding arc system. The results showed that increasing stage number of plasma reactors, applied voltage and electrode gap distance enhanced both CH₄ and CO₂ conversions, in contrast with the increases in feed flow rate and input frequency. The gaseous products were mainly H₂ and CO, with small amounts of C₂H₂, C₂H₄ and C₂H₆. The optimum conditions for hydrogen-rich syngas production using the four-stage AC gliding arc system were a feed flow rate of 150?cm³/min, an input frequency of 300?Hz, an applied voltage of 17?kV and an electrode gap distance of 6?mm. At the minimum power consumption (3.3?×?10^?18?W?s/molecule of biogas converted and 2.8?×?10^?18?W?s/molecule of syngas produced), CH₄ and CO₂ conversions were 21.5 and 5.7?%, respectively, H₂ and CO selectivities were 57.1 and 14.9?%, respectively, and H₂/CO (hydrogen-rich syngas) was 6.9. The combination of the plasma reforming and partial oxidation provided remarkable improvements to the overall process performance, especially in terms of reducing both the power consumption and the carbon formation on the electrode surface but the produced syngas had a much lower H₂/CO ratio, depending on the oxygen/methane feed molar ratio. The best feed molar ratio of O₂-to-CH₄ ratio was found to be 0.3/1, providing the CH₄ conversion of 81.4?%, CO₂ conversion of 49.3?%, O₂ conversion of 92.4?%, H₂ selectivity of 49.5?%, CO selectivity of 49.96?%, and H₂/CO of 1.6.     

Reforming of CO<Subscript>2</Subscript>-Containing Natural Gas Using an AC Gliding Arc System: Effects of Operational Parameters and Oxygen Addition in Feed

In this research, the reforming of simulated natural gas containing a high CO₂ content under AC non-thermal gliding arc discharge with partial oxidation was conducted at ambient temperature and atmospheric pressure, with specific regards to the concept of the direct utilization of natural gas. This work aimed at investigating the effects of applied voltage and input frequency, as well as the effect of adding oxygen on the reaction performance and discharge stability in the reforming of the simulated natural gas having a CH₄:C₂H₆:C₃H₈:CO₂ molar ratio of 70:5:5:20. The results showed marked increases in both CH₄ conversion and product yield with increasing applied voltage and decreasing input frequency. The selectivities for H₂, C₂H₆, C₂H₄, C₄H₁₀, and CO were observed to be enhanced at a higher applied voltage and at a lower frequency, whereas the selectivity for C₂H₂ showed an opposite trend. The use of oxygen was found to provide a great enhancement of the plasma reforming of the simulated natural gas. For the combined plasma and partial oxidation in the reforming of CO₂-containing natural gas, air was found to be superior to pure oxygen in terms of reactant conversions, product selectivities, and specific energy consumption. The optimum conditions were found to be a hydrocarbons-to-oxygen feed molar ratio of 2/1 using air as an oxygen source, an applied voltage of 17.5 kV, and a frequency of 300 Hz, in providing the highest CH₄ conversion and synthesis gas selectivity, as well as extremely low specific energy consumption. The energy consumption was as low as 2.73 × 10⁻¹⁸ W s (17.02 eV) per molecule of converted reactant and 2.49 × 10⁻¹⁸ W s (16.60 eV) per molecule of produced hydrogen.     

Ethylene Epoxidation in Low-Temperature AC Dielectric Barrier Discharge: Effects of Oxygen-to-Ethylene Feed Molar Ratio and Operating Parameters

Ethylene oxide (EO), a valuable chemical feedstock in producing many industrial chemicals, which is industrially produced by the partial oxidation of ethylene, so-called ethylene epoxidation, has been of great interest in many global research studies. In this work, the epoxidation of ethylene under a low-temperature dielectric barrier discharge (DBD) was feasibly investigated to find the best operating conditions. It was experimentally found that the EO yield decreased with increasing O₂/C₂H₄ feed molar ratio, feed flow rate, input frequency, and electrode gap distance, while it increased with increasing applied voltage up to 19 kV. The highest EO yield of 5.6% was obtained when an input frequency of 500 Hz and an applied voltage of 19 kV were used, with an O₂/C₂H₄ feed molar ratio of 1:1, a feed flow rate of 50 cm³/min, and an electrode gap distance of 10 mm. Under these best conditions, the power consumption was found to be as low as 6.07 × 10⁻¹⁶ Ws/molecule of EO produced.     

Ethylene Epoxidation in Low-Temperature AC Dielectric Barrier Discharge: Effect of Electrode Geometry

In this work, the epoxidation of ethylene under a cylindrical dielectric barrier discharge (DBD) reactor and a parallel DBD reactor was comparatively studied. The effects of important operating parameters—feed O₂/C₂H₄ molar ratio, applied voltage, input frequency, and residence time—were investigated on the reaction performance in terms of reactant conversions, product selectivities, product yields, and power consumptions per molecule of ethylene converted and per molecule of ethylene oxide produced. The optimum conditions obtained from the operating parameter investigation were used for a comparative performance evaluation of both DBD reactor systems. It was found that under the optimum conditions of each system, the cylindrical DBD system exhibited superior epoxidation performance for ethylene oxide production compared to the parallel DBD system, indicating that the electrode geometry (electrode edge length-to-electrode surface area ratio) plays a significant role in the ethylene epoxidation.     

Reforming of CO<Subscript>2</Subscript>-Containing Natural Gas Using an AC Gliding Arc System: Effect of Gas Components in Natural Gas

The objective of the present work was to study the reforming of simulated natural gas via the nonthermal plasma process with the focus on the production of hydrogen and higher hydrocarbons. The reforming of simulated natural gas was conducted in an alternating current (AC) gliding arc reactor under ambient conditions. The feed composition of the simulated natural gas contained a CH₄:C₂H₆:C₃H₈:CO₂ molar ratio of 70:5:5:20. To investigate the effects of all gaseous hydrocarbons and CO₂ present in the natural gas, the plasma reactor was operated with different feed compositions: pure CH₄, CH₄/He, CH₄/C₂H₆/He, CH₄/C₂H₆/C₃H₈/He and CH₄/C₂H₆/C₃H₈/CO₂. The results showed that the addition of gas components to the feed strongly influenced the reaction performance and the plasma stability. In comparisons among all the studied feed systems, both hydrogen and C₂ hydrocarbon yields were found to depend on the feed gas composition in the following order: CH₄/C₂H₆/C₃H₈/CO₂ > CH₄/C₂H₆/C₃H₈/He > CH₄/C₂H₆/He > CH₄/He > CH₄. The maximum yields of hydrogen and C₂ products of approximately 35% and 42%, respectively, were achieved in the CH₄/C₂H₆/C₃H₈/CO₂ feed system. In terms of energy consumption for producing hydrogen, the feed system of the CH₄/C₂H₆/C₃H₈/CO₂ mixture required the lowest input energy, in the range of 3.58 × 10⁻¹⁸–4.14 × 10⁻¹⁸ W s (22.35–25.82 eV) per molecule of produced hydrogen.     

Combined Reforming and Partial Oxidation of CO<Subscript>2</Subscript>-Containing Natural Gas Using an AC Multistage Gliding Arc Discharge System: Effect of Stage Number of Plasma Reactors

The effect of stage number of multistage AC gliding arc discharge reactors on the process performance of the combined reforming and partial oxidation of simulated CO₂-containing natural gas having a CH₄:C₂H₆:C₃H₈:CO₂ molar ratio of 70:5:5:20 was investigated. For the experiments with partial oxidation, either pure oxygen or air was used as the oxygen source with a fixed hydrocarbon-to-oxygen molar ratio of 2/1. Without partial oxidation at a constant feed flow rate, all conversions of hydrocarbons, except CO₂, greatly increased with increasing number of stages from 1 to 3; but beyond 3 stages, the reactant conversions remained almost unchanged. However, for a constant residence time, only C₃H₈ conversion gradually increased, whereas the conversions of the other reactants remained almost unchanged. The addition of oxygen was found to significantly enhance the process performance of natural gas reforming. The utilization of air as an oxygen source showed a superior process performance to pure oxygen in terms of reactant conversion and desired product selectivity. The optimum energy consumption of 12.05 × 10²⁴ eV per mole of reactants converted and 9.65 × 10²⁴ eV per mole of hydrogen produced was obtained using air as an oxygen source and 3 stages of plasma reactors at a constant residence time of 4.38 s.     

Effect of Steam in CO2 Reforming of CH4over a Ni/CeO2–ZrO2–Al2O3 Catalyst

CO₂ reforming of CH₄ was carried out with and without steam over a Ni/CeO₂–ZrO₂–Al₂O₃ catalyst. The catalytic performance, amount of carbon deposit and the EXAFS of the Ni K-edge of samples were measured. The results show that when the catalyst is used for CO₂ reforming of CH₄ without the addition of steam, the catalyst gradually deactivates, however, addition of a small amount of steam to the feed gas can significantly inhibits the deactivation, which is due to the great suppression of coke formation on the catalyst during the reaction. The EXAFS result shows that, maybe due to the penetration of more carbon atoms into the Ni lattice, the coordination number of the nearest Ni–Ni of the sample after the reaction without steam reduces more than that of samples after the reaction with a small amount of steam in the feed gas.     

Ethylene Epoxidation over Alumina- and Silica-Supported Silver Catalysts in Low-Temperature AC Dielectric Barrier Discharge

In this work, ethylene epoxidation reaction for ethylene oxide production over silver catalysts loaded on two different supports (silica and alumina particles) in a low-temperature AC dielectric barrier discharge (DBD) reactor was investigated. The DBD plasma system was operated under the following base conditions: an O₂/C₂H₄ feed molar ratio of 1/4, a total feed flow rate of 50 cm³/min, an electrode gap distance of 0.7 cm, an input frequency of 500 Hz, and an applied voltage of 19 kV. From the results, the presence of silver catalysts improved the ethylene oxide production performance. The silica support interestingly provided a higher ethylene oxide selectivity than the alumina support. The optimum Ag loading on the silica support was found to be 20 wt%, exhibiting the highest ethylene oxide selectivity of 30.6%.     

Silver Loading on DBD Plasma-Modified Woven PET Surface for Antimicrobial Property Improvement

In this work, the hydrophilic improvement of a woven PET surface was accomplished by a plasma technique. The woven PET surface was plasma-treated by dielectric barrier discharge (DBD) under various operating conditions (electrode gap distance, plasma treatment time, input voltage, and input frequency) and various gaseous environments (air, O₂, N₂, and Ar) in order to improve its hydrophilicity. It was experimentally found that a decrease in electrode gap distance and an increase in input voltage increased the electric field strength, leading to higher hydrophilicity of the PET surface characterized by wickability and contact angle measurements. In comparisons among the studied environmental gases, air gave the highest hydrophilicity, being comparable to O₂, while Ar and N₂ gave lower hydrophilicity of the woven PET surface. The optimum conditions for a maximum hydrophilicity of the PET surface were an electrode gap distance of 4 mm, a plasma treatment time of 10 s, an output voltage of 15 kV, and a frequency of 350 Hz under air environment. After the plasma treatment under the obtained optimum conditions, the woven PET was loaded with Ag particles using a AgNO₃ aqueous solution in order to obtain the antimicrobial property. The plasma-treated woven PET loaded with Ag particles exhibited good antimicrobial activity against both E. coli (gram-negative bacteria) and S. aureus (gram-positive bacteria).     

Dry Reforming of Methane with Carbon Dioxide Using Pulsed DC Arc Plasma at Atmospheric Pressure

Dry reforming of CH₄ with CO₂ to produce syngas was investigated in a plasma reactor without catalysts at atmospheric pressure. The reactants passed through the plasma zone and reacted in milliseconds with high conversions and selectivity due to the localized high temperature. The results showed that both conversions and selectivity were higher when using a DC arc discharge than using a pulsed DC arc. Increasing the input energy density promoted the conversions of reactants. At an input power of 204 W, the conversions of CO₂ and CH₄ reached 99.3 and 99.6%, respectively, and the selectivity to products was almost 100%, where the molar ratio of CO₂/CH₄ was 1 with the reactants flow rate of 100 ml/min. Very little coke was formed during the course of reaction. Key parameters such as the pulse frequency, the input power and the total feed flow rate were studied to find the optimum operating condition.     

DC-Pulsed Plasma for Dry Reforming of Methane to Synthesis Gas

The carbon dioxide reforming of methane to synthesis gas under DC-pulsed plasma was investigated. The effects of specific input energy and feed ratio on the product distribution and also feed conversion was studied. At the input energy of about 11 eV/molecule per methane and/or carbon dioxide the feed conversion of 38% for CH₄ and 28% for CO₂ and product selectivity of 74% has been attained for H₂ and CO at feed flow rate of 90 ml/min. The energy consumption in this work displays potential to further study and optimization of the process. The importance of the electron impact reactions in the process was discussed. The results show that by prudent tuning of system variables, the process be able to run in the way of synthesis gas, instead of hydrocarbon production.     

Ethylene Epoxidation in Cylindrical Dielectric Barrier Discharge: Effects of Separate Ethylene/Oxygen Feed

The effects of separate C₂H₄/O₂ feed and C₂H₄ feed position on the ethylene epoxidation reaction in an AC cylindrical dielectric barrier discharge reactor were investigated. The highest EO selectivity of 34?% and EO yield of 7.5?%, as well as the lowest power consumption of 1.72?×?10^?16 Ws/molecule of EO produced, were obtained at a C₂H₄ feed position of 0.25, an O₂/C₂H₄ feed molar ratio of 1/4, an applied voltage of 13?kV, an input frequency of 550?Hz, and a total feed flow rate of 75?cm³/min. The results demonstrated, for the first time, that the separate feed of C₂H₄ and O₂ could provide better ethylene epoxidation performance in terms of higher EO selectivity and yield, and lower power consumption, as compared to the mixed feed. All undesired reactions including C₂H₄ cracking, dehydrogenation, oxidation, and coupling reactions are lowered by the ethylene separate feed because of a decrease in opportunity of ethylene molecules to be activated by generated electrons.     

Dry Reforming of Methane by DC Spark Discharge with a Rotating Electrode

A novel type of plasma reactor having a rotating electrode is proposed for CO₂ reforming of methane without catalyst at room temperature and atmospheric pressure. Results indicated that employing rotating ground electrode leads to a stable discharge for any period of time. Effects of feed composition, feed flow rate, applied power and electrodes separation on the carbon dioxide and methane conversions as well as the products selectivity were investigated. Increasing CO₂/CH₄ molar ratio in the feed favors the reagents conversion and consequently promotes the formation of hydrogen and carbon monoxide. If the target product is hydrogen, it is proposed to operate the reactor at CO₂/CH₄ = 1 molar ratio and if the target product is carbon monoxide then CO₂/CH₄ = 3 molar ratio is the preferred option for feed composition. This reactor system has advantages of stable operation and high conversion ability. Also, the obtained syngas with flexible molar ratio of H₂ to CO is suitable for vast industrial applications.     

The oxidative stream reforming of methane to syngas in a thin tubular mixed-conducting membrane reactor

The oxidative stream reforming of methane (OSRM) to syngas, involving coupling of exothermic partial oxidation of methane (POM) and endothermic steam reforming of methane (SRM) processes, was studied in a thin tubular Al₂O₃-doped SrCo_0.8Fe_0.2O_3−δ membrane reactor packed with a Ni/γ-Al₂O₃ catalyst. The influences of the temperature and feed concentration on the membrane reaction performances were investigated in detail. The methane and steam conversions increased with increasing the temperature and high conversions were obtained in 850–900 °C. Different from the POM reaction, in the OSRM reaction the temperature and H₂O/CH₄ profoundly influenced the CO selectivity, H₂/CO and heat of the reaction. The CO selectivity increased with increasing the temperature or decreasing the H₂O/CH₄ ratio in the feed owing to the water gas shift reaction (H₂O + CO → CO₂ + H₂). And the H₂ selectivity based on methane conversion was always 100% because the net steam conversion was greater than zero. The H₂/CO in product could be tuned from 1.9 to 2.8 by adjusting the reaction temperature or H₂O/CH₄. Depending on the temperature or H₂O/CH₄, furthermore, the OSRM process could be performed auto-thermally with idealized reaction condition.     

Production of hydrogen by oxidative steam reforming of methanol over Cu/SiO2 catalysts

Selective production of hydrogen by oxidative steam reforming of methanol (OSRM) was studied over Cu/SiO₂ catalyst using fixed bed flow reactor. Textural and structural properties of the catalyst were analyzed by various instrumental methods. TPR analysis illustrates that the reduction temperature peak was observed between 510?K and 532?K at various copper loadings and calcination temperatures and the peaks shifted to higher temperature with increasing copper loading and calcination temperature. The XRD and XPS analysis demonstrates that the copper existed in different oxidation states at different conditions: Cu₂O, Cu⁰, CuO and Cu(OH)₂ in uncalcined sample; CuO in calcined sample: Cu₂O and metallic Cu after reduction at 600?K and Cu⁰ and CuO after catalytic test. TEM analysis reveals that at various copper loadings, the copper particle size is in the range between 3.0?nm and 3.8?nm. The Cu particle size after catalytic test increased from 3.6 to 4.8?nm, which is due to the formation of oxides of copper as evidenced from XRD and XPS analysis. The catalytic performance at various Cu loadings shows that with increasing Cu loading from 4.7 to 17.3?wt%, the activity increases and thereafter it decreases. Effect of calcination shows that the sample calcined at 673?K exhibited high activity. The O₂/CH₃OH and H₂O/CH₃OH molar ratios play important role in reaction rate and product distribution. The optimum molar ratios of O₂/CH₃OH and H₂O/CH₃OH are 0.25 and 0.1, respectively. When the reaction temperature varied from 473 to 548?K, the methanol conversion and H₂ production rate are in the range of 21.9–97.5% and 1.2–300.9?mmol?kg^?1?s^?1, respectively. The CO selectivity is negligible at these temperatures. Under the optimum conditions (17.3?wt%, Cu/SiO₂; calcination temperature 673?K; 0.25 O₂/CH₃OH molar ratio, 0.5 H₂O/CH₃OH molar ratio and reaction temperature 548?K), the maximum hydrogen yield obtained was 2.45?mol of hydrogen per mole of methanol. The time on stream stability test showed that the Cu/SiO₂ catalyst is quite stable for 48?h.     

Application of non-thermal atmospheric pressure ac plasmas to the carbon dioxide reforming of methane

Methane conversions of 11.9%, yields of hydrogen as high as 23.3% and energy yields of 1.0 mol H₂/kWh have been achieved from CO₂ reforming of CH₄ in non-thermal, atmospheric pressure plasma reactors with Pt coated electrodes. Two reactors have been studied. A novel fan type reactor consisting of a movable rotor and immobile stator produced the highest yields in contrast to a tube type (silent discharge) reactor with a glass dielectric barrier. Conversions, yields of hydrogen and energy yields (expressed as mol H₂/kWh) were studied for CO₂/CH₄ concentrations of 1.1% and 5.0% in He as a function of flow rate and input voltage. Hydrogen yields are observed to increase as the input voltage is increased from 411 V to 911 V and the flow rate is decreased from 100 cc/min to 30 cc/min. Energy yields vary only slightly with input voltage and flow rate. Hydrogen yields show little dependence on CO₂/CH₄ concentrations, but energy yields are approximately five times greater for the 5.0% mixture than the 1.1% mixture. Selectivities to H₂, CO, coke, and low molecular weight hydrocarbons were also evaluated and compared to data obtained without CO₂ in the feed. Hydrogen selectivities of nearly 100% were obtained, with small amounts of ethane and propane as the only observed side products and the selectivites were approximately the same whether CO₂ was present or absent in the mixture. However, the reaction proceeds much more cleanly when CO₂ is present, producing CO. The syngas product has an H₂ : CO ratio of 1.5 with the fan type reactor and 0.67 with the tubular reactor. In the absence of CO₂, coke is the main carbonaceous product. Under all conditions studied the fan type reactor demonstrated higher methane conversions (up to 11.9%) and selectivities to hydrogen.     

Activities of δ-Al2O3-supported bimetallic Pt?NiO and Co?NiO catalysts for methane autoreforming: Oxidation studies

The methane oxidation activities of Pt−NiO and Co−NiO bimetallic catalysts have been investigated as part of a larger research program on the autothermal reforming of methane (combined methane oxidation and steam reforming) in a fluidized bed reactor. Experiments at atmospheric pressure and 783–1023 K for both catalysts showed that the reaction was more selective towards H₂ production at CH₄∶O₂ ratios greater than unity. Light-off temperature increased with decreasing CH₄∶O₂ ratios, but increase in gas velocity (beyond minimum fluidization) increased the light-off temperature. Co−NiO was as promising as the more expensive Pt−NiO catalyst for the oxidation.     

Ethylene Epoxidation in an AC Dielectric Barrier Discharge Jet System

In this work, ethylene epoxidation was investigated in a dielectric barrier discharge jet (DBDJ) with a separate ethylene/oxygen feed under oxygen lean conditions. The ethylene (C₂H₄) stream was directly injected behind the plasma zone in order to reduce all undesired reactions, including C₂H₄ cracking and further reactions, while the oxygen (O₂) balanced with argon was fed through the plasma zone totally to maximize the formation of active oxygen species. The effects of various operating parameters, such as total feed flow rate, O₂/C₂H₄ feed molar ratio, applied voltage, input frequency, and C₂H₄ feed position on the ethylene epoxidation activity, were investigated to determine the optimum operating conditions for this new DBDJ system. The highest ethylene oxide (EO) selectivity (55.2 %) and yield (27.6 %), as well as the lowest power consumption (3.3 × 10^?21 and 6.0 × 10^?21 Ws/molecule C₂H₄ converted and EO produced, respectively) were obtained at a total feed flow rate of 1,625 cm³/min (corresponding to a residence time of 0.022 s), an O₂/C₂H₄ feed molar ratio of 0.25:1, an applied voltage of 9 kV, an input frequency of 300 Hz, and a C₂H₄ feed position of 3 mm behind the plasma zone. The superior activity of the ethylene epoxidation in the DBDJ system resulted from a small reaction volume as well as a separate ethylene/oxygen feed.     

Chemical and Physical Characteristics of Pulsed Electrical Discharge Within Gas Bubbles in Aqueous Solutions

The chemical and physical characteristics of pulsed electrical discharge within gas bubbles immersed in an aqueous solution were investigated using a reactor with long protrusion length high voltage needle electrodes. Argon gas was introduced at the base of the needle electrode causing gas bubbles to flow upwards in contact with the needle. The effects of needle protrusion length were evaluated by using 2, 4, and 6 cm length needles under a wide range of power input (3–78 W). No significant differences in chemical or electrical characteristics were found among the different protrusion lengths. H₂ and H₂O₂ generation rates were proportional to input power and the energy yield efficiency for these species was not affected dramatically by input power. The results of discharge within bubbles in aqueous solution were also compared with those for direct liquid phase discharge and gas phase discharge above the liquid surface.     

Hydrogen Production by Catalytic Reforming of Gaseous Hydrocarbons (Methane &; LPG)

Hydrogen has been attracting great interest as a major energy source in near future. The lack of an infrastructure has led to a research effort to develop fuel processing technology for production of hydrogen. In this review, we are reporting the catalytic reforming of gaseous hydrocarbons carried out in our research group, covering dry-reforming of CH₄, tri-reforming of CH₄, the electrocatalytic reforming of CH₄ by CO₂ in the SOFC (solid oxide fuel cell) system and steam reforming of LPG. Especially, we have focused on our work, though the related work from other researchers is also discussed wherever necessary. It was found that tri-reforming of CH₄ over NiO–YSZ–CeO₂ catalyst was more desirable than dry-reforming of CH₄ due to higher reforming activity and less carbon formation. The synthesis gas produced by tri-reforming of CH₄ can be used for the production of dimethyl ether, Fischer–Tropsch synthesis fuels and high valued chemicals. To improve the problem of deactivation of catalyst due to carbon formation in the dry reforming of CH_4, the internal reforming of CH₄ by CO₂ in SOFC system with NiO–YSZ–CeO₂ anode catalyst was suggested for cogeneration of a syngas and electricity. It was found that Rh-spc-Ni/MgAl catalyst showed long term stability for 1,100 h in the steam reforming of LPG under the tested conditions. The addition of Rh to spc-Ni/MgAl catalyst restricted the deactivation of catalyst due to carbon formation in the steam reforming of LPG and diesel under the tested conditions. The result suggested that the developed reforming catalysts can be used in the reforming process of CH₄, LNG and LPG for application to hydrogen station and fuel processor system.