Methane Conversion to Hydrogen and Carbon Black by DC-Spark Discharge

A continuous production of hydrogen and carbon black from methane without CO₂ emission in atmospheric pressure has been investigated by non thermal decomposition of methane using a system of direct current (DC)-spark discharge plasma, which has great advantages over other systems, like thermal plasma or catalytic conversion of methane in H₂ production. A plasma reactor with specific design of electrodes was employed to examine the reactor performance regarding operating conditions such as feed flow rate, input power and electrodes distance. The experimental results showed that designed reactor increases not only the concentration of the produced hydrogen in continues condition but also guarantees stable plasma. As the methane supply rate increased, the hydrogen concentration decreased but on the other hand the hydrogen volume flow rate increased. In general, under the specified operating condition (power?=?21 W and methane flow rate?=?150?ml/min), the plasma converter produced a hydrogen concentration of 45?% at hydrogen volume flow rate of 75?ml/min.     

Carbon Blacks Produced by Thermal Plasma: the Influence of the Reactor Geometry on the Product Morphology

Carbon black (CB) nanopowders were obtained by plasma decomposition of methane at various flow rates using inductively coupled thermal plasma torch system of 35 kW. Nitrogen was also introduced in some experiments along with the methane. Using a cylindrical shape reactor the obtained powders were composed mainly of spherical particles, non-uniform in terms of particles size with diameters between 30 and 150 nm. The shape and size of this reactor resulted in the presence of recirculation areas enabling the formation of large CB particles and other secondary volatile compounds. Changing the reactor to a conical geometry resulted in the production of CB powders showing a crystalline and flake-like morphology made of sheets having 6–16 graphitic planes. The conical shape avoids the presence of recirculation areas and promotes the formation of a uniform powder morphology throughout the reactor.     

Characterization of plasma polymerized hydrocarbons using CP–MAS 13C-NMR

Plasma polymerized hydrocarbons made from ethane and methane were produced under different reactor conditions and probed by solid-state carbon-13 nuclear magnetic resonance (¹³C-NMR) with cross-polarization and magic-angle sample spinning. NMR experiments provided structural information about the plasma polymers. The conditions of low power, high hydrocarbon gas flow rate, and no added hydrogen gas appeared to give the highest amount of nonprotonated sp³ hybridized carbons in the films for the reactor design used. The use of methane or ethane as reactor gas did not affect plasma polymer structure significantly.     

Carbon Nano-Flakes Produced by an Inductively Coupled Thermal Plasma System for Catalyst Applications

Carbon material was produced using an inductively coupled thermal plasma torch system of 35 kW and a conical shape reactor. The carbon nanopowders were obtained by plasma decomposition of methane at various flow rates and show a uniform microstructure throughout the reactor. The product has a crystalline graphitic structure, with a stacking of between 6 and 16 planes and a nano-flake morphology with particles dimensions of approximately 100 nm long, 50 nm wide and 5 nm thick. Nitrogen was also introduced in some synthesis experiments along with the methane precursor using flow rates of 0.1 and 0.2 slpm. The resulting product has the same structural properties and the nitrogen is incorporated into the graphitic structure through pyridinic type bonds.     

Carbon Nanoparticle Production by Inductively Coupled Thermal Plasmas: Controlling the Thermal History of Particle Nucleation

The process control for reproducibility, uniformity, and achievement of desired structures for carbon black generated in thermal plasma devices is studied in this paper through modeling, and correlated with experimental results. A numerical simulation of the flow and energy fields, stream function lines and the quench rates of the plasma gas in a conical shape reactor at different pressures was made. An argon plasma is used with highly diluted methane (0.6–7%) as the carbon precursor. The quench rates were studied in order to observe the flow development and hence the thermal history of particle nucleation. Three pressure cases of 20.7, 55.2 and 101.3 kPa and two plasma powers cases of 10 and 20 kW were studied. The modeling results enabled carbon nanoflakes production in the experimental tests performed on an inductively coupled thermal plasma system. Results indicate a robust process control enabling very little particle morphology variation over this wide range of reactor pressure values and varying plasma power, and a very high reproducibility of the particle morphologies obtained.     

Gasification of Municipal Solid Wastes in Plasma Arc Medium

Many thermal processes have been developed in order to eliminate the municipal solid wastes or produce energy from them. These processes include a wide range of applications from the simplest burning system to plasma gasification. Plasma gasification is based on re-forming of molecules after all molecules convert to smaller molecules or atoms at high temperatures. In this work, the production of fuel gas is aimed by plasma gasification of municipal solid wastes in high temperatures. Because of this, a plasma reactor of the capacity of 10 kg h^?1 was designed which can gasify municipal solid wastes. Plasma gasification with and without steam and oxygen was performed in temperatures of 600, 800, 1000, 1200, 1400 and 1600 °C in the reactor. A gas mixture containing methane, ethane, hydrogen, carbon dioxide and monoxide, whose content varies with temperature, was obtained. It was found that plasma gasification (or plasma pyrolysis, PG), plasma gasification with oxygen (PGO) and plasma gasification with steam (PGS) were more prone to CO formation. A gas product which was consisted of 95% CO between 1200 and 1400 °C was produced. It was observed that a gas with high energy capacity may be produced by feeding oxygen and steam into the entrance of the high temperature region of the reactor.

     

Hydrogen Production from Methane Decomposition Using a Mobile and Elongating Arc Plasma Reactor

Plasma Chemistry and Plasma Processing - Hydrogen and solid carbon were produced through methane decomposition in a plasma reactor with a parallel set of screw type helix and rod-like electrodes....     

有氧气氛下等离子体甲烷偶联反应的研究

近年来,非平衡等离子体应用于甲烷直接转化的研究备受关注,但多数研究工作采用的是低气压下微波或高频放电产生的非平衡等离子体[1－9].在常压下获得非平衡等离子体一般是通过脉冲电晕放电或介质阻挡放电产生的[10,11].Liu等[12]采用电晕放电（非脉冲）研究了CH4＋O2＋He(pCH4=2.03×104Pa,pO2=5.07×103Pa,He平衡)体系的甲烷偶联反应.　　如前文[13]所述,脉冲电晕等离子体是一种新型常压非平衡等离子体,其电子通过上升沿陡峭的窄脉冲电场加速而获得能量（1～20eV）.将其应用于甲烷偶联反应,不仅具有反应条件温和（常温常压）…     

Nitrogen Functionalization of Carbon Black in a Thermo-Convective Plasma Reactor

We have developed a simple plasma reactor for functionalizing powders. The reactor uses thermo-convective cells to mix the powder during the treatment and to ensure high homogeneity. The reactor has been used to treat batches of 50–150 mg of carbon black in a gas mixture of He/N₂ at 40 Torr. By using repetitive treatments on fractions of carbon black recovered from the cap of the treatment vessel (due to its fluidization during the treatment), we were able to fix a concentration of nitrogen functionalities of 13% at. N/C (as measured by XPS). We report the working conditions of the reactor and the results obtained.     

Experimental Comparison of Methane Pyrolysis in Thermal Plasma

Methane pyrolysis via thermal plasma was investigated experimentally on a 2 kW DC arc plasma setup in argon atmosphere. Two widely applied methane pyrolysis profiles, i.e., pre-mixing methane and argon before fed into plasma torch, and injecting methane into pure argon plasma jet at torch outlet, were compared. Performances of methane pyrolysis regarding to methane conversion, acetylene selectivity, acetylene specific energy requirement (SER), and plasma stability were concluded. Results showed that pre-mixing methane and argon before fed into plasma torch would be efficient in converting methane and acetylene production, with higher conversion of methane and lower SER to acetylene at a given specific energy. Also, methane in arc zone would cause periodic fluctuations of plasma voltage and power, which could be reduced by controlling methane fraction in feed. On the other hand, when methane was injected into argon plasma jet at torch outlet, the energy efficiency in converting methane and producing acetylene would be lower. And the plasma would barely participate in the reaction other than providing heat, but the erosion of electrode was much slower and slighter. It was also validated that the SER of acetylene was limited by the thermal loss of the setup due to size-effect of reactor.     

A High-Efficiency Reactor for the Pulsed Plasma Conversion of Methane

The authors recently developed a high-frequency pulsed plasma process for methane conversion to acetylene and hydrogen using a co-axial cylindrical (CAC) type of reactor. The energy efficiency represented by methane conversion rate per unit input energy has been improved so that such a pulsed plasma has potential for commercial acetylene production. A pulsed plasma consists of a pulsed corona discharge and a pulsed spark discharge. Most of energy is injected over the duration of the pulsed spark discharge. Methane conversion using this kind of pulsed plasma is a kind of pyrolysis enhanced by the pulsed spark discharge. In this study, a point-to-point (PTP) type of reactor that can produce a discharge channel over the duration of a pulse discharge was used for the pulsed plasma conversion of methane. The energy efficiency and carbon formation on electrodes have been improved. The influences of pulse frequency and pulse voltage on methane conversion rate and product selectivity were investigated. The features of methane conversion using PTP and CAC reactors were discussed.     

Direct partial oxidation of methane to methanol： Reaction zones and role of catalyst location

Direct partial oxidation of methane to methanol was investigated in a specially designed reactor. Methanol yield of about 7%-8% was obtained in gas phase partial oxidation. It was proposed that the reactor could be divided into three reaction zones, namely pre-reaction zone, fierce reaction zone, and post-reaction zone, when the temperature was high enough to initiate a reaction. The oxidation of methane proceeded and was completed mostly in the fierce reaction zone. When the reactant mixture entered the post-reaction zone, only a small amount of produced methanol would bring about secondary reactions, because molecular oxygen had been exhausted in the fierce reaction zone. A catalyst, if necessary, should be placed either in the pre-reaction zone, to initiate a partial oxidation reaction at a lower temperature, or in the fierce reaction zone to control the homogeneous free radical reaction.     

Quenching Experiment Study on Thermal Plasma Pyrolysis Process of Coal Tar

Quenching is a key approach to obtain high acetylene yield in the process of coal tar pyrolysis to produce acetylene in a thermal plasma reactor due to the thermodynamic characteristics of acetylene. Experiments of coal tar pyrolysis were carried out in a lab-scale H₂/Ar plasma reactor under various quenching conditions. Meanwhile, thermodynamic analysis was performed to assist the optimization of quenching temperature and the maximization of acetylene yield. As quenching media in the experiments, hydrogen, argon, methane, and water were used separately to study the influence of quenching process on acetylene yield and specific energy requirement. The experimental results indicate that the acetylene concentration in quenched product gas was significantly affected by quenching operation, and the acetylene yield was significantly affected by quenching medium flow rate. The acetylene yields of 24.6, 17.8, 44.9 and 23.6 wt% can be reached by using hydrogen, argon, methane, and water as quenching media, respectively. The specific energy requirement analysis indicates that process energy efficiency can be improved by a suitable quench operation.     

Conversion of Methane and Carbon Dioxide in a DBD Reactor: Influence of Oxygen

A continuous plug flow reactor supported by a dielectric barrier discharge (DBD) is used to study the conversion of methane, carbon dioxide, and oxygen at different compositions. The three studied gases were diluted with helium to 3 % with an overall flow rate of 200 sccm. The 13.56 MHz plasma was ignited at atmospheric pressure. The product stream and the inlet flow were analyzed by a FTIR spectrometer equipped with a White-cell and by a quadrupole mass spectrometer. The DBD reactor generates hydrogen, carbon monoxide, ethane, ethene, acetylene, formaldehyde, and methanol. Additional oxygen in the feed has positive effects on the yield of methanol, formaldehyde and carbon monoxide and reduces the total consumed energy. The hydrogen yield reaches its maximum at medium amounts of oxygen in the inlet flow. The conversion of methane increases to a limiting value of about 35 %. Methane rich feeds increase the yield of hydrogen, ethane and methanol. On the other hand, additional oxygen has a negative influence on the produced amount of C2 hydrocarbons. The conversion of methane and carbon dioxide as well as the yield of synthesis gas components and C2 hydrocarbons increases by changing the plasma power to higher values.     

Methane dimerization via microwave plasmas

Methane can be converted to ethane and ethylene in a microwave plasma reactor at pressures from 10 to 100 mm Hg. The total methane conversion has a linear correlation with power ? (45 + pressure)/flow and can be as high as 90%. The conversion of methane to ethylene varies from 0 to 11%. It reaches a maximum at a value of Power ? (45 + Pressure)/Flow of 2200 W?mm Hg?s/mL. The energy efficiency of driving this thermodynamically unfavourable reaction is 2%.     

Conversion of natural gas to C2 hydrocarbons via cold plasma technology

The plasma technology served as a tool in unconventional catalysis has been used in natural gas conversion, because the traditional catalytic methane oxidative coupling reaction must be performed at high temperature on account of the stability of methane molecule. The focus of this research is to develop a process of converting methane to C2 hydrocarbons with non-equilibrium plasma technology at room temperature and atmospheric pressure. It was found that methane conversion increased and the selectivity of C2 hydrocarbons decreased with the voltage. The optimum input voltage range was 40-80 V corresponding to high yield of C2 hydrocarbons. Methane conversion decreased and the selectivity of C2 hydrocarbons increased with the inlet flow rate of methane. The proper methane flow rate was 20-40 ml/min (corresponding residence time 10-20 s). The experimental results show that methane conversion was 47% and the selectivity of C2 hydrocarbons was 40% under the proper condition using atmospheric DBD cold plasma technology. It was found that the breakdown voltage of methane VB was determined by the type of electrode and the discharge gap width in this glow discharge reactor. The breakdown voltage of methane VB,min derived from the Paschen law equation was established.     

Conversion of natural gas to C_2 hydrocarbons via cold plasma technology

The plasma technology served as a tool in unconventional catalysis has been used in natural gas conversion,because the traditional catalytic methane oxidative coupling reaction must be performed at high temperature on account of the stability of methane molecule.The focus of this research is to develop a process of converting methane to C2 hydrocarbons with non-equilibrium plasma technology at room temperature and atmospheric pressure.It was found that methane conversion increased and the selectivity of C2 hydrocarbons decreased with the voltage.The optimum input voltage range was 40-80 V corresponding to high yield of C2 hydrocarbons.Methane conversion decreased and the selectivity of C2 hydrocarbons increased with the inlet flow rate of methane.The proper methane flow rate was 20-40 ml/min (corresponding residence time 10-20 s).The experimental results show that methane conversion was 47% and the selectivity of C2 hydrocarbons was 40% under the proper condition using atmospheric DBD cold plasma technology.It was found that the breakdown voltage of methane VB was determined by the type of electrode and the discharge gap width in this glow discharge reactor.The breakdown voltage of methane VB,min derived from the Paschen law equation was established.     

Comparison of Simple Particle-Radiation Coupling Models Applied on a Plasma Black Process

The effect of soot formation on the radiative heat transfer inside a plasma reactor for carbon black synthesis has been modelled. For this purpose, three methods to quantify the soot volume fraction have been tested and evaluated: (1) Assuming local thermodynamic equilibrium, (2) assuming instantaneous conversion of the hydrocarbon and (3) using a single-step soot model. These approaches have been studied using a two-dimensional axis-symmetric and a three-dimensional steady computational fluid dynamics (CFD) model based on the commercial software FLUENT (v.5.6). The CFD model includes turbulence effects (by standard k– model), an electric arc sub-model to describe the time-average and spatial-average Lorentz forces and ohmic heating generated by the three-phase power-supply, methane transport in a nitrogen plasma and radiation calculations. The calculations show that for the simulated operating conditions the resulting temperature distributions obtained are very similar with the three methods in spite of major differences in the treatment of particle formation in the different methods.     

Influence of the Electromagnetic Forces on Momentum and Heat Transfer in a 3-Phase ac Plasma Reactor

A new 3-phase ac plasma reactor has been developed within the framework of research on hydrocarbon cracking for the production of carbon black and hydrogen. ^(1,2) One of the main characteristics of the system is related to the 3-phase, 50 Hz ac current plasma generator which induces a very particular arc motion affecting the heat and mass transfer inside the reactor. In a first step, the general flow inside the reactor in the absence of hydrocarbon injection has been studied. A simplified approach to characterize the heat and mass transfer inside the reactor is presented in this paper. The arc zone analysis is carried out simultaneously by a theoretical analysis of the electromagnetic forces and by an ultrahigh-speed cine-camera analysis. The flow in the reactor is modeled with a CFD commercial code. Results are compared with experimental temperature measurements.     

Methane Pyrolysis Stimulated by Admixture of Atomic Hydrogen: 1. An Experimental Study

A method for enhancing the hydrocarbon pyrolysis process by introducing atomic hydrogen into the reaction medium from an arcjet plasma source was considered. It was shown that hydrogen atoms could effectively be introduced by mixing under low pressure. The atomic hydrogen–stimulated methane pyrolysis process was experimentally studied in a continuous stirred reactor with a plasma plume. When hydrogen atoms were present in the plasma jet, the amount of the valuable product increased by a factor of two.