Investigation on Methane Decomposition and the Formation of C2 Hydrocarbons in DC Discharge Plasma by Emission Spectroscopy

The IR emission spectra of methane were measured under DC glow discharge conditions. The distinct difference in time between methane decomposition and C2 hydrocarbons formation was specially pointed out. Ca hydrocarbons formed at the end of methane decomposition. The optimum condition for C2 hydrocarbon formation was studied and the optimum combination between electric current density and methane input quantity was suggested. The appropriate reaction conditions for methane decomposition and Ca hydrocarbons formation are different, so high yield of Ca hydrocarbons will be probably obtained when different conditions are taken.

Conversion of Methane to C_2 Hydrocarbons and Hydrogen Using a Gliding Arc Reactor

Methane conversion has been studied using gliding arc plasma in the presence of argon.The process was conducted at atmospheric pressure and ambient temperature.The focus of this research was to develop a process of converting methane to C2 hydrocarbons and hydrogen. The main parameters,including the CH4/Ar mole ratio,the CH4 flow rate,the input voltage,and the minimum electrode gap,were varied to investigate their effects on methane conversion rate, product distribution,energy consumption,carbon deposit,and reaction stability.The specific energy requirement（SER） was used to express the energy utilization efficiency of the process and provided a practical guidance for optimizing reaction conditions for improving energy efficiency. It was found that the carbon deposition was not conducive to methane conversion,and the gliding arc plasma discharge reached a stable state twelve minutes later.Optimum conditions for methane conversion were suggested.The maximum methane conversion rate of 43.39%was obtained under the optimum conditions.Also,C2 hydrocarbons selectivity,C2 hydrocarbons yield,H2 selectivity, H2 yield and SER were 87.20%,37.83%,81.28%,35.27%,and 2.09 MJ/mol,respectively.

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.

Screening of MgO- and CeO_2-Based Catalysts for Carbon Dioxide Oxidative Coupling of Methane to C_(2+) Hydrocarbons

The catalyst screening tests for carbon dioxide oxidative coupling of methane (CO2-OCM) have been investigated over ternary and binary metal oxide catalysts. The catalysts are prepared by doping MgO- and CeO2-based solids with oxides from alkali (Li2O), alkaline earth (CaO), and transition metal groups (WO3 or MnO). The presence of the peroxide (O2-2) active sites on the Li2O2, revealed by Raman spectroscopy, may be the key factor in the enhanced performance of some of the Li2O/MgO catalysts. The high reducibility of the CeO2 catalyst, an important factor in the CO2-OCM catalyst activity, may be enhanced by the presence of manganese oxide species. The manganese oxide species increases oxygen mobility and oxygen vacancies in the CeO2 catalyst. Raman and Fourier Transform Infra Red (FT-IR) spectroscopies revealed the presence of lattice vibrations of metal-oxygen bondings and active sites in which the peaks corresponding to the bulk crystalline structures of Li2O, CaO, WO3 and MnO are detected. The performance of 5%MnO/15%CaO/CeO2 catalyst is the most potential among the CeO2-based catalysts, although lower than the 2%Li2O/MgO catalyst. The 2%Li2O/MgO catalyst showed the most promising C2+ hydrocarbons selectivity and yield at 98.0% and 5.7%, respectively.

Co-Generation of C_2 Hydrocarbons and Synthesis Gases from Methane and Carbon Dioxide: a Thermodynamic Analysis

This paper deals with thermodynamic chemical equilibrium analysis using the method of direct minimization of Gibbs free energy for all possible CH4 and CO2 reactions. The effects of CO2/CH4 feed ratio, reaction temperature, and system pressure on equilibrium composition, conversion, selectivity and yield were studied. In addition, carbon and no carbon formation regions were also considered at various reaction temperatures and CO2/CH4 feed ratios in the reaction system at equilibrium. It was found that the reaction temperature above 1100 K and CO2/CH4 ratio=1 were favourable for synthesis gas production with H2/CO ratio unity, while carbon dioxide oxidative coupling of methane （CO2 OCM） reaction to produce ethane and ethylene is less favourable thermodynamically. Numerical results indicated that the no carbon formation region was at temperatures above 1000 K and CO2/CH4 ratio larger than 1.

Methane Conversion to C_2 Hydrocarbons Using Glow Discharge Plasma

The infrared emission spectra of methane, H, CH and C2 hydrocarbons in natural gas were measured. The process of methane decomposition and C2 hydrocarbons formation was investigated. The experiment showed that the time and conditions of methane decomposition and C2 hydrocarbons formation were different. Methane conversion rate increased with the increase in the current and decrease in the amount of methane. Furthermore, an examination of the reaction mechanisms revealed that free radicals played an important role in the chain reaction.

Cascade adsorptive separation of light hydrocarbons by commercial zeolites

Adsorptive separation of light hydrocarbons by porous solids provides an energy-efficient alternative to state-of-the-art cryogenic distillation.However,an optimal balance between the cost,performance and stability of the sorbent material is yet to be achieved for industrial applications.Here,we report the efficient separation of C2 and C3 hydrocarbons by a faujasite zeolite(Na-X,Si/Al=1.23).A tandem configuration of two fixed-beds packed with Na-X affords complete dynamic separation of the ternary mixture of C_(2)H_(2)/C_(2)H_(4)/C_(2)H_(6)(1/49.5/49.5;v/v/v)under ambient conditions.Pressure-swing desorption on the latter fixed-bed gives ethylene(>99.50%,1.80 mmol g^(-1))and ethane(>99.99%,1.41 mmol g^(-1)).In situ synchrotron X-ray powder diffraction revealed the binding sites for C_(2)H_(2)and C_(2)H_(4)in Na-X.This study highlights the potential application of commercial zeolites for challenging industrial separations.

Guangdong Dapeng LNG cold energy utilization-C_2++ extraction process integration

This paper makes a study of some technical and engineering aspects by using C2 ＋ hydrocarbon separation facility at Guangdong Dapeng liquefied natural gas （GDLNG） terminal. In the C2＋ hydrocarbon extraction process, the cold energy contained in LNG will be utilized. In order to ensure the optimum operating conditions of the temlinal and C2 ＋ hydrocarbon extraction facility by optimizing the current operating processes of the terminal, the C2 ＋ hydrocarbon extraction facility construction plan is proposed. We conducted numerous calculations and simulations using such specific analysis software as PRO II 〈 version 7.0 〉. Additionally available flow data are used to verify the cyclic send-out rates from the terminal, thus establishing the current and future projected load factors. This study is intended to make sure that GDLNG can continue to supply gas via the pipeline system safely without interruptions and most significantly solves the effects of flow fluctuations at the terminal gasification send-out facility on the hydrocarbons extraction, ensuring optimum pipeline operations and ensuring safe and effective means for such C2＋ hydrocarbons extraction process as well. At the same time, the terminal is also in the optimum operation condition. This is very significant to the terminal safety operation and the energy conservation and emission reduction.

Effect of Cooling Methods on Methane Conversion via Dielectric-Barrier Discharges

Effects of cooling methods on stability and methane conversion rate using dielectric-barrier discharges （DBD） were systematically investigated in this article. The results showed that the methane conversion rate was as high as 44.43% in a pure methane system at a flow rate of 100 mL·min^-1 and an input power of 234.2 W with air cooling. A dark greenish and soft film-like carbon was deposited on the outer surface of quartz tube when the outer electrode was watercooled, which decreased the methane conversion. With air cooling of inner electrode the selectivity of C2 hydrocarbons was higher than that with other cooling methods, while the C3 hydrocarbons had higher selectivity with flowing water cooling. Cooling the inner electrode could restrain the carbon deposition, but would decrease the methane conversion rate. The stability of both reaction and plasma operation can be improved through cooling the reactor. From thermodynamic analysis, it was found that the effective collisions frequency among the reactant molecules and free electrons （e^-） increased with temperature, which in turn led to a higher methane conversion rate and a change in the distribution of products.

Methane conversion in the presence of oxygen under low-temperature radio frequency plasma

Methane conversion in the presence of oxygen under low-temperature radio frequency （RF） plasma was investigated.The experiment results indicated that the following four factors,i.e.,discharge voltage,discharge area,O2/CH4 molar ratio and total gas flowrate,affected remarkably the reaction performance.The optimum reaction conditions of methane conversion in the presence of O2 under RF plasma are as follows：discharge voltage 1050 V,discharge area 989.1mm 2,O2/CH4 molar ratio 1/10 and total gas flowrate 200 ml/min.A methane conversion of 91% could be reached under the optimum conditions.Oxygen is good for the breaking of C-H bonds and also acts as a sort of thinner.According to the low-temperature plasma characteristics,the macroscopic kinetics model of methane conversion in the presence of O2 under radio frequency plasma was studied.

Novel Plasma Reactor with Rotary Helix Electrode Used in Coupling of CH_4 at Atmospheric Pressure

At the ambient temperature and pressure a glow discharge plasma was used as a new approach for the coupling of methane with the newly-developed rotary multidentate helix electrode. In the presence of hydrogen, the effects of the input peak voltages and gas flow rates on methane conversion, C2 single pass yield and selectivity were investigated, and then the results were compared with those from the three-disc multidentate electrode. This demonstrated, on an experimental scale, that the rotary multidentate helix electrode was better than the multidentate three-disc electrode as there was little accumulation of coke, and the C2 yield per pass was 69.85% and C2 selectivity over 99.14% with 70.46% methane conversion at an input peak voltage of 2300 V and 60 ml/min gas flow rate.

A quantum cascade laser infrared spectrometer for CO_2 stable isotope analysis：Field implementation at a hydrocarbon contaminated site under bio-remediation

Real-time methods to monitor stable isotope ratios of CO_2 are needed to identify biogeochemical origins of CO_2 emissions from the soil–air interface. An isotope ratio infra-red spectrometer（IRIS） has been developed to measure CO_2 mixing ratio with δ~13C isotopic signature, in addition to mixing ratios of other greenhouse gases（CH_4, N2_O）. The original aspects of the instrument as well as its precision and accuracy for the determination of the isotopic signature δ~13C of CO_2 are discussed. A first application to biodegradation of hydrocarbons is presented, tested on a hydrocarbon contaminated site under aerobic bio-treatment. CO_2 flux measurements using closed chamber method is combined with the determination of the isotopic signature δ~13C of the CO_2 emission to propose a non-intrusive method to monitor in situ biodegradation of hydrocarbons. In the contaminated area, high CO_2 emissions have been measured with an isotopic signature δ~13C suggesting that CO_2 comes from petroleum hydrocarbon biodegradation.This first field implementation shows that rapid and accurate measurement of isotopic signature of CO_2 emissions is particularly useful in assessing the contribution of contaminant degradation to the measured CO_2 efflux and is promising as a monitoring tool for aerobic bio-treatment.

Conversion of methane through dielectric-barrier discharge plasma

Methane coupling to produce C2 hydrocar-bons through a dielectric-barrier discharge(DBD)plasma reaction was studied in four DBD reactors.The effects of high voltage electrode position,different discharge gap,types of inner electrode,volume ratio of hydrogen to methane and air cooling method on the conversion of methane and distribution of products were investigated.Conversion of methane is obviously lower when a high voltage electrode acts as an outer electrode than when it acts as an inner electrode.The lifting of reaction temper-ature becomes slow due to cooling of outer electrode and the temperature can be controlled in the expected range of 60℃-150℃for ensuring better methane conversion and safe operation.The parameters of reactors have obvious effects on methane conversion,but it only slightly affects distribution of the products.The main products are ethyl-ene,ethane and propane.The selectivity of C2 hydrocar-bons can reach 74.50%when volume ratio of hydrogen to methane is 1.50.

Non-Oxidative Methane Conversion Using Lead- and Iron-Modified Albite Catalysts in Fixed-Bed Reactor

Raw and modified albite catalysts, including Pb/Atbite and Fe/Albite catalysts, have been investigated for methane conversion to C2 hydrocarbons under non-oxidative conditions. Introduction of Pb to albite improved the activity and selectivity to non-coke products. Based on characterization, it was found that Pb entered into the alkali and alkaline-earth metal sites of albite, while partial Fedoped in the tetrahedron sites and the other loaded on the surface of albite. At the reaction temperature of 1073 K, methane gas hourly space velocity （GHSV） of 2 L.gcat-1·h-1, catalyst dosage of 0.25 g （300 mesh）, the methane conversion catalyzed by raw albite in the fixed-bed micro reactor exhibited a methane conversion of 3.32%. Notably, introducing a Pb content of 3.4 wt% into albite greatly enhanced the conversion of methane up to 8.19%, and the selectivity of C2 hydrocarbons reached 99% without any coke under the same reaction conditions. While Fe-doping could weakly heighten the methane conversion to 3.97%, and coke was formed. Thus, a comparison of Pb/Albite and Fe/Albite catalysts demonstrates that the catalytic activity of albite is mainly decided by alkali and alkaline-earth metal sites, and lead-modification can effectively improve the catalytic activity of albite.