Characterization and Activity of Cr, Cu and Ga Modified ZSM-5 for Direct Conversion of Methane to Liquid Hydrocarbons

Direct conversion of methane using a metal-loaded ZSM-5 zeolite prepared viaacidic ion exchange was investigated to elucidate the roles of metal and acidity in the formation ofliquid hydrocarbons. ZSM-5 (SiO_2/Al_2O_3=30) was loaded with different metals (Cr, Cu and Ga)according to the acidic ion-exchange method to produce metal-loaded ZSM-5 zeolite catalysts. XRD,NMR, FT-IR and N_2 adsorption analyses indicated that Cr and Ga species managed to occupy thealuminum positions in the ZSM-5 framework. In addition, Cr species were deposited in the pores ofthe structure. However, Cu oxides were deposited on the surface and in the mesopores of the ZSM-5zeolite. An acidity study using TPD-NH_3, FT-IR, and IR-pyridine analyses revealed that the totalnumber of acid sites and the strengths of the Broensted and Lewis acid sites were significantlydifferent after the acidic ion exchange treatment. Cu loaded HZSM-5 is a potential catalyst fordirect conversion of methane to liquid hydrocarbons. The successful production of gasoline via thedirect conversion of methane depends on the amount of aluminum in the zeolite framework and thestrength of the Broensted acid sites.

Catalysis Conversion Methane into C_(2) Hydrocarbons via Electric Field Enhanced Plasma

In this paper the effect of catalyst and carrier in electric field enhanced plasma on methane conversion into C2 hydrocarbons was investigated. Methane coupling reaction was studied in the system of continuous flow reactor on Ni, MoO3, MnO2 catalysts and different ZSM-5 carriers. The per pass conversion of methane can be as high as 22%, the selectivity of ethylene can be as high as 23.8%, of acetylene 60.8%, of ethane 5.4% and of total C2 hydrocarbons was more than 90%. ZSM-5-25 was the better carrier and MnO2 was the better active component. The efficiency of energy was as high as 7.81%.

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.

Methane conversion into higher hydrocarbons with dielectric barrier discharge micro-plasma reactor

We reported a coaxial,micro-dielectric barrier discharge(micro-DBD)reactor and a conventional DBD reactor for the direct conversion of methane into higher hydrocarbons at atmospheric pressure.The effects of input power,residence time,discharge gap and external electrode length were investigated for methane conversion and product selectivity.We found the conversion of methane in a micro-DBD reactor was higher than that in a conventional DBD reactor.And at an input power of 25.0 W,the conversion of methane and the total C2+C3 selectivity reached 25.10% and 80.27%,respectively,with a micro-DBD reactor of 0.4 mm discharge gap.Finally,a nonlinear multiple regression model was used to study the correlations between both methane conversion and product selectivity and various system variables.The calculated data were obtained using SPSS 12.0 software.The regression analysis illustrated the correlations between system variables and both methane conversion and product selectivity.

Methane formation route in the conversion of methanol to hydrocarbons

The influence factors and paths of methane formation during methanol to hydrocarbons （MTH） reaction were studied experimentally and thermodynamically. The fixed-bed reaction results show that the formation of methane was favored by not only high temperature, but also high feed velocity, low pressure, as well as weak acid sites dominated on deactivated catalyst. The thermodynamic analysis results indicate that methane would be formed via the decomposition reactions of methanol and DME, and the hydrogenolysis reactions of methanol and DME. The decomposition reactions are thermal chemistry processes and easily occurred at high temperature. However, they are influenced by catalyst and reaction conditions through DME intermediate. By contrast, the hydrogenolysis reactions belong to catalytic processes. Parallel experiments suggest that, in real MTH reactions, the hydrogenolysis reactions should be mainly enabled by surface active H atom which might come from hydrogen transfer reactions such as aromatization. But H2 will be involved if the catalyst has active components like NiO.

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.

Effects of Temperature, Acetate and Nitrate on Methane Generation from Petroleum Hydrocarbons

In this study, the effects of temperature, acetate and nitrate on methane gas production from biodegradation of petroleum hydrocarbons were investigated. The results indicated that methane gas production at 35 ℃ was higher than that obtained at 55 ℃. The acetate addition significant enhanced the methane production at 35 ℃, however, at 55 ℃ the nitrate addition could largely promote the methane production. The microbial community structures were revealed by PCR-DGGE. The Actinobacteria, Clostridia, Clostridiales, Syntrophus, Pseudomonas, and Proteobacteria-like bacteria and Methanocellales, Methanosaeta, Methanomicrobiales, Methanolinea, Thermoprotei-like archaea had been enriched at 35 ℃ in the acetate addition test. The Thermoprotei, Proteobacterium, Thermodesulfovibrio-like bacteria and Methanocellales-like archaea had been enriched at 55 ℃ in the nitrate addition test. The results may shed light on the bio-utilization of marginal oil reservoirs for enhancing energy recovery.

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.

Methane to Liquid Hydrocarbons over Tungsten-ZSM-5 and Tungsten Loaded Cu/ZSM-5 Catalysts

Metal containing ZSM-5 can produce higher hydrocarbons in methane oxidation. Many researchers have studied the applicability of HZSM-5 and modify ZSM-5 for methane conversion to liquid hydrocarbons, but their research results still lead to low conversion, low selectivity and low heat resistance. The modified HZSM-5, by loading with tungsten （W）, could enhance its heat resistant performance, and the high reaction temperature （800 ℃） did not lead to a loss of the W component by sublimation. The loading of HZSM-5 with tungsten and copper （Cu） resulted in an increment in the methane conversion as well as CO2 and C5＋ selectivities. In contrast, CO, C2-3 and H2O selectivities were reduced. The process of converting methane to liquid hydrocarbons （C5＋） was dependent on the metal surface area and the acidity of the zeolite. High methane conversion and C5＋ selectivity, and low H20 selectivity are obtained over W/3.0Cu/HZSM.

Conversion of Methane to C_2 Hydrocarbons via Cold Plasma Reaction

Direct conversion of methane to C_2 hydrocarbons via cold plasma reactionwith catalysts has been studied at room temperature and atmospheric pressure. Methane can beconverted into C_2 hydrocarbons in different selectivity depending on the form of the reactor, powerof plasma, flow rate of methane, ratio of N_2/CH_4 and nature of the catalysts. The selectivity toC_2 hydrocarbons can reach as high as 98.64%, and the conversion of methane as high as 60% and theyield of C_2 hydrocarbons as high as 50% are obtained. Coking can be minimized under the conditionsof: proper selection of the catalysts, appropriate high flow rate of inlet methane and suitableratio of N_2 to CH_4. The catalyst surface provides active sites for radical recombination.

Quantification of Methane Fluxes from Hydrocarbon Seeps to the Ocean and Atmosphere:Development of an in situ and Online Gas Flux Measuring System

Natural hydrocarbon seeps in the marine environment are important contributors to greenhouse gases in the atmosphere. Such gases include methane, which plays a significant role in global carbon cycling and climate change. To accurately quantify the methane flux from hydrocarbon seeps on the seafloor, a specialized in situ and online gas flux measuring(GFM) device was designed to obtain high-resolution time course gas fluxes using the process of equal volume exchange. The device consists of a 1.0-m diameter, 0.9-m tall, inverted conical tent and a GFM instrument that contains a solenoid valve, level transducer, and gas collection chamber. Rising gas bubbles from seeps were measured by laboratory-calibrated GFM instruments attached to the top of the tent. According to the experimental data, the optimal anti-shake time interval was 5 s. The measurement range of the device was 0–15 L min^(-1), and the relative error was ± 1.0%. The device was initially deployed at an active seep site in the Lingtou Promontory seep field in South China Sea. The amount of gas released from a single gas vent was 30.5 m^3 during the measurement period, and the gas flow rate ranged from 22 to 72 Lh^(-1), depending on tidal period, and was strongly negatively correlated with water depth. The measurement results strongly suggest that oceanic tides and swells had a significant forcing effect on gas flux. Low flow rates were associated with high tides and vice versa. The changes in gas volume escaping from the seafloor seeps could be attributed to the hydrostatic pressure induced by water depth. Our findings suggest that in the marine environment, especially in the shallow shelf area, sea level variation may play an important role in controlling methane release into the ocean. Such releases probably also affect atmospheric methane levels.

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.

Methane Decomposition and C_2 Hydrocarbon Formation under the Condition of DC Discharge Plasma

The infrared emission spectra of methane, H, CH' and C_2 hydrocarbons in natural gas were measured. The processes of methane decomposition and formation of C_2 hydrocarbons were studied. The experiment shows that methane decomposition can be divided into three periods as the reaction proceeds. In the first period, a large number of free radicals were formed. While in the last period, the formation of C_2 hydrocarbons and the decrease of free radicals were observed. The time and conditions of methane decomposition and formation of C_2 hydrocarbons are different.

Comparison on Determination Results of Methane and Total Hydrocarbons by Glass Syringe Method and Air Bag Method

Samples at different setting time were determined by glass syringe method and air bag method, and their results were analyzed. The results showed that concentrations of methane and total hydrocarbons obviously declined with the prolonging of setting time by glass syringe method, and recovery rate of sample declined to 60% after 8 h. In air bag method, analysis results of methane and total hydrocarbons were stabler, and recovery rate of sample was 93% after 8 h.

Industrial Feasiblity of Direct Methane Conversion to Hydrocarbons over Fe-Based Fischer Tropsch Catalyst

Recently, as a direct consequence of the dwindling world oil reserves and the growing awareness of the environmental problems associated with the use of coal as energy source, there is growing interest in cheaper, abundant and cleaner burning methane. The Gas-to-Liquid technology offers perhaps the most attractive routes for the exploitation of the world huge and growing natural gas resources. Using this process the erstwhile stranded gas is converted to premium grade liquid fuels and chemicals that are easily transported. However, a widespread application of the GTL process is being hampered by economical and technical challenges. The high cost of synthesis gas, for instance, weighs heavily on the economics and competitiveness of the process limiting its wider application. This work presented a modified Gas-to-Liquid process that eliminates the costly synthesis gas production step. The proposed process utilized an alternative pathway for methane activation via the production of chloromethane derivatives which are then converted to hydrocarbons. It established that hydrocarbons mainly olefins can be economically produced from di- and tri-chloro- methanes over a typical iron-based Fischer Tropsch catalysts in a moving bed reactor at industrially relevant conditions. Some of the attractions of the proposed process include a) the elimination of the costly air separation plant requirement b) high process selectivity and c) significant reduction of carbon dioxide emissions thereby saving on feedstock loss and the costly CO2 removal and isolation processes.

Kinetic Parameters of Methane Generated from Source Rocks in the Kuqa Depression of Tarim Basin and Their Application

In a thermal simulation experiment of gold tubes of closed-system, calculating with the KINETICS and GOR-ISOTOPE KINETICS software, kinetic parameters of gas generation and methane carbon isotopic fractionation from Triassic-Jurassic hydrocarbon source rocks in the Kuqa depression of Tarim Basin are obtained. The activation energies of methane generated from Jurassic coal, Jurassic mudstone and Triassic mudstone in the Kuqa Depression are 197-268 kJ/mol, 180-260 kJ/mol and 214-289 kJ/mol, respectively, and their frequency factors are 5.265×10^13 s^-1, 9.761×10^11 s^-1 and 2.270×10^14 s^-1. This reflects their differences of hydrocarbon generation behaviors. The kinetic parameters of methane carbon isotopic fractionation are also different in Jurassic coal, Jurassic mudstone and Triassic mudstone, whose average activation energies are 228 kJ/mol, 205 kJ/mol and 231 kJ/mol, respectively. Combined with the geological background, the origin of natural gas in the Yinan-2 gas pool is discussed, and an accumulation model of natural gas is thus established. The Yinan- 2 gas is primarily derived from Jurassic coal-bearing source rocks in the Yangxia Sag. Main gas accumulation time is 5-0 Ma and the corresponding Ro is in the range from 1.25 %-1.95 %. The loss rate of natural gas is 25 %-30 %.

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.

Optimization of methane conversion to liquid fuels over W-Cu/ZSM-5 catalysts by response surface methodology

The conversion of methane to liquid fuels is still in the development process. The modified HZSM-5 by loading with Tungsten （W） enhanced its heat resistant performance, and the high reaction temperature （800℃） did not lead to the loss of W component by sublimation. The loading of ZSM-5 with Tungsten and Copper （Cu） resulted in an increment in the methane conversion, CO2, and C5＋ selectivities. The high methane conversion and C5＋ selectivity, and low H2O selectivity are obtained by using W/3.0Cu/ZSM-5. The optimization of methane conversion over 3.0 W/3.0Cu/ZSM-5 under different temperature and oxygen concentration using response surface methodology （RSM） are studied. The optimum point for methane conversion is 19% when temperature is 753 ℃, and oxygen concentration is 12%. The highest C5＋ selectivity is 27% when temperature is 751 ℃. and oxwen concentration is 11%.

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.

Effect of surface structure on the catalytic behavior of Ni:Cu/Al and Ni:Cu:K/Al catalysts for methane decomposition

Methane decomposition using nickel, copper, and aluminum （Ni：Cu/Al） and nickel, copper, potassium, and aluminum （Ni：Cu：K/Al） modified nano catalysts has been investigated for carbon fibers, hydrogen and hydrocarbon production. X-ray photoelectron spectroscopy （XPS）, static secondary ion mass spectrometry （SSIMS）, thermal gravimetric analysis （TGA）, Fourier transform infrared （FT-IR）, secondary electron microscopy/X-ray energy dispersive （SEM-EDX）, and temperature programmed desorption （TPD） were used to depict the chemistry of the catalytic results. These techniques revealed the changes in surface morphology and structure of Ni, Cu, Al, and K, and formation of bimetallic and trimetallic surface cationic sites with different cationic species, which resulted in the production of graphitic form of pure carbon on Ni：Cu/Al catalyst. The addition of K has a marked effect on the product selectivity and reactivity of the catalyst system. K addition restricts the formation of carbon on the surface and increases the production of hydrogen and C2, C3 hydrocarbons during the catalytic reaction whereas no hydrocarbons are produced on the sample without K. This study completely maps the modified surface structure and its relationship with the catalytic behavior of both systems. The process provides a flexible route for the production of carbon fibers and hydrogen on Ni：Cu/Al catalyst and hydrogen along with hydrocarbons on Ni：Cu：K/Al catalyst. The produced carbon fibers are imaged using a transmission electron microscope （TEM） for diameter size and wall structure determination. Hydrogen produced is COx free, which can be used directly in the fuel cell system. The effect of the addition of Cu and its transformation and interaction with Ni and K is responsible for the production of CO/CO2 free hydrogen, thus producing an environmental friendly clean energy.