Conversion of methane through dielectric-barrier discharge plasma

Methane coupling to produce C₂ hydrocarbons 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 temperature becomes slow due to cooling of outer electrode and the temperature can be controlled in the expected range of 60°C–150°C 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 ethylene, ethane and propane. The selectivity of C₂ hydrocarbons can reach 74.50% when volume ratio of hydrogen to methane is 1.50. __________ Translated from Petrochemical Technology, 2007, 36(11): 1099–1103 [译自: 石油化工]     

Methane conversion to C2 hydrocarbons and hydrogen in atmospheric non-thermal plasmas generated by different electric discharge techniques

Methane conversion to C₂ hydrocarbons and hydrogen has been investigated in a needle-to-plate reactor by pulsed streamer and pulsed spark discharges and in a wire-to-cylinder dielectric barrier discharge (DBD) reactor by pulsed DC DBD and AC DBD at atmospheric pressure and ambient temperature. In the former two electric discharge processes, acetylene is the dominating C₂ products. Pulsed spark discharges gives the highest acetylene yield (54%) and H₂ yield (51%) with 69% of methane conversion in a pure methane system and at 10 SCCM of flow rate and 12 W of discharge power. In the two DBD processes, ethane is the major C₂ products and pulsed DC DBD provides the highest ethane yield. Of the four electric discharge techniques, ethylene yield is less than 2%. Energy costs for methane conversion, acetylene or ethane (for DBD processes) formation, and H₂ formation increase with methane conversion percentage, and were found to be: in pulsed spark discharges (methane conversion 18–69%), 14–25, 35–65 and 10–17 eV/molecule; in pulsed streamer discharges (methane conversion 19–41%), 17–21, 38–59, and 12–19 eV/molecule; in pulsed DBD (methane conversion 6–13%), 38–57, 137–227 and 47–75 eV/molecule; in AC DBD (methane conversion 5–8%), 116–175, 446–637, and 151–205 eV/molecule, respectively. The immersion of the γ-Al₂O₃ pellets in the pulsed streamer discharges, or in the pulsed DC DBD, or in the AC DBD has a positive effect on increasing methane conversion and C₂ yield.     

介质阻挡放电常压低温等离子体转化甲烷制C2及高碳烃的研究

对介质阻挡放电(DBD)反应器用于甲烷常压低温等离子体转化过程,分别就停留时间、输入功率、内电极材料及温度、介质厚度等对反应的影响进行了研究。实验结果表明,甲烷转化率随停留时间、输入功率的增加而增加,但增加的幅度逐渐减小。内电极材料对反应积炭有很大的影响。紫铜和紫铜(镀银)材料能够有效地抑制积炭的产生,从而可以增加反应寿命,还对甲烷转化率有很大的影响。较低的内电极温度可以抑制积炭,但是甲烷转化率有所降低,同时液态高碳烃选择性增加。在甲烷流量较低时介质厚度对反应的影响很小,但随着甲烷流量的提高会逐渐增大,并且介质厚度越小,甲烷转化率越高。     

Production of gasoline range hydrocarbons from catalytic reaction of methane in the presence of ethylene over W/HZSM-5

The catalytic conversion of a methane and ethylene mixture to gasoline range hydrocarbons has been studied over W/HZSM-5 catalyst. The effect of process variables, such as temperature, percentage of volume of ethylene in the methane stream and catalyst loading on the distribution of hydrocarbons was studied. The reaction was conducted in a fixed-bed quartz-micro reactor in the temperature range of 300–500 °C using percentage of volume of ethylene in methane stream between 25 and 75% and catalyst loading of 0.2–0.4 g. The catalyst showed good catalytic performance yielding hydrocarbons consisting of gaseous products along with gasoline range liquid products. The mixed feed stream can be converted to higher hydrocarbons containing a high-liquid gasoline product selectivity (>42%). Non-aromatics C₅–C₁₀ hydrocarbons selectivity in the range of 12–53% was observed at the operating conditions studied. Design of experiment was employed to determine the optimum conditions for maximum liquid hydrocarbon products. The distribution of the gasoline range hydrocarbons (C₅–C₁₀ non-aromatics and aromatics hydrocarbons) was also determined for the optimum conditions.     

The simultaneous activation of methane and carbon dioxide to C2 hydrocarbons under pulse corona plasma over La2O3/γ-Al2O3 catalyst

The pulse corona plasma has been used as an activation method for reaction of methane and carbon dioxide, the product was C₂ hydrocarbons and by-products were CO and H₂. Methane conversion and the yield of C₂ hydrocarbons were affected by the carbon dioxide concentration in the feed. The conversion of methane increased with increasing carbon dioxide concentration in the feed whereas the yield of C₂ hydrocarbons decreased. The synergism of La₂O₃/γ-Al₂O₃ and plasma gave methane conversion of 24.9% and C₂ hydrocarbons yield of 18.1% were obtained at the power input of plasma was 30 W. The distribution of C₂ hydrocarbons changed by using Pd-La₂O₃/γ-Al₂O₃ catalyst, the major C₂ product was ethylene.     

Dielectric barrier micro-plasma reactor with segmented outer electrode for decomposition of pure CO2

Four coaxial cylinder dielectric barrier discharge micro-plasma reactors were designed for the non-catalytic decomposition of pure CO₂ into CO and O₂ at low temperature and ambient pressure. The influence of segmented outer electrodes on the electrical characteristics and the reaction performance was investigated. Experimental results indicated that the introduction of segmented outer electrodes can significantly promote the decomposition of CO₂. Encouragingly, the highest conversion of 13.1% was obtained at an applied voltage of 18 kV, which was a substantial increase of 39.4% compared to the traditional device. Compared with other types of dielectric barrier discharge plasma reactors, the proposed segmented outer electrode micro-plasma reactor can give a higher CO₂ conversion and acceptable energy efficiency. The increase in conversion can be attributed mainly to the enhanced corona discharge caused by the fringe effect at electrode edges, the increase in energy density and the increase in the number of micro-discharges. In addition, detailed electrical characterization was performed to reveal some trends in the electrical behavior of proposed reactors.     

等离子体与Cu-Pd/S-1催化剂协同催化甲烷转化制低碳烯烃

采用等体积浸渍法制备了Pd、Cu-Pd改性的S-1催化剂,利用介质阻挡放电（DBD）等离子体反应器研究了甲烷无氧转化制低碳烯烃（C₂~C₄⁼）的性能,重点关注了乙烯的产量。探讨了Ar的添加和特定输入能量（SIE）对甲烷转化率以及产物分布的影响。实验结果表明,等离子体与催化剂协同催化与仅使用等离子体相比性能更优异,使乙烯选择性提高了3.1倍,C₂~C₄⁼的选择性提高了2.7倍;与S-1相比,Pd/S-1具有更高的乙烯选择性,这是因为在S-1上负载金属Pd有助于乙炔原位加氢生成乙烯;适宜的Pd负载量有利于提高烯烃选择性,而过高的Pd负载量倾向于不饱和烃的连续加氢,导致了烷烃的生成;与单金属Pd改性相比,Cu-Pd双金属改性抑制了乙烯的进一步加氢,提高了乙烯的选择性。通过扫描电子显微镜（SEM）、透射电子显微镜（TEM）、高倍透射电子显微镜（HRTEM）、X射线粉末衍射（XRD）、X射线光电子能谱（XPS）对催化剂进行了表征分析。结果表明,Cu的加入使自身电子向Pd转移,增加了Pd电子密度;另外,Cu的存在提高了Pd的分散性。以2Cu-0.1Pd/S-1为催化剂时可以得到更优异的反应性能。     

Reaction pathways of methane conversion in dielectric-barrier discharge

Conversion of methane to C₂, C₃, C₄ or higher hydrocarbons in a dielectric-barrier discharge was studied at atmospheric pressure. Non-equilibrium plasma was generated in the dielectric-barrier reactor. The effects of applied voltage on methane conversion, as well as selectivities and yields of products were studied. Methane conversion was increased with increasing the applied voltage. Ethane and propane were the main products in a dielectric-barrier discharge at atmospheric pressure. The reaction pathway of the methane conversion in the dielectric-barrier discharge was proposed. The proposed reaction pathways are important because they will give more insight into the application of methane coupling in a DBD at atmospheric pressure.     

Reaction mechanism of methane activation using non-equilibrium pulsed discharge at room temperature

The reaction mechanism of methane activation using non-equilibrium pulsed discharge was largely clarified from the emission spectroscopic study and experiments with higher hydrocarbons and some kinds of isotopes. The strong emission of atomic carbon and C₂ swan band system was observed as well as H Balmer series emission. This indicates that methane was highly dissociated into C and H by electron impact, which is consistent with the result of high C₂D₂ composition in produced acetylene when the mixture of CH₄ and D₂ was fed into discharge region. High electron energy contributed to produce atomic carbon directly from methane, and high electron density promoted the dehydrogenation from CH₃, CH₂ and CH to produce atomic carbon consecutively. The reason for the high selectivity to C₂H₂ was the high concentration of CH or C₂ formed from atomic carbon, and the repetition mechanism of decomposition and recombination among C, CH, C₂ and C₂H₂.     

Hydrogen production from methanol through dielectric barrier discharge

The hydrogen fuel cell is a promising option as a future energy resource and the production of hydrogen is mainly depended on fossil fuels now. In this paper, methanol reforming to produce H₂ through dielectric-barrier discharge (DBD) plasma reaction was studied. Effects of the power supply parameters, reactor parameters and process conditions on conversion of methanol and distribution of products were investigated. The best reaction conditions were following: input power (45 W), material of inner electrode (stainless steel), discharge gap (3.40 mm), length of reaction zone (90.00 mm), dielectric thickness (1.25 mm), and methanol content (37.65%). The highest conversion of methanol and the yield of H₂ were 82.38% and 27.43%, respectively.     

Oxidative coupling of methane in fluidized- and packed-fluidized-bed reactors

Oxidative coupling of methane to higher hydrocarbons (C₂₊) using NaOH/CaO and pure CaO as catalyst was studied in fluidized- and packed-fluidized-bed reactors at 700°C to 800°C, partial pressures of methane from 0.5 to 0.7 bar and oxygen from 0.05 to 0.25 bar and a total pressure of ca 1 bar; oxygen conversion amounted generally to 50 to 100 %. C₂₊ selectivity depends for both reactors markedly on temperature and oxygen partial pressure. The optimum temperature ranges between 750 and 800°C. Highest selectivities (ca 76 %) were achieved at the lowest oxygen partial pressure (ca 0.06 bar); maximum yields (ca 13.5 %), however, were obtained at an oxygen partial pressure of ca 0.14 bar. The application of the fluidized-bed reactor is more favourable than the packed-fluidized-bed reactor with respect to operability and C₂₊ selectivity.     

Plasma methane conversion using dielectric-barrier discharges with zeolite A

Experimental investigation on plasma methane conversion in the presence of carbon dioxide using dielectric-barrier discharges (DBDs) has been conducted. Zeolite A has been applied to inhibit the formation of carbon black and plasma-polymerized film during such plasma methane conversion. A co-generation of syngas, light hydrocarbons and liquid fuels has been achieved. The conversions and selectivities are determined by the CH₄/CO₂ feed ratio, residence time and input power. Compared to the use of zeolite X within the DBDs, plasma methane conversion with zeolite A leads to a higher selectivity of light hydrocarbons (C₂–C₄).     

Improved performance of non-thermal plasma reactor during decomposition of trichloroethylene: Optimization of the reactor geometry and introduction of catalytic electrode

The decomposition of trichloroethylene (TCE) by non-thermal plasma was investigated in a dielectric barrier discharge (DBD) reactor with a copper rod inner electrode and compared with a plasma-catalytic reactor. The particularity of the plasma-catalytic reactor is the inner electrode made of sintered metal fibers (SMF) coated by transition metal oxides. In order to optimize the geometry of the plasma reactor, the efficiency of TCE removal was compared for different discharge gap lengths in the range of 1–5 mm. Shorter gap lengths (1–3 mm) appear to be more advantageous with respect to TCE conversion. In this case TCE conversion varies between 67% and 100% for input energy densities in the range of 80–480 J/l, while for the 5 mm discharge gap the conversion was lower (53–97%) for similar values of the input energy. As a result of TCE oxidation carbon monoxide and carbon dioxide were detected in the effluent gas. Their selectivity was rather low, in the range 14–24% for CO₂ and 11–23% for CO, and was not influenced by the gap length. Several other chlorinated organic compounds were detected as reaction products.

When using MnOx/SMF catalysts as the inner electrode of the DBD reactor, the TCE conversion was significantly enhanced, reaching 95% at 150 J/l input energy. The selectivity to CO₂ showed a major increase as compared to the case without catalysts, reaching 58% for input energies above 550 J/l.     

C2 hydrocarbons formation from methane on silver membrane

The formation of C₂ hydrocarbons from methane has been investigated by membrane process using an oxygen diffusion through the silver membrane. Oxidative coupling of methane over the silver catalysts has been studied. The results indicate that strongly bound atomic oxygen, formed by diffusion of dissolved oxygen to silver surface, is responsible for the formation of C₂ products. Weakly bound atomic oxygen also can react to form C₂ hydrocarbons but mainly it leads to complete oxidation.     

H2 production by ethanol decomposition with a gliding arc discharge plasma reactor

A gliding arc discharge (GRD) reactor was used to decompose ethanol into primarily H₂ and CO with small amounts of CH₄, C₂H₂, C₂H₄, and C₂H₆. The ethanol concentration, electrode gap, input voltage and Ar flow rate all affected the conversion of ethanol with results ranging from 40.7% to 58.0%. Interestingly, for all experimental conditions the S_H2/S_CO selectivity ratio was quite stable at around 1.03. The mechanism for the decomposition of ethanol is also described.     

CO, H2 or C3H8 assisted catalytic combustion of methane over supported LaMnO3 monoliths

The effect of the addition of a second fuel such as CO, C₃H₈ or H₂ on the catalytic combustion of methane was investigated over ceramic monoliths coated with LaMnO₃/La-γAl₂O₃ catalyst. Results of autothermal ignition of different binary fuel mixtures characterised by the same overall heating value show that the presence of a more reactive compound reduces the minimum pre-heating temperature necessary to burn methane. The effect is more pronounced for the addition of CO and very similar for C₃H₈ and H₂. Order of reactivity of the different fuels established in isothermal activity measurements was: CO>H₂≥C₃H₈>CH₄. Under autothermal conditions, nearly complete methane conversion is obtained with catalyst temperatures around 800 °C mainly through heterogeneous reactions, with about 60–70 ppm of unburned CH₄ when pure methane or CO/CH₄ mixtures are used. For H₂/CH₄ and C₃H₈/CH₄ mixtures, emissions of unburned methane are lower, probably due to the proceeding of CH₄ homogeneous oxidation promoted by H and OH radicals generated by propane and hydrogen pyrolysis at such relatively high temperatures.

Finally, a steady state multiplicity is found by decreasing the pre-heating temperature from the ignited state. This occurrence can be successfully employed to pilot the catalytic ignition of methane at temperatures close to compressor discharge or easily achieved in regenerative burners.     

Direct synthesis of middle iso-paraffins from synthesis gas on hybrid catalysts

This paper focuses on the synthesis of iso-paraffin-rich hydrocarbons by Fischer–Tropsch synthesis (FTS) over silica gel supported Co catalyst (Co/SiO₂). The basic concept is to isomerize and/or hydrocrack the primary FTS hydrocarbon products. A physical mixture consisting of a small amount of zeolite or Pd/zeolite mixed with Co/SiO₂ enhanced the formation of C₄–C₁₀ iso-paraffins while suppressing the formation of higher molecular hydrocarbons, probably because of the selective cracking of these hydrocarbons on them. In separate experiments, a two-reactor system was used. The first reactor contained a physical mixture of Co/SiO₂ and zeolite, and the second reactor contained zeolites or Pd-supported zeolites. The two-reactor system gave sharp C-number distribution within C₃–C₆ and iso-paraffins-rich products. The hydrocracking of n-octane and n-decane (model compound simulating products of the FTS reaction) over mixed catalysts composed of various compositions of Pd/SiO₂ and ZSM-5 in the presence of gaseous hydrogen showed high and stable activity, and produced primarily iso-paraffin-rich hydrocarbons. The isomerization was favored for mixtures rich in Pd/SiO₂. The role of Pd was thought to be the inlet of hydrogen spillover to the zeolite surface.     

The effects of kinetics, hydrodynamics and feed conditions on methane coupling using fluidized bed reactor

A previously developed model describing bubbling fluidized bed reactors is used in this investigation to study the effect of various important hydrodynamic, operating and design parameters on the performance of a large scale fluidized bed reactor used in oxidative coupling of methane. Three kinetic schemes obtained from the literature have been used in this study. The model predicted fairly well the experimental results reported recently under different reaction conditions. The simulation results revealed that increasing the ratio of methane to oxygen in the feed leads to lower methane conversion but higher C₂ selectivity. As the ratio is decreased the system loses its fixed-point stability to a periodic stability. Higher methane conversion and product selectivity are obtained upon decreasing the feed flow rate and particle diameter.     

Deactivated iron catalyst in the fischer-tropsch synthesis

The selectivity for higher hydrocarbons (C₁₁–C₁₇) has been studied in the Fischer-Tropsch synthesis using fresh and used fused iron catalysts under different reaction conditions. On increasing the temperature higher hydrocarbon products were formed in the C₁₁–C₁₇ range. The deactivated fused iron catalyst is less active but selective to heavier hydrocarbon chain molecules. The product distribution is shifted towards heavier hydrocarbons due to the effects of the pore volume, presence of potassium and site densities at the surface.     

OXIDATIVE COUPLING OF METHANE ON SUPERCONDUCTOR-TYPE CATALYTIC MATERIALS

Oxidative coupling of methane to higher hydrocarbons was investigated using alkali and rare earth cuprates such as YBa₂Cu₃O_7-x, La_1.8Ba_0.2CuO and La₂CuO₄. Oxygen and methane in helium were fed to the reactor in a cofeed mode. Approximately, 5 g of catalyst in powder form was placed in a quartz flow reactor in all experiments. Oxygen partial pressure was changed as a parameter (P₀ = 0.5 to 9.1 kPa) while keeping methane partial pressure and temperature constant at 18kPa and 1023 K respectively. Investigation of catalytic activity in terms of overall methane conversion and C₂ + (C₂H₄+C₂H₆) product selectivity indicated that higher conversions and lower selectivities were obtained as O₂ partial pressure was increased at a constant methane partial pressure of 8kPa. In comparing the performance of the two catalysts, La_1.8Ba_0.2CuO and La₂CuO₄; the selectivity results indicated a positive influence of incorporation of Ba into La₂CuO₄ structure. Similarly, selectivity values substantially increased teaching 86.3% at a reaction temperature of 1023 K and at P_CH4./P_O3, = 6 when La was replaced by Y and Ba.