Ce-promoted Mn/Na2WO4/SiO2 catalyst for oxidative coupling of methane at atmospheric pressure

A series of Ce-promoted Mn-Na2WO4/SiO2 catalysts were prepared by incipient wetness impregnation method, and their catalytic performance for oxidative coupling of methane (OCM) was investigated at atmospheric pressure in a micro-quartz-tube reactor. The catalysts were characterized by X-ray diffraction (XRD), temperature program reduction (TPR) and BET surface area. Ce promoter increased surface area and Na2WO4 species dispersion, which enriched the amount of the surface species. In addition, Ce promoter in...     

Kinetic study of oxidative coupling of methane over Mn and/or W promoted Na_2SO_4/SiO_2 catalysts

A comprehensive kinetic model for oxidative coupling of methane(OCM)over Mn and/or W promoted Na2SO4/SiO2 catalysts was developed based on a micro-catalytic reactor data.The methane conversion and ethylene,ethane,carbon monoxide and carbon dioxide selectivities were obtained in a wide operating condition range of 750 - 825-C,CH4/O2=2.5 - 10 and contact time=267 - 472 kg s m-3.Reaction networks of six models with different rate equation types were compared together.The kinetic rate parameters of each reaction network were estimated using linear regression or genetic algorithm optimization method(GA).A reaction network suggested by Stansch et al.for OCM was found to be the best one and was further used in this work.The suggested model could predict the experimental results of OCM reaction within a deviation range of ± 20%.     

Scale up and stability test for oxidative coupling of methane over Na2WO4-Mn/SiO2 catalyst in a 200 ml fixed-bed reactor

The study of scale up for the oxidative coupling of methane （OCM） has been carried out in a 200 ml stainless steel fixed-bed reactor over a 5wt% Na2WO4-1.9wt% Mn/SiO2 （W-Mn/SiO2） catalyst. The effects of reaction conditions were investigated in detail. The results showed that, with increasing reaction temperature, the gas-phase reaction was enhanced and a significant amount of methane was converted into COx; with the CH4/O2 molar ratio of 5, the highest C2 （ethylene and ethane） yield of 25% was achieved; the presence of steam （as diluent） had a positive effect on the C2 selectivity and yield. Under lower methane gaseous hourly space velocity （GHSV）, higher selectivity and yield of C2 were obtained as the result of the decrease of released heat energy. In 100 h reaction time, the C2 selectivity of 66%-61% and C2 yield of 24.2%-25.4% were achieved by a single pass without any significant loss in catalytic performance.     

Kinetic simulation of oxidative coupling of methane over perovskite catalyst by genetic algorithm： Mechanistic aspects

The reaction kinetics of oxidative coupling of methane catalyzed by perovskite was studied in a fixed bed flow reactor. At atmospheric pressure, the reactions were carried out at 725, 750 and 775 ℃, inlet methane to oxygen ratios of 2 to 4.5 and gas hourly space velocity (GHSV) of 100 min-1. Correlation of the kinetic data has been performed with the proposed mechanisms. The selected equations have been regressed with experimental data accompanied by genetic algorithm (GA) in order to obtain optimized parameters. After investigation the Langmuir-Hinshelwood mechanism was selected as the best mechanism, and Arrhenius and adsorption parameters of this model were obtained by linear regression. In this research the Marquardt algorithm was also used and its results were compared with those of genetic algorithm. It should be noted that the Marquardt algorithm is sensitive to the selection of initial values and there is possibility to trap in a local minimum.     

Oxidative coupling of methane over （Na2WO4＋Mn or Ce）/SiO2 catalysts： In situ measurement of electrical conductivity

The effects of manganese oxide or ceria promoters on the performance of Na2WO4/SiO2 catalysts for oxidative coupling of methane (OCM) are reported. The OCM reaction was performed in a continuous-flow microreactor at 800 ℃, atmospheric pressure and under GHSV = 13200 ml gC-1at h-1. Catalysts were characterized by in situ conductivity measurement, FT-IR spectroscopy, XRD, SEM and temperature programmed reduction analysis. Manganese oxide promoted Na2WO4/SiO2 is considered as one of the active and selective ca...     

Effects of operating parameters on oxidative coupling of methane over Na-W-Mn/SiO2 catalyst at elevated pressures

The effects of operating parameters on oxidative coupling of methane (OCM) over Na-W-Mn/SiO2 catalyst have been studied at elevated pressures of 0.2, 0.3 and 0.4 MPa under low gaseous hourly space velocity (GHSV) and low temperature conditions. Experimental results show that when the operating pressure is increased, C2+ yield slightly decreases, while the maximum ratio of ethylene to ethane remains unchanged. Moreover, it has been found empirically that increase of pressure does not affect the catalyst behavior permanently, the catalyst recovers its original low pressure performance without hysteresis behavior by reducing the pressure. Under the investigated conditions, when oxygen is completely consumed, the increase of GHSV leads to improvement in C2 selectivity, while C3+ and COx selectivities decrease slightly. The C2+ selectivity increases by increase of nitrogen diluent in the feed, but the C3+ hydrocarbons selectivities decrease with increase of nitrogen since it is possible that further dilution at high pressure may reduce the probability of collision between CH3 and C2+ hydrocarbons. During the stability test at high pressure, the catalyst performance remains unchanged throughout the 20 h running. The fresh and used catalysts were characterized using XRD, SEM and N2 adsorption-desorption methods. It was found that the phase transformation of the support from α-cristobalite to tridymite and quartz does not have obvious effect on catalyst performance at high pressure.     

Synthesis of Na2WO4-MnxOy supported on SiO2 or La2O3 as fiber catalysts by electrospinning for oxidative coupling of methane

The oxidative coupling of methane (OCM) is an attractive route to convert natural gas directly into value-added chemical products (C₂₊). This work comparatively investigated SiO₂- or La₂O₃-supported Na₂WO₄-Mn_xO_y (denoted as NWM) catalysts in powder and fiber forms. The powder catalysts were prepared using a co-impregnation method and the fiber catalysts were prepared successfully using an electrospinning technique. The NWM/La₂O₃ fiber catalysts were activated at low temperature (500 °C) and had a 4.7% C₂₊ yield, with the maximum C₂₊ yield of 9.6% at 650 °C, while the NWM/SiO₂ fiber catalyst was activated at 650 °C and had a maximum C₂₊ yield of 20.4% at 700 °C. The XPS results in the O 1s region indicated that NWM/La₂O₃ had a lower binding energy than NWM/SiO₂, suggesting that the lattice oxygen species is easily released from the catalyst surface and creates vacancy sites that enhance performance. The stability test of the catalysts indicated that the La₂O₃-containing catalysts had excellent activity and high thermal stability, while the SiO₂-containing catalysts had a higher C₂₊ yield when the prepared catalysts were compared at 700 °C. Considering the same component catalysts, the fiber catalysts achieved higher performance because their heat and mass transfer properties were enhanced.     

Studies on the structure and catalytic performance of S and P promoted Na-W-Mn-Zr/SiO2 catalyst for oxidative coupling of methane

A series of Na-W-Mn-Zr/SiO2 catalysts promoted by different contents of S or/and P were prepared and their catalytic performance for oxidative coupling of methane was investigated to clarify the effect of S and P on the Na-W-Mn-Zr/SiO2 catalyst. The catalysts were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). From the characterization results, it is found that the addition of S and P to the Na-W-Mn-Zr/SiO2 catalyst helps the formation of active phases, such as α-cristo...     

Concerning the dependence of the selectivity of the formation of ethane and ethylene on the degree of methane conversion during its oxidative coupling

The dependences of the maximum selectivity and the limiting yield of C₂ hydrocarbons on the degree of methane conversion during its gas-phase oxidative coupling were calculated by means of kinetic simulation. The correlation between the results of the calculations and the rersults obtained in the experimental studies dealing with catalytic oxidative coupling of methane is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 568–570, March, 1995.     

甲烷氧化偶联Na2WO4-Mn/SiO2催化剂热效应的研究

采用固定床微型反应装置,研究了甲烷氧化偶联反应过程中Na2WO4-Mn/S iO2催化剂床层的热效应和催化性能的关系,考察了反应炉温、CH4/O2比和反应气体空速对催化剂床层热点分布的影响.研究结果表明,甲烷氧化偶联催化剂床层的热效应强烈依赖于反应条件.反应炉温越高,CH4/O2比越低,反应气体空速越大,催化剂床层的热点温度越高.结合催化性能和热效应关系的研究,为优化甲烷氧化偶联的反应操作提供了实验依据.     

Suppressed formation of CO2 and H2O in the oxidative coupling of methane over La2O3/MgO catalyst by surface modification

Oxidative coupling of methane (OCM) is a promising way to convert methane into C_2 hydrocarbons. However, CO_2 and H_2O are by-products of the reaction. To utilize the higher activity of lanthanum oxide and save its usage, MgO supported La_2O_3 catalyst was prepared. Surface modification of the catalyst with nitric acid was made to suppress the formation of the by-products. Experimental results indicated that the addition of nitric acid increased the surface oxygen species with binding energy of ca. 531.7 eV and at the same time reduced the pore volume of the catalyst. These effects of nitric acid finally led to the increase of C_2 selectivity and the decrease of the by-products formation. Hydrogen selectivity was found about 14%- 18% over the catalysts adopted in this work.     

LiCl对Fe_2O_3/SiO_2甲烷氧化偶联反应的助催化作用

使用穆斯堡尔谱，ESR和XRD等技术表征了未添加助剂和添加LiCl的Fe2O3／SiO2催化剂．XRD结果指出，添加LiCl的Fe2O／SiO2催化剂出现铁酸盐和α-方石英的衍射峰，这种结果的出现与该催化剂有较高的C2烃选择性密切相关。穆斯堡尔谱结果表明：添加LiCl的Fe2O3／SiO2催化剂有更高的结构对称性．这种结构对分子氧的活化起着重要的作用．氯的存在大大降低了氧的离解吸附的速率，减少了原子氧的吸附位的数目，并可除去吸附的原子氧，该氧种对COx的生成有利．     

甲烷氧化偶联制烯烃的热力学平衡限度

选择适宜的热力学模型对甲烷氧化偶联制烯烃体系的热力学平衡进行分析,考察温度﹑压力﹑进料组成对体系组分的平衡限度影响。研究发现,在甲烷氧化偶联制烯烃体系中,H2、CO的生成相对容易,C2产物（C2H4、C2H6）不容易生成。通过计算,得到了该体系有利于烯烃生成的反应条件,500℃～800℃、1.5MPa、烷氧摩尔比为7。实验为甲烷氧化偶联反应器和催化剂的开发研究提供热力学依据。     

Oxidative coupling of methane over La-promoted CaO catalysts： Influence of precursors and catalyst preparation method

The oxidative coupling of methane to C2 hydrocarbons has been studied over a series of La-promoted CaO (La/Ca = 0.05) catalysts, prepared using different precursor salts for CaO and La2O3 (viz. acetates, carbonates, nitrates and hydroxides) and catalyst preparation methods (viz. physical mixing of precursors, co-precipitation using ammonium carbonate/sodium carbonate as a precipitating agent), under different reaction conditions (temperature: 700-850℃, CH4/O2 ratio: 4.0 and 8.0, and GHSV: 51360 cm3 g-1 h-1)...     

Oxidative coupling of methane over BaCl2-TiO2-SnO2 catalyst

The performance of BaCl2-TiO2-SnO2 composite catalysts in oxidative coupling of methane reaction has been investigated. A series of BaCl2-TiO2, BaCl2-SnO2, TiO2-SnO2, and BaCl2-TiO2-SnO2 catalysts were prepared, and characterized by BET, XRD, XPS, CO2-TPD and H2-TPR, respectively. The synergistic effect among BaCl2, SnO2 and TiO2 compositions enhances the catalytic performance. The best C2 selectivity and ethylene yield are obtained on the catalyst with the equal molar amount of the three compositions (BaCl2 : TiO2 : SnO2 molar ratio of 1 : 1 : 1). The optimal reaction conditions are as follows: 800°C, 44 mL·min-1 for methane, 22 mL·min-1 for oxygen and a space velocity of 5000 mL·h-1 g-1, and the C2H4 yield over the catalyst is 20.1% with the CH4 conversion of 43.8% and C2 selectivity of 53.3%.     

硫酸钠对Mn/SiO2催化剂结构及其甲烷氧化偶联反应性能的影响

 采用等体积浸渍法制备了Na2SO4改性的Mn/SiO2催化剂,考察了Mn-Na2SO4/SiO2催化剂中各组分对甲烷氧化偶联合成C2产物(C2H4+C2H6)的影响,并采用X射线衍射、 X射线光电子能谱、 Raman光谱和程序升温还原等手段表征了催化剂中的物相结构、表面组分价态与含量以及氧化还原性能. 结果表明,在Mn/SiO2催化剂中添加Na2SO4可使载体SiO2由无定形转变为α-方石英相,使催化剂表面的Mn物种由Mn3O4转变为Mn2O3, 从而大大提高了甲烷转化率和目标产物C2的选择性. 因此,推测Mn2O3物种在反应条件下构成了甲烷氧化偶联反应的活性中心.