Kinetic limit of the ethane and ethylene yield in the gas phase condensation of methane

A kinetic simulation of the initiated oxidative condensation of methane in the gas phase showed that the additional generation of methyl radicalsvia the reaction CH₄ + O₂ CH₃ + HO₂ causes a nearly tenfold increase in the C₂ hydrocarbon yield. However, a kinetic limit of the yield exists that is close to that determined in experiments on the catalytic oxidative condensation of methane.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 380–382, February, 1995.     

Kinetic studies of the oxidative coupling of methane over the Mn/Na2WO4/SiO2 catalyst

Oxidative coupling of methane is a direct way to obtain C2 hydrocarbon,and Mn-Na-W/SiO2 catalyst is the most promising among all the catalysts.The 2%Mn/5%Na2WO4/SiO2 catalyst was prepared by the incipient wetness impregnation method.A 7-step heterogeneous reaction model of the oxidative coupling of methane to C2 hydrocarbons was conducted by co-feeding methane and oxygen at a total pressure of 1 bar over the catalyst.The kinetic measurements were carried out in a micro-catalytic fixed bed reactor.The kinetic data were obtained at the appropriate range of reaction conditions (4 kPa＜Po2 ＜20 kPa,20 kPa＜PCZH4 ＜80 kPa,800℃＜T＜900℃).The proposed reaction kinetic scheme consists of three primary and four consecutive reaction steps.The conversions of hydrocarbons and carbon oxides were evaluated by applying Langrnuir-Hinshelwood type rate equations.Power-law rate equation was applied only for the water-gas shift reaction.In addition,the effects of operating conditions on the reaction rate were studied.The proposed kinetic model can predict the conversion of methane and oxygen as well as the yield of C2 hydrocarbons and carbon oxides with an average accuracy of ±15%.     

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。     

Experimental investigation of fluidized-bed reactor performance for oxidative coupling of methane

Performance of the oxidative coupling of methane in fluidized-bed reactor was experimentally investigated using Mn-Na2WO4/SiO2,La2O3/CaO and La2O3-SrO/CaO catalysts.These catalysts were found to be stable,especially Mn-Na2WO4/SiO2 catalyst.The effect of sodium content of this catalyst was analyzed and the challenge of catalyst agglomeration was addressed using proper catalyst composition of 2%Mn2.2%Na2WO4/SiO2.For other two catalysts,the effect of Lanthanum-Strontium content was analyzed and 10%La2O 3-20%SrO/CaO catalyst was found to provide higher ethylene yield than La2O3/CaO catalyst.Furthermore,the effect of operating parameters such as temperature and methane to oxygen ratio were also reviewed.The highest ethylene and ethane (C2) yield was achieved with the lowest methane to oxygen ratio around 2.40.5% selectivity to ethylene and ethane and 41% methane conversion were achieved over La2O3-SrO/CaO catalyst while over Mn-Na2WO4 /SiO2 catalyst,40% and 48% were recorded,respectively.Moreover,the consecutive effects of nitrogen dilution,ethylene to ethane production ratio and other performance indicators on the down-stream process units were qualitatively discussed and Mn-Na2WO4/SiO2 catalyst showed a better performance in the reactor and process scale analysis.     

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%.     

Influence of alkali metal doping on surface properties and catalytic activity/selectivity of CaO catalysts in oxidative coupling of methane

Surface properties （viz. surface area, basicity/base strength distribution, and crystal phases） of alkali metal doped CaO （alkali metal/Ca= 0.1 and 0.4） catalysts and their catalytic activity/selectivity in oxidative coupling of methane （OCM） to higher hydrocarbons at different reaction conditions （viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm^3 ·g^-1·h^-1） have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties （viz. surface area, basicity/base strength distribution） and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity （strong basic sites） and the C2＋ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO （Na/Ca = 0.1, before calcination） catalyst （calcined at 750 ℃）, showed best performance （C2＋ selectivity of 68.8% with 24.7% methane conversion）, whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.     

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.     

Comparative study of kinetic modeling for the oxidative coupling of methane by genetic and marquardt algorithms

Overall kinetic studies on the oxidative coupling of methane, OCM, have been conducted in a tubular fixed bed reactor, using perovskite titanate as the reaction catalyst. The appropriate operating conditions were found to be: temperature 750-775 ℃, total feed flow rate of 160 ml/min, CH4/O2 ratio of 2 and GHSV of 100 min-1. Under these conditions, C2 yield of 28% was achieved. Correlations of the kinetic data have been performed with lumped rate equations for C2 and COx formation as functions of temperature, O2 and CH4 partial pressures. Six models have been selected among the common lumped kinetic models. The selected models have been regressed with the experimental data which were obtained from the Catatest system by genetic algorithm in order to obtain optimized parameters. The kinetic coefficients in the overall reactions were optimized by different numerical optimization methods such as: the Levenberg-Marquardt and genetic algorithms and the results were compared with one another. It has been found that the Santamaria model is in good agreement with the experimental data. The Arrhenius parameters of this model have been obtained by linear regression. It should be noted that the Marquardt algorithm is sensitive to the first guesses and there is possibility to trap in the relative minimum.     

Effect of lithium addition on the performance of proton-conducting catalysts for oxidative coupling of methane under microwave irradiation

The oxidative coupling of methane over lithium modified proton-conducting catalysts irradiated by microwaves has been studied. Compared with protonconducting catalysts, lithium addition to proton-conducting catalysts resulted in changes in product species and product selectivities, favoring the production of C₂ compounds.     

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...     

Formation of hydrogen in oxidative coupling of methane over BaCO3 and MgO catalysts

Hydrogen formed in oxidative coupling of methane （OCM） over BaCO3 and MgO catalysts was measured since the data of H2 selectivity were missing almost in all articles published heretofore. It was found that H2 selectivity achieved about 18%, when C2 hydrocarbon＇s selectivity was maintained at 48%-45% over BaCO3 catalyst at the feed molar ratio of CH4/O2 = 4 in temperature range of 780 °C-820 °C. Under similar conditions, H2 selectivity was about 14%-16% over MgO catalyst, with C2 selectivity maintained at 41%-42%. Possible routes for hydrogen formation in OCM reaction were discussed. Effect of addition of alkali metallic ions was also investigated.     

Control of the directions of oxidative transformation of methane over nickel-based catalysts by acid-base properties

Two completely different directions of the oxidative transformation of methane (OTM) were performed on nickel-based catalysts due to the different acid-base properties of those catalysts. The relatively acidic LaNiO_x and LiNiLaO_x/Al₂O₃ catalysts exhibit excellent Partial Oxidation of Methane to Syngas (POM) performance. However, the relatively basic LiNiLaO_x catalyst has a good Oxidative Coupling of Methane to C₂ Hydrocarbons (OCM) activity. The basic properties of the catalyst makes it difficult to reduce nickel and keeps it in the oxidized state. Reduced nickel is necessary for POM and oxidized nickel for the OCM reaction.     

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.     

Characterization and catalytic behavior of Na-W-Mn-Zr-S-P/SiO2 prepared by different methods in oxidative coupling of methane

Na-W-Mn-Zr-S-P/SiO2 catalysts for oxidative coupling of methane (OCM) were prepared by incipient wetness impregnation, sol-gel and mixture slurry methods. The catalyst prepared by mixture slurry method showed the best catalytic performance among all samples. In addition, the effects of different addition sequences of Na, W, Mn, Zr, S and P on the catalytic performance were studied. The absence of Na before the addition of Mn and Zr in the catalysts preparation depressed the formation of the active phases of Mn2O3 and ZrO2 and decreased the activities of the catalysts significantly.     

Influence of the composition of perovskites based on SrMnO<Subscript>3</Subscript> on their catalytic properties in the oxidative coupling of methane

The oxidative coupling of methane (OCM) in a periodic regime over the SrMnO₃ and its derivatives has been investigated. It has been established that partial replacement of the strontium ion by alkali metal ions leads to an increase in both catalytic activity and in selectivity with respect to higher hydrocarbons. Comparison of the results obtained in the present work with those obtained earlier for catalysts based on SrCoO₃ led to the conclusion that the Co-containing catalysts were preferable to the Mn-containing catalysts for carrying out oxidative coupling of methane in a periodic regime.__________Translated from Teoreticheskaya i Éksperimentalnaya Khimiya, Vol. 41, No. 1, pp. 30–34, January–February, 2005.     

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.     

CFD modeling of reaction and mass transfer through a single pellet: Catalytic oxidative coupling of methane

In this study a mathematical model of a small scale single pellet for the oxidative coupling of methane(OCM)over titanite pervoskite is developed.The method is based on a computational fluid dynamics(CFD)code which known as Fluent may be adopted to model the reactions that take place inside the porous catalyst pellet.The steady state single pellet model is coupled with a kinetic model and the intra-pellet concentration profiles of species are provided.Subsequent to achieving this goal,a nonlinear reaction network consisting of nine catalytic reactions and one gas phase reaction as an external program is successfully implemented to CFD-code as a reaction term in solving the equations.This study is based on the experimental design which is conducted in a differential reactor with a Sn/BaTiO3 catalyst(7-8 mesh) at atmospheric pressure,GHSV of 12000 h-1,ratio of methane to oxygen of 2,and three different temperatures of 1023,1048 and 1073 K.The modeling results such as selectivity and conversion at the pellet exit are in good agreement with the experimental data.Therefore,it is suggested that to achieve high yield in OCM process the modeling of the single pellet should be considered as the heart of catalytic fixed bed reactor.     

Effect of methane co-feeding on the selectivity of ethylene produced from oxidative dehydrogenation of ethane with CO2 over a Ni-La/SiO2 catalyst

A Ni-La/SiO₂ catalyst was prepared through the incipient wetness impregnation method and tested in the oxidative dehydrogenation of ethane (ODHE) with CO₂. The fresh and used catalysts were characterized by XRD and SEM techniques. The Ni-La/SiO₂ catalyst exhibited catalytic activity for the oxidative dehydrogenation of ethane, but with low ethylene selectivity in the absence of methane. The selectivity to ethylene increased with increasing molar ratio of methane in the feed. The carbon deposited on the catalyst surface in the sole ODHE with CO₂ was mainly inert carbon, while much more filamentous carbon was formed in the presence of methane. The filamentous carbon was easy to be removed by CO₂, which might play a role in improving the conversion of ethane to ethylene. The introduction of methane might affect the equilibrium of the CO₂ reforming of ethane and the ODHE with CO₂. As a consequence, the synthesis gas produced from CO₂ reforming of methane partly inhibited the reaction of ethane and promoted the ODHE with CO₂, thus increasing the selectivity of ethylene.