Oxidative Coupling of Methane over Lithium Doped (Mn+W)/SiO_2 Catalysts

Modification and performance of Li induced silica phase transition of （Mn＋W）/SiO2 catalyst, under reaction conditions of oxidative coupling of methane （OCM）, have been investigated employing textural characterizations and redox studies. Stability and precrystalline form of fresh Li induced silica phase transition catalyst depend on the Li loading. A catalyst, with high lithium loading, destabilizes on OCM stream. This destabilization is not due to Li evaporation at OCM reaction conditions, α-cristobalite is proposed to be an intermediate in the crystallization of amorphous silica into quartz in the Li-induced silica phase transition process. However, the type of crystalline structure was found to be unimportant with regard to the formation of a selective catalyst. Metal-metal interactions of Li-Mn, Li-W and Mn-W, which are affected during silica phase crystallization, are found to be critical parameters of the trimetallic catalyst and were studied by TPR. Role of lithium in Li doped （Mn＋W）/SiO2 catalyst is described as a moderator of the Mn-W interaction by involving W in silica phase transition. These interactions help in the improvement of transition metal redox properties, especially that of Mn, in favor of OCM selectivity.

Reaction Chemistry of W-Mn/SiO2 Catalyst for the Oxidative Coupling of Methane

Reaction chemistry of the OCM reaction on W-Mn/SiO_2 catalyst has beenreviewed in this account. Initial activity and selectivity, stability in a long-term reaction,reaction at elevated pressures and a modelling test in a stainless-steel fluidized-bed reactor showthat W-Mn/SiO_2 has promising performance for the development of an OCM process that directlyproduces ethylene from natural gas. A study on surface catalytic reaction kinetics and used catalyststructure characterization revealed a possible reason why C_2 and CO_x selectivity changed duringthe long-term reaction. Further improvement of the catalyst composition and preparation methodshould be a future direction of study on OCM reaction over W-Mn/SiO_2 catalyst.

Kinetics of oxidative coupling of methane:Bridging the gap between comprehension and description

The development of notions about the mechanism of the oxidative coupling of methane （OCM） over oxide catalysts and corresponding progress in its kinetic description are reviewed and discussed. The latter becomes essential at the stage of scaling up and optimization of the process in pilot and industrial reactors. It is demonstrated that the main achievements in the development of kinetic models can be reached by combining the approaches conventionally used in homogeneous gas-phase kinetics and in heterogeneous catalysis. In particular, some important features of the OCM process can be described if several elementary reactions of free radical species （formation and transformation） with surface active sites are included into the detailed scheme of methane oxidation in gas. However, some important features, such as a non-additive character of the reciprocal influence of methane and ethane in the case of their simultaneous presence in the reaction mixture, cannot yet be described and comprehended in the framework of schemes developed so far. Possible ways towards an advanced kinetic model, accounting the main principles of catalyst functioning （redox nature of active sites） and pathways of product formation （via free radicals） are traced.

Rule of 100:An inherent limitation or performance measure in oxidative coupling of methane?

The oxidative coupling of methane over La203/CaO type-catalyst in a fixed-bed reactor is studied under a wide range of operating conditions （973〈T〈 1103 K, 55〈 Ptotal 〈220 kPa, and 3.7〈 mcat/VTp 〈50 kg.s/m^3）. A ten-step kinetic model incorporating all main products was used to predict the behavior of the system. Methane conversions and C2 selectivities were calculated by varying methane to oxygen ratios in the feed under different operating conditions which were also compared with the rule of 100. The results show that deviation from this rule depends on the operating conditions. Within the range studied, an increase in pressure, temperature and contact time results in smaller deviation from the rule. This rule is best approximated when the catalyst operates near its optimal performance. For negative deviations, common to the most catalysts, it is found that the optimal performance should occur at methane conversion levels lower than 50%. A plot of selectivity versus conversion for high-yield reported performance data of a large variety of catalysts shows that data points concentrated roughly in 20%-50% methane conversion region, confirming the generality and prediction of modeling.

METHANE OXIDATIVE COUPLING OVER METAL OXYFLUORIDE CATALYSTS

The MOC reaction over ZrO_2/LaF_3, CeO_2/LaF_3 and ThO_2/LaF_3 catalysts indicated that these catalysts had high activity and high C_2 selectivity at low temperature. In the temperature range 480℃ to 650℃. The methane conversion was 24. 4% to 30. 8% and the C_2 selectivity was 40. 0% to 55. 4%. The XRD characterization of the catalysts indicated that O^2. and F exchang happened and LaOF was formed.

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.

Kinetic studies of the oxidative coupling of methane over the Mn/Na_2WO_4/SiO_2 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〈PcH4〈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 Langmuir-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%.

Studies on the structure and catalytic performance of S and P promoted Na-W-Mn-Zr/SiO_2 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-ZffSiO2 catalyst helps the formation of active phases, such as α-cristobalite, Na2WO4, ZrO2, and Na2SO4. Moreover, the addition of S and P increases the concentration of surface-active oxygen species by improving the migration of active components from the bulk phase to the surface of the catalyst. According to the activity test, impressive methane conversion and C2 hydrocarbons yield were obtained at a low temperature of 1023 K over the six-component Na-W-Mn-Zr-S-P/SiO2 catalyst, which contained 2 wt% S and 0.4 wt% P simultaneously. The deactivation of Na-W-Mn-Zr-S-P/SiO2 was due to the loss of surface active components.

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.

Ce-promoted Mn/Na_2 WO_4/SiO_2 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 increased the Na/W species reduction, but the reduction peak shifted to higher temperature. Stability test of 5wt%Ce catalyst indicated suitable performance and stability. The selectivity and yield of C^2＋ hydrocarbons after 50 h operation reached 65.5% and 19.6%, respectively, at 840 ℃ over 5wt%Ce-2wt%Mn5wt%Na2WO4/SiO2 catalyst.

Scale up and stability test for oxidative coupling of methane over Na_2WO_4-Mn/SiO_2 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.

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,C 2 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 CO_2 on the structural variation of Na_2WO_4/Mn/SiO_2 catalyst for oxidative coupling of methane to ethylene

In this work,the influence of CO2 on the structural variation and catalytic performance of Na2WO4/Mn/Si O2 for oxidative coupling of methane to ethylene was investigated. The catalyst was prepared by impregnation method and characterized by XRD,Raman and XPS techniques. Appropriate amount of CO2 in the reactant gases enhanced the formation of surface tetrahedral Na2WO4 species and promoted the migration of O in MOx,Na,W from the catalyst bulk to surface,which were favorable for oxidative coupling of methane. When the molar ratio of CH4/O2/CO2 was 3/1/2,enriched surface tetrahedral Na2WO4 species and high surface concentration of O in MOx,Na,W were detected,and then high CH4 conversion of 33.1% and high C2H4 selectivity of 56.2% were obtained. With further increase of CO2 in the reagent gases,the content of active surface tetrahedral Na2WO4 species and surface concentration of O in MOx,Na,W decreased,while that of inactive species（Mn WO4 and Mn2O3） increased dramatically,leading to low CH4 conversion and low C2H4 selectivity. It could be speculated that Na2WO4 crystal was transformed into Mn WO4 crystal with excessive CO2 added under the reaction conditions. Pretreatment of Na2WO4/Mn/Si O2 catalyst by moderate amount of CO2 before OCM also promoted the formation of Na2WO4 species.

Effects of operating parameters on oxidative coupling of methane over Na-W-Mn/SiO_2 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.

Characterization and catalytic behavior of Na-W-Mn-Zr-S-P/SiO_2 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.

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.

Formation of hydrogen in oxidative coupling of methane over BaCO_3 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.

Surface coupling of methyl radicals for efficient low‐temperature oxidative coupling of methane

Selective coupling of methyl radicals to produce C_(2) species(C2H4 and C2H6)is a key challenge for oxidative coupling of methane(OCM).In traditional OCM reaction systems,homogeneous transformation of methyl radicals in O_(2)‐containing gases are uncontrollable,resulting in limited C_(2) selectivity and yield.Herein,we demonstrate that methyl radicals generated by La_(2)O_(3)at low reaction temperature can selectively couple on the surface of 5 wt%Na2WO4/SiO_(2).The controllable surface coupling against overoxidation barely changes the activity of La_(2)O_(3)but boosts the C_(2)selectivity by three times and achieves a C_(2)yield as high as 10.9%at bed temperature of only 570℃.Structure‐property studies suggest that Na_(2)WO_(4) nanoclusters are the active sites for methyl radical coupling.The strong CH_(3)·affinity of these sites can even endow some methane combustion catalysts with OCM activity.The findings of the surface coupling of methyl radicals open a new direction to develop OCM catalyst.The bifunctional OCM catalyst system,which composes of a methane activation center and a CH_(3)·coupling center,may deliver promising OCM performance at reaction temperatures below the ignition temperature of C2H6 and C2H4(~600℃)and is therefore more controllable,safer,and certainly more attractive as an actual process.

Methane Oxidative Coupling over Fluoride-Promoted Cerium Oxide Catalysts

Since the pioneer work of Keller and Bhasin on the oxidative coupling of methane, many catalyst systems, mostly based on the oxides or complex oxides of alkali metals, alkali earth metals and rare earth metals, have been developed. In some studies, halides, especially chlorides and bromides, have been added to these oxides in order to improve the catalvtic activitv and selectivity. howevek of