CHAPTER 3. Oxidative Coupling of Methane in Membrane Reactors

An oxidative coupling of methane (OCM) is a promising process to convert methane into ethylene and ethane; however, it suffers from the relatively low selectivity and yield of ethylene at high methane conversion. In this study, a membrane reactor is applied to the OCM process in order to prevent the deep oxidation of a desirable ethylene product. The mathematical model of OCM process based on mass and energy balances coupled with detailed OCM kinetic model is employed to examine the performance of OCM membrane reactor in terms of CH4 conversion, C2 selectivity, and C2 yield. The influences of key operating parameters (i.e., temperature, methane-to-oxygen feed ratio, and methane flow rate) on the OCM reactor performance are further analyzed. The simulation results indicate that the OCM membrane reactor operated at higher operating temperature and lower methane-to-oxygen feed ratio can improve C2 production. An optimization of the OCM membrane reactor using a surface response methodology is proposed in this work to determine its optimal operating conditions. The central composite design is used to study the interaction of process variables (i.e., temperature, methane-to-oxygen feed ratio, and methane flow rate) and to find the optimum process operation to maximize the C2 products yield.

The performance of the Oxidative Coupling of Methane (OCM) reactions in a porous ceramic packed bed membrane reactor was experimentally investigated using an Mn–Na2WO4/SiO2 catalyst. A novel practical method was applied to modify the available commercial α-alumina membrane and shape it to the form of an inert fine oxygen distributor in an OCM membrane reactor. The characteristics of such modified membrane and the performance of the resultant OCM membrane reactor are reviewed in this paper. It was observed that establishing a 2 bar pressure gradient across the modified membrane ensures a safe and efficient oxygen-dosing along the OCM membrane reactor. Moreover, using a modified membrane with a descending permeation profile instead of a uniformed permeation profile improved the observed C2 selectivity (ethylene and ethane) by 10% in average. The efficient design of the membrane reactor setup and the stability of the prepared catalyst provided a robust operation and replicable results. In this experimental analysis, a very promising 25.5% C2 yield and 20.3% ethylene yield with 66% C2 selectivity were achieved under very low (20%) diluted reaction atmosphere for the methane-to-oxygen ratio 2. By proper exploiting the carbon dioxide instead of nitrogen dilution, the C2 yield was improved by 1–2% in average.

A direct method of converting natural gas into ethylene is the heterogeneously catalyzed oxidative coupling of methane (OCM), however, only with hydrocarbon yields limited to 30-35% despite enormous efforts to optimize the catalysts. By combining the exothermic OCM with a secondary process, namely steam reforming of methane (SRM), the methane conversion can be increased significantly while improving temperature control and simultaneously producing valuable synthesis gas. In this thesis, two different reactor concepts were developed to integrate the OCM and SRM reactions in an overall autothermal process, so that the OCM process is effectively cooled and the generated reaction energy is efficiently used to produce synthesis gas. The integration is most optimally achieved on the catalyst particle scale, which would eliminate the need for external heat exchange and opens up the possibility to use distributive oxygen dosing with which much higher product yields can be achieved. It is proposed to use a dual function catalyst particle in which the two chemical processes are physically separated by an inert, porous layer, such that additional diffusional resistances are intentionally created to control the reaction rates. This concept was studied with numerical simulations on the scale of a single catalyst particle and on reactor scale. It was found that the SRM and OCM reaction rates could be effectively tuned to achieve autothermal operation at the reactor scale, while the methane conversion was enhanced from 44% to 55%. An alternative integrated process can be achieved by combining OCM and SRM in a heat exchange reactor comprising of two separate reaction chambers which are thermally coupled. The OCM is carried out in packed bed reverse flow membrane reactor tubes submerged into a fluidized bed where the unconverted methane and byproducts from OCM are reformed, thus producing synthesis gas and consuming the reaction heat liberated by OCM. The feasibility of this concept is supported by experiments of OCM on a Mn/Na2WO4/SiO2 catalyst in a packed bed (porous Al2O3) membrane reactor. The results demonstrated that a C2 yield of 25-30 % can be achieved and that distributed feed of oxygen is optimal for the combined OCM/SRM reactor concept.

Design and demonstration of an experimental membrane reactor set-up for oxidative coupling of methane

The oxidative coupling of methane (OCM) in a dense BSCFO membrane reactor (MR) was theoretically studied using a two-dimensional reactor model. The simulation results indicated that increasing the operating temperature results in increased CH4 conversion and decreased C2 selectivity. An increase in the methane feed flow rate lowers the CH4 conversion but increases the C2 selectivity; however, the effect of the air flow rate on the OCM membrane reactor exhibits an opposite trend. The optimum configuration of the dense BSCFO-MR to provide the best performance was 0.018 m in diameter and 0.2 m in length at a GHSV of 38904.54 h-1 and temperature of 1073 K. Under these optimal conditions, the CH4 conversion is 43.713 %, the C2 selectivity is 61.352 % and the C2 yield is 26.82 %.

Analysis of oxidative coupling of methane in dense oxide membrane reactors

A new and very promising application of auto-thermal reactors is the coupling of endothermic and exothermic reactions where the product of the endothermic reaction is the desired one. Therefore, in this work, a reactor in which oxidative coupling of methane (OCM) and steam re-forming of methane (SRM) reactions take place simultaneously was modeled. The results were obtained in a wide range of different conditions such as inlet feed, inlet temperature, portions of OCM and SRM catalysts, and inlet velocity. In selection of the catalysts, more attention was drawn to prevent re-forming of OCM products. The main parameters of each reaction under different conditions such as conversion of the feed components, products selectivity and yield, temperature in the length of reactor, and component's concentration in the reactor were considered in course of this study. The results revealed that simultaneous OCM and SRM reactions in one reactor will tend to be auto-thermal, and the waste of energy will be reduced. The results also show that complete conversion of water and majority of methane and oxygen will decrease the amount of unwanted products at the reactor's discharge-a constraint that exists in single reactors of each reaction specially OCM.

Oxidative coupling of methane (OCM) on a conventional fixed-bed reactor (FBR) and a ceramic dense membrane reactor (DMR) packed with Li/MgO catalyst is analyzed using plug-flow reactor models. The validity of OCM kinetic equations employed in the modeling is confirmed by excellent agreement between the simulation and experimental data for OCM on FBR. For FBR, a high methane to oxygen feed ratio favors the OCM reaction, with a low C2 yield because of insufficient oxygen supply. The highest C2 yield achieved with a feed mixture consisting of 70% methane and 30% oxygen is 20.7% at a selectivity of 53% and operating temperature of 750 °C. The C2 yield and selectivity increase slightly at a higher operating temperature. The optimal feed ratio does not change with temperature. DMR is made of a mixed-conducting ceramic membrane tube packed with an OCM catalyst. The membrane tube separates the methane and oxygen feed. The oxygen concentration in the DMR is much lower and more uniform than that in the FBR because ...

The oxidative coupling of methane (OCM) is an attractive technology for the production of ethane (C2H6) and ethylene (C2H4); and significant performance and efficiency gains as well as reduced carbon dioxide (CO2) emissions are expected when OCM takes place within mixed ionic and electronic conducting (MIEC) ceramic membrane reactors (CMRs). So far, research on OCM in CMRs has been limited to unstable and incompatible materials investigated under short-term measurements that hinder upscaling and commercial application. To this end, this work demonstrates long-term stable OCM performance enabled by a BaFe0.9Zr0.1O3−δ (BFZ91) perovskite utilized as the oxygen-ion MIEC membrane and lanthanum oxide (La2O3) used as the OCM catalyst. Experimental measurements conducted in the temperature (T) range of 750–900 °C and at inlet methane (CH4) mole fractions (XCH4in) of 0–30% revealed a highly stable performance during 23 days of continuous operation, which was further confirmed by material characterization. Under the aforementioned operating conditions, BFZ91 offers a high oxygen (O2) permeation flux (JO2) between 0.5−1.5 (μmol/cm2/s); CH4 conversion (CCH4) reached ∼35% while the selectivities to C2H6 (SC2H6) and C2H4 (SC2H4) were as high as ∼50% and ∼40%, respectively, showing a strong dependency on the operating conditions. Yields of C2H6 (YC2H6) and C2H4 (YC2H4) in the range of 1–5% and 1–7%, respectively, were measured, with more C2H4 being produced at higher T. In the absence of La2O3, CCH4 and C2 (C2H6 and C2H4) yields are lower confirming that BFZ91 does not promote CH4 oxidation, reforming, or coupling on its surface at high rates. The OCM performance of BFZ91 with La2O3 was also found to be stable under partial O2 consumption and pure CH4 conditions. Furthermore, a detailed analysis of the mixture composition allowed the identification of the primary reactions in the OCM chemistry. Our results reveal that within our reactor, CH4 full oxidation to CO2 and steam (H2O) happens simultaneously with CH4 oxidation to C2H6 and H2O (both on the La2O3 catalyst), but the production of the valuable C2H4 is primarily taking place through the C2H6 non-oxidative dehydrogenation in the gas phase; this reaction was not found to proceed on the La2O3 catalyst. Besides the promise of the investigated materials toward commercialization, the methods to study the OCM chemistry and the membrane catalyst coupling presented here are expected to promote further advances in the field of OCM.

Oxidative coupling of methane (OCM) is a promising route for the production of ethylene by fully utilizing the abundance of methane feedstock. However, this process suffers from the relatively low selectivity and yield of ethylene at a higher methane conversion due to the complete oxidation of methane and ethylene products. To overcome this limitation, the application of a membrane reactor in which oxygen selective membrane is used to prevent the deep oxidation of a desirable ethylene product is a potential alternative. In this study, a multi-stage dense tubular membrane reactor is proposed to improve the performance of the oxidative coupling of methane. Mathematic model of the membrane reactor based on conservative equations and detailed OCM kinetic model is employed to analyze the effect of key operating parameters such as temperature, methane-to-oxygen feed ratio and methane flow rate, on the efficiency of the OCM process in terms of CH4 conversion, C2 selectivity and C2 yield. Adjustment of feed distributions at each membrane stage under isothermal and non-isothermal conditions is also studied. The performance of the multi-stage membrane reactor is compared with a single stage membrane reactor. The result shows that the distributed feeding policy improves the performance of the OCM process. A surface response technique is further employed to determine the optimal operating condition of the OCM process with the aim to maximize the C2 products.

Conceptual Process Design and Economic Analysis of Oxidative Coupling of Methane

Catalytic Properties of Oxygen Semipermeable Perovskite-Type Ceramic Membrane Materials for Oxidative Coupling of Methane

Oxidative coupling of methane (OCM) is a process to directly convert methane into ethylene. However, its ethylene yield is limited in conventional reactors by the nature of the reaction system. In this work, the integration of different membranes to increase the overall performance of the large-scale oxidative coupling of methane process has been investigated from a techno-economic point of view. A 1D membrane reactor model has been developed, and the results show that the OCM reactor yield is significantly improved when integrating either porous or dense membranes in packed bed reactors. These higher yields have a positive impact on the economics and performance of the downstream separation, resulting in a cost of ethylene production of 595–625 €/tonC2H4 depending on the type of membranes employed, 25–30% lower than the benchmark technology based on oil as feedstock (naphtha steam cracking). Despite the use of a cryogenic separation unit, the porous membranes configuration shows generally better results than dense ones because of the much larger membrane area required in the dense membranes case. In addition, the CO2 emissions of the OCM studied processes are also much lower than the benchmark technology (total CO2 emissions are reduced by 96% in the dense membranes case and by 88% in the porous membranes case, with respect to naphtha steam cracking), where the high direct CO2 emissions have a major impact on the process. However, the scalability and the issues associated with it seem to be the main constraints to the industrial application of the process, since experimental studies of these membrane reactor technologies have been carried out just on a very small scale.

Oxygen permeation and oxidative coupling of methane in membrane reactor: A new facile synthesis method for selective perovskite catalyst

Direct conversion of methane into ethylene through the oxidative coupling of methane (OCM) is a technically important reaction. However, conventional co-fed fixed-bed OCM reactors still face serious challenges in conversion and selectivity. In this paper, we apply a finite element model to simulate OCM reaction in a plug-flow CO2/O2 transport membrane (CTM) reactor with a directly captured CO2 and O2 mixture as a soft oxidizer. The CTM is made of three phases: molten carbonate, 20% Sm-doped CeO2, and LiNiO2. The membrane parameters are first validated by CO2/O2 flux data obtained from CTM experiments. The OCM reaction is then simulated along the length of tubular plug-flow reactors filled with a La2O3-CaO-modified CeO2 catalyst bed, while a mixture of CO2/O2 is gradually added through the wall of the tubular membrane. A 12-step OCM kinetic mechanism is considered in the model for the catalyst bed and validated by data obtained from a co-fed fixed-bed reactor. The modeled results indicate a much-improved OCM performance by membrane reactor in terms of C2-yield and CH4 conversion rate over the state-of-the-art, co-fed, fixed-bed reactor. The model further reveals that improved performance is fundamentally rooted in the gradual methane conversion with CO2/O2 offered by the plug-flow membrane reactor.