Unreacted CH4 Research Articles

Direct Conversion of Methane to Ethylene and Acetylene over an Iron-Based Metal-Organic Framework.

Conversion of methane (CH4) to ethylene (C2H4) and/or acetylene (C2H2) enables routes to a wide range of products directly from natural gas. However, high reaction temperatures and pressures are often required to activate and convert CH4 controllably, and separating C2+ products from unreacted CH4 can be challenging. Here, we report the direct conversion of CH4 to C2H4 and C2H2 driven by non-thermal plasma under ambient (25 °C and 1 atm) and flow conditions over a metal-organic framework material, MFM-300(Fe). The selectivity for the formation of C2H4 and C2H2 reaches 96% with a high time yield of 334 μmol gcat-1 h-1. At a conversion of 10%, the selectivity to C2+ hydrocarbons and time yield exceed 98% and 2056 μmol gcat-1 h-1, respectively, representing a new benchmark for conversion of CH4. In situ neutron powder diffraction, inelastic neutron scattering and solid-state nuclear magnetic resonance, electron paramagnetic resonance (EPR), and diffuse reflectance infrared Fourier transform spectroscopies, coupled with modeling studies, reveal the crucial role of Fe-O(H)-Fe sites in activating CH4 and stabilizing reaction intermediates via the formation of an Fe-O(CH3)-Fe adduct. In addition, a cascade fixed-bed system has been developed to achieve online separation of C2H4 and C2H2 from unreacted CH4 for direct use. Integrating the processes of CH4 activation, conversion, and product separation within one system opens a new avenue for natural gas utility, bridging the gap between fundamental studies and practical applications in this area.

Thermodynamic equilibrium analysis of oxy‐dry reforming of biogas with CO2 sequestration using Aspen HYSYS

AbstractHydrocarbon reforming route has gained immense attention for producing energy‐effective renewable fuels and/or chemicals in the recent era. In this simulation study, O2 addition and CH4 recycling's effect on the dry oxidative reforming reactor's performance was investigated. Aspen HYSYS simulation software was used to assess a biogas‐to‐syngas conversion process's feasibility by integrating with the CH4 recycling loop and CO2 sequestration in a dry oxidative reforming process. Simulation runs were performed by varying the O2/CH4 ratio content from 0 to 0.20 and temperature (450 to 700°C). Results illustrated that CH4 conversion improved by re‐injecting of unreacted CH4, followed by CO2 sequestration to a great extent. In dry oxidative reforming, at stoichiometry O2/CH4 ratio of 0.17, CH4 conversion (21.7%), and CO2 conversion (3.3%) were obtained at 500°C, with 1.2 H2/CO ratio. Further, 0.308 kg mole/h of H2 could be produced with biogas (1.0 kg mole/h) at optimal parameters 500°C (temperature) and 0.17 (O2/CH4 ratio) by using recycling loop in one cycle. Thus, dry oxidative reforming coupled with the CH4 recycling unit provides a better option for syngas/H2 production and remarkably addresses high energy demand in the dry reforming process.

Methane-to-aromatics in a gas recycle methane reactor/hydrogen membrane separator

Direct non-oxidative methane conversion (DNMC) is one of the most promising options to convert methane (CH4) in natural gas in remote extraction sites to liquid aromatics, which is easier to transport compared to CH4 gas. The main constraint of the DNMC is low CH4 conversion, and thus aromatics product yield due to thermodynamic limitation. This work reports a gas recycle CH4 reactor/hydrogen (H2) membrane separator to achieve high CH4 conversion and aromatics yield by circumventing the thermodynamic limitation. The DNMC took place over an iron/silica (Fe/SiO2) catalyst in a packed-bed reactor to produce C2 (i.e. ethane, ethylene and acetylene) and aromatics, along with reaction product H2. The product stream passed through a condenser to collect aromatic products and then a H2-permeable membrane separator to remove H2. The unreacted CH4, C2 products and H2 residual in the product stream were sent to the recycle loop for the next round of DNMC reaction and H2 removal. The results demonstrated that >90 % product selectivity toward aromatics and >50 % aromatics yield are achieved in the gas recycle CH4 reactor/ H2 membrane separator system.

Multi-Scale Analysis of Integrated C1 (CH4 and CO2) Utilization Catalytic Processes: Impacts of Catalysts Characteristics up to Industrial-Scale Process Flowsheeting, Part II: Techno-Economic Analysis of Integrated C1 Utilization Process Scenarios

In the second part of this paper (Part II), the potentials and characteristics of an industrial-scale Oxidative Coupling of Methane (OCM) process integrated with CO2-hydrogenation, ethane dehydrogenation, and methane reforming processes are highlighted. This novel process concept comprises a direct conversion of methane to ethane and ethylene and further conversion of the resulted carbon dioxide and remaining unreacted methane, respectively, to methanol and syngas. In this context, the selected experimental results of the catalytic CO2-hydrogenation to methanol reported in the first part of this paper (Part I), were utilized to represent its industrial-scale performance. The experimental results of the mini plant-scale operation of an OCM reactor and CO2 removal units along with the experimental and industrial data available for representing the operation and performance of all process-units in the integrated process structures were utilized to perform a comparative techno-economic environmental analysis using Aspen-Plus simulation and an Aspen Economic Process Analyzer. The experimental procedure and the results of testing the sequence of OCM and CO2-hydrogenation reactors are particularly discussed in this context. It was observed that in the sequential operation of these reactors, ethylene will be also hydrogenated to ethane over the investigated catalysts. Therefore, the parallel-operation of these reactors was found to be a promising alternative in such an integrated process. The main assumptions and the conceptual conclusions made in this analysis are reviewed and discussed in this paper in the light of the practical limitations encountered in the experimentations. In the context of a multi-scale analysis, the contributions of the design and operating parameters in the scale of catalyst and reactor as well as in the process-scale represented by analyzing the type and operating conditions of the downstream-units and the process-flowsheets on the economic and environmental performance of the integrated process structures were studied. Moreover, the economic impacts of extra ethylene and methanol produced respectively via the integrated ethane dehydrogenation and CO2-hydrogenation sections were analyzed in detail. The required capital investment was found to be even smaller than the yearly operating cost of the plant. The environmental impacts and sustainability of the integrated OCM process were found to be enhanced by securing a minimum direct CO2-emission and energy-efficient conversion of CO2 and the unreacted CH4, respectively, to methanol and syngas. Besides producing such value-added by-products, efficient operation of downstream process-units was secured by minimizing the energy usage and ethylene losses. Under the considered conditions in this analysis, the specifications of the finally selected integrated OCM process structure, providing the fastest return of investments (less than 8 years), are highlighted.

Facile CO2 separation and subsequent H2 production via chemical-looping combustion over ceria-zirconia solid solutions.

A novel chemical-looping combustion scheme is proposed, where facile gas separation via steam condensation enables the production of sequestrable CO2 from alkanes, such as CH4, and pure H2 from H2O. This cycle consists of two steps, namely, (1) the endothermic reduction of a ceria-based solid solution via the complete oxidation of CH4, followed by (2) the exothermic oxidation of the reduced metal oxide via H2O splitting. Relative to iron oxide-based materials and undoped ceria, ceria-zirconia solid solutions possess favorable partial molar enthalpic and entropic properties; this promotes selective production of complete combustion products, H2O and CO2, during the reforming reaction. Thermodynamic predictions suggest that the complete oxidation of CH4 is possible by increasing the Zr content to 20 mol%, operating below 600 °C, increasing total pressure, or reducing the amount of delivered reactant. Furthermore, any H2, CO, or unreacted CH4 that may persist is thermodynamically favored to oxidize if exposed to unreacted oxide downstream, as is typical for a packed-bed or downer reactor configuration. Experiments were performed to validate the thermodynamic trends using isothermal thermogravimetry coupled with residual gas analysis, which confirmed that high selectivity towards H2O and CO2 is attainable for methane-driven reduction of Ce0.9Zr0.1O2; selectivities greater than 0.70 were observed at initial reaction extents. Importantly, metal oxide oxidation via H2O splitting and selective production of H2 (or CO if CO2 is the delivered oxidant) is also thermodynamically favored at the operating conditions considered for the first step. This work ultimately presents a viable avenue for the carbon-neutral conversion of CH4 (or other alkanes) to H2 if a renewable energy resource, such as solar energy, is leveraged to supply process heat.

Measuring the Unmeasurable by IR Spectroscopy: Carbon Deposition Kinetics in Dry Reforming of Methane.

Dry reforming of methane converts two greenhouse gases to syngas, and Ni catalysts are commonly used for this reaction. A major catalyst deactivation mechanism is carbon deposition. Although numerous kinetic modelling works have been performed on carbon formation, there have been only scarce attempts to measure carbon deposition kinetics under relevant (but not real) conditions, owing to technical difficulties. Here, we report the first successful measurements of the kinetics under real reaction conditions. This was made possible by using a novel algorithm that we have developed. We use IR to measure the molar fractions of unreacted CH4 and CO2 , and reaction products, CO and H2 O, in the effluent from the reactor. By applying the general mass balance principle and the relevant reaction stoichiometries, the carbon deposition rate as well as the flow rates of all these gases in the effluent, including H2 , are calculated. Compared to the dominant GC-based approach for catalyst performance evaluation, this method has much higher time resolution and much smaller measurement errors.

Hollow ZSM-5 zeolite grass ball catalyst in methane dehydroaromatization: One-step synthesis and the exceptional catalytic performance

One-step hydrothermal preparation method of hollow ZSM-5 zeolite grass ball (HGB-ZSM-5) was developed at the near-neutral circumstance. The electrostatic assembly among EDTA2−, n-butylamine+ and aluminosilicate species led to the self-transformation of irregular amorphous precursor into “Organic-Inorganic hybird ball” ([(SiO)4Al)−]m(C4H12N+)x(EDTA2−)y(C4H12N+)z[(SiO)4Al)−]n), which directly crystallized into hollow ZSM-5 zeolite grass ball. After the loading of Mo species, the catalytic performance of Mo/HGB-HZSM-5 catalyst was tested in MDA process. Compared with conventional Mo/ZSM-5 catalyst, Mo/HGB-HZSM-5 catalyst exhibited higher CH4 conversion and aromatic selectivity, as well as longer lifetime, which was attributed to the hollow assembly mode. Hollow grass ball structure not only improved the synergistic effect by promoting the formation of more Mo-acid sites and their uniformly distribution, but also increased the contact time as the unreacted CH4 and primary products diffused outward from the inside cavity through Mo/HZSM-5 shell, giving rise to the exceptional catalytic performance. Furthermore, this unique structure bestowed Mo/HGB-HZSM-5 with the smaller bulky density and the reduce of the sites concerned with the catalyst deactivation, which inhibited the side reactions and strengthened molecules diffusion, showing the higher catalytic stability.

Catalyst Deactivation of Rh-Coated Foam Monolith for Catalytic Partial Oxidation of Methane

The catalyst deactivation behavior of rhodium-coated foam monolith was systematically investigated in order to understand the means to improve the durability of the rhodium catalyst applied for catalytic partial oxidation of methane (CPOM). The overall CPOM reactions on the foam structured catalyst have been acknowledged to take place first in an oxidation zone and thereafter in a reforming zone. Severe metal sintering near the entrance of the structured catalyst (i.e., in the oxidation zone) was identified to be responsible for the observed deactivation of rhodium catalyst in the course of a 1000 h time-on-stream test under quasi-adiabatic conditions. Further analyses on the deactivation process indicated that the reaction pathway in the oxidation zone near the entrance can be summarized by a mixed mechanism, that is, two oxidation reactions and one reforming reaction, where H2 is the indirect product of steam reforming of the unreacted CH4. Detailed studies on the dependence of the catalyst stability on...