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J2-7319

Direct Conversion of Methane to Higher Hydrocarbons Using Superacid Catalysts

Project leader: Dr. Likozar Blaž

 

Content description of the project

Methane is available not only as a fossil resource, a major component in natural gas, coal-bed gas and shale gas, but also from a variety of renewable sources such as biogas. It could provide an economical and sustainable alternative to petroleum. Furthermore, methane is one of the most destructive greenhouse gases. Thus, the transformation of methane to liquid fuels or building-block chemicals has received much renewed interest in recent years, especially beyond the established technologies, such as methane reforming.
The high-capital investment and the large-scale requirements of the reforming process hinder the utilization of remote and scattered natural gas or shale gas resources or small-scale biogas refineries. However, the direct transformation of methane to building-block chemicals such as olefins and oxygenates is a very difficult challenge. Generally, the difficulty arises from two aspects. Firstly, methane only possesses saturated C–H bonds with a high bond dissociation energy (435 kJ/mol), and thus, the conversion of methane usually needs to overcome a high energy barrier and stringent conditions. Secondly and more seriously, the reactivity of the target products is typically much higher than that of the methane molecule.
Within the framework of the proposed project, new liquid and solid superacids shall be synthesized and characterized. We shall firstly use these catalysts in a plug flow reactor to explore the methane conversion and hydrocarbons selectivity at mild reaction conditions (( 300 °C; ( 2 bar) or with micro-plasma activation. In order to remove the thermodynamic limitations of methane conversion and prevent any undesired reactions we shall also use gradient reactor with C5+ product removal. In situ and ex situ X-ray diffraction, FTIR, NMR and XPS spectroscopies will be used to characterize catalyst structural changes, as well as reacting species and intermediates. Consequently, this will enable us to propose a tentative reaction mechanism and reaction rate equation. A detailed computational fluid dynamics (CFD) analysis of the designed reactor, coupled with the established reaction kinetics will be used to optimize the overall performance.
Proposed project covers new process solutions, which are ultimately to result in, for example, modular or containerized set-ups providing resource intensity reduction as well as the reduction of emissions. Beyond this, the proposed project encourages interdisciplinary cooperation (materials science, chemical and mechanical engineering) as important elements of the project-related R&D effort. In general terms, the market for methane conversion is with about 800 billion m3/year huge, and still a growing one, while the natural gas share in the energy mix expected to increase to 31% by 2035 (BP Energy Outlook 2035). The global demand for natural gas is also expected to increase at a rate of 1.6%/year over 2015–2035, the fastest of all the primary fossil resources, according to the World Energy Outlook 2014.
In terms of equipment development, the main outlooks, as streamlined by the European Commission, engulf process intensification (e.g. the proposed merger of reaction and product separation) and energy input decrease (the proposed targeted plasma activation). Project proposers are thus to take into account the complementary and synergistic research of the existing projects (H2020, SPIRE, MefCO2, KI as the main public partner, PI: Blaž Likozar; H2020, SPIRE, ADREM, PIs: Blaž Likozar & Janez Levec; COST, CM1205, CARISMA, representative: Blaž Likozar).
The project is in general terms departing from the Technology Readiness Level (TRL) 3, as the underlying concepts have already been experimentally proven in the laboratory-scale by the project participants themselves. Having the materials and processes proven feasible on analogous systems, renders the success rate of the overall concept higher, ultimately targeting TRL 4 for the superacid-catalysed activation.

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