Projects / Programmes
Direct Conversion of Methane to Higher Hydrocarbons Using Superacid Catalysts
| Code |
Science |
Field |
Subfield |
| 2.02.04 |
Engineering sciences and technologies |
Chemical engineering |
Catalysis and reaction engineering |
| Code |
Science |
Field |
| T350 |
Technological sciences |
Chemical technology and engineering |
| Code |
Science |
Field |
| 2.04 |
Engineering and Technology |
Chemical engineering
|
Methane; Hydrocarbons; Catalysis; Superacids; Chemical Engineering
Researchers (16)
Organisations (2)
Abstract
Abstract
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.
Significance for science
The proposed project is relevant to the development of science, and particularly, chemical engineering scientific field through tackling novel methane activation materials (1) and processes (2), methane representing the primary source of energy and chemicals in the upcoming decades. The latter makes methane activation of utmost importance, probably only being able to be paralleled by carbon oxide reduction or its alternative activation and use as an energy-vector or chemical precursor after a suitable conversion, which is to some extent also be addressed in the proposal (co-feeding of methane and carbon dioxide). While developing appropriate materials for the mentioned transformations is directly related to materials science, chemical and mechanical engineering, especially reaction engineering and catalysis, the relevance and impact is much broader in terms of scientific field(s). In addition to novel materials, as well as reactor and process prototypes being developed, one of the main advances proposed is the activation by using “green” electricity (via plasma generation) as the energy source for the transformation (3). This is in accordance with novel energy sources, such as plasma, microwaves, ultrasound, etc., recently being explored to on one hand use a direct renewable power source (e.g. solar or wind) and on the other to try to achieve a higher energy efficiency, for example, to use plasma or microwaves to induce activation in situ and not use the thermal energy to heat reaction mixture bulk, as it is performed conventionally, inadvertently resulting in vast losses. The three mentioned contributions to the pertinent scientific fields are mirrored by the corresponding latest trends, the proposed project thus addressing three emerging issues, and moreover, doing so in a trans-disciplinary manner. While all three issues have been recognized by the scientific community, the advantage of the proposed project is to tackle them in an integrated manner (by developing a reactor/process prototype), whereas not much literature exists covering such integrated (and hence realistic) approach, making it highly likely to impact the above mentioned scientific fields.
Significance for the country
Proposed project covers new methane activation catalysts and adaptable reactors for a flexible and decentralized production at a high process performance. These new process solutions 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. The market for the production of base chemical is currently dominated by producers using highly-optimized large-scale (e.g., for ethylene, more than 1 million ton/year) traditional processes. These processes possess only limited potential for further improvements. The emerging competing processes promise strong improvements in the efficiency and flexibility, as well as strong decreases in the environmental impact. They also open possibilities for the utilization of smaller in capacity or fluctuating sources (e.g. biogas or to methane converted biomass-originating syngas). For instance, the proposed processes (direct valorisation) would also significantly increase the incentive to use the methane that is currently flared due to the absence of pipelines or storage possibilities, by providing a robust economic advantage over the existing technologies. The gas flaring alone amounts to about 150 billion m3/year (i.e. 5% of the production, equal to about 30 billion USD) and contributes correspondingly to the greenhouse effect with a null efficiency.
Most important scientific results
Interim report,
final report
Most important socioeconomically and culturally relevant results
Interim report,
final report
