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Feasibility study of a novel technology for natural gas liquefaction based on plasma catalysis and fischer-tropsch synthesis

Deliverables

This result has fundamental, academician character and is a scientific breakthrough. Current stage of development of this result is scientific knowledge (basic research). This result will be used at design the theory of elementary processes of microwave strimer and stationary discharge. Our activity of implementation of this results is to introduce to the world, European and native scientific society with result. So our end-users of result is physical and technical university and institute, conferences, academies scientific society and We plan to use result for high education and training. We plan to take part at such conferences as International Symposium on Plasma Chemistry, European Congress Thermal Plasma Processes, International Conferences of Phenomena in Ionized Gases, World Hydrogen Energy Conference, submit materials to referred journals as Journal of Applied Chemistry, Plasma Chemistry and Plasma Processes, Petroleum Chemistry and take part at at international exchange and trainings. Since this result is fundamental, it is difficult to estimate the economic benefit from it application. It may be applied at design and construction of devise and engine, which will operate on the base of microwave discharge. Potential market of application of such machine may be gas conversion (not only natural gas, but also hydrocarbons and other gases), aviation (at gas turbine for ignition processes of fuel), chemical industry (syn gas production for methanol producing), microelectronic branch (spheroidization of powders and high silicon production) and many others.
The first studies in GREMI on the methane steam reforming indicated that the gliding discharge reactors must be improved in order to obtain better conversions. The experimental conditions can lead to quite a high selectivity (60-80%) and low energy costs (0.4 and 0.2 Wh/l H2). The weak point of our first technical approach (i.e. the low chemical conversion), had suggested the improvement of reactor design in order to cover with the arcs as much as possible from the reaction volume. The second technical approach lead to a new three-phases reactor which has been proposed with good results, the conversion increasing up to 60% with a hydrogen production energy cost of 1-2 Wh/Nl of H2. We have performed experiments using an inlet mixture: H2O, CH4, O2 (5%). The main effect of oxygen is to modify the power and the discharge behaviour without significant change of the other results. We have modelled the chemical processes occurring in the "glidarc" reactor starting from conclusions drawn in our experimental studies. Taking into account the specific energy consumption, there are hopes that the final cost of the produced hydrogen could be lowered to about 0.1 EURO /m3 which would become competitive with classic technologies.
Oil exploration is accompanied by the production of large amounts of casing head natural gas (about 20% of the world's natural gas production), which in the case of remote oil fields cannot be utilised with the currently existing technology. Frequently this gas is flared. An important step in the conversion of natural gas to useful products is the reforming into hydrogen and carbon monoxide. The current technology that is based on catalytic steam reforming or partial oxidation requires high operating temperatures and hence is cost intensive and only economic in very large-scale plants. The research and technology development during the SYNFUELS project has lead to a better understanding of the novel approach to reforming involving plasma activation. We observed that the dielectric barrier discharge is suited for the chemical activation at low temperatures that would simplify interfacing to the Fisher-Tropsch synthesis. In particular the steam assisted partial oxidation seems a promising candidate for compact and mobile reforming plants that can produce hydrogen or synthetic fuel on-site and on demand.
The novel type of the catalyst bed for the RCPR - the porous catalyst packing with high heat conductivity was developed. The methodology of the catalyst packing (further denoted as "permeable composite monolith", PCM) preparation was developed. We achieved high productivity of 150-200 g/(hr.cm3) of the PCM volume at 483 K, 2,1MPa while keeping high selectivity (a = 0.84). This productivity is 3 fold higher than that of commercial FTS plants with slurry catalyst bed. The methodology of PCM preparation is based on the state-of-the-art methods of powder metallurgy, which will facilitate the technology scale up. The absence of the separation problem, possibility of horizontal placement, small reactor size together with high productivity and selectivity of PCM-based FTS, allows using the PCM technology on shelf, swamps, and permafrost territories. PCM-FTS looks as the efficient process even for small-scale production especially in remote regions. Application of PCM to the FTS will give the chance to utilize efficiently casing-head gas in the remote oil fields, as well as produce motor fuels in the remote regions of Far North, Far East and West Siberia. Thus, PCM technology will lower the greenhouse gases emissions and improve sustainability of the remote regions development.
Potential applications for this result: This result may be used for the design of new technologies of natural gas recovery into syn-gas on the basis of microwave discharge applying at the partial methane oxidation. End-users of this result: For application of this result, there may be several user groups and market sectors. Oil output and oil fields, where natural gas is by-product and currently is not used. Technology allows convert methane into syn-gas on the first stage and further liquefaction into motor fuel at the second stage. Chemical industry methanol and others chemicals production, where syn-gas is required as initial compounds. Sector of fuel cells, which operate on hydrogen or syn-gas mixture. This result may be applied for hydrogen production for hydrogen transport. Main innovative features/benefits: Production of syn-gas from methane by partial oxidation at microwave discharge accelerates burning process is also capable of supporting methane burning under conditions, when burning does not occur without the discharge and allows to carry conversion process with low energy expenses. Plasma-chemical production of syn-gas (and hydrogen) from methane has some advantages in comparison with the traditional catalytic technology: - Non-inertial - Practically, - Start-up; - Absence of catalysis serving; - Absence of catalysis coking (charring); - No problem of catalysis utilization (recovery). Analysis of the market or application sectors: We are at an early innovative stage. But preliminary consideration shows the great potential for implementation of this result. For example, Norway has 47.7 trillions cubic foot reserves of casing-head. The recovery of casing-head only in Russia is 26 billion cubic meters per year. The world production of methanol has greatly increased from 20 million tons in 1980 up to 37.5 million tons at 2000 and has a turnover $ 12 billion and created 100,000 work places. Potential barriers: For high productivity and low energy expenses our result is innovative and promising. But practical application depends on the different various factors such as: oil and gas output costs, costs of electricity at the oil fields, expenses for transport of products to customers, national regulations of preservation of environment, government privilege for manufacturers, national taxes and others.
The reforming of natural gas could in the future become an important source of hydrogen or synthesis gas. Hydrogen is currently under discussion as a future fuel, and synthesis gas may be processed into valuable chemicals or clean synthetic motor fuels. Since thermal reforming has serious drawbacks due to the high process temperatures required, we developed a combined approach using catalysis and plasma excitation in a dielectric barrier discharge (DBD). In order to move towards a practical implementation, not only research towards understanding the process was conducted, but also a rugged and compact reactor that could be adapted to a wide range of operating parameters was developed. The core of the design is a silicon carbide monolith, the durability of which was proven in diesel exhaust soot filters. The flexibility is achieved by the potential to adapt the number of monolith channels and flow velocity over a wide range without re-designing the plasma source. This allows us to maintain process conditions, like the contact time in the optimum regime.
This result has fundamental, academician character and is concerned optical spectroscopy. Therefore we plan to introduce to scientific and education centres with this result. It may be used at formulation the elemental processes in theory of microwave plasma. The end users of this result may be theoretical laboratories and groups of spectroscopic diagnostics of plasma. We plan to interact with reductions of scientific journals, organizing committees and education centres to implicate this result. This result encloses information about active zone of impulse discharge and therefore it may used also by designers and constructors, who design installation based on microwave discharge. Such systems may operate for gas conversion (not only natural gas, but also hydrocarbons and other gases), aviation (at gas turbine for ignition processes of fuel), chemical industry (syn-gas production for methanol producing), microelectronic branch (spheroidization of powders and high silicon production), waste treatment and many others.

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