Gas to liquids (GTL) is a refinery process to convert natural gas or other gaseous hydrocarbons into longer-chain hydrocarbons, such as gasoline or diesel fuel. Methane-rich gases are converted into liquid synthetic fuels. Two general strategies exist: (i) direct partial combustion of methane to methanol and (ii) Fischer–Tropsch-like processes that convert carbon monoxide and hydrogen into hydrocarbons. Strategy ii is followed by diverse methods to convert the hydrogen-carbon monoxide mixtures to liquids. Direct partial combustion has been demonstrated in nature but not replicated commercially. Technologies reliant on partial combustion have been commercialized mainly in regions where natural gas is inexpensive. The motivation for GTL is to produce liquid fuels, which are more readily transported than methane. Methane must be cooled below its critical temperature of −82.3 °C in order to be liquified under pressure. Because of the associated cryogenic apparatus, LNG tankers are used for transport. Methanol is a conveniently handled combustible liquid, but its energy density is half of that of gasoline.
Fischer–Tropsch process
A GtL process may be established via the Fischer–Tropsch process which comprises several chemical reactions that convert a mixture of carbon monoxide (CO) and hydrogen (H2) into long-chained hydrocarbons. These hydrocarbons are typically liquid or semi-liquid and ideally have the formula (CnH2n+2). In order to obtain the mixture of CO and H2 required for the Fischer–Tropsch process, methane (main component of natural gas) may be subjected to partial oxidation which yields a raw synthesis gas mixture of mostly carbon dioxide, carbon monoxide, hydrogen gas (and sometimes water and nitrogen). The ratio of carbon monoxide to hydrogen in the raw synthesis gas mixture can be adjusted e.g. using the water gas shift reaction. Removing impurities, particularly nitrogen, carbon dioxide and water, from the raw synthesis gas mixture yields pure synthesis gas (syngas). The pure syngas is routed into the Fischer–Tropsch process, where the syngas reacts over an iron or cobalt catalyst to produce synthetic hydrocarbons, including alcohols.
Mobil process Methanol is made from methane (natural gas) in a series of three reactions:
Steam reforming CH4 + H2O → CO + 3 H2 ΔrH = +206 kJ mol−1 Water shift reaction CO + H2O → CO2 + H2 ΔrH = −41 kJ mol−1 Synthesis 2 H2 + CO → CH3OH ΔrH = −92 kJ mol−1 The methanol thus formed may be converted to gasoline by the Mobil process and methanol-to-olefins.
Methanol to gasoline (MTG) and methanol to olefins
In the early 1970s, Mobil developed an alternative procedure in which natural gas is converted to syngas, and then methanol. The methanol reacts in the presence of a zeolite catalyst to form various compounds. In the first step methanol is partially dehydrated to give dimethyl ether:
2 CH3OH → CH3OCH3 + H2O The mixture of dimethyl ether and methanol is then further dehydrated over a zeolite catalyst such as ZSM-5, and in practice is polymerized and hydrogenated to give a gasoline with hydrocarbons of five or more carbon atoms making up 80% of the fuel by weight. The Mobil MTG process is practiced from coal-derived methanol in China by JAMG. A more modern implementation of MTG is the Topsøe improved gasoline synthesis (TiGAS). Methanol can be converted to olefins using zeolite and SAPO-based heterogeneous catalysts. Depending on the catalyst pore size, this process can afford either C2 or C3 products, which are important monomers. Methanol to olefins technology is widely used in China in order to produce plastics from coal gasification. It is also discussed as a method to make fossil-free plastics in the future.
Syngas to gasoline plus process (STG+)
A third gas-to-liquids process builds on the MTG technology by converting natural gas-derived syngas into drop-in gasoline and jet fuel via a thermochemical single-loop process. The STG+ process follows four principal steps in one continuous process loop. This process consists of four fixed bed reactors in series in which a syngas is converted to synthetic fuels. The steps for producing high-octane synthetic gasoline are as follows:
Methanol Synthesis: Syngas is fed to Reactor 1, the first of four reactors, which converts most of the syngas (CO and H2) to methanol (CH3OH) when passing through the catalyst bed. Dimethyl Ether (DME) Synthesis: The methanol-rich gas from Reactor 1 is next fed to Reactor 2, the second STG+ reactor. The methanol is exposed to a catalyst and much of it is dehydrated to DME (CH3OCH3). Gasoline synthesis: The Reactor 2 product gas is next fed to Reactor 3, the third reactor containing the catalyst for conversion of DME to hydrocarbons including paraffins (alkanes), aromatics, naphthenes (cycloalkanes) and small amounts of olefins (alkenes), mostly from C6 (number of carbon atoms in the hydrocarbon molecule) to C10. Gasoline Treatment: The fourth reactor provides transalkylation and hydrogenation treatment to the products coming from Reactor 3. The treatment reduces durene (tetramethylbenzene)/isodurene and trimethylbenzene components that have high freezing points and must be minimized in gasoline. As a result, the synthetic gasoline product has high octane and desirable viscometric properties. Separator: Finally, the mixture from Reactor 4 is condensed to obtain gasoline. The non-condensed gas and gasoline are separated in a conventional condenser/separator. Most of the non-condensed gas from the product separator becomes recycled gas and is sent back to the feed stream to Reactor 1, leaving the synthetic gasoline product composed of paraffins, aromatics and naphthenes.
Biological gas-to-liquids (Bio-GTL) With methane as the predominant target for GTL, much attention has focused on the three enzymes that process methane. These enzymes support the existence of methanotrophs, microorganisms that metabolize methane as their only source of carbon and energy. Aerobic methanotrophs harbor enzymes that oxygenate methane to methanol. The relevant enzymes are methane monooxygenases, which are found both in soluble and particulate (i.e. membrane-bound) varieties. They catalyze the oxygenation according to the following stoichiometry:
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