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New Solid Catalyst for the Direct Low-Temperature Oxidation of Methane to Methanol

A team led by Ferdi Schüth at the Max Planck Institute of Coal Research in Mülheim (Germany) and Markus Antonietti at the Max Planck Institute for Colloids and Interfaces in Potsdam-Golm (Germany) has developed a novel catalyst for the direct low-temperature oxidation of methane to methanol. A report on their work was published online 4 August in the journal Angewandte Chemie.

While methanol is again attracting attention as a possible energy source for fuel cells or as a substitute for gasoline, it requires a complex synthesis process from natural gas via a detour through synthesis gas. One interesting alternative that was earlier pursued and then abandoned is the direct low-temperature oxidation of methane to methanol. The new catalyst could spur a return to commercial development of this type of process, which could result, among other applications, in the efficient conversion of stranded natural gas on site.

The development of catalyst systems for the direct low-temperature oxidation of methane to methanol has been one of the major challenges in catalysis over the last decades.

—Ferdi Schüth

The bonds in methane are very strong (binding energy of 435 kJ mol-1) and difficult to break. In addition, under the reaction conditions required, methanol has the tendency to react further to form carbon dioxide. The process thus requires not only highly active but also highly selective catalysts.

Earlier catalysts targeted at this process, however, mostly suffered from irreversible reduction and bulk metal formation, together with consequently poor selectivity, the authors noted.

One breakthrough was the development of a platinum complex by a research group led by Roy Periana. This complex catalyzes the low-temperature oxidation of methane in concentrated sulfuric acid at temperatures around 200 °C to form methyl sulfate—which can be converted into methanol—in good yield and high selectivity.

Despite highly promising results, the complex separation and difficult recycling of this dissolved catalyst, among other things, hampered the commercial application of this process. Development proceeded to the pilot-plant stage before being abandoned.

A solid catalyst that can be easily separated could make such a process viable on a small scale, making possible the efficient, decentralized consumption of natural gas.

—Ferdi Schüth

The German researchers have now been able to develop such a solid catalyst, whose high reactivity and selectivity, and its stability through numerous recycling steps, have raised prospects for its industrial implementation.

The development is based on the recent discovery of a new class of high-performance polymer frameworks. Polymerization of a ring-shaped molecule, an aromatic nitrile, results in a network known as a “covalent triazine-based framework”, abbreviated as CTF. The materials are thermally stable up to 400 °C and resist strongly oxidizing conditions, which made them appear promising as a solid matrix for methane oxidation along the lines of Periana’s work, the authors wrote.

Loading this substance with platinum results in a highly active, easily separated, and recyclable catalyst.

The platinum-modified material was tested in the direct methane oxidation in concentrated sulfuric acid according to the conditions described by Periana et al. In principle, utilization of sulfuric acid and sulfur trioxide as oxidants, as schematically described in Equations (a)–(d), would allow design of a continuous process. All process steps, including methane oxidation to methyl bisulfate (a), hydrolysis to form free methanol (b), and reoxidation of SO2 (c) could be integrated in such a system. A solid catalyst, with its advantages of easy separation and recyclability, would facilitate the implementation of such processes to allow efficient conversion of natural gas on-site.

—Palkovits et al.

CH4 + H2SO4 + SO3 → CH3OSO3H + H2O + SO2 (a)

CH3OSO3H + H2O → CH3OH + H2SO4 (b)

SO2 + ½O2 → SO3 (c)

ΣCH4 + ½O2 → CH3OH (d)


  • Regina Palkovits, Markus Antonietti, Pierre Kuhn, Arne Thomas, Ferdi Schüth (2009) Solid Catalysts for the Selective Low-Temperature Oxidation of Methane to Methanol. Angewandte Chemie International Edition 48, No. 37, 6909-6912, doi: 10.1002/anie.200902009


fred schumacher

This line of research could lead to on-farm biofuel production with the lowest energy input process: cellulosic biomass moved a short distance to an anaerobic digester, which produces methane gas, which is converted to methanol, an easily transportable, storable fuel. (Think of the creamery truck coming by twice a week to pick up milk.)


Nice work on the part of these German researchers.


This is good work and good news. Every time I've ever checked, the price of methanol is always below .60-.70 cents per gallon. If they can make it even cheaper then it would be hard to understand why we wouldn't consider this as a way to reduce our dependence on imported oil.

Actually, I don't know why we're not making a big push for it in the US even today!!! Can someone tell me why we ignore methanol and only do ethanol in this country?

Henry Gibson

This is an interesting prospect. Lobbyists are the reason for ethanol instead of methanol.

Methanol was used until recently in some major car races until lobbyists were paid a lot of money to promote ethanol as being more politically correct.

Obviously methanol can be used in regular production cars with some changes in materials that would likely cost less than $100. One of the oil companies has a catalyst that changed methanol into gasoline if necesssary.

What is needed is a fuel cell that takes in methane and air and puts out electricity and methanol. The step SO2 to SO3 can produce electricity in a simple fuel cell. ..HG..


I would assume that this would be more of interest for recovering stranded natural gas in remote locations than to convert biogas into methanol. Biogas production facilities are usually grid connected and can burn directly the methane on site, recovering heat and producing electricity.

Alex Kovnat

The reason why ethanol is preferred over methanol as a gasoline extender or substitute fuel is 1) methanol is highly corrosive, ethanol less so; 2) methanol has only half the energy content of gasoline while ethanol is somewhat better, 3) methanol in even small concentrations causes a huge jump in vapor pressure when added to gasoline while ethanol is less obnoxious in this regard.

As for the Indianapolis 500 and realted auto races, I've heard stories about how methanol engines are shut down on gasoline because of m's highly corrosive nature.

In spite of this, I hope that direct oxidation of methane to methanol will work out. However it may be better to use a methanol-ethanol-propanol-butanol mixture rather than pure methanol as an automotive fuel.


Whether this is better suited to stranded gas or biogas, it is a worthwhile advance.

Methanol is a far better motor fuel than gasoline.  It can be used with much higher compression ratios and produces more energy per mole of oxygen.  If it was being used as an on-demand octane booster for something like the Ford-MIT direct alcohol injection engine, it would be superior to ethanol.  Using a methanol-water mixture would do even better and be cheaper yet.

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