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Researchers develop new lower-temperature process for conversion of natural gas alkanes to alcohols

14 March 2014

Researchers from The Scripps Research Institute (TSRI) and Brigham Young University have devised a new and more efficient method to convert natural gas into liquid products at much lower temperatures than conventional methods.

Their work, reported in the journal Science, uses main-group metals such as thallium and lead to oxidize methane and the other alkanes contained in natural gas (ethane and propane) to liquid alcohols at about 180 °C instead of the more than 500 °C used in current processes, said SRI Professor Roy Periana, who led the research. This creates the potential to produce fuels and chemicals at much lower cost.

… we report that the electrophilic main-group cations thallium(III) and lead(IV) stoichiometrically oxidize methane, ethane, and propane, separately or as a one-pot mixture, to corresponding alcohol esters in trifluoroacetic acid solvent. Esters of methanol, ethanol, ethylene glycol, isopropanol, and propylene glycol are obtained with greater than 95% selectivity in concentrations up to 1.48 molar within 3 hours at 180°C.

—Hashiguchi et al.

Methane, ethane and propane, the major components in natural gas, belong to a class of molecules named alkanes that are the simplest hydrocarbons and one of the most abundant, cleanest sources of energy and materials. However, transportation can be expensive and converting these alkanes into other useful forms such as gasoline, alcohols or olefins is expensive and often inefficient.

At the core of technologies for converting the alkanes in natural gas is the chemistry of the carbon-hydrogen bond. Because of the high strength of these bonds, current processes for converting these alkanes employ high temperatures (more than 500 °C) that lead to high costs, high emissions and lower efficiencies.

The development of lower temperature (less than 250 °C), selective, alkane carbon-hydrogen bond conversion chemistry could lead to a major shift in energy and materials production technology.

Periana has designed some of the most efficient systems (Periana et. al., Science 1993, 1998 and 2003) for alkane conversion that operate at lower temperatures. However, when Periana and his team examined these first-generation systems they realized that the precious metals they used, such as platinum, palladium, rhodium, gold, were both too expensive and rare for widespread use.

Approaching the problem both theoretically and experimentally, the team hit on inexpensive metals known as main group elements, some of which are byproducts of refining certain ores. Interesting, the new findings run contrary to their predictions from the earlier studies.

The reaction of alkanes with this class of materials we’ve identified is novel. They can react with methane, ethane as well as propane at lower temperatures with extraordinarily selectivity—and produce the corresponding alcohols as the only the desired products. These products are all major commodity chemicals and are also ideal, inexpensive sources for fuels and plastics.

—Roy Periana

In addition to Periana and Hashiguchi, authors of the study, “Main-Group Compounds Selectively Oxidize Mixtures of Methane, Ethane, and Propane to Alcohol Esters,” are Michael M. Konnick, Steven M. Bischof and Niles Gunsalus of The Scripps Research Institute; and Samantha J. Gustafson, Deepa Devarajan and Daniel H. Ess of Brigham Young University.

This study was supported by the US Department of Energy (DE-SC0001298).

Resources

  • Brian G. Hashiguchi, Michael M. Konnick, Steven M. Bischof, Samantha J. Gustafson, Deepa Devarajan, Niles Gunsalus, Daniel H. Ess, and Roy A. Periana (2014) “Main-Group Compounds Selectively Oxidize Mixtures of Methane, Ethane, and Propane to Alcohol Esters,” Science doi: 10.1126/science.1249357

March 14, 2014 in Fuels, Gas-to-Liquids (GTL), Natural Gas | Permalink | Comments (14) | TrackBack (0)

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Comments

This sounds very good - if you could convert abundant natural gas to liquids, it would be a real boon - you could move to flex fuel cars in a big way.

You could establish a real market for large amounts of CO2 which would probably work better than sequestering it.

Better still if you could make longer chain alcohols, at least to ethanol, preferably to butanol.

Mahonj: Where does the market for CO2 come into it?

There are viable technologies for large gas fields or small ones close to markets for example the recently reported CompactGTL in Kazakhstan. But that "small" project was for ~800,000 m^3 a day of gas. So I hope that this alcohol ester production leads to technology viable in the small scale.

Trifluoroacetic acid (TFA) is the organofluorine compound with the formula CF3CO2H.

More chemistry and catalysts are one way, but if you use the waste heat from power plants you can take natural gas to DME to gasoline more efficiently. We throw away a LOT of heat from power plants, might as well use it to make fuel.

Im interested since years and years to buy synthetic fuel for my gas dodge neon 2005. I will prefer to buy butanol instead of e85 as my car is not flex fuel like said by mahonj.

One thing that is sure is that these patents are bought by exxon that put them to shelfs to protect their conventional high paying petrol business. It's not the first time I read a novel breakthrough method to produce synthetic fuels like this one. It will happen the same thing with this method as the others and we will never see it commercialised in any way BECAUSE it is efficient and cheaper. This is the dark side of these subsidized studies, the patents are sold to ExxonMobil instead of been put into useful production. Since then I have to pay high dollar for mud they call petrol for my cheap dodge neon.

There is almost an infinite ways to propel a car for cheap and this website is unable completely to make it happen. The simplest way will be to stop the cartel of petrol and gasoline and we will see gasoline at 80 cents a gallon.

Video here:
http://phys.org/news/2014-03-method-usable-fuels.html

@DavidJ:
To make the longer chain alcohols carbon must be added, so it would be great if we could source that from CO2.

@DavidJ, they seem to use o2 directly, so there would not be a market for the CO2 - Oh well
(See the video above)

@mahonj:
Surely they need carbon as well as oxygen?

@Davemart:

You are inserting an oxygen atom between a carbon atom and hydrogen atom to make an alcohol. You do not need carbon, only oxygen. On another note, thallium is extremely toxic and trifluoroacetic acid is extremely corrosive, so this process is not likely scalable.

This is one of those lab findings no one knew about which may not be worth much in a commercial application but could be valuable to people who do lab work.

CH4 methane becomes CH3OH methanol becomes CH3OCH3 DME becomes synthetic gasoline. TOTAL the oil company in France and others have a method that skips the methanol part, goes from methane to DME and then gasoline using zeolites.

You can go from methane to DME at about 70% efficiency and then to gasoline at over 60% efficient. Using waste heat from power plants you might get from natural gas to gasoline at close to 70% which is not much worse than tar sands to high octane gasoline.

Here is how to upscale this new GTL technology. Utilize solvent extraction of hydrocarbons from coal (google that) to separate the pentane and lower alkanes from coke and sulfates, all of which take up huge refinery capacity. Burn your clean coal for electriciy and have plenty of CHP for gasoline synthesis.

This should be more straightforward and efficient than hydrocracking the lower grade alkanes and olefins, and besides, your more modern oil refineries must now burn oil coke for basic energy. The whole GTL-CHP could actually have greater energy efficiency than advertised.

You could put the petcoke from refineries into a carbon fuel cell, take the CO2 that comes out of the cell and combine it with hydrogen made from the electricity generated by the fuel cell to make gasoline.

There is a good slide set from a guy at Lawrence Berkeley Labs that hints at this. I thought it was a good concept and still do. Petcoke is a huge waste product from refineries, with tar sands we will have even more of it.

SJC, do youself an efficiency analysis on your scheme.  It'll be a good piece of education for you.

You tell that to the scientist at LBL, you know so much more.

Way to not even try to understand your own notions.

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