Chemistry Nobel Laureate writes a monograph on the methanol economy.

[NNadir]

Since winning the Nobel for his work on carbocation chemistry, George Olah has devoted significant energy (pun intended) to the methanol powered fuel cell.

I am suspicious of methanol on toxicity grounds, but I do note that methanol can be synthesized by hydrogenation of CO2. Even better it is an excellent intermediate in the preparation of dimethyl ether, which can be used to power chainsaws in maine.

Here is the book, from my favorite scientific publishing house, John Wiley and Sons:

http://www.wiley-vch.de/templates/pdf/3527312757_c01.pdf



Some quotes from the sample chapter:

Synthetic oil is feasible, its production having been proven feasible from coal or natural gas via synthesis-gas, a mixture of carbon monoxide and hydrogen obtained from the incomplete combustion of coal or natural gas (which are themselves non-renewable). Coal conversion was used in Germany during World War II and in South Africa during the boycott years of the Apartheid era. Nevertheless, the size of these operations hardly amounted to 0.3% of the present United States consumption. This route – the so-called Fischer–Tropsch synthesis – is also highly energy consuming, giving complex, unsatisfactory product mixtures, and can hardly be seen as the technology of the future. To utilize still-existing large natural gas reserves, their conversion to liquid fuels through syn-gas is presently developed for example on a large scale in Qatar, where major oil companies including ExxonMobil, Shell or ChevronTexaco, have recently committed over $20 billion to the construction of gas-to-liquid (GTL) facilities, mainly to produce sulfur-free diesel
fuel. However, when completed, this will provide a daily total of some 100 000 t compared with present world use of transportation fuels in excess of 6 Mt per day...

...CO2 can, as mentioned earlier, even now be readily recovered from flue gas emissions of power plants burning carbonaceous fuels (coal, oil, and natural gas), from fermentation processes, and from the calcination of limestone (cement production), production of steel, or other industrial sources. As these plants emit very large amounts of CO2 they contribute to the so-called “greenhouse warming effect” of our planet, which is causing grave environmental concern. The relationship between the atmospheric CO2 content and temperature was first studied scientifically by Arrhenius as early as 1898. The warming trend of our Earth can be evaluated only over longer time periods, but there is clearly a relationship between the CO2 content in the atmosphere and Earth’s temperature. Recycling CO2 into methanol (or dimethyl ether) and, through this into useful fuels and synthetic hydrocarbons and products, will not only help to alleviate the question of our diminishing fossil fuel resources, but at the same time help to mitigate global warming caused at least in part by man-made greenhouse gases. One highly efficient method of producing electricity directly from fuels is achieved in fuel cells via their catalytic electrochemical oxidation, primarily that of hydrogen.

As always, I prefer dimethyl ether to methanol, on toxicity grounds, but this is damn interesting work.

[Dead_Parrot]

1. Good news for me...

...It's not in the library yet, and I can't afford it, thereby saving me from using my brain. I'll keep my eyes open, though - it looks interesting.

[tocqueville]

2. why methanol when ethanol contains more energy and far

easier to produce ? From what energy sources will he get hydrogen without using nuclear power ?

[eppur_se_muova]

3. Unfortunately, mostly the H2 is made from natural gas or coal.

natural gas (methane):
CH4 + H2O --> CO + 3H2 (IIRC -- may go to CO2)
then
CO + 2H2 --> CH3OH (methanol)
overall:
CH4 + H2O --> CH3OH + H2
If the H2 is combined with CO2, it will consume only 1/4 as much CO2 as is produced by burning the CH3OH:
3CH4 + 2H2O + CO2 --> 4CH3OH

coal:
2C + 2H2O --> 2CO + 2H2
then
CO + 2H2 --> CH3OH
overall:
2C + 2H2O --> CO + CH3OH
the CO can be burned for energy, or converted to more H2 by the "water gas shift reaction":
CO + H2O <--> CO2 + H2
giving an overall conversion:
3C + 4H2O --> 2CH3OH + CO2

The carbon must be very hot in the first reaction, and this is usually achieved by "coking", in which impurities (and some coal) are burned off in a deficit of oxygen to leave red-hot coke. Live steam (takes more energy to get hot) then reacts to give "water gas", or synthesis gas. So some of the CO/H2 has to be burned to produce heat to run the process. Likewise, the CH4 reformation reaction has to burn some fuel, to provide energy input. Don't ask me about the energy balance, I don't have it offhand. And a ChE could give you a more real-world answer anyway.

H2 could, of course, be made by electrolysis, particularly near hydro or nuclear installations. But if industry were to suddenly start consuming more H2 to make methanol, you can bet it would come from coal or gas, because that's the cheapest way right at this very moment.

[NNadir]

4. George Olah has a whole chapter in the book on thermochemical water

splitting via nuclear means. This is basically the hydrogen-iodine cycle.

http://www.aspentech.com/publication_files/TP51.pdf

He's a big pro-nuke guy.

Reactors to run this cycle are being built in China and planned in many other places, including Japan and maybe South Africa.

[eppur_se_muova]

10. Oh ho! Need to read up on H2-I2. Always thought that would be considered

a little expensive. HI easily equilibrates with H2 + I2, thermally or photochemically, but I2 is not the cheapest thing around. OTOH, toxicity would be fairly low.

Thanks for the pdf.

I saw a job op a few years back where the Air Force was looking to regenerate HI from I2 by electrolysis to make synthetic jet fuel, sounded iffy at the time.

ON EDIT: SULFUR/iodine cycle, even more interesting. Sulfur chemistry is hugely flexible, which makes sulfur one of my favorite elements. Still lots of interesting practical chemistry to be done with sulfur.

[NNadir]

11. Iodine, IIRC, costs about $7/kg. However the system is closed.

Once charged, the system will require no inputs of iodine. The iodine is a catalyst, not a reactant.

(The iodine prices are at a MT scale. In general people avoid iodine chemistry industrially since this is considered a very high price.)

Note that there is also an iron bromine system that is similar.

Iodine is a fission product. Ton quantities are available from reprocessed nuclear fuel, although they are slightly radioactive owing to the presence of long half-life I-129. Probably it will be the case that virgin iodine will be preferred.

The amount of iodine actually required would be a function of the cycle time.

[eppur_se_muova]

14. "closed, until it leaks."

Any ChE will tell you that NO system is completely closed--you're always making up losses. And with I2 being volatile that is a particular concern. Still, it sounds doable, as long as make-up costs aren't excessive.

The FeBr3 sounds interesting as well.

[NNadir]

5. Ethanol is not easier to produce.

Even the most rabid (and I think deluded) ethanol advocates claim "it could" produce about 30% of fuel requirements.

The ability to produce methanol from hydrogen and carbon dioxide is much larger than that.

He intends to get some hydrogen from biomass and other means, but mostly he has nuclear power in mind since this is scalable to any level and does not depend so intimately on the weather.

[JohnWxy]

12. Oak Ridge National Laboratory- source of 30% of fuel requirements estimate

Oak Ridge National Laboratory - well known source of rabid delusionals. LOL!

Why don't you give them a call and straighten them out. I'm sure they will be glad to here from ..."WHO???"


http://www.ornl.gov/info/press_releases/get_press_release.cfm?ReleaseNumber=mr20050421-01

"Our report answers several key questions," said Bob Perlack, a member of ORNL's Environmental Sciences Division and a co-author of the report. "We wanted to know how large a role biomass could play, whether the United States has the land resources and whether such a plan would be economically viable."
~~
Looking at just forestland and agricultural land, the two largest potential biomass sources, the study found potential exceeding 1.3 billion dry tons per year. That amount is enough to produce biofuels to meet more than one-third of the current demand for transportation fuels, according to the report.

Such an amount, which would represent a six-fold increase in production from the amount of biomass produced today, could be achieved with only relatively modest changes in land use and agricultural and forestry practices.

"One of the main points of the report is that the United States can produce nearly 1 billion dry tons of biomass annually from agricultural lands and still continue to meet food, feed and export demands," said Robin Graham, leader for Ecosystem and Plant Sciences in ORNL's Environmental Sciences Division.

The benefits of an increased focus on biomass include increased energy security as the U.S. would become less dependent on foreign oil, a potential 10 percent reduction in greenhouse gas emissions and an improved rural economic picture.

Current production of ethanol is about 3.4 billion gallons per year, but that total could reach 80 billion gallons or more under the scenario outlined in this report.

ANd what about Bob Perlack? From the Oak Ridge National Laboratory web-site:

www.ornl.gov/sci/psr/Bob%20Perlack.pdf

Ph.D., Resource Economics, 1978, University of Massachusetts, Amherst
Over 25 years experience in energy/environmental economic assessment, global climate change analysis, and policy analysis

1980 to present Oak Ridge National Laboratory, Oak Ridge, TN
      Environmental Sciences Division, Bioenergy Systems Group
      • Providing economic and technical analysis and management to a variety of projects for the U.S. Department of Energy, the U.S. Federal      Energy Regulatory Commission, and the U.S. Agency for International Development.

      • Recent activities: economic and policy analysis of bioenergy systems; adaptation responses to climate change; strategic environmental and economic assessments in developing countries; water policy studies involving conflicts between off-stream and in-stream uses; analysis of benefits at federal headwater dams; evaluation and development of performance metrics; and analysis of land use management strategies for greenhouse gas mitigation.

There were numerous published articles listed on this site I didn't bother to copy.

[NNadir]

13. I've been hearing 30% - 100% for ethanol for 30 years, kid.

How about you and Bob Perlack take a look at the drought monitor this week:



If it was so damn easy, 30 years of talking and x brazillion dollars of subsidies (it's easy to lose count with the Presidential caucuses being in Iowa) would have brought to an exajoule level.

Here, not some kids talking about what they could do, is the nation reporting what they did do:

http://www.eia.doe.gov/cneaf/solar.renewables/page/trends/table_5b.xls. Less than an exajoule.

I don't have to call somebody up to hear all about the magical renewable future. I know something about scale and I'm not some credulous kid.

[skids]

15. methanol is pretty darn easy to produce, from biomass.

"pyrolisis"

Fuel energy content is not the end-all and be-all of a fuel's viability, either. Methanol is used in race cars, where weight really matters, for crash safety resons.

NNadir is right to want better analysis of methanol's potential for damage if an environmental release occured.

Also if used in an ICE, a properly tuned engine is of utmost importance to prevent emissions of formaldehyde/formic acid. However in a fuel cell that won't be a concern.

[phantom power]

6. I don't quite follow the toxicity argument.

I mean, ethanol, DME, or for that matter diesel fuel or gasoline are all toxic. I can "safely" ingest a few ounces of ethanol, but a tankful would kill me just as dead as a tankful of gasoline.

[NNadir]

7. Dilute ethanol, if not denatured, is not toxic.

It gets you drunk, but other than that, the effects are survivable. So ethanol is relatively safe when compared to methanol.

Methanol, even in small chronic exposures, can be fatal. If not fatal, it can cause blindness and other health problems. It is completely miscible with water. Thus any spilled on the ground, or leaked from tanks or pipelines will get into the water supply. Moreover, there really isn't any good technology for removal of methanol from water. Even distillation doesn't work all that well.

Unfortunately, methanol is frequently used as a denaturant for ethanol.

Dimethyl ether is generally not that toxic. It is, in fact, now the propellant in lots of hair spray. It is soluble in water, but it's boiling point is very low and it can be removed simply by bubbling air through the water.

In large concentrations, like ethyl ether, it can have some mild anesthetic properties, but it is certainly not deadly.

DME can be liquefied easily: It's critical temperature is higher than that of boiling water, but on release of pressure, such as might occur in a spill, it rapidly evaporates and becomes gaseous, albeit somewhat slowly as it is also a refrigerant and will self cool.

Thus not all that much will get into the water in the first place.

Finally the atmospheric life time of DME is on the order of a few days. It doesn't survive very long in the atmosphere - although it does break down to give formaldehyde, carbon monoxide and carbon dioxide. Note for comparison, that atmospheric lifetime of natural gas, methane, is on the order of decades - methane is the second most important greenhouse gas.

[phantom power]

8. I see, thanks!

[NNadir]

9. You see because you haven't drank any methanol.

;-)

You're welcome.

[Oerdin]

16. Anything with a methyl group attached to it

should be avoided if possible. It's nasty stuff and it loves to stick to fat cells so it easily works its way into the food chain. I'm happy someone is trying to think of ways to remove carbon from the athosphere and find ways to sequester it but the reality is these are not going to be affordable solutions.