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TreasonousBastard Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Apr-28-06 05:02 PM
Original message
Methanol, not Ethanol
I was listening to Science Friday on NPR and George Olah was the guest. A Nobel chemist, he is claiming that methanol, not ethanol or hydrogen, is the answer.

Methanol can fuel fuel cells, is more efficient and safe than gasses for transport and storage, and can be made from almost anything cheaper than ethanol or biodiesel. In fact, some of the processes using the stuff as fuel can be reversed to make methanol out of the resulting carbon dioxide. Not exactly perpetual motion, but more like plants photoysnthesizing CO2 during the day and using some oxygen at night. Not a perfect answer, but a a definite reduction in our carbon footprints without major changes in lifestyles.

Race cars have been using methanol for years, so much of the groundwork for internal combustion engines is already done. Electricity production, heating, etc. would not be all that far behind.
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4dsc Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Apr-28-06 05:07 PM
Response to Original message
1. Life expectancy of fuel cells??
I heard that fuel cells are only made to last about 4-5 years. Can anyone substantiate that bit of sad information??
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mrcheerful Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Apr-28-06 05:09 PM
Response to Original message
2. What don't anyone get about the oil scam?
Until theres not another drop oil to be found on earth will they ever go to alternative fuels. Oh sure every few years they'll beat the drums get everyone worked up then drop the price to below what its selling now and the sheep will fall in line. Remember 1970? Small cars are the way to go, Big gas guzzlers are a thing of the past, Detroit will lose because they can't build a small car worth the metal its made out of. 30 years later here we are again same old shit different day.
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hunter Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Apr-28-06 05:38 PM
Response to Reply #2
5. Yeah, I remember 1970...
That was peak oil for the United States.

What the hell, we figured, we can import oil... and we did. A lot of oil from unsavory places like the Middle East and Africa.

Now it's peak oil for planet earth.

Importing oil is not an option.

Do I think the oil companies are ripping us off? Yes.

Do I think huge new oilfields will appear like magic somewhere? No.

And if if there is more oil, it's probably not wise to use it. Same thing with coal. All this carbon dioxide in the air is likely to make very bad things happen, things that are going to kill our economy.

Maybe it will be hurricanes and rising sea levels. Imagine all coastal cities looking like New Orleans does today and you get the picture...
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iconoclastNYC Donating Member (1000+ posts) Send PM | Profile | Ignore Thu May-04-06 01:15 PM
Response to Reply #5
37. It was OPEC that triggered the fuel crisis in the 70s
So I don't really understand why you think we "figured we could import" oil... we were doing it then.

What happened was OPEC wised up and realized that they shouldn't kill the goose that laid the golden egg. By encouraing alternatives they were cutting off thier face to spite thier face. So they increased supply which lowered price and made the alternatives uneconomical.

The only reason this hasn't continued is because of peak oil. They wells are drying up.
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JohnWxy Donating Member (1000+ posts) Send PM | Profile | Ignore Mon May-01-06 01:51 PM
Response to Reply #2
33. Oil & gas industry gives 80% - 84% to REpublicans - guess they no
where they can get a good deal (price) on the Government.

http://www.opensecrets.org/industries/indus.asp?Ind=E01
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elifino Donating Member (331 posts) Send PM | Profile | Ignore Fri Apr-28-06 05:11 PM
Response to Original message
3. Methanol, not Ethanol
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eppur_se_muova Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Apr-28-06 05:14 PM
Response to Original message
4. Hmmm... is it NNadir's birthday?
:)
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NNadir Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Apr-28-06 06:35 PM
Response to Reply #4
7. I've been talking up this one for a while. This makes renewable
energy more attractive I note.

If this works, it will be better than any birthday present I could possibly imagine.

If these devices can be industrially scaled, it is effectively an outstanding way of converting any electrical energy to a liquid fuel, wind, solar, nuclear.

This is a very big deal, if it works and can be industrially scaled.

I have read excerpts of the patent. The chemistry involves supported precious metal catalysts, specifically ruthenium/platinum supported on organic substrates. The patent is US6,821,659.

The world supply of these metals is limited, although I happily note that there is a great deal of ruthenium available in so called "nuclear waste."

I do not support methanol fuel, because of its toxicity and miscibility with water. However methanol is easily dehydrated to give DME, which will easily be the best fuel ever used by the human race.
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4dsc Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Apr-28-06 06:41 PM
Response to Reply #7
8. Here's all the info you need about methanol
http://www.peakoil.com/fortopic18329.html

Great discussion at peakoil.com about methanol. But it looks as though it take a huge amount of electricity to produce it. Our only real options for cheap carbon neutral electricity are: nuclear and (offshore)wind.

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eppur_se_muova Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Apr-28-06 08:15 PM
Response to Reply #8
11. Electricity to produce MeOH??
Edited on Fri Apr-28-06 08:19 PM by eppur_se_muova
All I can say is, HUH? Whoever suggested that?

Maybe 'energy' to produce MeOH, electricity not specified? Sounds more likely.

ON EDIT: If it's in the Popular Mechanics links, I'm having trouble accessing them ... ignore if so.
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NNadir Donating Member (1000+ posts) Send PM | Profile | Ignore Sat Apr-29-06 06:54 AM
Response to Reply #11
16. The Olah fuel cell produces methanol from electricity, water, and CO2.
The overall reaction is the reduction of carbon dioxide to methanol electrolytically.

If the carbon dioxide can be removed from air through an equilibrium driven approach (and that may prove far more problematic) the implications of this invention are enormous.

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eppur_se_muova Donating Member (1000+ posts) Send PM | Profile | Ignore Sat Apr-29-06 10:51 AM
Response to Reply #16
19. So this is IN ADDITION TO the thermal processes he's investigated ??
He's been busier than I realized.

I thought his emphasis was on converting the nuclear thermal energy directly to chemical energy. May as well pursue both if both will work, and the electrical may be more versatile (at least for immediate use).
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NNadir Donating Member (1000+ posts) Send PM | Profile | Ignore Sat Apr-29-06 01:01 PM
Response to Reply #19
21. He did not do work on the thermal processes for nuclear conversion.
Edited on Sat Apr-29-06 01:06 PM by NNadir
Those thermal processes for nuclear conversions are a different body of work.

George Olah speaks prolifically on the need for nuclear power, but he does not work on nuclear systems per se.

He has long been working on the methanol fuel cell; and devoted himself to it actively after winning the Nobel Prize. He is not one of those Prize Winners who sits back and basks in the glory or allows himself to be obstructed from further work by it. This is somewhat new for him, as is Nobel was for carbocation chemistry, chemistry that has had most of its direct application in the technology of fossil fuels.

His initial goal, as I understand it - and I'm in no way privy to his thinking, was to create a fuel cell that could be fueled by a convenient fluid fuel other than the very inconvenient hydrogen. The reversibility of the cell he developed is a surprise, I think, although one could be sure that he would look for it.

I note that one could argue that such a fuel cell, if developed, will go a long way to enhancing a growing role for renewable technologies like solar and wind. The possibility exists to make relatively environmentally benign storage systems - an issue that complicates the nature of energy choices, since environmentally benign freely scalable energy storage technologies do not really exist. One could, for instance, recover wind energy in the Dakotas in early autumn and ship it to New York for use in winter. In some sense, over the long term, it could make them environmentally and economically competitive with nuclear power - something that is not now the case. If nuclear technology and renewable technology truly become competitors not only to fossil fuels but to each other, this is a win for humanity.

As I often say, I will be thrilled to discuss the relative merits of technologies that replace fossil fuels once they are replaced.

It may prove that Olah will rank among the Chemistry Nobel Laureates whose work have had the most profound economic (and environmental) importance in history. He may at the end of the day been included among the ranks of people like Fritz Haber, Watson and Crick, and Glenn Seaborg as a man whose work has had profound direct effects on the outcome of the human race. If he makes this work, he should certainly deserve a second Nobel, and the profound thanks of all humanity.

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eppur_se_muova Donating Member (1000+ posts) Send PM | Profile | Ignore Sat Apr-29-06 03:12 PM
Response to Reply #21
22. Hey, what about Papa Pauling? He DID get a 2nd Nobel. nt
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NNadir Donating Member (1000+ posts) Send PM | Profile | Ignore Sat Apr-29-06 04:03 PM
Response to Reply #22
23. I meant no disrespect for Pauling.
Edited on Sat Apr-29-06 04:04 PM by NNadir
Pauling's second Nobel was for Peace, though, and though it was for an activity that had a direct effect (the banning of open air nuclear testing) on humanity - it was not for an activity that had a direct effect because of the elucidation of chemistry with an immediate technological/industrial application. Even though one can argue that Pauling's work on the chemical bond is essential to all industry, the application was not direct, unlike Haber's work on nitrogen fixation, for instance or Seaborg's discovery of plutonium and his elucidation of its chemistry specifically and the chemistry of actinides in general.

I note that Pauling's work on protein structure though did have more direct effects. The use of proteins in industry is of significant economic importance, and has been so for many, many years. I note he almost beat Watson and Crick to the punch on DNA as well. He could have easily been a man with three Nobels.

Pauling was a very great man, of course and is, I believe, the only person to have won two Nobel Prizes in two different categories.

I have also probably been more than a little amiss in neglecting another double winner, Marie Curie. It is certain that her work did have direct technological and industrial effects as well. Indeed a whole industry, the now maligned radium industry, grew out of her work. Actually it went beyond illuminated watch dials and clock faces, in fact. The use of radioactive materials in tracer work, in manufacturing, and in medicine are all of industrial importance. All of this industry originated from work done in her laboratories. Indeed she lit the way for Seaborg.

Undoubtedly I have overlooked others though. The folks I mentioned just stick in my mind.

If Olah's work creates a whole industry, so much the better. It will and should elevate him even higher in the exclusive pantheon he already occupies.

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NI4NI Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Apr-28-06 06:58 PM
Response to Reply #7
9. Could ethanol or methanol fueled generators
be manufactured to produce electricity? Or air compressors that would produce air power/speed to a wind turbine that could generate electricity?
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NNadir Donating Member (1000+ posts) Send PM | Profile | Ignore Sat Apr-29-06 06:59 AM
Response to Reply #9
17. The methanol fuel cell, or better the DME fuel cell, will be effectively
a battery that can be recharged instanteously by adding either liquid methanol or gaseous DME directly to it.

The Olah cell works with both fuels. DME is to be preferred because of its lower pollution profile.
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rfkrfk Donating Member (1000+ posts) Send PM | Profile | Ignore Sun Apr-30-06 05:31 AM
Response to Reply #17
24. so the methanol fuel cell could power a digital watch ...
Edited on Sun Apr-30-06 05:38 AM by rfkrfk
or maybe some other micropower appliance

no application for vehicles

I foubd this Wiki article to be interesting,
follow the links to you favorite fuel cell.

http://en.wikipedia.org/wiki/Fuel_cell

edited for speling

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eppur_se_muova Donating Member (1000+ posts) Send PM | Profile | Ignore Sun Apr-30-06 01:27 PM
Response to Reply #24
25. Actually, I think there are some laptop PC fuel cells out there already.
I was worried about this already ... airline passengers carrying flammable fuel for their laptops. They make you give up cigarrete lighters, so now what?
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hunter Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Apr-28-06 05:50 PM
Response to Original message
6. Methanol, like ethanol is toxic to aquatic systems.
Spills are bad, in some circumstances worse than diesel spills.

A closely related synthetic fuel is dimethyl ether (DME). It's a "bottled gas" like propane or butane. It's easily synthesized from methanol, or directly from the same sources methanol might be made from, and it's a good fuel for diesel engines, combined cycle power plants, cooking stoves, etc.; better in fact than methanol.

http://www.aboutdme.org

The only way methanol might win out over DME is if it truly is better in some sort of fuel cell, especially a reversible sort of fuel cell that could take an electric current and efficiently make methanol from carbon dioxide and water.
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eppur_se_muova Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Apr-28-06 08:01 PM
Response to Reply #6
10. Well, ethanol is produced by Nature, as I recall.
All it takes is sugar + bacteria. It even happens in the guts of elephants (picture terrified park rangers hearing elephant approaching, drunkenly trumpeting). And it's metabolized by many organisms besides us (converted by microorganisms into acetic acid --that's where vinegar comes from). So while the dose makes the poison, I'd rather face a spill of ethanol than one of methanol. Dilution would render the ethanol relatively harmless.

Dimethyl ether is a better fuel than methanol because it's basically 2MeOH molecules minus one H2O molecule. H2O is the "ash" of combustion, so stripping out the H2O before burning gives higher energy density, which is good for lots of reasons (including cheaper to transport, hotter burning).

On a sour note, I note that tert-butyl methyl ether, TBME, is not water-miscible but is water-soluble, and for that reason has become a problematic environmental pollutant. TBME was added to gasoline to give smoother burning (and lower emissions, IIRC, with low confidence) and turned out to leak easily from underground fuel tanks (it's low boiling, so evaporates from gasoline, then dissolves in groundwater) into the water supply. I find it all too easy to imagine Me2O might do the same. Also, Me2O would seem to be a candidate for smog generation, though maybe not too bad in that regard. And oh yeah -- check to see if Me2O forms a water clathrate.

Dimethyl ether, FWIW, is an isomer of ethanol (both have the same formula, C2H6O) and since both are "saturated" molecules, should be *roughly* equal in energy. It might very well be possible to convert dimethyl ether to EtOH by, say, a Wittig rearrangement over hot barium oxide or other catalyst. That's probably been tried; I'll have to search.

Unfortunately, the term "DME" is already in use, both scientifically and industrially, to indicate "1,2-dimethoxyethane", a common industrial solvent (at least in the fine chemicals/pharma sector). I'd like to encourage "Me2O" as an abbreviation for dimethyl ether.

PS: chances are MeOH is a MUCH better candidate for fuel-cell than Me2O. It's a much simpler molecule, which means it only takes one or two steps to go to complete combustion. Too many steps would make reaction difficult to execute in a fuel cell. And while fuel cells are not an area I know a whole lot about, I'm pretty sure that MeOH fuel cells are up and running already.
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rfkrfk Donating Member (1000+ posts) Send PM | Profile | Ignore Sat Apr-29-06 02:06 AM
Response to Reply #10
13. fuel cells run only on hydrogen
why would you want to, throw energy away to get hydrogen,
then use the energy in a device that is hardly
better than a diesel?
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skids Donating Member (1000+ posts) Send PM | Profile | Ignore Sat Apr-29-06 02:13 AM
Response to Reply #13
14. Untrue.

Fuel cells run on many things, some of them not even hydrocarbons. There are several designs of fuel cell, in fact, that use a metal as the fuel, producing metal oxide as a waste product.


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rfkrfk Donating Member (1000+ posts) Send PM | Profile | Ignore Sat Apr-29-06 04:20 AM
Response to Reply #14
15. how much electricity is produced
in some non-hydrogen fuel cells,
compared to using the 'stripped-off hydrogen'?

OK, so I forgot about the vanadium-redox reaction
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skids Donating Member (1000+ posts) Send PM | Profile | Ignore Sat Apr-29-06 10:50 AM
Response to Reply #15
18. Wasn't referring to vanadium redox.
Edited on Sat Apr-29-06 10:51 AM by skids
The ones I was referring to use sheets or pellets of aluminum, nickel, etc.

As to energy efficiency, it's a known problem with fuel cells. However, one has to keep in mind that up
here in the northern climate, we need our car engines to produce a certain amount of heat, or we'll freeze. Likewise in home use, waste heat is useful for water preheating.

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eppur_se_muova Donating Member (1000+ posts) Send PM | Profile | Ignore Sat Apr-29-06 10:57 AM
Response to Reply #13
20. There are many types of fuel cells, just as there are many types of ...
"batteries". A fuel cell is really just an electrochemical cell in which the fuel and oxidant can be pumped in and the waste products pumped out. Close off the inlet and outlet and it's just a cell -- a "battery".

(Battery is in quotes above because strictly speaking, a battery refers to cells linked together. "C cells, D cells" are just that, cells, not batteries.)

H2/O2 is just one of the most advantageous fuel cells -- two gases as input, pure water as output, with high voltage (for a cell). But there are lots of other things you could use as fuels.
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JohnWxy Donating Member (1000+ posts) Send PM | Profile | Ignore Sun Apr-30-06 02:59 PM
Response to Reply #10
26. Thanks for such an informative post! Regarding Ethanol and
Fuel Cells, they are being developed (also ethylene glycol) with a reformer. It is better than methanol primarily because of the toxicity of methanol. Also, it has greater availability than methanol.

MTBE is being phased out by Oil companies and being replaced by ethanol. that's why ethanol prices have bumped up recently. The oil companies are buying up ethanol like mad now (after years of saying, adding ethanol to gasoline would be so difficult and costly!). Big Oil hates to have to add a component to their product the production and supply of which they don't totally control. Replacing MTBE with ethanol will bring up the percentage of ethanol in gas to 5% to 10% (depending upon what part of the country the gas is intended for).

Thanks for the post. Really interesting. Informed reasoning, what a refreshing change!!




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eppur_se_muova Donating Member (1000+ posts) Send PM | Profile | Ignore Sun Apr-30-06 05:39 PM
Response to Reply #26
28. "Big Oil hates to have to add a component to their product"...
Edited on Sun Apr-30-06 05:41 PM by eppur_se_muova
"...the production and supply of which they don't totally control."

Wow, that rang a bell. I had started reading Devra Davis's "When Smoke Ran Like Water", and found this about 'leaded' gasoline:


At the same time that the automobile, gasoline, and tire companies were eliminating the trolley as competition, they also set in motion plans for cornering the market on fuel. Early cars tended to have a pinging, popcorn-popping, knocking sound when running, especially when going up hills. Faster engines were said to require fuel that burned more efficiently to avoid these noises of inefficiency. Ordinary alcohol--ethanol--easily made from agricultural crops such as corn, provided a possible solution because it could boost efficient fuel burning, but it would take up about 10 percent of the volume of a gas tank. Furthermore, ethanol could not be patented, nor could its production or price be controlled by the car and fuel companies. These firms began promoting a newly invented, specially formulated compound that bound a single atom of lead to twenty atoms of hydrogen and eight of carbon. This compound's hydrocarbon chains each held four {sic! two} carbon atoms, known as ethyl branches; thus the liquid was called tetraethyl lead. The public already had a dim view of lead and a vague sense of its toxicity. To soften its image, the founders of the company gave their new firm a popular woman's name, Ethyl {sic--woman's name spelled Ethel}.
***
... A month later, on October 27, 1924, the front page of the New York World read "Gas Madness Stalks Plant, Two Die, Three Crazed." At the Elizabeth, New Jersey, plant of Standard Oil Company, workers were suffering the acute effects of lead poisoning. William McSweeney, a former general in the Irish Republican Army and an employee at the plant, was reported to have died after three days, "clamped in a straightjacket on an iron cot in Reconstruction Hospital." Management at Standard Oil explained this outbreak of madness and death at its Elizabeth plant by saying:"These men probably went insane because they worked too hard."

The affected workers were producing hundreds of gallons of the acutely toxic liquid, tetraethyl lead, to be added to gasoline. These first efforts at mass production proved catastrophic. Even a few drops of lead in this fluid form penetrated the skin, coursed through the bloodstream, and ended up damaging nerves and destroying the brain.

After word of these disastrous consequences spread, the public became understandably queasy about the prospects of adding lead to gasoline. New Jersey and Pennsylvania suspended sales of ethyl gasolline. Public health officials were lining up against the additive. In response, Ethyl pulled its product from the market in 1924 and asked Surgeon General Hugh S. Cummings to set up a panel of scientists to recommend what should be done.
***
In extolling the virtues of tetraethyl lead gasoline, by contrast, the advertisers never used the word lead. One image from October 1927 included a flying car with wings. If you ride with Ethyl, the ad promised, you will get the benefits of high compression and the assurance that ethyl gasoline "has absolutely no ill effect on the motor or its parts." ... "


Although public hearings were held about the safety of leaded gasoline, the decision seems to have been made behind closed doors. Of course, the greater danger later turned out to be the slow accumulation of traces of lead in the environment. I'm still reading that chapter of the book, describing the pioneering work of Mary Amdur, whose conclusions regarding the health effects of exposure to pollutants were rejected by the scientific and medical establishment at the time. It's really a fascinating story, almost like a secret history.

edit for a little formatting
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skids Donating Member (1000+ posts) Send PM | Profile | Ignore Fri Apr-28-06 09:29 PM
Response to Original message
12. Been saying it for... sheesh... a decade and a half now.

Did a report on biomass pyrolysis for producing methanol for ICEs in college, in fact :-)
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JohnWxy Donating Member (1000+ posts) Send PM | Profile | Ignore Sun Apr-30-06 03:43 PM
Response to Original message
27. All the positive aspects of methanol apply also to ethanol - BUT
Methanol is toxic and ethanol is not.

I know the oil and gas industry is gung-ho on methanol because you need to use natural gas to make it from biological sources (such as wood). It sounds like a green fuel but it's not. Ethanol requires only a fraction of the fossil fuel needed to make methanol (just the fossil fuel to make nitrogen fertilizer and to operate farm equipment and provide energy at the ethanol plant). (ethanol production will be using more bio-fuels in the future - biodiesel for farm equipment and methane from manure for the ethanol production process - enabling it to use even less fossil fuel). But much less fossi fuel is required to make ethanol compared to methanol.


NPR is I'm afraid committed to being toadies to the Republican Party. I guess they feel they need to do this to survive (much the same goes for Public Broadcasting Corp -(tv).

When cellulosic ethanol becomes commercially viable in 5 to 6 years ethanol will be made form agricultural and forest product wastes and fast growing energy crops. This will be several times as productive as starch based ethanol.


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eppur_se_muova Donating Member (1000+ posts) Send PM | Profile | Ignore Sun Apr-30-06 06:13 PM
Response to Reply #27
29. Methanol can be made from coal or methane by purely chemical methods.
Edited on Sun Apr-30-06 06:14 PM by eppur_se_muova
THAT's why the "energy companies"x( are so devoted to it. They've already got all the hardware in place to turn the "other" fossil fuels into MeOH for vehicles.

Methanol -- the other white meat?

(Edit to add: Not just toxic--burning MeOH produces traces of formaldehyde, a carcinogen, in exhaust.)
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NNadir Donating Member (1000+ posts) Send PM | Profile | Ignore Sun Apr-30-06 07:59 PM
Response to Reply #29
30. I note that formaldehyde is also an oxidation product of ethanol.
Edited on Sun Apr-30-06 08:06 PM by NNadir
It is further one of the most important oxidation products of natural gas, and represents (along with methanol and formic acid) one of the main reasons one cannot recover water from burning natural gas. Formaldehyde is also a common product in the decomposition of certain types of styrofoam, and many types of insulation.

I note that the decomposition of methane released into the atmosphere - although the process has a half-life of decades - involves formaldehyde intermediates.

All primary alcohols decompose into formaldehyde intermediates when they are burned. The main difference between ethanol and methanol in their pollution profiles is that, lacking a carbon-carbon bond, methanol has almost zero tendency to produce soot. Ethanol does produce soot, although generally not as much as, say, diesel fuel.

Many other products give formaldehyde as a combustion product. The combustion of wood, as you would expect from the structure of sugar, gives off formaldehyde. (In fact the historical method of producing methanol, which is also known as "wood alcohol" was the destructive distillation of wood under a vacuum. This same process takes place when wood is burning, and so it follows that there would naturally be some formaldehyde produced.) Thus DME has no advantage over natural gas unless it is made from carbon dioxide or biomass.

In combustion properties, it is difficult to imagine a liquid fuel with better burning properties than methanol. The big problem is its water toxicity, although I note that ethanol is very toxic to certain types of creatures, notably fish.

If methanol is transformed into DME, almost all of the toxicity issues go away completely. DME is for practical purposes non-toxic.

An interesting review article covering most of what I say here can be found in Good, D.A. and Francisco, J.S., Chem. Rev. 2003, 103, 4999-5023. The article is entitled "Atmospheric Chemistry of Alternative Fuels and Alternative Chlorofluorocarbons." It's a good read.

I'll quote a few bits from that article relevant to DME, merely noting that with respect to cost, the article was written when the price of oil was around $30/barrel.

3.3. Dimethyl Ether.

Dimethyl ether (DME) is a colorless, nearly odorless, gas at room temperature and atmospheric pressure. DME is quite stable and reacts or decomposes only at extreme conditions. Currently, 150,000 metric tons of DME is produced per year. The DME produced is mostly used as a propellant in aerosol cans. In 1986, a patent described a method for burning a fuel composed of 94-99.9% DME in a diesel engine.21 Early testing of DME as a diesel fuel indicated lowered NOx emissions, essentially zero particulate matter, and lower noise without loss of efficiency. The low emissions of particulate matter are due to the absence of carbon-carbon bonds in the molecular structure. Emissions of hydrocarbons and carbon monoxide are slightly higher for DME-fueled engines unless an oxidation catalyst is used. Emission tests have demonstrated the potential for meeting California’s ULEV standards for medium- and heavy-duty vehicles.23,24 DME has a high cetane number and is thus suited to compression ignition applications. The energy density of DME is higher than that of methanol or ethanol but is significantly lower than that of conventional diesel fuel. The use of dimethyl ether would require 1.8 times the volumetric flow of diesel fuel to obtain the same power output. In addition, the cost of production of DME is currently higher than that of conventional diesel fuel. DME is produced from methanol in dehydration plants. Thus, the cost of DME is roughly 2 times the cost of diesel fuel. Alternatively, DME can be produced directly from synthesis gas generated from various feedstocks ranging from natural gas to coal and biomass.


No mention is made, of course, on the possible use of Olah fuel cells to make methanol, and neither are any economics are included. (The economics of the Olah fuel cell are essentially unknown - and that is a giant caveat.)

As mentioned in the reference, the oxidation of DME in combustion does produce some formaldehyde as well as some methanol and formic acid. The atmospheric degradation pathway of DME, which has a half-life of a few days in air, also includes these common oxidation products.

From a pollution standpoint however, it is clear that DME (via methanol or other means) can be made directly from carbon neutral sources. Then its advantages are incalculable. The Olah fuel cell reduces carbon dioxide to give methanol. The Olah fuel cell is just one such source, however. Direct hydrogenation of carbon dioxide is also known to work to give either methanol or DME directly. This is in my view, by far, the most useful use to which hydrogen can be put, DME manufacture. (See for instance Bull. Korean. Chem. Soc. 19, 4, 466-71 (1998).)

The processing moreover - unlike the case with ethanol - can be made to have low energy intensity and can be easily modified for continuous flow. This reduces both the pollution profile and the cost (especially on scale up) of manufacture. I note that the bottom of DME cost is certainly not reached since the application remains small and limited - propellant. That is about to change big time.

With respect to physical properties, DME is superior to natural gas inasmuch as its critical point is above the boiling point of water. Thus it can be shipped and stored as a liquid under pressure and natural gas cannot be without the investment of massive energy for refrigeration.

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eppur_se_muova Donating Member (1000+ posts) Send PM | Profile | Ignore Sun Apr-30-06 08:55 PM
Response to Reply #30
31. Ethanol also produces acetaldehyde, which isn't pleasant.
Wasn't meaning to imply that MeOH is the *only* source of formaldehyde, or of unwanted pollutants in general (I'm assuming everyone counts CO2. OK, everyone but Bush**). I remember that when the question of "alternative" fuels was being discussed back in the Clinton era, the greater risk of formaldehyde from MeOH vs acetaldehyde from EtOH was considered a big strike against MeOH. Given that the structure of formaldehyde (H2C=O) is just MeOH (H3C-OH) minus two hydrogens, it just seems obvious that MeOH burned in too little air would result in some formaldehyde. The obvious countermeasure is good engine tuning/maintenance, and catalytic conversion after combustion. But you always have to worry about those horrid old wrecks driving around with the leaky mufflers, perforated exhaust pipes, etc. ... Human nature more or less requires that we worry about what pollutants are formed under very suboptimal conditions, as well as optimal ones. I'll have to look up that article (uh, AFTER the job search is done) to see what actual measurements of CH2O production are. Glad the data's getting out, in any case, so we have more facts to go on. (BTW, one other thing to worry about is what happens to CH3OH vapor in air, in the presence of sunlight. If CH2O is formed from CH4, I would think it would form even more easily from CH3OH. Oh, well, I'll see if that's in the review.)

Each of the possibilities being bandied about has something to recommend it, but none is perfect. MeOH has a lot of advantages, as does Me2O. My real concern in my previous post was this: that the energy companies may very well commit to MeOH for all the wrong reasons. If MeOH can be made from biomass or electoreduction, fine and good. But EVEN IF THOSE TECHNOLOGIES WORK WELL, keep your eye on the coal and gas companies -- they will do everything they can, backed up by thick checkbooks, to use MeOH's status as a (potentially) green alternative to squeeze more profits out of the resources they already hold (which plummet in value otherwise), converting tons of sequestered carbon into CO2 in the process. It's NOT necessary to do that to bring MeOH to market, but as long as there's a profit motive to do so, you bet they will. And of course our present maladministration would not only encourage them to do so, but probably manage to handicap, if not cripple, the low/no-GHG alternatives in the process. (This is why I get worried when someone starts slamming one alternative. It makes me suspect a vested interest in a competing technology. Big business has always operated this way.) This may be a case of a good solution in the wrong hands being as bad as the original problem. Keep your eyes open, and watch where those subsidies go.
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NNadir Donating Member (1000+ posts) Send PM | Profile | Ignore Mon May-01-06 06:18 AM
Response to Reply #31
32. I hear what you're saying, but I think it necessary to divorce technical
issues from political/business issues.

One may legitimately limit how the technology is applied, tax structure, profit distribution, wealth distribution, public lands, etc, through any number of means.

Too often though, technical questions in modern times become inextricably tangled in political/economic/legal considerations that can be changed independent of the technology, especially as the technology evolves and its limits and benefits become clearer. The laws of physics and chemistry do not change however. Whether we "build socialism," or have laissez-faire capitalism, or construct a mixture - a well regulated socially and environmentally sustainable capitalism, DME is still a superior fuel. From an environmental standpoint, compounds having minimal carbon/carbon bonds introduce few particulates into the environment. They are easy to make, and in some cases have physical properties that make them easy and relatively safe to transport and store. It is easy to manage their output of nitrogen oxides and they produce no sulfur oxides. They are simply the best fuels, no matter whether they are made by Exxon or by small farmers in North Dakota operating a few windmills and a bank of Olah fuel cells or by General Atomics.

The best role government can play right now is to streamline the building of an infrastructure and a research base to build these systems. The technology is more or less there. Now we need to do it. Obviously we in the United States are severely disabled by an incompetent and dogmatic government. But we have to start somewhere. We among the Democrats simply need to have a clear goal in our heads, if we are to have any chance whatsoever to save our country.

In the current emergency I think we err in making the perfect the enemy of the good, simply because everything is really, really, really bad.
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JohnWxy Donating Member (1000+ posts) Send PM | Profile | Ignore Mon May-01-06 01:53 PM
Response to Reply #29
34. could you share any links on this??
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eppur_se_muova Donating Member (1000+ posts) Send PM | Profile | Ignore Mon May-01-06 03:15 PM
Response to Reply #34
36. I googled "methanol from coal" and got several interesting hits...
Edited on Mon May-01-06 03:16 PM by eppur_se_muova
mostly fairly politically charged, or at least with an obvious ax to grind. I note one refers to methanol from coal as the "cleanest choice"(!) while another calls it "prohibitively expensive", so lots of folks still arguing.

http://www.google.com/search?hl=en&q=methanol+from+coal&btnG=Google+Search

Here's a link to a study by U. of Florida on production of MeOH for powering fuel cells for transportation. Skimming it quickly, their conclusion was that rising prices of natural gas will make the coal-to-MeOH route the most economical one.x( This is a very detailed report, which considers economic, social, and political factors as well as the technology. Looks like a good long read for later.

http://fuelcellbus.georgetown.edu/files/MethanolFromCoalFinalReport04-2004.pdf

Here's a link to something I didn't know about, a process using a mineral-oil slurry as the reaction medium to convert "synthesis gas" (CO + H2) to methanol. (Involatile solvent, instead of gas-phase process.)

http://www.netl.doe.gov/publications/press/2003/tl_liqphasemethanol_success.html

The chemical reactions to make "synthesis gas" from coal/coke are long established, as is the "water gas shift reaction". I learned about these in school so long ago I don't keep any kind of reference or link...I just know them, like anything learned as a freshman. I wrote out a series of balanced reactions for production of CH3OH from coal or methane a few months ago; can't search for it now without a star (I'm "between engagements":eyes:), but wikipedia gives the equations for production from methane:

http://en.wikipedia.org/wiki/Methanol#Production

The equations for production from coal/coke just require that you start from hot carbon:

C + H2O ---> CO + H2

and from there the equations are similar to those from methane. I'll link the earlier post if I can find it.
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hunter Donating Member (1000+ posts) Send PM | Profile | Ignore Mon May-01-06 02:32 PM
Response to Reply #27
35. To humans yes, ethanol is less toxic, but to aquatic life not so much.
The toxicity of ethanol and methanol are roughly equivalent in aquatic systems. Both are bad. Some organisms are actually more sensitive to ethanol than they are to methanol. Both substances are readily degraded by bacteria and in these situations the Biochemical Oxygen Demand (BOD) is an important aspect of the problem. An oil that does not dissolve readily in water might actually do less damage to an ecosystem than a solvent that does.

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