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Author: Subject: Hypothetically drinkable ethanol from methylated spirits
AJKOER
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[*] posted on 10-6-2017 at 16:31


I read that methanol is much more vigorous in reacting with a Mg alloy (or Mg with a catalyst including chlorides of Hg, Cd, Pd, Co, Ni,..., which could than form a galvanic couple, see G.H. Lee, et al, "Magnesium in Methanol (Mg/MeOH) in Organic Syntheses", published in Current Organic Chemistry, 2004, 8, 1263-1287 1263, full text available at https://www.google.com/url?sa=t&source=web&rct=j&... , which is an SM talk file ) than ethanol.

You may be able to use this to quickly visually (as distinct from smell based methods) estimate CH3OH content by running comparative tests with a pure methanol and a pure ethanol sample for your particular magnesium alloy source.

The reaction between Mg and methanol is said, after a possible inception period, to proceed in an exothermic manner that may require cooling. One of the products of the reaction is Mg(CH3O)2.

Example of some possible reaction paths with a galvanic couple producing a current:
2 CH3OH + 2 e- = 2 CH3O- + H2

Or, a path leading to HCHO:
H2O + e- = .H + OH-
CH3OH + .H = .CH2OH + H2
.CH2OH + Fe(lll)/Co(lll) = HCHO + H+ + Fe(ll)/Co(ll)

Reference: See equations (1), (3) and (4) in the open article, "Dehydrogenation of anhydrous methanol at room temperature by o-aminophenol-based photocatalysts", by Masanori Wakizaka, et al, in Nature Communications 7, Article number: 12333, (2016), doi:10.1038/ncomms12333:fc "Dehydrogenation of anhydrous methanol at room temperature by o-aminophenol-based photocatalysts", by Masanori Wakizaka, et al, in Nature Communications 7, Article number: 12333, (2016), doi:10.1038/ncomms12333, Link: http://www.nature.com/articles/ncomms12333

Another reference, in the possible use of magnesium metal, cites Mg turnings, pretreated with HCl and employed at 50 C, in select organic synthesis (please see commentary at: http://pubs.acs.org/doi/abs/10.1021/jo00210a035 . Article: "Magnesium in methanol: substitute for sodium amalgam in desulfonylation reactions", by Alan C. Brown and Louis A. Carpino, in The Journal of Organic Chemistry, Vol. 50: Issue. 10: pages. 1749-1750, 1985).

[Edited on 11-6-2017 by AJKOER]

[Edited on 11-6-2017 by AJKOER]
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draculic acid69
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[*] posted on 23-4-2019 at 18:39


I was about to start a post about this exact thing and as I googled the page I was looking for this post popped up.https://forums.whirlpool.net.au/archive/2235624 is the best discussion on this topic so far.i would try a sodium bisulfite addition to trap ketones and aldehydes.or a boil with hydroxides to break any esters and polymerize ketones and aldehydes. I'd also recommend a cryogenic crystallization to freeze out any unwanted substances.in the above link the guy describes an olive oil purification that sounds like a really clever trick.
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Boffis
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[*] posted on 10-5-2019 at 10:18


We use a clear "bio-ethanol" in table warmers. It has a distinct small of MEK so today I tried a little experiment and add a few ml of 50% sodium hydrogen sulphite solution to it. The alcohol became cloudy but that could be jst the low solubility of Na H sulphite in 95% alcohol. The label on the can does not state what the denaturants are but distillation alone did not remove the smell of MEK. Interestingly the bisulphite solution did! I filtered off the white precipitate, the quantity was tiny and is drying at present but when mixed with a little dilute acid it regenerates the ketone smell plus sulphur dioxide.

The filtered alcohol was treated with calcium hydroxide to precipitate the excess SO2 as calcium sulphite. Tomorrow I'll filter and distill it.
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Pumukli
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[*] posted on 12-5-2019 at 11:25


Great! Please keep us updated on how well/unwell the process really went! I've been working with MEK denatured ethanol recently and reached a point where this denaturant really caused problems. (No, it was not about strengthening apple cider.)
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zed
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[*] posted on 14-5-2019 at 18:22


Hnuh?

Converting methylated spirits to drinking likker?

Gosh! Sounds like a great idea.

Keep us posted!

But, buy yerself a braille-keyboard, or a voice activated computer system, and practice with it for a while, before you embark on the ultimate drinkin' experiment.

That way, if things go squinky, you can still share your results with us.
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Pumukli
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[*] posted on 15-5-2019 at 01:51


In these parts of the globe "methylated spirits" is a misnomer, the actual product doesn't contain methanol. It is pure ethanol but made undrinkable by addition of methyl-ethyl-ketone and/or denatonium benzoate, sometimes a dye also added.

So if one could get rid of the denaturant ketone the resulting ethanol would -in theory- become drinkable.

Getting rid of the ketone is the tricky part of course, because it forms an azeotrope with the ethanol and can't be separated easily.
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draculic acid69
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[*] posted on 15-5-2019 at 07:20


Here in Australia the metho as it's known contains no methanol either. I think it's denatonium benzoate mek, ethyl acetate and some other stuff suspected to be cyclohexyl something or other. I think the purple stuff has a different composition to it as it smells different.but I think they can definitely be made drinkable.
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zed
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[*] posted on 16-5-2019 at 15:30


Ah! Well, here in the USA, "Methylated" means "Methylated".

Often 20% Methanol, or higher. I recently considered purchasing some Methylated Spirits for lab use. Had so much Methanol and other weird shit in it, that I decided it just wouldn't work out. The Methanol to Ethanol ratio, was very unfavorable.

This stuff will blind you and kill you. Might have enough Methanol present, to kill you, three times over.

Moreover, the ATF (Alcohol, Tobacco, and Firearms) is wildly enthusiastic about imprisoning folks who produce distilled ethanol products, without paying the beverage tax.
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[*] posted on 16-5-2019 at 21:45


Zed The reason i started this thread was not to make a cheap source for ethanol for drinking purposes, the thread title might be a tad misleading (i had assumed people would understand the hypothetical part).

Im pretty sure we all have access to methylated spirits OTC for cheap and so i just wanted to find a way to make this stuff pure enough to use for any chemical reaction no matter how scrupulous the required conditions.
I know a few people have tried using methylated spirits ethanol in certain preps and found it to fail whereas ethanol prepared from fermentation tends to work fine.
The issue is that we cannot all do our own ferment and sugar isn't cheap.

I think i have come to the conclusion that in reality if i needed ethanol for a very sensitive reaction i would happily just make it via fermentation or dig into the drinking stock, then just use the methylated spirits for making ether and the likes.

But the topic still carries merit atleast for curiosity sake, I mean come on surely you haven't atleast considered how pure you could make that stuff?




Sufficiently advanced science is indistinguishable from madness.
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Pumukli
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[*] posted on 17-5-2019 at 03:38


Back to the topic: once I tried dissolving NaOH (a few percent) into the stuff and then added a few grams of kitchen Al foil pieces. The content of the flask was stirred with a magnetic stirrer. Reaction was fairly vigorous. The addition of the foil took 1-2 hours, expect heavy bubbling, frothing, anything.

With the help of Al foil one could remove all water and maybe reduce the MEK to sec-butanol. Sec-butanol boils around 100 C, hence the conversion -theoretically- would give you 20-22 C difference in the boiling points. With a fractionating column it may be possible to get pure (absolute!) ethanol from the "sludge".

The smell of the stuff after this treatment changed appreciably, maybe the reduction was successful, I don't know. I just distilled (without column) the contents of the flask. I don't have a decent column so I did not bothered.

I think MEK can ruin the smell/taste of ethanol even at 0.02% concentration, so this method even with 99% conversion (I doubt that rate) would yield an undrinkable spirit. But that spirit would be much better suited for chemical reactions and would be absolute (in the sense of free from water) ethanol!

Anyway it is just something one can ponder about. ;)
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AJKOER
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[*] posted on 18-6-2019 at 07:12


Perhaps a different approach in the case of other organic additives that CH3OH, add Mg to create the magnesium ethoxide and hydrogen. Isolate the solid salt free from moisture (assuming no other magnesium salts are formed).

When in need of the ethanol for an application, add water (which can react violently liberating pure ethanol and Mg(OH)2).

Note: This is immediate prep for the ethoxide and not ethanol via distillation (which may be an important legal distinction).

Obvious economic issue is the cost of the magnesium source metal.
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[*] posted on 18-6-2019 at 07:27


I read somewhere that ethanol and higher alcohols are hard to convince to react with magnesium. Only methanol reacts with it relatively readily.
I've seen it myself: I could make Mg-methoxide but only after a few drops of ethylene-bromide were added to the Mg - methanol mixture to activate my magnesium. My denatured ethanol did not react with the same Mg.
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AJKOER
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[*] posted on 18-6-2019 at 07:54


Surface area of the Mg makes a difference, and surface preparation by either pre-washing it with dilute HCl, conc NH4Cl(aq), dibromoethane, stirring with added glass shards to expose fresh metal, or crushing magnesium turnings, ..., are among many other recommendations presented by researchers available at:
https://www.researchgate.net/post/Does_anyone_know_the_best_...

Magnesium metal reactions with many inorganic and some organics compounds has been reported in some old publications for a specified surface area of magnesium (see https://books.google.com/books?id=jvjmAAAAMAAJ&pg=RA1-PA... ).

The source also notes that a magnesium amalgam (created by heating Mg and Hg together) is more reactive.

[Edited on 18-6-2019 by AJKOER]
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[*] posted on 18-6-2019 at 08:40


Quote: Originally posted by Pumukli  
I read somewhere that ethanol and higher alcohols are hard to convince to react with magnesium. Only methanol reacts with it relatively readily.
I've seen it myself: I could make Mg-methoxide but only after a few drops of ethylene-bromide were added to the Mg - methanol mixture to activate my magnesium. My denatured ethanol did not react with the same Mg.


Have you tried this with your denatured ethanol, Mg and ethylene-bromide?
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