Sciencemadness Discussion Board - JJay Makes Anhydrous Ethanol

can't get anhydrous EtOH through distillation. dreaded azeotrope

Right, but once it's already anhydrous, it can be kept that way by distilling it in anhydrous conditions (which would involve a device such as a sulfuric acid trap or perhaps a calcium chloride tube).

arkoma - 4-11-2015 at 04:46

can't get anhydrous EtOH through distillation. dreaded azeotrope

what need to distill a pure/anhydrous product?

JJay - 4-11-2015 at 05:00

I need to prepare some products that can only be produced in anhydrous conditions.

JJay - 4-11-2015 at 05:07

I am now collecting the fraction that distills over 78 C. It smells like vodka

It looks like I'll probably get around 100 mL. I started with about 600 mL... that's a pretty lousy yield, but I guess it isn't too bad considering that I started with only about 200 mL of ethanol in solution. Of course, it still requires further purification, so this is going to be some very expensive anhydrous ethanol.

[Edited on 4-11-2015 by JJay]

JJay - 4-11-2015 at 10:36

I ended up getting only about 40 mL of high-boiling fraction.... I can and probably will try to recover more ethanol from the low-boiling fraction before further purifying the high-boiling fraction. Right now I am storing the fractions in 1 qt. mason jars that are clearly labeled as POISON. I think I might want to make more fractions and mix fractions....

[Edited on 4-11-2015 by JJay]

aga - 4-11-2015 at 11:26

turbo yeast + white sugar + ten days= 25% ethanol.

The yeast dies well before 25% - it's poisoned in it's own ethanol excreta.

Around 10%~15% should be used as a workable estimate unless you can directly measure the ethanol with a refractometer, or do a titration.

Using a Vigreux column should get you at or near the 96% azeotrope.

Maybe use a 'Thumper' if you have not got a Vigreux column.
http://www.sciencemadness.org/talk/viewthread.php?tid=61566

JJay - 4-11-2015 at 12:03

Quote: Originally posted by aga

turbo yeast + white sugar + ten days= 25% ethanol.

Interesting idea... but a thumper wouldn't help much for eliminating methanol. Actually, I think using one would be counterproductive.

I have a Vigreux, pictured above. I wonder if maybe I should pack it with glass beads and see if I can get a better division between fractions.

JJay - 4-11-2015 at 12:05

Ethanol can be titrated with what... sodium dichromate..?

Detonationology - 4-11-2015 at 12:12

Ethanol can be titrated with what... sodium dichromate..?

A much better option to figure out the % alcohol is by it's density (i.e. a hydrometer).

[Edited on 11-4-2015 by Detonationology]

JJay - 4-11-2015 at 12:30

Quote: Originally posted by Detonationology

Ethanol can be titrated with what... sodium dichromate..?

A much better option to figure out the % alcohol is by it's density (i.e. a hydrometer).

[Edited on 11-4-2015 by Detonationology]

True... but how to determine methanol concentration....

aga - 4-11-2015 at 13:17

Ethanol can be titrated with what... sodium dichromate..?

Also included in the 'Thumper' thread :-

Attachment: ethanol titration.pdf (166kB)
This file has been downloaded 662 times

Quote: Originally posted by Detonationology

A much better option to figure out the % alcohol is by it's density (i.e. a hydrometer)

I'm sure you're right.

Analytical chemistry techniques are just for idiots.

Metacelsus - 4-11-2015 at 13:25

True... but how to determine methanol concentration....

Gas chromatography is what's usually used, but that's generally out of reach for the amateur. You might be able to buy an enzymatic test kit.

[Edited on 4-11-2015 by Cheddite Cheese]

JJay - 4-11-2015 at 14:53

It is theoretically possible to calculate the concentration of MeOH, EtOH, and H2O after measuring density and doing a titration, but tables with the density of various concentrations would be required.

[Edited on 4-11-2015 by JJay]

aga - 4-11-2015 at 15:02

Strange you got SM and no Google power.

Logically i'd remove the MeOH and EtOH fractions as best i could to eliminate the majority of water.

Then i'd start with separating the MeOH and EtOH from each other.

That's just me.
Us druknen idiots think the Wrong way most of the time.

JJay - 4-11-2015 at 16:20

I'm not seeing a lot of good data available free online on the densities of ternary mixtures of EtOH, H2O, and MeOH....

http://www.slideshare.net/paperpublications3/some-excess-properties-of-ternary-liquid-mixture-of-water-methanol-ethanol-at-several-temperatures doesn't have a lot of data and overstates its claims.

http://www.nist.gov/srd/upload/jpcrd566.pdf omitted any data for the combination MeOH + EtOH + H2O, probably because they are miscible.

I don't know if Lange's handbook or the CRC handbook would have density tables for ternary solvent mixtures.

MolecularWorld - 4-11-2015 at 16:25

On the topic of legality, I am pretty sure that distilling denatured alcohol for purposes of preparing a chemical reagent is completely legal in my jurisdiction.

Lucky. In my "jurisdiction" (the United States), distillation of ethanol FOR ANY PURPOSE without a permit is illegal under federal law. "Under current law and regulations, we cannot allow you to conduct experiments involving distillation of alcohol at your home." For production of ethanol for purposes other than drinking, an Alcohol Fuel Producer permit can be obtained, although I've heard it takes months to process, and the fine print basically states you waive your right to unlawful search of the ethanol production facilities (which could include your home and entire property). State laws can be more restrictive, but not less. In my state, I don't know of any more restrictive laws on ethanol distillation, but I recently found one banning the "unauthorized manufacture" of methanol, benzene, acetone, and more.

JJay - 4-11-2015 at 16:32

Quote: Originally posted by MolecularWorld

On the topic of legality, I am pretty sure that distilling denatured alcohol for purposes of preparing a chemical reagent is completely legal in my jurisdiction.

An educational institution is supposed to obtain a permit, correct, but it is legal to manufacture ethanol for scientific use in most states, regardless of whether you have a permit.

MolecularWorld - 4-11-2015 at 16:49

The part I quoted specifically states "at your home". The Mythbusters also needed a permit to distill. "While individuals of legal drinking age may produce wine or beer at home for personal or family use, Federal law strictly prohibits individuals from producing distilled spirits at home (see 26 United States Code (U.S.C.) 5042(a)(2) and 5053(e))."

I've never seen exceptions for ethanol produced for "scientific use"; please link to where you read "it is legal to manufacture ethanol for scientific use in most states".

[Edited on 5-11-2015 by MolecularWorld]

arkoma - 4-11-2015 at 17:06

Quote: Originally posted by aga

turbo yeast + white sugar + ten days= 25% ethanol.

The yeast dies well before 25% - it's poisoned in it's own ethanol excreta.

http://www.sciencemadness.org/talk/viewthread.php?tid=61566

nope. not "turbo". personally used this product. Probably GMO,

Turbo Yeast

I am a redneck, we moonshine.

[Edited on 11-5-2015 by arkoma]

JJay - 4-11-2015 at 17:15

Well, I'm covered under U.S. Code Title 26.E.51.D § 5273 (c).

If I were making food grade spirits, we'd be talking about something completely different. I found a law that would probably work in the case of food grade alcohol for scientific use, but I would have to do some more research to be really sure.

arkoma - 4-11-2015 at 17:46

Well, I'm covered under U.S. Code Title 26.E.51.D § 5273 (c).

If I were making food grade spirits, we'd be talking about something completely different. I found a law that would probably work in the case of food grade alcohol for scientific use, but I would have to do some more research to be really sure.

It is all about taxes. I would check the BATFE website.

JJay - 4-11-2015 at 19:43

I'm doing another run on the low-boiling fraction, this time with a controlled temperature water bath and magnetic stirring, in hopes of recovering more ethanol. The residue in the distilling flask had two layers and smelled like rubber cement.

zombiedude1 - 4-11-2015 at 20:32

You'll need a Federal Fuel Alcohol permit to distill ethanol legally for non-consumption purposes. Very easy to obtain which allows you to distill a certain amount per year. Looks like you took my advice. Anyway, I think U.S. Code Title 26.E.51.D § 5273 (c) applies to employee's working under a permit (not entirely sure - I'm not a lawyer - but just know, regardless, it's illegal without a permit if the police want to bust you for it; they can).

Under no circumstances should you ever distill or sell alcohol without a permit. (If you wanna be legal)

Arkoma is correct, turbo yeast is a good solution for making ethanol & depending on the strain it will not spill its guts out over 20%; but not so much for consumption (heard it doesn't have good taste if using a pot still).

Honestly, distilling ethanol through glassware and a vigreux column is a waste of time (imo). I have a separate 15.5gal all copper and stainless steel ethanol distillation setup with different columns which I use once in a very rare while to produce what I need quickly and lots of it. (DON'T WORRY -- I store my copper parts in ethanol

)

My first test with my glassware was re-running a previous ethanol distillation mixture of heads and tails to use for cleaning. Took too long, never gonna do that again unless I want small volumes!

What someone else said is correct; you won't be able to distill anhydrous ethanol due to azeotrope. 95% is about as high as you need for anything anyway.

A proof and trall hydrometer is what you'll need to measure ABV; I highly recommend one.

[Edited on 5-11-2015 by zombiedude1]

[Edited on 5-11-2015 by zombiedude1]

JJay - 4-11-2015 at 20:47

The police could bust me for selling it, but seeing how I'm not, I could have a neon sign out front saying that I'm offering free tours of my alcohol still to the public, and the most they could do is give me a lecture before mosying on out the door.

I'm perfectly aware of the azeotrope, but the plan, of course, is to use 3A molecular sieves to remove the remaining water. Distilling through a column definitely works better than distilling without one, and 95% is *not* high enough for several purposes.

Mesa - 5-11-2015 at 00:16

I skimmed this patent a few weeks ago, it might be interesting/relevant to you.
http://www.google.com/patents/US4696720

It's a hell of a lot easier to dry methanol or isopropanol to a significantly anhydrous state compared to drying ethanol past it's azeotrope. This could be a practical solution for ethanol in amateur/home preps.

JJay - 5-11-2015 at 01:51

I'm still not getting very good separation of fractions. I've come up with a procedure for getting good separation, but it's pretty labor intensive....

Basically, I'll want to set up 10 (or so) large test tubes and assign each one a 2 (or so) degree fraction. I'll start by distilling out each fraction. Then I'll take each fraction, from low to high, and distill it, distributing the fractions to their respective test tubes. Once I've redistilled each fraction, I'll start over with the lowest fraction. The procedure will end when I make a pass through each fraction without redistributing any part of any fraction to the other fractions.

Then I'll take the ethanol-water fraction and dry it with molecular sieves.

JJay - 5-11-2015 at 01:53

I skimmed this patent a few weeks ago, it might be interesting/relevant to you.
http://www.google.com/patents/US4696720

It's a hell of a lot easier to dry methanol or isopropanol to a significantly anhydrous state compared to drying ethanol past it's azeotrope. This could be a practical solution for ethanol in amateur/home preps.

Sometimes there are no substitutes for ethanol.

arkoma - 5-11-2015 at 02:24

Quote: Originally posted by zombiedude1

Arkoma is correct, turbo yeast is a good solution for making ethanol & depending on the strain it will not spill its guts out over 20%; but not so much for consumption (heard it doesn't have good taste if using a pot still).

Makes "neutral" spirit like no ones biz though, with no pesky/poisonous denaturants and the overall cost per litre is so low as to approach "free". Turbo will also ferment plain old white sugar. The package has all the stuff the lovely little beasties need, nutrient wise, to belch CO₂ and piss EtOH. The seller in the earlier link is a prompt shipper, too.

MolecularWorld - 5-11-2015 at 07:07

The police could bust me for selling it, but seeing how I'm not, I could have a neon sign out front saying that I'm offering free tours of my alcohol still to the public, and the most they could do is give me a lecture before mosying on out the door.

That would be true if the laws only referred to "distribution" or "consumption". They do not. Most of them refer to "production". It's illegal the second the ethanol vapors start condensing. Do you really think when they find thousand-gallon stills full of mash hidden in the woods, they wait to make sure the guy is selling the products? Even if he's using them for fuel, he would need a permit.

Nor does it matter that your still is smaller, and not making "food grade" products. A lot of what has been produced under the guise of 'moonshine' is not "food grade" (no offense to producers of Artisanal White Whiskey like arkoma). "For example, if a manufacturer produces isobutanol by a fermentation process that also generates ethyl alcohol and the manufacturer separates the materials using distillation, the manufacturer may be required to qualify as a distilled spirits plant under 27 CFR part 19."

Don't get me wrong: do whatever you want, as long as you're not hurting others. Just don't proclaim it's legal without good evidence. I'd advise you read some of the horror stories (search for "bust") on this board before putting up that neon sign; if it looks illegal and sounds illegal, the cops can smash your glass, tear apart your house, and hold you for weeks before they realize they screwed up.

Back to chemistry...
In that photo, is your condenser (and a Keck clip) supporting the full weight of the separatory funnel‽

JJay - 5-11-2015 at 12:06

Quote: Originally posted by MolecularWorld

I'm not trying to be rude about this, but you really need to read the law I cited - what I am doing is completely legal, and if they arrested me/took my equipment/etc. I could sue for damages and win. I'm not putting up a neon sign, but I'm completely on the right side of the law here.

JJay - 5-11-2015 at 12:14

Running another distillation... I'm going to capture 2 degree fractions and then redistill them.

MolecularWorld - 5-11-2015 at 12:23

I'm not trying to be rude either. I read the law you cited, and, taken out of context, it seems like a good loophole. But, having read it in context with the rest of that law, I agree with what zombiedude1 said above:

Quote: Originally posted by zombiedude1

Anyway, I think U.S. Code Title 26.E.51.D § 5273 (c) applies to employee's working under a permit (not entirely sure - I'm not a lawyer - but just know, regardless, it's illegal without a permit if the police want to bust you for it; they can).

Since your still is less than 1 gallon, you paid for your ethanol (sales tax and all), and you're not selling your product, you probably wont have any problems. But probably ≠ definitely. You're in a grey area at best.

JJay - 5-11-2015 at 12:33

I've taken two fractions, one below 62 and one from 62-64. They are both very small fractions. The fraction from 64-66 looks like it is going to be a big one.

[Edited on 5-11-2015 by JJay]

Mesa - 5-11-2015 at 13:32

Sometimes there are no substitutes for ethanol.

If you read the patent I linked, you'll see I wasn't talking about substituting anything. I was pointing out how Methanol/Isopropanol can be used to dry ethanol efficiently.

That's the subject of this thread no?

JJay - 5-11-2015 at 13:36

Quote: Originally posted by MolecularWorld

I'm not trying to be rude either. I read the law you cited, and, taken out of context, it seems like a good loophole. But, having read it in context with the rest of that law, I agree with what zombiedude1 said above:

Quote: Originally posted by zombiedude1

You sound like a cop

TBH, I'm probably going to sell small quantities of some products, but ethanol isn't one of them. I may file some documents in the future, but it's not strictly required, nor should it be.

Oh and yes, the sep funnel is supported by nothing more than a Keck clamp. It's a pretty small funnel; if I had my 1L hooked up, I'd have to support it with something that can bear more weight.

JJay - 5-11-2015 at 13:42

Sometimes there are no substitutes for ethanol.

Methanol and isopropanol can be used to dry ethanol? I'm not aware of any procedure that would use either of those to dry ethanol without other reagents.... (I don't have any ion exchange resins.) Usually, people dry ethanol with benzene.

Mesa - 5-11-2015 at 14:24

You don't have a pet shop or aquarium store nearby?

$20 per kilogram aluminosilicate(zeolite) material sold for aquarium use would be applicable here. There's no requirement for a commercial/synthetic resin.

aga - 5-11-2015 at 14:31

I'm not seeing a lot of good data available free online on the densities of ternary mixtures of EtOH, H2O, and MeOH....

For that data to be Known somebody has to put in the effort, verify the data (more effort) and then publish the data for free on the internet (more effort).

If it is not freely available knowledge, you have the Power to make it so.

Do the Science, make the results freely available.

arkoma - 5-11-2015 at 18:56