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Elemental Phosphorus
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Extraction of ethanol from gasoline
Many people, me included, have trouble sourcing ethanol as a solvent. As you know, at least here in the US, ethanol is blended into gasoline as a
money handout to big agribusiness. Therefore I would like to extract ethanol from gasoline, ideally from E85 gas. Yesterday, I ran an experiment using
10% ethanol gasoline. 3ml of water was added to 60ml of gas. The mixture was added to a separatory funnel and aqueous layer collected. The gasoline
was dried over CaCl2 to render it usable. The water/ethanol layer was dried over anhydrous NaCl. Some of the cloudiness cleared, but the mixture
remained somewhat cloudy. I think this is due to either the NaCl not being completely anhydrous. It seems unlikely that slightly water-soluble
hydrocarbons from the gasoline would cause cloudiness, although these will definitely be present as an impurity. Over the weekend I will try to find
time to distill this. Any input on cloudiness or a way to separate somewhat water-soluble hydrocarbons?
Also, I do not know whether or not a cosolvent is present, as that would make things much harder. I will also experiment with E85 when I can find it.
(They don't sell it at the closest station to me)
Thanks for the input.
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Dr.Bob
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By cosolvent, do you mean one of the hundred plus chemicals in "pure" gasoline? The have all sorts of stuff in there. Also, CaCl forms complexes
with ethanol, it is not a good drying agent for it.
If you want to bother trying this, start with E85, it is already 85% ethanol, and widely available. Then you will have to distill a few times, plus
some other stuff to get anything approaching useful ethanol.
If you search, there are at least 3 or 4 older threads that have beat this subject to death, the simplest way is to just ferment your own, and distill
it, even that will have traces of methanol and esters to remove by double distillation or a really good distillation system (with a good fractionating
column).
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Texium
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Thread Moved
24-2-2017 at 14:05 |
Elemental Phosphorus
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The ethanol/ water fraction was not dried with CaCl2. Also, by cosolvent I meant a non-hydrocarbon chemical used to facilitate the mixing of the
ethanol and gasoline. I chose not to go down the fermentation route because I have heard the legality of that brought into question. I will buy E85
and use that. However, the purpose of my previous post was basically: are there any useful hydrocarbon-selective reactions that can be used to remove
various water soluble hydrocarbons like toluenes, etc. (I say toluene because it could be particularly difficult to separate as it forms azeotropes
with both ethanol, water, and a three-component azeotrope of all three). Maybe reaction with NaOH over MgSO4 then boil off hydrocarbon and hyrolyse
the ethoxide, and distill off ethanol?
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j_sum1
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My understanding is that gasoline mixtures are pretty much intractable. Isolating any one component is almost impossible.
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Corrosive Joeseph
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I find this very interesting, but like j_sum says, I would think
or at least, VERY difficult......... But as always, I could be wrong. I do try not to be doh................
Pump gasoline/petrol is quite a soup of chemical compounds. This is the standard for my local brew.
http://transportpolicy.net/index.php?title=EU:_Fuels:_Diesel...
I would imagine a few of those hydrocarbons have some miniscule, slight solubility in water and who knows how many azeotropes are present and that's
even before the water is added.
Alkanes, alkenes, alcohols, ethers, aromatics................ And some..........
I would still love to see this work though, and a quick google search is seems to suggest it might be possible.
I have an ongoing project happening at the moment pursuing non-polar solvents from my local 95RON involving a series of distillations. I did wonder
about phase separation to get rid of the alcohols but didn't give it any more thought again until I seen this thread..................
Just for visuals............. 'Phase Separations in Ethanol-Gasoline'
https://www.youtube.com/watch?v=Wrb4pl03xCg
Don't forget your gas/petrol alreadyprobably has some fuel stabilizer(s) added to it already..........
Snippets -
http://www.lcbamarketing.com/phase_separation_in_ethanol_ble...
http://www.accessnorton.com/make-your-own-ethanol-free-gasol...
Some attachments -
Attachment: Ethanol-Water Phase Separation White Paper.pdf (230kB)
This file has been downloaded 1167 times
Attachment: Phase Separation.pdf (148kB)
This file has been downloaded 434 times
Attachment: Water Phase Separation in Oxygenated Gasoline.pdf (15kB)
This file has been downloaded 927 times
Please post some links/research/experiments. I would love to know how this goes and maybe someone knows more................
I'm guessing a few fractionations are going to be necessary to get anywhere near a pure enough product if it is possible.......... I ferment all my
own ethanol and I would NEVER dream of ingesting anything that ever had gasoline/petrol in it. I don't drink alcohol myself but I guess I had to
mention that. ..............
Hope this helps
/CJ
[Edited on 25-2-2017 by Corrosive Joeseph]
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Elemental Phosphorus
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Yes, as it turns out both water and ethanol form large numbers of azeotropes with hydrocarbons. Isolating any one hydrocarbon component would prove
near impossible, but I am hoping to take advantage of the reaction of ethanol with NaOH to boil off hydrocarbons and then hydrolyse the ethoxide.
Would magnesium sulfate be a suitable drying agent to drive the equilibrium toward ethoxide? Of course I would never drink ethanol purified from
gasoline but it may make a suitable lab solvent.
The page you linked for fuel compositions is somewhat worrying to me because it shows that other alcohols are present. Therefore these would form
alkoxides as well and I will have a lot of fractioning to do to separate methanol. Here is a PDF of azeotrope data:
http://biopent.uv.es/~roberto/Docencia2013/LQFI/P6/06_35_86....
[Edited on 25-2-2017 by Elemental Phosphorus]
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Texium
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I think you'd be better off just buying (or, if you're underage, getting someone to buy) some Everclear. It's just food grade azeotropic ethanol so
it's probably the purest stuff you can get OTC and is not that expensive. Saves a lot of headaches and labor for sure.
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Elemental Phosphorus
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Well, yes but for a larger scale application this is the cheapest way. I happen to have free supply of waste vegetable oil and for making biodiesel
this is the cheapest alcohol I can find. I will however, try to get some everclear. Also, I like how OTC a method using gasoline is if I can't find
everclear.
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Elemental Phosphorus
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Photos of it burning
Here is a photo of it burning. The liquid burns with the characteristic blue of ethanol, not the orange of gasoline, but it smells different than
either ethanol or gasoline. I didn't have a watchglass so this is a pipe endcap.
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JJay
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If you're making biodiesel, be really careful with mineral acids and bases on polyester carpet - one drop will produce shockingly enormous blobs of
goo and destroy the carpet.
It would be best to keep them away from carpet entirely.
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Elemental Phosphorus
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Yeah I usually do all my experiments outside but today it was pouring rain. Looking at it, burning something in a metal vessel on a plastic carpet
wasn't the smartest idea but I put it out right after the photo.
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Corrosive Joeseph
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Looks like you are SOL with the phase separation then.............
Failing that I guess multiple fractionations on E85 will probably yield a half decent solvent but it will always have traces of the other compounds in
it.................. Not good if your solute reacts with any of them................
I still believe turbo yeast, sugar and dedicated copper still is the only way to go for OTC ethanol..............
You will have solvent on tap and it frees up glassware for other more interesting things
/CJ
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Elemental Phosphorus
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Here in the US I have heard distilling and fermenting your own alcohol requires an ATF license. What do you mean by SOL? I am not familiar with
certain shorthand. Also, I forgot to mention that light hydrocarbons like methane, ethane, propane and butane burn blue, but do pentanes burn blue? If
so, the burning test does not confirm that those are not present.
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Aquakidney
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You can ferment anything you want, but distilling ethanol requires a permit. There are two kinds, one for beverages and one for industrial/fuel use.
Getting either one is a colossal pain in the neck and requires much paperwork, site inspections from BATF agents, posting expensive bonds, etc.
Nevertheless, if you're discreet and don't try to sell it, nobody will notice or care.
The amount of methanol formed during fermentation will be almost nothing. Just discard the first few mL of distillate to be sure.
If federal crimes make you skittish, another option is to buy a few 1.75L jugs of cheap vodka and redistill it through a good fractionating column.
That should get you close to 95% and the rest of the water can be removed by the procedures in Vogel's Handbook.
Oh, and SOL means "Shit Outta Luck".
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Archenemy_6
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I purchased a 750ml bottle of 95% everclear a couple weeks ago it was right around $20 I think. I've only used it with my soxhlet extractor so far.
The cheap vodka might be a good route if you can find it cheaper than the everclear and don't mind spending some time distilling it.
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Elemental Phosphorus
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So distilling your fermented product is not okay, but say filtering and then drying over anyhydrous MgSO4 is fine? The drying agent could then be
regenerated to produce a cheap, relatively pure product maybe?
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Texium
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Look, the bottom line is that law enforcement is not going to care whether you actually distilled your ethanol or dehydrated it using a ludicrous
amount of MgSO4, so if you're just squeamish about breaking the law, you'd be best off buying denatured alcohol or legal, taxed drinking alcohol.
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Elemental Phosphorus
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That is why I'll get back to the original thing. I will be able to conduct the extraction from gasoline soon. The price of E10 gas is about $2.30 per
gallon where I live. Despite the available sources, I cannot see the harm in a gas extraction. For a solvent, purity is relatively important, but for
biodiesel it should be fine and also leave me with gasoline for burner fuel. This altogether would leave me with a price of about ~$7 for a liter of
ethanol, as well as lots of leftover fuel which would be suitable for use in vehicles as well if dried appropriately to remove dissolved water. I may
just ferment and distill, but the original purpose of the thread was to talk about extraction from gasoline. So, if the crude ethanol was added to
NaOH with a drying agent to drive the equilibrium toward ethoxide, would it yield ethoxide so lower boiling components could be separated? The comment
about filtering a ferment and drying was stupid, but I also meant to say that there being a rule on distilling only being strange and an odd way for
the government to regulate, that is if they really care.
[Edited on 28-2-2017 by Elemental Phosphorus]
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JJay
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Alcohol laws in the U.S. tend to be somewhat arbitrary. It is perfectly legal to produce a high-proof beverage without a distiller's license using
non-distillation techniques such as this one: https://www.youtube.com/watch?v=gAqKvM7JHkw Yet distilling a sugar wash to produce a solvent for lab use is illegal.
Law enforcement is not going to care about the morality of your technique for concentrating ethanol; they only care about whether it is legal and if
there is money involved. You can give your uncle enough wine to cause intoxication right before he gets into a car accident, killing a family of four,
and be totally in the clear, legally speaking. With alcohol, they are only concerned with enforcing the letter of the law.
There are some circumstances under which you can distill denatured ethanol without a license, but if they can show that you intend to prepare a
beverage with denatured ethanol, you may have some problems.
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Praxichys
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Yes, unfortunately distilling ethanol at all in the USA is illegal.
https://www.ttb.gov/spirits/home-distilling.shtml
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Within title 26 of the United States Code, section 5601 sets out criminal penalties for activities including the following. Offenses under this
section are felonies that are punishable by up to 5 years in prison, a fine of up to $10,000, or both, for each offense.
5601(a)(1) – Possession of an unregistered still.
5601(a)(2) – Engaging in business as a distiller without filing an application and receiving notice of registration.
5601(a)(6) – Distilling on a prohibited premises. (Under 26 U.S.C. 5178(a)(1)(B), a distilled spirits plant may not be located in a residence or in
sheds, yards, or enclosures connected to a residence.)
5601(a)(7) – Unlawful production or use of material fit for production of distilled spirits.
5601(a)(8) – Unlawful production of distilled spirits.
5601(a)(11) – Purchase, receipt, and/or processing of distilled spirits when the person who does so knows or has reasonable grounds to believe that
Federal excise tax has not been paid on the spirits.
5601(a)(12) – Removal or concealment of distilled spirits on which tax has not been paid.
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This includes re-distilling legally distilled spirits or fuel alcohol.
On top of this, many states also have laws against this. In Michigan where I live, anything under 8 liters is a civil infraction (like a traffic
ticket), 8 to 80 liters is a 93-day misdemeanor, and over 80 liters is a 4-year felony. I imagine this would add onto the federal charges described
above.
That said, I doubt law enforcement has the resources to be concerned with small private distillers. These laws have been on the books since
prohibition and were designed to quench the huge incentive to make homebrew at the time. As long as the state isn't missing out on tax money and
you're not endangering the public (i.e. you're not selling/distributing it/distilling in an apartment building) I doubt anyone will really care. Just
don't go showing off your apparatus and methods to your friends and neighbors. All it takes is one cop with big ears looking for a promotion to
initiate an investigation.
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JJay
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Having researched this thoroughly, I can tell you that this is not the case.
https://www.law.cornell.edu/uscode/text/26/5273 specifically gives permission for distilling denatured alcohol. It is worth noting that a large
body of additional regulations apply to "specially denatured" alcohol, which is discussed here: https://www.ttb.gov/industrial/sda.shtml
E85 belongs to the class of "completely denatured" ethanol mixtures, so it's generally legal to distill it without a permit as long as you aren't
boiling off the denaturants into the atmosphere or trying to prepare a beverage. Note that if you're selling it, there are additional regulations, and
you should of course keep a lab notebook and keep the ethanol from falling into the hands of people who might drink it and so forth. It is pretty easy
to obtain a permit for distilling fuel alcohol if you want to make it yourself from natural sources, though.
[Edited on 28-2-2017 by JJay]
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Praxichys
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Yes, but denatured alcohol is not ethanol. It is a mixture, and as you mention, it is perfectly legal to distill. (Unless you're in Texas!  )
Distilling E85 or gasoline to obtain substantially pure ethanol (which is what the OP hopes to do) can be legally construed as "removing the
denaturants" and is therefore illegal.
It may be straightforward to get a fuel alcohol permit, but you need to own specially zoned land to actually do it legally. Your fuel still will be
inspected prior to its operation by a BATFE agent. Your premises will also be subject to random inspection and recordkeeping audits, as well as
special taxation. It is not at all practical for the home chemist.
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JJay
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I haven't researched home fuel alcohol production thoroughly, but I do know that it is less regulated than spirit production. Most chemists want it to
use ethanol as a reagent.
If you're distilling some denatured alcohol to remove water, that's generally legal. But doing it to prepare a nontoxic product is generally illegal.
I haven't reviewed the OP's plans thoroughly... it's clearly legal, in an appropriate location, to remove some of the non-ethanol components from E85
by distillation as long as the resulting product is still toxic or if it's distilled directly into a toxic mixture or consumed in a chemical reaction,
etc. These components certainly have some value as fuel, so I assume you'd still want to keep them around. I should add that there is probably no good
reason not to obtain a permit for your planned use, even though it might not be 100% legally necessary, depending on your recordkeeping and storage
practices and so forth.
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MrHomeScientist
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From the discussion it sounds like distilling ethanol from gasoline is legal (being a mixture), but then if you take that same ethanol and redistill
it for better purity it's now illegal?
Weird.
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Lefaucheux10
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For better separation of ethanol from the gazolin why not use aqueous calcium chloride and then distill ethanol from the aqueous calcium chloride
ethanol mixture ?
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