This is very intresting... (oils & alcohol in distilling)

[Dumdeedum]

Check this out:

http://journeytoforever.org/biofuel_lib ... arate.html" onclick="window.open(this.href);return false;" rel="nofollow

Look at the "Separating Ethanol From Water Via Differential Miscibility" part, it's the only safe one since it uses oil and the other uses sulfur.

Summary:

Oil and water do not mix. Alcohols and water mix only because of the -OH group that alcohol has. The basic rule here is "like dissolves like," so alcohol is partly "like" water but mostly "like" oils, hence ethanol's solubility in water.
The theory is that when the wash is good and done, adding oil to it will separate the ethanol from the water. This happens (theoretically) because almost all of the ethanol (about 99% of it) will mix with the oil instead of the water because alcohol is, again, mostly like oil.
The new mixture will be less dense than the water, so it will neatly float on top of the water, the water now containing almost no ethanol (less than 1%) and all of the solids.
You can then skim the oil/ethanol off of the water and distill it to get the good stuff. Distilling the oil should lead to an incredibly high ABV ethanol solution, and since oil evaporates much less readily than water, it will be much easier too.

I've been saying theoretically but I have extensive schooling in chemistry and I can wholeheartedly vouch for the process. All the chemistry makes perfect sense.

What do you all think?

I'd like to try it but I don't have a mash ready and I don't have a decent still either... But for anybody who wants to try it, to calculate the amount of oil you should put you match is to the ethanol content in the initial wash.
So a 20 L wash at 14% ABV should need (.14 X 20 L = 2.8L) 2.8 L of oil.
This is a "too be on the safe side" calculation, it's might be a bit too much but it's definitely not too little.
You might invariably get some oil vapor along with the final ethanol, but it's not that much cholesterol and it defiantly wont be more unhealthy than the booze themselves.
Only saturated oils should be used.

Anybody going to try it? I'd kill to see what happens!

[Dumdeedum]

Damn it! This should have been in the theory and practice discussion... Oh well.

[HookLine]

Moved.

[Ayay]

Very interesting thank you and much food for thought.

So it's important to get rid of the water (by skimming off the oil) before distilling the oil/ethanol?

I'm thinking of the cheapest vegetable oil on the market...must be palm oil or the genettically modified canola oil?

[plonker]

Hey Dumdeedum, Im have trouble connecting to that website. Is is still OK for you?

[Dumdeedum]

Yeah I connected to the website fine. Here it is again:
http://journeytoforever.org/biofuel_lib ... arate.html" onclick="window.open(this.href);return false;" rel="nofollow

And an alternative link if that first one is not cooperating (same stuff, sort of summarized):
http://www.techbriefs.com/component/con ... ?task=view" onclick="window.open(this.href);return false;" rel="nofollow

You wouldn't need to skim the oil/ethanol off of the water, if you heat the thing up to the boiling temp of ethanol it should still evaporate from the top oil layer, but I imagine skimming it off will make life easier.

It can be any oil (palm oil or canola oil should be fine). Saturated oil should just better (in theory), but it wouldn't make that much of a difference anyway, or the difference would be negligible. Any oil should do.

[seravitae]

Yes, this works. NASA has a patent on it.
However, not 'any old oil' will work. I did investigations into the creation of a differential miscibility based still, and the only oil that can be used is castor oil. This is due to an unsually placed hydroxyl group on the alkyl chain, leading to more polar properties that can solublise alcohols...

[Dumdeedum]

Oh and thanks for the move Hookline!

This process was originally though up for making ethanol for fuel, but ethanol is ethanol, so it shouldn't matter, right? If it works it works...

Maybe in the near future we will be able to get drunk at gas stations... People taking it right from the ethanol hose, one for the car, one for the driver. That would be a wonderful world!

[Dumdeedum]

Oddly enough I just saw your post Seravitae.

Only castor oil?
Hm... I guess things are different in practice. I would have guessed that the a normal saturated oil (without the -OH group) would be the most effective oil, but looking at it now, I think I can see why Castor oil is the only oil. I thought that an -OH group will be a less efficient addition on the oil since it would mess up with the water, but I guess that wouldn't happen since the Castor oil is substantially Cs and Hs, with only one OH per chain that would increase the alcohol's solubility.

Only castor oil.
Live and learn!

[pumpman]

This is very interesting. Is there a problem with using caster oil?

[schnell]

This is really interesting.

It amounts to a liquid liquid seperation followed by redistillation. It's very clever. I can see the problems with finding other suitable oils. Most oils we have about the house are fatty acids (carboxyls) that can esterify. Hydrocarbons might work, but I don't wanna do a benzene or toluene extraction on my booze.

Castor oil is a triglyceride polyalcohol with enough hydrocarbon character to help seperate a small alcohol from water. It's an excellent choice for this purpose. However, It might go rancid over time. It might be relatively inexpensive in smaller volumes and be commercially accessible.

This is definately interesting.

Seravitae -can you point us to the patent?

[N0N4M3]

Quite interesting, I'm gonna see if I can find more info on this.
I'm not gonna try it, I don't really want booze with laxative effects

[kiwistiller]

I've got some sugar wash that is going to be done soon, I'll give this a lash when it is (and when I find a cheap source of castor oil).

I'd like to try it but I don't have a mash ready and I don't have a decent still either... But for anybody who wants to try it, to calculate the amount of oil you should put you match is to the ethanol content in the initial wash.
So a 20 L wash at 14% ABV should need (.14 X 20 L = 2.8L) 2.8 L of oil.

I'm a bit interested in this... are you assuming that the oil can dissolve an equal quantity of alcohol or are you guessing?
Also, I presume some sort of mixing will be required, and the oil won't work simply sitting on top of the mash?

[seravitae]

Oddly enough I just saw your post Seravitae.

Only castor oil?
Hm... I guess things are different in practice. I would have guessed that the a normal saturated oil (without the -OH group) would be the most effective oil, but looking at it now, I think I can see why Castor oil is the only oil. I thought that an -OH group will be a less efficient addition on the oil since it would mess up with the water, but I guess that wouldn't happen since the Castor oil is substantially Cs and Hs, with only one OH per chain that would increase the alcohol's solubility.

Only castor oil.
Live and learn!

Yeah, it's "odd" at first but you need to consider that polarity is a scale - "oil and water" is merely an extreme opposition of polarity. In fact, a very small proprotion will still mix, of the two.

The issue is that oils are very nonpolar, and water is very polar, so none will mix. However ethanol is quite polar, only a little bit nonpolar (check a table of solvent dielectrics to see what I mean). This means that it's possible that ethanol won't dissove in 'very nonpolar oils' but will dissolve in slightly polar oils. That hydroxyl group enhances the polarity, which is disfavoured in terms of water solubility, but is a critical requirement in terms of ethanol solubility.

Also, castor oil is nontoxic, which is useful. That said with anything, oils still have a vapour pressure, so I'd consider redistilling your product before using it in a food grade scenario. (there may be a very slightly small trace amount of castor oil in your distillate, not enough to worry about, but after a second distillation of your distillate isolated from any castor oil should totally clean the product up).

I dunno where I found the patent before, but I do know nasa has some rights to it because it was released through their techncial brief.
Bear in mind that these processes cant' be 'patented' as a theory, just as an engineering process. There's probably 50 odd people out there holding patents for modified ethanol distillations of a similar manner (for instance, azeotropic entrainers...).

There's lots of cool ways/things you can do with chemistry.

Last I read was vacuum fermentation - yeast hold up to high vacuums with no biological problems, so people have been lowering the pressure in fermentation tanks so low that the ethanol distills off at fermentation temperatures, meaning you can constantly dump in more sugar and the yeast never hits alcohol toxicity due to continuous removal.

[astrangebrew]

This is a very cool concept but the viability of the process comes down to how much of the ethanol will leave the water and mix with the castor oil & how fast the ethanol can transition the across the oil water boundary when heated.
This looks simple enough to run some tests and get some data.
It also looks like it would break down to a modified Rayleigh equation…

Anybody smarter than me think they could crunch some numbers and make some predictions?

[Hawke]

It would need to be well stirred, then left to stratify for it to work.

I think that heating the water under the oil would cause too much convectional mixing for that to work.

Skimming, then vacuum distilling, would give the lowest contamination factor.

[schnell]

the vacuum fermentation trick is also neat. i've done it in the lab in a rotovap with no harm to the yeast on a rum wash that was about half way done. after it was distilled it finished fermenting.

[seravitae]

This is a very cool concept but the viability of the process comes down to how much of the ethanol will leave the water and mix with the castor oil & how fast the ethanol can transition the across the oil water boundary when heated.
This looks simple enough to run some tests and get some data.
It also looks like it would break down to a modified Rayleigh equation…

Anybody smarter than me think they could crunch some numbers and make some predictions?

Having done hundreds of organic extractions in the lab, you'd be suprised how quickly substrates equilibrate solubility over two interfaces. (even with the substrate freely soluble in both).

I can't remember the formula since i did it years ago but there is one based on the partition coefficient, the volume of both layers and something raised to the power of the number of successive extractions that indicates how much % of a material would be left in a particular phase.

However, as a general rule of thumb when doing extractions, the organic phase volume is to match the aqueous phase, and 3 extractions are done, 4 if you are really really desperate or require high yeilds. Though most likely in organic extractions due to the solvent polarity and substrate polarity, the partition coefficient is strongly skewed in your favour. However we can simplify things a bit if we take some assumptions in to place.

Assuming the partition coefficient for ethanol in water and caster oil is 0.5, meaning that half ends up in each (which is what's likely to occur with solvents freely miscible in both phases). Essentially each phase for an equal volume of oil to ethanol/water solution would extract 50% of the ethanol each time.

Thus 100mL of 50% ethanol washed with 3 equal volume parts of castor oil would leave (0.5^3)*100 = 12.5% of ethanol remaining in the aqueous phase. In reality its a bit better because each wash removes some ethanol, reducing the total volume (the oil is now in excess) meaning more ethanol is distributed in the oil with each successive wash.

Gentle stiring would be plenty to continuously equilibrate the phases.

Pumping off the oil with a food grade pump and distilling it seperately is one way to remove the ethanol, but there is another way:

Build your fermentor out of something that can be used to distill, and make a condensor/chiller coil halfway up. connect it inline to your condensor. Have a heating element in the oil layer (which floats on top) and use the chiller coil below the element to ensure the aqueous phase with yeast in it is kept at ferment temps. The top of the solution can be made to boil the ethanol off (~80-90C) whereas the lower aqueous phase can be held at fermenting temperatures. It's all in the one pot.

[seravitae]

the vacuum fermentation trick is also neat. i've done it in the lab in a rotovap with no harm to the yeast on a rum wash that was about half way done. after it was distilled it finished fermenting.

Yeah its quite nifty. Also using vapour recompression in tandem is awesome. By using the vacuum to remove the ethanol (in gaseous state), you can compress it straight away, making it really hot, which feeds the fermenter or boiler with heat. Kinda like a heat pump, only with ethanol as the working fluid.

[piratesteve]

has anyone followed through with any of these experiments???

[LOGGONON]

I done some testing on this about a month ago and yes it works to a point.
I think seravitae is about correct on the numbes. My testing was pritty rough and ready though it teach me a thing or two about it. 1 the castor oil was a pain to get my grubby hands on i ended up getting it from a Model aero/car fuel supplier it was about $30AUD a L or that could have been for the two L(if anyone is intrested ill dig up the link or you can Pm me about the leftovers i have, AS im done with this method).
2. I started with about 500ml 70% and dumped in 1L of castor heated and seperated and it took up bugger all sprits 100ML max (so now have a jar that i could be bother redistilling)
I Then went back to the drawing board to see what was going on and it proved to be a process that if done straight from the 10% wash it would be easer to pull out near 100% of the sprits though i could not see the point in this if i need to heat the wash/castor((-seperate-distill)-or(distill)) i may as well just run a normal still withough the castor-oil.
3 castor/water at room temp has a strange interaction (this levels out silghty beter with heat) though unlike say vegi-oil/water where the seperation level is prity much a straight line, the castor/water has a very wavy seperation level even with like a little vortex looking funnels into the two layers.

well thats my 2cents on the topic.

hopefully someone here try's it and comes out the other side with a better view of it than myself.

[Centimeter]

Thus is the usual complication with extractions- emulsions. You had the right idea heating it. Another thing you could try would be to add salt. You may want to look up "emulsion breaking" on google too for some other ideas.

Also, your extraction doesn't seem all that bad. 100ml of virtually pure ethanol out of a total of 350ml of ethanol is nothing to scoff at. Also, usually in extractions you want to split your solvent into three treatments. You'll get better extraction by using three 333ml washes rather than one 1L wash. Of course the emulsion formation makes this significantly less practical. Let us know if you do any more fiddling!

[cemik1]

I made some tests. Mixture was 40ml 90% alcohol and water to volume 240ml (~16ABV). Next it was mixed with 40ml of oil. After 24h in temerature 40deg C.

From left castor, from right rapeseed oil. I can not see any alcohol extraction. The volume of upper layer is ~40ml.

[Centimeter]

Thanks for posting this. I wouldn't be so quick to discount this. I think you guys are expecting more than is reasonable. Here are some things to keep in mind. First, when you mix two liquids together, they can form a mixture with a volume greater/less than the sum of the component volumes. This is a function of intermolecular interactions destabilizing/stabilizing the mixture. It's very possible that the oil has dissolved a small amount of ethanol, even though no significant volume change has been observed. Second, your initial alcohol concentration was quite low. If the oil does not dramatically stabilize the ethanol by dissolving it, one would expect the ethanol to simply diffuse into the oil to increase its entropy. That being the case, the ethanol would try to achieve a mostly uniform concentration between the two solvents. Since your initial concentration was only 16%, you wouldn't end up with much ethanol being dissolved. Third, extractions often necessitate using large volumes of solvent. You can't just throw in 40ml of oil on top of ~300ml of ethanol solution and expect a complete extraction. There would have to be a tremendous difference in the solubility of ethanol between the two solvents for that to effect a good extraction. The fact is, water and ethanol are miscible, and it is unlikely that ethanol would prefer the oil over the water to a significant degree. That being the case, you would need to use a pretty large volume of oil to get a good extraction. Although a large volume of oil would be needed, it could be reused easily enough.

Something you might want to try. Add a bunch of salt to the mixtures. Try to saturate the water with it. The salt molecules will coordinate the water to form hydration shells, pulling it away from the ethanol. This should force more ethanol into the oil layer.

Personally, I would guess that this method is not very economical or effective. A water ethanol solution is just too dang stable already. There's simply not enough free energy to make an extraction all that thermodynamically advantageous. Were it effective, I would guess that it would be being used to make bundles of money.

[azeo]

By accounts, corn grits (or even some kinds of kitty litter!) are an economical method to remove the last bit of water, and can be re-used by drying with hot C02 or nitrogen. I've seen pics (or read description) of column arrangements used in tandem with a reflux column. I'd like to find out whether when the grits eventually lose their effectiveness, they could then be used for feedstock or if the starch has been so modified or dissiapated it's no longer suitable for conversion. Also interested in how much alcohol is actually left in the grits, if it's worthwhile recovering as part of the drying process, and if vacuum drying can be used.

Castor oil seems to be one of the few oils that will mix with "wet" Etoh without a surfactant - although there's definitely a limit to the amount of water it takes before it mixes like an emulsion. I've been using it recently as an upper cyl/valve lubricant and corrosion stabiliser for fuel for an old m'bike that was about 92-93%, the best thing was the smell, nothing like the smell of burnt castor oil out the exhaust! At least it's non toxic, but ahem, it's medicinal use is to assist the elimination process so over exposure could give one the proverbials! The technical explanations for it's miscibility are fascinating but I need to go and study up on chemistry to try and understand how it's working!

The problem with drying out ethanol is that unless it's in a sealed container, or vented with a dessicant. it'll suck in every bit of atmospheric moisture it can until it's back to 96% or thereabouts, so unless the dryness is required for a certain purpose (say purity, chemical extractions perhaps, fuel cells maybe, or mixing reliably with gas to make E85 that doesn't separate at low temperatures), it can be alot of effort for something that may not be practically required. Fun tho'...

May well be playing with vacuum distillation/fermentation/heat pumps this year - will post anything interesting if and when it happens

[LOGGONON]

I dont believe that this method will ever see a use in production,
Ive found that at a lower starting wash say 10% for 1L of wash you will need to play with about 10L oil and run this 3 times too pull the majorty out.
Say at a 1L +50% wash you will need more oil and still need to run it through a few times (and get past the seperation via centerfusal force or equivlent)
that being said the amount of energy required including heating, pumping, spinning, distillling repeat the production effenctiny would not come close to that of more conventional distilling methods.

though saying that
Im also guessing that there may be a way. A setup much like a pot still could be setup with a 25% wash 75% oil and continiously replace a small percentage of the wash. keeping the water from boiling the ethanol should run up into the oil layer where it would boil off. The still should not require any reflux making the system run more efficent.

cheers

[frosty]

Yes, I came across that link and decided to try it out myself.

Here is some information on castor oil that is useful...

Castor oil is a vegetable oil obtained from the castor bean (technically castor seed as the castor plant, Ricinus communis, is not a member of the bean family).

Castor oil has an unusual composition and chemistry, which makes it quite valuable. Ninety percent of fatty acids in castor oil are ricinoleic acid. Ricinoleic acid, a monounsaturated, 18-carbon fatty acid, has a hydroxyl functional group at the twelfth carbon, a very uncommon property for a biological fatty acid. This functional group causes ricinoleic acid (and castor oil) to be unusually polar, and also allows chemical derivatization that is not practical with other biological oils. Since it is a polar dielectric with a relatively high dielectric constant (4.7), highly refined and dried Castor oil is sometimes used as a dielectric fluid within high performance high voltage capacitors. Castor oil also contains 3-4% of both oleic and linoleic acids.

Castor oil maintains its fluidity at both extremely high and low temperatures. Sebacic acid is chemically derived from castor oil. Castor oil and its derivatives have applications in the manufacturing of soaps, lubricants, hydraulic and brake fluids, paints, dyes, coatings, inks, cold resistant plastics, waxes and polishes, nylon, pharmaceuticals and perfumes. In internal combustion engines, castor oil is renowned for its ability to lubricate under extreme conditions and temperatures, such as in air-cooled engines. The lubricants company Castrol takes its name from castor oil. However, castor oil tends to form gums in a short time, and its use is therefore restricted to engines that are regularly rebuilt, such as motorcycle race engines.

Castor oil is vegetable-based oil because it's made from Castor plant seeds; thus, it naturally biodegrades quickly and comes from a renewable energy resource (plants). Many plants and seeds in the natural world have toxins because it's universal that living matter can have defense mechanisms or protection (i.e. toxins) against predators, insects, etc. Likewise, the Castor seed contains the toxin ricin. Ricin is a protein (a solid); whereas, Castor oil is a fatty acid or oil (a liquid), and cold pressing Castor seeds separates the two. The toxin (solid) stays with the seed because it's not oil (liquid); thus, cold pressed and filtered Castor oil is non-toxic.

And here is an abstract that seems to indicate that at 95% ethanol to 5% water a phase exists where castor oil, water, and ethanol are buddies..

Abstract
A phase diagram was drawn of the ternary System, Castor Oil, 95% alcohol, and water. The various ratios at which solutions of these three components can be prepared were determined from the diagram. This study was undertaken to illustrate the practical use of the phase rule in pharmacy in the preparation of solutions of two immiscible liquids, utilizing a third liquid which is miscible with both.

I did not purchase the report.

Castor oil specific gravity or relative density to water at 25C is 0.95614

The first concern for me was smell. I had heard castor oil is smelly. Turns out that the stuff at the supermarket has no odor or taste. So far so good..

Mixing equal volumes of ethanol and water results in only 1.92 volumes of mixture. Close enough to 2 for my experiment, but I couldn't find anything about ethanol and castor oil on the internet so that is where I started.



I used the quarter cup spoon and added equal parts castor oil and everclear together. Then I measured them back out and no significant change or surprise here, one half cup of mixture. They were cloudy at first but became clear when stirred with a fork. The castor oil by itself is about as viscous as cheap pancake syrup. Not as bad as honey though.

I added one half cup of water and the castor oil/ethanol mix floated on top. There is a strong everclear smell coming off. So I will let it sit and evaporate. I marked the boundary and the top for reference.



The water did not increase in volume (by absorbing ethanol from the castor oil) so this is good. That means the ethanol has a strong tendency to move into the castor oil and leave the water. I will verify this by mixing the everclear with the water first next time and then adding the oil. There should be an increase in the oil layer and a decrease in the water level as the ethanol migrates from the water to the oil.

For now I hope to find that the oil level drops by half as the everclear evaporates and that the water level drop is insignificant (I suspect 2.5% as that corresponds to the amount of water that should be in solution with the oil and ethanol according to the abstract).

Will report back tomorrow..

[frosty]

Maybe the water should be replaced with prune juice and the drink called a "flat-liner" to be served at retirement homes...

Anyhow the temperature in my apartment is 52 deg F (the heater is down and I'm wearing 3 coats). So I decided to set the glass in a bowl of warmed water from the microwave..
But the concoction has separated a third top layer of ethanol. Not a 50/50 divide though so I'm thinking that ethanol is only miscible in castor oil up to a certain percentage and that the excess has come out of solution on top (specific gravity of ethanol is 0.79)

Also ethanol vapor is heavier than air so having this in such a tall glass with no ventilation is going to make for a slow evaporation. I will let it sit overnight but will stop by the store tomorrow for another shorter glass before trying the next experiment.
Nothing looks discouraging so far however.

[frosty]

I stopped by Rite Aid and picked up a cheap graduated glass made in China. When filled with 5 tablespoons of eth/water it came up to the 4 Tblspoon mark. Not very accurate. But at least there are marks to reference by.
I used 2 1/2 Tablspoons each water, ethanol and castor oil. I mixed the ethanol and water, stirred and let it sit for 10 minutes. Then I added the oil.
Before adding the oil the water/ethanol was at the 60ml mark. After adding the oil everything was at the 90 ml mark.

1st observation: The oil now sinks to the bottom since the mix of eth/water is now lighter than the oil.

The oil is rounded up like a loaf of bread in a round pan and hits the 30ml mark.

For a 20% mash. 0.8*1.0 + 0.2*0.79 = 0.958 about the same as castor oil !

This still leaves the possibility of a light mash, maybe even a continual mash where the concentration of alcohol never gets high enough to kill the yeast.
(Or the oil can be pre-charged with ethanol to lighten it and make it less viscous)

Coming up to 2 hrs and it looks like the oil has increased from the 30 ml to the 40 ml mark so about a 30% increase in volume. Some tiny balls of oil are floating about in the water neither rising nor sinking.
The bulk of the oil may be adhered to the glass. It is sticky. 5 ml has been lost to evaporation from the water/eth mixture so far.

I'm wondering if coconut oil might be better for this. It is lighter (0.92), does not go rancid, and has a pleasant flavor.
The water can be made more dense (1.2 or so with corn starch).

I am heating a bowl of water in the microwave to set the glass in.
I am not discouraged by the need to heat things up. Increasing the temperature of a liquid is still a far cry less than the energy requirements to evaporate it.
1 cal/gm per degree C to heat, 539 cal/gm to evaporate. (water w/o ethanol that is)

2hrs and 15 minutes and now reaching 45 ml. Evaporation has reduced another 5 ml overall.

another 10 minutes and...

maybe this is how the lava lamp was discovered..

This test went as expected. Looks like the idea will work.

[frosty]

Stopped at Home Depot and bought my 1st worm... (A line is about to be crossed)
I'm an artist - so it'll be a sculpture...

What I am hoping again is that the ethanol can be vaporized w/o vaporizing the water (except the 5%).
I will 1st distill some water to get used to this. Then see how well vaporization of water can be blocked with a layer of castor oil on top.
Then I will try a 15% water/ethanol mix with the oil pre-charged with ethanol (a jump start and to lighten it to be sure it floats well)
Last I will repeat w/o the oil to verify there was a significant difference in energy requirements and to see a difference in the purity of the end product.
I will add a photo of the rig once I have cleaned it up and assembled it..