Sciencemadness Discussion Board

Nicotine Extraction and purification

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procrastinator - 3-5-2009 at 13:36

I've been playing with Cheapskate's acid / base extraction method. I've gotten decent yields (~1.1g alkaloid / 100g rolling tobacco) with a few modifications. Here are my notes, for anyone who wants to play with this stuff.

First we have the addition of the NaOH to the tobacco. Simply mixing up 50mL of solution and pouring it into the tobacco won't give you much nicotine—I tried this and ended up with 0.3g alkaloid / 100g tobacco. I'm not even sure if there was any nicotine in there because I accidentally decomposed it before I could “test” it.

You have to wet all of the plant matter in order to get any appreciable amount of nicotine out and pouring in 50mL isn't going to soak much. The way to do this is to work it in manually. First put your tobacco in a zip-lock bag. Next, dissolve 20g of NaOH into 120-130mL of aqueous solution. Pour this into the bag and seal it. Wearing gloves, knead until all of the tobacco is soaked. If you add the right amount of liquid, the tobacco will absorb every last drop. The voluminous mass of shredded tobacco will be reduced to a more manageable moist clump.

The next modification I made was introducing a de-waxing step. After you finish squeezing all of the kerosene from the plant matter, you'll end up with 500-600mL of orange solution. Add 100mL of saturated NaCl solution to this, shake, and let it settle. Pour off the organic top layer and discard the lower water layer and the emulsion between the two phases. Trust me, this step will make subsequent extractions much less painful.

Don't worry too much about the nicotine left behind in the water. Nicotine has a 15:1 oil / water partition coefficient, so even without the salt <2% of it will dissolve in the water. That's ~20mg per run from my experience, not worth the effort. Note that if you really want to minimize losses, you can re-use the water for a few subsequent extractions. Just don't do it too many times or the waxes will build up to where they won't settle with the water after shaking and leave you with a cloudy kerosene layer after the phases separate.

I don't think it's necessary, but I transferred the nicotine between the salt form in water and freebase in kerosene a few times. This was mainly to get the volume down to something I felt comfortable working with. I started with 500-600mL of crude kerosene extract, transferred the nicotine to 50mL of acidic water, freebased it again with NaOH, dissolved it in 40mL kerosene, then finally extracted that with 10mL of acidic water. Each time I got more of the waxes and particulate matter out. In the end, I ended up with a crystal clear solution without a single filtration because all of the particulate matter got trapped in emulsions.

I didn't have any naphta available, so I just evaporated those 10mL down to 5mL under a fan. I think that all of the kerosene evaporated with the water. Someone please correct me if I'm wrong here.



Now, about the purity. This acid / base extraction looks like it would leave you with a mixture of all of the alkaloids in the tobacco. How do you get the impurities out? Specifically, I'm worried about the carcinogenic nitrosamines formed during the tobacco's curing process. Does anyone know of any way to destroy or remove these without destroying the nicotine? I really don't feel like getting mouth cancer...

Here's the general structure of nitrosamines:

procrastinator - 22-8-2009 at 07:22

I've been extracting nicotine by cheapskate's method for a while, but I'm getting tired of wringing kerosene out of smelly plant matter. Isn't there another source of nicotine available?

As it turns out, there is: e-liquid. This is the liquid that so called “electronic cigarettes” vaporize to create a nicotine-laden mist.

The typical composition is 0.8 – 2.4% nicotine in either propylene glycol or glycerol with a trace of fragrance and / or flavoring. The question is, how do we get the nicotine out of this stuff?

I've tried a few methods, but none have succeeded. Here's a brief overview:

Two phase extraction: Nicotine has an octanol / water partition coefficient of ~15:1. I thought that simply shaking the e-liquid with kerosene would make the nicotine come over into the oil layer, but this simply isn't the case. Virtually no nicotine comes over this way. Saturating the alcohol with NaOH (an attempt at salting the nicotine out) has no significant effect. It seems that the partition coefficient here is very high and in the wrong direction.

Forming a salt: Much to my dismay, nicotine salts are soluble in alcohols and whatever alcohol I was dealing with (not sure if it was glycerol or PG) was no exception. Adding an acid to the e-liquid changed the color a bit, but nothing else. I also tried shaking the e-liquid with acidified brine and hoping it would form a separate layer, but it just mixed with the alcohol.

Purification through the zinc chloride double salt: I added zinc sulfate, sulfuric acid, and NaCl to the liquid in hopes of precipitating the double salt, but nothing came out. The yellow color stayed dissolved. Popping it in the freezer didn't help. Maybe I'll try cooling it down with some dry ice next.

Steam distillation: Tried distilling 50/50 e-liquid / water, didn't get anything noteworthy. Got the same result fractionating the mixture. (Nicotine forms an azeotrope with water: 2.5% nicotine 97.5% water.)

Diffusion through a latex membrane: My latest attempt was putting sodium bisulfate in a small latex balloon with a very thin wall and plopping that in the e-liquid. I was hoping that the nicotine would diffuse through the latex (it is soluble in damn near everything) and get trapped as a salt inside the balloon. No dice. Heating to increase the reaction rate makes the latex dissolve. This is a variation on the apple trick a few pages back.


Other methods I've considered:

Vacuum distillation: This one might work, but I don't have the equipment for it. I'm working on it, though.

Liquid-Solid Chromatography: Might work, but there's just too much raw material to process to get any significant amount of product.

Liquid-Liquid Chromatography: Worth a try, but dubious due to the absurd partition coefficient.

Electrophoresis: Protonate the nicotine in the e-liquid and use an electric field to move it through a semipermeable membrane into plain water. I have two questions though: 1) Is there a readily available membrane that would be suitable for this application? 2) what happens to the counter-ions? Do I end up with two electrically charged liquids?


I'm running out of ideas here. The nicotine is just too strongly bound to the alcohol for anything to suck it out. Does anyone have any other ideas on how to do this separation?

[Edited on 22-8-2009 by procrastinator]

[Edited on 22-8-2009 by procrastinator]

not_important - 22-8-2009 at 08:23

Perhaps passing through a column of acidic ion exchange resin, sulfonated polystyrene for example, would work as the salt would be a polymer. Flush the column with NaOH in alcohol, evaporate, extract the solids with something less polar to leave the NaOH behind.

procrastinator - 22-8-2009 at 13:57

That sounds like it's worth a try. Now to find a source of such a resin. I'll probably take apart a water softener and charge the resin with sulfuric acid.

I don't get one thing, though: wouldn't the equilibrium for this type of reaction lie far to the side of the reactants due to the nicotine ion's low charge density? I guess the column would take care of that, countercurrent-exchange style.

I froze the zinc complex in dry ice and still saw no signs of precipitation. So much for that route.

edit: Now I understand how the resin extraction would work. The protons are immobilized in the resin, so the nicotine ions that are formed when the solution flows through the column are also immobilized. Wouldn't freebasing the nicotine afterwards make it dissolve in the resin, though? It might be better to flush the column out with another ion or an acid then extract the nicotine from the elutent.

I've considered the resin idea before but never thought to react an acidic resin with a freebased nicotine solution. Thanks for the idea.

I'd still like some input on the electrophoresis idea. The resin thing sounds promising, but then again every promising idea I've come across so far has yielded nothing in the end.

[Edited on 23-8-2009 by procrastinator]

procrastinator - 31-8-2009 at 19:07

I'm experimenting with an acidic cation exchange resin at the moment. The reaction between the nicotine and the resin is very slow, but it does happen. It takes 10-15 minutes of shaking for a 50% solution of e-liquid to come to pH 7. This method definitely shows promise. It's the first one I've tried that frees the nicotine from the clutches of the glycerin / glycol.

Now for the million dollar question: how do we get the nicotine back out? I've tried NaCl and NaOH but neither suck out any appreciable amount. I'll try MgSO4 and NaHSO4 next, but I'm not keeping my fingers crossed. Any other ideas?

dann2 - 8-9-2009 at 03:43

Hello,

Checked the thread and could not find the attached file.
It's a recommended download IMHO.

ALKALOIDS OF TOBACCO
KIRBY E. JACKSON
Department of Chemistry, Vanderbilt University, Nashville, Tennessee
Received November 86, 1940

Nicotine extraction etc etc etc
74 pages
File too big to attach (3.8Mb)
Link to file http://www.thevespiary.org/hex/Nicotine.pdf

Have a good bedtime read



Dann2

[Edited on 8-9-2009 by dann2]

read.jpg - 18kB

not_important - 8-9-2009 at 20:29

Quote: Originally posted by procrastinator  
...
Now for the million dollar question: how do we get the nicotine back out? I've tried NaCl and NaOH but neither suck out any appreciable amount. I'll try MgSO4 and NaHSO4 next, but I'm not keeping my fingers crossed. Any other ideas?


Assuming that you have a sulphonated resin, you are working with the salt of a strong acid - about as strong as H2SO4 or HCl. Neutral or even mildly acid salts aren't going to do much.

You could try an alcohol solution of NaOH, extracting the free base into the alcohol, or a large excess of 10% to 20% hydrochloric acid, extracting the salt into the water.

When using resins, doing so in column is often more effective than just dumping them into the solution in bulk, d the same goes when flushing something from the resin. Allow the hydochloric acid to slowly flow through a column containing the resin, a few drops per minute.

Grow Goddess - 8-10-2011 at 11:46

Thanks for all of your efforts and information.
I found this site because I plan to try to make my own nicotine oil to aid in quitting smoking. I have some experience at making highly concentrated hemp oil (legally of course). In the process of making concentrated hemp oil, I use nothing less than 99% isopropyl alcohol. I soak the cannabis in the alcohol for a couple of hours, shaking and stirring and such. Instead of filtering it with a regular paper coffee filter, I use one of those gold reusable coffee filters. Then I take the liquid and put it into a rice cooker until I believe I have evaporated out about 90 - 95% of the alcohol. Then I simply pour it into a metal cup and let it sit on a coffee cup warmer until the material stops bubbling, that is when I know all of the alcohol has evaporated out. The material looks like thick black tar. Then I suck it up into a syringe before it completely cools. At that point it is ready for use. The difference with the oil compared to regular cannabis is huge. One drop of the hemp oil can medicate a patient for an entire day. Where as smoking cannabis in its normal state, it is only effective for a couple of hours at best. There is evidence that hemp oil has great medicinal values, one is in curing certain types of cancer. The best way to vaporize the hemp oil is with a hand held Eclipse Vapor pipe. I am hoping to achieve something similar with nicotine. I will try to post back my results within 6 months.

hissingnoise - 8-10-2011 at 12:13

Quote:
I have some experience at making highly concentrated hemp oil (legally of course).

Hmmm, I know of no jurisdiction where making hash-oil is legal!
Except, possibly, some lawless regions in Afghanistan . . .

S.C. Wack - 8-10-2011 at 14:44

BTW a couple years ago I grew rustica and extracted nicotine following nothing but general sensible ideas. The nicotine is easily lost even in plant form so when your garage runs about 110F it is noticeable. Other than that, what can I say, extraction with dilute H2SO4, addition of NaOH, steam distillation into dilute HCl. I still have some picrate. Hydrodistillation does take a lot of water but is easily followed with a pH meter.

Rustica is not a large plant but does require good soil for high nicotine, and the flowers smell exactly like dog shit. It blooms all damn summer unless you pick the flower spike off, which is a must. They are not unpleasant when you hold them up to your nose, but as the concentration goes down it smells stronger and more like dog shit, and from 20 feet away from a few plants it smells like your whole yard is covered in dog shit. I wanted seeds for mass planting. Never again at home.

Synthesis of Nicotine Salts, RJ Reynolds internal document:

Attachment: 514901221-1237.pdf (735kB)
This file has been downloaded 2634 times

GreenD - 8-10-2011 at 17:32

Sorry if this has been said - I've been wanting to do a nicotine extraction for sheets and gaggles, but I have 2 cents from other plant extractions:

1. Has anyone tried wetting the plant material and continually freezing/thawing - this breaks the cell walls and inner structure of the plant and allows for easier access to the nicotine. It won't matter too much with such a "supple" plant, but may prove worth doing.

2. You are all having trouble with waxes - why not just do an acidification, wash with naptha or hexanes - should get rid of alot of fats and waxes. then start from beginning?

1.1g/100 grams is about is pretty freekin good though - considering wikipedia says 1.6% is the amount in most plant material today.

edwould - 11-2-2012 at 23:22

Google Patent Search produced 1920 results for 'nicotine extraction' consisting of pending applications and awarded patents to such notables as Phillip Morris. Most appear to be methods, techniques, and processes.
I bet PM has a good one.
http://www.google.com/search?q=nicotine+extraction&btnG=...

niertap - 1-8-2012 at 15:19

A simple, yet likely important observation I've made.

Whenever I'm smoking at night and have to grab something from my car, I set the lit cig on the roof. When I pick it up again, it always has a little pool of liquid around/in front of the end.

Literature generally says that smoking usually burns most of the nicotine. I postulate that the lower temperature from the smoldering end is much less destructive than the forced airflow upon inhaling. Also, the nicotine appears to condense quite easily on a slightly cold car.

Lastly, the nicotine is intercalated into the polymeric cellulose. Solvents will not dissolve the cellulose or loosen its grip. However, destroying the cellulose will very easily release the the nicotine.


Very slowly and carefully burning it, then passing the smoke/vapor over a condenser seems like the best solution. A slightly reduced oxygen atmosphere or reduced pressure would likely increase yield.


Adas - 3-8-2012 at 00:22

Quote: Originally posted by niertap  
A simple, yet likely important observation I've made.

Whenever I'm smoking at night and have to grab something from my car, I set the lit cig on the roof. When I pick it up again, it always has a little pool of liquid around/in front of the end.

Literature generally says that smoking usually burns most of the nicotine. I postulate that the lower temperature from the smoldering end is much less destructive than the forced airflow upon inhaling. Also, the nicotine appears to condense quite easily on a slightly cold car.

Lastly, the nicotine is intercalated into the polymeric cellulose. Solvents will not dissolve the cellulose or loosen its grip. However, destroying the cellulose will very easily release the the nicotine.


Very slowly and carefully burning it, then passing the smoke/vapor over a condenser seems like the best solution. A slightly reduced oxygen atmosphere or reduced pressure would likely increase yield.




The liquid you observed is probably 99% tar. Nicotine content is negligible. But nicotine evaporation is a nice idea of extraction, and even better would be to condense it on citric acid to avoid it escaping.

Yo-Yo - 22-9-2012 at 23:13

Tobacco preparations such as pipe or rolling tobacco contain a fair amount (5-20%) of glycerol and/or propylene glycol. Aside from the other problems of nicotine extractions, it will cause a lot of troubles as no phase will be "pure". Staring with raw-tobacco will at least make extractions easier

Random - 17-11-2012 at 14:05

those nicotine vapours sound like a fun...
























...way to die

Isnt one or few drops of pure nicotine going to kill you?

[Edited on 17-11-2012 by Random]

quinoxaline man - 17-11-2012 at 18:04

"Does anyone know of any way to destroy or remove these without destroying the nicotine? I really don't feel like getting mouth cancer..."


Try Vitamin C.

Henry
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