Lots of foam during defat, what did I do wrong?

[Nexchem]

I tried my first tek recently and it seems that it was mostly a failure. I'll spare you the details since my primary goal here is to figure out where I went wrong, so I think it's reasonable for me to only talk about when things first started going wrong which was near the beginning on the tek.

I mostly relied on Vovin's tek for guidance but (perhaps stupidly) put my own spin on it.

Here's what I did and I'll stop at the first red flag:

1. I started with chipped root bark. I powdered it in a coffee grinder.

2. I put the powder in a mason jar and filled the rest of the jar up with vinegar. I pressure cooked the jar for an hour.

3. I strained out the liquid with buchner funnel/filter paper. It went through pretty easily with only one piece of filter paper.

4. I added the solids back to the mason jar and added more vinegar and pressure cooked again for an hour.

5. I tried to repeat the filtering but it was much harder this time. Much sludgier, had to use many filter papers and ended up with less liquid in the end.

6. Ran the whole liquid (vinegar from both cooks) through filter paper a couple more times.

7. Let it sit overnight in the fridge. Lots of sludge was settled at the bottom the next day. I poured off the vinegar mixture and tossed the sludge at the bottom.

8. I started trying to do a defat. I realize this is probably unnecessary for good MHRB but I wanted to try it anyway. I added the vinegar mixture (probably around 300mL at this point) to a (1L) seperatory funnel along with 100mL of naphtha. I turned it around and around and swirled it, careful not to shake it violently.

9. The layers seemed to separate quite quickly. But the naphtha layer didn't look like naphtha, it was all bubbles! A very thick foam. I set the foam layer aside and repeated the defat again 3 more times with 100mL fresh naphtha each time. Each time I ended up with most of this very thick foam.

10. I now had a beaker full of this very thick naphtha foam. I still have it a day later and the foam is still there, thick as ever. Each subsequent defat resulted in just as much of this thick foam.


I continued with the rest of the extraction anyway, but I don't think it went so well. Basification (to 12.5 pH with NaOH) turned it from purple to gray to black. The sodium carbonate wash I tried to do was a mess because the water wasn't fully separating from the naphtha, it left little droplets and also made the naphtha cloudy (which somehow cleared up later. And I don't think it was due to oversaturation of DMT). And the final naphtha pulls had a messy foam to them as well which made it hard to separate out the naphtha. This foam did somewhat settle though, allowing me to eventually get mostly clean naphtha out (though the foam never fully went away). Freeze precipitation was mostly useless, I got maybe 6mg fluffy white crystals out, but I'm not even sure they're DMT. They sorta disappear if I rub them with my fingers and are very fluffy, not hard crystals. That may be normal though. Regardless, I'm in the process of trying to evap the remaining naphtha and see what comes out, if anything, my hopes aren't high though.


Sorry for the long post, but if you got this far thanks for reading. I'm really curious why my tek went so poorly and why my defats were endlessly pulling out this foamy substance. Was pressure cooking MHRB powder and vinegar a bad idea? Is my MHRB just really bad quality? Already at the defat stage I knew I did something very wrong.

 

[Nexchem]

Update: Tried cyb's salt tek on 50g more bark. Followed it pretty much exactly, measurements and all. First/second pull had pretty much everything, the other pulls didn't precipitate much. And got 400-500mg of yellow crystals. Not a great yield, but at least it's not nothing. Still would like to do a re-x, we'll see how much mass I lose.

 

[padawan]

I hate defats on the initial acid soup. Emulsions every time... such a drama. For MHRB just skip it altogether, and re-x the combined yields to remove the majority of fats/oils/gunk that makes it that far.

If you must do a defat, then I suggest doing an A/B and instead of pouring your solvent pulls into a freeze precipitation or evap tray, pour them straight into a jar or beaker of acidified solution (eg. one part vinegar to two parts water) and shake, shake, shake. The goodies move from freebase form in the non-polar solvent back into salt (acetate) form in the acidified solution, while the oils and fats that came across in your initial pulls stay trapped in the solvent. The two layers separate cleanly and instantly and it's super easy to remove the solvent with a pipette or separatory funnel. Do that for each pull and you end up with low volume acid solution full of goodies and almost no oils. Then basify with your lye/calcium hydroxide or whatever you use and resume the solvent pulls straight into your evap or freeze precipitation tray.

 

[Nexchem]

Hmm, so padawan, are you saying that taking the defat solvent pulls and mixing them with acidified solution will break the emulsion? And that you think the defat pulls have tapped some DMT in freebase form, even though it should already have been in acetate form from the initial acidification?

I still wonder why so much foam was forming during my final pulls from the basified solution. I didn't add a ton of lye, only enough to raise pH to 12.5 (as measured with a probe). I know that less lye = more emulsion. But still, I didn't shake it like crazy or anything. And the sodium carbonate washes were also such a mess... I can't understand why.

Btw, after re-x of my second attempt I'm left with <250mg of crystals. They look very nice, but <0.5% yield is pretty bad. Although it's certainly better than nothing

 

[Simply_Me]

Hmm, so padawan, are you saying that taking the defat solvent pulls and mixing them with acidified solution will break the emulsion? And that you think the defat pulls have tapped some DMT in freebase form, even though it should already have been in acetate form from the initial acidification?

Nexchem,

That is not what Padawan is saying.

If you must do a defat, then I suggest doing an A/B and instead of pouring your solvent pulls into a freeze precipitation or evap tray, pour them straight into a jar or beaker of acidified solution (eg. one part vinegar to two parts water) and shake, shake, shake.

Go through the entire A/B with no defat step and when you pull your DMT and other stuff mix solvent with acidified water instead of trying to crystallize or evap. Brilliant. I will do this myself next time. BTW, I don't sweat yellow crystals nor should you...

I still wonder why so much foam was forming during my final pulls from the basified solution. I didn't add a ton of lye, only enough to raise pH to 12.5 (as measured with a probe). I know that less lye = more emulsion. But still, I didn't shake it like crazy or anything. And the sodium carbonate washes were also such a mess... I can't understand why.

Btw, after re-x of my second attempt I'm left with <250mg of crystals. They look very nice, but <0.5% yield is pretty bad. Although it's certainly better than nothing

Try 1 part MHRB to 1 part Lye. Don't be afraid, it's not coming with you.

 

[blue.magic]

I am using a pressure cooker for the first cooking - 10 psi for 20 minutes seems to suffice, but 15 psi for 30 minutes to be safe.

Instead of de-fatting, I would do mini A/B. It makes more sense as instead of working on complex mother liquor, you extract all nonpolar compounds and then further purify that.

But like others, I resort to re-x (with n-heptane). The resulting product can be even powdered, so there is very little lipid content.

Last time I had extremely oily pulls and the product was gunky, yet after re-x it was just fine.

 

[Nexchem]

Hmm, so padawan, are you saying that taking the defat solvent pulls and mixing them with acidified solution will break the emulsion? And that you think the defat pulls have tapped some DMT in freebase form, even though it should already have been in acetate form from the initial acidification?

Nexchem,

That is not what Padawan is saying.

If you must do a defat, then I suggest doing an A/B and instead of pouring your solvent pulls into a freeze precipitation or evap tray, pour them straight into a jar or beaker of acidified solution (eg. one part vinegar to two parts water) and shake, shake, shake.

Go through the entire A/B with no defat step and when you pull your DMT and other stuff mix solvent with acidified water instead of trying to crystallize or evap. Brilliant. I will do this myself next time. BTW, I don't sweat yellow crystals nor should you...

Thank you for clarifying, I think I understand better now: we are essentially doing two A/Bs. After we take our pulls from the first A/B, we essentially do a second A/B on those pulls instead of bark. That actually makes a lot of sense.

I still wonder why so much foam was forming during my final pulls from the basified solution. I didn't add a ton of lye, only enough to raise pH to 12.5 (as measured with a probe). I know that less lye = more emulsion. But still, I didn't shake it like crazy or anything. And the sodium carbonate washes were also such a mess... I can't understand why.

Btw, after re-x of my second attempt I'm left with <250mg of crystals. They look very nice, but <0.5% yield is pretty bad. Although it's certainly better than nothing

Try 1 part MHRB to 1 part Lye. Don't be afraid, it's not coming with you.

I'm not afraid, really. But using less lye is nice from a waste standpoint. Also I'm a bit of an idealist and since most resources indicate that 12.5pH is all you need I'd love to stick to that theory.

 

[padawan]

Thank you for clarifying, I think I understand better now: we are essentially doing two A/Bs. After we take our pulls from the first A/B, we essentially do a second A/B on those pulls instead of bark. That actually makes a lot of sense.

Exactly. It's also what Blue Magic meant by mini A/B. When you try it you'll see just how easily the fats and oils can be removed. Use a glass pipette or separators funnel to remove the solvent. Just takes more time and patience. You can visibly see how over successive mini pulls there are less and less fats/oils collecting in the solvent - demonstrates how you're pulling all the alks plus fats/oils out of the original A/B. Initially the solvent goes cloudy yellow, but several pulls later is more a cloudy white.

Incidentally, this "double" or "mini" A/B defatting process is very well suited to Acacia extractions, if anyone is having trouble with the different and more voluminous fats/oils in Acacias.

 

[blue.magic]

Here are some details from my correspondence with pete666. Might be helpful if you plan to re-extract:

Well, because we titrate, we know how much dmt fb was salted. The salted water is reduced. NaOH is added. I don't measure anything, just add enough. More NaOH won't hurt anything.
So when we have super cloudy basified water + dmt fb, we can add heptane - about 20ml/g of dmt fb. Then we heat it up to about 60C and mix thorougly. Heptane gets colored. I do it in erlenmeyer flask. Once mixed, I use 50ml pipette to remove heptane and pour it into beaker. The pipette is heated by clean hot heptane beforehand, so dmt won't precipitate in it. The beaker with heptane is left to cool down to room temp slowly, then put into fridge, then into freezer. The yellow precipitate first, dmt later. After removed from freezer and dried 12h with airflow I use knife to scrape just the white crystals, not the yellow. It is easy, as yellow has different structure. Yellow stays in the beaker for next heptane pull.
I repeat the same process with less heptane (next pull). The same beaker with yellow residue is used, so all the yellow from all pulls stays in one beaker. After freeze-precip you know how much the solution was saturated. The crystals in the beaker tell you tell you whether to do next pull.
The yellow residue can be re-x'ed as much as desired. I usually leave half of the yield in the white and half in the yellow. The yellow is broken up by knife and dried with air-flow over few days, with ocassional crushing. The result is dry yellow powder.

The color of (properly basified, rather more than less) basic water with dmt fb tells you when to stop too. You simply don't see any dmt in it