Cloudy limonene

[holidayyy]

I am working through a small test batch using Q21’s Tek.

I started with 120g powdered MHRB in 120ml vinegar, which sat for three days. I then added calcium hydroxide and water to yield a solution around pH 12 of porridge consistency. This solution sat for four days, with intermittent mixing. Over the next week or so I did three pulls using about 60ml of limonene per pull. Each limonene pull, including the first, was mostly colorless but quite cloudy (this is in contrast to what many posts describe as reddish and clear). Q21 does mention limonene clouding in his tek but that is after salting with vinegar, whereas I’m seeing clouding before the salting step.

I tried freezing the limonene to precipitate out any impurities or water, as suggested by one threads I found on cloudy limonene. This did not resolve the cloudiness.

I’m wondering if anyone has ideas about what could be causing the clouding or why the color might be relatively neutral instead of reddish. Ultimately I’m trying to determine if I should continue to salt with vinegar or if I should start over.

Thanks for the read and help

 

[downwardsfromzero]

Clouding is likely due to lime particulates suspended in the limonene. You can pull from the limonene with vinegar but your crude acetate will most probably be contaminated with calcium acetate; there is a simple test for this - once you've evaporated the crude acetates down to dryness, take a sample of the resulting ~resin and add a little 95+% ethanol or 91+% isopropanol and any calcium acetate will form gelatinous blobs.

If this turns out to be the case, the best thing to do is return the crude acetates to the bark/lime paste (after evaporation of the test alcohol) and repeat the pulls. With any luck you will have removed the problematic particulates with the first pulls. Limonene is a bit finnicky though. And it sounds to me like your lime paste is too runny (depending on how you like your porridge) and this will have contributed to the cloudiness. So if it seems remotely sloppy, before doing the next pulls be sure to stir in some more lime carefully and thoroughly - no lumps! - to get a pastry-dough-like consistency. You can always add a tiny dash of water if it turns out to be unworkably firm.

 

[Phenethylamine23]

I've been experimenting with dlimonene and found similar issue. Research is ongoing.

Process is as follows:

Water extracted 220 grams of dried acacia bark. 3 X 1 L boiling water with teaspoon citric acid each. 15-30 minute each steep. Poured through cotton cloth to filter and collect in 3.5 L glass jug.

Defated with 100ml dlimonene. No problem, lots of emulsion. Seperated and kept bark tea solution.

Made a solution of 2 tablespoon sodium hydroxide in 200 ml water. Slowly added to bark tea while stirring. Solution turned black. Ph tested 12+

Extracted with 2 x 400ml shellite non polar solvent. Kept in warm bath (about 50 degrees C) for 1+ hour each and seperated. Freeze precipitated shellite for 24 hours and yeilded nothing

Decided to try dlimonene. 2 x 200 ml dlimonene pull of basified solution. Siphoned the bark tea into another 3.5 L jar containing 200ml dlimonene, so all of it has to pass through the solvent. Immediately turned milky white. Thought that is good sign.

Collected the 400 ml dlimonene.
Placed in freezer for 2+ hours. Still cloudy.
Warm bath for 2+ hours. Still cloudy.
Washed with 100ml vinigar to salt out any alkaloids. Seperated and evaporated vinegar yielding 180 mg, 60 mg, and 120 mg of redish goo on the third salt out totalling 380 mg.
Each wash with vinigar the dlimonene got less cloudy.

My guess is potentially yielding alkaloids after evaporation but could also be just acetic acid, although it does tastes bitter and smells like dreams.

Anyway the point I'm getting at, and now the interesting part. I wondered why the dlimonene going cloudy, is it from pulling stuff from basified solution?

To be sure I made a 15 ml solution of sodium hydroxide and water and added 15 mls of new dlimonene. It went cloudy and the basic water turned piss colour.

So the sodium hydroxide basic solution alone makes dlimonene cloudy, reacts with the dlimonene and the water turns piss colour.

Thinking perhaps it's the H20. 15ml of water only was mixed with 15ml dlimonene. Both remained clear.

Then 15 ml of cloudy dlimonene pulled from basified tea bark was added to 15 ml water only. The cloudiness didnt transfer to the water, even after 24+ hours.

So as far as my experiments have shown, sodium hydroxide basic solution reacts with dlimonene and causes it to go cloudy. Yet the cloudiness can be pulled out with vinigar but not H20 water.


UPDATE: I wanted to see if dlimonene reacts the same way with other bases. 15 ml of calcium hydroxide solution added to shot glass togther with 15ml of 100% dlimonene.

The limonene immediately went cloudy and the solution turned a tinge of piss colour within about 10 minutes. The dlimonene cleared up after a number of hours with the white sediment settling ontop of the aqueous layer but kicking back up when agitated.

This tells me that most likely all strong bases react with d-limonene causing milky cloudiness. Saponification, emulsion, perhaps a physical phase change but not necessarily chemical one.

The point is cloudiness of D-limonene not to be confused with actually taking up freebased alkaloids, and it could be potential unwanted contamination in final product.

‐--------------------------------------------------

Another question I have is why Shellite goes opaque/cloudy when salting out with vinigar? It was clear ontop of basified layer until after seperation and acid wash.

A test was conducted. 100 ml vinegar added to 200 ml fresh shellite directly into shellite bottle. After 24+ hours still both liquids are clear. No change.

This tells me that something solubilized within the non polar shellite pulled from baseified tea extract is reacting in the presense of vinegar acidic solution causing shellite to go cloudy, and not the presents of the vinegar alone.

Something extracted from the basic tea within the non polar solvent has reacted with the acidic solution forming amphipathic molecules which are neither fully soluble in the polar or non polar solvents. Wonder what it is and how to isolate it further.

 

[Transform]

I've been experimenting with dlimonene and found similar issue. Research is ongoing.

Process is as follows:

Water extracted 220 grams of dried acacia bark. 3 X 1 L boiling water with teaspoon citric acid each. 15-30 minute each steep. Poured through cotton cloth to filter and collect in 3.5 L glass jug.

Defated with 100ml dlimonene. No problem, lots of emulsion. Seperated and kept bark tea solution.

Made a solution of 2 tablespoon sodium hydroxide in 200 ml water. Slowly added to bark tea while stirring. Solution turned black. Ph tested 12+

Extracted with 2 x 400ml shellite non polar solvent. Kept in warm bath (about 50 degrees C) for 1+ hour each and seperated. Freeze precipitated shellite for 24 hours and yeilded nothing

Decided to try dlimonene. 2 x 200 ml dlimonene pull of basified solution. Siphoned the bark tea into another 3.5 L jar containing 200ml dlimonene, so all of it has to pass through the solvent. Immediately turned milky white. Thought that is good sign.

Collected the 400 ml dlimonene.
Placed in freezer for 2+ hours. Still cloudy.
Warm bath for 2+ hours. Still cloudy.
Washed with 100ml vinigar to salt out any alkaloids. Seperated and evaporated vinegar yielding 180 mg, 60 mg, and 120 mg of redish goo on the third salt out totalling 380 mg.
Each wash with vinigar the dlimonene got less cloudy.

My guess is potentially yielding alkaloids after evaporation but could also be just acetic acid, although it does tastes bitter and smells like dreams.

Anyway the point I'm getting at, and now the interesting part. I wondered why the dlimonene going cloudy, is it from pulling stuff from basified solution?

To be sure I made a 15 ml solution of sodium hydroxide and water and added 15 mls of new dlimonene. It went cloudy and the basic water turned piss colour.

So the sodium hydroxide basic solution alone makes dlimonene cloudy, reacts with the dlimonene and the water turns piss colour.

Thinking perhaps it's the H20. 15ml of water only was mixed with 15ml dlimonene. Both remained clear.

Then 15 ml of cloudy dlimonene pulled from basified tea bark was added to 15 ml water only. The cloudiness didnt transfer to the water, even after 24+ hours.

So as far as my experiments have shown, sodium hydroxide basic solution reacts with dlimonene and causes it to go cloudy. Yet the cloudiness can be pulled out with vinigar but not H20 water.


UPDATE: I wanted to see if dlimonene reacts the same way with other bases. 15 ml of calcium hydroxide solution added to shot glass togther with 15ml of 100% dlimonene.

The limonene immediately went cloudy and the solution turned a tinge of piss colour within about 10 minutes. The dlimonene cleared up after a number of hours with the white sediment settling ontop of the aqueous layer but kicking back up when agitated.

This tells me that most likely all strong bases react with d-limonene causing milky cloudiness. Saponification, emulsion, perhaps a physical phase change but not necessarily chemical one.

The point is cloudiness of D-limonene not to be confused with actually taking up freebased alkaloids, and it could be potential unwanted contamination in final product.

‐--------------------------------------------------

Another question I have is why Shellite goes opaque/cloudy when salting out with vinigar? It was clear ontop of basified layer until after seperation and acid wash.

A test was conducted. 100 ml vinegar added to 200 ml fresh shellite directly into shellite bottle. After 24+ hours still both liquids are clear. No change.

This tells me that something solubilized within the non polar shellite pulled from baseified tea extract is reacting in the presense of vinegar acidic solution causing shellite to go cloudy, and not the presents of the vinegar alone.

Something extracted from the basic tea within the non polar solvent has reacted with the acidic solution forming amphipathic molecules which are neither fully soluble in the polar or non polar solvents. Wonder what it is and how to isolate it further.

Yours is a similar but different issue to the OP (although you have tested with lime as well, tbf).

Two questions arise at first:
What colour is your limonene? Not all 'limonene' is pure limonene - some of it is citrus terpenes, and the expressed stuff (as opposed to steam-distilled) has an even wider range of components,

And what kind of water are you using? Hard water (tap or spring) will precipitate calcium hydroxide (along with varying amounts of carbonate) when mixed with sodium hydroxide.

There could well be stuff from the extraction like plant sterols or triterpenoid saponins depending on the plant material used, as well as certain flavonoids of varying orders of condensation, all of which could fulfill the surfactant role that you envisage.

Add to all this that limonene isn't 100% stable - it slowly oxidises in air, forming carvone. Carvone will react with bases to form condensation products. It would seem best to use really fresh, pure limonene.