Manipulating super critical co2 solvent density to target specific compounds in cannabis

Greetings hash wizards and warlocks,

In my never-ending quest to better understand the nuances of CO2 extraction, I wanted to direct some of my long-lasting questions to the CO2 extraction gurus within this forum to start a dialogue about methods and theories.

I have ~8 years of CO2 extraction experience with the legal industry space, but this experience has been mostly focused on the extraction of premium CO2 terpenes and highly potent oil in a production based setting, rather than any kind of R&D.

I am interested in doing some R&D to try to extract THCa from undecarbed plant material, but i dont know where to start. My question lies in the nature of manipulating solvent density to target specific compounds within the plant, namely THCa. I understand that changing solvent density is the single most important factor in determining what type of compounds are extracted, but my understanding of this concept is entirely practical and lacks the deeper theoretical understanding of this phenomena.

Can someone point me towards some academic articles that dive into the physics behind what is occurring when solvent density is manipulated? Why is it that terpenes and other volatile compounds are selectively extracted at a solvent density of ~0.2 - 0.35 g/m^3, while decarbed cannabinoids are extracted at higher SD, say ~ 0.6- 0.9 g/m^3. I get that it is a gradient and the compounds most soluble in the solvent will extract first, and less soluble compounds take more time, but I do not understand what is happening on a molecular level.

How is the polarity of the solvent changed as its solvent density is adjusted? Why are more polar compounds pulled at higher solvent densities, especially in supercritical settings? How is it that CO2, a non-polar molecule, can pull water during terpene-extraction parameters?

Finally, how can one approach finding the correct parameters to pull THCa from plant material while also not pulling waxes/lipids and other undesirables from the plant? I assume it will take some post-processing cleanup steps to try to isolate the THCa from the rest of the extract.

I am eager to hear your points of view on this topic, or if you can point me in the right direction to some resources that will help me better educate myself on this topic.

Thanks

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Nice ask!

Might find some starting points here Beyond CO2 density, "vapor pressure" method boosts THCa throughput

Pretty sure there are a couple of other discussions around here that have links to the primary literature. Probably in reference to terpene extraction…don’t recall a deep dive into the theory

Poke around a little, imo it’s pretty easy to see who the friendly CO2 wizards are…and it looks like you’ve been here for a bit.

Consider tagging individuals you think might have the knowledge you seek into the discussion directly…or simply asking if they have any suggestions for reading material when you figure out who they are…(they provide salient advice in another relevant thread)

wow! You seem to have a good handle on the theory, any chance you can point me at appropriate resources for getting there myself?

Maybe see

Manipulating super critical co2 solvent density to target specific compounds in cannabis

To get an idea where my head is?

I have absolutely seen crystalline THCa in an early Apex or Eden lab separator…

They thought it was so neat, they bought the thing to a high times event, and were offering dabs (apparently NOT from the THCa)

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Thanks for the response @cyclopath. I’ve perused through that thread and just about every other thread pertaining to this, but there are no specifics on the method or approach. Was hoping someone here who is a long-time CO2 user might be able to break it down a bit more than just the regular surface level explanation. @ExTek90 @JonaaronbrayAzoth @Photon_noir @Roguelab @Soxhlet @misterMR @GreenSolvent @TharProcess
Want to share any input on this?

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I have done supercritical for 9 years now. There are settings which will make the extraction yield mostly just terpenes, but I found that when extracting cannabinoids there isn’t a way to select for them (but there are different settings to make a high cbda extraction or high thca extraction faster). Since biomass is usually high in one or the other, the minor cannabinoids are still extracted by the time you are done extracting the primary cannabinoid. I also found that CO2 results in a higher decarb of THCa/CBDa

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I’ve heard that Ethanol is the Cannabinoid grabber and the C02 is the terpene grabber.

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@EverettMarm @Muzik_CO2tech in case they have anything to add.

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No hands on CO2 extraction experience here, but I am a fan of physical chemistry.

You are asking some tough questions, which can lead down as long of a rabbit hole as you are willing to explore. Tons of computational chemistry research is based around describing and predicting solubility on the quantum mechanical level.

Some non-cannabis specific journal articles I found on a quick Google search. SciHub is your friend if you hit a paywall

https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/cphc.201700434

https://pubs.acs.org/doi/10.1021/ar040082m

https://www.sciencedirect.com/science/article/abs/pii/S0896844622002480

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As soon as I left my job i basically forgot everything. Different pressures will extract different cannabinoids for sure. We had settings for thc, terpenes and cbd. For cbd, the setting was for when we ran crude cbd not extracting thc and cbd at the same time. I did run across settings in one of these threads on this site.

Did you follow this

Here?

https://wnvnl.academia.edu/HelenePerrotinbrunel

If I’m hearing your question correctly, you want to understand why CO2 changes properties depending on where you are on the phase diagram & how that effects the solubility/extraction efficiency of the various molecules involved?

If you are looking to target THCA don’t decarb the material first which is recommended by the equip mfgs for a better yield.

Whatever you extract without decarbing will contain THCA. You can dewax and recover the ethanol below decarb temps as well so you should be able to isolate from there if you use another solvent.

There are methods of getting THCA to form on the wall in a crystalline structure but it’s formed with all the other full spectrum stuff too so not necessarily an isolate

I dont expect it to extract an THCa isolate, CO2 isnt specific enough to only target one cannabinoid (it’s always a gradient), but am looking for super or subcritical parameters that will produce a THCa heavy extract from undecarbed plant material. This is where fractionation comes into play.

I’ve heard other people insinuate that subcritical is better for this, and doing it at a low enough solvent temp that it doesnt incidentally decarb the THCa during extraction, but nothing specific beyond that.

This is my best guess at it so far: do a terpene pull first at normal supercritical parameters (we use ~1150psi, 105˚F solvent temp for a solvent density of ~0.269 g/cm^-3). Then increase the solvent density greatly to around 0.9 g/cm^-3 (subcritical) to try to target the cannabinoids. This would be around 1200psi and 50˚F solvent temp. Our cannabis is THCa dominate, so while it will extract many different cannabinoids and cannabinoid acids, hopefully it will be THCa rich. I’m expecting the supercritical fluid to pull waxes/lipids first, so i will likely need to harvest after 1 hour fraction increments at these parameters to see how the extract changes over time. Just not sure if it will pull a lot of other desirables like chlorophyll along the way as it is undecarbed.

going back to my original question, the @Photon_noir post about Extraction & van der Waals Forces is excelllent and extremely thorough and the closest thing i’ve come across on this website that describes what is going on at a molecular level. I’m still trying to decode it :thinking:. He say’s " Simply put, propane and CO2 are also, for these same reasons, harder and much harder , respectively, to induce into polarity". Nonetheless, supercritical CO2 will pull a significant water fraction during a terpene pull. I think this has to do with the “Debye force”, but not sure how to apply that in practice. Despite being a rigid non-polar molecule, it can definitely extract polar molecules, and therefore it is possible to tune the solvent to extact a relatively polar molecule like THCa…

The interactions between scCO2 and solute are, I believe, more quadrupole-dipole than dipole-dipole as CO2 does have a quadrupole rather than a dipole moment.

THCA pulls can be done with lowish yields… the higher your solvent flow the better your yield will be because scCO2 is a shit solvent so recirculation is necessary. Like you want a system capable of 500 kg/hr or more for scale extractions. Also you’ll be pulling fats/waxes as well, so CRY media or similar is a good idea.

These are THCA from cured material. The center is with CRY CO2 media.

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If you turn up the volume you can hear the crystals clink. It’s all yellowish because I just mixed the terps straight with the yellow crystals.

This one wasn’t blended well. You can see waxy chunks of you zoom in.

Looks ranged from this to baby shit without CRC. You could dial it in and get better product for sure.

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