Fast crash and defective diamond remediation

Hash and Stuff Crystallization
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Let me start advising that I don’t know much about many of the processes employed by extractors - my strong suit is in high purity specialty gases and chemicals. I propose we look at both the fast crash and medusa diamond formation from a different perspective.

My grandma used to make rock candy by dissolving a lot of sugar in heated water to get a saturated solution. As the water cooled it became very syrupy as it was holding more sugar than it could normally hold at room temperature. This super-saturated solution contained a solute that was out of equilibrium with the solvent and the formation of concentrated crystals in the syrup form so that equilibrium could be restored.

I also read a lot about such crystal formation and dissolving those formations.

https://sites.pitt.edu/~bandik/organicweb/recrystallization.html

There are a lot of similarities with fast crashed and medusa stones. Both are formed in supersaturated solutions, that formation can be sped-up by using seed crystals and both can be re-dissolved in similar heated solvent (another hydrocarbon), where crystals can be re-formed by original process.

I’ve watched more than one video in this site where lids were partially removed from super saturated syrup of THC in butane. Fast crashing always starts at the surface and spread down through the syrup. If the lid was resealed quickly, the fragile fast crash formation disappeared back into solution, If the lid was completely removed, the crashing continued through the entire solution.

Proper diamonds, Medusa diamonds and even chalky stones form in supersaturated solutions. These too can be re-dissolved and reformed in other solvents as they seek equilibrium in the solvent.

In my opinion, the formations of rock candy and diamonds, defective or not have far too many similarities to ignore. Blame has been assigned to butane containing each of the following: Hydrogen Peroxide, isobutane, neopentane, ethylene, propylene, ppb contamination of obscure molecules and likely others.

Can any readers comment with explanations as to:

Why fast crashing appears as mason jar lids are opened?
Why initial formation of fast crash can disappear if the jar lids are quickly resealed?
Why the problem doesn’t re-occur if the precipitate is re-dissolved in a heavier hydrocarbon like pentane?

Of course I have a theory to answer those questions, but would like some feedback before continuing.

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  1. Lack of pressure
  2. Pressure
  3. Has happened to me with pentane but i havent done pentane reX much.
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Supersaturation at the right temperature will cause cold crashing if everything is right, especially if there is some propane in the mix (opening the lid).

Too hot and it will oil out instead of crystallize, which can be done with either increase of temperature or increase of pressure (closing the lid).

Heavier / longer chain solvents don’t cool as much when depressurized as the lighter / shorter chain solvents.

Personally, I prefer to cold crash in a propane heavy solvent since it will crash at a warmer temperature and can create a purer isolate with less energy and time.

We typically see the entire run crashed in 20 minutes or so with my ProJak refrigeration technology, whereas a butane heavy blend usually takes closer to 40 minutes.

At atmospheric pressure:
Pentane boils at +36.1c … Molecular Weight: 72.15 g/mol
Butane boils at -1c … Molecular Weight: 58.12 g/mol
Propane boils at -42c … Molecular Weight: 44.097 g/mol

Since at saturation pressure = temperature and temperature = pressure (boiling/condensation state), introducing a like molecule the temperature becomes a mixture of the to at their ratio at their pressure. So for instance a mixture of 70/30 propane:butane would have a boiling/condensation point of its pressure such that at atmospheric pressure a 70/30 mixture would boil roughly at -25.57c. This boiling point changes with pressure and consequently, its condensation point also changes with pressure, as its condensation temperature = its boiling temperature. If you are one degree above or below this value at the defined pressure then you are either a fully boiled and superheated vapor or fully condensed and sub-cooled liquid.

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“Everything is right” is so minimally achieved too. Run a molsieve and cold, and a pass through baked crc. Then it doesn’t wanna do anything but drop out.

Even with just n-tane we’ve wet poured into stainless pots right next to the fan of our booth and let it sit there and pour off the mother liquor after “cold crash” for some lighter bulk sugars after an operator sent too much bio through a crc.

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I don’t know why you feel like you need theories for known parts of chemistry. Seems like you have answers based on sugar (which is a different type of crystal structure AND has less potential constituents…)

  1. Like @NorCal said lack of pressure. That pressure is keeping all the “gas” in solution. And that means the saturation of the solution is staying mostly consistent. Opening the lid changes this and there by that saturation level. Secondly - it doesn’t always happen this way either (because of other constituents and variations in hydrocarbons and purity).

  2. Like @NorCal said pressure. Same thing holds true here - all the sudden those gas molecules are bouncing around inside a closed area, keeping all the molecules inside instead of outside. Again - it doesn’t always happen this way, and again because of other constituents and variations in hydrocarbons and purity.

  3. What the fuck kind of question is this? Why does a reaction that requires specific constituents including specific kinds of solvents, temperatures, and pressures NOT FUCKING HAPPEN when you take those specific constituents away. What planet are you living on dude? Why don’t you try and see if you can recrystallize a fast crash in water? In HCL? In DCM?

And also - heavier isn’t necessarily the answer here either. Temperature changes, access to other constituents, etc can assist.

I’m not sure why you decided to start a new thread to have this conversation in (as there are already many threads about this with way more information than your sugar theory has provided).

But you could also consider - oh I don’t know - doing any of these tests at bench chemistry. (There are people doing this pure science academic work…) A recent study came out about this specific to how subtle changes in constituents can radically change the thermo-kinetics of cannabinoids (I shared that link earlier this week).

That impacts how crystallization works. And those subtle differences are on the molar levels - right like less than 0.01% in the PPB range of things. Moving thing from First Order to pseudo-first order and beyond.

So pushing it out like it is somehow similar to sugar crashing is neat and all - but it goes so much further because of all the unknown constituents. And looking for the KNOWN contaminates and making sure those are not present so then the UNKNOWNS can be isolated more clearly is important.

Maybe you are actually looking at all of that stuff but based on what you shared here, I highly doubt it.

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Thanks for the information and insights. True there’s a lot of known chemistry involved, three might also be some physics.

@Zack_illuminated wrote about 100% butane fully crashing out at about 40 minutes with a blend of 70P / 30 B crashing in half that time. When the lid is removed, the containment pressure is removed and the crash begins with the formation of unstable crystal structurers on the surface of the solution. I call those structures unstable because if the lid is quickly replaced, they disappear in the solution. Were they stable, they would remain as a concentrated crystal of the solute, with no inclination to go back into a super saturated solution.

Does the fast crash go back into solution? @thesk8nmidget showed it does. a couple posts above the link below the fast crash is shown in video.

https://future4200.com/uploads/default/original/3X/d/f/df825ffc8b8b67dc2f654d569288ced590191932.jpeg

Did I do any experiments on the bench? Even though pure butane at room temperature boils readily, a solution with benzene content will boil as well.

So, what is causing the formation of the unstable crash structures at the surface?

At room temperature, butane has a vapor pressure of 16-17 psig, just slightly above atmospheric.
Butane boils at -0.5C. While temperature and pressure are related, I believe the fast crashing is directly related to the temperature of the butane evaporating at the surface of the solution. Boiling butane creates a surface temperature below the freezing temperature of water. Is there enough atmospheric moisture / humidity to produce ice molecules at the surface that would act as seeds for the formation of defective crystals in the super saturated solution? If yes, would that explain the faster formation of defective structures if the solvent boiled at a lower temperature like it does with a 70P / 30N blend. If yes, it also explains why there is no crashing with pentane as the solvent - it isn’t close to boiling at room temperature.

Here’s a pic of pic showing the ice formed when fresh butane is poured into a pan exposed to atmpspheric moisture:

Pan 11.25
Pan 11.251500×2000 288 KB

The ice forms at the surface, then drops to the bottom surface because at 0C ice has a density of 0.92 gr/cm3 while butane’s is 0.6 gr/cm3.

Here’s the ice remaining after the butane evaporated:

Pan 2.22
Pan 2.221500×2000 465 KB

Some atmosphere enters the jar when the lid is opened. Enough to form some crystals that serve as seeds? I think yes.

Finally, here’s a pic of fresh butane released into the same pan in a box where we replaced the atmosphere with a flow of heavier argon gas - no atmosphere present.

20230130_120521
20230130_1205211920×2560 277 KB

All this is a theory that folks smarter than I might dismiss in favor of ppb contamination that for some reason forces formation of defective crystals at the surface of the solution. I’m just trying to help and don’t deserve being berated for my efforts.

Jim

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I think the biggest difference for most of us (there are years long threads about this) - is that we saw a change in normal behavior that we had been working with for years and that inconsistent with all our benchwork, data points, and which we had difficulty repeating until we controlled for all things including looking for impurities.

I think your statement of ppb contamination is a misunderstanding of the issue. Most of the time when I see the contaminates (which I now control for during production as do most people…) I see them in the 10-100ppm range. Occasionally, I see them lower than that but its also worth noting that most vendors are not testing for all the things I’d like to see.

Glad you are here helping - pretty sure we work together sometimes. :wink: Although I could be completely mixing you up with other Jim’s from Ohio. <3

I think the correlation is (as I noted above) a good one, but that misses some important parts related to prior experience, experience with contaminates, and experience with processes designed to remove those contaminates so issues don’t happen anymore.

Since I started hunting out reasons for these issues I’ve had people tell me it was all kinds of stuff. Your post is the first time that someone said that its just ice that has formed due to evaporative cooling in the jar.

There’s also been quite a bit of testing done, which indicated that the white formations where not water. Doesn’t mean that water in the atmosphere that is potentially getting inside a jar might have an impact on crystal formation.

Especially when you consider how people control for moisture presence in solution and in the environment. Some people even do this work blanketed without access to “air” - you know?

I know this is a strange question to ask but some of us tried all kinds of things to fix the issue and arrived at a solution of distilling gas and using clean tanks to prevent this from happening. Some of us have put steps in place to test incoming gas and distilled gas to monitor for potential issues.

So the benchwork has been present with different qualities of cannabinoids, percentages of THCa, percentages of terpenes, ratios of solvent constituents, and even looking into contaminates on biomass (of which there are many!!) to see if we could isolate those to prevent clogging of equipment and to allow for larger crystal formations.

After controlling for as much as was possible we arrived at some conclusions about specific ratios that work better, specific contaminates that cause more problems than others, and processes that have become best practice to prevent issues from happening.

Hell - when I first started down this path, my extractor was convinced that the grower was spraying the plants with something weird that was fucking with the pour. :stuck_out_tongue: I had to go through WEEKS of video footage to guarantee that wasn’t what happened (because he didn’t just want to trust the grower…)

You are probably working with ASTM D37 on this issue, yes? There’s two task forces on this for standards related to testing for impurities more specific to cannabis production hydrocarbons and another for tank inspection and another for tank cleaning.

Seems like you have a passion for it. So I hope you’re willing to come and share your thoughts with those of us that are trying to get the standards in place to prevent contaminates from getting into products and from contaminates impacting processes. <3

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Cold crashing is just cold crashing… nothing special about it. Was doing it in our propane rotary miner for years pre-medusa.

But also, I haven’t really ran into medusa that I know of on any of our systems. This could be because my method is different from what everyone else is doing and typically has less solvent loss than the typical system.

We can extract 1000 lbs of bio with only 70lbs of solvent and still get the cannabinoids out, as my patented cycling tech has “unlimited” solvent per-se. We use exponentially less solvent with a very good recovery such that the potential impurities are so small the effects might have gone un-noticed. :person_shrugging: :mechanical_arm:

Edit: The actual amount of solvent needed to extract #### lb is proportional to the system utilizing it. Our smallest system runs on 10lbs and the R600 uses 70lbs.

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Hi Cassin,

Yeah, I’m that Jim from Ohio. You and I have been communicating on issues related to issues plaguing the extraction industry. I’ve been active on all threads involving hydrocarbon solvents since I joined the forum in 2020 - if I missed any of them it was an accidental oversight. Most hydrocarbon threads have been related to fast crash / medusa / chalky diamond (FC/M/CD) formation OR benzene contamination. Going to leave benzene alone for the time being.

Many in the botanical extraction industry have suggested potential gremlins causing FC/M/DC since they first appeared 3 years ago. Despite all the efforts and finger pointing, the cause of each or a unified theory has yet to be proven.

When the FC/M/CD issues started getting reported, some extractors noted that it came from the initial withdrawal from a new solvent tank, some from a mid-way withdrawal and some from the final withdrawal that emptied the solvent tank. No constant with withdrawal.

Some pointed their fingers at: neopentane, isopentane, propylene, methanol, ethanol & ethanolamine. No proof of anything came to be and despite claims from manufacturers they developed methods to remediate / remove the culprits. The problems persists.

You pointed out, several have tweaked with controlling issues and developing processes to prevent the issues. Extraction facilities mostly claim that they are using the same SOP’s with the same biomass they have always used. Did the chemical footprint of n-butane change in 2021? I certainly can’t rule it out, but like everyone else I’ve been unable to pinpoint the gremlin(s) involved.

As an industry outsider, I’m in a unique position to consider theories that might not occur to those actually involved in the extraction process. I also realize that nothing is “pure” and it’s impossible to analyze for every potential contaminate down to ppb levels. Rather, I keep looking for a unified theory that would address all the variances in data reported by actual extractors.

Might atmospheric humidity be part of a unified theory to explain everything?

  • It covers why there is no consistency in the early/mid/late timing withdrawal of solvent from the tank
  • It is not likely monitored because it’s never be considered to be a potential problem
  • I’ve demonstrated that ice crystals develop when n-butane is exposed to atmosphere.
  • Once present, they could certainly at as seeds for the formation of an unstable defective crystal lattice.
  • A fast crash lattice might well dissolve back into a butane solution that becomes warmer as it stops boiling because of it’s defective formation.
  • As the solute crystalizes properly, the solution is no longer supersaturated and any ice crystals formed would no longer have an effect on the solution.
  • Ice sinks in the solution and small crystals would sink to the bottom, quite possibly causing the formation of the slightly defective Medusa structure as well as stones that chalk up over time.

I’ve shown that by replacing atmosphere with argon, no ice forms as butane boils away at room temperature, but I’m not an extractor and cannot perform tests on actual solutions generated by extraction with n-butane.

Will someone please test atmospheric replacement with argon when jars are burped and lids are removed? At 0C air has a relative density of 1.23 gr/liter. Argon comes in at 1.68. I’ll even supply krypton gas with a density of 3.74 gr/liter for experimentation. Worst case is that the problem persists and the output needs to be rexd in pentane or some other heavier hydrocarbon.

Any takers?

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I’m not a chemist. I don’t run butane or propane extraction. I’ve never dealt with medusa/fast crash, I have no direct experience with it other than keeping an eye on these threads and chatting with friends in the industry.

But I do know from both direct experience as well was conversations with others that under certain conditions water can act as an anti solvent for cannabinoids in alkane solvent systems.

And I believe that many of the remediation methods I’ve seen discussed would also remove water.

So I think the idea is worth exploring or at least considering.

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I agree. Water is a pretty intense culprit for all kinds of unpleasantness but we do actively work to control it. Most of us control our environment (including monitoring temperature, humidity, and other things like relative levels of gasses in the air.

Even if we did this test - we’d first have to contaminate everything to get the system not working smoothly. If you had asked me to do that two years ago, I probably would have said yes. But in today’s market? After spending a fuckton in method development and process changes to fix the issues we thought were happening.

And the only people I hear still complaining about this are the ones that are uninterested in the additional downtime and costs related to using the processes I have mentioned above. So they exist but the bigger issues for the industry, in my opinion, go back to new gas providers with contaminates (benzene being see across the West Coast), gas providers in Europe and Africa with completely different standards showing similar issues, and the broader implication of unreasonable regulatory restrictions on the cannabis industry for using hydrocarbons, when other industries don’t have that.

But I digress. I’ll reach out to folks and ask about doing this specific experiment. Most of us already blanket things with N2 or Argon - that’s not terribly new.

The first time I saw this issue it was in a facility were we blanketed everything with Argon to prevent oxidation from the atmosphere. Didn’t stop it then - doesn’t mean it wouldn’t stop it now.

I’m controlling the temperature in my rooms at CRT - 18-22C and RH at 50% +/- 5% (you know to help with static). I know there’s lots of people who run their rooms colder - but I’m old school pharma so I stick with what I have been doing for decades.

But then again - I’ve decided that I prefer ethanol extraction because the regulatory costs are significantly less so my hydrocarbon system sits idle, eh?

I’m going to shake the tree here in Michigan and see if there are any takers. Convincing the team to fire up the hexapod… and then NOT distilling the gas first, to hopefully create a crappy product, is maybe not possible. But perhaps some people near by are having this issue today. Never know!

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That puts a pretty big mark in the “water is not actually the issue” column for me.

Conceptually, it still might be interesting to try to utilize a high-humidity headspace as a way to induce nucleation. I’ll put it on the giant list of “fun science stuff I’ll probably never get around to.”

Once we’re back up and running and have all of the bugs worked out later this year I should invite you (and a handful of others) up for a tour. Water is pretty friendly from a regulatory perspective, and I suspect we’re doing things a little different than almost everyone else. Our fire marshall sure likes it a lot more than he did alcohols and alkanes.

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I have been contemplating moving our anti-microbial water filter to strip water from the extract for some time now instead of just pulling water from the exhaust gas.

Heavy metals and pesticides typically follow the water as well, though metals can get “stuck” on the molecule… But I have never tried pulling water from the crude, which in theory might pull all of the water soluble impurities out along with it.

Works great in the current position but I really want to try it on the crude side.

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Forgive me for throwing more info. The relative humidity was 22% when we generated the ice crystals on the butane in our test pan.

I think N2 is too light to act as a shield to atmosphere. Ar worked for our little demo, but If someone is willing to experiment, I’d prefer to use krypton and would be happy to donate the gas.

G’night all.

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