double post
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At this point it appears that Counter-Current LLE is producing more uniform results that LVE.
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Well that at least helps me to reassure that Iām not as far off as what Iām thinking. Thank you for reassuring!
Geez Louiseā¦ Thatās what I think of when I think of watching the liquid phase of butane with water LOL
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Hereās what it looks like with a little crude mixed in.
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LVE leaves too many unknowns regarding diffusion, temperature and pressure. LLE is more uniform in regards to density and surface area and will get more consist results.
When trying to treat vapor, there are usually several different pressure levels. All of these will have varying amounts of atomized water if being boiled from a contaminated puddle of solution. Because itās a vapor, and at a relatively low pressure, there is very little interaction with desiccant in the amount that is normally used in BHO systems.
It is much easier to separate water from liquid butane. The higher concentration of water by means of being in a liquid state makes it much easier to coalesce and separate from butane than in a vapor state.
The contaminants that are being targeted are mostly water soluble. Water is cheap. Through dilution over multiple washes or a thorough counter current wash, followed by decent dewatering, this problem will disappear.
Iāll be posting some interesting results in the next day or 2 regarding some tests. The most interesting thing I saw today was adding 10ml of DEA to a methanol/butane/crude solution made the the butane and wax soluble in methanol.
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Another update week ending 8-19-22:
Still no response from Isaac, so I contacted Vici Metronics technical support and asked for their assistance. Alas, they just contacted Isaac, who acknowledged he owed me a memo but was busy.
Since from my perspective more than a memo is overdue, Iām recommending that we move on and if Vici Metronics eventually comes through, we will consider it in perspective at that time.
Moving on, I contacted Avanator Sciences technical support, a division of VWR, and asked for their recommendations on either a prepacked column, or packing material for removing methanol and diethanolamine, and am researching other column and packing producers.
Along those lines, there are two efforts in motion that Iām aware of. Cameron tells us that Carbon Chemistryās solution is imminent and I learn that the firm Remi works for, which I believe is Corter Gas, will also be offering a solution in the next couple of weeks.
Interestingly, after talking to Remi, I have a better insight as to why he thinks methanol and diethanolamine are the bad actors in Medusa, as well as what test he used to determine it, given its low concentration.
Because of its low concentration in the gas, he inspected the column that he used to remove the mystery content, instead of inspecting the gas itself and found enriched oxgenate and nitrogen layers, which he then analyzed.
Adhering to KISS and the principle that the fish trap exists only because of the fish, do we really need to analyze the gas before and after running through a scrubbing column, if we know that the gas produced Medusa effects prior to running through a column and didnāt afterwards?
For scientific data collection, as well as our joy and amazement, might we not following Remiās lead by simply inspecting the column, and would it not be easier and more effective?
And on the subject of scientific data collection, Highestzen has samples ready for analysis, where he has added methanol and diethanolamine to gas to induce Medusa effect and needs support analyzing them.
He has also built his own continuous Counter Current Liquid to Liquid Extractor (CC-LLE) which he has used successfully for over 100 runs ādegummingā LPG. He is reluctant to invest further money and effort into his design until after he see test results on his diethanolamine samples.
Since CC-LLE also shows promise for removing terpenes from recycled LPG and is ostensibly a cheaper long-term solution for bulk scrubbing than columns, Highestzenās progress is encouraging.
By the same token, CC-LLE may not scale down enough to be a cost-effective solution for lower volume users, where columns can with their lower capital investment, but ostensibly higher operating costs.
Bringing me back to how I found gas scrubbing columns in the first place, and that was observing the scrubbing cartridge on the inlet of my MRI GC, which is there to protect the device against contaminants in the ostensibly clean gas supplied by others.
If as production managers we are to insure quality levels approaching Six Sigma, we have to either perform a receiving inspection of all our components, or we have to somehow protect ourselves against vendorās with manufacturing quality control that is less stringent than Six Sigma.
In our case, we are purchasing a grade of LPG that continues to meet LPG industry standards for that grade, continues to meet the needs of the balance of their industry, and which up until recently met our pharmaceutical extraction needs.
Pharmaceutical is a small segment of the LPG market, and those growing diamonds or otherwise adverse to fast crash are a small segment of that segment. A segment we now understand (believe) needs a better grade, which restricts methanol and diethanolamine to a lower PPB level for our purposes.
Rather that debate who shot the duck, would we not be better served by putting our resources together and resolving the issue with solutions that float all boats?
Itās certainly an open market window for a supplier bellying up to the bar with such an LPG grade.
Likewise for equipment manufacturers and consumables suppliers serving both the person scrubbing the gas for the supplier, as well as some of the end users scrubbing their own.
Since the only way to insure Six Sigma quality in our own products, is to either ensure that quality in our components, or protect our product from quality excursions in our process constituents with prophylactics, I believe that it speaks for itself that greater quality controls is required, whether current industry standards are met or not.
Even if we are CC-LLE scrubbing our own gas or buying āpristine organic 100X Mothers Milkā from a trusted supplier, Six Sigma quality requires a receiving inspection, which as noted above is problematic at PPB levels, as well as expensive, but a scrubber column serving as an inlet prophylactic would ostensibly fill that purpose.
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Any word on your test results for amines from this sample?
How about the mystery peaks?
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Struggling a bit financially to conclude this test as a lot of them cost decent money. Hoping I can figure out what these are soon. Also want to test many many more new tanks from multiple providers so I can take a step back and look at everything we are potentially facing.
If the LOD of diethanolamine is low, you will have to preconcentrate it in order to detect. Passing a lot of gas over an adsorbant is the best way I can think of to do this instead of directly analyzing the gas.
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Wouldnāt a low limit of detection be a good thing in this case?
The statement from the lab says ābut its detection limit is poor.ā
Doesnāt that mean the LoD is high and it canāt be resolved at low concentrations?
Iām not trying to nitpick, genuinely curious.
Iām still a little confused as to how/why these substances (meOH and DEA) are not being concentrated and remaining with the oil after the first few runs in an extraction system just like mystery oil would.
With boiling points of 65C for methanol and a whopping 269C for DEA, how are these not able to be distilled out?
I know people think itās co-distillation but Iām surprised that would happen with such a low concentration (PPB) of these contaminates to start.
Could fractional distillation possibly be a solution? A cartridge filter sounds like the easiest solution so far, but water washing sounds a little complicated especially if the gas needs to be re dried afterward.
@anon64373531 What do you think about the ion chromatography testing Ahay5280 mentioned in his post? I donāt really know what that is exactly but do you think it would work and possibly give an accurate test result?
@Ahay5280 out of curiosity, how much does that test cost?
It generally means the LOD is higher than the expected concentration
Also remember that with the fast crash we are likely talking about catalytic activity, which means that the catalyst is recycled and active at very low concentrations.
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Iām assuming itās just essentially passing the gas or liquid over an ion exchange resinā¦ anything that preconcentrates will be better than not, and this would do that trick.
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Absolutely on the money brotha 
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Apologies, I totally missed this question. We may be on the same trackāpressure housing for a spin on disposable filter packed with a proprietary media. Prototypes are in production for testing as I write. In lab testing to commence in a few weeksāconfident these will be successful as the media proved successful in prior testing, we just want to ensure we have flow rates dialed in and draft an SOP. Iām drafting a post now with more (but still vague) detail.
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Here is the latest Medusa team update:
Medusa project update of 9-2-2022
Moving along, as of today no response from Isaac Delgado of Vici Metronics, so I have dropped Vici Metronics from our list of possible vendor solutions with my apologies for wasting of time. They were an excellent vendor in the past.
Ramiās update suggests that in addition to the remedial columns previously discussed, Cortera Gas is also pursuing a more stable supply chain. Here is his latest update:
ā While we have procured and implemented the remediation for a variety of contaminants we are now investigating producers who donāt add them to the product whatsoever. We have begun receiving truckloads of this product we have developed rapport with and are still cycling through our purification system but also requesting non additive starting material for the fractionation plant. We are very excited and will keep everyone in the loop as the progress for Cortera Gas continues.ā
Carbon Chemistry plans to offer materials for packing column and are moving from proof of concept testing to field beta testing .
In the spirit of the project, Dillon provided me with conceptual column sketch pro bono and I provided him with CAD drawings with build details for their column pro bono.
Itās a straight forward 4ā X 24ā 600 psi design encompassing two media sections, with a membrane between them, and which breaks into sections for easy refill.
GasLogix-Adam has announced their upcoming spin on filter packed with proprietary media, with prototypes currently in production for testing.
Solvent Direct team continues with their own Medusa task force that is cooperating and collaborating with us. Thank you Dr. R for the offer of a Diethanolamine standard for Josh and Nigelās GC!
I contacted Erich @ Pharmex for his recommendations for a chromatography column packing material and he is researching and ordering samples of zeolites for testing.
Highestzen has had notable success with his CC-LLE water wash system, but has a limited budget and requires lab support testing his samples to ASTM-D7599 before proceeding. So far no one with lab access has bellied up to the bar, which is a shame given the ostensible benefits of his system.
I approached Lew Swan of Sub Zero Scientific with our potential equipment needs and have added him to our project summary distribution. I also connected him with Dillon and Highestzen to review their column and CC-LLE equipment needs for potential common interest.
In aerospace, Six Sigma quality levels are required for some processes, but one of the things that has been highlighted by this trip down the Medusa rabbit hole is that some pharmaceutical extraction and formulation processes require greater than 99.999,999% purity, due to the catalytic action of contaminants in the PPB level.
For those labs negatively affected by Medusa syndrome to win, the offending contaminants must be removed from the LPG prior to processing, whether they do it themselves or it is done for them.
Even if it is done for them, Six Sigma quality still requires a receiving inspection sample plan, or a prosthesis against deviations in quality, such as a scrubbing cartridge on the inlet similar to those used to protect sensitive equipment like gas chromatographs against inlet gas quality excursions.
We have several different approaches under way to scrub the LPG, but for Six Sigma or greater quality, the rest of the supply chain issues must be addressed and one of the elephants in the room is tank cleanliness.
There doesnāt appear to be a universally accepted standard for cleaning returned tanks before refilling and tanks typically get mixed between customers.
In discussing tank cleaning with different LPG suppliers, I found a spectrum ranging from never venting any residual VOC and just topping, to cleaning tanks that failed the āsniff testā, to cleaning 100% of the tanks, with other in between standards.
It goes without saying that if contaminants at the PPB level are of concern, a regimented cleaning process is required.
I have yet to tour any tank wash operations, but in aerospace the exotic alloys must be meticulously cleaned prior to heat treat or welding, and the various investment casting configurations have numerous passageways.
The method typically used for the purpose is a hot alkaline wash bath, followed by a 10 to 15KSI high pressure hot water wash.
They are then dried in a hot air oven.
It should be easy to semi automate the high-pressure wash with a large pump and multiple nozzles while rotating the tank on its axis. Final inspection could be by borescopic cameras and recorded.
Regardless of how itās done, tank quality must be insured to maintain quality levels in the PPG levels for that LPG negatively affected by Medusa, so most certainly those tanks must be adequately maintained.
As the pharmaceutical extraction industry is but a small portion of the overall LPG market, and those negatively affected by Medusa smaller still, we need solutions that address our issues, without inconveniencing and driving up the price for the balance of the industry.
One solution might be color code those tanks used for that purpose and for the gas supplier to give them more stringent attention than the balance of the tanks in circulation.
That would lessen the impact on gas suppliers not cleaning each and every tank and ensure higher quality to the affected consumer.
The consumer could add another layer of protection by buying or leasing their own tanks, so that they were never in general circulation.
Iāve added Dillon, Erich, Josh, and Lew to this distribution.
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does removing the valve (repeatedly) shorten the useful service life of the tank?
are we putting the same valve back in, or a new one?
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Most suppliers boast they put new valves in, to my knowledge. I know Kaplan does it for solvent direct with each tank.
Just to be clear. Kaplan is SD main supplier and is the one doing the tank cleaning. They are the ones cleaning each and every tank each return. Not just from solvent direct. With everyone they supply. Itās easier for them to do this, vs singling out just the tanks from SD. This is directly from Kaplan mouth into my ears.
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which I would interpret to mean āyesā (assumed for liability reasons) to thread damage on the valves, but probably ānoā on shortening the life of the steel tank repeatedly installing those brass valves.
thanks!
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Whatās crazy is when i talked with Devon from Kaplan about a year ago he said solvent direct had only got a pallet or two from them and only used them in a pinch. Lots of stuff could have changed since then tho.
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Other way around now. They use them primarily and will absolutely use someone else in a pinch. He sponsored my last class in Michigan last winter.
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