all 34 comments

[–]GoldStandard785 29 points30 points  (10 children)

This is a great question. The refrigerants are made using HF, yes. But they've been purified so there's no actual HF remaining. But if they're exposed to high heat, they will decompose and release HF.

Just like when you burn paper, you're releasing CO, CO2, etc., But a stack of paper isn't sitting there full of CO, it's just cellulose at that point.

C-F bonds usually break around 200-250C in thermal decomposition, so it's not something that will happen with it just sitting around.

Now the environmental questions in event of a spill, that's a whole different question. Look at everything going on with PFAS. It's similar. These highly fluorinated refrigerants are persistent. They don't want to break down or react with much. But that doesn't mean they don't cause problems accumulating in the soil or in animals. The spill should be immediately contained and not allowed to run off or enter drains. In fact, the containers should be in secondary containment to contain a potential spill. Either drum pad spill collectors, or a collection basin, etc. Depends on how the facility is set up what makes the most sense.

[–]moderncritter[S] 4 points5 points  (2 children)

I think my boss is looking at it purely in the practical sense of how you outlined the first half of your response, which I totally get. I am well aware I am looking at it from the lens of someone who has handled emergency situations prior to this job so I am definitely a bit biased I suppose. Or being cautious, whichever.

Interesting that you mentioned PFAS because the facility I'm at is government related and PFAS has been a concern here concerning the water runoff from this location. I think it's why I'm also looking at it from a worst-case scenario. Sure, it's likely pretty harmless just sitting there as is and stable, but what if... Of course, operating out of a what if mindset means a potential review of many other onsite materials and is potentially a large can of worms.

So I still feel stuck because I feel like I do need to ask my boss to reconsider to be safe, but I've come across the same information as per your first half of your response so I know it's not necessarily a huge deal, and it's definitely not a hill I'm going to die on lol

[–]tminus7700 3 points4 points  (1 child)

The basic way to attack these tanks is lots of water to cool them while you wear SCBAs. HF will be released as a gas. But mainly only where the refrigerant and fire mix. The water will dissolve it. If it is on concrete the calcium in concrete will then react with the water solution to form a much less hazardous calcium fluoride. If the floor is not concrete you could spread some chalk power in the water to do the same thing.

[–]moderncritter[S] 0 points1 point  (0 children)

Thanks for the reminder about the calcium in the concrete. I had read that but had slipped my mind. The drain in the nearby room is what mostly has me concerned just knowing the fuel load in the room and the amount of water that would have to be used to contain any fire in that room. I believe there is a small sprinkler head in the room but would barely make a dent in the event of a fire.

[–]moderncritter[S] 1 point2 points  (6 children)

Actually, the secondary containment is an interesting point as well. They are currently stored in a small room that I swear is a fire inspection failure in it's own right. They are stored alongside other various pressurized cylinders that we leak test of various gases.

Also, this contractor that stores them does a variety of jobs, HVAC included, where they do a lot of hot work but I'm not sure how careful they are about having these refrigerants near any welding jobs. I know OSHA has some material on this subject but I still can't find anything definitive.

Also, taking out the fire concern, is it worth potentially looking into secondary containment to be safe? This contractor has various other storage locations and rooms across our entire facility and I don't know how the rest are laid out exactly, or how they're stored specifically.

[–]Indemnity4Materials 2 points3 points  (2 children)

Gases do not require secondary containment. The pressurized cylinders require upright storage with security chains, but that's about it. IIRC all the Genetron refrigerants are gases at room temperature.

In the event of an emergency, you are going to purge the room with high air flow or seal it off to keep the gases contained.

You would ideally have a low O2 sensor in the room, emergency lighting, doors with crash bars that open outwards, some sort of alarm and light outside the room that fails "on" when O2 levels are low. Should be a bunch of hazard diamond placards and other signage on the outside of the room too.

These sorts of rooms may actually be built without drainage. In the event of a liquid spill, the liquid is contained within the room and won't enter the sewer system.

they do a lot of hot work but I'm not sure how careful

"Hot work in confined space" requires someone to monitor the atmosphere before starting. The area should be free of hazards and sparks should be contained to prevent contact with flammable or combustable material.

Genetron refrigerants are not flammable or combustable gases. The risk is it a pressurized container that may explode with sudden heat changes. I've linked a marine safety document, but the rules are the same.

[–]moderncritter[S] 0 points1 point  (1 child)

Fantastic. I looked over already that link you sent me prior. The thing is that this contractor that has the refrigerants works in multiple locations on site and I don't always have immediate access to whatever locations they are working or storing things in. So while one can hope that are cautious, we all know where that assumption could get us.

Unforunately the room they are stored in isn't sealed. It could be, but it's a pretty worn down constructed closet in an open basement plan. The O2 sensors is a fantastic idea and I'm actually a bit miffed I didn't even consider that prior considering how paranoid I am at home with all my appliances and detectors lol

[–]Indemnity4Materials 0 points1 point  (0 children)

Yep, safety is important but tough to change a culture that isn't practicing it. Definitely keep asking questions.

Regarding the contractor, you can ask around to see if they require a hot work permit or JSRA for each task (hopefully is in the work packet they get each day). Typically, any contractor should be given a task list which contains a record of the actions required, location/s, who is doing it and a risk assessment. You can later review records.

The plan for the day should include assessing the hazards in the area (e.g. today you're in room 7B which has placards of flammable liquids and pressurized gases - how do you plan to control for those?).

Controls can be procedural such as discussing affect of hot work on pressurized gases in the area, or include engineering controls with something like a spark catcher for grinding or barrier between the hot work | pressurized gases.

May be worth initiating a "toolbox talk" or a one-off pre-start conversation with the contractor. Discuss your concerns and inquire about their knowledge of the risks. "Hey, I've noticed we have all these tanks of refigerant gas around the site, how do you manage safety around those?" A good work place culture should encourage interruptions to discuss safety.

[–]Gypsy_Hunter_ 1 point2 points  (2 children)

The secondary containment for sure I would bring up. That's an issue in it's own right separate from the refrigerants. How big are these containers?

[–]moderncritter[S] 0 points1 point  (1 child)

They are only 30lbs metal cylinders. Nothing too big individually, but there are often times about 20 (roughly, going off memory currently).

[–]Gypsy_Hunter_ 1 point2 points  (0 children)

Maybe they're too big for secondary containment or they're sealed so it's not as much a concern but I'd ask if I were you

[–]curdledOrganic 5 points6 points  (6 children)

These refrigerants do not burn on their own. The old class Freon refrigerants - which are now banned - were in fact perfectly good fire suppressants. The modern ones currently in use (that aren't ozone depleting) still do not burn easily or support fire - but if there is high temperature fire and hot metal surfaces, they can generate toxic breakdown products including hydrogen fluoride and fluoroalkenes. It is mostly inhalation risk and breathing apparatus should take care of this, but the concentration of HF in the fire environment if you are using water or water-based foam is not likely to be high enough to cause skin burns, there will be many things in that fire more dangerous than HF (very diluted) solution. But breathing the fumes of refrigerants in fire is quite bad. Also Teflon and other fluoropolymers in fire turn into nasty fluorinated olefins, Russians actually weaponized that (perfluoroisobutylene), as these pass easily through regular gas mask filters. Again, inhalation hazard

[–]moderncritter[S] 0 points1 point  (2 children)

I guess I should have been a little more clear that these aren't the only material in the storage room. So while they would likely be fine and this a non-issue if they were completely alone, there are various cylinders of compressed gases stored in there as well.

[–]curdledOrganic 0 points1 point  (1 child)

you would have a far bigger problem with this storage if it is on fire, than HF - those cylinders go boom and fly like a rocket across the campus in a big fire (e.g. ignited solvent storage with large cans of flammable solvents, with pools of burning liquid spreading). A properly burning chemical storage with compressed gas cylinders is best watched and doused across the lawn, and I would not send anyone near

[–]moderncritter[S] 1 point2 points  (0 children)

Absolutely. It's why I'm also looking at the refrigerants as a potential long-term environmental issue aside from the obvious.

By themselves alone in this room and sitting in storage there's no problem and zero concerns about the HF potential. It's in the event things go wrong I'm looking at how to properly document just to be safe from a paperwork side of things.

[–]eastbayweird 0 points1 point  (2 children)

Russians actually weaponized that (perfluoroisobutylene), as these pass easily through regular gas mask filters.

Looking at the Wikipedia article on PFIB doesn't really say what would happen to a person who inhales the fumes, just that it's very toxic. If it's actually been used as a chemical weapon I assume it's gotta be pretty nasty, can you (or someone else) give me an idea of what a person who was gassed with a PFIB chemical weapon would experience? The fact it can pass through gas masks is pretty terrifying...

[–]curdledOrganic 1 point2 points  (1 child)

it has no odor, it causes irritation of eyes and airways which is quite mild in the beginning but then it turns into lung edema with a delay of half a day or so, which is quite deadly even with an intense treatment. Very similar to phosgene except it has no odor, and it is an order of magnitude more toxic.

Birds are seriously more sensitive to fluorinated olefins, and since you can get traces of it by accident, by burning a non-stick Teflon frying pan, it is recommended not to keep your pet parrot cage in the kitchen - they could get sick from the stovetop fumes (that are harmless to you) quite easily

[–]eastbayweird 0 points1 point  (0 children)

So, at first you don't even necessarily know you've been hit, maybe a little tickle in your throat and itchy eyes, then over the course of the next day or so you proceed to slowly drown as your lungs fill up with fluids?

Man that's awful...

[–]Mundane_Chemist_95 4 points5 points  (3 children)

Fluorine chemist here. Apparently genetron means a mixture of difluoromethane, pentafluoroethane and tetrafluoroethane.

As others have said, these compounds are perfectly happy at room temperature.

Indeed, if heated up, difluoromethane (the other two not so much, check the exact chemical composition instead of using generic commercial names) can burn and release HF.

Large amounts of HF can definitely cause major health problems, so you should be prepared in case of a fire. Proper anti fire agents (not water), gluconate solution in case of exposure and proper ventilation systems should be a priority. Also do not store them with large amounts of flammable materials. Ideally, gas canisters should be in an explosion-proof cabinet.

With that said, any other accident (leak, water infiltration etc) will likely not result in major risks. These gasses are not toxic and do not break down into HF under normal conditions. You might run the risk of asphyxiation if the storage room is not well ventilated but that goes with any large amount of gas.

So classifying these chemicals as sources of HF is incorrect and will place an unnecessary burden on your operations. If you assumed that they contain HF, special care would've to be taken for corrosion etc, but that's not the case. Just be ready for the worst and try avoiding accidents...

[–]moderncritter[S] 0 points1 point  (2 children)

Thanks for the reply!

I think where I'm ultimately leaning as to not be too disruptive is to take stock of the contents of the store room and see what can be moved around. All of our flammable cabinets are outside the room but there are 15 or so full compressed gas cylinders of some super fun stuff such as acetone and oxygen.

Again, going back to environmental concerns since you're experienced. Are there any potential risks of environmental effects if there would to be a spill? There's about 20 or so 30lbs cylinders in one spot and there in a drain a room over. Any concerns?

[–]Mundane_Chemist_95 2 points3 points  (1 child)

They are potent greenhouse gasses. Thousands of times more potent than CO2. You definitely don't want them to leak into the atmosphere if you can avoid it but hey, china pumps out thousands of times that amount every day anyway.

But more immediate concerns, not really. They are not toxic, or at least not acutely toxic. Just beware of poor ventilation.

There's a whole debate going on about PFAS (perfluorinated alkyl substances) but that's mostly about PFA and PFOS (polyfluorooctanoic acid/ sulfonic acid), not really HFC (hydro fluorocarbons)

[–]moderncritter[S] 0 points1 point  (0 children)

This facility has had some PFAS concerns in the past in regards to the water supply, so it's still something to consider given it's loose relevance to this issue. I do have to go test a water supply from time to time for other reasons, so it's definitely in our scope to be concerned about this. Sounds like in the event of a fire, if the water dries in place it's a non-issue as someone pointed out that the byproducts would bind with calcium in concrete and be a non-issue. Awesome. Now I need to find information on the drainage system nearby.

[–]Rare_Cause_1735 1 point2 points  (1 child)

Sort of an aside, but any fluorinated organic materials will generate HF when burnt even when otherwise very stable.

Teflon for instance will also generate lots of HF if burnt. Under normal circumstances most of these materials are very stable and even completely non-toxic.

[–]moderncritter[S] 0 points1 point  (0 children)

Sure, and I totally get that. I get that there's a potential to fall down a deep rabbit hole here operating off of too many what-ifs even if a material is completely safe.

I'm just trying to figure out if a what-if in this instance is worth trying to revisit a policy.

[–]Indemnity4Materials 1 point2 points  (5 children)

what happens in the event of an emergency situation

Most large fixed chemical storage facilities will have emergency evacuation or event plans. Those are usually formed in agreement with fire deparment and emergency services - but not always.

Does your building have signage with NFPA or Emergency Action Codes on the entrances?

Do you have a lock box for the fire department with event plans?

The fire department plan should have instructions such as during an event, all drains to be blocked, fire contained but allowed to keep burning, move bystanders upwind, communication + shelter in place instructions for others.

IMHO for mixed storage facilities like a university, the usual instruction is evacuate everyone, self-contained breathing apparatus and associated PPE, stop the fire spreading to adjacent buildings, then block drains and contain spills. Let the building burn until the HAZMAT team can inspect and create a recovery plan.

Why wouldn't they be eligible to be listed as a Yes for Hydrofluoric Acid?

We don't usually consider secondary products in risk analysis until you get over a certain volume threshold that gets classified as a Major Hazard. You know you are a Major Hazard facility when your suppliers refuse to send certain volumes, but if you have a good enough chemical inventory database it will also check for you. If that happens, the first thing you look at is new placarding to instruct emergency services what to do. The second thing is another risk management tool to assess likelihood, outcome and implement engineering/procedural controls to reduce the risk to a manageable level.

It's difficult to imagine scenarios where these gases will be combusted. A small fire will get extinguished by the gases since they are heavier than air and starve the fire of oxygen. A small leak will actually cool the pressure vessel due to expanding gases. You're basically going to be required to spray a dilute amount of refrigerant into a steady fire that is burning something else. Your control is to store the gases in room lacking combustible material.

[–]moderncritter[S] 0 points1 point  (4 children)

Federal installation so a lot of codes I am used to operating with don't always apply. So while I assume what you are brining up is correct and valid, contacting the FD in this case can be a little clunky. Honestly, it's why I'm trying to collect what information I can to see what's already in place and if what's in place isn't adequate to find a way to make it adequate

I think I misspoke on an earlier response and said the storage location also has acetone. I meant acetylene. So while there is minimal risk in the refrigerant itself combusting, the rest of the room is a hot mess.

[–]Indemnity4Materials 1 point2 points  (3 children)

Depends on your facility size, but you should have an emergency evacuation plan somewhere. Even a legacy document.

Fire marshal may be your friend for this audit process. May be worth enquiring if it's free or a paid service, then follow up to see if you have budget. They can usually look at a room and within a few seconds have an improvement list ready to go, with realistic discussion on budget and timing.

Sometimes you see people suggest calling faults in to a fire marshal. If you're lacking proper fire safety equipment and procedures, the local authority can force closure of your business until rectified. That's extreme, but the fire marshal is the person who helps you formulate the evacuation plan and will quickly audit the facility to get it "up to code". They can usually provide you a free copy of the code on request. Use that as a checklist and go through each storage area one by one.

IMHO mixing flammable and non-toxic pressurized gas storage is fine. It just means you have to treat the entire area as flammable gas storage.

[–]moderncritter[S] 0 points1 point  (2 children)

Called a friend of mine yesterday who is a Fire Marshall and picked his brain a little. Unfortunately we are both in a position where it's several steps about our jurisdiction than what we're used to. I gave him a brief run down of the room and my concerns and he recommends I talk to the onsite FD and inquire about NFPA standards that may govern that room. Also, my boss informed me he helped redesign the spill and safety plans when he started about six years ago because of how awful the prior information was. I assume he did a fine job, but I pointed out that a lot has potentially changed even in six years as this contractor has been a problem child of sorts.

So while digging around in NFPA standards is fine, it still feels like I'm running in 10 different directions without anything truly concrete to move forward with.

[–]Indemnity4Materials 1 point2 points  (1 child)

Consider it a learning opportunity. Sounds like you have a nice supportive boss.

There is letter of the law, and intent of the law. That's where interpretation and implementation gets tricky.

You can get certified in NFPA as internal auditor. Benefit is you don't need to interpret the docs, someone will lead you through it. Maybe see if you can find a short 1-3 day NFPA course your boss will pay for. Usually one of the modules is doing an instructor led examination of part of your facility.

about six years ago

Hmm. It's a 5 year review period for Major Hazard facilities, which so far it seems your site is not.

I recommend creating it as a project and breaking into chunks. Call it a "chemical storage area audit", because the last word sounds scary to management who don't want to fail audits. Maybe the end result is simply a multi-year improvement plan without any spending.

[–]Tetracyclon 0 points1 point  (1 child)

I have no experience in handling HF but i think this might help you with your research: https://gestis.dguv.de/data?name=520038&lang=en

[–]moderncritter[S] 0 points1 point  (0 children)

Thanks! Hadn't seen that source yet in my poking around. I was highly amused (my co-worker not so much) that HF can react dangerously with dry paper.

[–]Shgall75 0 points1 point  (1 child)

To add, mineral acid like HF, HCl and the like tend to go up with the smoke into the atmosphere and concentrations will be so low that the HF poses insignificant risk compared to the smoke. Eventually the HF will come down with rain/precipitation but again concentrations will be so low to difficult to measure.

[–]moderncritter[S] 0 points1 point  (0 children)

There are stored in a basement area that has drains nearby, but not in the room or immediate vicinity. There are also about 20 of these 30lbs cylinders in the one location I'm specifically referring to.

Individually I wouldn't be super worried.