By on November 7, 2011

Germany’s Autobild continues to bang the drum about HFO-1234yf, an air-conditioning coolant sold by US supplier Honeywell as an “environmentally-friendly” alternative to other refrigerants. Problem is, C02 seems to be not only more environmentally safe, but safer for humans (notably rescue workers) as well…

Though the basic problem is that nobody outside of the manufacturer of the substance has much of an idea of what its real risks are, there are a couple of lines of criticism that researchers want to test.

  • Flammability. Honeywell knew HFO-1234yf is flammable, and initially marketed it mixed with a fire extinguishing substance. That igniion-retarding iodine compound was later implicated in ozone depletion, and Honeywell now simply downplays concerns about flammability.
  • Toxicity: HFO-1234yf breaks down into trifluoroacetic acid, a phytotoxic substance Autobild calls an “insidious poison.” In an experiment undertaken for Autobild, a chemist exposed a pig’s head to ten grams of the substance and “within a half hour, its skin had turned grey and its eyes had become dull and milky.”
  • Alternatives: German automakers abandoned HFO-1234yf in 2007 for these very reasons, but went back on their decision in 2009. Industry-watchers blame lobbying and the automakers’ desire to increase the volume of their orders from Honeywell (which also supplies other systems) for the about-face, although the official reason was that the main alternative (C02) was more expensive. Autobild argues that this is a specious argument, as C02 is a far cheaper refrigerant, and that it amortizes its extra up-front cost after “a few refills.”

Rescue workers are now leading the charge to undertake independent testing of the coolant, which was first produced in 1946. Alex Lechleuthner, Head of the Cologne Fire Brigade’s Department of Emergency Medicine says there are “very high operational and personnel expenses” associated with such tests, but that they independent testing is crucial as “previously known information from the manufacturer could be judged very differently depending on the viewing angle.”

And there’s more than just the possible risk of eye-dulling toxicity for rescue workers: according to one EPA document’s abstract:

Automobile air conditioning HFO-1234yf emissions are predicted to produce concentrations of TFA (trifluoroacetic acid) in Eastern U.S. rainfall at least double the values currently observed from all sources, natural and man-made. Our model predicts peak concentrations in rainfall of 1264 ng L(-1), a level that is 80x lower than the lowest level considered safe for the most sensitive aquatic organisms.

But what kind of world would we live in if C02 emissions were less harmful than their alternatives? Especially if one of those alternatives were proprietarily manufactured by a supplier that could charge $150 per kilo for the stuff? Well, when faced with the Autobild attack, that very supplier Honeywell responded [presentation PDF here], arguing that

The new gas has already been approved for use in the US, Japan and Europe and was recently given the all clear by the German firefighter association Deutscher Feuerwehr Verband (DFV) which said it was convinced it had the same safety standards as R134a. The DFV described the toxicity of R1234yf as low and comparable to R134a and was safe for passengers and emergency services.

The chemical manufacturers point out that HFO1234yf has undergone significant testing for safety and efficacy by independent testing groups, including the SAE International Cooperative Research Program, which comprises leading automakers. The SAE testing found HFO1234yf to offer “superior environmental performance” to CO2 while having “the lowest risk for use in mobile air conditioning systems in meeting environmental and consumer needs.”

Separately the EPA reports [PDF] that the SAE test found that

the risk for excessive HF exposure is less than one ten-thousandth the risk of a highway vehicle fire and one fortieth or less of the risk of a fatality from deployment of an airbag during a vehicle… The highest risk identified for HFO-1234yf is potential consumer exposure to HF from decomposition and ignition, which is of the same order of magnitude of risks of HF from the current most common automotive refrigerant, hydrofluorocarbon collision

Dig around long enough and you’ll find a middle ground in HFO-1234yf analysis, like this one from the Auto Parts Accessories Journal, which identifies the long-term risks of TFA buildup and Honeywell/DuPont’s monopoly on supply (and the resulting high price of the substance) as the two major drawbacks of the coolant. That piece concludes

As people who love good engineering, we admit to being just a bit regretful that the CO2 systems were not at least given a chance to prove themselves. It’s difficult to believe that in terms of total environmental impact, from manufacture, distribution, maintenance and actual use, that CO2 would not have a greatly reduced environmental impact over any complex chemical refrigerant. We’ve just emerged from an era where the poor decisions of major automakers have caused their businesses to collapse. Often those decisions were made on the basis of what was most convenient, rather than what mechanics would recognize instantly as good technologies. Let’s be hopeful that HFO-1234yf turns out to be a good technology, and not just a convenient one.

We had better hope that’s the case, as the forthcoming 2013 GM products will be the first in the US market to use HFO-1234yf, starting next year.

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18 Comments on “German Media Warns Of C02-Substitute “Killer Coolant”...”


  • avatar
    redmondjp

    Great – just what we need, more pressurized, flammable substances underneath the hood. Recently there have been a number of cases of accidents involving refrigerated shipping containers, most likely due to the use of a flammable refrigerant (most likely propane or butane) while the units were serviced in Vietnam:

    http://blogs.ft.com/beyond-brics/2011/11/07/vietnams-exploding-reefers/#axzz1d3j4RmX9

    http://www.msnbc.msn.com/id/45128660/ns/local_news-seattle_wa/

  • avatar
    psarhjinian

    Switching from C02 to CO2 and back looks sloppy, though I can’t tell if this is the source article being quoted, or TTAC.

    Second, well, are we talking about R-134A being replaced?

    • 0 avatar
      redmondjp

      Yes, R-134A is going away – it’s the R12 of this generation:

      http://www.icis.com/Articles/2009/06/12/9224012/chemical-firms-face-the-cold-reality-of-refrigerant.html

      http://www.aa1car.com/library/newac2k.htm

    • 0 avatar
      Twin Cam Turdo

      Refrigerant should also be used in place of coolant as well.

    • 0 avatar
      toplessFC3Sman

      Agreed; plus, why does a large part of the media have a problem with replacing the letter “O” with the number zero in chemical combinations. CO2, H2O, NO & NO2 etc, they all contain the second most abundant (and most reactive) element in our atmosphere. Plus, if it were meant to be a zero, couldn’t we just say C2, N2… there’d be no N-zero, and i don’t imagine H-twenty would be very stable or last very long.

  • avatar
    stuart

    You can bet that whatever the Industry is pushing is NOT the best alternative.

    CO2 hasn’t been used because it needs dramatically higher pressures (e.g. 1kPSI versus 300PSI for R12 or R134A). That’s not “dangerous,” it just means the system costs more.

    IMHO, R12 should’ve been replaced with propane/butane. Yes, it’s flammable, but so was R12 when mixed with refrigeration oil (normal in any A/C system). Plus, propane/butane has 0% ODP, is non-toxic, and works fine in an R12 system (or a suitably altered R134A system).

    stuart

    • 0 avatar
      Patrickj

      Besides, what’s a pound and a half of propane/butane when there’s a can of flat-fix with most of a pound of the same stuff in the trunk and 100 pounds of gasoline in the tank?

  • avatar
    pgcooldad

    What is the flash point of gasoline, -40C (and F)? And we are supposed to be concerned with something in close proximity to our engine that burns at 970C (1778F)?

    Oooohh, I’m scared.

  • avatar
    Felis Concolor

    A new chemical refrigerant or an easily handled, commonly available gas: how long ago did DuPont’s patent on R134a run out?

  • avatar
    shaker

    “HFO-1234yf breaks down into trifluoroacetic acid, a phytotoxic substance Autobild calls an “insidious poison.” In an experiment undertaken for Autobild, a chemist exposed a pig’s head to ten grams of the substance and “within a half hour, its skin had turned grey and its eyes had become dull and milky.”

    What… we’re going to hurt the profitability of an up-standing American company by worrying about the somewhat less appetizing appearance of head cheese? That’s what they make artificial coloring for!

    Bring on the Poison, baby!

  • avatar
    golden2husky

    CO2 was pushed heavily by the Germans, but was found to be unworkable. As pointed out by stuart above, the pressures needed were too high to br practical in a car. Dealing with such high pressures meant that the equipment would be heavy, expensive, and less efficient. Not to mention more trouble prone. The change from 134a has nothing to do with patents or ozone depletion. In fact, there are no plans to stop production of 134a. The driver for switching away from 134a is (I hate to open the trolling can but it is what it is) that 134a has a Global Warming Potential (GWP) of I believe 1400 against the baseline of CO2 which was set at a GWP of 1. 1234yf has a GWP of 4. 134a was successful in not blowing a hole in the ozone, but the buildup in the atmosphere was the reason the Europe took the first hard look at something else. They pushed for CO2 but gave up when the technological hurdles became too great. 1234yf was chosen because its property profile is very very close to 134a. This new refrigerant is classified as mildly flammable in the US. As to the video, I just think of Dateline and GM pickups. ‘Nuff said there. The EU differentiates gases into two categories: highly flammable and non-flammable. That is why 1234yf has to be called highly flammable in Europe. Keep in mind that while good old R-12 and R22 (used in non mobile sources) may not be flammable, when exposed to very high temperatures they break down to highly toxic phosgene gas…

  • avatar
    zamoti

    I feel compelled to ask, how about hydrocarbon based systems? I’ve used them as a replacement in a previous R-12 system with no issues. I have noticed that around the web, anytime someone mentions or asks about hydrocarbon AC recharging (a la RedTEK or Duracool) the common response is to quote out of some fake industry document that says you’ll die in a fiery blaze for using them.
    (Oops, missed that someone mentioned butane already. Oh well.)

  • avatar
    zamoti

    Speak of the devil, there it is! That article uses loaded phrases like “Existing mobile air conditioning systems are not designed to use a hydrocarbon refrigerant that is highly flammable and similar to what supplies the fire in your backyard barbeque,”
    If it were that dangerous then why have people been using it for years in various countries around the world?
    And of course, there’s no financial reason for MACS (the supposed author of that “article”) to support the needs of Honeywell and/or DuPont in recommending that nobody use hydrocarbons for AC refrigerant. Being cheap, readily available and NOT covered by a patent couldn’t possibly have any bearing on the bottom line of these organizations. There’s no financial reason to demonize HC, right? While I don’t see any obvious relationships between MACS, Ward Atkinson or any other parties mentioned in the Fireball paper, I wouldn’t be terribly surprised if one exists.
    However, I don’t like having this sort of evidence that contains no facts, no real evidence or proof of true danger. It’s just a bunch of talking heads using fear-charged language to make strong recommendations. If we are concerned with dying in a ball of fire caused by our cars, then I suppose we should stop using gasoline.

    • 0 avatar
      ptschett

      The sentence you’ve quoted is absolutely true… vehicle engineers do not design air conditioning systems to use hydrocarbon refrigerants. The fact of people using it in mobile applications, even the fact of it providing acceptable refrigeration performance cheaply, still doesn’t make it a good idea. The financial incentive for the MVAC industry is to avoid liability in the case of injury or death resulting from a fire from a leak in a conventional A/C system having had HC refrigerant improperly installed… no need to look for other financial connections.

      The difference between gasoline and HC refrigerant is that the vehicle fuel system (at least on modern vehicles) is designed to be isolated from the passenger compartment to contain and reduce any risk of passenger injury from a fire resulting from a collision; the A/C system is not designed this way, because the engineer expects it to have a practically non-flammable substance like R134a.

    • 0 avatar
      Caboose

      Or stop having A/C in our cars. I mean, that *would* solve this whole concern. Ban air con as “environmentally hostile” which, in turn, is a step towards getting us out of cars and onto utopia-cycles.

  • avatar
    zamoti

    The sentence I quoted is pure rubbish, hence the reason I quoted it. A gas grill runs on propane which ignites at about 870F where most hydrocarbon-based refrigerants designed for automotive use are formulated to have higher auto ignition points. So-called “light hydrocarbons” are claimed to have auto ignition points of well over 1200F! My complaint with the Fireball article is that it’s not using any good data, just scare tactics.
    Also, you state that r134a is “practically” non-flammable. Well, that may be true, but the PAG or ester oil that the system requires to function is not. For both R134a and hydrocarbon, a VERY high temperature condition (greater than 900F) must be present and also in both cases most systems will contain not more than maybe 18-20 OZ of the airborne gas (or aerosolized oil). In both cases that may at best sustain a 4 second flame in the engine compartment.
    The notion that the auto refrigerant could enter the passenger compartment is the same regardless of content–in neither situation good, but also unlikely. An accident serious enough to crush the supply lines at the firewall and permit the gas into the passenger compartment would be pretty awful and possibly kill the occupants before the refrigerant of choice had a chance. If there were a slow leak, most HC refrigerants contain mercaptin (the smelly stuff in propane), so at least you’d know there is a leak. If R134a were to leak, you would be unlikely to know unless you’re familiar with the subtle “aroma” (smells minty to me).
    Regarding fuel safety, sure the gasoline isn’t routed into the passenger compartment that’s true. But if there is a leak and it pools underneath the vehicle and ignites, you’ve got quite a dangerous condition. At least the HC would blow away if there were no suitable ignition source. The gas may evaporate quickly on a hot day but otherwise it will be under the car for a while.
    My point is that rather than going for yet another expensive chemical of unknown toxicity, why not take the opportunity to make a real change? This game will have to be played yet again when a patent runs out and other people will have the same discussions. Why not find a way to make hydrocarbons safe by designing a system for them? The choice is to spend a lot of time/money to re-engineer systems for a new chemical and get it adopted or to modify those same systems to safely use a cheap and abundant resource–one that’s not subject to irritating expiring patents.


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