To two of my favorite colleagues---
Just like lead and silica, this has been an issue for a long time (obviously not to the extreme of lead and silica). I am taxing my brain, but this may be the exact same refinery (probably a different owner back then) that had an issue with the removal of a blind on a large fitting in the alkylation unit. As you may know, the bolting pattern for removal must be followed to be sure not to over torque the fittings. The line had been certified as drained and clean. On the removal of the 6th bolt of 8, the fitting was lose enough to result in a pressurized spray of HF (98% anhydrous). There were two mechanics working on the fitting at chest height. They were both sprayed and each ran immediately in opposite directions in the fog that was formed by the interaction of the anhydrous HF and water vapor in the air. A standby person directed a fire hose on the cloud that was formed. As might be expected the airlines hoses ran out and both men removed their respirators. The suits were permeation resistant as were the gloves and hoods. The HF mists entered the hoods where the airlines were and resulted in immediate chemical burns (erosion) of the neck and ears of both men which is why they ran. It was a miracle that they survived but both were badly scarred.
I wrote a note on this incident
Mansdorf, S.Z., "Anhydrous Hydrofluoric Acid," American Industrial Hygiene Association Journal, 48(7), 1987.
Extreme precautions must be taken with HF at high concentration (fully encapsulating suit with SCBA) and also at concentrations above 5% but less than 25% where there can be delayed burns.
My final war story---..(true story). Worker A on the day shift mixing HF from 20% to 5% put his work gloves (permeation resistant) on the barrel. Worker B on the next shift uses these gloves and goes home. Worker A goes to the emergency room with burns under the finger nails and they call his work. Worker C has already worn the gloves which had a pin hole and were contaminated inside the gloves at the finger tips (one hand only). All three workers had to sustain the shots under the finger nails!
Zack
From: ACS Division of Chemical Health and Safety <DCHAS-L**At_Symbol_Here**PRINCETON.EDU> On Behalf Of Monona Rossol
Sent: Wednesday, October 16, 2019 1:41 To: DCHAS-L**At_Symbol_Here**PRINCETON.EDU
Subject: Re: [DCHAS-L] CSB Releases Update and Animation Detailing the Explosion and Fire at the PES Refinery in Philadelphia, PA
We talked about the better option some years past, and I have that information somewhere in a file. But as long as Armour has the calcium gluconate recommendation on the SDS, that's what I need to go with for now. And my real aim is to get this etch the hell out of the schools until, and unless, there is someone in these art and theater departments that could even be educated enough to use the calcium gluconate intelligently. Then maybe on to a better fix. Monona
-----Original Message-----
From: Alan Hall <oldeddoc**At_Symbol_Here**GMAIL.COM>
To: DCHAS-L <DCHAS-L**At_Symbol_Here**PRINCETON.EDU>
Sent: Wed, Oct 16, 2019 12:52 pm
Subject: Re: [DCHAS-L] CSB Releases Update and Animation Detailing the Explosion and Fire at the PES Refinery in Philadelphia, PA
Monona, my Worthy Adversity (Everyone needs a Worthy Adversary to keep them in check),
We have the same goals, just different ideas about how to achieve them
Ammonium biflouride is very toxic. It used to be marketed as a disinfectant for fish tanks. A kid whose case I consulted on drank the entire undiluted product, and despite all our efforts died. Calcium gluconate is not a bad treatment for HF dermal exposures, but there's a much better option (not currently available in the US, but in at least 40 other countries). Offline, I'd be happy to talk/type to anyone interested, but not on this listserve.
Such a big accident. But I'm writing up yet another HF death for my newsletter and thought it might be interesting to slide down frm 5000 pounds to less than three ounces of a compound that delivers HF on dermal or oral exposure. I'll quote two sections from a longer article in the Journal of Occupational and Environmental Medicine: September 2019 - Volume 61 - Issue 9 - p e394-e395 titled: "What Should OEM Physicians Know About Ammonium Bifluoride?"
A healthy 12-month-old, 9.5 kg, girl played near a table while her mother worked on a glass etching art project. A 3-ounce bottle of consumer Armor Etch (Armour Products, Hawthorne, New Jersey) glass etching cream containing 40% to 70% AB [ammonium bifluoride] fell from the table and spilled on the child's walker tray. Moments later, the mother found the child splashing her hands in the etching cream and touching her mouth. The mother immediately dialed 911. The emergency dispatcher connected to poison control where realization of a potentially life-threatening ingestion prompted dispatch of helicopter transport to the home in order to speed the child directly to a tertiary care pediatric emergency department (ED). The child was believed to have arrived to a pediatric ED within 30 minutes of exposure. She arrived tachycardic, but with otherwise normal vitals, and was noted to be crying but otherwise acting age appropriate. She subsequently received external decontamination with soap and water, oral calcium carbonate, and a topical calcium solution. A mildly depressed ionized calcium level of 0.96 mmol/L (normal range 1.16 to 1.32 mmol/L) was noted, and the patient was started on a calcium gluconate 1 g IV (90 mg elemental calcium, approximately 9 mg/kg dose) infusion. Approximately 3 hours postexposure, and with little warning, the child decompensated into cardiac arrest with torsades de pointes. Pediatric advanced life support (PALS) protocol was initiated, and multiple doses of epinephrine, magnesium sulfate, and calcium gluconate were administered. Despite multiple attempts at defibrillation over 40 minutes, resuscitation efforts were unsuccessful. The child expired approximately 4 hours postexposure.
The article then lists other similar cases and concludes:
Exposure to AB-containing products can result in clinical toxicity that is virtually the same as that of HF. Severe systemic toxicity may result in severe hypocalcemia, ventricular dysrhythmias, or death, even with seemingly minimal amounts of oral and dermal exposure. The apparent misunderstanding that AB is safer than HF may lead to delays in recognition of toxicity and treatment.
I see this product and other almost identical products in art schools regularly. The faculty and students have no idea how toxic it is. There is no calcium gluconate in the place or anyone who would have a clue about what to do with it. Monona
-----Original Message-----
From: DCHAS Membership Chair <membership**At_Symbol_Here**DCHAS.ORG>
To: DCHAS-L <DCHAS-L**At_Symbol_Here**PRINCETON.EDU>
Sent: Wed, Oct 16, 2019 11:48 am
Subject: [DCHAS-L] CSB Releases Update and Animation Detailing the Explosion and Fire at the PES Refinery in Philadelphia, PA
Chemical Safety Board Releases Factual Update and New Animation Detailing the Events of the Massive Explosion and Fire at the PES Refinery in Philadelphia, PA
Philadelphia, PA, October 16, 2019 - Today, the US Chemical Safety Board (CSB) released a factual update into the June 21, 2019, explosion and fire at the Philadelphia Energy Solutions (PES) Refinery in Philadelphia. The factual update notes that a pipe elbow, which had corroded to about half the thickness of a credit card, appears to have ruptured in the refinery's alkylation unit, releasing process fluid that included over 5,000 pounds of hydrofluoric acid, or HF. The leaking process fluid formed a large ground-hugging vapor cloud. Two minutes later, the cloud ignited, causing a massive fire and explosions.
Interim Executive Dr. Kristen Kulinowski said, "Since 2015, the CSB has investigated three major incidents at refineries that utilize HF for alkylation. Incidents in Superior, WI, and Torrance, CA, fortunately did not result in an HF release. That was not the case here in Philadelphia. Though the main tank holding HF was not breached, HF was a component of the process fluid released from the alkylation unit. We are lucky there were no serious injuries or fatalities."
While the CSB's investigation is still ongoing, the factual update notes important details of the incident collected through interviewing witnesses, gathering evidence and ultimately, piecing together the events that led to the explosion:
- The piping was susceptible to corrosion from the hydrofluoric acid that was in the process fluid. The elbow that ruptured corroded faster than the rest of the piping in this part of the process.
- While pipe thickness in this section of the unit was periodically measured to monitor corrosion rates, the thickness of the elbow that failed had not been monitored for corrosion. The piece of piping that failed had a high nickel and copper content. Various industry publications have found that carbon steel with a higher percentage of nickel and copper corrodes at a faster rate than carbon steel with a lower percentage when used in a process with hydrofluoric acid.
- A secondary event at the PES refinery occurred when the V-1 Treater Feed Surge Drum ruptured , which launched a fragment of the vessel weighing 38,000 pounds across the Schuylkill River. Two other large fragments landed within the PES Refinery.
CSB Supervisory Investigator Lauren Grim said, "Corrosion is not a new issue for the CSB. In its prior investigation of a 2012 Chevron Refinery fire we determined that corrosion caused the rupture of a piping component. Similarly, the 2009 Silver Eagle refinery fire was also caused by the failure of piping that had thinned due to corrosion."
The CSB's interim animation details the events which occurred at the PES refinery on June 21 st , view the full animation at
http://www.idevmail.net/message.aspx?d=86&m=2029
During the news conference Interim Executive Kulinowski noted that moving forward the CSB is examining the need for more robust reviews of corrosion mechanisms as well as looking more closely at the use of HF in the refining process.
The CSB is an independent, non-regulatory federal agency whose mission is to drive chemical safety change through independent investigations to protect people and the environment. The agency's board members are appointed by the President and confirmed by the Senate. CSB investigations look into all aspects of chemical incidents, including physical causes such as equipment failure as well as inadequacies in regulations, industry standards, and safety management systems. For more information, contact public**At_Symbol_Here**csb.gov.
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