“HF Release Hazards” by George Harpole, Ph.D.


In 2016, TRAA Science Advisory Panel member Dr. George Harpole wrote the seminal article on the equivalent behavior of HF and MHF. Since then, the conclusions of his article has been validated by two of the world’s leading experts on the issue and by the Technical Staff the South Coast AQMD.

In this presentation, HF Release Hazards,” Dr. Harpole, describes the terrifying consequences of a worse-case HF release from the Torrance or Valero refineries. See the presentation by clicking here.

The maps below summarize the results of Dr. Harpole’s analysis. (Click on each to enlarge.)

Consequences of a Worst-Case HF Release at the Torrance Refinery
Consequences of a Worst-Case HF Release at the Valero Refinery

The TRAA Science Advisory Panel Blog

This blog is a collection of curated, select posts comprising the most compelling current and past pieces on efforts to eliminate a potentially catastrophic release of hydrogen fluoride (HF) from the Torrance and Valero refineries in the South Bay of Southern California, as well as from HF refineries across the nation. The blog also presents articles by TRAA Science Advisory Panel members that reveal and refute the false assertions of HF refineries. A list of blog posts appears in the right-hand column of every blog page.

TRAA Science Advisory Panel

1986 Hydrofluoric Acid Release Test

Video of the 1986 “Goldfish” Release Test of hydrofluoric acid (HF), one of the world’s most dangerous industrial chemicals, shows the formation and spread of a ground-hugging toxic cloud. The test, carried out by Lawrence Livermore National Laboratory research scientist Dr. Ronald R. Koopman, simulated the accidental release of superheated HF from a small rupture in the bottom of an alkylation-unit settler tank. The video shows a test where 8,300 lbs. of HF were released within 2 minutes.

Although the test was carefully designed and constructed to catch and weigh the amount of HF that fell to the ground, to the great surprise of the researchers, 100% of the HF became airborne in a dense, ground-hugging cloud. None fell to the ground. Two miles downwind, the HF cloud had more than twice the lethal concentration. Consider that each of the two settler tanks at the Torrance Refinery holds 50,000 lbs. of HF — six times more than the 1986 “Goldfish” Release Test.

Compare these “Goldfish” test results to the large-scale accidental release of 84,00 lbs. of sulfuric acid at the Tesoro Refinery in Martinez, California, on February 12, 2014. In contrast to superheated HF, sulfuric acid used in refineries is highly subcooled. There was no formation of an aerosol cloud. All the acid fell to the ground, and there were no offsite consequences.

While the Torrance and Wilmington Valero refineries use Modified Hydrofluoric Acid (MHF) with 6-10% sulfolane to reduce vapor pressure and hence the amount of superheat, the amount of sulfolane is far too little to prevent a toxic cloud, a fact that has been confirmed by both the TRAA Science Advisory Panel and the SCAQMD Technical Staff.

Besides sulfuric acid, which has long been used at Chevron’s El Segundo refinery, other modern alkylation catalysts are now commercially available that are vastly safer than HF. A third U.S. HF refinery has just announced it is converting to one.

Click the image above to watch the video and click the title below to read the 1988 Los Angeles Times article on the test:
Experts Warn of Lethal Risk Posed by Acid in L.A. Refineries

TRAA Announces Campaign Urging Governor Gavin Newsom To Request an Investigation of the Torrance Refining Company and Wilmington’s Valero Refinery

The Campaign

Copy of the letter to Governor Gavin Newsom being delivered to the Torrance Refining Company at 8:50.a.m. on Tuesday, February 18, 2020, the precise time of the 5th Anniversary of the February 18, 2015 Torrance Refinery Explosion.

On the five-year anniversary of the Torrance refinery explosion, the Torrance Refinery Action Alliance (TRAA)  announced a campaign urging Governor Gavin Newsom to request Atty. Gen. Xavier Becerra’s office to investigate — based on newly available irrefutable evidence — the lack of basis for two legal processes that allow the Torrance Refining Company and Wilmington’s Valero Refinery to use massive amounts of hydrogen fluoride that imperil the surrounding communities. An investigation is the essential precursor to a lawsuit by the State Attorney General to ban the use of HF in the refineries.

The campaign was kicked off with the delivery of the letter below from the six-member TRAA Science Advisory Panel  to  Governor Gavin Newsom on Tuesday, February 18, 2020 — the 5th Anniversary of the February 18, 2015 Torrance Refinery Explosion. It will continue over the next several months with TRAA enlisting elected officials of the affected region, city and neighborhood councils, community organizations, and members of the community to add their voices to call for an investigation. TRAA will continue to inform the public of the danger posed by the refineries and the deceptive information and science that they continue to disseminate. The TRAA Science Advisory Panel will stand by to assist Atty. Gen. Xavier Becerra’s Staff in the investigation.

Background and Rationale

The full realization of the hazard of hydrogen fluoride (HF) as an alkylation catalyst in refineries happened in the 1986 Nevada HF release tests conducted for Amoco by Lawrence Livermore National Laboratory under the direction of Dr. Ronald Koopman. The results surprised and shocked the engineering community — 100% of the HF liquid released under refinery conditions formed a ground-hugging cloud of aerosol and vapor. Contrary to what was anticipated, none fell to the ground. Watch Dr. Koopman’s illuminating presentation to the AQMD Refinery Committee.

The refineries’ primary response was an additive they relentlessly and falsely claim results in the majority of an HF release falling to the ground, in spite of the fact that the additive has to be kept at such a low level it is ineffective.

Over the last three decades, in a David-and-Goliath struggle between the innovation of converting to a vastly safer alkylation catalyst and the South Bay refineries’ clinging to the status quo — hoping a calamitous event beyond their control won’t release their store of HF into the community — the refineries have won at every turn: 1) the 1989 Walker Initiative, 2) the 1990 Torrance lawsuit settled in a consent decree allowing the Torrance refinery to use HF, 3) the original 1991 AQMD 1410 Rule overturned on a clerical error, 4) the AQMD/Ultramar MOU allowing Valero to use HF, 5) two bills in the State Assembly that died in committee, and 6) the recent collapse of the second AQMD Rule 1410.

Innovation at loggerheads with the status quo is a subject of the celebrated book Men, Machines, and Modern Times by Elting Morrison (1909–1995), renowned Professor of Science and Technology at MIT. The book, based on a series of famous lectures Morrison gave at Caltech, sets out a roadmap for progress illustrated by a case study of an innovation around 1900 that greatly increased the accuracy of guns on U.S. Navy warships and the Navy’s opposition to it. The innovation/status-quo deadlock was broken in favor of innovation only when the issue was elevated to a higher level of authority, Theodore Roosevelt, the President of the United States at the time. TRAA won’t be elevating the HF issue to the current (45th) holder of the office of President. Instead, TRAA is elevating the issue to the informed leadership of Governor Gavin Newsom and Atty. Gen. Xavier Becerra.

The Letter to Governor Newsom


February 18, 2020

Governor Gavin Newsom
1303 10th Street, Suite 1173
Sacramento, CA 95814

Dear Governor Newsom:

The Torrance Refinery Action Alliance (TRAA) applauds your leadership in asking Atty. Gen. Xavier Becerra’s office to investigate whether California’s oil and gas suppliers are involved in price-fixing or other unfair practices, as reported in the Los Angeles Times.

There is, however, a far graver concern that needs to be investigated. On this five-year anniversary of the Torrance refinery explosion, we urge you to request an investigation of how, over the last three decades, two refineries in Southern California’s South Bay — the Torrance Refining Company and Valero in Wilmington — have been allowed to use massive quantities of hydrogen fluoride (HF), one of the world’s most dangerous industrial chemicals.

Continue reading . . . 

TRAA Announces Press Conference & Community Call To Action on 2/15/20 for the 5th Anniversary of the Torrance Refinery Explosion

5th Anniversary of the February 2015 Torrance Refinery Explosion:
Press Conference & Call to Action

Torrance Refinery Explosion 2015

Saturday, February 15, 2020
9:00 –10:00 a.m.

Doubletree Hotel
21333 Hawthorne Blvd., Torrance, California

Click image to see full-size agenda

The TORRANCE REFINERY ACTION ALLIANCE (TRAA) announces a Press Conference and a Community Call To Action for the 5th anniversary of the Torrance Refinery explosion. The event at the Doubletree Hotel in Torrance on Saturday, February 15, 2020 from 9:00 to 10:00 a.m., will include speakers, short TRAA-produced videos, and an announcement of a major new campaign to mandate that the Torrance Refining Company and Valero in Wilmington — the only two refineries in California that use HF — to convert to one of the modern, vastly safer processes.

Coffee, Tea, Bagels, and Pastries Provided

Update: Press coverage and videos of February 15 event have now been posted on the TRAA Website. Watch by clicking here.

TRAA Video – Invited Speaker Daniel Horowitz’ Speech at the February 15, 2020 Press Conference & Community Call To Action


Daniel Horowitz, Ph.D. — organic chemist and former Managing Director of the U.S. Chemical Safety Board

Click the image above (or here) to watch Dr..Daniel Horowitz’ keynote speech at the TRAA Press Conference & Community Call To Action marking the 5th anniversary of the Torrance Refinery explosion. Dr..Daniel Horowitz’ speech was delivered from his home in Virginia via recorded video. 

The event, held at the Doubletree Hotel in Torrance on Saturday, February 15, 2020, included speakers, short TRAA-produced videos, and an announcement of a major new campaign to mandate that the Torrance Refining Company and Valero in Wilmington convert to one of the modern, vastly safer processes.

Click here to see the event agenda with links to the videos shown.

Dr. Horowitz recently wrote the compelling opinion piece for The New York Times:
This Chemical Kills. Why Aren’t Regulators Banning It?

“This Chemical Kills. Why Aren’t Regulators Banning It?” – New York Times Opinion Piece

by Daniel Horowitz, an organic chemist and former managing director of the U.S. Chemical Safety Board.

A fiery refinery blast in Philadelphia could be just the beginning.

Last month’s spectacular explosions at a large Philadelphia oil refinery complex injured five workers, terrorized city residents and drove up gasoline prices. But the impact could have been vastly worse had the explosions triggered a release from the refinery’s huge inventory of toxic hydrogen fluoride — up to 420,000 pounds’ worth, according to information the company filed with the Environmental Protection Agency in 2017. That disaster, had it occurred amid the chaos on the morning of June 21, would have imperiled hundreds of thousands of people living within a few miles of the plant. …

Continue reading on the New York Times website by clicking:
This Chemical Kills. Why Aren’t Regulators Banning It?

“Air board kills regulation of dangerous refinery acid in favor of oil industry plan” ‑ Los Angeles Times

Tony Barboza
Friday, September 6, 2019

Michael Owen Baker / Los Angeles Times

Steve Goldsmith of the Torrance Refinery Action Alliance said air board members “caved into the pressure by the oil industry” with a decision that “leaves South L.A. County residents exposed to catastrophic danger.”

Air quality regulators on Friday killed a years-long push for stronger regulation of a dangerous acid used at two South Bay refineries that has frightened many neighbors, voting instead to accept a voluntary, oil industry pledge to enhance safety measures.

The decision by the South Coast Air Quality Management District governing board came just one week after the two refineries, in Torrance and Wilmington, offered a way to avoid tougher restrictions. They sent letters offering to install improved safety systems in the coming years if regulators ended their pursuit of a rule or agreement to reduce the risk of a catastrophic release of modified hydrofluoric acid, also referred to as MHF.

Continue reading by clicking:
“Air board kills regulation of dangerous refinery acid in favor of oil industry plan”

“Fire and Explosions at Philadelphia Energy Solutions Refinery Hydrofluoric Acid Alkylation Unit” – U.S. Chemical Safety Board

On Friday, June 21, 2019 at 4:22 a.m., a third and the largest explosion occurred when the V‑1 Treater Feed Surge Drum violently ruptured. A fragment of the vessel weighing approximately 19 tons flew across the Schuylkill River. It was launched at the speed of an Indy 500 race car, but weighed 24 times more than one. Click the image to watch a dramatic video of the explosion, which, at t = 4 seconds, shows the fragment being hurled through the sky.

PES estimated that 5,239 pounds of hydrofluoric acid released from piping and equipment during the incident. It estimated that 1,968 pounds of the released hydrofluoric acid [38%] was contained by water spray within the unit and was processed in the refinery wastewater treatment plant, and that 3,271 pounds of hydrofluoric acid [63%] released to the atmosphere and was not contained by water spray.

Factual Update  — October 16, 2019 — Incident Summary

On June 21, 2019, a major process loss of containment caused a fire and explosions at the Philadelphia Energy Solutions Refining and Marketing LLC (PES) Refinery in Philadelphia, Pennsylvania.

Continue reading by clicking:
Fire and Explosions at Philadelphia Energy Solutions Refinery Hydrofluoric Acid Alkylation Unit

“Faulty, old pipe caused PES refinery explosion, sending a bus-size piece of debris flying across Schuylkill” – NPR

by Susan Phillips

Click the image to watch CSB’s two-minute animation. The federal Chemical Safety Board reported that the Philadelphia Energy Solutions (PES) refinery explosion in Philadelphia on Friday, June 21, 2019 released an estimated 5,239 pounds of highly toxic hydrogen fluoride. A 19-ton piece of hurled debris — about the same weight of a fully loaded Greyhound bus — landed almost a half mile away across the Schuylkill River.

PES estimated that 5,239 pounds of hydrofluoric acid released
from piping and equipment during the incident. . . . Dr. Ron Koopman, Lawrence Livermore National Laboratory senior scientist (retired),  said the HF that was released at PES was likely dispersed by the intense explosion. “The explosion is nasty — it could kill people, but it’s not the principal hazard. It’s the toxic gas [HF] that could continue to be toxic downwind. Sometimes, the explosion and the fire is your friend.”

A piece of pipe, long overdue for replacement, spilled highly combustible hydrocarbons mixed with a dangerous chemical and caused the devastating explosions and fire at the Philadelphia Energy Solutions refinery in the early morning of June 21. One explosion sent a 38,000-pound vessel — about the same weight as a firetruck — across the Schuylkill River, where it landed on the waterway’s banks, near the company’s tank farm. PES estimates the incident released about 676,000 pounds of hydrocarbons, most of it — about 608,000 pounds — burned in the fire and explosions.

“PES had a policy that any pipe thinner than 0.18 inch would be replaced. The Chemical Safety Board’s investigation found that the ruptured pipe was only 0.012 inch thick [the thickness of three sheets of copy paper] — less than a tenth of the thickness that would have triggered a replacement.”

Those are some of the details in a report released Wednesday by the federal Chemical Safety and Hazard Investigation Board. The report also says an estimated 3,271 pounds of the dangerous hydrofluoric acid was released into the atmosphere, while the refinery’s water spray system contained about 1,968 pounds of HF. The release of the chemical did not cause any injuries. City officials had previously reported they did not detect any HF escaping.

Continue reading by clicking:
Faulty, old pipe caused PES refinery explosion, sending a bus-size piece of debris flying across Schuylkill

“Refinery Explosions Raise New Warnings About Deadly Chemical” – NPR

by Susan Phillips

Click image to watch a terrifying video of the Philadelphia Energy Solutions refinery explosion on Friday, June 21, 2019. Note object being hurled from the explosion to the right. With the PES refinery closing, now Torrance CA has the infamous distinction of having the densest population around an HF refinery. The video is from 6abc/WPVI−TV Action News in Philadelphia.

“How many times do we try this before we actually get a release that kills 1,000 people? . . . People should never have been allowed to live this close to these refineries. It’s just unconscionable to have allowed that to happen.”
~ Dr. Ron Koopman, conductor of the 1986 “Goldfish” hydrogen fluoride release tests in the Nevada desert

In the predawn hours of June 21, explosions at the Philadelphia Energy Solutions refinery in South Philadelphia shook houses, sent fireballs into the air and woke up nearby residents.

“Three loud explosions, one after the other, boom, boom boom!” says David Masur, who lives about two miles from the plant and has two young kids. “It’s a little nerve-wracking.”

Masur watched as the refinery spewed black smoke above the city, easily visible from his home. But what he didn’t know at the time was just how close he and his family came to getting exposed to hydrogen fluoride, one of the deadliest chemicals used by refiners and other industrial manufacturers.

Continue reading by clicking:
Refinery Explosions Raise New Warnings About Deadly Chemical

Listen to the companion interview with NPR’s Susan Phillips by clicking here

Living Near Oil Production Is Deadly. Why Don’t California Lawmakers Care?

“The state may be phasing out gas-powered cars, but it’s still legal to put an oil well right next to an elementary school.”

A 4-minute Opinion Video for the New York Times by Josiah Edwards, who is a climate organizer in Carson, California, and documentary filmmaker, Matty Neikrug.

Also, see in The Los Angeles Times:

Op-Ed: Where are drilling protections for California residents?

By Michael Freeman and Colin O’Brien
Friday, February 26, 2021

Michael Freeman and Colin O’Brien are environmental attorneys working on oil and gas issues at Earthjustice in Colorado and California, respectively.

A Rule 1410 Performance Standard to Protect the Community

TRAABy the Torrance Refinery Action Alliance Science Advisory Panel

A Performance Standard Must Be Designed to Protect the Community, Not Tailored to What the Refineries Are Able to Meet with Enhanced Mitigation

Executive Summary

A Performance Standard, with hydrogen fluoride (HF) phase-out if it cannot be met, has become the central approach adopted by the South Coast Air Quality Management District Staff for either a regulation or a memorandum of understanding (MOU) with Valero in Wilmington and PBF’s Torrance Refining Company, the only two refineries in California that use HF. SCAQMD welcomes community input, and the TRAA Science Advisory Panel of six South Bay scientists and engineers is providing expert professional advice with A Rule 1410 Performance Standard to Protect the Community. Its three parts are: 1) A Benchmark, which must be met to ensure the community remains safe if a major HF release occurs, 2) Release Scenarios, which could be caused by Earthquakes, Accidents, or Terrorists (EAT), and 3) Ground rules for the refineries’ attempt to Demonstrate by analysis, modeling, and testing that they can meet the Benchmark. Interim measures are also specified to increase community protection until HF is phased out.

The Performance Standard is summarized below and given with full rationales in the following sections.

    The general population, including susceptible individuals, shall not experience “irreversible or other serious, long-lasting adverse health effects, or an impaired ability to escape,” as proscribed by Acute Exposure Guideline Level 2 (AEGL 2). All points from the refineries’ fenceline and beyond, shall not exceed any of the AEGL 2 threshold concentrations for exposure durations of 10 minutes, 30 minutes, 60 minutes, 4 hours, and 8 hours.
    A rupture of any of the refinery’s HF Containment Subsystems releasing the entire amount of HF: 1) in any duration from 5 seconds to 4 hours or, 2) from the break of any size subsystem pipe.
    Only passive mitigation measures, defined by the EPA as “equipment, devices, or technologies that function without human, mechanical, or other energy input,” shall be allowed in the demonstration attempt. In accordance with the EPA’s RMP Guidance for Offsite Consequence Analysis for worst-case releases, active mitigation measures such as water spray shall not be allowed because they can be deactivated by the same calamitous event that causes the rupture.

    No proprietary data shall be allowed in the analysis or modeling. If after six months the refineries can show they have a creditable plan that can meet the Benchmark, three years shall be allowed for the refineries to carry out a full-scale experimental demonstration to validate their analysis and modeling. Failure of the modeling or experimental verification shall mean all HF shall be removed from the refinery grounds within four years from the initial approval of Rule 1410.
  1. To protect the public from HF releases in the interim, the refineries shall enhance their mitigation system as much as feasible as determined by the SCAQMD.
  2. The refineries shall have a SCAQMD-approved emergency plan in place within six months, and then institute it, at their expense, to remedy the shocking lack of medicine and facilities to treat victims of a major HF release.
  3. The refineries shall certify within six months, to the satisfaction of SCAQMD, that their operations are safe from a cyber-attack.
  4. The refineries shall demonstrate within six months that they have financial resources in place — through liability insurance, bonds, or corporate resources — to cover claims against them from 15,000 deaths (the estimated fatalities in the 1987 Bhopal, India catastrophe, which released a similar amount of toxic chemical found in one Torrance refinery settler tank). Bankruptcy is not an acceptable response.

Continue reading . . . 

TRAA Community Response at the June 22 SCAQMD Refinery Committee Meeting

TRAAPresented by TRAA Member Cliff Heise:

We’re here because two refineries in the South Bay use massive quantities of one of the world’s most dangerous industrial chemicals, “hydrogen fluoride.” An additive touted by refineries for decades as the community’s primary safeguard has been unmasked as completely ineffective. As Congressmember Ted Lieu has stated, the community has been “hoodwinked.” Elimination of hydrogen fluoride is the only measure that will ensure community safety.

Performance Standards

The AQMD has adopted a Performance Standard approach. If the refineries fail to demonstrate that they can protect the public from a major release, then hydrogen fluoride must be phased out.

A Performance Standard Must Be Designed to Protect the Community, Not Tailored to What the Refineries Are Able to Meet with Enhanced Mitigation
We respectfully implore the Refinery Committee to give direction to Staff to create a Performance Standard to protect the community.

Continue reading “TRAA Community Response at the June 22 SCAQMD Refinery Committee Meeting”

“HF and MHF – Equivalent Ground Hugging Fog Hazards” by George Harpole, Ph.D.

GeorgeHarpoleTRAA Science Advisory Panel member Dr. George Harpoles’ seminal article on the equivalent behavior of HF and MHF in a catastrophic accidental release concludes with the paragraph:

“Dangerous concentrations of HF could persist miles away from the refinery. The typical layers-of-protection approach (barriers, water sprays, pumps to spare vessels, etc.) may save lives for certain smaller leaks. However, a more catastrophic rupture, simultaneous with failure or bypass of the protection systems, is easy to imagine – in large earthquakes, accidental or deliberate explosions, or fire. Moreover, the delivery trucks traveling to the refinery carry MHF in similar quantities, and are even more vulnerable. They have no spare vessel or water-spray system. They are exposed to the public and subject to crashes. There is clear danger to the community in the use of MHF at refineries in urban settings.”

Read the full article by clicking:
HF and MHF – Equivalent Ground Hugging Fog Hazards (Wonkish)

Two of the World’s Leading HF Experts Answer the $64,000 Question: “Does MHF behave the same as HF?”

Some Thoughts on the South Coast AQMD Rule 1410 Refinery Committee Meeting by the TRAA Science Advisory Panel

Several members of the TRAA Science Advisory Panel attended the AQMD Refinery Committee Meeting in Wilmington CA on September 22, 2018. This was a particularly important meeting because two of the world’s leading experts on the dangers of hydrogen-fluoride use in refineries gave presentations: Dr. Ronald Koopman on the large-scale HF release experiments — The Goldfish Tests — he conducted in the Nevada desert in 1987, and John Cornwell of Quest Consultants, conductor of the only field-scale MHF release tests in Quest’s Oklahoma facility in 1993.

The high point of the meeting was when these two experts answered the $64,000 Question: “Would 6-wt-% MHF act the same as pure HF?

Dr. Koopman expressed his profound skepticism that the additive would do much good — “I would guess that would be a very small effect.” (Watch: https://youtu.be/qwo08BtEQuM?t=7460)

John Cornwell emphasized the small amount of additive is unlikely to have much of an effect, and there’s no data to show that it does. He pointed out that physical chemists use mole percent (molecule count), and states, “If MHF is 6% by weight and 1% by mole, and you are going to modify the vapor pressure or modify the characteristics of the fluid, you’ve got to have some data to show that’s true” (Watch: https://youtu.be/qwo08BtEQuM?t=8874).

This publicly-stated testimony by the world’s two leading experts expressed a high degree of skepticism of the refineries’ safety assertions for MHF. They are in line with the TRAA Science Advisory Panel and the SCAQMD Staff. MHF and HF behave the same and both form ground-hugging toxic clouds.

“ToRC Misinformation in Postings about MHF” by George Harpole, Ph.D.

GeorgeHarpoleTorrance Refining Company’s (ToRC) MHF website postings deliberately spread misinformation that is not only misleading, but also dangerous in that it conveys a false sense of safety with MHF.

In one of ToRC’s March 30, 2017 “Setting the Record Straight” videos, Tim Shepperd, lobbyist with HF Alkylation Consultants, presents “Why MHF Works.” He features a false analogy between water (a compound) and MHF (a mixture). Fifth-grade science standards in California include: a) that properties of a chemical compound are entirely different from those of its constituents, while b) properties of a mixture retain the properties of its constituents. Water, which is a safe compound of oxygen and hydrogen, is in no way analogous to MHF, which is an unsafe, highly toxic, volatile mixture of sulfolane and hydrofluoric acid.
Continue reading ““ToRC Misinformation in Postings about MHF” by George Harpole, Ph.D.”

Five Points TRAA Science Advisory Panel Members Would Have Liked to Make at the Rule 1410 Refinery Committee Meeting

TRAAThe one-minute allowed each public speaker at the SCAQMD Rule 1410 Refinery Committee Meeting on September 22, 2018 wasn’t enough for TRAA Science Panel members to make substantial contributions to the meeting’s discussion. Here are five points the TRAA Science Panel members would have liked to make:
Continue reading “Five Points TRAA Science Advisory Panel Members Would Have Liked to Make at the Rule 1410 Refinery Committee Meeting”

“HF Boil-Off from an MHF Spill on Hot Highway Pavement” by Jim Eninger, Ph.D.

Jim Eninger“A major trucking spill of MHF onto hot highway pavement could vaporize thousands of pounds of hydrofluoric acid — more than twice the largest release of the 1986 Goldfish test.”

Boil-off is one of several paths that highly toxic Hydrogen Fluoride (HF) can go airborne into the community. In the past, the primary focus has been on the release of superheated HF and Modified Hydrofluoric Acid (MHF) from oil refineries’ settler tanks, because flash atomization causes 100% to form a visible, ground-hugging, highly toxic cloud (see: Flash Atomization of HF and MHF).

Mobil’s original intent to suppress flash atomization was to add sufficient additive that the MHF was subcooled, that is, the boiling point is above the operating temperature. (As we now know, an additive level sufficient for subcooling is incompatible with the alkylation process.) However, even subcooled MHF spraying under high pressure from a rupture of a tank will break up into small droplets. While not nearly as fine as droplets from flash atomization, they nevertheless evaporate. Evaluation of how much was the objective of the large-scale MHF release tests conducted by Quest Consultants in 1993 (see: Superheated MHF Excluded from the Only Large-Scale Test Series).

Another significant path for MHF to go airborne is boil-off. This occurs, for example, if the rupture is in the top section of a settler tank. At the release of pressure, the superheated hydrocarbons (typically isobutane with a boiling point of 11F) and MHF (boiling point of  71F at 6-wt% sulfolane) are highly out of thermodynamic equilibrium at the tank process temperature of 106F. The tank’s contents will boil violently and much will be expelled from the tank before plunging in temperature to the low boiling point of the remaining liquid. The volatile hydrocarbons and MHF will then boil off at a rate governed by the transfer of heat from the environment through the tank walls to the cold liquid.

A second example of boil-off is the primary focus of this post as well as of item III from the post Five Points TRAA Science Advisory Panel Members Would Have Liked to Make at the Rule 1410 Refinery Committee Meeting.  Except for a 15 wt% sulfolane additive used for transportation, which increases the boiling point of HF modestly from 67F to 76F, MHF trucks have none of the other refinery-based mitigation systems. With an air temperature of 87F, highway surfaces can reach 143F. The stored solar heat in a hot highway will vaporize MHF. In addition, the direct heat from the sun over the duration of the spill will add significantly to the boil-off.

Consider a massive spill from a truck transporting 33,000 lbs of 15 wt% MHF (boiling point 76F) onto a sun-baked highway pavement at 140F. The MHF immediately cools the surface of the pavement to its boiling point of 76F. The temperature response of the pavement with typical parameters is shown in Figure 1.

MHF Hot-Highway-Pavement Boiling-Off Transient Temperature Profiles of Pavement
Figure 1 – Temperature profiles in 11-inch-thick pavement initially at 140F with an 15 wt-% MHF spill (boiling point = 76F)

Continue reading ““HF Boil-Off from an MHF Spill on Hot Highway Pavement” by Jim Eninger, Ph.D.”

“Superheated MHF Excluded from the Only Large-Scale Test Series” by Jim Eninger, Ph.D.

MHF Vapor Pressure vs Temperature at various levels of sulfolane. Vapor-pressure curves by Dr. George Harpole are anchored to data from U.S. Patent 5,654,251. Other publicly available data from Material Safety Data Sheets (MSDS) and European Patent EP0796657B1 are shown on the graph. (Click graph for full view.)

On the heels of the 1986 “Goldfish” Release Test of hydrofluoric acid (HF), Mobil engineers sought some method to prevent the HF from forming a ground-hugging toxic cloud. In his illuminating presentation at the September 22, 2018 AQMD Refinery Committee Meeting (Watch: https://youtu.be/qwo08BtEQuM?t=5108), Goldfish Test Principal Investigator Dr. Ronald Koopman stated that the affect of the HF release “was much larger than we had expected and the downwind distance was further than we had expected” and “we found that the HF that was released all flashed into an aerosol and a vapor and so there was nothing that ended up on the collection pan or in that tank — nothing was captured — and that was a great surprise to us.”

In their attempt to do something to prevent the formation of a toxic cloud, in the early 1990s, Mobil engineers settled on the additive sulfolane to suppress the vapor pressure and move HF fluid properties into the subcooled regime, where flash atomization will not occur.  But, as seen in the graph above, at least 45% sulfolane by weight (45 wt%) is needed to achieve subcooled HF at a typical settler-tank temperature of 105F. Although they did not know it at the time,  this level of sulfolane is far higher than the alkylation process can tolerate and still function. In refineries that use MHF, the sulfolane level is as low as 6 wt%. That’s 1 mole% or one molecule of sulfolane for every 100 molecules of HF.
Continue reading ““Superheated MHF Excluded from the Only Large-Scale Test Series” by Jim Eninger, Ph.D.”

“Flash Atomization of HF and MHF” by George Harpole, Ph.D.

Liquid flowing out of a pressurized tank will flash atomize if the liquid superheat (temperature difference above the boiling point) is large enough. Fthenakis claimed, “The critical superheat typically ranges from 5 to 15K [9 to 27°F] for many fluids of interest.”1 Flash atomization is the shattering of liquid jets into very small (often submicron) aerosol droplets due to the rapid vapor bubble growth of boiling. By contrast, subcooled (below the boiling point) liquid jets will still atomize when exiting an orifice, but then to droplets that are orders of magnitude larger, hundreds of microns in diameter.

Read the full article by clicking:
Flash Atomization of HF and MHF (Wonkish)

“Is a phase-out of dangerous chemical used at Torrance, Wilmington refineries getting closer?” – Daily Breeze

The twisted remains of the Torrance refinery in the wake of the 2015 explosion that caused the plant to shut down for months causing gas prices to spike. (02/18/15 Photo by Brad Graverson/The Daily Breeze)

“Activists hope they are edging nearer a long-sought ban on a highly-toxic chemical used at refineries in Torrance and Wilmington after the local pollution watchdog for the first time set a deadline — May 19 — for the industry to produce additional safety information about what’s called modified hydrofluoric acid.”

Read Nick Green’s 9/25/2018 article in the Daily Breeze by clicking:

“Torrance group launches public outreach over refinery dangers” – Daily Breeze

TRAA !00,000 Door Hanger Campaign
Volunteers with the Torrance Refinery Action Alliance are knocking on doors and talking to Torrance residents about the dangers of hydrofluoric acid being used at the refinery. Volunteer Steve Goldsmith scans homes along 188th St. in Torrance to see who may be home so he can share dangers of living near the refinery using the acid. Photo by Robert Casillas, Daily Breeze/SCNG

“In a weeklong public safety awareness blitz, local activists are distributing 100,000 door hangers to South Bay homes surrounding the Torrance refinery, the same number they say could be affected by a catastrophic leak of a toxic chemical the plant uses to refine gasoline. . . .”

Read Nick Green’s 11/1/2017 article in the Daily Breeze by clicking:

The TRAA Door Hanger


message on the back . . .

One of the world’s most dangerous industrial chemicals, hydrofluoric acid (HF) is used in massive quantities in only two California refineries, Torrance and Valero, Wilmington. The refineries claim a chemical they add to the HF makes it safe. But at only one or two additive molecules per hundred, it’s too little to make a difference. “Modified” hydrofluoric acid (MHF) is just as deadly as HF. If released, it forms a ground-hugging cloud that can drift for miles, causing death and injury. The refineries’ other mitigation measures, like water sprays and barriers, are also ineffective. Mass casualties can result from an MHF release — wind direction determines who dies.

For decades, the South Bay has battled the refineries’ all-too-successful campaign to keep using HF rather than converting to a much safer process, such as is used at Chevron in El Segundo and the other California refineries. Following the massive Torrance refinery explosion in February 2015, which nearly released 50,000 lb of MHF, investigations by TRAA and the U.S. Chemical Safety Board uncovered the true threat MHF poses. Now, the South Coast Air Quality Management District (SCAQMD) is considering Rule 1410 to require MHF/HF replacement with a safer alternative at both refineries. But industry is fighting back with well-financed campaigns. The next few months are critical! 

Learn more by taking the full scroll of the TRAA Science Advisory Panel Blog by clicking the “Home” button above or click here:

“Who is telling the truth about the Torrance refinery?” – TRAA Science Advisory Panel opinion piece in the Daily Breeze

Daily Breeze Opinion Piece by the TRAA Science Advisory Panel

DailyBreezeRefineryImageIn his Daily Breeze Opinion piece, Torrance Refinery manager Steven Steach categorically asserts, without any specifics, that warnings on the TRAA door hangers in its recent 100,000 door-hanger campaign are incorrect and misleading and contain false claims about risks caused by the Torrance Refinery. The TRAA Science Advisory Panel of eight local scientists and engineers with extensive experience with highly toxic chemicals, carefully reviewed the door-hanger content and found it to be an accurate, concise statement of the current situation with no misleading information.

At least we can agree with the Torrance Refinery and the experts Mr. Steach cites that Hydrogen Fluoride (HF) is far too dangerous for a refinery to use in a highly populated area. Of the EPA’s list of 255 extremely hazardous substances that require a Risk Management Plan, HF is in the group of the top 5% that are the most dangerous. And, of Department of Homeland Securities’ Chemicals of Interest (COI) list of the 187 substances with toxic releases, HF is in a group of six with the highest danger, edged out by only one chemical — the infamously deadly phosgene, which killed about 85,000 in World War I. Mr. Steach states that the refinery phased out HF in 1997. But did it really? . . .

Continue reading by clicking:
Who Is Telling the Truth About the Torrance Refinery

Published in the Daily Breeze on November 28, 2017  (original version above lightly edited for publication)

“US Refineries Persist in Using Toxic Acid, Despite Safer Alternatives” – Truthout

GettyImages-539997880-1280x720“Fifty refineries across the United States use hydrofluoric acid. Because this highly toxic substance can travel for miles in the form of a potentially fatal ground-hugging cloud, however, use of the chemical continues to prove highly controversial — rarely more so than now, given recent accidents at some of these refineries and potential rule changes that call into question the chemical’s long-term future in the oil refining industry.

“In January 2017, California regulators announced that they were taking steps to potentially phase out a modified version of the acid being used at the two refineries in the state, but the rule is still being thrashed out, and it’s too soon to say whether an outright ban on hydrofluoric acid will be enacted there. . . .”

Continue reading the full article on Thruthout by clicking here.

“Haifa Ammonia Tank Emptied after Years-Long Saga” – The Times of Israel

Israeli High Court order to close the facility came over warnings a leak could kill tens of thousands

The ammonia storage tank in the northern city of Haifa, Israel.

“Haifa Chemicals had completed emptying its controversial ammonia tank for the first time in decades, complying with an Israeli High Court ruling that said the risk of a leak from the tank outweighed its benefits.

“The tank, located in the Haifa Bay, was first ordered emptied in 2013, sparking a struggle between local residents concerned over the potential for a deadly chemical leak against officials who said its closure would adversely affect the economy.

“In its final decision on the matter in May 2017, the court said that even though the probability of a leak was small, the damage it could cause would be unbearable.”

Although 30-times less toxic than hydrogen fluoride, but with the same ground-hugging toxic-cloud behavior on accidental release,  the Israeli High Court decision to close the 12,000-ton-capacity tank came after local officials, led by Haifa Mayor Yona Yahav, warned that tens of thousands of people could die should it rupture. Continue reading in The Times of Israel by clicking the image above or click here.

“The Sabotage of the Torrance-Mobil Consent Decree” by Sally Hayati, Ph.D.


Dr. Sally Hayati is former President of TRAA .

This article summarizes Dr. Hayati’s  ground-breaking investigation in the wake of the February 18, 2015 explosion at Mobil’s Torrance refinery that uncovered how Mobil sabotaged the Consent Decree, which settled a 1989 lawsuit brought by the City of Torrance to rid the City of threat of a catastrophic release of hydrofluoric acid.

Essential reading, this well-documented, two-page article could provide the plot to a screenplay of a dramatic movie with the last chapter yet to be written. View the article by clicking:
The Sabotage of the Torrance-Mobil Consent Decree