Israeli High Court order to close the facility came over warnings a leak could kill tens of thousands
“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.
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.
Click the image above to watch TRAA’s short three-minute video featuring a presentation by Dr. Sally Hayati, former TRAA President. Warning: this video contains disturbing images of the aftermath of the Bhopal catastrophe.
To get an idea how dangerous hydrogen fluoride is, consider just half an ounce — one tablespoon or ⅓ of a whiskey jigger — released into a large 10×10 meter conference room with a 3-meter ceiling (33′×33′×10′). A simple calculation, which a high-school chemistry student could easily verify, shows that the room would be raised above the Emergency Response Planning Guidelines’ ERPG-3 level of 50 parts per million, resulting in life-threatening health effects. Now consider that each of the two alkylation-unit settler tanks at the Torrance Refinery contains up to 50,000 lbs of hydrogen fluoride, or 1.6 million of the 1/2-oz samples. That’s nearly twice the population of the entire South Bay. It’s important to note that MHF is just as toxic as HF.
The TRAA Science Advisory Panel made an important discovery about toxicity of sulfuric acid that reveals a fatal flaw in the Consent Decree, which settled the lawsuit between the City of Torrance and Mobil. The Consent Decree was modified in the mid-1990s to allow MHF if Mobil’s Quantitative Risk Assessment (QRA) could show MHF was no more dangerous than sulfuric acid. However, QRAs are notoriously infamous for wildly varying over orders of magnitude in predictions depending on the numerous assumptions made. Mobil’s QRA is kept from public disclosure by claims of “proprietary and sensitive” information.
It’s a mystery to the public that defies common sense how Mobil’s QRA could predict very-low-volatility sulfuric acid, which doesn’t require an EPA Risk Management Plan, could be as dangerous as highly volatile hydrofluoric acid. And it is especially troubling that Quest Consultant’s excellent 1995 paper, Effectiveness of Mitigation Systems in Reducing Hazards of Hydrogen Fluoride Leaks by David W. Johnson and John B. Cornwell, which directly contradicts Mobil’s assertion that MHF is as safe as sulfuric acid, was not mentioned in reports to the Court by the Safety Advisor, who was handpicked by Mobil.
Johnson and Cornwell’s assessment was that for the major release they considered, the worst-case toxic distance (to ERPG-3) was 300 feet for sulfuric acid, compared to 14,000 feet (2.7 miles) for MHF with 50 wt% sulfolane additive (see Table 2 — Acid Dispersion Analysis for Alkylation Unit in the paper referenced above). Note that Quest’s 1995 assessment of sulfuric acid’s behavior was confirmed in the 84,000-pound sulfuric-acid release from an alkylation-unit settler tank at the Tesoro Refinery in Martinez, California on February 12, 2014. There was no offsite consequence to the community.
We do know a thing or two about Mobil’s QRA from the Consent Decree’s Safety Advisor in his 1995 Report, where he writes (page V-36),
“The quantitative risk comparison uses ERPG-3s, which can be regarded as thresholds for potentially fatal effects, as a basis for comparison of the two substances. The Safety Advisor considers that this is a reasonable choice because the ERPGs have been carefully developed and peer reviewed”.
We discovered that the ERPG-3 used in Mobil’s Quantitative Risk Assessment overstates the toxicity of sulfuric acid by a factor of four. The 1995 Safety Advisor Report shows that 30 mg/m3 for the EPRG-3 value for sulfuric acid was used in Mobil’s QRA (see Table V.4 on page v-36). Today’s accepted value is 120 mg/m3. An unbiased competent engineer would immediately recognize that such a large change in a primary parameter invalidates Mobil’s QRA. Thus, there is no legal basis for Mobil Refining Company to be using MHF.
In 2014, there was a very large release of sulfuric acid at a refinery in Martinez, California that demonstrated its safety in the community compared to what would have happened if the refinery had used hydrogen fluoride. Before going into details of the Martinez release, first some background on the two chemicals. It is widely acknowledged in the industry that sulfuric acid alkylation is vastly safer than hydrogen fluoride (HF) with respect to offsite consequences. An additive refineries uses in a failed attempt to make HF safer is at such a low level it hardly makes a difference.
Sulfuric acid is vastly safer because its molecules are strongly bound in the liquid state. Even at elevated temperature, there is no tendency for them to go airborne as an aerosol or vapor. One measure of sulfuric acid’s extremely low volatility is its high boiling point of 639F. Sulfuric acid in a beaker placed in a kitchen oven at 500F will remain as a liquid and not boil. Compare this to HF, whose molecules are only weakly bound in the liquid state. Considered a “fuming liquid,” HF boils at 67F. An open beaker at room temperature on the kitchen counter will spontaneously spew a white vaporous cloud. Another measure of volatility is vapor pressure. At room temperature, HF’s vapor pressure is a million times higher than sulfuric acid’s.
Definitive field-scale experiments on the release of sulfuric acid from an alkylation unit were conducted in 1991 by Quest Consultants in Oklahoma and documented in Sulfuric Acid Release Report. Thirty-six releases of sulfuric acid — alone and mixed with hydrocarbons — were conducted. In every case, virtually all of the released sulfuric acid was collected on the floor of the test cell downstream of the release.
The United States Environmental Protection Agency (EPA) requires facilities that use extremely hazardous substances to develop a Risk Management Plan (RMP). Hydrogen fluoride is on the list of extremely hazardous substances that require one. Sulfuric acid, so long as it’s not mixed with sulfur trioxide, which makes it fume, is not on the list. Thus the EPA explicitly acknowledges the stark difference in the threat to the community between sulfuric acid and HF.
The 2014 Sulfuric Acid Release at the Tesoro Refinery in Martinez CA
The U.S. Chemical Safety Board (CSB) reported on an accidental release of 84,000 pounds of sulfuric acid over two-and-a-half hours from an alkylation-unit settler tank at the Tesoro Refinery in Martinez, California, on February 12, 2014. The release was onto the refinery grounds and into a process sewer system. There was no vapor cloud or offsite consequences to the community. The spill burned two workers, who were transported to the nearest hospital burn unit by helicopter. They survived and returned to work after five months.
A Modified Hydrofluoric Acid (MHF) release of this magnitude would have had cataclysmic consequences not only for refinery workers, but also for the surrounding community. A ground-hugging toxic cloud would be lethal for more than eight miles downwind. (For comparison, there are 50,000 pounds of MHF in one Torrance refinery settler tank.) This full-scale incident is further dramatic evidence that sulfuric acid alkylation is vastly safer than MHF alkylation, contrary to the claims of Exxon-Mobil and the Torrance Refining Company.
The DuPont™ ConvEx℠ HF Alkylation Conversion to Safer Sulfuric Acid Alkylation Technology
A leader in sulfuric acid alkylation, DuPont offers a cost-effective alkylation conversion from hydrofluoric acid (HF) alkylation to a modern, vastly safer sulfuric acid alkylation technology.
CDAlky® Alkylation Technology
According to McDermott International, Inc., “The CDAlky process is the most advanced sulfuric acid alkylation technology. The technology is simple, innovative, flexible and robust with respect to both feedstock and operation. Until now, sulfuric acid alkylation is one of the few refinery processes that remained essentially unchanged since its introduction in the early 20th century. The CDAlky process represents the first step change in sulfuric acid alkylation technology.” It uses 50% less sulfuric acid than conventional sulfuric acid alkylation technology.
Two U.S. Refineries Currently Undergoing Conversion from HF to New Safer Alternatives
Two U.S. refineries are are in the process of conversion to other vastly safer alkylation technologies.
UPDATE: In a February 2021 Press Release, CVR Energy Proceeds with KBR on Second Phase Scope for Alkylation Revamp Project, KBR President Doug Kelly said, “We are extremely happy to continue working with CVR Energy on its efforts to migrate from a traditional hydrofluoric acid-based alkylation process to KBR’s innovative and groundbreaking K-SAAT process that delivers higher alkylate yield and quality.”
Click the image above to watch TRAA’s short two-minute video where Dr. Sally Hayati, former TRAA President, refutes the claim of Torrance Refinery manager that alternative emerging technology may never be available.
See the elected officials, as well as other prominent community-minded individuals and organizations, who have have written letters to the South Coast AQMD in support of a Rule 1410 banning MHF by clicking here
“When the Torrance refinery exploded in February 2015, showering residential neighborhoods with industrial ash, the event ignited a three-year public debate over hydrofluoric acid that continues to this day.
The TRAA Science Advisory Panel is an ad hoc volunteer group of eight local scientists and engineers with extensive relevant experience with highly toxic chemicals including hydrogen fluoride:
Charles Clendening, Ph.D. Dr. Charles Clendening completed his undergraduate work at the Case Institute of Technology in 1968, and earned his doctorate in physics from Cornell University in 1974. He has worked in high energy laser development for over thirty years, first for the United States Air Force and then for TRW, which later became Northrop Grumman. He is a past recipient of two TRW Chairman Awards for Innovation, and a TRW Distinguished Patent award. Dr. Clendening served as Chief Scientist at Northrop Grumman for the Air Force’s Airborne Laser Program and won the 2009 AIAA Plasmadynamics and Lasers Award. Charles resides in Torrance.
James Eninger, Ph.D., Editor of the TRAA Science Advisory Panel Blog Dr. James Eninger retired in 2005 after a 33-year career at TRW in Redondo Beach. At TRW, he was a Senior Staff Engineer and Project Manager of programs that included safely dealing with hydrogen fluoride in the exhaust of high-energy chemical lasers. He holds a B.S.M.E. and an M.S. & Ph.D. in Aeronautics and Astronautics from Stanford University, specializing in Fluid Mechanics and Physical Gasdynamics. He resides in Torrance and is a past member of the Torrance Refining Company Community Advisory Panel.