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Another acid leak at Tesoro refinery

Less than a month after two workers were injured in an acid leak at a Tesoro refinery in Martinez, Calif., two more workers were burned in another acid leak at the same refinery. The second workers were injured on March 10 when they cut into a sulfuric acid pipe as part of planned maintenance, the Sacramento Bee reported.

“The men were initially protected from injury by their protective suits, but some acid remained on the garments and drained onto their necks after the men took decontamination showers,” other workers told SFGate.

The workers injured in the previous leak were not wearing similar protective gear, according to the U.S. Chemical Safety & Hazard Investigation Board (CSB). CSB is investigating the incidents, although in February Tesoro blocked CSB investigators from the site and refused to preserve the first scene.

The company eventually allowed investigators back on the grounds, SFGate reported. “But the company ‘has yet to provide some of the key documents sought’ and did not preserve some evidence from the incident,” CSB spokesperson Hillary Cohen told SFGate.

In 2012, Tesoro dropped out of two volunteer worker-safety programs, reported the Contra Costa Times. One was the “Triangle of Prevention” program developed by the Oil, Chemical and Atomic Workers International Union and continued by the United Steelworkers. The other program was the “Voluntary Protection Program,” which is a cooperative program with the California Division of Occupational Safety & Health. Refinery spokesperson Tina Barbee told the Times that the refinery had replaced the Triangle of Prevention program with a system that has “better root cause analysis during incident investigation,” and that it was technically ineligible to participate in the Voluntary Protection Program.

A survey of refinery workers, however, indicated that safety conditions had deteriorated at the site since 2007,” United Steelworkers representative Tracy Scott told the Times.

The two acid leaks come on the heels of a CSB draft report on a 2010 fire at a Tesoro refinery in Anacortes, Wash.. That incident killed seven workers. CSB has released two videos about that incident, “Animation of Explosion at Tesoro’s Anacortes Refinery” and “The Human Cost of Gasoline.”

Tesoro says CSB lacks jurisdiction to investigate acid leak

On Feb. 12, two Tesoro workers were injured in an acid leak at a refinery in Martinez, Calif. News accounts say that the workers were airlifted to the University of California, Davis, medical center, treated for first- and second-degree burns, and released.

The incident occurred mere weeks after the U.S. Chemical Safety & Hazard Investigation Board released a draft report on a 2010 fire at a Tesoro refinery in Anacortes, Wash., that killed seven workers. (For more on what’s going on with that draft report, see my colleague Jeff Johnson’s story, Regulatory Overhaul Stumbles.)

CSB investigators deployed to Martinez as well and made it onto the site initially. Then Tesoro barred the investigators from further access. “We’ve certainly faced our share of jurisdictional challenges, but I can’t think of another refinery or chemical plant that has taken a position that injuries aren’t serious enough for us to investigate and that we lack jurisdiction,” CSB managing director Daniel M. Horowitz told the Contra Costa Times.

Yesterday, CSB board members responded to Tesoro in writing, including some details of what the agency already learned about the incident:

We point out that our investigation team has determined already that approximately five gallons a minute was leaking until isolated. Acid splashing on worker’s unprotected faces or other parts of the body, resulting in first and second-degree burns requiring air evacuations to a hospital burn unit, treatment, and subsequent significant lost time at work, absolutely constitute serious injuries. …

Our draft report on the 2010 accident at Tesoro’s Anacortes refinery which killed seven workers on January 30, 2014, found a multitude of shortcomings in Tesoro’s plant safety culture. The CSB is interested in examining safety culture issues stemming from the February 12 incident, providing another legal ground for our inquiry.

At the Martinez facility, despite your counsel’s efforts to block our access, we have proceeded in our investigation and have determined that a mechanical integrity failure occurred on equipment connected to a 100,000 gallon process vessel containing flammable hydrocarbons and concentrated sulfuric acid, resulting in the sprayed acid, and that operators being sprayed by acid and caustic during routine sampling activities is a common occurrence.

We have also learned that protective equipment required by procedure for sampling was not provided for the workers at the time – operators did not have ready access to face shields and acid suit jackets at the Martinez facility.

Furthermore, some workers have made the assertion to us and to their union representatives that they have been fearful for their jobs at times when they wished to express safety concerns. We therefore seek further access and renewed cooperation with your company in order to determine all the facts.

Whatever happens with CSB, Tesoro certainly can’t bar the California Division of Occupational Safety & Health from the site. The Washington state Department of Labor & Industries cited Tesoro for 40 willful and five serious labor code violations and fined it $2.39 million for the Anacortes explosion.

Dow worker death likely due to reaction of trimethylindium with cleaning fluid

On Oct. 9, 2013, an explosion and fire at a Dow Chemical electronic materials facility in North Andover, Mass., led to the death of production operator Carlos A. Amaral, 51. According to a statement released by Dow and dated the end of January, the company’s investigation into the incident concluded that:

• An employee sustained injuries as a result of the overpressure of a small stainless steel manufacturing vessel during an operation associated with a Trimethylindium (TMI) manufacturing batch.
• An undesired and unexpected reactive chemical event occurred within the vessel as the employee was transporting the vessel from the glove box to the next manufacturing unit for further processing.
• The overpressure resulted in a release of reacted and unreacted materials and a fire.

The most highly probable cause of the unplanned event was the ingress of cleaning liquid from the cavity space of the ball valve into the crude TMI. Due to the nature of the event, it is impossible to completely validate this conclusion.

I asked Jeremy Cole, business communications manager at Dow Electronic Materials, whether Dow is changing anything regarding cleaning or other handling of the reaction vessel. He said yes, but so far he has declined to provide additional details.

The federal Occupational Safety & Health Administration is investigating the incident, because Massachusetts does not have its own occupational safety and health program. OSHA currently lists the case as open.

Feb. 26 update–Some more information from Dow’s Cole:

the following is the facility’s action plan:
• Prior to TMI production restart, the facility will consider alternate cleaning processes that use cleaning materials that do not react with TMI. If an alternate cleaning process is not feasible, the facility will define a means to confirm the absence of cleaning materials in void spaces and the vessel prior to addition of raw materials.
• The facility will consider modifications to the manufacturing process to increase the tolerance of intrusion of small amounts of cleaning materials as well as variability of raw materials.
• The facility will conduct a review of its Process Hazard Analyses and determine whether any improvements are recommended. Improvements will be captured in appropriate process documentation.

Tesoro refinery fire caused by weakened steel

Last week, the U.S. Chemical Safety & Hazard Investigation Board released its draft report about a 2010 fire at a Tesoro refinery in Anacortes, Wash., that killed seven workers. The fire occurred when a naphtha heat exchanger ruptured, the report says. The cause of the rupture was high temperature hydrogen attack, which occurs when hydrogen atoms diffuse into carbon steel and react with the carbon to form methane. The methane accumulates in the steel and causes stress and fissures. CSB found that curves established by the American Petroleum Institute to predict high temperature hydrogen attack are inaccurate. “CSB has learned of at least eight recent refinery incidents where HTHA reportedly occurred below the carbon steel Nelson curve,” the report says.

Here’s CSB’s video about the incident:

Additionally,

The CSB found several indications of process safety culture deficiencies at the Tesoro Anacortes Refinery. Refinery management had normalized the occurrences of hazardous conditions, including frequent leaks from the [naphtha hydrotreater unit] heat exchangers, by using steam to mitigate leaks, ineffectively correcting heat exchanger design issues, commonly requiring additional operators during [naphtha hydrotreater unit] heat exchanger startups, and exceeding the staffing levels that procedures specified.

and

The refinery process safety culture required proof of danger rather than proof of effective safety implementation. For years, technical experts used design data to evaluate the B and E heat exchangers for HTHA susceptibility. Data for actual operating conditions were not readily available, and these technical experts were not required to prove safety effectiveness in reaching their conclusion that the B and E heat exchangers were not susceptible to HTHA damage.

CSB noted several similarities between the Tesoro fire and a Chevron refinery fire in Richmond, Calif., in 2012:

  • The Chevron “incident was also the result of a metallurgical failure caused by a well-known damage mechanism called sulfidation corrosion, and Chevron process safety programs failed to identify the hazard before the major incident that endangered the lives of 19 Chevron employees.”
  • “Mechanical integrity programs at both Tesoro and Chevron emphasized inspection strategies rather than the use of inherently safer design to control the damage mechanisms that ultimately caused the major process safety incidents.”
  • “Rather than performing rigorous analyses of damage mechanisms during the PHA process, both companies simply cited non-specific, judgment-based qualitative safeguards to reduce the risk of damage mechanisms.”

One of the recommendations CSB makes in its Tesoro report is that Washington state implement a “safety case” approach to regulation, in which companies develop their own process safety requirements that are closely overseen by state regulators. The agency made the same recommendation to California in its Chevron report, but that report fell to a divided vote by CSB board members, with board members Beth Rosenberg and Mark Griffon wanting CSB to study regulatory options further. An expected vote on the Tesoro report last week was delayed. What happens from here is an open question. Given criticism of CSB that the agency is taking too long already to complete its investigations, holding reports for further study seems untenable. The federal budget passed last month allotted CSB “$11 million for fiscal 2014, slightly less than previous years and below the Administration’s request of $11.5 million.”

Feb. 5, 2014: Title changed to reflect the fact that although I saw the heat exchangers as a bundle of tubes inside a larger tube, CSB tells me that engineers view the outer structure as a shell, not a tube. In any case, weakened steel from high temperature hydrogen attack was still the problem.

When is an explosion really an explosion, take two

A few weeks back, we had a letter to the editor in C&EN that took us to task for using “blast” and “explosion” to describe two industrial incidents. We have more in this week’s issue (which, I might add, is a particularly awesome one in celebration of C&EN’s 90th anniversary). The consensus? The rupture of a nitrogen line is a mechanical explosion, and C&EN used the words appropriately. Here’s what our readers said:

Regarding Richard Rosera’s letter “Choosing the Right Words,” explosion is the correct term (C&EN, Aug. 5, page 4). The definition of the word explosion is the rapid expansion of a gas.

To quote Rosera, the case at hand was “caused by the rupture of a nitrogen line or vessel by overpressure.”

Rob Kovacich
Hood River, Ore.

Recalling my years dealing with hazard evaluation led me to question Rosera’s letter. An explosion is defined as the rapid increase in volume and release of energy in an extreme manner. Or, as Frank T. Bodurtha explains in his book “Industrial Explosion Prevention and Protection,” “an explosion is the result, not the cause, of a rapid expansion of gases. It may occur from physical or mechanical change.”

Thus, the rupture of a nitrogen line or vessel does indeed result in an explosion, as does the rupture of an overfilled tire.

Robert G. Robinson
Lawrenceville, N.J.

As a chemistry educator and professional pyrotechnician, I answer myriad questions regarding explosions. If the term explosion is used to refer to “the rupture of a nitrogen line or vessel by overpressure,” it is more specifically a mechanical explosion, but it’s an explosion nonetheless.

The criticism leveled by Rosera is unwarranted. Both the mainstream press and C&EN are correct in addressing the CF Industries accident as an explosion. Although physical failure of materials containment may be due to either chemical or mechanical reasons, the result is still an explosion.

Kathleen Holley
Arlington, Texas

At the time of the original news story, the cause of the explosion at a Williams C. ethylene plant in Geismar, La., was unknown. A July 31 story in the New Orleans Times-Picayune indicates that it was still unknown by that time. I can’t find anything more recent, but the U.S. Chemical Safety & Hazard Investigation Board is investigating it, so we’ll have an answer eventually. The incident killed two workers.

A caution on procedures in organic synthesis journals

Organic Process Research and Development editor Trevor Laird, founder of Scientific Update, recently penned an editorial on “Safety Culture in Industry and Academia”. I’ll highlight one particular paragraph:

Unfortunately, many companies and most universities are still not using the literature to find out more safety information (and not just MSDSs); for example, Bretherick’s Handbook of Reactive Chemical Hazards is a superb resource to access the literature with respect to safe handling of chemicals, in particular on the issues with scaling up. In the organic synthesis literature, I have seen so many unsafe procedures using perchloric acid/perchlorates and azides/hydrazoic acid, for example, that it is surprising there have not been more explosions in university laboratories. Yet a look through recent issues of Organic Process Research & Development (OPRD) will garner several fine articles which describe exactly the dangers of azides, how to overcome those dangers and to scale up the processes, as well as a book review on this topic.

There’s clearly a challenge here for researchers to figure out what’s a safe procedure and what isn’t. Just because a journal published something doesn’t mean it’s been vetted for safety. Is there a good way to teach students to be appropriately skeptical of literature procedures? Also, aside from using Bretherick’s and OPRD, are there other good resources for people trying to evaluate a procedure for safety?

Fatal incidents at Louisiana’s CF Industries and Williams Cos. plants

I’ll save a full round-up for tomorrow, but I wanted to point to two fatal accidents last week in Louisiana that C&EN is following:

Williams Cos.

  • Explosion at 8:30 AM on Thursday, June 13, in Geismar, La., at an olefins plant that produces ethylene and propylene
  • Two people died: Zachary Green, 29, and Scott Thrower, 47; more than 75 others were injured
  • The root cause is still being investigated, but the fire was reportedly fed by propylene and propane; pipe corrosion resulted in a propylene leak in December, 2012
  • The investigation will also have to take into account that the facility had racked up 12 straight quarters (three years) of noncompliance with federal Clean Air Act regulations and hadn’t been inspected by OSHA, the Occupational Safety and Health Administration, in a decade.”
  • Despite the environmental compliance failings, the Louisiana Department of Environmental Quality had approved a $400 million plant expansion project that would increase ethylene capacity by 50%
  • The Chemical Safety Board is investigating
  • New Orleans Times-Picayune coverage, company information

CF Industries

Dow launches Lab Safety Academy website

Yesterday at the Council for Chemical Research meeting, Dow unveiled a publicly-accessible website with a comprehensive set of lab safety training videos plus additional resources. The website is at safety.dow.com. More details on the development of the site are in my C&EN story on the project. One tidbit that didn’t make it into the news story: While the video hosts are professional actors, the supporting roles are played by Dow scientists.

On the importance of teaching safety

From this week’s issue of C&EN, a letter to the editor from Dow’s William F. Banholzer, Corning’s Gary S. Calabrese, and DuPont’s Pat Confalone discusses whether laboratory safety should have been included in “Advancing Graduate Education in the Chemical Sciences“:

As members of the ACS Presidential Commission on Graduate Education in the Chemical Sciences, we challenge Richard N. Zare’s comment on the inappropriateness of including a recommendation about laboratory safety in our report “Advancing Graduate Education in the Chemical Sciences” (C&EN, March 4, page 51). While admitting that safety is important, Zare states the report “should instead have been about preparing graduate students, about the future.”

What is more important in graduate education than ensuring students complete their research as safe and healthy as the day they entered graduate school? A graduate education is the ideal place to instill the mind-set that if you can’t do research while carrying out the best safety practices, then you shouldn’t do it at all. The recommendation to include safety in the final report was unanimously supported by all commission members. …

The facts are unequivocal. Occupational Safety & Health Administration statistics demonstrate that researchers are 11 times more likely to get hurt in an academic lab than in an industrial lab. There have been serious accidents in academic labs in recent years—including fatalities—that could have been prevented with the proper use of protective equipment and safer laboratory procedures.

Most chemistry and chemical engineering graduate students will find employment in industry. As new hires come on board, many companies spend weeks on remedial safety training before new hires are allowed to work in their labs. This clearly shows that the current state of graduate safety education is lacking and that there is a clear need to address it. If the report is supposed to focus on “preparing graduate students, about the future,” how can this not be a relevant topic? …

The “11 times more likely” statistic is inaccurately framed. I followed up on it with the letter authors and Lori Seiler, Dow’s associate director for environmental health and safety in research and development. The numbers actually compare the overall injury and illness rate for academic institutions (including those that might occur, for example, in grounds keeping or a dining hall as well as in laboratories) to Dow’s overall rate. Seiler adds that the injury and illness rate for Dow’s research laboratories is consistent with the company’s overall rate, when calculated per employee.

That said, it seems like it would be wise for the academic community to take this letter to heart.  Banholzer, Calabrese, and Confalone are not writing in a vacuum—they see the skills that chemistry graduates lack, and those skills are necessary whether those graduates are going on to work in industry, academia, or elsewhere.

On a related note, yours truly will be heading  to Virginia next week for the Council for Chemical Research annual meeting on May 19-21. On the afternoon of Sunday, May 19, I’ll be moderating a panel discussion on the pilot laboratory safety program that Dow began last year with the University of Minnesota, Pennsylvania State University, and the University of California, Santa Barbara.

Ripped from the pages: More on the West Fertilizer explosion in Texas

Texas explosion facts emerge, report Glenn Hess and Jeff Johnson in C&EN this week, although much remains unknown:

According to state and federal records, the retail facility stored some 270 tons of ammonium nitrate and 54,000 lb of anhydrous ammonia for sale to local farmers. …

The facility appeared not to segregate ammonium nitrate, nor did it have automatic sprinkler systems, structural fire barricades, or other mechanisms to limit fires. Whether first responders were aware of what was in the warehouse and its potential for explosion is unknown. …

Ammonium nitrate storage and use are controlled by state and federal regulations. However, it appears that West Fertilizer’s reports to regulators held conflicting information about what materials and quantities were stored, so this small retail distribution facility may not have triggered regulators’ notice. …

Meanwhile, C&EN Deputy Editor-in-Chief Josh Fischman writes in an editorial about a 1947 ammonium nitrate explosion in Texas that killed nearly 600 people, including 27 firefighters, and destroyed 500 homes:

On Oct. 20, 1947, C&EN reported that an expert at the President’s Conference on Fire Prevention said the disaster could have been prevented if “reasonable safety rules had been observed.”

Apparently that hasn’t happened.

There’s also been a West-related dust-up in California. Earlier this year, Texas Governor Rick Perry launched an ad campaign in California and visited the state to try to woo businesses “with promises of low taxes, loose regulations and a hard stance on organized labor,” reported the Los Angeles Times in February. Sacramento Bee cartoonist Jack Ohman subsequently responded to the West Fertilizer explosion with this cartoon. Perry responded that the cartoon inappropriately “mock[ed] the tragic deaths of my fellow Texans and our fellow Americans.” What say you, Safety Zone readers? Was the cartoon appropriately provoking or insensitive?