Preventing Chemical Disasters
Protects Workers, Communities
and Creates Jobs
Clean Burning Gasoline – Where It All
Begins
 Refiners achieve high octane, clean
burning gasoline by adding alkylate
 Refining process of alkylation uses a
chemical catalyst with petroleum feed
materials
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Alkylation in Refineries
Extremely Hazardous Chemical
Processes
 Approximately 1/3 of U.S. refineries (50)
use very large quantities of Hydrofluoric
Acid (HF) in alkylation
 Some have >1/2 million pounds on site
 HF readily vaporizes in the atmosphere. A
large release can form a vapor cloud that
can travel great distances
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Alkylation Catalyst
HF – Extremely Toxic
 OSHA & EPA regulate as highly toxic – a Toxic
Inhalation Hazard (TIH)
 Damages eyes, skin, nose, throat, respiratory system
and bones
 Fast acting, can cause deep, severe burns and can
cause permanent damage
 High concentrations are immediately dangerous to life
and health (IDLH 30 ppm)
 Serious exposures require a knowledgeable health
practitioner to administer antidote – calcium gluconate –
as soon as possible after exposure
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Nevada HF Release Test
August 1986, Industry Sponsored HF Dispersion Experiment: A seven
minute controlled release of anhydrous HF at the Nevada Test Site.
The test release created a hydrofluoric acid cloud over 10 feet high and
visible from as far as ¾ of a mile
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Metropolitan Areas at Great Risk from Refineries Using Hydrofluoric Acid
City/Area
Number of
Refineries
Number of
Persons at Risk
Workers
Community
Location
Company
Chicago
2
Hundreds
1 to 2 million
Joliet
Lemont
ExxonMobil
CITGO
Minneapolis
1
Hundreds
2 million
St Paul Park
Marathon
New Orleans
4
Over 1,000
300,000 to
1 million
Belle Chasse
Chalmette
Garyville
Meraux
ConocoPhillips
ExxonMobil
Marathon
Murphy
Salt Lake City
3
Hundreds
200,000 to
1 million
Salt Lake City
N. Salt Lake
Woods Cross
Chevron
Flying J
Holly
Canton, OH
1
Hundreds
900,000
Canton
Marathon
Memphis
1
Hundreds
800,000
Memphis
Valero
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Recent Releases
HF Related Oil Industry Incidents – Let the Record
Speak for Itself:

Marathon Canton, OH (February 23, 2011) release of
145 pounds of HF
 CITGO Corpus Christi, TX (July 19, 2009) explosion,
fire, HF release critically injured one
 Sunoco Philadelphia, PA (March 2009) HF release
sends 13 workers to hospital
 Giant Industries, Ciniza, NM (April 4, 2004) 4 workers
seriously in fire on HF unit
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Most Recent
HF release in South Korea. Five workers killed, 18 injured, 3,000
treated for exposure. Numerous cattle and crops were affected.
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CITGO Video
Citgo, Corpus Christi, TX. July 2009 explosion and fire in the HF alkylation
unit severely injured one worker and burned for two days. According to the
CSB investigators, about 10% of the estimated 42,000 pound release traveled
beyond the refinery fenceline.
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Dangerous Industry
Other Oil Industry Incidents – Let the Record
Speak for Itself:

Deep Water Horizon (April 20, 2010) killed 11
workers, catastrophic environmental disaster
 Tesoro Anacortes, WA (April 2, 2010) refinery
explosion killed 7 workers
 BP Texas City (March 23, 2005) killed 15
workers, injured 180
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USW HF Report
Selected Preliminary Findings:
Quantities of HF at Refineries
 The 23 refineries collectively have
over 5 million pounds of HF on site
 Per refinery range from 5,200 lbs. to
870,000 lbs.
 Per refinery average of 233,000 lbs.
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Preliminary Findings
Selected Preliminary Findings:
 High Number of OSHA Violations (since
2005).

293 violations of Process Safety Management
Standard: at 20 sites (plus 593 at BP Texas
City)
 Extraordinary
2010 gross operating
profits

over $121 billion for eight oil companies
operating 18 study refineries
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Preliminary Findings
Selected Preliminary Findings:
 Ineffective
Integrity of Alkylation
Process Safety Systems

<50% rated 8 key alkylation safety systems as
very effective: e.g., sewer systems,
mechanical integrity of piping, pumps valves,
seals, and maintenance
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Preliminary Findings
Selected Preliminary Findings:
 Ineffective HF-related Process, Storage and
Transfer Systems



<25% rated 3 systems as very effective. (e.g., audit
programs; maintenance; and health hazard
information).
<50% rated 6 systems as very effective. (e.g.,
operating manuals and procedures; utility systems;
pre-start-up safety reviews).
>50% rated 2 systems as very effective. (e.g.,
control, relief and neutralization systems)
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Preliminary Findings
Selected Preliminary Findings:
 Widespread Alkylation Unit Incidents and NearMisses
 >75% reported at least one HF-related incident or
near miss in the past 36 months
 18 sites; 131 events; 2.4 per site per year
• 83% spills or releases
• 17% fires/explosions
• All reported the events either did or could have caused
injuries to workers on-site.
• 50% reported events could have caused injuries to people in
the community
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Preliminary Findings
Selected Preliminary Findings:
 Unprepared to Respond. (Refinery’s on-site
emergency responders, local off-site
responders, sites nursing/medical personnel,
local hospitals).

Lowest levels of preparedness were for possible HF
releases that could threaten community members
(4% – 22% very prepared and 48% – 61%
unprepared for the 4 groups)
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Preliminary Findings
Selected Preliminary Findings:
 Ineffective
HF Release Mitigation and
Response Systems.

<25% very effective for 5 systems. These included: off-site alarms and notification
systems, utility back-up
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Conclusions
Conclusions
 HF disaster potential at refining operations
is so great that it may be impossible for
refineries to be fully prepared to respond
once a major incident is underway
 Overall, HF-using refineries are not fully
prepared to prevent or to respond to HF
incidents especially those traveling off-site
or involving worst case scenarios
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Conclusions
Conclusions
 Substituting safer processes using safer
chemicals is the only real solution
 Much, much safer alternative chemicals
and processes are available.
Examples
 solid acid catalyst
 ionic liquid catalyst
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Recommendations
Eight Steps to Safer Refineries
(Preliminary)
 USW
is calling for refineries and other
primary stakeholders to engage in the
following:
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Recommendations
Eight Steps to Safer Refineries
(Preliminary)
1. Educate Workers and the Public
About the Dangers of HF
2. Investigate Safer Alternatives to HF

Explore sites using safer, alternative
alkylation processes to develop competencies
for transitioning to safer processes and
operations.
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Recommendations
Eight Steps to Safer Refineries (Preliminary)
3. Test Alternative Solutions

Each refining company should test pilot alkylation
operations using an existing safer alternative method
including solid acid and liquid ionic processes.
4. Share Lessons to Speed Effective Transition

Share lessons learned from pilot operations to enlist
all stakeholders in moving alternatives forward.
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Recommendations
Eight Steps to Safer Refineries (Preliminary)
5.
Commit to Getting the HF Out

6.
Commit to a goal of replacing all HF-using alkylation processes with safer
alternatives as soon as possible (e.g., within 10 years).
Make Existing Processes & Operations Much Safer

Apply all necessary resources to ensure that HF processes
and mitigation systems are in optimal working order, regularly
inspected, and subject to rigorous audits and preventative
maintenance.

Engage in an open process for developing, testing and
critiquing prevention, preparedness and response capabilities
including drills.

At least annually, appraise all stakeholders with a site-based
record of significant operational upsets and loss of primary
containment incidents, equipment failures, etc.
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Recommendations
Eight Steps to Safer Refineries (Preliminary)
7. Comprehensively Inspect and Enforce Regulations
During the Transition to Safer Chemicals/Processes

Increase inspections and assessments to ensure full
compliance with all applicable regulations, standards,
laws and ordinances.
8. Ensure Staffing to Sufficiently Prevent, Prepare and
Respond
 Use nuclear industry and other models to ensure
staffing (numbers, qualifications, experience and
competencies) to ensure optimal safety during all
operations including emergencies.
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