Preventing Chemical Disasters Preventing Chemical Disasters Protects Workers, Communities Protects Workers, Communities
and Creates Jobsand Creates Jobs
Clean Burning Gasoline – Where It All Clean Burning Gasoline – Where It All Begins Begins
Refiners achieve high octane, clean Refiners achieve high octane, clean burning gasoline by adding alkylateburning gasoline by adding alkylate
Refining process of alkylation uses a Refining process of alkylation uses a chemical catalyst with petroleum feed chemical catalyst with petroleum feed materialsmaterials
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Alkylation in RefineriesAlkylation in Refineries
Extremely Hazardous Chemical Extremely Hazardous Chemical ProcessesProcesses
Approximately 1/3 of U.S. refineries (50) Approximately 1/3 of U.S. refineries (50) use very large quantities of Hydrofluoric use very large quantities of Hydrofluoric Acid (HF) in alkylation Acid (HF) in alkylation
Some have >1/2 million pounds on siteSome have >1/2 million pounds on site HF readily vaporizes in the atmosphere. A HF readily vaporizes in the atmosphere. A
large release can form a vapor cloud that large release can form a vapor cloud that can travel great distancescan travel great distances
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Alkylation CatalystAlkylation CatalystHF – Extremely Toxic HF – Extremely Toxic OSHA & EPA regulate as highly toxic – a Toxic OSHA & EPA regulate as highly toxic – a Toxic
Inhalation Hazard (TIH) Inhalation Hazard (TIH) Damages eyes, skin, nose, throat, respiratory system Damages eyes, skin, nose, throat, respiratory system
and bonesand bones Fast acting, can cause deep, severe burns and can Fast acting, can cause deep, severe burns and can
cause permanent damagecause permanent damage High concentrations are immediately dangerous to life High concentrations are immediately dangerous to life
and health (IDLH 30 ppm) and health (IDLH 30 ppm) Serious exposures require a knowledgeable health Serious exposures require a knowledgeable health
practitioner to administer antidote – calcium gluconate – practitioner to administer antidote – calcium gluconate – as soon as possible after exposureas soon as possible after exposure
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Nevada HF Release TestNevada HF Release Test
August 1986, Industry Sponsored HF Dispersion Experiment: A seven minute August 1986, Industry Sponsored HF Dispersion Experiment: A seven minute controlled release of anhydrous HF at the Nevada Test Site. The test release 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 created a hydrofluoric acid cloud over 10 feet high and visible from as far as ¾ of a milea mile
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Metropolitan Areas at Great Risk from Refineries Using Hydrofluoric AcidMetropolitan Areas at Great Risk from Refineries Using Hydrofluoric Acid
City/AreaCity/Area Number of Number of RefineriesRefineries
Number ofNumber of
Workers Workers
Persons at RiskPersons at Risk
CommunityCommunity
LocationLocation CompanyCompany
ChicagoChicago 22 HundredsHundreds 1 to 2 million1 to 2 million JolietJolietLemontLemont
ExxonMobilExxonMobilCITGOCITGO
MinneapolisMinneapolis 11 HundredsHundreds 2 million2 million St Paul ParkSt Paul Park MarathonMarathon
New OrleansNew Orleans 44 Over 1,000Over 1,000 300,000 to 300,000 to 1 million1 million
Belle ChasseBelle ChasseChalmetteChalmetteGaryvilleGaryvilleMerauxMeraux
ConocoPhillipsConocoPhillipsExxonMobilExxonMobilMarathonMarathonMurphyMurphy
Salt Lake CitySalt Lake City 33 HundredsHundreds 200,000 to 200,000 to 1 million1 million
Salt Lake CitySalt Lake CityN. Salt LakeN. Salt LakeWoods CrossWoods Cross
ChevronChevronFlying JFlying JHollyHolly
Canton, OHCanton, OH 11 HundredsHundreds 900,000900,000 Canton Canton MarathonMarathon
MemphisMemphis 11 HundredsHundreds 800,000800,000 MemphisMemphis ValeroValero55
Recent ReleasesRecent ReleasesHF Related Oil Industry Incidents – Let the Record HF Related Oil Industry Incidents – Let the Record
Speak for Itself:Speak for Itself: Marathon Canton, OHMarathon Canton, OH (February 23, 2011) release of (February 23, 2011) release of
145 pounds of HF 145 pounds of HF CITGO Corpus Christi, TXCITGO Corpus Christi, TX (July 19, 2009) explosion, (July 19, 2009) explosion,
fire, HF release critically injured onefire, HF release critically injured one Sunoco Philadelphia, PASunoco Philadelphia, PA (March 2009) HF release (March 2009) HF release
sends 13 workers to hospitalsends 13 workers to hospital Giant Industries, Ciniza, NMGiant Industries, Ciniza, NM (April 4, 2004) 4 workers (April 4, 2004) 4 workers
seriously in fire on HF unitseriously in fire on HF unit
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Most RecentMost Recent
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HF release in South Korea. Five workers killed, 18 injured, 3,000 HF release in South Korea. Five workers killed, 18 injured, 3,000 treated for exposure. Numerous cattle and crops were affected. treated for exposure. Numerous cattle and crops were affected.
CITGO VideoCITGO 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 IndustryDangerous Industry
Other Oil Industry Incidents – Let the Record Other Oil Industry Incidents – Let the Record Speak for Itself:Speak for Itself:
Deep Water Horizon (April 20, 2010) killed 11 Deep Water Horizon (April 20, 2010) killed 11 workers, catastrophic environmental disasterworkers, catastrophic environmental disaster
Tesoro Anacortes, WA (April 2, 2010) refinery Tesoro Anacortes, WA (April 2, 2010) refinery explosion killed 7 workersexplosion killed 7 workers
BP Texas City (March 23, 2005) killed 15 BP Texas City (March 23, 2005) killed 15 workers, injured 180workers, injured 180
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USW HF ReportUSW HF Report
Selected Preliminary Findings:Selected Preliminary Findings:Quantities of HF at Refineries Quantities of HF at Refineries The 23 refineries collectively have The 23 refineries collectively have
over 5 million pounds of HF on siteover 5 million pounds of HF on site Per refinery range from 5,200 lbs. to Per refinery range from 5,200 lbs. to
870,000 lbs. 870,000 lbs. Per refinery average of 233,000 lbs. Per refinery average of 233,000 lbs.
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Preliminary FindingsPreliminary Findings
Selected Preliminary Findings:Selected Preliminary Findings: High Number of OSHA Violations (since High Number of OSHA Violations (since
2005). 2005). 293 violations of Process Safety Management 293 violations of Process Safety Management
Standard: at 20 sites (plus 593 at BP Texas Standard: at 20 sites (plus 593 at BP Texas City)City)
Extraordinary 2010 gross operating Extraordinary 2010 gross operating profitsprofits over $121 billion for eight oil companies over $121 billion for eight oil companies
operating 18 study refineriesoperating 18 study refineries
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Preliminary FindingsPreliminary Findings
Selected Preliminary Findings:Selected Preliminary Findings:
Ineffective Integrity of Alkylation Ineffective Integrity of Alkylation Process Safety Systems Process Safety Systems <50% rated 8 key alkylation safety systems as <50% rated 8 key alkylation safety systems as
very effectivevery effective: e.g., sewer systems, : e.g., sewer systems, mechanical integrity of piping, pumps valves, mechanical integrity of piping, pumps valves, seals, and maintenanceseals, and maintenance
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Preliminary FindingsPreliminary Findings
Selected Preliminary Findings:Selected Preliminary Findings: Ineffective HF-related Process, Storage and Ineffective HF-related Process, Storage and
Transfer Systems Transfer Systems <25% rated 3 systems as <25% rated 3 systems as very effectivevery effective. (e.g., audit . (e.g., audit
programs; maintenance; and health hazard programs; maintenance; and health hazard information). information).
<50% rated 6 systems as <50% rated 6 systems as very effectivevery effective. (e.g., . (e.g., operating manuals and procedures; utility systems; operating manuals and procedures; utility systems; pre-start-up safety reviews). pre-start-up safety reviews).
>50% rated 2 systems as >50% rated 2 systems as very effectivevery effective. (e.g., . (e.g., control, relief and neutralization systems)control, relief and neutralization systems)
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Preliminary FindingsPreliminary FindingsSelected Preliminary Findings:Selected Preliminary Findings: Widespread Alkylation Unit Incidents and Near-Widespread Alkylation Unit Incidents and Near-
Misses Misses >75% reported at least one HF-related incident or >75% reported at least one HF-related incident or
near miss in the past 36 months near miss in the past 36 months 18 sites; 131 events; 2.4 per site per year 18 sites; 131 events; 2.4 per site per year
• 83% spills or releases 83% spills or releases • 17% fires/explosions 17% fires/explosions • All reported the events either All reported the events either did did or or could have caused could have caused
injuries to workers on-siteinjuries to workers on-site. . • 50% re ported events could have caused injuries to people in 50% re ported events could have caused injuries to people in
the communitythe community
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Preliminary FindingsPreliminary Findings
Selected Preliminary Findings:Selected Preliminary Findings: Unprepared to Respond. Unprepared to Respond. (Refinery’s on-site (Refinery’s on-site
emer gency responders, local off-site emer gency responders, local off-site responders, sites nurs ing/medical personnel, responders, sites nurs ing/medical personnel, local hospitals). local hospitals). Lowest levels of preparedness were for possible HF Lowest levels of preparedness were for possible HF
releases that could threaten community members releases that could threaten community members (4% – 22% (4% – 22% very preparedvery prepared and 48% – 61% and 48% – 61% unpreparedunprepared for the 4 groups) for the 4 groups)
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Preliminary FindingsPreliminary Findings
Selected Preliminary Findings:Selected Preliminary Findings:
Ineffective HF Release Mitigation and Ineffective HF Release Mitigation and Response Sys tems. Response Sys tems. <25% <25% very effectivevery effective for 5 systems. These in for 5 systems. These in
cluded: off-site alarms and notification cluded: off-site alarms and notification systems, utility back-up systems, utility back-up
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ConclusionsConclusions
Conclusions Conclusions HF disaster potential at refining operations HF disaster potential at refining operations
is so great that it may be impossible for is so great that it may be impossible for refineries to be fully prepared to re spond refineries to be fully prepared to re spond once a major incident is underwayonce a major incident is underway
Overall, HF-using refineries are not fully Overall, HF-using refineries are not fully prepared to pre vent or to respond to HF prepared to pre vent or to respond to HF incidents especially those traveling off-site incidents especially those traveling off-site or involv ing worst case scenariosor involv ing worst case scenarios
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ConclusionsConclusions
ConclusionsConclusions Substituting safer processes using safer Substituting safer processes using safer
chemicals is the only real solutionchemicals is the only real solution Much, much safer alternative chemicals Much, much safer alternative chemicals
and processes are available. and processes are available. ExamplesExamples solid acid catalyst solid acid catalyst ionic liquid catalystionic liquid catalyst
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RecommendationsRecommendations
Eight Steps to Safer Refineries Eight Steps to Safer Refineries (Preliminary)(Preliminary)
USW is calling for refineries and other USW is calling for refineries and other primary stakeholders to engage in the primary stakeholders to engage in the following:following:
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RecommendationsRecommendationsEight Steps to Safer Refineries Eight Steps to Safer Refineries
(Preliminary)(Preliminary)1. 1. Educate Workers and the Public Educate Workers and the Public
About the Dangers of HFAbout the Dangers of HF2. 2. Investigate Safer Alternatives to HFInvestigate Safer Alternatives to HF
Explore sites using safer, alternative Explore sites using safer, alternative alkylation processes to develop competencies alkylation processes to develop competencies for transitioning to safer processes and for transitioning to safer processes and operations.operations.
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RecommendationsRecommendations
Eight Steps to Safer Refineries (Preliminary)Eight Steps to Safer Refineries (Preliminary)
3. 3. Test Alternative Solutions Test Alternative Solutions Each refining company should test pilot alkylation Each refining company should test pilot alkylation
operations using an existing safer alternative method operations using an existing safer alternative method including solid acid and liquid ionic processes.including solid acid and liquid ionic processes.
4. 4. Share Lessons to Speed Effective TransitionShare Lessons to Speed Effective Transition Share lessons learned from pilot operations to enlist Share lessons learned from pilot operations to enlist
all stakeholders in moving alternatives forward.all stakeholders in moving alternatives forward.
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RecommendationsRecommendationsEight Steps to Safer Refineries (Preliminary)Eight Steps to Safer Refineries (Preliminary)5. 5. Commit to Getting the HF OutCommit to Getting the HF Out
Commit to a goal of replacing all HF-using alkylation processes with safer Commit to a goal of replacing all HF-using alkylation processes with safer alternatives as soon as possible (e.g., within 10 years).alternatives as soon as possible (e.g., within 10 years).
6. 6. Make Existing Processes & Operations Much SaferMake Existing Processes & Operations Much Safer Apply all necessary resources to ensure that HF processes and Apply all necessary resources to ensure that HF processes and
mitigation systems are in optimal working order, regularly mitigation systems are in optimal working order, regularly inspected, and subject to rigorous audits and preventative inspected, and subject to rigorous audits and preventative maintenance.maintenance.
Engage in an open process for developing, testing and critiquing Engage in an open process for developing, testing and critiquing prevention, preparedness and response capabilities including prevention, preparedness and response capabilities including drills.drills.
At least annually, appraise all stakeholders with a site-based At least annually, appraise all stakeholders with a site-based record of significant operational up sets and loss of primary record of significant operational up sets and loss of primary containment incidents, equipment failures, etc.containment incidents, equipment failures, etc.
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RecommendationsRecommendationsEight Steps to Safer Refineries (Preliminary)Eight Steps to Safer Refineries (Preliminary)7. 7. Comprehensively Inspect and Enforce Regulations Comprehensively Inspect and Enforce Regulations During the Transi tion to Safer Chemicals/ProcessesDuring the Transi tion to Safer Chemicals/Processes
Increase inspections and as sessments to ensure full Increase inspections and as sessments to ensure full compliance with all applicable regulations, standards, compliance with all applicable regulations, standards, laws and ordin ances.laws and ordin ances.
8. 8. Ensure Staffing to Sufficiently Prevent, Prepare and Ensure Staffing to Sufficiently Prevent, Prepare and RespondRespond
Use nuclear industry and other models to ensure Use nuclear industry and other models to ensure staffing (numbers, qualifications, experience and staffing (numbers, qualifications, experience and competencies) to ensure optimal safety during all competencies) to ensure optimal safety during all operations including emergencies. operations including emergencies.
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