# Oil Refineries and
Hazard Reduction

# NEEDLESS RISK:

O IL 

# R EFINERIES AND 

# H AZARD 

# R EDU C TION

M EGHAN 

# P URVIS



# M ARGARET 

# H ERMAN



# U.S. PIRG E DUCATION 

# F UND



# A UGUST 

# 2005

# A CKNOWLEDGMENTS

Copyright 2005 U.S. PIRG Education Fund

Cover photo of oil refinery obtained from the Hawaii State Department of B usiness, Economic Development & Tourism, at http://www.hawaii.gov/dbedt/ert/refinery.html . Note th at this photo is for illustrative use only; this refinery do es not use hydr ofluoric acid. Photo of children playing courtesy of Denny Larson of the National Refinery Reform Campai gn, www.refineryreform.org . This photo shows children from the Carver Terrace federal housing project playi n g in the shadow of the Premcor refi nery in West Port Arthur, Texas. Photo of homes near an oil refinery obtained from Ec oIQ.com Online Images. Photo of emergency
medical tech nicians obtai ned from the City of Norfolk at www.norfolk.gov/NFR/images/emsp ic.JPG

.

The authors would like to acknowledge Alison Cassady of U.S. PIRG Education Fund for coordinating the research and distribution of this report, as wel l as her endl ess editorial support and cover design.

In addition, we would l i ke to th ank Paul Or um, senior advisor to the Working Group on Community Right-to-Know, for his research lead ersh ip and editorial review. We would also like to thank the U.S. PIRG Education Fund interns for their help in collecting the data.

The U.S. PIRG Educati on Fund’s Toxics and E n vironmental Health Program is grateful to th e Bauman Foundation, the Beldon Fund, and individual contributors for their support.

The authors alone are res ponsible for any factual errors. The recommend ations are thos e of the U.S. PIRG Education Fund. The views expressed in this report are those of the authors and do

not necessari ly reflect the views of our funder s or those who provided editorial review.

The U.S. PIRG Education Fund is the research an d public education center for the U.S. Public

Interest Res e arch Group (PIRG), the national ad vocacy office of the state PIRGs. The stat e PIRGs are a nationwide n etwork of no nprofit, nonpa rtisan, state-based public interest ad vocacy organizations. The state PIRGs’ mission is to de liver persistent, result-oriented activis m tha t protects th e environment, encourages a fair ma rketplace for co nsumers and fosters responsive, democratic g o vernment.

For additional copies of this report, send $20 (including shipping) to:

U.S. PIRG Education Fund 218 D Street, SE Washington, DC 20003
202-546

- 9707 uspirg@pirg.org www.uspirg.org

For more information ab out the sta te PIRGs, visit our Web site at http://www.pirg.org

.

# T ABLE OF 

# C ONTENTS

EXECU T IV E SUMMARY

.............................................................................................................. ......................... 4

CHEMICAL INSECURI TY: HAZA RD S LEAVE COMMUNITI ES EXPOSE D

...................................... 6

HYD R OFLU ORIC A C ID AND THE P E TROLEUM INDUSTRY

.............................................................. 8

H YDROFLUORIC 

### A CID 

### : A T HREAT TO 

### H E A LTH A ND 

### S AFETY



### .............................................................. 8

U SE OF 

### H YDROFLUORIC 

### A CID IN THE 

### P ETROLEUM 

### I NDUSTRY



### .......................................................... 8
C HEMICAL 

### A CCIDE NTS 

### I NV OLV I N G 

### H YDROFLUORIC 

### A CID



### ................................................................ 9

H YDROFLUORIC 

### A CID 

### : A T ERRORIST 

### T ARGE T 

### .....................................................................................10

REPO RT FINDINGS: COMMUNITI ES AT RIS K .........................................................................................12

HOW POLICYMAKE RS AND INDUS T RY SHOUL D PRO T E C T COMMUNITIES .........................15

A P REVENTIVE 

### A PPROA CH 

### ........................................................................................................................15

INHE REN T SAFETY A T REFIN E RIE S : ALTERNA T IVES TO HYDRO F LUO R IC ACI D .............16

P REVENT THE 

### P OSSIBILITY 

### : S OLID 

### A CID 

### C ATALY S T 

### ............................................................................16

R ED UC E THE 

### S EV ERITY 

### : S ULFURIC 

### A CID 

### A S AN 

### O PTION 

### ...................................................................17

R ED UC E THE 

### P ROBABILITY 

### : H YDROFLUORIC 

### A CID 

### M O D IFIERS 

### .......................................................18

REDU CING CHEMICAL HAZA RDS THROUG H P O LICY MEA SURES .............................................21

I NADE QUACI E S OF 

### E XISTING 

### P OLICIES 

### ..................................................................................................21
T HE 

### R IGHT 

### -T O 

### -K NOW AS A 

### S A F ETY 

### T OO L 

### ...........................................................................................22

P ROTE CTING 

### C OMMUNITIE S THROUGH 

### I N H EREN TLY 

### S AF E R 

### T ECH N OLOGY 

### ...............................23

METHO D O L OGY

.................................................................................................................... ..............................24

APPENDIX: OIL REFIN E RIES USIN G OR STORI NG HY DRO F LUORIC A C ID ON-SI T E .........25

END NO TE S

...................................................................................................................... ......................................27

# E XECUTIVE 

# S UMMARY

Across the country, petroleum r e fineries, chemical plants and other industrial facilities use and store large am ounts of ha zardous
chemicals th at could be released in the even t of an accident or terrorist attack. Such
releases cou l d endanger thousands or even millions of p e ople who live in communities in close proxim ity to these facilities. A ccording
to the En vironmental Protection Agency (EPA), 106 facilities would each endanger at least one million people in the event of a
worst-case chemical release. Anoth e r 3,000 facilities would endanger at least 10,000 people. Nearly 5,000 facilities store morethan 100,000 pounds of at least one EPAclassified “extremely hazardous substance.”

Many of these facilities, however, present an unnecessary risk to their surrounding

communities . Industries often have multiple options for carrying out similar processes, and some of these options are inhere ntly safer
than others. Facilities that use f ewer or smaller quantities of hazardous chemicals, or even make changes to storage pressure or other processes, can eliminate the possibility
of on-site chemical a c cidents and make
themselves l e ss appealing terrorist targets.

Petroleum refineries sta n d as a stark example of the needless risk posed by such facilities in
the event of an attack or accident as well as the opportu nity to mitigate this risk by using
safer alternatives to toxic chemicals.

Many petroleum refineries use hydr ofluoric
acid in their processing, which poses a great public safety risk both because of its extreme toxicity to h u mans as well as its propensity to
form a toxic aerosol cloud when relea s ed. A catastrophic event at one of these facilities could cause a poten tial ly lethal rel e ase of hydrofluoric acid, forming a stable aerosol cloud above the facility and surrounding neighborhoods. Exposure to hydrofluoric acid results in devastating burns, and pain associated with the exposure may be delayed for up to 24 hours. If the bur n is not addressed, ti ssue destruction may continue for days. Inhalation of fumes can cause symptoms ranging from severe throat irritation to pulmonary edema.

To estimate the numb er of Americans a t needless risk of exposure to hydrofluoric acid in the event of a catastrophic accident or

terrorist atta ck at a petroleum refinery, we examined the Risk Management Plans
submitted b y oil refineries to EPA. These plans estimate how far a chemical could travel
off-site in th e event of a release and r e port th e number of people living within the
“vulnerabilit y zone,” the area potentially affected by the release. Based on thi s data, we found that petroleum refineries using hydrofluoric acid endanger millions of people.

Specifically:

• Of the 148 petroleum refineries in the United States, 50 use hydrofluoric acid in their processing or store it on-site. The remainder use safer alternatives, such as
sulfuric acid.

• These 50 refineries, using and storing 10.6 million pounds of hydrofluoric acid, endanger more than 17 million people living in su rrounding communities in 20
different states.

4 Needl ess Ris k 

### • With 12 refineries using hydrofluoric acid, Texas has more than any state. Louisiana has five oil refineries that currently use hydrofluoric acid, and Montana has four.

### • Refineries using hydrofluoric acid in Pennsylvania endanger more than 4.4 million people residing in their vulnerability zones, according to conservative estimates. Refineries using hydrofluoric acid in both Illinois and New Jersey endanger more than 3.1 million people living within the vulnerability

zones.

• Seven petroleum refineries using hydrofluoric acid repor ted toxic release
“worst-case” scenarios in which more
than one mil lion people could be affected. Furthermore, 15 refineries could place
more than 5 00,000 people in harm’s way, and 28 refineries could endanger more than 100,000 people in the even t of a worst-case hydrofluoric a c id release.

• The compan ies operating refineries using hydrofluoric acid with the most people residing in their vulnerability zones include Sunoco, Valero Energy Corporation, Marathon Ashland Petroleum, ConocoPhillips, CITGO, and ExxonMobil, each endangering at least two million people in total.

• Many companies owning refineries using hydrofluoric acid also operate refineries without that technology. ConocoPhillips, ExxonMobil, Valero Energy Corporation, and Marathon Ashland, f o r example, own refineries using hydrofluoric acid as well as refineries that use other technologies.

Fortunately, hydrofluoric acid is not the only
material oil r e fineries can use in their refinin g processes. Many other refineries already use sulfuric acid, a safer alternative, in the alkylation pr ocess. Thi s cost-effective and widely-used alternative d i minishes the appeal of refineries as a terrorist target and mitigates the public health and safety consequences of an accident. In addition, a new technology, solid acid catalysts, will soon be avail a ble for widespread commercial use, offering an even safer option than the use of sulfuric acid.

Petroleum refineries are but one example of the facilities that pose an immediate risk to public health in the even t of a terrorist attack
or chemical accident. R e fineries also are not the only exa m ple of facilities that cou l d make cost-effective changes to ma n u facturing

processes to reduce or eliminate th e use of
hazardous chemicals.

Nee d le ss Ri sk 5 

### Unfortunately, most industrial facilities have not respond ed to the increased awar eness of
terrorism b y switching to inherently safer technologies. Instead, industry organizations
such as the American C h emistry Co uncil, the American Petroleum Institute, a n d th e National Petrochemical and Refiners Association have emphasized increasing physical security at faci lities. Hiring more guards, bui l d ing hi gher fences, and placing more lights may all be part of a strong security plan, but this does not actually reduce the
threat to the community. Switching chemicals and processes to something less vo latile not only reduces the chem ical hazard to th e community, but also reduces the need for costly add-on security measures and the
attractiven e s s of the facility as a target for
attack.

# C HEMICAL 

# I NSEC URI T Y 

# : H AZARDS 

# L EAVE


# C OMMUNI TIES 

# E XPO S E D

Across the United States, thousa nds of
industrial facilities use and store hazardous chemicals in large quantities that pose major risks to their neighbors. According to the Environmental Protection Agency (E PA), 106 facilities would each endanger at least one million people in the event of a worst-case
chemical release. An other 3,000 facilities
would enda nger at least 10,000 people. Nearly 5,000 facilities store more than 100,000 pounds of at least one EPA-classified “extremely hazardous substance.” 1



### Accidents at chemical and industrial facilities

are common

. Each year tens of thou sands of spills and gas leaks occur as a result of the ongoing use of hazardous chemical s. 2 

### A s recently as March 2005, an explosion at a BP oil refinery in Texas City, Texas killed 15 employees. In Gulfport, Mississippi in February 2003, a cloud of toxic ammonia leaked from a chemical plant after an intruder broke into a fenced comp ound, attem pting to steal the chemical to make illegal drugs. The
toxic cloud led to the evacuation of seven hotels and the closure of Gulfport-Biloxi
International Airport and a 10-mile stretch of
Interstate 10 for seven hours. 3



### Since September 11, 2001, it has become increasingly apparent that these facilities pose a more sinister threat, as they ma y b e come th e target of a terrorist attack. A report by th e Army Surgeon General ranked an attack on a chemical pla n t second only to a widespread biological attack in magni t ude of th e h a zard to the public. 4 

### On Feb r uary 12, 2003, the
National In frastructure Protection Center warned, “Al Qa’ida oper a tives...may attempt
to launch conventional atta cks against th e U.S. nuclear/chemical-industrial infrastructure to caus e contamina t ion, disruption, and

terror.” 5



### Even before September 11, 2001, the Agency
for Toxic Substances a n d Disease Registry (ATSDR) a ddressed the weak security at chemical facilities. In 1999, ATSDR p u blished a study of chemical site security at two key
chemical co mmunities – the Kanawha Valley in West Virginia and Las Vegas, Nevada. The study found the industry poorly prepared for terrorist attacks, noting that industrial chemicals p r ovide terrorists with “effective and readily accessible materials to develop improvised explosives, incendiaries and poisons.” 6



### Across the country, select facilities have made major progress by s w itching to safer
chemicals a n d processes that pose less of a
threat to s u rrounding communities in the event of a major chemica l release. Soon after September 1 1 th 

### , for example, the Blue Plains Sewage Trea tment Plant in Washington, DC switched from using and storing chlorine and sulfur dioxide on-site to using sodium hypochlorite bleach in its processes. For weeks after September 1 1 th 

### , workers at Blue
Plains remo ved up to 900 tons o f liqu i d
chlorine and sulfur dio x i d e. Whereas chlorine gas from the Blue Plains facility co uld have enveloped downtown Washington, DC, Anacostia, Reagan National Airport, and Alexandria in a toxic cloud, sodium hypochlorite bleach is far more benign if accidentally released. 7



### 6 Needl ess Ris k 

### Unfortunately, too few other chemical
facilities have followed the lead of the Blue
Plains facilit y, changing the processes and chemicals they use to make their facilities inherently safer. Instead, industry groups

### have empha sized increas i ng physical security at facilities, such as guards and fences. The
American C h emistry Co uncil, the chemical industry’s lobbying orga nization, has issued site security guidelines for its memb er companies a n d requires these comp a n ies take part in its R e sponsible Care program in order to continue membership in the organization. This set of guidelines, however, focuses mainly on si te security a n d does not include
minimum standards that facilities must follow. For example, it does not require that facilities provide for protection against an armed intruder. In addition, Responsible Care does not require that facilities use inherently safer technology to reduce the threat these facilities pose to surrounding communities. The industry does not even require members to set public goals and timelines to reduce chemical dangers.

Hiring more guards, building higher fences, and placing more lights may all be part of a good security plan, but this does not actually reduce the threat to the community. Switching chemicals and proces ses to something less volatile not only reduces the
chemical ha zard to the community, but also reduces the cost of physical security and the
attractiven e s s of the facility as a target for
attack.

Furthermore, some in industry and the government have proposed limiting the public’s access to information on the potential impact of a major chemical release on public health and safety. Limitations h a ve been placed on th e information any indivi dual can obtain to protect themselves and their families from chemical releases at neighboring facilities. Instead of safeguarding these
facilities fro m terrorists, these efforts merely deny public accountabi lity measures tha t encourage industry reform.

Nee d le ss Ri sk 7

# H YDROFLUORIC 

# A CID AND THE 

# P ETROLEUM 

# I ND USTRY

Petroleum refineries sta n d as a stark example of the safety hazards posed by using toxic
chemicals in the manufa cturing process and the opportunities to switch to safer
alternatives.

Petroleum refineries are responsible for nearly 11% of all of the high-risk processes i n EPA’s Risk Management Program, the a g ency’s primary chemical a ccident prevention program established under the 1990 Clean Air
Act Amend m ents. 8 

### Most notably, many of these refineries use hydrofluoric acid, also known as hydrogen fluoride, as a catalyst to produce an a dditive to ga soline. This additive
is then us ed to increase the octan e levels in gasoline, which addres ses the problem of engine “knocking.” Currently, 148 petroleum refineries operate in the United States, 50 of which use hydrofluoric acid as a catalyst to produce alkylate. 9



### H YDRO FL U O RIC 

### A CID 

### : A T HREAT TO


### H EALTH AND 

### S AFETY



### Highly toxic, hydrofluoric acid has many acute consequences for human health, as well as the ability “to kill people on the spot,” according to Jonathan Ward, director of toxicology at the University of Texas. 10 

### Even slight contact with hydrofluoric acid m a y caus e a v a riety of acute symptoms, including skin burns and deep tissue burns, whic h may not be felt for up to 24 hours after ex posure. In addition, hydrofluoric acid exposure commonly causes eye irritatio n and can lead to p e rmanen t damage. If inhaled, the acid can cause irritation of the nose, throat, an d lungs, causing coughing and dyspnea, or s hortness of breath. Severe exposure can caus e cyanosis, an indicator of hypoxemia, lung injury and a build up of fluid in th e lungs, known as pulmonary edema. 11 

### Once hydrof luoric acid penetrates body tissue,
it can react with the cal c ium and magnesium in the blood stream, causing abnorm a lly low
calcium co ncentrations and a condition known as hypocalcaemi a

. 12



### Case studies have shown hydrofluoric acid to be fast acting, reporting insta n ces of respiratory irritation in less than one minute after acute inhalation of 122 parts pe r million (ppm). 13 

### The Occupation a l Safety and Health
Administrati on estimates that the lowest lethal

concentra t ions range from 50-250 ppm for a five-minute exposure. 14



### U SE OF 

### H YDRO FLUO RIC 

### A CID IN THE


### P ETROLEU M 

### I NDUSTRY



### Petroleum refiners use hydrofluoric acid as a catalyst in th e alkylation process. With tighter standards on fuel emissions, alkylate has
become a k ey additive in gasoline b ecause i t offers a high octane with very low su lfur and nitrogen content.

Alkylation is the chemical process b y which high-octane gasoline is made. Light

, gaseous hydrocarbons, made up of compou nds like propylene a n d butylenes , feed into a reactor,
where conta ct with the a c id catalyst results in a reaction that produces a heavy mixture of hydrocarbons, along wit h excess heat, which must be removed. It is the liquid portion of this mixture that is known as alkylate, and it is responsible for the anti-knocking property of unleaded gasoline. 15 

### Lastly, becaus e s o me of
the a c id cata lyst leaves the reaction chamber along with the alkylate, further treatment to neutralize the acid is required as well in order to prevent corrosion further down the production line.

8 Needl ess Ris k

### C HEMICAL 

### A CCIDE NTS 

### I NV OL VING


### H YDRO FL U O RIC 

### A CID



### Hydrofluoric acid has a boiling point of 67o F (19.4o C) at atmospheric pressure, and most reactions take place at about 100o F (37.8o C) in petroleum refineries. Therefore, the aci d will vaporize whenever the container is penetrated. 16 

### Furthermore, when th e outside temperature is 67o F or greater, the containment unit housing hydrofluoric acid becomes pr essurized because of the acid’s high volatility. Therefore

, if hydrofluoric acid
is released from contain m ent, under certain atmospheric conditions it will form a stable
aerosol cloud.

Amoco, Mobil, Allied C h emical and DuPont tested the possibility of a release of hydrofluoric acid from one of their refineries
then under construction i n a Nevad a desert in
1986. Unde r conditions similar to those in an alkylation unit, lethal concentrations of hydrofluoric acid aeroso l were present up to five miles (8 km) from the release points, at
levels much higher tha n anticipated. 17 

### T h e amount of hydrofluoric acid released in the test was relatively small—1,000 gallons in two
minutes. 18



### Hydrofluoric acid refiner i es have long had a history of accidental rel e ases that p r ove the potentially devastating effects of a release caused by simple human error. The National Response Center recorded more than 400
incidents at refineries and other facilities involving h y drofluoric acid or hydrogen
fluoride fro m 1990 to 2005. 19 

### Simple malfunctions, ruptured valves or pipes, or
valves acci dentally op ened often caus e significant leaks that can harm b o th the people and the environment surrounding the refinery.

• On October 30, 19 87, a cran e at Marathon Oil’s Texas City refinery dropped its load on a storage tank, rupturing a pipe and releasing 30,000 pounds of hydrofluoric acid, the l a rgest known release. The resu lting vapor cloud sent 1,037 people to the hospital suffering from respiratory problems and skin rashes and forced 3,000 residents out of their homes for three days . “There were houses right up against the fence,” said Ronald Koopman of Lawrence Livermore. “The only thing that s a ved people was that the [ h ydrofluoric acid] plume shot 200 feet up in the air, and it
went abou t 900 meters downwind b e fore it actually came down into the neighborhood. If it had squirted out sideways, it would have killed hundreds, if
not thousands.” 20



### • On March 2, 2003, 13 ele ctricians wor k ing at the Marathon Ashland oil refinery in St. Paul Park, Minnesota were hospitalized after being exposed to hydrofluoric acid. They had been hired to repair damage to the facility caused by a fire a few days
earlier. Wh ile working, a pump le aked one cup of hydrocarbons with trace amounts of hydrofluoric acid, which immediately vaporized and entered their lungs. 21



### • An accidental hydrofluo r ic acid release in 1991 killed two workers and injured five
others at S o uthwestern Refining Co. in
Texas. 22



### • Between 1995 and 1997, four separate one-pound releases of hydrofluoric ac id at the Sunoco refinery in Philadelphia injured one worker in each acciden t

. 23



### Nee d le ss Ri sk 9 

### • On October 2, 2001, 150 pounds of hydrofluoric acid in low concentr ation
leaked with in the Valero refinery in Paulsboro, New Jersey. Because the wind
was blowi n g towar d neighboring
Greenwich Township, a nearby elementary school was forced to secur e all

### the children and staff in the gym by sealing the d oors and wi ndows with duct tape and plas tic. 24



### • On March 19, 1988, at the Sun Co. refinery in Tulsa, Oklahoma, an accid e ntal release of 210 pounds of hydrofluoric acid
sent a cloud of hydrofluoric acid drifting five miles through downtown. Had the
accident o c curred on a weekday, more people woul d have been injured. One resident, living in the downtown area, said, “I did n ’t realize i t was hazar d ous until I could see it leave orange particles everywhere...And th en my eyes b u rned, my throat bu rned and my head ached.” 25



### • On March 23, 2005, an explosion at a BP oil refinery in Texas killed 15 employees and injured more than 100. Th is wa s the third major acciden t i n a year at this facility. Although it did not involve a release of hydrofluoric acid, the presence of this chemical on-site was a major cause
for concern. 26



### H YDRO FL U O RIC 

### A CI D 

### : A T E RRO RIST 

### T ARGET



### According to Neil Livingstone, board chairman of Global Opti ons, a security firm in Washington, DC, hydrofluoric acid is a “known quantity to some terrorists,” particularly those from oil-producing countries where hyd r ofluoric acid is commonly u s ed. 27 

### Terrorist atta cks over the past 10 years have consistently targeted petroleum facilities throughout the world
because of their vulnerability, value to economies, and high volumes of toxic chemicals stored onsite. A few examples of coordinated attacks on petroleum facilities over the past 10 years include:

• During the Croatian wa r, Serbian armies
attacked a n a tural gas refinery in eastern Slovenia that stored ethane, propane, and
butane with rockets and cluster bomb s

. 28



### • Serbian forces attacked l a rge fuel storage tanks along the highway from Belgrade to the outskirts of Zagreb and started large fires at Osijek, Sisak, and Karlovak. 29



### • A refinery in Sisak, which pr oduced liquefied petroleum gas, fuel, petroleum coke, and solvents, was attacked with thousands of Serbian artillery rounds, which hit 38 petroleum s t orage tanks. If
these attacks had destroyed existing stored
chemical co ntainers, leth al concen trations
of chemicals would have covered a wide

area. 30



### • In October 2001, a group of Tamil Sea Tigers attacked and set ablaze th e oil tanker MV Silk Pride. It was carrying 225
tons of low-sulfur die s el, 160 tons of kerosene oil, and 275 tons of auto diesel. 31



### An organized attack on a U.S. oil refinery, similar to the attack on the Sisak refinery by Serbian forces, would be nearly impossible for security guards to prevent.

10 Needle ss R i sk 

### Furthermore, it is relatively simple for individuals to gain access to plants with the level of security comm on at refineries. As recently as J a nuary 2002, a robber carrying a shotgun made his way into a CITGO facility
in Texas. CITGO was o n e of the co mpanies
that claim e d to have dramatically in creased security mea sures after September 11, 2001. 32 

### In addition, activists a n d reporters have breached security at refineries and chemica l facilities across the country. Greenpeace
activists entered Dow C h e mical’s Plaquemine,
Louisiana fa cility in February 2001 th rough an unlocked gate and gained access to the control panel tha t regulates wastewa ter di scharges
into the Mi ssissippi River. 33 

### A reporter in Pennsylvania skirted inadequate security at
more than 30 chemical facilities and found

### that he “could walk or drive right up to tanks, pipes and control rooms considered key targets for terrorists. ” 34



### Assuming that on-site security was able to prevent all unauthorized access to a refinery and water mitigation systems a 

### were installed throughout the refinery, it would still not be
difficult to release hydrofluoric a c id into surrounding communiti es. Accor d ing to Carol Coy, a California regulator whos e agency push ed for an en d to hydrofluoric acid use in southern California, saboteurs could deactivate the mitigatio n systems s i mply by shutting off the electricity. 35 

### Furthermore,
munitions fired from an offsite location could puncture the storage tanks holding hydrofluoric acid.

National security exper t s recognize that a
terrorist attack on chemical facilities and refineries is more likely than an atta ck with a
conventional chemical weapon. Creating chemical weapons is a complex and expensive process, whereas industrial facilities provide relatively ea sy access to large am ounts of
chemicals fr om which a significant chemical
release coul d harm con s iderable numbers of people. In a Senate co mmittee hea r ing on June 15, 2005, even the Department of Homeland Security (DH S ) expressed concern about the consequences of a terrorist attack on a chemical facility. 36 

### Robert Stephan, an
undersecreta ry in the D H S, noted that, as an aspect of America’s “critical infrastructure,” chemical facilities indeed represent a dangerous terrorist target. In addition, chemical facilities have many eas y acces s points, making facility security more difficult. According to Stephan’s testimony:

a Water mitiga ti on systems are desi gned to co ol nearb y liquid p e trol eu m ga s con t aini ng vess els and columns to insure thei r st r u ct ural int e g r it y

and to re du ce hyd r og en fluoride vapo rs if a leak wer e to oc cu r. For wa te r mitiga tion sys t ems to eff e c t ively re du c e hyd r og en fluorid e vapor s in the event o f a leak , sen s ors to d e t e c t the l e ak must b e installed. 

### “DHS has identified five areas as the focus of our primary preparedness work with the industry: access and acces s control, operational s ecurity, process control, facility systems operations, and local first responder and external response and recovery coordination. These preparedness planning variables must be refined with reference to potential methods of attack. These include perhaps most impo rtantly: insider threats or sabotage; cyber atta ck; a n d atta cks u s ing explosives or other weaponry.” 37



### Amy Smiths on, director of the Chem i cal and Biological Weapons Non- Proliferation Project
at the H e nr y L. Stimson Center, testified to this in a House of Representatives co mmittee hearing:

Nee d le ss Ri sk 11 

### “Although assembling fr om scratch an unconventional weapons capability that
could cause mass casualties is not that elementary, there are tangible routes whereby terrorists could inflict
considerable harm with chemical and biological substances. One shortcut involves foul play with indus t rial
chemicals... Logic dictates that if the same result [mass casualties from a
chemical r e lease] can be a c hieved through a less arduous route, terrorists intent on causing mass casualties with chemicals would probably engineer the
intentional r e lease of ind ustrial chemi c als rather than wrestle with the complexities of making large quantiti e s of the cl assic chemical warfare agents.” 38

# R EPOR T 

# F INDINGS 

# : C OMMUNI TIES AT 

# R ISK

Under the Clean Air Act’s chemical acciden t prevention requirements, industrial plants th at use large volumes of certain toxic materials must file accident prevention plans (Risk Management Plans) with EPA that include
worst-case accident scen arios. These estimate
how far a chemical coul d travel off-site and
still maintain toxic concentrations in certain
weather con d itions and r e port the nu mber of people living within that distance, na med the
“vulnerabilit y zone.” b 

### We examined the most
recent Risk Management Plans for the 50 petroleum refineries in the United States using hydrofluoric acid in their processing or storing it on-site. These 50 refineries comprise o n e-third of the 148 refineries operating in the U.S.; meaning, two-thirds of
all refineries use tech nology other tha n hydrofluoric acid.

These 50 refineries, using and storing 10.6 million pounds of hydrofluoric acid, endanger
more than 17 millio n people living in surrounding communities in 20 states (Table 1). See the Appendix for a list of all 50 refineries using hydrofluo r ic acid in the U.S.

Texas is home to the most hydrofluoric acid refineries, w i th 12; Loui siana is second with
five facilities ; and Montana is third with four
facilities. These states are not home to the
refineries that collectivel y endanger the most people, however; often a single refinery can endanger millions. Just two refineries using hydrofluoric acid in Pe nnsylvania endanger
more than 4. 4 million people residing in their vulnerability zones, a ccor d ing to cons ervative
estimates. I n New Jersey, a single refinery using hydrofluoric acid endangers more than

b It is importan t to note th at not all p e ople living within a vulnerability zone would be affected by a single chemical release; tho s e living downwind during a
che m ical r e leas e a r e mos t likel y to be aff e c t e d

. 

### 3.1 million people living with in the vulnerability zone. Three Illinois-based refineries also endanger 3.1 million people living within the vulnerability zones.

Table 1. Oil Refineries by State and Popul a tion at Ri sk
in Each State in Event of Worst-Ca se Release of Hydrofluoric ( H F) Acid

State # of Oil

Refineries # of Refineries Using HF Acid Population Endangered By

HF Releas e A L 3 0

- A K 6 0

- A R 2 0

- C A 2 1 2 360,00 0

C O 2 0

- D E 1 0

- G A 1 0

- H I 2 0

- I L 4 3 3,183,00 0

I N 2 1 8

, 0 0 0

K S 3 3 6 3

, 8 0 0

K

Y 2 1 300,00 0

L

A 1 7 5 1,436,41 1

M I 1 0

- M N 2 1 2,200,00 0

M S 4 0

- M T 4 4 183,70 4

N V 1 0

- N

J 6 1 3,170,00 0

N M 3 2 1 8

, 8 2 9

N D 1 1 6 8

, 0 1 3

O H 4 1 940,00 0

O K 5 3 113,38 8

O R 1 0

- P A 5 2 4,400,00 0

T N 1 1 791,88 8

T X 2 6 1 2 1,930,80 5

U T 5 3 680,00 0

V

A 1 0

- W

A 5 1 120,00 0

W

V 1 0

- W I 1 1 180,00 0

W

Y 5 2 6 3

, 0 6 7

Total 148 50 17,040,905 c

Data on number o f oi l ref i neri

es b y state obta i n ed fro m Energy Info rma t i o n Admin i str

a tion. 39 Data on oil refiner i es using hydr ofluor ic ac id and t h e populat i on at r i sk
obtai n ed

fro m co mpany Ri s k Management Pl ans (see methodolog y f

o r more deta i l s).



### 12 Needle ss R i sk c This is not the agg r e g at e tot a l of th e s t a t e to tals, as it
takes in to account overlapping vulnerability zones
betwe e n sta t es

. As s u ch , this is a conse r vativ e esti mat e

.

### Table 2. Ten Refineries Endangeri n g the Most People in
Event of Worst-Case Releas e of Hydrofluoric Acid

Facili ty Na me Locat i on
Sunoc o Phil a d elphi a Refi ne ry Philadel phi a, PA

Valer o Re fini ng Co

. Paulsbor o, NJ

PDV Midwest Refini ng ( C I T GO ) Lemo nt, IL

ConocoP hilli ps Trainer R e f i n e r y T r a i n e r , P A

Marat h o n As hla n d Petr ole u m, MN Refi ning Div. St. Paul Park, MN

Chal me tte Ref i ning Chal me tte, L A Murphy Oil U S A, Inc. Meraux Refinery Meraux, LA

Exxo nMobil Oil Cor por ati on J o liet Refi nery Cha n na ho n, I L

Marat h o n As hla n d Petr ole u m, Ohio Ref i ning Div. Can t o n , O H

ConocoP hilli ps Alliance Refi nery Belle Chasse, LA

Data on oil ref i neri es u s i n g hydro fluori c ac

i d o b tai n ed

fro m co mpany Ri sk Man a gement Pla n s (see metho d olog

y fo r more det a ils).



### In some cases, however, the vuln erability zones of two or more refineries overlap, posing an ev en greater d a nger to peo p le who
live and work within the overlapping areas. In Philadelphia, for example, the vuln erability
zones of two refinerie s overlap a c ross the
Delaware R i ver, encompassing the airport, sports stadiums, and many neighborhoods. 40 

### In Corpus C h risti, Texas, four refineries using hydrofluoric acid are located near each other; similarly, three refineries using hydrofluoric acid are situated close together near New Orleans, Louisiana.

Single refine ries can end a nger thousands or millions of people. Seven petroleum refineries with hydrofluoric acid alkylation facilities reported toxic release “worst-case”
scenarios in which mor e than one million people could be affected. Furthermore, 15 refineries could place more than 500,000 people in ha rm’s way, an d 28 refineries could endanger m o re than 10 0,000 people in the event of a worst-case hydrofluoric acid
release.

The 10 facilities putting the most people at
risk in the event of a worst-case release of hydrofluoric acid are found in Illinois, Louisiana, Minnesota, New Jersey, Ohio, and Pennsylvania (Table 2). Many parent companies put mil lions of people at ris k from the hydrofluoric a c id they
use and store at their refineries. The companies with the mo st people residing in the vulnerability zones of refineries using hydrofluoric acid include Sunoco, Valero Energy Corporation, Marathon Ashland Petroleum, ConocoPhillips, CIT G O, and ExxonMobil (Table 3). These companies each put at least two million people at risk.

Table 3. Pare nt Companie s With at Least One Million People Living in Vu lnerability Zo nes of
Their Refineries U s ing Hyd r ofluoric Acid

Parent Compa n y Population at
Ris k

Sunoco

, Inc. 4,400,000

Valero En ergy Corporation 4,366,193

Marathon Ashl and Petroleum 4,132,993

C o n o c o P h i l l i p s 3

, 5 3 2

, 7 6 3

CITGO 3,415,420

E x x o n M o b i l 2

, 3 9 3

, 8 4 7 Murphy Oil Co rporation 1,236,000

Premco r In c. 1,121,888

Data on o i l ref i ner

i es using hy droflu oric acid and the p o pulat i on at ris k
obtai n ed

fro m co mpan y Ri sk Managemen t Plans (see methodolog y for more details).



### Nee d le ss Ri sk 13 

### Many companies that utilize the dangerous hydrofluoric acid technology also use
refineries without that technol ogy.

### ConocoPhillips, ExxonMobil, Valero Energy Corporaton, and Marathon Ashland, for example, own refineries t h at use hydrofluoric
acid as well as refineries that use other technologies.

• ConocoPhillips owns six refineries t h at report to EPA’s Risk Management Program for their use of hydrofluoric acid, but run s 12 refineries in the United
States. The other six facilities presumably use a safer technology than hydrofluoric acid.

• Valero Energy Corporation owns sev e n refineries in the United States that use hydrofluoric acid and five others that do not use that technology. One Valero refinery in Wilmington, California has responded to concerned residents and is switching from hydrofluoric acid to a
safer technol ogy. 41



### • ExxonMobil owns or co-owns four refineries that use hydrofluoric acid and
three oth e r refineries in the United
States tha t d o not.

• Marathon Ashland owns six hydrofluoric acid refineries in the U.S. and one refinery that does not use that technology.

Companies owning faciliti es that use different types of chemicals in their alkylation processes illustrate not only that alternative

processes ar e possible to implement, but tha t some companies have knowledge of safer alternatives and choose not to implement
them.

14 Needle ss R i sk

# H OW 

# P OLICY M AKER S A N D 

# I ND USTRY 

# S HOULD 

# P ROTECT



# C OMMUNI TIES

A P REVE NT IVE 

### A PPR OA CH



### The actions of American industry—and American regulatory policy—have historically focused on preparing for or managing
chemical a c cidents and releases rather than preventing them. The continuing legacy of
chemical accidents and un-addressed
vulnerabilities in the Unit ed States is evidence
that this stra tegy has failed to protect public safety. Furthermore, the events of September

11 th 

### make plain the need for preventive action. Safety valves may mitigate th e effects of a n accidental release, and employee trai ning may reduce the chances of an accident, but neither can protect public safety if a terrorist parks a
truck bomb at a chemi c al plant or refinery. Designed to protect onl y against accidental releases, many accident m i tigation technologies could be foiled by a deliberate
saboteur.

Reducing or eliminating chemical hazards offers the best strateg y to fully protect
American communities from both accidents and terrorist attacks involving industrial
chemicals. Hazard redu ction means making a chemical pro cess inherently safer by eliminating the use of highly toxic, volatile, or flammable chemicals or using chemicals i n safer quantities or conditions. The concept of inherent safety leads to a hierarchy to guide decisions on the use and management of
chemicals: First , reduce or eliminate the possibility of
a chemical release by choosing inherently
safer materia ls and techn o logies.

Second , reduce th e probability of a
chemical release th rough secondary prevention measures such as safety valves and double-walled vessels. In preventing terrorism, increasing site security is an additional secondary prevention measure (although inadequate i n the con text of
modern terrorists’ tactics ).

Third , reduce the potenti a l severity of the impacts of a chemical release through mitigation measures (containment dikes, sprinkler systems) or emergency response plans. 42



### Again, the first option—inherent safety— provides the best respo n se to the threat of
chemical releases caused by acts of terrorism because it eliminates the poten tial hazard. Add-on security and mitigation measures
could make minor contributions toward preventing an act of terrorism, but traditional tools of terrorists—truck bombs, suicide bombers, and now airplanes—wou l d likely render such measures useless. Site security measures could prevent a terrorist from entering the grounds of a facility, but in the embassy bo mbings in Africa, the trucks containing bombs wer e parked near, not inside, facilit y grounds. Increasing physical security woul d have been of little help.

Nee d le ss Ri sk 15

# I NHER ENT 

# S AFETY AT 

# R EF INERI E S 

# : A LTERNA TI VES TO



# H YDROFLUORIC 

# A CID

Three optio ns are avai lable to petroleum refineries using hydrofluoric acid as a catalyst for alkylates in order to make this process inherently safer.

• Change the alkylation process to use a solid acid catalyst;

• Convert the hydrofluoric acid alkyl a tion
unit into a sulfuric acid un it; or

• Add modifiers to the hydrofluoric acid
that decrea se the gas e ous nature of hydrofluoric acid and install mitigation

systems.

P REVE NT THE 

### P OSSIBI LITY 

### : S OLID 

### A CID 

### C ATALYST



### The best option available to oil refineries is switching from using hydrofluoric acid to a solid acid catalyst, which completely
eliminates th e need to us e either hydrofluoric acid or sulfuric acid to produce alkylate. Industry experts report that a variety of solid acid catalysts will be a v ailable for use in alkylation facilities within the next four years. Critics, however, insist this technol ogy has
been available since the la te 1990s, and simple industry inertia has kept solid acid catalysts from becoming the popular choice for refinery alkylation process e s. 43



### Solid acid catal y sts have tr emendous environmental and safety advantag es over both hydrofluoric acid and sulfuric acid
because th ey are neither corrosive nor particularly hazardous to people or the environment. Furthermore, in the event that the container housing the catalyst is breached, no further damage would result. Using a solid acid catalys t provides many benefits, including
reduced wa ste disposal costs and hazards, possibility to expand capacity at a lowered capital cost, and less corrosion of the equipment, resulting in lower mai n tenance

costs. 44



### Considerable research is being condu cted on solid acid catalysts, and three main options currently exist: Albemarle Co rp./ABB Lummus Global/Fortum Oil’s Alky Clean TM

, UOP’s Al kylene TM , and Exelus Inc.’s

ExSact TM

.

AlkyClean TM ’s demonstration phase at Fortum’s facilities in Porvoo, Finla n d was completed in January 2 0 05 and is currently
commerciall y available. Accordin g to the manufacturers, the opera ting and capi tal costs of the AlkyClean TM process rival those of the liquid acid catalyst processes and produce an alkylate of similar high q u ality. 45



### This solid acid cataly s t also can replace existing hydrofluoric acid or sulfuric acid alkylation un its, reusing the existing feedstock pretreatment and product distillation/recycle facilities. Converting to a solid acid catalyst would save the facility m oney over a sulfuric acid plant because this technology does not require refrigeration for the reactio n to take place. Furthermore, there is no need to
remove aci d from the finished product, thereby eliminating yet another step in th e
process. 46



### 16 Needle ss R i sk 

### UOP’s Alkyl e ne TM operates similarly, with the primary difference betw een the two available processes consisting of how the solid acid is regenerated. The biggest difference is tha t AlkyleneTM does not h a ve the energy savings associated with AlkyClea nTM. Furthermore,
the feedstock does have to be treated to

### remove imp u rities. Yet, even with these differences, AlkyleneTM is still very cost competitive with hydrofluoric and sulfuric
acid facilities. 47 

### Recent industry publications report this technology has “overall economics superior to sulfuric acid techn o logy.” 48 

### AlkyleneTM also has recently become
commerciall y available, though there is limited
interest so fa r in the United States and Europe given the need to cons truct new s o lid acid

units. 49 

### In February 2005, however, th e Baku Heydar Aliyev Refinery of Azerbaijan awarded

UOP a contr a ct for the d e sign of a new highoctane gas facility, which included, among other technologies, the world’s first Alkylene TM unit. Production is estimated to start by 2008. 50



### Exelus Inc. also has a n ew solid aci d catalys t technology (ExSact TM ) th at is currentl y in its
six to nine month dem onstration phase that precedes co mmercialization. This technology not only incl udes a stabl e and active catalyst,
but also a fixed-bed reactor that enha nces th e efficiency of the reacti on and reduces the

cost. 51 

### According to a representa tive of Exelus Inc, U.S. petrochemical co mpanies, not refineries, have shown interest in this technology; oil refineries in Norway and

Eastern Eur ope have demonstrated i n terest. 52



### All three of these alkyl a tion proces ses cost significantly less than sulfuric acid alkylation units and virtually the same as hydrofluoric acid units. Manufacturers expect the market for solid acid catalyst technology to increase significantly as oil refinery alkylation units age and have to be replaced. The mounting costs of physical site security also add an incentive
for refineries to s e lect alternati v es to dangerous hydrofluoric a c id.

R EDUCE TH E 

### S EVERITY 

### : S ULFU RIC 

### A CID 

### A S

AN 

### O PTION



### Sulfuric acid is often us ed in the alkylation process instead of hydr ofluoric acid because when released, it will not readily form a toxic aerosol cloud. Instead, sulfuric acid is released as a liquid fo rm, making it much

easier to co ntain and p r event expo sure to those offsite. As a result, sulfuric acid does not pose as much as a th reat to life outside of the facility.

Converting a hydrofluoric acid alkylation unit into a sulfuric acid alkylation unit requires several equipment chan ges. First, a sulfuric acid alkylation unit requires a refrigeration

process. d 

### Second, if the hydrofluoric acid facility conta i ns the meta l monel, it must be replaced because it reacts with sulfuric acid. Finally, an acid regeneration facility also
should be constructed on site so as to decrease the need to frequently tr ansport sulfuric acid, which poses the risk of offsite consequences.

The fundamental difference between using hydrofluoric acid and sulfuric acid in the production of alkylate i s in how the acid is regenerated, once the acid beco mes to o contamina t ed with imp u rities. Hydrofluoric acid can be distilled to remove impurities. However, sulfuric acid must go t h rough a series of steps that first break down the aci d
into sulfur dioxide and then mix the sulfur
dioxide with water to create reg e nerated
sulfuric acid. 53 

### Sulfuric acid catalysts inevitably co st about fifty cents per barrel of alkylate mor e than hydr ofluoric acid catalysts because of the elaborate regeneration process that sulfuric acid requires. 54



### Although sulfuric acid is less hazardous than hydrofluoric acid, direct exposure to sulfuric
acid can caus e many detrimental health effects

at concen trated levels, such as burns or severe irritation to the eyes, skin, and respiratory

Nee d le ss Ri sk 17 d Th e cat a lyti c rea c tion usin g hydrofluori c acid takes place aroun d 1 00o F, which o n ly nec e ssi tat e s the us e of

wate r cooling t o wers to maint a in an op timu m r e a c tio n

te mper at ur e. The r e a c tion t o produ ce alky late usin g sulfuri c acid i s optimized at 45o-50o F (7 o-10o C), requiring refri g eration to maintain th e optimum

rea c tion te mpe r atu r e

.

### tract if concentrated fumes are inhaled. Because sulfuric acid is often regenerated offsite, there is a risk of an accident involving sulfuric acid during transportation. Once onsite, however, it can be regenerated indefinitely if the refinery builds a regeneration facility.

Two options exist to switch the al kylation process from hydrofluoric acid to sulfuric acid: using a conversion system or building a new sulfuric acid alkylatio n unit. One system for switching from h y drofluoric acid to sulfuric acid is the AlkysafeTM conversion/expansion process, offered by STRATCO®. Alkysaf e TM reuses both the
reaction and distillation sections of the alkylation facility. e 

### D u e to the short
downtime a n d the amou nt of equipment tha t is reused, STRATCO claims that Al kysafeTM is cost-competitive with mitigation systems being installed on hydrofluoric acid alkylation units. These mitigation systems, on average, will cost a refinery between $20 million and $30 million, with costs reaching at most $50
million. 55



### The cost of building a su lfuric acid alkylation unit varies according to th e amount of alkylate the refinery produces ea ch day. As a general rule, a new alkylation unit will cost about $5,000 per barrel of alkylate produced, per day. Theref ore, a new al kylation unit capable of producing 10,000 barre ls of alkylate per day would cost about $50 million. ST RATCO’sAlkysafeTM process is estimated to cost onehalf to two-thirds the cost of installing a new sulfuric acid alkylation unit. 56



### ExxonMobil also offers a sulfuric acid alkylation process that can replace hydrofluoric acid alkylati on systems, although the cost of the process is higher than using the STRATCO designs. However, this

e The distillation section of the alkyl a tion unit
neutralizes an y aci d l e aving th e r e a c tion cha m ber with the alkylat e

. 

### process also would be competitive with building a new hydrofluoric acid alkylation

unit. 57 

### It is currently in use in approximately
12 refineries. 58



### R EDUCE TH E 

### P ROBABILITY 

### : H YDRO FL U O RIC 

### A CID 

### M OD IFIERS



### The final option availa ble to decrease th e threat of a hydrofluoric acid rel e ase is to invest in alkylation modifiers and install active mitigation units, such as water spray systems. This option, however, does not remove the possibility of a terrorist threat, and an adversary co uld thwart m i tigation systems.

Modified hydrofluoric acid reduces the ability of the acid to form an aerosol cloud by a certain percentage, ther eby mitigati ng the impact the toxic clou d will have on the surrounding community. UOP and Texaco estimate the cost of modifying a hydrofluoric acid alkylation refinery using Alkad, a passive mitigation system, at $7 million. This estimate, ho wever, does not include the cost of active mitigation systems, which would be necessary in order to truly reduce the potential severity of a release. 59 

### Mitigation systems cost, on average, betw een $20 million and $30
million to install. 60



### ConocoPhillips and ExxonMobil have devised
their own al kylation mo difier under the name ReVAP, wh ich has the ability to reduce hydrofluoric acid aerosol formation when leaked by 60% to 90%. ReVAP is currently licensed at five refineries, including the Woods Cross Refinery in Utah and the Torrance Refinery in Cali fornia. 61



### 18 Needle ss R i sk 

### In 2003, public pressure succeeded in persuading t h e Valero Energy Corporation to switch to modified hydrofluoric a c id at its Wilmington, California refinery, near Los Angeles. Since an explosion that caused an accidental release of hydrofluoric a c id at a neighboring Torrance refinery in 1987, the
local com m unity and government hav e

### pushed to sh ut down two refineries that used hydrofluoric acid and required a third facility to change to modified hydrofluoric acid. The community was abl e to n e gotiate a n agreement with the South Coast Air Quality Management District with regards to the Valero facility; Valero decided on ConocoPhillips’ ReVap technology and will pay a fine up to $1 millio n if the renovation is not complete by the end of 2005. The change is expected to cost Valero abo u t $30
million. 62

, 63



### Since both modification systems canno t completely r e duce th e th reat of a hyd r ofluoric acid release, active mitiga tion units also must be installed. Active mitigation for hydrofluoric acid requires sensors to detect a hydrofluoric acid release; acid pumps to quickly move the acid to remote loca ti ons and decrease the amount of acid that is released; and water sp ray systems that knock th e acid to the ground and prevent it from affecting surrounding communities . If the sensors are working properly and detect a leak immediately, water spray systems ca n knock up to 90% of the hydr ofluoric acid to th e ground; however, tests have shown that i t requires at least 40 volumes of water for each volume of hydrofluoric acid released.
Effective wa ter spray systems often include water spray curtains an d remotely operated

water cann o n s. 64



### Nee d le ss Ri sk 19

### T ABLE 

### 4. C OMPARISO N OF 

### I NHERE N TLY 

### S AFER 

### T ECHNOLO G IES FOR 

### P ETROLE UM 

### R EFINERIE S 

### U SING 

### H YDRO FLUO RIC 

### A CID

Sulfuric A c id Solid A c id Catalys t HF modifier

How Catalys t Regenerated Decompos ed i n to sulf ur dioxi d e , th en re gen e ra te d b y mixing wi th water vapor Frequent regen e ration
with dissolv ed hydrogen

ever y two to fo ur w eeks

. Distilled

Required Facility
Modification Some versions require a new refrigeration fac ility and design change an d mo difications of

cur r en t equip m ent ; oth e r versions canno t be fi tted to existing alk y

lati on processes. AlkyleneTM and
ExS a c t TM r e q u ire entirely new alkylation facilities, while AlkyCleanTM o n ly

req u ir es a new
reg e n e ra tion s y ste m

. Addi tional separation

e quipme n t need ed t o remove l e aching acid fro m alkylate.

Advantage over HF Alkylation
Unit Will not fo rm an aerosol clo u d and will not po se a th reat to life outside the facility. No co rrosiv e a c id can le ave t h e re ac t i on chamb e r

. No threat of a chemical spi ll to anyone. De cr eas e H F a e rosol
formation from 60% to
90% in the eve n t of a le ak, dep e ndin g on v e rsion
used.

Additional Mitigation Systems
Needed N o n e N o n e Active mi tigati on sys t e m s

ne ed ed.

Safety
Concerns Acid spill durin g transport to the re finer y

and to th e
regen e ration facility if th e
regen e ration facility is not p a rt of the refinery. None Active mi tigati on sys t e m s can fail.

Cost of
Conversion Varies dep e ndi n g on th e daily

outpu t r e q u ire d

. Esti ma te d to cost betw een $2,500 to $3 ,333 per b a rrel of al kylate pro d uced

per da y fo r on e version

, $5,000 per barrel for anoth e r. Cost comp etiti v e with installing a new hydrofluori c aci d uni t
, less than installing a

s u l f u r ic ac id a l ky l a t

i o n unit. Valero is payin g an esti mated $30 million to
convert its Wil m ington

, CA refinery; most modifi ers cost $7 million plus th e cost of ac tive mitiga tion s y st e m s.



### 20 Needle ss R i sk

# R EDUC ING 

# C HEMICAL 

# H AZARDS 

# T HR OUGH 

# P OLICY



# M EASURES

The possibility that terrorists could turn American industry into weapons that threaten
Americans’ s a fety provides policy-makers with a clear imperative to revise existing policy on
lethal ch emi c al releases. Furthermore, more
action is needed th a n simply increasing physical security at chemical facilities; more physical security measures do not offset the possibility of terrorists taking extreme
measures to orchestrate a chemical rel e ase.

I NADEQUAC IES OF 

### E XI S T ING 

### P OLICIES



### Industry Ca nnot Be Left to Volunta r y Measures

Since September 11, 2001, our na tion has tightened security in a variety of venues. Airports and airlines have numerous new regulations they must fo llow; airplanes have routinely pa trolled our water sup ply; our government has even established an entire new governmental department, the Departmen t of Homela n d Security. Despite the repeated admission by government officials that the chemical industry poses a significant security threat, however, n o federal regulations exist that require oil refin e ries or any chemica l facility to reduce their hazards when they ar e able to do so.

Instead, some facilities subscribe to a voluntary industry program known as Responsible Care. Res ponsible Care is an initiative developed by the Chemical
Manufacturers Associati on (CMA), now the
American C h emistry Council (ACC), in 1988 to respond to the public’ s lack of confidence in the chemical industry. The CMA n eeded to act to address the poor public image or “end up in worse shape than the atomic industry,” according to John Johnstone, a former
chairman of CMA. 65 

### Fifteen years later, the ACC requires all member companies to comply with this voluntary initiative to improve security. Responsible Care, however, only requires facilities to install physical security and does not address preventing
accidents or terrorist attacks by r e quiring companies to switch to s a fer technol ogy.

A former m e mber of th e Security C o mmittee of the American Chemistry Council, as well as a former Security Manager for Georgia-Pacific Company, has addressed just how inadequate these voluntary guidelines are. In a June 2005 hearing in the Hous e Subcom mittee on Economic Security, Infra s tructure Protection

, and Cybersecurity, Sal DePasquale said, “it may be argued that inner city liquor stores are better protected than are the facilities that manufacture and use highly toxic a n d lethal chemicals.” Despite i n dustry’s claims of effective self regulation, he continued, “if the industry will not issue sub stantive standards, it cannot say that it is self r e gulating. It is simply
a contradicti on in terms.” 66



### Furthermore, ACC is made up of only around 160 of the largest chemical co mpanies, meaning that, according to Department of Homeland Security statistics, 20% of chemical companies i n the United States do not fall under any s o rt of voluntary chemica l security
standards. 67



### The EmergencyPlanning and Community Right-toKnow Act

Nee d le ss Ri sk 21 

### After the 1984 Union Carbide chemical disaster in Bhopal, India, which killed thousands of people, grassroots pressure convinced Congress to pass the Emergency Planning and Community Right-to-Know Act (EPCRA). This act esta blished a network of

### Local Emergency Planning Committees (LEPCs) and required facilities to disclose a baseline of important information on
chemical ri sks, including the am ount of hazardous materials stored at particular
facilities.

Despite some positive results of EPCRA, including the creation o f the Toxics Release Inventory a n d a gener a l decline i n toxic releases, this law did not address the need to prevent chemical releases before they happen

. Instead, it only addressed the need to prepare for and respond to them. The LEPCs lack the authority to manda te hazard reduction, and many ar e inactive. 68



### The Clean Air Act and Risk Management Planning Program

In response to an explosion at a Phillips chemical facility in Texas that killed 23 workers in 1989, Congress took further action by adding amendments to the Clean Air Act

in section 112(r). These a m endments established the Risk Management Planning (RMP) program that requires ind ustry to develop a hazard assessment tha t covers various release scenarios, off-site consequences, and a five-year accid e nt history; a preventi on progra m that manages procedural areas such as training and safety audits; and an emergency response program.

Therefore, the Risk Management Planning program addresses the management of chemical risks, but not their prevention. If the RMP program were fully implemented as EPA originally intended, the wo rst-case scenario estimates of off-site impacts o f
chemical releases would be available in a national database and could help reduce chemical hazards, much as the Toxics Release Inventory has. Althoug h originally available to the public online, the RMP plans have been removed from public view and are now
difficult fo r individuals to obtain. The case stu d y of the voluntary ch anges at th e Valero refinery in California shows that when a community is aware of the threat a local refinery poses to its safety, public pressure

may succes sfully persua de the facility to change its ch emicals and processes in order to
reduce th e threat. In order for the RMP program to be successful, risk management plans must be readily available to the public.

EPCRA and RMP Too Specific to Address Threat

In addition to the limitati ons addressed above, both EPCRA and the RMP program were not designed to address the threat of a terrorist
attack a t a chemical facility, and cons equently pertain only to certain chemicals, i n dustries, and facilities using qua ntities of chemicals
above certai n thresholds.

Smaller quantities of chemicals are easier to manage onsi te and therefore pose less of a concern for accidental releases. Terrorists, however, could specifically target smaller quantities of chemicals and stil l causesignificant harm. For example, a single oneton cylinder of chlorine gas can fal l below thresholds for the RMP program. The quantity of chlorine gas in this cylinder, however, co uld result in toxic concentrations nearly two m iles off-site.

T HE 

### R IGHT 

### -T O 

### -K NOW AS A 

### S AFETY 

### T OOL



### The federal government should not limit the public’d access to information about chemical
use and rel e ases in th e effort to prevent chemical terrorism.

22 Needle ss R i sk 

### Ensuring a community’s right-to-know about chemicals used, stored and released has long been a useful tool in protecting public safety
from toxic hazards. In Massachusetts, for example, companies are required to assess and disclose all chemicals used by their facilities as
well as com p lete toxics use reductio n plans. Simply by completing these plans, and not necessarily even implementing them,

### Massachusetts comp anies have redu ced th eir overall use of toxic chemicals by 4 0 %, the waste generated b y 70%, and their
environmental releases b y 92% between 1990 and 2003. At the same time, production
increased 23% at these facilities. 69



### New Jersey has seen similar success with its Pollution Prevention Act, which requires companies to assess and report ch emical use. As a result of these reporting requirements
and the To xic Catastro phe Prevention Act,
hundreds of drinkin g water facilities and sewage treatment facilities have stopped using chlorine gas.

Based on th ese examples, it is likely that if a petroleum r e finery com p leted an as sessment of available inherently safer technologies, and was required to disclose the findings to the public, it would be compelled to switch to a
safer technol ogy.

P ROTECTIN G 

### C OMMUNI TIES THROUGH


### I NHERENT L Y 

### S AFER 

### T E C HN OL OGY



### The most effective m e ans of pr otecting
American co mmunities from the cons equence of an act of chemical terrorism is to require facilities to implement inherently safer technologies.

In the case of hydrofluo r ic acid in alkylation units, inherently safer technology exists and is proven to work. Facilitie s should change their chemicals and processes to a safer tec hnology as soon as possible, and new facilities should be built using the safest technology available. Policymakers could require refineries to change thei r processes or to co nduct a technology options anal ysis. 70 

### A technology options anal ysis is a way to address a range of industries and require them to make a
concerted ef fort to identify inherently safer options in their chemica l uses and processes. Furthermore, a technology options analysis provides an opportunity for facilities to adopt technologies with acceptable cost and appropriate performance characteristics and to explain why tech nologically feasible options

were not s e lected. Th es e tech nology options analyses should be made publi c , while protecting legitimate confidential business information, in order to inform communities of safety measures at nearby facilities as well
as to disseminate information on innovative technologies.

Nee d le ss Ri sk 23 

### Oil refineries using hydrofluoric acid on site pose an unnecessary risk to surrounding communities. By requiring facilities to switch
to inherentl y safer tech nologies, as well as requiring th em to publicly disclose plans to

protect su rrounding commun i ties, oil refineries could greatly reduce th eir risk. As
oil refineries are not the only facilities that pose unnecessary risk to surrounding

communities , these sa me policy changes should apply to a variety of industries and facilities. Future policy must f o cus on significantly reducing or eliminating the potential har m posed by terrorist attacks on
industrial fa cilities, instead of focusing on physical secu rity and the unachievable task of mitigating the consequ e nces of a major
chemical release.

# M ETHODOL O GY

The vulnerability zone d a ta in this report were collected from Risk Management Planning reports obtained at public reading rooms operated by the Environmental Protection Agency in Washington DC, in compliance
with all rules that cu rrently govern the
collection of such data. We collected this data in June and July 2005.

Facilities had to repor t their latest Risk Management Plans to EPA starting in June 1999 with revised reports due no less often then every five years. T h e data used in thi s report are current as of Decemb e r 2004. Facilities are required to file RMPs if they
store hazard ous chemica l s listed in section 112(r) of the Clean Air Act above a threshold level used in regulated processes. These facilities span a broad spectrum of industries, including chemical manu facturers, petroleum refineries, agricultural wholesalers, drinking water and wastewa ter treatment systems, electric utiliti e s, and other s

.

To estimate the total number of people living in the vulnerability zones in each state an d nationally, we reviewed the geographic location of each facility, as oil refineries are often grouped together o n ly a few miles apart.
In order t o avoid double counting, we
assumed if t h e vulnerability zones of two or more facilities overlapped that they overlapped entirely. In these insta n ces, we included the highest at-risk population from
the facilities in our calculations.

As a result, the rep o rted totals are a conservative estimate of the to tal p opulation
at risk in each state. In a ddition, the totals do not reflect the fact that many individuals are

at a heightened risk because th ey liv e within the vulnerability zone of two or more oil refineries using hydrofluoric acid.

24 Needle ss R i sk

# A PPENDIX 

# : O IL 

# R EFINERI E S 

# U SI NG OR 

# S TORING



# H YDROFLUORIC 

# A CID 

# O N 

# -S IT E

Nee d le ss Ri sk 25 State Facility Na me City Parent Compa n y
CA ExxonMobil Torran c e Refin e ry Torrance ExxonMobil

CA Ultram ar In c. d/b/a Val e ro Wi lmington R e fi n e ry Wilmington Valero En ergy Corporation

IL ExxonMobil O il Corporation Jolie t Refinery Channahon ExxonMobil

IL PDV Mi dwest Refining, LLC Lemont CITGO

IL Marathon Ashl and Petroleum LLC IRD R obinson Marathon Ashl and Petroleum LLC

IN Countrymark C ooperative, Inc. Mt. Vernon Countrymark C ooperative, Inc.

KS Coffeyville Resources R e fining & M a rket ing Coffeyville Coffeyville Resources, LLC

KS Frontier El Do rado Refining Compan y El Do rado Frontier Oil Co rporation

K S N a t i o n a l Cooperative R e finery Associ ation McPherson Cenex

K

Y C a t l e t t s b u rg Refining , LLC Catlettsb u rg Mara thon Ashl and Petroleum LLC

LA ConocoPhillips Compan y Alliance R e fi nery Belle Chasse ConocoPhillips

LA Chalme tt e Re fi ning, L. L.C

. Chalme tt e Chalmette Refi ning, L.L.C (ExxonMobil and Petroleos de
Venezuela S.A

. )

LA Marathon Ashl and Petroleum, LA R e fining
Division Garyville Marathon Ashl and Petroleum LLC

LA Murphy Oil USA, In c. Meraux Refi nery Meraux Murphy Oil Co rporation

LA Placid Refining Co. L.L.C

. -Po r t Allen R e fine ry Port Allen Placid Refining Co./Petro-Hunt

MN Marathon Ashl and Petroleum, MN R e fining Div. St. Paul Park Marathon Ashl and Petroleum LLC

MT ConocoPhillips Billings R e finery Billings ConocoPhillips

MT Montana R e fini ng Comp any Great Falls Holly Corpo r ation

MT CHS Inc

. - L a urel Refin e r y Lau r el Cene x
MT ExxonMobil Bi llings Refinery near Billings ExxonMobil

ND Teso ro Man d an Refinery Mandan Teso ro Co rporation
NJ Valero Refining Co. - New Jersey Pa ulsboro Valero En ergy Corporation

NM Navajo R e fining Comp any Art e sia Holly Corpo r at ion

NM Ciniza Refinery Jamestown Giant In dustri es

OH Ohio Refining Division Canton Marathon Ashl and Petroleum LLC

O K T P I Petroleum I n c

. A r d m o r e V a l e r o En ergy C o r p o r a t i o n

OK ConocoPhillips Refinery - Pon c a Ci ty , Oklaho ma Ponca City ConocoPhillips

OK Wynn ewood R e fining Co mpany Wynn ew ood Gary-Williams Energy Corpo r ation

P A S u n o c o Philadelphia Refinery Philadelphia Sunoco

, Inc.

PA Train e r R e finery Train e r ConocoPhillips

TN The Pr em cor R e fining Group I n c. Memphis Pre m co r In c.
TX Alon USA Bi g Spring Refinery Big Sp ring Alon USA LP

TX Borger Refin e ry an d NGL C e n t e r B o r g e r C o n o c o P h i l l i p s
TX Flint Hills Reso urces, L.P.

- CC West R e finery Corpus Christi Koch Industries

TX Valero Refining Co. - Texas, L.P. - West Pl ant Corpus Christi Valero En er gy Corpora t ion

TX CITGO Co rpus Christi Refin e ry Ea st Pl ant Corpus Christi CITGO

TX Valero Refining Co - Texas, L.P. - East Pl ant Corpus Christi Valero En er gy Corpora t ionState Facility Na me City Parent Compa n y
TX Crown Cen t ral Petroleum, Ho uston R e finery Pasaden a Crown Cen t ral LLC

TX Premco r Po rt Arthu r Refinery Port Arth ur Premco r In c.
TX Marathon Ashl and Petroleum Texas Refining Texas City Marathon Ashl and Petroleum LLC

TX BP A m e r ica

, B P T e x a s Ci ty Site Te xas Cit y BP

TX Valero Refining - Texas, L.P. Te xas City Valero En ergy Corporation

TX Diamon d Sha m rock R e fine ry - Thr ee Riv e rs Three Riv e rs Valero En ergy Corporation

UT Big West Oil LLC North Salt Lak e Flying J, In c.

U T C h e v r o n T e x a c o Salt Lak e R e f i n e r y S a l t L a k e C i t y C h e v r o n T e x a c o Corporation

UT Woods Cross R e finery Wood s Cross Holly Corpo r ation

WA ConocoPhillips Compan y Fern dal e ConocoPhillips

WI Murphy Oil USA Sup e rior Refi nery Superior Murphy Oil Co rporation

WY Frontier R e fining Inc. Chey enne Frontier Oil Co rporation

WY Wyo m ing Refining Compan y Ne w c astle Hermes Consol idated



### 26 Needle ss R i sk

# E ND 

# N OTES

1 Congressional Research Service, RM P Facilities in the United States as of M a y 200 5 , r e lea s e d b y R e pr esen tativ e E d wa rd J. Ma rke y , Ju ly 6, 2005.

2 U.S. EPA, As se

ssment of th e Ince ntives Creat e d by Pu blic Disclo sure of O ff-Si te Cons eq uence Analysi s Information for Redu ction in
the Risk o f

Accidental Releases , April 18, 2000: 2

. 3 “Am m onia l e a k s rous ts tou r is ts f r om Gulf h o tels ,” S un Herald , February 23, 2003.

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, March 12, 2002.

5 National Infrastructure Protection Center, “Homelan d Security In fo rmati on Update,” February 12 , 2003

. 6 Agen c y for To xic Subst a nc es and Dise ase Re gistr y , “I n d us tri a l Chemicals an d Terroris m : H u man Health Trea t Analysis Mi tigation and Prevention,” 1999.

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, “In th e Sha d ow of D a ng er : Th e Ch emi c al Pla n t P e ril How S a fe , How Se cu r e ?” Philadelphia Inquirer

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25 Don Steward and San d i M c Daniel, “Dan ger A d rift: Chaos rei g ned after Sun Co. Spill,” Tul s a Tribune , April 2 8

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26 La ura El der, “ G roup wants p o werful a c id o u t of BP ’s plan t,” The Ga lveston Dail y Ne ws , March 27, 2005.

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, “In th e Sha d ow of D a ng er : Th e Ch emi c al Pla n t P e ril How S a fe , How Se cu r e ?” Philadelphia Inquirer

, April 20, 2003.

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.



### Nee d le ss Ri sk 27 31 Theo dore Karasik, “To x ic Warfar e,” RAND Project Air Fo rce, 2002

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, “Thief breaks refinery security: Two work ers l o se wall ets,” S a n Antonio Ex press-News , Feb r ua ry 16

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33 Theo dore Karasik, “To x ic Warfar e,” RAND Project Air Fo rce, 2002

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, “La x s e c u rit y expo ses l e thal ch emi c al s u pplies

, ” Pittsburgh Tribune-Review , April 7, 2002, and “Compani es respond to in filtration of faciliti e s,” Pittsburgh Tribune-Review, May 5, 2002.

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37 Alexi s Grant, “Chemi cal plan ts not s e cur e aga i nst at ta ck, offi cials s a y , ” Houston Chronicle, Jun e 15, 2005.

38 Testimon y of Amy E. Smithson, Di re cto r , C h emical an d Bi ological Weapo n s Nonproliferation Pr oj ect, Henry L.
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.

ac ce ssed at www.eia.do e.go v/oil_gas/p e troleum/da ta_p ublications/petroleum_supply_a nnual/p sa_volume1 /psa_volume1 .ht

ml

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41 Bill Wal s h, “Toxins Mak e Lo cal Plan ts Possi ble Target for Terrorists,” Ne w Orl e ans Time s-Picayune , July 6

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.



### 28 Needle ss R i sk 61 ConocoPhillips Technology Solutions, “ReV ap in Action,” Accessed July 1 4 , 2005 at http://www.coptechnologysol ut ions.com/alk ylation / reva p/revap_action/in dex.h t m

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, 2003.

63 South Coas t A i r Qu ality Mana gem e nt Dis t ri ct , “ H ighly To xic Chemical to b e Phas ed Out at Valero Refin e r y ,” February 7

, 200 3, availabl e at http://www.aqmd.gov /news1 /2003/hfval e ro .html

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65 John Holusha, “Chemical Mak e rs Identify a New Haz a rd,” N e w York Times, Augus t 12 , 1991.

66 Sal DePasqual e , Testi m ony b e fore the House Ho me lan d Securi ty Committee hearing, Jun e 15, 2005.

67 Testimon y of Martin Durbin of th e Am eri c a n Chemi s tr y Co uncil, Sena te C o mmit t ee on H o melan d S e curi ty and
Govern men t al Affairs hearing, Jul y

13, 2005, available at
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Hazar d R e d u c t ion, pr epar e d fo r U.S

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.



### Nee d le ss Ri sk 29 70 ConocoPhillips Technology Solutions, “ReV ap in Action,” Accessed July 1 4 , 2005 at http://www.coptechnologysol ut ions.com/alk ylation / reva p/revap_action/in dex.h t m

.