Alternatives

to using Modified Hydrofluoric Acid at ExxonMobil

Sally Hayati
Torrance Refinery Action Alliance
July 10, 2015

Three viable alternative technologies to replace MHF are described. A fourth option would be for
ExxonMobil to stop alkylation at the Torrance refinery and perform it elsewhere. Any of these
options would be preferable to continuing the use of MHF in Torrance.

Brief Introduction to Modified Hydrofluoric Acid (MHF)

Exxon Mobils Torrance refinery has 250,000 lbs. of modified hydrofluoric acid (MHF) onsite for use in the
alkylation unit. This unit produces alkylate, an additive used to boost the octane content of gasoline.
Hydrofluoric acid (HF) is dangerous because of extreme toxicity and volatility. Upon release under refinery
conditions of heat and pressure, it doesnt fall to the ground. Instead, the entire amount of released acid forms a
dense toxic cloud that can drift for miles outside the refinery. MHF is a proprietary form of HF that is just as
toxic. It was developed with the hope of eliminating cloud formation. Its developers and users, however, can
only claim a 65% reduction in the amount of airborne acid. Thus, 35% becomes airborne when MHF is
accidentally released (vs. 100% for HF). This 35% forms a (smaller) dense toxic cloud that can move with the
air for miles outside the refinery. But with 250,000 lbs. of MHF onsite, the relative reduction in cloud size is
small comfort for those who live within 10 miles of the refinery. A 1986 test showed that within two minutes
of release, a 1,000-gallon (8,300 lb.) spill of HF produced a toxic cloud lethal to all exposed within a range of 5
miles, and immediately dangerous to life and health as far away as 7.5 miles. But the same results would be
achieved by the accidental release of 2,860 gallons of MHF. The ExxonMobil refinery has more than ten times
that amount of MHF onsite (and the Valero refinery in Wilmington has some comparable amount). ExxonMobil
itself has confirmed the dangers of MHF in documents submitted to the EPA for the Risk Management
Programs worst-case toxic release scenario, as shown in this map:

Solid Acid Catalyst Method

In the 1990s when it seemed that HF alkylation would be banned altogether, considerable research
was performed on safer alkylation methods.1 One of the most promising was Solid Acid Catalyst (SAC)
alkylation, which is safe for workers and the community and environmentally more benign than
either acid. 2 Three primary solid acid alkylation processes were developed: CB&I Alkyclean, UOP
Alkylene, and Exelus ExSact. Pilot plant tests indicate that the alkylate product from UOPs Alkylene
has octane numbers and production costs comparable with traditional processes.3 In 1995 NIST
funded a 3-year research project into solid acid catalysts for alkylation.4 Out of this effort, the ABB
Lummus Global, Inc., Albemarle Corporation, and Neste Oil Corporation joint venture developed and
optimized a solid acid alkylation demonstration plant that produced 10 barrels per day from 2002 to
2004 in Finland. As of 2005, the joint venture was in negotiations with several large energy
companies to establish the first commercial-scale plant to produce upwards of 10,000 barrels per day.
At least one contract was made for the resulting product, CB&Is Alkyclean, at Hyperion Refining in
South Dakota, which planned to open a refinery processing 400,000-barrel-per-day of heavy crude
from Canada.5 Expecting environmental opposition, the refinery chose SAC in an effort to portray
their refinery as a clean operation. Yet there was stiff opposition from inhabitants of the rural area,
and the refinery was never built. In 2013, the company announced a contract from Shandong Wonfull
Petrochemical Group Co., Ltd. to provide processing engineering design for a first-of-a-kind solid acid
alkylation unit to be located in China. The unit was to be capable of producing 100,000 tons per
annum of alkylate and is scheduled for startup in early 2014. Theres no word on progress.

According to Exelus, the octane obtained with ExSact alkylate is higher than that obtained by liquid
catalysts.6 According to one Exelus study commissioned by a refiner, HF alkylation units are well-
suited for revamping to ExSact alkylation.7 Several parts
of the HF unit can continue their operation unchanged,
reducing cost. Some equipment used for HF alkylation,
like brick-lined vessels, acid containment and
neutralization equipment, and refrigeration equipment
are not necessary with SAC, reducing capital
expenditures. Exelus has a discussion of the technical
issues related to revamping of HF units on their website.
The HF revamp option may save considerable capital over
other alkylation options. Exelus estimates the capital cost
of the revamp at about 50% of a grassroots ExSact unit
and about 20% of a new sulfuric acid facility (including
acid regeneration).

In addition to eliminating the possibility of a catastrophic accident, SAC promises to deliver long-term
economic benefits. Manufacturers claim that if all 112 domestic alkylation plants were retrofitted, the
process could save approximately $580 million in processing costs per year.8 Yet, no US refinery has a
SAC alkylation unit. This is typical for a new technology whose primary benefits are safety and
environmental, even for those offering long-term savings but with initial conversion costs. Unless
companies are forced to use such technologies, they generally chose not to. The incentive to adopt
alternative catalysts went away when MHF and water suppression systems were demonstrated in
19949 and government agencies were lulled into complacency. Ironically, MHF is less deadly, not safe,
and only 20% of HF units ever actually converted. Although SAC would effect long-term savings,
upfront costs discourage retrofitting efforts. With few new refineries being built, SAC is unlikely to
make headway without government mandates for inherently safer technology in existing refineries.


Composite ionic liquid alkylation
Composite ionic liquid alkylation (CILA) is an inherently safer technology that was developed by Shell
and Chinese technologists. Since it is a liquid, existing alkylation unit retrofits are simplified. Ionic
liquids (IL) are liquid salts: not salts dissolved in liquid, but salt that exists in the liquid phase. ILs are
non-volatile (no cloud will form), low in toxicity, non-flammable, relatively inexpensive to
manufacture, and far less corrosive than HF or H2SO4.10 They usually exist as liquids well below room
temperature and up to a temperature as high as 200oC.11 One type of CILA called Ionikylation was
proven in a pilot plant and then retrofitted into an existing 65,000-tonne/year H2SO4 alkylation unit
in China by 2006. In 2013 a new 100,000-tonne/year CILA alkylation unit was successfully started up
in China.12 The retrofit allegedly increased the yield of the process compared to sulfuric acid and
increased the capacity of the process units by 40%, with attractive economics.13 The quality of the
alkylate from Ionikylation compares favorably to alkylate from HF and H2SO4 units,14 as shown in the
following table of pilot test results.15 CILA
process reactions take place at ambient
temperatures and moderate pressures, further
reducing risk. The reactor used in Ionikylation
is a commercial mixer that is much simpler and
cheaper than the reactor used in the H2SO4
alkylation process. Ionikylation can be easily
retrofitted to an existing H2SO4 or HF
alkylation unit. Whatever technical challenges
remain in the development of CILA can be
easily rectified with the development of a
market through government regulation
Figure 2. RON & MON are M otor Octane Numbers: the higher the better
eliminating HF.16

Sulfuric acid technologies
Sulfuric acid (H2SO4) and hydrofluoric acid (HF) technologies have nearly equal shares of the
alkylation market overall in the US. About 30% of alkylation units on the West Coast, Alaska, and
Hawaii use HF technology, 50% on the Gulf Coast, and a full 71% in the Rocky Mountain region use
HF. Only two of twenty California oil refineries17 use MHF (none use unmodified HF). Both are in the
Greater South Bay: the Torrance ExxonMobil and Wilmington Valero refineries.

Sulfuric acid (H2SO4) has a clear advantage over MHF from a safety and environmental standpoint.
The American Petroleum Institute has issued a Recommended Practice specifically for HF alkylation
units (API RP 751). This publication recommends that access to an HF alkylation unit be strictly
limited due to the potential hazards of HF. No similar, specific safety document is required for sulfuric
acid alkylation.18 HF and MHF are on the Department of Homeland Securitys (DHS) Chemical of
Interest (COI) list for potential use by terrorists. H2SO4 is not on the list. HF is a toxic, volatile gas
under refinery conditions, while H2SO4 is a toxic liquid. Therefore, H2SO4 is much easier to contain in
the event of an accidental release. Tests conducted in 1991 by Quest Consultants, Inc. showed that
there is virtually no potential for H2SO4 aerosol formation from an alkylation unit release. That means
that released H2SO4 will not form a cloud that can move into neighborhoods adjacent to the refinery.
Instead, it falls onto the ground as a liquid, with minimum vaporization posing a risk only to workers
on the scene of the accident, not to the surrounding community.

The primary safety and environmental disadvantage of H2SO4 is due to the larger amounts of fresh and
spent acid that must be brought in and out compared to HF. If truck transport were used, far more

trucks would be required than for HF. Even so, the risk from trucks full of HF is significantly greater
than from trucks full of H2SO4. There are no MHF mitigating measures available on the roads. But
piping acid in from Carson, utilizing an existing pipeline, would all but eliminate this disadvantage,
especially when combined with the use of on-site H2SO4 regeneration facilities.19

In 1994, Mobil won approval to use MHF at the Torrance refinery by claiming, to the Safety Advisors
satisfaction, that MHF plus mitigation (safeguards) is no more dangerous than H2SO4 alkylation.20
Few experts agree with this unusual assessment. The decision reflected a heedless reliance on
unverified proprietary claims shrouded in secrecy and on safeguards with inherent limitations and
vulnerabilities. Why are refineries reluctant to give up the use of HF or MHF in densely populated
areas? In 1990, Mobil refinery general manager Wyman Robb estimated that it would cost more than
$100 million and take three to four years to convert to sulfuric acid.21 Yet it took a similar effort with
possibly greater cost to research, develop, and install MHF and mandated mitigation measures.

The answer is that HF technology is apparently the most profitable process for alkylate production.22
The acid consumption rate for HF alkylation is less than 1% of the rate for H2SO4. Its not community
danger from increased acid transportation that concerns ExxonMobil, but increased material cost.
Sulfuric acid alkylation also requires chilling equipment to maintain a low reaction temperature,
which HF alkylation unit does not. And HF alkylation plants may process a wider range of feedstock
mix and give somewhat higher-octane products than H2SO4 plants.23 Yet close to 50% of alkylation is
done with H2SO4, which is clearly viable and competitive with HF. The HF benefit is real but marginal.
Nevertheless, since the safety and environmental risks and costs of HF are externalities that enter into
a cost-benefit analysis only as a minimal insurance cost, that marginal advantage is sufficient
motivation for ExxonMobil to put hundreds of thousands of peoples lives at stake by choosing HF.

1 2000-08-28 A solid idea (and a liquid one), Oil & Gas Journal, <http://www.ogj.com/articles/print/volume-98/issue-35/regular-features/journally-
2 2009-11-09, Revamp of HF alkylation unit employs solid-acid catalyst, Mitrajit Mukherjee, et al. <http://www.ogj.com/articles/print/volume-

107/issue-42/Processing/revamp-of-hf-alkylation-unit-employs-solid-acid-catalyst.html>
3 <http://www.ogj.com/articles/print/volume-98/issue-35/regular-features/journally-speaking/a-solid-idea-and-a-liquid-one.html>
4 National Institute of Standards and Technology (NIST), September 2006, Advanced Technology Program (ATP), Status Report - Number 4, NIST Special

Publication 950-4, p. 43, Solid Acid Catalyst government research funded,

<http://www.atp.nist.gov/eao/status_reports/chemistry_and_materials_edition/sp_950_4_complete.pdf>
5 2013-12-20 No. 9 story of '13: $10B South Dakota refinery derailed, Sioux City Journal, [Solid acid catalysts, SAC]
<http://siouxcityjournal.com/business/local/no-story-of-b-south-dakota-refinery-derailed/article_eb327ce9-e67d-59cf-a114-e5081f11f78a.html
6 http://www.exelusinc.com/exsactbenefits.shtml
7 Exelus, HF Alkylation Revamp ExSact, <http://www.exelusinc.com/exsactrevamphydo.shtml>
8 National Institute of Standards and Technology (NIST), September 2006, Advanced Technology Program (ATP), Status Report - Number 4, NIST Special
Publication 950-4, p. 43, Solid Acid Catalyst government research funded,
<http://www.atp.nist.gov/eao/status_reports/chemistry_and_materials_edition/sp_950_4_complete.pdf>
9 2000-08-28 A solid idea (and a liquid one), Oil & Gas Journal, <http://www.ogj.com/articles/print/volume-98/issue-35/regular-features/journally-
speaking/a-solid-idea-and-a-liquid-one.html>
10 http://www.google.com/patents/EP2520558A1?cl=en
11 http://www.youblisher.com/p/950250-Ionic-Liquids-Its-Applications/
12 New Refinery Alkylation Process: Composite Ionic Liquid Alkylation, Zhichang Liu, China University of Petroleum, Beijing, China, [Solid acid catalyst
status chart] <http://www.pecj.or.jp/japanese/overseas/conference/pdf/conference14-13.pdf>
13 http://www.ionicliquid.org/en/application/2014-04-24/40.html
14 http://www.ogj.com/articles/print/volume-104/issue-40/processing/ionic-liquid-alkylation-process-produces-high-quality-gasoline.html
15 New Refinery Alkylation Process: Composite Ionic Liquid Alkylation, Zhichang Liu, China University of Petroleum, Beijing, China, [Solid acid catalyst
status chart] <http://www.pecj.or.jp/japanese/overseas/conference/pdf/conference14-13.pdf>
16 http://pubs.acs.org/doi/abs/10.1021/ef500684r
17 http://energyalmanac.ca.gov/petroleum/refineries.html
18 http://stratfordengineering.com/articles/safety-issues-in-alkylation-units
19 https://www.chemours.com/Sulfur_Technologies/en_US/products/sar_sgr_technologies/sulfuric_acid_regeneration.html
20 How Modified Hydrofluoric Acid Came To Be Used At ExxonMobil, Sally Hayati, Torrance Refinery Action Alliance, July 9, 2015,
<https://www.scribd.com/doc/271094084/Modified-Hydrofluoric-Acid-at-Torrance-Refinery>


21 1990-01-12 AQMD Urges Ban on Refinery Usage of Toxic Chemical : Safety: Staff members surprise and please Torrance city officials by suggesting a

ban on hydrogen fluoride, Act 1410. JANET RAE-DUPREE, LA Times, <http://articles.latimes.com/1990-01-12/local/me-247_1_chemical-hydrogen-

fluoride
22 2015-06-04 Despite Risks, HF is Still Top Alkylation Choice for U.S. Refiners, Stratas Advisors, <https://stratasadvisors.com/Insights/HF-Acid-
Alkylation>.
23 http://www.rsc.org/chemistryworld/News/2009/August/13080902.asp