Risk Analysis for Operation

of Aluminum Heat Exchangers

Contaminated by Mercury
S. Mark Wilhelm
Mercury Technology Services, Tomball, TX; smw@hgtech.com (for correspondence)
Published online 16 April 2009 in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/prs.10322
Brazed aluminum plate-fin heat exchangers are
extensively used in gas separation processes including
LNG, LPG, NGL, nitrogen rejection and olefins manufacture. In situations where mercury is a trace component of feed gas or liquid feeds to crackers, condensation of liquid or precipitation of solid mercury can
occur in heat exchanger passes, even with functional
mercury removal systems in place. Mercury in liquid
phase causes, under certain well-defined conditions,
liquid metal embrittlement of susceptible metallurgy
or amalgam corrosion of core fins, both of which can
lead to sudden loss of pressure containment. Mercury-contaminated aluminum heat exchangers
require close scrutiny and quantitative risk assessment to allow safe operation, remediation or to justify
replacement. The risk analysis procedure involves
computational prediction of mercury deposition,
inspection of critical areas, detailed assessment of
metallurgy and fabrication, strain analysis of temperature changes during trips and shutdowns and oxide
fatigue analysis. Assigning probability of equipment
failure requires a complete understanding of the
mechanisms of liquid metal embrittlement and amalgam corrosion that operate on aluminum plate-fin
heat exchangers. Statistical correlations to known
failures are essential to assignment of probabilitybased risk factors. Probabilities of leak and rupture
failure modes can be estimated using amounts and
locations of mercury deposits determined from
focused inspection or calculated thermodynamically.
! 2009 American Institute of Chemical Engineers
Process Saf Prog 28: 259266, 2009
Keywords: mercury, aluminum, heat exchange,
metal embrittlement, amalgam corrosion

! 2009 American Institute of Chemical Engineers

Process Safety Progress (Vol.28, No.3)

INTRODUCTION

Deposition of liquid elemental mercury in aluminum

heat exchangers (AHXs) can compromise their structural
integrity. One mechanism by which this can occur is
referred to as liquid metal embrittlement (LME), which
has been responsible for a number of failures of aluminum equipment in the gas processing industry over the
past 30 years. A second mechanism by which mercury
can attack aluminum is amalgam corrosion (AMC),
which requires both mercury and water in order to oxidize and thus degrade aluminum equipment.
In most cases, the LME failure mode is a leak in
proximity to a weld but occasionally LME cracks
propagate to greater distances to produce a rupture
that allows sudden discharge of large quantities of
gas and/or liquids. The AMC failure mode varies in
location but fin corrosion can allow plate separation,
again resulting in a sudden gas release. The consequences of sudden, unexpected loss of pressure containment by gas processing equipment are well
known to the industry and necessitate stringent safety
engineering, risk analysis and risk minimization
efforts. If mercury is discovered in aluminum equipment, or if estimated to have deposited due to a plant
upset, operators must make decisions on plant operation, remediation and possible replacement of critical
equipment. Risk analysis then becomes a key tool to
assist educated decisions thus to ensure safety and
plant integrity.
Several steps are required to analyze and quantify
risks associated with operation of aluminum plate-fin
heat exchangers potentially contaminated by mercury. The major risk analysis steps are:
Acquisition of analytical data for mercury in feed

to the cryogenic equipment both current and

historical
Computational analysis to predict amount and
location of mercury deposition
September 2009 259

 Heat exchanger inspection to quantify degree of

contamination, location, and size of deposits

and to confirm predictions
Compilation of circumstantial evidence including
historical operating conditions and practices
Scrutiny of metallurgy, welding procedures, and
heat exchanger design
Information from these steps is then compared to
the statistical compilation of circumstantial causes of
prior AHX failures so as to assign probability of leak
or rupture. The consequences of failure are assessed
as a separate exercise to complete the risk assessment in a quantitative manner. The procedures discussed herein comply with those specified in API
Recommended Practice (RP) 580 [1]. LME or AMC
failures of aluminum equipment reside in a special
category of failure mechanisms, however, and thus
require an extraordinary understanding of mechanism to assign risk probability. Failure consequences
can be quantified using the prescriptions of API (RP)
580 but estimating the probability of failure is the
more difficult task, especially in the case of LME or
AMC.
Figure 1. Aluminum heat exchanger.
MERCURY IN ALUMINUM HEAT EXCHANGERS

Mercury is a naturally-occurring trace component

of natural gas, liquids associated with gas, and crude
oil. Of the variety of mercury compounds that may
exist in gas reservoirs, elemental mercury is the dominant mercury species in gas after separation of produced water and condensate. In crude oil and condensate, several other mercury species are typically
present in addition to the elemental form [2,3]. Elemental mercury is the primary mercury species
responsible for damage to equipment. Throughout
the following discussion, when the term mercury is
used, elemental mercury is meant unless otherwise
stated.
Aluminum heat exchangers used in cryogenic natural gas separations receive mercury in the gas being
liquefied and fractionated, in which case elemental
mercury is the vastly dominant species. For processes
with liquid feeds such as naphtha or gas condensate,
the various mercury species dissolved or suspended
in the feed liquid typically are converted to the elemental form by conditions (heat 1 hydrogen) in the
furnace or cracker. Thus for olefins and syngas processes also, the elemental form of mercury is the mercury species that enters the AHX.
Details of construction of AHXs can be found in
the specification document from the Aluminum PlateFin Heat Exchanger Manufacturers Association [4].
For most equipment manufactured before year 2000,
and many since then, high strength aluminum alloys
(5083 and 6061) were used to construct headers, nozzles, flanges and manifold piping (see Figure 1). The
high strength aluminum alloys that contain magnesium as the strengthening agent give rise to metallurgical features that increase susceptibility to LME [5].
AMC is not alloy dependent.
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MECHANISM OF LME

Mercury deposits in cryogenic heat exchangers by

condensation (to liquid Hg) of mercury vapor in gas
or by precipitation (to solid Hg) of mercury dissolved
in liquid hydrocarbon. The phase transitions are
caused by cooling in the heat exchanger itself or by
external cooling from a Joule-Thomson (J-T) valve or
turbo-expander. Mercury can accumulate in the aluminum equipment as either liquid or solid deposits.
In cold liquid streams, solid (frozen) mercury particles can carry long distances and thus mercury
deposits are often found in areas of limited flow far
from the point of actual condensation or precipitation. Solid deposits become liquid when heat
exchangers warm during a shutdown or trip.
LME requires mercury to be in liquid phase and in
physical contact with metal, not just the oxide on the
surface. LME cracks in high strength aluminum alloys
propagate in an intergranular manner. LME is distinct
from stress corrosion cracking in that no purely electrochemical processes are involved. The LME mechanism is illustrated simplistically in Figure 2.
The key ingredients for initiation and propagation
LME cracks in aluminum are as follows:
Temperature above the freezing point of mer-

cury (238.98C). Necessary for both initiation

and propagation.
Mechanical, thermal, or residual stress. Necessary
for propagation.
A breach in the aluminum oxide layer that covers the surface to allow mercury to come in
direct contact with aluminum metal. Necessary
for initiation.
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Figure 3. Intergranular attack of Al 5083.

Figure 2. Liquid metal embrittlement of aluminum.

Metallurgy and microstructural condition condu-

cive for LME crack initiation and propagation.

Metallurgy
The statistics and morphology of mercury related
failures of aluminum heat exchangers suggest LME
crack initiation is much more likely when the affected
aluminum alloy contains magnesium as an alloying
element. The statistical correlation is that virtually all
LME failures of brazed aluminum plate-fin heat
exchanges exhibit cracks that initiate at welds
between aluminum-magnesium alloys. The 5000 and
6000 series alloys have 0.26.0% magnesium additions to provide an ultimate tensile strength of
approximately 2050 ksi in the annealed condition.
Al-Mg alloys are welded using filler metal alloys that
also contain magnesium such that the weld achieves
the strength of the base metal.
Aluminum alloys with more than 23% magnesium
have the potential for sensitization. Sensitization is
the partition of the non-metallic or inter-metallic compounds to grain boundaries primarily during welding,
heat treatment or high temperature service. In the
case of Al-Mg alloys, the inter-metallic compound
Al3Mg2 segregates to grain boundaries during welding
thus producing a microstructure especially prone to
mercury LME. Nelson proposed mercury reacts with
the Al3Mg2 in grain boundaries to form a HgMg
inter-metallic compound that is insoluble in the mercury in the propagating crack [5,6].
Hg Al3 Mg2 ! Hg2 Mg

While some disagreement may exist on exact

mechanism, all known LME failures of aluminum heat
exchangers involve intergranular cracks, all involve
aluminum alloys that contain magnesium in appreciable quantities and almost all initiate at locations
having sensitized microstructures (Figure 3).
Oxide Fatigue
Mercury deposition on the surface of a susceptible
aluminum alloy is a necessary, but insufficient condition for LME to initiate. Crack initiation requires some
Process Safety Progress (Vol.28, No.3)

mechanism to allow the surface mercury to reach the

underlying metal. The surface of fabricated aluminum
is covered by an oxide (Al2O3) having variable thickness and mechanical properties that depend on fabrication method. Under normal conditions (isothermal,
isobaric, benign chemical environment), the oxide on
aluminum is resilient and impervious to mercury that
may reside on its process-side surface. Mercury can
breach the oxide on aluminum in several ways. Abrasion by particulate matter can damage the oxide sufficiently to allow contact. Corrosion from chemicals
introduced upstream can also disrupt the normally
protective alumina layer. Most commonly in cryogenic service, the aluminum oxide is damaged by
thermal and mechanical strains that produce oxide
fractures caused by what is termed oxide fatigue.
Oxide fatigue is the cumulative disruption of the
aluminum oxide crystalline structure by strain
induced micro-fracture events. Fractures occur when
there is disproportionate strain in the aluminum metal
substrate and the aluminum oxide surface layer. In
actual practice, AHXs that have failed typically have
experienced numerous cycles in temperature
and pressure before the mercury that may be present
is able to penetrate the oxide completely. This time
and strain event dependency is attributed to oxide
fatigue [7].
The difference in the coefficient of thermal expansion of aluminum and aluminum oxide is such that
aluminum metal expands in physical dimension
about three times as much as its oxide with increasing temperature. When a heat exchanger is operating
cold, the oxide is in compression. When an AHX is
allowed to warm, the oxide on the surface will
stretch and may fracture to some extent due to the
greater expansion of the aluminum metal to which it
is attached. In practice, AHXs contaminated with mercury resist some number of temperature excursions
before mercury attack (LME) initiates, if all other
necessary conditions for LME are present.
The thermal or mechanical strain rate is also important to the amount of damage done to the oxide
and hence the time to initiate cracks. Although not
precisely quantified, rapid changes in pressure or
temperature are especially detrimental to the oxides

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September 2009 261

ability to resist penetration by mercury [7,8]. Sudden

pressure changes used to dislodge particulate material
in clogged heat exchanger passes are extremely detrimental. If mercury contamination is present in the
clogged heat exchanger pass, efforts to blow out the
solids by sudden pressure release upstream can cause
LME failure in only a few attempts.
Oxide fatigue can be quantified by measuring
cycles to failure in the laboratory or from correlations
of strain events in service to actual failure time [7].
Time to failure depends on the temperature (or pressure) difference in the cycle, the rate of temperature
(or pressure) change and on the thickness and mechanical properties of the oxide. Oxide fatigue curves
are used to estimate time in service to crack initiation
by examination of the service history of the heat
exchanger and comparison to experimentally measured cycles to failure under conditions similar to those
seen in service. A thorough examination of service history typically reveals number of trips and shutdowns
and temperature change associated with each.
Other mechanisms, such as abrasion and chemical
attack, also exist whereby the normally protective
surface oxide on aluminum can lose its ability to prevent contact of surface mercury with the underlying
metal. Statistically, failures correlate strongly with
equipment age thus implying oxide fatigue is the root
cause of LME initiation and other factors have secondary influence.

Figure 4. Core separation due to amalgam corrosion.

detect slow-growing cracks (acoustic emission,

ultrasonic techniques) typically are ineffective to
locate LME cracks.
Metallurgical defects that impact crack initiation
in other mechanisms likely have little influence
on LME. For example inclusions such as tungsten in welds do not encourage crack initiation.
MECHANISM OF AMALGAM CORROSION

Fracture Mechanics
One unusual aspect of LME, as opposed to other
fracture processes, is that the crack propagation rates
can be exceedingly rapid and the stress intensity
required for crack propagation can be very low
[9,10]. Crack velocities on the order of cm/s have
been measured in the laboratory. Theoretical and empirical studies have suggested that LME crack propagation is influenced by numerous factors that include
rate of liquid mercury surface and bulk diffusion in
cracks, by the concentration of Al3Mg2 in grain boundaries (degree of sensitization) and by the dissolution
rate of aluminum into mercury at the crack tip and
by solid-phase fracture mechanics parameters [914].
The rate of crack propagation tends to argue against
chemical reaction and dissolution as rate controlling.
Low temperature crack propagation rates have not
been measured. Thus it is not certain as to whether
cracks that may initiate at ambient temperature will
propagate at cryogenic temperatures. If crack propagation rates at low temperatures are proportional to
the rate of liquid mercury diffusion and aluminum
dissolution into liquid mercury, then propagation
rates should be essentially zero below the freezing
point of mercury. The aspects of fracture mechanics
studies that impact risk assessment are:
Propagation requires very low stress hence

efforts to eliminate stress are typically futile. In

assessing the likelihood of crack propagation in
equipment, the stress criterion is always satisfied.
Propagation rates are fast, especially at ambient
temperatures. This means that methods used to
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Amalgam corrosion of aluminum is similar to LME

in the sense that the oxide on the surface must be
breached to allow physical contact of mercury and
aluminum. Contact of mercury with any aluminum
alloy will produce amalgamation (simple dissolution).
Amalgam corrosion occurs spontaneously if water
vapor or liquid water contacts the amalgam. The rate
of amalgam corrosion penetration is proportional to
humidity. The reaction scheme is:
Hg Al ! HgAl amalgamation

HgAl H2 O ! Al2 O3 $ 3H2 O H2 Hg

Hg Al ! HgAl

Amalgam corrosion (see Figure 4) does not consume the mercury and hence is self-propagating so
long as mercury is in contact with aluminum metal
and water is available. If sufficient moisture and mercury are present, aluminum structural components
can be penetrated rapidly. The rate of attack is mass
transfer limited and the aluminum oxide corrosion
products inhibit the access of moisture to the amalgam surface eventually. The amalgam corrosion reaction is not alloy-specific. All aluminum alloys can be
affected.
If mercury deposits are discreet and not continuous and liquid water is present, amalgam corrosion
can be localized in the form of pits. The pits propaDOI 10.1002/prs

Process Safety Progress (Vol.28, No.3)

upstream of the AHX are now seen as marginally

able to remove mercury to level sufficiently low that
some mercury precipitation or condensation does not
occur. Even though rates of deposition may be small,
over time significant deposits may develop.
INSPECTION

Figure 5. Mercury pits on aluminum.

gate when the exchanger is warm and water collects

in low areas that have surface mercury contamination. In borescope inspections, mercury pits are rarely
but occasionally seen in manifold piping and appear
as white spots on the shoreline of water deposits
(Figure 5).
PREDICTION OF MERCURY DEPOSITION

Computational analyses can be performed to

determine the conditions under which mercury will
condense in the AHX or across J-T valves and turboexpanders (any cooling process). The objective is to
calculate location and amounts of deposition. The following assumptions typically are employed in the
modeling of mercury in the process:
All mercury is in the elemental form.
Separations are at equilibrium.
The solubility of mercury in hydrocarbon liquids

depends on liquid composition and temperature

with minor correction for pressure.
The vapor pressure of mercury in two phase
separations can be estimated using a thermodynamic equation of state.
Equilibrium concentrations of mercury in gas and
liquid phases are calculated to obtain the partition
ratio (CL/CV). Partition ratios are sensitive to phase
composition and become increasingly uncertain
below the freezing point of mercury. Empirical data,
if available, are used to verify predictions.
The location of mercury deposits in equipment
and piping depends, in part, on piping and equipment orientation since gravity influences accumulation of deposits. Fluid dynamics must also be considered because solid mercury precipitates as very small
particles that can travel long distances suspended in
liquids. Predictions of the locations of deposition rely
heavily upon experience gained from inspections.
As computational analysis techniques have
improved, so has understanding of mercury concentration limits for precipitation of mercury in cryogenic
systems. Likewise analytical measurements of mercury concentrations in gas streams have become
much more sensitive, to where detection limits now
have approached 0.001 lg Hg/Sm [3] of gas. For
some cold gas separations, functional and welldesigned mercury removal systems positioned
Process Safety Progress (Vol.28, No.3)

If mercury deposition is predicted by computational analysis or circumstantially suspected, an

inspection is warranted. Inspections are normally performed during a scheduled turn-around. Since warm
conditions are potentially harmful to aluminum heat
exchangers, a shutdown for the sole purpose of
inspection adds to the risk of oxide fatigue. The primary objective of the inspection is to document the
location and quantity of mercury in the AHX so as to
verify or refute predictions obtained from the computational analysis and to gain additional information
not available from other sources (water, corrosion,
etc.). The size and complexity of most AHXs preclude
inspection of all piping welds, headers, nozzles and
manifolds. Locations for inspection are selected based
on the computational analysis and based on statistical
probability.
Heat exchanger inspection is essential to assignment of failure probability. Non-intrusive radiographic inspections and invasive video-borescope
inspections are used as well as ultrasonic techniques
in some instances. Mercury deposits are easily
detected using conventional (film) or computed v-ray
or g-ray techniques. The trade off is better resolution
with v-ray and easier source orientation with g-ray.
The utility of borescope inspection is that locations
inaccessible to radiography can be examined. In
addition, corrosion processes and the precursors of
corrosion processes can be identified by borescope
inspection but not by radiography. Borescope inspection should be conducted when the equipment is
under nitrogen purge so that moisture cannot enter
the equipment.
QUANTIFICATION OF RISK

Circumstantial Risk Factors

An AHX that becomes contaminated by mercury is
at some risk of failure but risks often can be managed
and minimized to allow safe operation if the amount
and location of the mercury in the equipment can be
assessed accurately and circumstantial risk factors can
be eliminated or minimized. The initial phase of the
risk analysis attempts to determine the likelihood of
failure of the aluminum equipment due to contact
with condensed liquid mercury. The likelihood of
failure, defined as loss of pressure containment due
to LME or amalgam corrosion, depends on circumstances, both historical and those existing at the time
of analysis. In the analysis of risk, information on circumstances that impact probability of LME or AMC is
compiled. Answers to the following questions are
typically sought:
Is (or was) mercury present in the feed to the

plant?

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September 2009 263

Figure 6. Mercury in backing ring crevice.

Figure 7. Mercury deposits and crack length.

What is (or was) the concentration of mercury

in gas entering the aluminum equipment?

Is there an upstream mercury removal unit

(MRU) and does it perform to specification?

Can mercury condense to a liquid or solid phase
in the heat exchanger passes due to cooling?
Are mercury deposits known to be present the
aluminum heat exchanger (AHX)?
What is the amount and distribution of the contamination?
Is liquid mercury in contact with welds? Do
welds have backing rings?
Is liquid mercury in contact with aluminum
welds having a susceptible metallurgical microstructure?
At the locations of mercury deposits, are stresses
present that have sufficient magnitude to allow
LME?
What is the frequency of strain events (trips,
shutdowns, upsets)? Are strains dynamic?
How old is the equipment? Who made it and
what are the construction details?
Is the pressure drop across the equipment constant or increasing?
Is the upstream dehydration system working
properly?
What unusual operating procedures
are
employed such as methanol injection, derime
procedures, particulate intrusion, upstream
chemical usage, etc.?
Probability
For contaminated heat exchangers, the probability
of failure by leak or rupture is estimated by comparison of AHX circumstances and inspection data to
those of heat exchangers that have failed by known
causes. Failure statistics, although limited in some categories, are available for both leaks and ruptures and
include the following selected examples:
Failure frequency correlates with equipment

age, frequency of trips and shutdowns and with

strain rate.
Mercury deposits behind backing rings (see Figure 6) have a high probability to allow crack initiation but the amount of mercury in the pipe/
ring crevice is seldom sufficient to allow extended circumferential cracks. Thus leaks at
backing rings are much more likely than rup264 September 2009

Published on behalf of the AIChE

ture. Other locations of high probability are

revealed from failure statistics and include circumferential welds in manifolds, nozzle to
header tank welds and reboiler piping welds.
Leaks are more likely when equipment is pressurized after a scheduled shutdown of prolonged duration (days). Leaks in service associated with trips and unscheduled shutdown
events of short duration are statistically less
likely than leaks after long plant shutdowns.
Ruptures are rare but they do occur [15]. Ruptures require sufficient mercury on the surface to
feed dissolution inside the crack (see Figure 7).
The mercury inside a crack is saturated with aluminum (high Al surface area, low Hg volume).
Dissolution at the crack tip can only occur if
there is unsaturated mercury on the surface to
feed mercury to the crack and to accept aluminum dissolving into mercury in the crack and
diffusing according to the existing concentration
gradient. Substantial accumulation giving rise to
large deposits of mercury is therefore required
to provide conditions conducive to long cracks.
AMC failures correlate to the same characteristics
as LME crack initiation but also to the performance of upstream dehydration equipment.
Upsets in molecular sieve or glycol dehydration
systems, when coupled to mercury deposition in
the AHS, give rise to increased probability of
AMC.

FAILURE CONSEQUENCE AND RISK MINIMIZATION

The estimation of failure consequence is a separate

exercise to the assignment of failure probability. Consequences for leak or rupture scenarios are estimated
using conventional methods. The recommendations
of API RP 580 serve as a good guide to the methods
typically utilized. Incidents of AHX failure due to LME
have been reported that have led to major fires [15]
and personnel fatalities in some instances.
A major potential consequence of an LME or AMC
failure is plant down time. AHXs are in high demand
now for LNG and LPG manufacture and there are a
limited number of manufacturers. Orders for new
equipment can have long lead times. When assessing
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Figure 8. Decision tree for risk minimization.

failure scenarios down time becomes a major cost

factor, especially when contrasted with repair.
Repairs and/or partial replacements to an AHX or
associated piping can be accomplished if mercury
deposits are small and localized. For example contaminated header tanks, nozzles and piping sometimes
can be replaced in the field. Such exercises require a
separate risk analysis that examines LME resistance of
field repair welds, the procedures for pressure testing
and the risk involved with prolonged down time in
warm condition. Pressure and leak tests may be necessary to meet pressure vessel code but they carry
risk to initiate and propagate LME cracks.
The product of LME or AMC failure probability
and consequence can be summarized on a numerical
scale or using a matrix approach [1]. From the calculated risk for leak and rupture scenarios, one can
then address remediation and risk reduction. The
process to manage risk and thus remain in operation
is summarized in Figure 8. The decision on operation
depends mainly on the amount of contamination discovered by inspection or, is some cases, predicted by
computational modeling.
Process Safety Progress (Vol.28, No.3)

Risk minimization plans address at least four major

areas:
Improving the accuracy and frequency of analyt-

ical measurements such that better predictions

of accumulation are possible
Preventing mercury deposition in the equipment
bys use of mercury removal systems
Replacing older equipment with more mercury
tolerant designs
Minimizing conditions that allow oxide fatigue
or damage
Mercury tolerance in aluminum heat exchangers
can be acquired by using aluminum alloys more resistant to LME and by employing equipment designs
that eliminate crevices adjacent to welds and designs
that allow mercury deposits to drain away from areas
of susceptible metallurgy.
Mercury removal units (MRUs) employ sorbents to
capture elemental mercury in either gas or liquid
hydrocarbon streams and are the most often utilized
AHX risk minimization method [16]. A properly functioning and well maintained MRU, coupled with an

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September 2009 265

analytical monitoring plan that targets MRU performance will prevent mercury accumulation in most
processes. Over the course of time, however, even
well designed mercury removal systems may allow
some mercury deposition. These situations develop
when MRU sorbent beds for are damaged by liquid
or contaminant intrusion, when beds spend prematurely or when feed composition changes abruptly.
If an inspection finds moderate to high levels of
contamination, the options for remediation are limited. Possibilities to remove mercury deposits from
aluminum equipment include thermal desorption, solvent cleaning and chemical cleaning. All approaches
have limited chance of complete success if mercury
deposits are substantial. Chemical cleaning is possible
but seldom attempted due to the risk of damaging
the oxide and spreading contamination within the
equipment.
Remediation or replacement of aluminum equipment also must consider upstream mercury accumulation in steel piping and vessels. Steel absorbs mercury
reversibly such that mercury absorbed in warm
upstream piping and equipment can be reintroduced
into the gas stream entering the cold aluminum
equipment. Thus upstream remediation may be
required to prevent mercury deposition into new or
otherwise clean equipment.
CONCLUSIONS

Mercurys adverse interaction with aluminum

requires careful scrutiny of processes that employ
aluminum heat exchangers. Most feeds to natural gas
and syngas separation processes contain some mercury and many have concentrations that, although
low, are significant for aluminum cryogenic equipment. The need for concern is coupled to the fact
that many aluminum heat exchangers have entered,
or will enter soon, a period of service considered old
(10 or more years of operation) from the standpoint
of metal fatigue and oxide fatigue. Periodic inspection and risk analysis for operation are prudent exercises that are needed to safeguard personnel safety
and plant integrity. The probability of LME or AMC
failure can be quantified by examination of failure
statistics in comparison to the circumstantial risk factors revealed by an understanding of the LME and
AMC aluminum degradation mechanisms.
LITERATURE CITED

1. API Recommended Practice 580, Risk-based Inspection, American Petroleum Institute, Washington,
2002.
2. S.M. Wilhelm and N.S. Bloom, Mercury in petroleum, Fuel ProcessTechnol 63 (2000), 1.

266 September 2009

Published on behalf of the AIChE

3. N.S. Bloom, Analysis and stability of mercury speciation in petroleum hydrocarbons, Fresenius J
Anal Chem 366 (2000), 5.
4. Aluminum Plate-Fin Heat Exchanger Manufacturers Association (ALPEMA), Standards for
Brazed Aluminum Plate-Fin Heat Exchangers,
ALPEMA, Geneva, 1994.
5. D.R. Nelson, Mercury attack of brazed aluminum
heat exchangers in cryogenic gas service, Proceedings 73rd Annual GPA Convention, Gas Processors Association, 1994.
6. R.N. Bell, Understanding and Preventing Failure of
Aluminum Equipment in the Presence of Liquid Mercury, Proceedings - American Institute of Chemical
Engineers Spring Meeting, Atlanta, Georgia, 2005.
7. S.M. Wilhelm, Methods to Combat Liquid Metal
Embrittlement in Cryogenic Aluminum Heat
Exchangers, Proceedings 73rd GPA Convention,
Gas Processors Association, 1994.
8. S.M. Wilhelm and R.D. Kane, Use of Slow Strain
Rate Tests to Evaluate the Embrittlement of Aluminum and Stainless Alloys in Process Environments Containing Mercury, ASTM STP 1210, Philadelphia, Pennsylvania, 1993.
9. D. McIntyre, J. English, and G. Kobrin, Mercury
Attack of Ethylene Plant Alloys, Paper 106,
Proceedings Corrosion 89, National Association
of Corrosion Engineers (NACE International),
Houston, 1989.
10. J.A. Kapp, D. Duquette, and M.H. Kamdar, Crack
growth behavior of aluminum alloys tested in liquid mercury, J Eng Mater Technol, 108 (1996), 37.
11. H.W. Liu and L. Fang, Effects of surface diffusion
and resolved shear stress intensity factor on environmentally assisted cracking, Theor Appl Fracture Mech, 25 (1996), 31.
12. B. Joseph, M. Picat, and F. Barbiera, Liquid metal
embrittlement: A state-of-the-art appraisal, Eur
Phys J AP, 5 (1999), 19.
13. S.P. Lynch, Metal-induced embrittlement of materials. Mater Characterization, 28 (1992), 279.
14. R. Coade and D. Coldham, The interaction of mercury and aluminium in heat exchangers in a natural
gas plants, Int J Press Vessels Piping, 83 (2006), 336.
15. Aon Advanced RiskFinance Conference 2007,
How does an organisation treat and manage a
large complex material damage and business
interruption loss? Claims case studyMoomba explosion; available at: http://www.aon.com.au/
pdf/speakers_corner/2007/session4_claims_
case_study_moomba_explosion.pdf, 2007.
16. S.M. Wilhelm, Conceptual design of mercury removal systems for hydrocarbon liquids, Hydrocarbon Process, 1999.

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