Paper No.

02477
CORROSION 2002
Effective Corrosion Control Techniques for Crude Unit Overheads

Walter Giesbrecht
Koch Petroleum Group
P.O. Box 64596
St. Paul, MN 55164

George Duggan
Baker Petrolite Corporation
12645 West Airport
Sugar Land, TX 77478

Dan Jackson
Baker Petrolite Corporation
369 Marshall Ave.
St. Louis, MO 63119

ABSTRACT

This paper discusses the effective use of engineering tools to determine potential
corrosion issues of crude unit overheads. Fundamental technologies and concepts,
including the Ionic Model, design of water washing systems, metallurgical analysis, and
exchanger design principles are combined with proper application of wash water and
chemicals to develop a solution to corrosion problems in crude unit overhead systems.

INTRODUCTION

Controlling corrosion in crude unit overhead systems has been a challenge since the
very beginning of petroleum refining. For many systems, a fairly simple solution was the
addition of corrosion inhibitors and neutralizing amines. The more difficult-to-solve
problems were addressed with other solutions, such as water washing or upgrading
metallurgy. Over the years, the challenge has continued to grow. The crude oils
available today are heavier than before and contain higher levels of contaminant species
that equate to a more corrosive environment in the crude unit. Many refineries are facing
overhead corrosion problems never before experienced. On units where an additive
program was in the past sufficient for corrosion control, corrosion now represents a

Copyright
2002 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE International,
Publications Division, 1440 South Creek Drive, Houston, Texas 77084-4906. The material presented and the views expressed in this paper are solely those of the
author(s) and not necessarily endorsed by the Association. Printed in U.S.A.

1
throughput limitation. Clearly, a more comprehensive, engineering-based approach to
the problem is needed.

In dealing with crude unit overhead corrosion, there is always the temptation to treat
the symptoms. An example is upgrading the metallurgy of a bundle when tube leaks are
discovered. This approach may improve the corrosion resistance of the bundle, but other
components (e.g. exchanger shell) may still be vulnerable to the corrosive environment.
The design and implementation of a successful corrosion control program starts with a
root cause analysis (RCA) to define the problem. This analysis involves the use of a
number of diagnostic tools, including laboratory analytical, process simulation and
metallurgical analysis. Understanding the corrosion history and a thorough knowledge of
the process conditions and equipment design are also essential aspects of the RCA. Once
the root cause is known, the mitigation approach can be selected. There are many
available options, including steps to minimize contaminants, changes in processing
conditions, alternate additive chemistries, water washing, metallurgy improvements and
even equipment redesign. The choice of and implementation of the mitigation strategy is
driven by an economic analysis. The final, critical step in the process is the monitoring
program, which should allow the effectiveness of changes to be measured.

This paper describes some of the elements essential to understanding the cause of and
overcoming chronic overhead system corrosion. Two case studies are presented where a
root cause analysis led to the successful implementation of improved corrosion control
strategies.

ESTABLISHING R O O T CAUSE

The starting point to defining an effective corrosion control strategy is the root cause
analysis (RCA), which should involve the following:

Review of corrosion history

System audit
Analytical testing
Metallurgical analysis
Ionic equilibria process simulation

Corrosion History

In any situation where corrosion is a concern, it is helpful to know whether the

problem is new or simply represents an ongoing problem. If the problem has not been
experienced in the past, historical information will not exist. However, for cases where
corrosion is ongoing, the refinery inspection files may contain valuable information
relating to the root cause. Turnaround reports contain narratives of the visual inspection.
In some cases a metallurgical analysis may have been carried out, providing a first
assessment of the root cause.

2
System Audit

Next on the list of things to do is the system audit. This audit will include a thorough
review of systems critical for corrosion control, including desalting, slop oil practices and
facilities for caustic injection, water washing and additive injection. There are examples
where the best solution is a water wash approach, but misapplication of the water wash
defeats the effort to mitigate the corrosion. It is wise to question past efforts to mitigate
corrosion to see if the approach failed due to incorrect implementation. The system audit
is also an ideal opportunity to define process conditions that play a role in corrosion. For
example, corrosion is a function of temperature. Temperature dictates where water
condenses and corrosive amine salts deposit. As such, understanding the temperature
profile is important, even in the top of the tower, where cold reflux or pumparound return
streams can cause localized corrosive conditions to occur. Another critical process factor
is velocity, especially in today's refining environment where crude units are operated
well above design conditions. An increase in velocity can cause increased corrosion in
areas where corrosion was formerly not a problem. Lastly, the system audit is an ideal
time to identify the data and samples needed for analyses, such as deposit scales, failed
metallurgy specimens and data for ionic equilibria process simulation.

Analytical Testing

Analytical testing provides insight into the corroding species at work as well as
defining how these corrosive species enter the unit. The corroding species of most
interest are the acids and bases in the system. Acids include HC1, SOx, organic acids,
H2S and CO2. Bases of interest start with the organic amines used to neutralize acidity in
the overhead system, but also include "tramp", or uninvited, bases. The most common
tramp base is ammonia, but tramp organic amines are frequently encountered in crude
unit overhead systems. These tramp amines may come in with the crude oil, with
refinery slop streams, with the stripping steam and with the desalter wash water. Water
analyses for the acids and bases can identify the corrosive species present. Samples to
analyze include the overhead condensate, desalter wash and brine waters, slop and crude
oils as well as overhead reflux and samples obtained from deadlegs (e.g. low point
bleeders).

When available, analysis of scale samples from the corroded equipment can further
the effort to identify the root cause. These scales often contain residual evidence of the
corrodents. For example, a water extract of the scale may contain dissolved amine salts.
When this occurs, the water pH will be low (4.5 pH) and an analysis of the water will
show hundreds or even thousands of ppm of amine and HC1. If the scale sample was not
flushed with water prior to obtaining the sample, the levels of amine and HC1 can be in
the tens of percents.

Metallurgical Analysis

A metallurgical analysis of a portion of the failed equipment is an essential means of

pinning down the root cause. The metallurgical analysis may be as simple as a visual

3
inspection to determine the nature or morphology of the corrosion attack. A sample with
deep, concentric pits has most likely suffered from underdeposit corrosion. If the pits are
elongated, velocity may be a contributing factor. Widespread thinning or very shallow
pitting is often indicative of general acid corrosion as opposed to a localized attack. A
more in depth analysis of the specimen will involve sectioning and mounting for
microscopic inspection. Scanning Electron Microscopy (SEM) in combination with
Energy Dispersive Spectroscopy (EDS) can identify chemical constituents in the vicinity
of the corrosion. A microscopic examination of the grain structure can determine if
mechanical factors are important, such as damage caused by cavitation. Compositional
analysis of the metal sample can identify manufacturing or fabrication factors, such as
weld defects or incorrect alloy material. The composition of the metal in the corroded
area can also identify whether de-alloying has occurred.

Ionic Equilibria Process Simulation

Crude unit corrosion is most often due to one of two primary corrosion mechanisms:
acid corrosion in areas where water is present and under-salt corrosion in areas upstream
of the bulk water dew point. Being able to predict where these two phenomena are likely
to occur provides the corrosion engineer with valuable data to confirm the root cause and
to define the proper corrosion control strategy. Process simulation has been in use for
many years to design processing equipment and to rate the performance of existing
equipment in new service. These simulations are adequate for determining the phase
behavior of hydrocarbon fractions and water, but do not provide information on the
chemistry of acid and base interactions in the vapor and liquid phases. For the corrosion
engineer, the acid and base behavior is of utmost importance in understanding the nature
of corrosion in the system. Improvements and innovations during the last decade led to
the development of electrolyte-based simulation and the introduction of ionic equilibria
process simulation 1. This breakthrough technology now plays an important part in
determining root cause as well as in defining the proper corrosion control strategy.

Figure 1 depicts the various equilibria which come into play in a crude unit overhead
system. Standard process simulation distributes components between the vapor and
liquid phases, but does not account for the potential for salt formation in the vapor nor
does it address the ionic equilibria in the aqueous phase. The ionic equilibria simulation
technology addresses acid corrosion issues by treating the water as a solution of the ionic
contaminants (acids and bases), where as standard process simulation dealt with water as
a pure substance. The more rigorous ionic treatment of the water gives an accurate
material balance for the vapor/liquid/water phases because it deals with all equilibria that
occur. It also provides a calculation of the water pH, which is the ultimate measure of
acid corrosion potential. The ionic equilibria simulation also allows direct calculation of
the temperature at which amine- and ammonia-hydrochloride salts will form. This data is
essential for determining the potential for under-salt corrosion in the overhead system.

In addition to providing insight into the tendency for acid corrosion and salt
formation, the process simulation can be used to determine where and how much water to

4
inject for water washing. By including a rigorous exchanger simulation, local "shock"
condensation zones can be identified, further defining areas where corrosion is likely.

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Figure 1" Examples of Overhead System Reaction Equilibria

Clearly, the ionic equilibria process simulation is an essential tool for identifying why
and where corrosion occurs - in other words pinpointing the root cause. In addition to
aiding in definition of root cause, the technology also provides a means of evaluating and
choosing mitigation strategies. Options for mitigation of corrosion include

Water washing strategies

Equipment redesign/reconfiguration
Revised processing conditions
Altemate additive chemistry
Minimization of incoming contaminants
Metallurgy upgrades

Several of these are discussed in more detail in the section that follows.

MITIGATING CORROSION

Water Wash System Design and Best Practices

In many crude unit overhead systems, the best solution to a corrosion problem is
often the installation of a water wash system. The purpose of the water wash is threefold,
1) the water scrubs some of the salt forming contaminants from the vapor, before they
have a chance to react, 2) the water washes away salts that have already deposited, and 3)
the water acts to raise the pH at the dew point, which should occur at the point of

5
injection. In a typical water wash system, water is injected ahead of the corrosive
environment. The source of the water is usually re-circulated condensate from the
overhead accumulator, but can also be stripped sour water, boiler feed water, or other
sources of condensate. It is important to note that, while a water wash system can be a
very effective solution, a poorly designed and maintained system may just add to your
problems. Below, are outlined some of the key factors in water wash system design,
which will impact the success of this strategy.

Injection Location.

Water wash location is often the subject of controversy. Water can be injected in the
overhead line as far back as the tower itself, or the water can be injected close to the inlet
of the bundles. There are advantages and disadvantages to both locations. Injecting
water in the overhead line increases contact time, improves scrubbing efficiency, and
increases the likelihood that the stream will reach the water dew point. It also helps
protect the overhead line in the event that cold wall shock condensation occurs.
However, in multi-bank cooling systems, the water will not distribute evenly to all the
banks, which may leave some exchangers unprotected from contaminants that remain in
the vapor phase. Injecting water at the inlet of the exchangers takes care of the
distribution problem. In the ideal case, water will be injected at both locations, however
this is often cost prohibitive. Even under ideal conditions, contaminants will always
remain in the vapor phase, therefore injection of water at the inlet of the bundle is usually
preferred to ensure neutralized water is available for all the exchangers. Figure 2 shows
the ideal, two-step water wash system.

FI~ I v,,eterwashlocation
for maximummixing

waterwashlocation
for distribution

F,t t

J
Figure. 2 Ideal, Two-Step Water Washing System

6
 Water Wash Rate.

The minimum water wash rate is the volume required to bring the overhead stream to
the water dew point. This is usually determined using a process simulator. The
calculation should be done using a worst-case scenario, which is maximum overhead
flow rate and minimum stripping steam injection rate. In addition to the minimum
required amount of water, an excess of 25%-50% is added to account for process
variability and to ensure that free water is available at the outer extremities of the bundle
to remove deposited salt. Maintaining the minimum required amount of water is very
important. Anything less may do more harm than good. Reliable metering should be
installed to be sure that the prescribed quantity is being injected and in the correct
locations. Achieving accurate and reliable measurements of sour water flow can be
troublesome, therefore the meters should be part of the refinery preventative maintenance
program and checked at regular intervals. If the meters provide local flow indication
only, then these flows should be recorded by the operator's on their regular, daily rounds.

Spray Nozzles.

As mentioned earlier, one of the functions of the water wash is to scrub the vapor
stream of contaminants. In order to improve the scrubbing efficiency, a spray nozzle is
used to inject the water. The nozzle should be sized for sufficient pressure drop to
minimize droplet size and maximize surface area. The recommended pressure drop is
137.9 kPa [20 psi]. To minimize pluggage, the nozzle should have a single bore, which
will maximize the free passage for a given pressure drop. The nozzle should be oriented
co-current with the flow of vapor so the spray pattern will be maintained as long as
possible. The spray angle should be wide enough to provide full coverage of the pipe,
but should not allow direct impingement of the water on the side of the pipe. This will
cause premature coalescence of the droplets and possible corrosion on the side of the
pipe. The nozzle manufacturer or chemical representative can help in properly sizing the
nozzle and spray pattem. Figure 3 shows the location and proper orientation of a water
wash spray nozzle.

H I

I I
I
I

flow
.......... '"::"":::":::::::":"::::;;;i;i;:iiiiilji.i...
Figure 3. Water Wash Injection Details

7
 Overall, water wash systems are typically the most effective mitigation strategy, but
they must be applied properly. Often times, corrosion problems that cannot be explained
by conventional root cause analysis can be traced back to water wash issues. The
problems encountered most often are pluggage by particulates such as FeS and false
meter readings. The systems that are the most effective and reliable have the following
characteristics:

1) Sufficient water with an excess of 25%-50% at all times.

2) Injection in a location that will provide distribution of water to all the bundles.
3) A high pressure drop atomizing spray nozzle to provide good liquid-vapor contact
4) Reliable metering, such as an orifice type meter, which is maintained and monitored
on a routine basis.
5) A filtering system sized to remove particulate from the water.
6) Piping sized for adequate velocity and minimum dead zones that will tend to capture
solids.
7) A pump with sufficient head capacity to provide the necessary flow under partially
plugged conditions.

Equipment Redesign for Velocity Considerations

Velocity issues are becoming more common in today's refinery as the need to expand
unit production beyond the rated capacity is increasing. While high velocities are far
more common, low velocities can also be the root cause of failure as well.

High Velocity.

A high velocity problem will typically manifest itself at the inlet of the exchanger,
either on the tubes or the shell just below the inlet nozzle. This location often represents
a restriction in flow and is also the first location where saturated vapor and droplets are
able to impinge directly on a metal surface with maximum shear force. While the
velocity is not high enough to cause erosion of the steel, it is high enough to wear away
the less resilient corrosion product layer (usually FeS), which exposes fresh metal for
further corrosion. The corrosion product layer will normally act to greatly inhibit
corrosion if left intact.

Several techniques can be used to solve a high velocity problem depending on the
location of the corrosion. If the velocity is marginally high such that only the first row of
tubes is affected, it may suffice just to install an impingement plate (see Figure 4). Care
must be taken, however to ensure that the impingement plate itself does not cause a
restriction. There must be sufficient clearance between the impingement plant and the
top of the shell. The clearance should be greater than the cross-sectional area of the inlet
nozzle. If the clearance is not bigger, then the velocity-accelerated corrosion will simply
transfer itself to the shell or the nearest exposed tubes.

8
 16" ID--~

,MP.P~T~ I I I
-....
TIE ROD

i
~'~ \ 4" min. !
INLET TUBE AR F_,A !
B/~=F~..~,
oooooooooooooooooo
! TU BE SHEET
SHELL I /°°°o°°°°o°o°o°°°°°° .... '~ t

TOP TU BE ROW

CENTER ON NOZZ.

IMP. PLATEARRANGEMENT END VIEW IMP. PLATE AR R,a~GEMENTTOP VIEW

Figure 4. Exchanger Impingement Plate Arrangement- 16" Inlet

If the necessary clearance cannot be achieved between the impingement plate and the
shell wall, an alternative impingement design can be considered. One common design
utilizes solid bar stock arranged in a triangular pitch, similar to a typical tube
arrangement (see Figure 5). This design will protect the first row of live tubes without
creating a restriction in flow.

I I
-....
TIE ROO

TUBE SHEET
SHELL ID , ~ , ~

TOP TUBE ROW

CENTER ON NOZZ.
i

IMP. ARRANGEMENT END VIEW IMP. ARRANGEMENTTOP VIEW

Figure 5. Alternative Exchanger Impingement Arrangement

The arrangement shows an impingement design that extends just outside the inlet
nozzle diameter, however it can extend the entire width and length of the inlet baffle area
since it doesn't represent a restriction.

In cases of more severe velocity accelerated corrosion, an increase in nozzle diameter

should be considered. Installation of an inlet bell or swedge is not sufficient, because the
liquid droplets do not have time to lose momentum before entering the bundle. Our
experience in the industry suggests that properly sized inlet nozzles provide a velocity in
the range of 12.2 to 15.2 meters per second (mps) [40 to 50 feet per second (fps)].
Velocities in the 15.2 to 19.8 mps [50 to 65 fps] range are considered marginal,
depending on the specific gravity of the stream and the shear force (pv 2) it imparts on the

9
metal. Above 19.8 mps [65 fps] moderate to severe metal loss should be expected when
the exchanger is opened. Bear in mind that this is velocity accelerated corrosion, in
which there is a mechanical destruction of the protective corrosion product layer. In the
case in which the dew point pH is low (<5 pH) even a moderate velocity can result in
severe corrosion, as the protective corrosion product layer becomes soluble in the low pH
water.

Low Velocity.

Low velocity problems are less common and typically result in less severe corrosion.
Nonetheless, low velocity can be the root cause of failure. Low velocity problems
normally occur within the exchanger bundle. It causes poor distribution of liquid, namely
water, to low flow region. Typically, the baffle areas, the upper portions of the bundle
and the outer extremities in the 3 and 9 o'clock positions are affected. In these areas
solids and salts will accumulate with little opportunity to be washed away. Eventually
under-deposit corrosion will occur.

The solution to a low velocity problem is a little less straightforward and depends
greatly on the location of the dead zones. Installation of a restricting impingement plate,
installation of a strategically placed baffle, or moving the flow baffles closer together are
several options that can be considered. And some of these options will often result in
better heat transfer. In some cases, low velocity and poor distribution have been resolved
by the installation of additional wash nozzles in the shell. These nozzles can be used
intermittently or continuously. Figure 6 gives an example of these supplemental spray
nozzles.

aclclilonal was h nozzles

++

I
I
oulet oulet

Figure 6. Supplemental Water Wash - Shell Spray Nozzles

10
Other Mitigation Strategies

Revised Processing Conditions.

In some cases, changes in operating conditions arise due to the more difficult
"opportunity" crudes being processed. An example is a decrease in tower top
temperature to account for product end point requirements. The corrosion engineer must
consider the impact of processing conditions when determining the best corrosion control
strategy. The solution to corrosion may entail such requirements as placing a minimum
temperature specification on pumparound or reflux return streams or on the tower top
temperature itself. The possibility of revising operating conditions to control corrosion
is, in many cases, in conflict with refinery operating targets. Nonetheless, the mitigation
strategy must take into consideration the option of changing the process conditions.

Alternate Additive Chemistry.

The options for alternate additives usually involve selecting a different neutralizing
strategy. This may involve changing to a different organic amine or a blend of organic
amines. In some systems, ammonia is a viable option. Ionic equilibria process
simulation is the best tool for evaluating and selecting the proper neutralizing strategy.

While selecting the appropriate additive is important, equally important is selecting

the location for injection and the means of injection. The most important consideration is
distribution. Thus, injection at multiple locations may be necessary to assure that all
equipment is treated. The injection equipment is equally important, as is the use of
proper carrier streams, to aid in the distribution of the additives.

Minimizing Contaminants.

Since the influx of acidic and basic contaminants is linked to the root cause of
corrosion, controlling the presence of these contaminants is of obvious importance.
There exist many factors that influence contaminant levels. The following list
summarizes a few of the more frequently employed methods.

Improved desalting practices

Tank demulsification/pretreatment
)" Caustic injection (to reduce overhead chloride)
Re-routing slops away from crude unit
Alternate desalter wash water source

Metallurgy Upgrades.

When confronted with a leaking exchanger bundle, the temptation is to employ higher
grades of metallurgy to deal with the corrosion. As mentioned, this may solve the bundle
leakage problem, but does not protect other equipment in the system. However, there are
times where a metallurgy change is a desirable aspect of the corrosion control approach.

11
In such cases, proper metallurgy selection is essential. And that selection depends on a
firm knowledge of the underlying cause of corrosion. For example, copper-containing
alloys are generally better at dealing with low pH acid corrosion, but fail when employed
in an environment where amine salts are depositing. Care must also be taken when
contact between the different metals occurs. An example is constructing a bundle with
titanium tubes. Choosing the incorrect metallurgy for the support structure will often
negate the benefits of the higher cost metallurgy by creating new corrosion problems (e.g.
galvanic couple or titanium hydride formation).

MONITORING

Although monitoring does not directly affect the corrosion rate of the overhead, it is
certainly an important part of any mitigation strategy. If the monitoring program consists
of bundle inspection at the time of failure, then chances are a new program is needed.

Water Analysis

A good monitoring program starts with periodic water analysis. The key parameters
are pH, Chloride, Iron, and Ammonia. The pH should be determined a minimum of
twice per shift, so that neutralizer dosage can be adjusted. The pH can vary hour to hour,
and controlling it within the prescribed range will be necessary for a successful program.
Chloride should be determined two to three times per week, more often if it is being used
to control caustic injection rate. Soluble iron should also be determined two to three
times per week. The solubility of iron will vary with pH, so it is not a good absolute
indicator of iron loss, however, a good treatment program will typically result in iron
levels below the solubility level, so sudden increases in iron can be a good indicator that
something is wrong. Ammonia should be determined one to two times per week. If
ammonia is not being used as a neutralizer, then high levels of ammonia may be cause for
concern in other areas in the overhead system, namely the tower top.

Probes and Coupons

The monitoring program should also include strategically placed corrosion coupons
and/or electrical resistance (ER) probes. "Strategically placed" means that the probe or
coupon must be located within the corrosive environment in order for it to be useful. A
coupon or ER probe will both serve the same purpose. The advantage of an ER probe is
that it will yield results quicker (1-2 weeks) than a coupon, which will allow quicker
optimization of the program. And because the response time is faster, it is easier to relate
a measured corrosion rate to process changes or events. The disadvantage of an ER
probes is that it is more costly than a coupon, and in a more severe corrosive
environment, it will have to be replaced more frequently. Neither coupons nor probes are
good indicators of absolute corrosion or bundle life, because they measure corrosion at a
fixed point only and the point of maximum corrosion is a moving target. Nonetheless,
they will be good directional indicators of a higher or lower corrosion rate.

12
 Probes and coupons are typically installed with a device that allows retraction online
so the probe or coupon can be replaced (see Figure 7).

Packing Gland

Safety Cable

Figure 7. Example of ER Probe and Coupon Insertion Equipment

Ultrasonic Thickness Measurement

When corrosion is occurring on a pipe or vessel wall, it is often practical to measure

corrosion rate using Ultrasonic Thickness (UT) measurements. The advantage of UT is
that it is a metal thickness measurement and is, therefore an absolute measure of
corrosion rate. It is often necessary for determining expected life of a pipe or vessel. It
may prevent a costly failure and will likely reduce a few of the surprises at turnaround
time. UT monitoring still has the disadvantage that it measures corrosion at a fixed point.
It is a very useful technique for measuring general thinning, however it may be very
misleading in cases of severe localized corrosion such as pitting.

Visual inspection

The most reliable form of monitoring is visual inspection. The obvious disadvantage
of visual inspection is that it only occurs at infrequent intervals such as a turnaround, and
therefore optimization and troubleshooting can take years instead of months. Ideally, a
good monitoring program will allow planned outages at opportune times to pull and
inspect the bundle. If corrosion is discovered during visual inspection, then it should be
noted in detail. This is also the time to catch samples of fouling material, if it is
available. Every effort should be made to extract a corroded tube for detailed
metallurgical analysis.

CASE STUDIES

Case Study #1

Over the last 6 years there have been a very high number of failure in the crude tower
overhead exchangers. Even before this period the exchangers have failed far too often.

13
The expected life of the exchangers should be in the area of twelve plus years, while the
life has a historical average of approximately about two years. In the past, the failures of
the overhead exchangers were due to two main reasons:

1. Severe accelerated under-deposit corrosion at the back end (floating head end) of the
bundle because of severe NH4C1 fouling
2. Erosion at the inlet shell nozzle

With this short time between failures, a detailed root cause failure analysis (RCA)
was completed. A number of issues were determined to be contributing factors:

)' High exchanger nozzle vapor inlet

~' Low velocity in the shell
3" Wash water issues (location, distribution)
)" Possible pH control issues

As part of the RCA, a detailed ionic equilibria process simulation model [IEM] of the
crude unit overhead system was completed. The model calculated vapor velocities,
evaluated water wash location, and determined dew point pH. The IEM showed the inlet
vapor velocity of the exchanger to be in the moderate to severe range (19.8 mps [65 fps]).
Because of the high number of erosion failures at the exchanger inlet vapor, the problem
could not be called moderate. The tube failures at the shell inlet were all erosion related
and were all at the outer edge of the impingement plate.

The IEM also showed that because of the velocity of the gas stream and the location
of the wash water, most of the water was going to the front half [stationary tubesheet end]
of the bundle and leaving the back end of the bundle without sufficient wash water. The
wash water was being injected into the overhead line just upstream of a 90 ° elbow at the
exchanger inlet nozzle. This helped with the understanding as to why there were constant
failures in the back end of the exchanger due to severe NH4C1 fouling.

As a mitigation strategy in the past, the exchanger had three tubes installed in the top
of the bundle (evenly spaced) through which boiler feed water (BFW) could be injected.
The tubes had small holes drilled into the bottom of the tube for the full length. The
concept was to inject BFW into the tubes and this water would wash the complete length
of the bundle. With these tubes in place and BFW being injected, the failures continued
at the normal rate. From inspection of the tubes and from knowledge from the IEM, it
was determined that the water injection rate was too low and because of the high process
inlet temperature, the water in the tubes was not reaching past the shell inlet nozzle.
Hence, there was no wash water reaching the back end of the bundle.

Armed with the IEM knowledge and RCA leanings, a number of mitigation strategies
were implemented. To help with the shell inlet velocity problem of erosion around the
flat impingement plate a new designed impingement plate made of rods was designed and
installed. This design protected the tubes directly below the shell inlet and helped with
better gas distribution.

14
 Next the location of the wash water was changed. The old location just upstream of
the elbow was eliminated. A newly designed spray nozzle directly in the exchanger inlet
nozzle was installed. To ensure that constant wash water issues could be avoided, a
redesign of the wash water system was undertaken. This may sound bigger then it really
was, as the system was simplified to allow for increased flow.

Because of the low shell gas velocity and to ensure that there was sufficient washing
of the gas stream, four spray nozzles were added to the top of the exchanger shell. Two
spray nozzles on the front end of the exchanger and two sprays were placed on the back
end of the exchanger. The wash water was injected into the overhead line on a
continuous basis. A procedure was implemented where once a week the wash water was
shut off to the overhead line, and then the wash water was directed to the spray nozzles
on the front end of the exchanger and then to the back end of the exchanger. With the
wash water going to the shell spray nozzles, the wash water rate was also increased by --
100%. The high rate shell washing would continue for about 2 hours on each end. With
the procedure complete, normal operation of wash water injection into the overhead line
continued.

For better pH control, a change in neutralizer was also implemented.

With all these changes, the exchangers were placed back into service. Testing was
completed during the shell spray nozzles washing and showed that the C1- content of the
wash water did decrease during the shell washing. Much to our surprise the exchanger
life did not see a real increase. Approximately twenty months after all these changes
were implemented, there was another leak. The exchanger bundle was pulled and
replaced. From inspection, the bundle had two areas of concern:

1. Shell inlet nozzle area around some skid bars

2. Two small areas at each end of the bundle, which showed severe NH4C1 fouling along
with under-deposit corrosion.

The replaced bundle had some modifications made to the top inlet nozzle area where
the skid bars that were believed to be causing the problem were removed. The inlet area
also had pitting and it is not understood why. The front and back ends of the bundle
fouling issue will be addressed with the addition of one more shell spray nozzle being
added to the front and back ends of the exchanger shell. Also plans call for enlarging the
inlet shell nozzle to reduce the gas velocity.

Case Study #2

This is a newer crude unit than the unit described in Case Study #1. Mean time
between failures on the crude tower overhead exchangers was three to five years.
Although much better than the life for the Case Study #1 unit, the expected exchanger life
did not meet the Refinery's staff expectations. There were many things learned from

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Case Study #1 and with the relatively short life of these overhead exchangers, a detailed
review was completed on this crude unit.

The RCA was completed as well as an IEM. The following concems were identified:

pH control was a concem

Water wash was poorly distributed
Water atomization was poor
The overhead line had corrosion

Armed with the results of the RCA and IEM, a mitigation strategy for this crude unit
was prepared. The pH control issue was a relatively easy fix. A change in neutralizer
was put into place and better pH control was achieved from the onset. But, within six
months of the neutralizer change, the vacuum tower ejector system starting losing
performance. What was thought to be a simple fix now had an added complexity. A RCA
was completed and as it tums out, the salt forming temperature of the neutralizing amine
was very high. Resolution to the salt forming problem was a change in amine. This was
completed and there has not been any loss of ejector performance since the change was
made.

The next issue was the wash water. Water atomization was somewhat of an easy fix
as new spray nozzles were installed. With this simple change, the delivery system
became complicated. An extensive review of the delivery system revealed that the wash
water piping system was undersized for the required flow, as specified by the IEM. After
extensive piping modifications, the new system was placed into service. As with case
study #1, a special procedure for flushing the exchanger shell was put into place. Once
per week the wash water rate is maximized to each exchanger shell, at the inlet nozzle
and flushed with high volumes of wash water for two hours. With the high volume flush
completed the wash water is put back to normal rates.

The corrosion in the overhead line was somewhat easily solved, as well. It is
believed that the localized nature of the corrosion resulted from cold spots caused by
insulation inconsistencies. This was causing shock condensation and in turn caused the
corrosion. A new chemical injection location was installed at the top of the tower and
placed into service. It should be noted that caution must be exercised. Care must be taken
to ensure there is enough carrier present with the chemical, or severe localized corrosion
can occur.

CONCLUSIONS

The constantly changing nature of crude oil refining has greatly complicated the task
of controlling corrosion in the overhead system
It is common in today's refining environment for a mitigation strategy to be
comprised of multiple changes rather than one simple change
The first step to mitigate corrosion is to define the root cause or causes

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)" A successful root cause analysis will be comprised of several elements, including
ionic equilibria process simulation, metallurgical analysis, a process audit and use of
analytical methods to identify the underlying cause of the corrosion
Once the root causes are known, a mitigation strategy can be selected
)" The mitigation strategy can involve changes in process conditions, equipment
redesign, alternate metallurgy, contaminant reduction and improved water washing
systems, as well as adjustments to the corrosion control additive program
A well-defined monitoring program is imperative to determine the effectiveness of
the mitigation strategy and to determine when additional adjustments are needed,
since corrosion rates are constantly changing.

References:

1. G.G. Duggan, R.G. Rechtien, "Application of Ionic Equilibria Process Simulation For
Atmospheric Distillation Overhead Systems," CORROSION/98, paper no. 586,
(Houston, TX: NACE International, 1973).

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