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Paper No.

09332 2009

MULTIPLE CORROSION MECHANISMS


IN A CRUDE DISTILLATION OVERHEAD SYSTEM

George Duggan
Baker Hughes Incorporated, USA
12645 W Airport Blvd
Sugar Land, TX 77478
George.Duggan@BakerHughes.com

Randy Rechtien
Baker Hughes Incorporated, USA
369 Marshall Avenue
St. Louis, MO 63119

Lionel Roberts
Irving Oil Limited
340 Loch Lomond Road
Saint John, NB Canada
E2L 4H6

ABSTRACT

Troubleshooting efforts were devoted to addressing corrosion activity in multiple areas


of an atmospheric tower overhead system. These efforts indicated that three different sections
of the overhead were being simultaneously attacked---each section having its own distinct
corrosion mechanism. The areas affected and their mechanisms were as follows: 1) Corrosion
resulting from ammonium chloride deposits in a "dry" pressure relief valve header; 2) Wet
sulfide corrosion on 70/30 Cu/Ni exchanger tubes; and 3) Velocity accelerated corrosion at the
outlet elbows of these exchangers. The severity of these mechanisms correlated well with
variations in unit operating conditions. Several techniques were used to identify the
mechanisms involved, including electrolyte simulation modeling, metallurgical analysis of
weight loss coupons and ultrasonic thickness (UT) measurements. Recommended mitigation
plans and their effectiveness upon implementation will also be discussed.

Keywords: ammonia, chloride salts, deposition, cupro-nickel corrosion, velocity

Copyright
©2009 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, Copyright Division, 1440 South creek Drive, Houston, Texas 777084. The material presented and the views expressed in this paper are
solely those of the author(s) and are not necessarily endorsed by the Association. Printed in the U.S.A.

1
INTRODUCTION

More than four years ago, problematic episodes of corrosion occurred in the overhead
condensing system of the #3 Crude Unit atmospheric tower at Irving Oil Ltd. in Saint John,
New Brunswick, Canada. Corrosion occurred in three separate locations in the overhead, with
each location experiencing a different mechanism of attack. Though uncommon, there are
industry examples of the simultaneous occurrence of different corrosion mechanisms in a
single overhead system.1

For this particular system, the primary sources of corrosion were strongly related to unit
operating conditions, contaminant levels in the crude and, ultimately, contaminant levels in the
tower overhead itself. The refinery processed blends of either “sweet” or “sour” crudes in
blocked operation. These alternating crude slates, combined with seasonal variations in tower
operations, produced a wide range of corrosive environments in the overhead. In particular,
spikes in overhead hydrochloric acid (HCl) concentration increased the formation potential of
ammonium chloride (NH4Cl) salt and made pH control of overhead drum water more difficult.
During sour crude processing, increased levels of hydrogen sulfide (H2S) in the overhead
produced preferential attack on copper-based equipment. Higher system temperatures and
higher flow rates during some operating modes created localized zones in which velocity-
accelerated corrosion was prevalent.

The variations in system conditions required more diligence on the part of operators,
inspectors and corrosion control engineers to address the problems. Multiple analytical and
monitoring techniques were required to identify the cause of the corrosion mechanism and to
develop appropriate mitigation options. To this end, efforts were conducted to correlate
operational changes with periods of increased corrosion activity. Ionic modeling techniques
were employed to calculate amine-hydrochloride salt formation temperatures and to define
“safe” operating envelopes. Detailed compositional analyses of scale deposits and
metallurgical analyses of weight loss coupons were also performed. Traditional methods for
measuring metal loss rates provided insight into the magnitude of corrosion activity as well.

Given below is a detailed summary of these troubleshooting efforts and the methods
implemented to successfully reduce the threat of corrosion-related failures.

SYSTEM OVERVIEW

The #3 Crude Unit atmospheric distillation tower overhead (Figure 1) comprises a set of
two parallel shell-and-tube exchangers (E-22001 A/B) which are vertically oriented. In these
exchangers, process vapors exchange heat with cold crude oil. The exchanger outlet streams
are combined and then fed to a set of eight air coolers (E-22027 A-H). The vapor/liquid
mixture from the air coolers is separated in the D-22001 drum. Naphtha from the drum is
divided to both tower reflux and product. A portion of sour water from the drum is continuously
recycled to the overhead vapor line for use as wash water.

The E-22001 A/B exchanger tube bundles are constructed of 70/30 copper/nickel alloy
(UNS C71500). The remaining overhead equipment is constructed of carbon steel. The
existing corrosion control program includes an oil-soluble inhibitor injected to the overhead
vapor line via a reflux carrier. Neutralization is provided by an aqueous ammonia solution
(approximately 20% concentration) which is injected to the overhead line via the water wash.

2
Currently, the ammonia injection rate is adjusted to maintain a nominal target pH range of 6-
6.5 in the overhead drum. During the periods of corrosion activity discussed herein, the drum
was typically operated at a pH of 7.0 or higher.

Corrosion rate monitoring was measured via a combination of electrical resistance (ER)
probes and weight loss coupons at several locations in the overhead. Specifically, a total of
seven monitoring devices were installed as follows: the main overhead vapor line (x1); the E-
22001 A/B inlets (x4); and the E-22001 A/B outlets (x2). In addition, frequent UT
measurements were taken by the refinery’s inspection department. In general, the rates
measured at these locations were within acceptable ranges. However, there were occasional
periods of unacceptably high corrosion rates [>0.25 mm/year (>10 mil/year (mpy))] at these
locations. The periods of high corrosion rates usually correlated to variations in operating
modes and/or switches in crude blends.

The corrosion activity in the atmospheric tower overhead was most severe from late
2004 through late 2006. During this period, the refinery processed several different crudes of
varying sulfur content. Typically, the unit was operated in “blocked” operation: several days of
“sweet” crude and then several days of “sour” crude and so on. Crude blends with sulfur
contents below 1% were considered “sweet”. In addition to variations in crude sulfur, the tower
was operated on seasonal cycles (“summer” vs. “winter” operation). These seasonal modes
covered a relatively wide range of tower operations, particularly in terms of tower top
temperature and overhead flow rate. Table 1 summarizes the typical conditions under each of
the four primary operating modes.

There were three distinct areas of the overhead which experienced periods of excessive
corrosion activity:

• Pressure relief valves at the tower top


• E-22001 A/B tube bundles
• E-22001 A/B outlet elbows

Details of the corrosion mechanisms and associated mitigation steps for each of these
areas are provided in the sections below.

CORROSION MECHANISM 1: AMMONIUM CHLORIDE DEPOSITION

Background
Beginning in late 2004, there were indications of corrosion activity in several of the
pressure relief valves (PSV) located at the top of the distillation tower. These PSV’s were
connected along a common manifold which was un-insulated. UT measurements revealed
corrosion rates in the range of 0.5 – 1.0 mm/year (20 - 40 mpy) in this area. Measured
corrosion rates were at the high end of this range during the “winter” modes of operation. In
addition, radiography (X-Ray) measurements indicated the build-up of deposits on the PSV
internals and in the manifold piping. These monitoring results suggested that a corrosive
deposit, most likely an NH4Cl salt, was forming in the PSV header.

Troubleshooting Efforts
In an effort to confirm the damage mechanism, electrolyte-based process simulation
modeling (Ionic Modeling)2,3 was performed at tower top conditions. In particular, the salt

3
formation temperature of NH4Cl was determined using the average concentration of HCl and
ammonia in the D-22001 drum water under each operating mode. As shown in Table 2, the
tower top temperatures were higher than the calculated salt formation temperatures for all
operating conditions. These results suggested that salt formation was not favored at bulk
stream temperatures and average contaminant levels.

However, there were two additional effects which needed to be considered: 1) locally
colder temperatures on the PSV header wall and 2) variations in HCl and ammonia
concentrations. Further modeling efforts were then conducted to examine salt formation over
a wider range of operations and contaminant levels. A plot of these results for the Winter-Sour
mode is given in Figure 2. Each curve (isotherm) represents the phase boundary for NH4Cl
salt formation at the tower top temperature indicated. The typical ranges of HCl and ammonia
in the D-22001 drum water are represented by the shaded region.

Guidelines for avoiding localized salt deposition in the upper sections of towers have
been developed by Baker Petrolite(1). These guidelines require that the bulk tower top
temperature be at least 14°C (25°F) higher than the salt formation temperature. In this way,
the tower is protected against “shock cooling” caused by cold reflux as it enters the tower.
However, for un-insulated piping in cold weather climates, the guidelines call for a more
stringent minimum temperature differential of 28°C (50°F).

As shown in Figure 2, the range of NH4Cl formation temperatures given by the shaded
region is approximately 104 – 114°C (219 – 237°F). This salt formation temperature range is
only 15 – 25°C (27 – 45°F) below the tower top temperature of 129°C (264°F). As such, these
temperature differentials are less than the recommended minimum of 28°C (50°F) for cold
weather climates.

Considering that higher rates of metal loss were detected during “winter” operation, and,
given that the PSV manifold was un-insulated, these results confirmed that NH4Cl deposition
and its associated under-salt mechanism were the source of corrosion in this area.

Mitigation
Once the mechanism had been properly identified, several mitigation options were
considered. These mitigation options included the following:

• Increasing the tower top temperature


• Installing insulation or heat tracing on the PSV manifold
• Decreasing overhead HCl levels
• Periodically injecting water to the manifold

Increasing the tower temperature was ruled-out because of its adverse effects on tower
operation and desired product compositions. Fearing that too much damage had already
occurred, the refiner replaced the PSV header in early 2006. The new header was installed
with blind flanged connections and included heat tracing and insulation. In addition, the new
header has been water washed during post-2006 unit shutdowns to ensure that any salts
which may have deposited are removed.

__________________________________________
(1) Baker Petrolite is a division of Baker Hughes, Incorporated USA

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About a year after the new PSV header was installed, another key operational change
was implemented. In early 2007, a caustic addition program was initiated in which caustic was
injected to the desalted crude at a rate of about 3 ppmw (1 lb/1,000 bbl). With this caustic
application now in place, the levels of HCl in the overhead drum water are typically 20-30
ppmw. Prior to caustic use, HCl levels were always greater than 60 ppmw. As shown in
Figure 2, this reduction in overhead HCl has greatly minimized the potential for NH4Cl
formation at the tower top.

To monitor NH4Cl formation potential on an ongoing basis, a customized version of the


Ionic Model Field Monitor(2) was created. This tool, which resides with the local field staff, is an
extension of Ionic Modeling calculation methods.4 Using operating variables as input, the
monitoring tool determines salt formation on a frequent (even daily) basis. As such, the
monitoring tool serves as an “early warning” system to alert the refiner should NH4Cl formation
potential increase when crude types or tower conditions change.

Results
As a result of the mechanical and chemical mitigation steps employed, metal loss at the
PSV manifold has been stopped. There is no indication of corrosion activity from the most
recent UT measurements in these areas. These positive results have been confirmed by the
on-site monitoring tool which continues to be used to track tower operations.

CORROSION MECHANISM 2: HYDROGEN SULFIDE ATTACK ON COPPER

Background
In early 2005, during the same time that corrosion issues in the PSV’s were being
addressed, there were also corrosion concerns at the E-22001A/B exchangers. Corrosion
rates as measured by 70/30 Cu/Ni weight loss coupons located at the exchanger inlets ranged
from 0.25 – 0.60 mm/year (10 - 24 mpy). To determine the corrosion activity on the exchanger
shells and inlet piping, carbon steel coupons were also installed at the exchanger inlets. The
measured rates on the carbon steel coupons were consistently below 0.13 mm/year (5 mpy).
The monitoring indicated that corrosion activity on carbon steel was lower than that on 70/30
Cu/Ni at the operating conditions of the exchangers.

Assuming that the inlet coupons were a reasonable representation of the metal loss rate
on the tubes themselves, then the expected life of the existing bundles (which had been newly-
installed in 2003) was less than five years. Prior to the new installation, the previous set of
bundles had been in service for eight years. It should be noted that, during the previous eight-
year run, crude sulfur levels were lower than those during post-2003 operation. There was a
conjecture, then, that higher levels of overhead H2S and/or sulfur-oxygen (SOx) species were
contributing to the attack on the bundles.

Troubleshooting Efforts
To better identify the mechanism of attack, Ionic Modeling was performed at the
exchanger conditions for all operating modes. The modeling focused on three key areas: 1)
performance of the existing water wash; 2) the pH profile produced by the ammonia neutralizer
injection; and 3) vapor velocities at the exchanger inlets.

__________________________________________
(2) Ionic Model Field Monitor is a service tool of Baker Hughes, Incorporated USA

5
The existing water wash is injected via atomizing spray nozzles at a consistent rate of
756 liters/minute (200 gallons/minute). This rate is nearly twice that recommended by the
simulation modeling. At all points downstream of the water wash injection, the pH of the
aqueous phase was above 6.0. Modeling under all operating modes produced equivalent
results. Therefore, neither NH4Cl salt deposition (from inadequate water washing) nor low pH
aqueous corrosion was a likely mechanism in the exchangers.

The vapor velocities at the exchanger inlets ranged from 15 - 18 m/sec (50 - 60 ft/sec).
Though these velocities are at the upper end of typical concern levels,3,5 there was no visual
indication to suggest a velocity component to the corrosion observed on the Cu/Ni coupons.

Additional troubleshooting techniques were needed to confirm these modeling results


and to identify the cause of this corrosion. As part of this effort, metallurgical analysis was
conducted on a coupon removed from the system. Figure 3 shows a coupon which was
installed at the E-22001A inlet in late 2004. The measured corrosion rate on this coupon was
0.38 mm/year (15 mpy). Using Scanning Electron Microscopy (SEM), a cross-sectional,
magnified view of the coupon was generated (refer to Figure 4). In addition to the un-affected
base metal, the analysis revealed two distinct scale layers.

Electron Dispersion Spectroscopy (EDS) techniques were used to determine the


composition of the base metal and of the two scale layers. These elemental composition
results are summarized in Table 3. As shown, the nature of the scale layers is markedly
different: the inner layer was predominantly nickel sulfide while the outer layer was composed
almost exclusively of copper sulfide. As shown in Figure 4, the inner layer has a tighter, more
cohesive structure than does the outer layer. Therefore, it’s reasonable to conclude that the
nickel sulfide layer provided some protection against attack while the amorphous copper
sulfide scale did not.

To identify any water-soluble species present, Ion Chromatography (IC) was performed
on a water extract of the scale. As shown in Table 4, the scale contained chlorides, sulfates
and organic acids but very little ammonia and no other amines. Given that it is common to
measure percent levels of chlorides and amines in overhead system scales, these low levels
indicated that amine-hydrochloride salt corrosion was not the mechanism of attack. Note also
that the pH of the water extract was nearly neutral. The pH of a water extract from a scale
which contains chloride salts is typically less than 4.5. The scale analyses confirmed the
modeling results which precluded both under-salt and low pH aqueous corrosion as viable
mechanisms.

The most revealing piece of data was the high proportion of copper sulfide in the outer
scale layer which suggested a preferential attack on copper. Corrosion of copper alloys in
aqueous sulfide environments has been noted in the industry.6 Research in this area indicates
that copper corrosion can be accelerated in sour systems, particularly when the aqueous
phase approaches neutral or even alkaline pH.7 The conclusion here was that the inlet
coupons (as well as the exchanger bundles themselves) were subject to accelerated attack via
this aqueous sulfide mechanism. The rate of attack was almost certainly more pronounced
during the processing of sour crude blends as well as during those times when system pH was
at the high end of the range (above 6.5).

6
Mitigation
The main focus of mitigation efforts was improved pH control. When ammonia is used
as an overhead neutralizer, it is common to encounter periods of both high and low pH
excursions. As would be expected for this overhead, operation outside of the desired drum pH
target range was a frequent occurrence.

Other operational factors made pH control more challenging. Switching from one crude
blend to another led to short-term periods of impaired desalter efficiency. Also, some of the
crudes which were routinely processed were suspected to contain organically-bound chlorides.
As such, HCl levels in the overhead would rise sharply during a crude switch. These higher
HCl levels often caused the drum pH to drop below 5.0, and then, after the ammonia injection
rate was adjusted, the drum pH would often rise above 8.0.

To address the pH excursions, several mechanical and operational changes were


implemented. First, in late 2005, the refiner installed an on-line pH meter at the overhead
drum. The measured output from the meter was connected to the refinery’s distributed control
system (DCS) and the drum pH was displayed on all control monitors. In this way, operators
who were responsible for adjustments to the ammonia injection rate were continually aware of
the drum pH. In addition, an improved plan for addressing the problems of crude switches was
devised. For example, ammonia injection rates were often increased prior to crude switches in
anticipation of lower drum pH’s from increased overhead HCl levels.

Lastly, the drum pH target range was lowered in a step-wise fashion during 2006. In
this way, the pH at the exchanger inlets was correspondingly lowered in the hopes of
minimizing the preferential attack on the copper bundles. The results of these changes on
drum pH are shown in Figure 5. While pH excursions still occurred, the overall effect was a
much higher percentage of operation within the desired target ranges.

Results
The primary purpose for improving pH control was the reduction of corrosion on the
exchanger bundles. To this end, the mitigation steps were very successful. Since the
installation of the pH meter, the measured corrosion rates on the inlet coupons have
decreased by a factor of 2-3. As shown in Figure 6, metal loss rates are now typically below
0.15 mm/year (6 mpy). These results indicate that the attack on copper has been reduced and
that the expected life of the exchanger bundles has now been increased.

Building on the success of earlier efforts, the refiner has recently enhanced the pH
control program. Specifically, the adjustment of ammonia injection rates has now been
automated. The output signal from the pH meter is used to actuate the ammonia injection
pump so that the system is now a “closed-loop”. Though the system has only been in place for
a few months, the results are very positive: pH control is nearly always within range and
corrosion rates at the exchanger inlets remain low.

CORROSION MECHANISM 3: VELOCITY-ACCELERATED CORROSION

Background
In addition to the PSV’s and the E-22001A/B inlets, a third region of the overhead was
affected by corrosion during this same period. Unacceptably high metal loss was occurring at
the E-22001A/B outlets. Measurements from ER probes and UT monitoring indicated attack at

7
the outlet elbows of the exchangers. Measurements on piping areas adjacent to the elbows
did not indicate activity. The corrosion rates at the elbows ranged from 0.25 - 0.75 mm/year
(10 - 30 mpy). The area of attack was localized at the outer radii of both elbows. To prevent
the possibility of failure, the refinery welded external patches on the elbows in late 2004 and
then reinforced the patches again in early 2005.

Troubleshooting Efforts
A thorough review of operating conditions was conducted to identify those variables
which may have correlated with the periods of highest corrosion activity at the exchanger
elbows. This effort revealed several key findings. First, during all operating modes, total
overhead flow rates were found to be 10% above design rates. Second, there was a direct
correlation between measured corrosion rates and outlet elbow temperatures. As shown in
Table 1, the tower top temperature was typically higher during “summer” operation. Therefore,
the entire overhead (including the exchanger outlets) was generally operating hotter and at
higher rates during these periods.

In addition, there was an inverse correlation between measured corrosion rates and
drum pH. That is, during low pH excursions, corrosion rates were higher at the outlet elbows.
The review of operating data helped to confirm what was already suspected: the corrosion at
the elbows was more pronounced under those conditions which promote acidic aqueous
corrosion (higher temperatures and lower pH).

Given that the attack at the elbows was localized to the outer radii, there was a strong
suspicion that a velocity-accelerated mechanism was involved. Corrosion control in areas of
high vapor velocity is always a challenge. Higher velocities produce higher shear stresses at
the pipe wall. These localized forces remove the partially protective corrosion product scale at
the wall and expose fresh metal to more attack. In addition, the stresses at the wall place a
greater burden on the ability of inhibitors to film the surface. Even under mild pH regimes, high
vapor velocities can promote accelerated metal loss rates.

Vapor velocities at the elbows were calculated for all operating modes (see Figure 7).
As shown, depending upon operating mode and outlet temperatures, there is a wide range of
possible vapor velocities. For typical exchanger outlet temperatures of 89 - 99°C (192 - 210°F),
vapor velocities can range from 7 - 37 m/sec (23 - 122 ft/sec). A typical concern level for vapor
velocities in these environments is about 15 m/sec (50 ft/sec). For a significant portion of the
unit’s operating time, vapor velocities exceeded this threshold level. In fact, during periods of
“summer” operation, vapor velocities at the elbows were often well above 30 m/sec (100 ft/sec).

Mitigation
There were several options used to minimize the velocity effects at the elbows. First, it
must be noted that the mitigation options which have already been discussed benefited here
as well. The injection of caustic to the desalted crude helped to reduce HCl levels in the
overhead. The installation of the pH meter resulted in fewer low pH excursions and better pH
control overall.

To address the specific issues at the elbows, the refiner set an upper temperature limit
of 102°C (215°F) at the exchanger outlets. If system temperatures exceed this limit, then unit
operation is adjusted to meet the temperature target. In addition, the refiner is considering the
installation of new piping with larger diameter to reduce the vapor velocities at the exchanger

8
outlets. If this piping is installed, then the temperature limit can be relaxed and less frequent
operational adjustments will be required.

Lastly, as described earlier, because the on-site monitoring tool can calculate vapor
velocities at any location in the system, it has provided critical feedback on changes in
corrosion potential as a function of variations in operations.

Results
Improvements in pH control and adherence to recommended operating temperature
limits have greatly reduced the corrosion activity at the outlet elbows. Current metal loss rates
as measured by ER probes at the outlets typically range from 0.05 – 0.15 mm/year (2 - 6 mpy).
These results agree with UT measurements taken in the same areas.

CONCLUSIONS

Though the simultaneous occurrence of multiple corrosion mechanisms in this overhead


system was problematic, the issues were not insoluble. The cause of each mechanism, to one
degree or another, was found to be a function of crude types and operating conditions. Only
after the source of each mechanism was properly indentified via modeling and analytical
techniques could mitigation steps be employed. As detailed here, and as is frequently the
case, no single mitigation step could address all of the problems. Instead, a combination of
operational mechanical and monitoring options was required to minimize corrosion activity and
improve unit reliability.

ACKNOWLEDGMENTS

The authors would like to thank James Titus and Paul Winters for their assistance in
generating the data used in this study.

REFERENCES

1. Saab, M., O. Dias, and F. Faqeer, “Damage Mechanisms and Corrosion Control in a Crude
Unit Overhead Line”, NACE Corrosion 2005, paper no. 566
2. Duggan, G. and R. Rechtien, “Application of Ionic Equilibria Process Simulation for
Atmospheric Distillation Overhead Systems”, NACE Corrosion 1998, paper no. 586
3. Giesbrecht, W. and G. Duggan, “Controlling Salt Corrosion”, Hydrocarbon Engineering,
November 2007
4. Lack, J., “Stay on Top of Your Corrosion Control Strategy”, Hydrocarbon Engineering,
October 2008
5. Gutzeit, J., “Problems with Injection Facilities for Process Additives or Water Wash”, NACE
Corrosion 1996, paper no. 591
6. Sharma, S., “Reaction of Copper and Copper Oxide with H2S”, J. Electrochem. Society, Vol.
127, January 1980
7. Lenglet, M. and J. Lopitaux, et al, “Analysis of Corrosion Products Formed on Copper in
Cl2/H2S/NO2 Exposure”, J. Electrochem. Society, Vol. 142, November 1995

9
Relief
Valves Inhibitor Ammonia

E 22001 A/B

Water
Wash
T 22001

E 22027 A/H

Reflux Off Gas

D 22001

Sour Water

Naphtha
Product
FIGURE 1 – Schematic of Atmospheric Overhead System

TABLE 1
Typical Unit Conditions for Each Operating Mode
Operating Tower Top Stripping Steam Naphtha Naphtha Total
Mode Temp to Tower Reflux Product Naphtha
(BPD) (BPD) (BPD)
Winter- 129°C 11,022 kg/hr 38,100 23,000 61,100
Sour (264°F) (24,300 lb/hr)
Winter- 148°C 11,340 kg/hr 36,800 30,000 66,800
Sweet (298°F) (25,000 lb/hr)
Summer- 146°C 14,379 kg/hr 29,960 27,400 57,360
Sour (294°F) (31,700 lb/hr)
Summer- 152°F 13,926 kg/hr 28,000 33,300 61,300
Sweet (306°F) (30,700 lb/hr)
NOTE: For these operating modes, tower top pressures ranged from 234-241 kPa (34-35 psia)

10
TABLE 2
NH4Cl Salt Formation Temperatures for Each Operating Mode
Operating Mode Tower Top Temp NH4Cl Formation Temp
Winter-Sour 129°C (264°F) 111°C (232°F)
Winter-Sweet 148°C (298°F) 104°C (219°F)
Summer-Sour 146°C (294°F) 124°C (255°F)
Summer-Sweet 152°C (306°F) 116°C (240°F)

350

o o o o o
325 104 C 107 C 110 C 113 C 116 C

300
Ammonia in D-22001 Drum Water (ppm)

275
Range of Typical Operations
250

225

200

175

150

125

100

75

50
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180

Chloride in D-22001 Drum Water (ppm)

FIGURE 2 – NH4Cl Salt Formation Temperatures at Tower Top (Winter-Sour Operations)

11
FIGURE 3 – 70/30 Copper/Nickel Coupon Located in E-22001A Inlet Line

FIGURE 4 – Scale Layers Present in Copper/Nickel Coupon (400X Magnification)

12
TABLE 3
Elemental Analyses of Copper/Nickel Coupon Scales
Base Metal Inner Scale Layer Outer Scale Layer
(EDS 03) (EDS 02) (EDS 01)
Copper (wt%) 74 4 73
Nickel (wt%) 25 64 <1
Iron (wt%) <1 1 <1
Sulfur (wt%) ----- 31 26

TABLE 4
Water-Soluble Species in Copper/Nickel Coupon Scale
Chloride Sulfate Formic Acetic Propionic Ammonia pH
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (1% soln)
160 390 200 64 3 3 6.8

9.0
On-Line Lower Lower
pH Analyzer pH Target pH Target
8.5 Installed Range Range

8.0

7.5

7.0
Accumulator pH

6.5

6.0

5.5

5.0

4.5

4.0

3.5
Jan 2005 - Dec 2006

FIGURE 5 – D-22001 Drum Water pH (2005 and 2006)

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0.65
On-Line
0.60 pH Analyzer
Installed
0.55

0.50

0.45
Corrosion Rate (mm / yr)

0.40

0.35

0.30

0.25

0.20

0.15

0.10

0.05

0.00
Apr-06
May-05

May-08
Nov-06

Nov-07
Jan-05

Jul-05

Oct-05

Jan-06

Jul-06

Jan-07

Jul-08
Mar-05

Mar-07

Feb-08
FIGURE 6 – Corrosion Rates on E-22001 Inlet Coupons (2005 -2008)

80

75 Sour Crude, Winter

70 Sweet Crude, Winter


Sour Crude, Summer
65
Sweet Crude, Summer
60

55
Vapor Velocity (m/sec)

50

45

40 Range of Typical Operations

35

30

25

20

15

10

0
80 82 84 86 88 90 92 94 96 98 100 102 104 106
Temperature (oC)

FIGURE 7 – Vapor Velocities at E-22001 Outlet Elbows for Each Operating Mode

14