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Prediction and Assessment of Ammonium Bisulfide Corrosion Under Refinery Sour

Water Service ConditionsPart 2


Richard J. Horvath(1) (2)
Consultant
19003 White Candle Drive
Spring, TX 77388

Vishal V. Lagad
Honeywell International, Inc.
11201 Greens Crossing Blvd, Suite 700
Houston, TX 77067

Sridhar Srinivasan
Honeywell International, Inc.
11201 Greens Crossing Blvd, Suite 700
Houston, TX 77067

Russell D. Kane(1) (3)


iCorrosion LLC
2318 Huldy Street
Houston, TX 77019

ABSTRACT
This paper summarizes results of Phase II of a joint industry program (JIP) that addressed ammonium
bisulfide (NH4HS) corrosion. This phase of the program was focused on NH3-dominated sour waters
typically found in refinery services such as the overhead systems of some sour water stripper units.
Phase II extended the initial research work in Phase I of the program, commonly referred to as the Sour
Water JIP, which addressed NH4HS corrosion in H2S-dominated sour waters. This Phase II work in
NH3-dominated sour waters studied the impact of several process variables including NH4HS
concentration, NH3 partial pressure, H2S partial pressure, temperature, cyanide concentration, and
velocity (wall shear stress). Data collected from laboratory tests designed to characterize these
process variables were used to develop an enhanced software tool to predict corrosion rates for six
materials evaluated in the program. Key aspects of the data, parametric behavior, and corrosion
response of the different materials evaluated in the Phase II work are highlighted in this paper.
Keywords: sour water, ammonium bisulfide, NH4HS, hydrogen sulfide, H2S, ammonia, NH3, partial
pressure, isocorrosion diagram, temperature, cyanide, velocity, wall shear stress, materials selection,
software, sour water stripper.

_________________________
(1)

Consultant to Honeywell International, Inc.


Retired from Shell Global Solutions (US) Inc.
(3)
Formerly Director of Corrosion Services at Honeywell International, Inc.
(2)

INTRODUCTION
For several decades the selection of materials of construction to resist ammonium bisulfide (NH 4HS)
corrosion was primarily based on empirical findings that relied heavily on evaluations of operational
experience, along with very limited controlled laboratory tests. Limits on material utilization were for the
most part very general guidelines, usually based on the NH4HS concentration and velocity of the sour
water stream containing the NH4HS. However, in March 2000 a joint industry program (JIP) titled
Prediction and Assessment of Ammonium Bisulfide Corrosion Under Refinery Sour Water Service
Conditions was initiated to develop a quantitative engineering database and provide guidelines to
predict corrosion in hydrogen sulfide (H2S)-dominated alkaline sour water systems typically found in
refinery services such as the reactor effluent air cooler systems of hydroprocessing units. Phase I of
the program, commonly referred to as the Sour Water JIP, was completed in March 2003 and the
results were reported to the 16 sponsors in June 2003.
The Sour Water JIP used a specialized laboratory flow loop designed specifically to develop corrosion
data for 14 materials exposed to well-defined and controlled alkaline sour water environments. These
environments were generally characterized as H2S-dominated, with pH in the approximate range of 7 to
9. Corrosion response of the materials was evaluated as a function of NH4HS concentration, velocity
(wall shear stress), H2S partial pressure, temperature, chloride concentration, hydrocarbon content, and
chemical treatments. These data were used as the basis to develop isocorrosion diagrams for the
materials evaluated and to quantify the effect of the above variables on material corrosion behavior. In
addition, a corrosion prediction software tool was developed that successfully incorporated the data
obtained in the program with flow modeling calculations to predict NH4HS corrosion rates for actual
operating conditions.
The results of Phase I of the Sour Water JIP have been reported by Horvath et al.1 (considered Part 1
of this paper), Cayard et al.,2 and Kane et al.3 The increase in corrosion rate with increasing NH4HS
concentration confirmed that NH4HS concentration is a key variable influencing NH4HS corrosion. The
use of velocityespecially the use of the 20 ft/s (6.1 m/s) velocity limit for controlling NH4HS corrosion
of carbon steelas the second key variable influencing NH4HS corrosion was found to be inadequate.
Instead, wall shear stressa direct measure of the mechanical force produced on the inner pipe
surface by the flowing fluidwas found to be a much better scaling parameter than velocity for
correlating NH4HS corrosion performance of materials, especially in multiphase systems. The use of
only these two key variables (NH4HS concentration and the wall shear stress), however, was also
found to be inadequate for assessing the potential for NH4HS corrosion in H2S-dominated sour water
systems.
The key learning from the Phase I of the Sour Water JIP was that H2S partial pressure proved to be the
third key variable that must be considered when assessing the potential for NH4HS corrosion in alkaline
sour water systems. The influence of these three primary key variables, along with other variables
(e.g., temperature, presence of chloride, presence of hydrocarbons, presence of various chemical
treatments) were incorporated into the software tool for predicting NH4HS corrosion rates. Cayard et
al.2 confirmed the accuracy of the corrosion prediction model incorporated into the software tool by
comparing the predicted corrosion rates with actual field data in H2S-dominated sour water systems.
The isocorrosion diagrams and corrosion prediction software tool developed in Phase I of the Sour
Water JIP have already had a profound impact on the refining industry. They have been used in design
and operation of process units that contain sour waters covering a wide range of conditions, especially
associated with hydroprocessing unit reactor effluent air cooler systems. The Phase I results and their
successful application in refinery process units indicate conclusively that the innovative laboratory test
methodologies used to simulate alkaline sour water corrosion developed for the Sour Water JIP provide
a very good approximation of corrosion in actual sour water systems. Based on JIP sponsor use of the
software tool and comparisons with many actual process unit observations and case studies, the Phase

I results for H2S-dominated alkaline sour water systems have provided a sound engineering basis for
optimizing service performance and thereby improving safety, reducing costs, and reducing
unscheduled process unit downtime.
Effect of Ammonia Domination
During Phase I of the Sour Water JIP sponsor representatives presented case histories of severe
corrosion of stainless steel (SS) in very high pH ammonium bisulfide environments that could not be
predicted by Phase I data for H2S-dominated environments. These case histories involved Type 316
SS (UNS S31600) piping and cast alloy CF8M (UNS J92900) valve and pump components used in the
overhead system of the NH3 stripper in two elevated pressure sour water stripper units. The service
environments involved NH4HS concentrations in the range of 12 to 18 wt% and very low H2S partial
pressures (less than 1 psia [7 kPa]). However, these environments also contained very high levels of
ammonia (NH3) that produced partial pressures as high as approximately 65 psia (450 kPa absolute)
NH3 and a pH in the range of 10 to 11. Corrosion rates experienced by these SS materials in the NH3
stripper overhead system applications were in the range of 40 to 140 mpy (1 to 3.5 mm/y).
Extrapolation of Phase I data to these very low H2S partial pressures led to a predicted corrosion rate of
less than 1 mpy (0.03 mm/y) for Type 316 SS. This extrapolation was clearly beyond the range of
applicability, particularly in the absence of data at such high levels of NH3 partial pressure.
These service conditions fall outside the pH range and H2S-dominated region that were included in
Phase I of the Sour Water JIP because of the very high NH3 content (i.e., high NH3 partial pressure).
The Phase I data generally showed a trend of decreasing corrosion rate with increasing pH over the pH
range of approximately 7 to 9 with other key variables held constant. This was likely caused by the
dominance of H2S on the NH4HS corrosion reaction within this pH range. However, there were
concerns that this relationship between the pH and NH4HS corrosion rate would not hold, and in fact
might be reversed, when the pH was further increased into the 9 to 11 range by higher NH3 content in
the sour water environment. In fact, Damin and McCoy4 postulated that high corrosion rates observed
at high NH4HS concentration (and therefore high pH) may be attributable to the formation of a metalammonium complex that could adversely impact the normally protective sulfide film on the metal
surface. They further stated that a minimum ammonium ion concentration must be reached before this
complex is formed, and if an ammonium complex is formed with iron, it could act to strip the steel
surface of protective scales.
As a result, the need to extend the database and corrosion prediction methodology for Phase I of the
Sour Water JIP to cover higher pH, NH3-dominated conditions of NH4HS service was clearly evident.
These NH3-dominated conditions have been found in sour water stripper units and perhaps could even
occur in some hydroprocessing units where low sulfur feedstocks are processed under severe
operating conditions (that result in significant denitrification in addition to the desulfurization) to produce
ultralow sulfur finished products.
PROGRAM OVERVIEW
InterCorr International, Inc.,(4) in collaboration with Shell Global Solutions (US) Inc., initiated Phase II of
the Sour Water JIP in March 2003. Phase II was conducted from March 2003 to December 2006. The
final program report was issued in March 2007 to the 11 refining and engineering companies that jointly
sponsored this Phase II program.5
The goal of the Phase II program was to develop a quantitative engineering database and provide
guidelines to predict corrosion in NH3-dominated alkaline sour water systems (high NH3 partial
pressure) as a function of NH4HS concentration, velocity (wall shear stress), NH3 partial pressure,
temperature, and cyanide concentration.
(4)

InterCorr International, Inc. was acquired by Honeywell International, Inc. in 2005.

Program Tasks
The Phase II program included four tasks. The first three tasks involved data development using a
specialized laboratory flow loop designed specifically to handle the environments and particulars
associated with conducting experiments in NH4HS solutions. A fourth task involved the development of
a comprehensive software model to predict corrosion rates of the materials evaluated in NH4HS
environments.
First Task. The first task of the program addressed the parametric effect of NH3 partial pressure
(PNH3). It involved developing comprehensive baseline isocorrosion curves for six materials at three
NH3 partial pressures: PNH3 = 15, 60, and 90 psia (100, 410, and 620 kPa absolute). At each PNH3,
corrosion rates were determined as a function of NH4HS concentration and flow loop velocity at a
temperature of 130 F (55 C). Data were obtained at NH4HS concentrations ranging from 1 to 25 wt%
and flow loop velocities ranging from 0 to 80 ft/s (24 m/s).
Second Task. The second task involved experiments designed to evaluate the parametric
effect of temperature on NH4HS corrosion at the three levels of PNH3 used in the first task. In addition to
the baseline temperature of 130 F (55 C), series of tests were conducted at 110 F (43 C) and 190
F (88 C). Each series of tests determined the corrosion rates as a function of PNH3, NH4HS
concentration, and flow loop velocity at the given test temperature.
Third Task. The third task involved experiments designed to evaluate the parametric effect of
the free cyanide concentration in the NH4HS solution at the three levels of PNH3 used in the first task. In
addition to the baseline free cyanide concentration of 0 ppm, series of tests were conducted at free
cyanide concentrations of 17 ppm and 40 ppm. Each series of tests determined the corrosion rates as
a function of PNH3, NH4HS concentration, and flow loop velocity at the given free cyanide concentration
and baseline temperature of 130 F (55 C).
Fourth Task. The fourth task involved the development of a software model to predict NH4HS
corrosion rates over the full range of potential alkaline sour water conditions. This was intended to be
an extension of the corrosion prediction model developed for the H2S-dominated conditions in Phase I
to incorporate the NH3-dominated alkaline sour water conditions in Phase II.
Materials Evaluated
Six materials were evaluated in the Phase II program. These materials included carbon steel, Type
316L SS, two duplex stainless steelsAlloy 2205 (UNS S31803) and Alloy 2507 (UNS S32750)and
two nickel-based alloysAlloy 825 (UNS N08825) and Alloy C-276 (UNS N10276). A list of the
materials evaluated and their nominal compositions is provided in Table 1. These materials were
procured in round bars to facilitate machining of the flow-through coupons and in plate or sheet form for
preparation of the flat corrosion coupons evaluated in the static zone of the flow loop.

TABLE 1
MATERIALS EVALUATED AND NOMINAL COMPOSITIONS

Carbon Steel

UNS
Number
G10180

Type 316L SS

S31603

Alloy 2205

S31803

0.03
max

2.0
max

bal

21.0
23.0

4.5
6.5

2.5
3.5

Alloy 2507

S32750

0.03
max

1.2
max

bal

24.0
26.0

6.0
8.0

3.0
5.0

0.5
max

Alloy 825

N08825

0.05
max

1.0
max

bal

19.5
23.5

38.0
46.0

2.5
3.5

1.5
3.0

0.6
1.2

Alloy C-276

N10276

0.01
max

1.0
max

4.0
7.0

14.5
16.5

bal

15.0
17.0

2.5
max

3.0
4.5

Material

C
wt%
0.15
0.20
0.03
max

Mn
wt%
0.6
0.9
2.0
max

Fe
wt%
bal

Cr
wt%

Ni
wt%

Mo
wt%

Cu
wt%

Ti
wt%

Co
wt%

W
wt%

bal

16.0
18.0

10.0
14.0

2.0
3.0

EXPERIMENTAL PROCEDURES
Several aspects of the experimental procedures are described including a general description of the
test facility, description of the flow-through and static corrosion coupons and ionic modeling conducted
to determine the quantity of chemical ingredients to simulate the intended test conditions.
Test Facility
The test facility used for the tests conducted in Phase II was essentially the same as that used for
Phase I. Special testing techniques were again used to eliminate contamination by oxygen in the test
environments and to simulate the intense flow conditions producing high wall shear stress levels
commonly observed in multiphase flow. The flow loop incorporated an autoclave with an internal gear
pump driven by a magnetically coupled spinning attachment. The design allows for continuous flow
velocities up to 80 ft/s (24 m/s) through the flow-through corrosion coupons and continuous control of
test temperature. Because the test fluid was internally recirculated within the pressurized autoclave, the
risk of oxygen contamination was minimized.
Corrosion Coupons
Two types of mass-loss corrosion coupons were used for these Phase II testsexactly the same as
those used in the Phase I tests. The flow-through coupons subjected to the test fluid passing through
the pump consisted of in (12.7 mm) OD by in (19 mm) long coupons with a 0.15 in (3.8 mm) ID
bore that was exposed to the sour water test solution. Six flow-through coupons were evaluated in
each test. Each coupon was electrically isolated from the others and from the coupon holder assembly
using polytetrafluoroethylene (PTFE) or polyetheretherketone (PEEK) washers that also contained a
0.15 in (3.8 mm) ID bore. The OD of the flow-through coupons was shielded from the sour water test
solution with heat shrink tubing and further contained in an Alloy C-276 tubular coupon holder.
Corrosion coupons were also mounted in two stacks of three coupons underneath the pump to provide
static mass-loss corrosion rate results. These static zone corrosion coupons were also useful to verify
the corrosion rate trends observed on the flow-through coupons. The static zone coupons were
standard 2.0 in (51 mm) long by 0.500 in (12.7 mm) wide by 0.125 in (3.18 mm) thick flat coupons with
two in (6.35 mm) diameter holes for mounting.

Test Protocol
The flow-through corrosion coupons and flat corrosion coupons for the static zone were cleaned,
measured, and preweighed. The stack of six flow-through coupons was assembled and all coupons
were stored in a desiccator until they were mounted onto the pump prior to the testing. The required
pump speed to attain the desired test velocity was determined by calibration with water before each
test. After the water calibration, the pump, autoclave head and associated fixtures were thoroughly
dried. The test coupons (flow-through stack and static coupons) were then mounted onto the pump
and the autoclave head with pump assembly was assembled onto the autoclave body. The autoclave
was pressure tested with nitrogen and then evacuated under vacuum and backfilled with nitrogen five
times to deaerate the autoclave and pump assembly.
At this point the portion of the test protocol involving the preparation and loading of the test solution for
the Phase II tests differed from that used for the Phase I tests. The use of a separate external glass
mixing vessel to prepare the ammonium hydroxide (NH4OH) solution and saturate the solution with H2S
prior to transfer into the autoclavewhich worked well for the H2S-dominated sour water solutions in
Phase Icould not be used for preparing the NH3-dominated sour water solutions in Phase II. Instead,
the following procedure was used for the Phase II testing.
Based on the ionic modeling, described later in more detail, the prescribed amount of distilled water
was transferred into an external glass mixing vessel and purged with high purity nitrogen for a minimum
of 48 hours. The prescribed amount of NH4OH was then added (under a nitrogen cap) to the
deaerated distilled water in the glass mixing vessel. The aqueous NH4OH solution was then
transferred from the glass mixing vessel into the deaerated autoclave under a slight nitrogen pressure.
A very small volume of dilute sodium cyanide (NaCN) solution was injected into the autoclave to react
with any remaining trace of oxygen. The prescribed amounts (on a mass basis) of ultrapure (< 1 ppm
oxygen) H2S and excess NH3 were then added directly into the autoclave. Stainless steel sampling
cylinders that were deaerated and loaded with specific gram weights of liquid H2S and NH3 as dictated
by the ionic modeling to attain the required test conditions were used for these additions. An excess
pressure of high purity nitrogen was imposed so that all tests were run at an equivalent total pressure of
100 psia (700 kPa absolute) for tests conducted at 110 F (43 C) and 130 F (55 C), and 150 psia
(1,000 kPa absolute) for tests conducted at 190 F (88 C).
For tests with intended additions of cyanide, a larger and more concentrated solution of NaCN was
used that provided an initial cyanide dosage of 100 ppm or 500 ppm in the test solution. In these tests,
analyses for free cyanide were performed on liquid samples extracted from the test solution at test
initiation, midway through the test period, and at test conclusion. These samples were extracted under
pressure using a SS sampling cylinder that contained a moveable piston arrangement to ensure that a
full liquid sample was taken with no vapor space.
Subsequent to the transfer of the requisite test solution components into the autoclave, the pump was
initiated slowly to facilitate complete mixing. During this process, the autoclave was heated to the
intended test temperature. When test temperature was achieved the pump speed was adjusted to
attain the designated test velocity in the flow-through corrosion coupons. Solution pH was monitored at
test initiation, midway through the test period, and at test conclusion.
Each flow loop experiment was conducted for 48 hours at test conditions. After the final pH
measurement, the pump and heat were switched off, the autoclave head pressure was bled down
through a vent scrubber containing caustic, and the test solution was pushed out into a caustic
scrubber under nitrogen pressure. Caustic solution was pushed into the test autoclave and circulated
through the pump at a low speed. The caustic was pushed out and water was pushed into the
autoclave to rinse. Once the water was removed, the autoclave was opened and the corrosion
coupons were retrieved for cleaning and corrosion rate determination. A water calibration check was

performed to verify the flow rate versus pump speed. The autoclave and pump assembly were then
cleaned thoroughly prior to running the next test.
Ionic Modeling
Ionic modeling runs were performed to determine the appropriate amounts of distilled water, NH 4OH,
H2S, excess NH3, and nitrogen required to achieve the desired NH4HS concentration in equilibrium with
the desired NH3 partial pressure for the total system pressure at the intended test temperature. The
ionic modeling runs were conducted using the OLI Engine in conjunction with the Aspen Plus process
flowsheet simulator.(5) The ionic model contains a special electrolytes package and allows calculation
of the phase behavior of an aqueous NH4HS solution in equilibrium with its vapor as a function of
temperature, pressure and composition. It was critical to the design of suitable experiments to model
actual process unit conditions, within the constraints of available laboratory equipment. The model
further predicts the closed cup pH at both ambient temperature and at the test temperature.
The predicted pH values were compared to measured values of pH over the range of test conditions. It
was found that as the test solutions became more highly concentrated (higher NH4HS concentrations
and higher NH3 partial pressures), the actual pH deviated somewhat from the calculated values. This
relatively small error was assessed to have two potential causes: (a) evolution of gases from the
solution during sampling, and/or (b) errors in the ionic model attributable to the very high NH3
concentrations in the test environments.
RESULTS AND DISCUSSION
Baseline Isocorrosion Diagrams
The data development conducted under the first task was the most extensive and important in the
Phase II program. It established the baseline corrosion rates to which the data from the remaining tasks
to evaluate the effects of temperature and cyanide concentration were compared. The data in the first
task were collected at the baseline temperature of 130 F (55 C) and PNH3 = 15, 60, and 90 psia (100,
410, and 620 kPa absolute). The test matrix for this task involved NH4HS concentrations that varied
from 1 to 25 wt% and test velocities in the flow-through coupons that varied from 10 to 80 ft/s (3.0 to 24
m/s). Corrosion rates measured on the static corrosion coupons at the lowest test velocity were used
to represent the corrosion rates at 0 ft/s (0 m/s) for each material.
The resulting data were used to construct isocorrosion diagrams as a function of NH4HS concentration
and test velocity at constant PNH3. A set of three isocorrosion diagrams was produced for each alloy,
one for each level of PNH3 tested at the baseline test temperature. The analysis of the first task data
produced a total of 18 isocorrosion diagrams to cover the six materials included in the baseline tests.
Additional data plots were made for corrosion rate versus NH4HS concentration and velocity. These
were used for the evaluation and qualification of the corrosion data and to revise values in some cases
to reduce test scatter. This step helped to provide consistency across multiple variables required for the
development of consistent isocorrosion diagrams, parametric relationships and the numerical treatment
of these relationships required for use in the corrosion prediction software tool.
Careful analysis of the isocorrosion diagrams helped to identify some of the major characteristics of
corrosion behavior exhibited by the various materials included in the Phase II baseline tests. The
behavior of different materials varied considerably.

(5)

Aspen Plus is a registered trademark and process modeling product of Aspen Technology, Inc. OLI Engine, a
combination of thermophysical models, solvers, and databank, is a product of OLI Systems Inc. Both products
are independently licensed from each vendor and assembled by the client.

Carbon steel corrosion rates were generally less than approximately 25 mpy (0.64 mm/y) at all baseline
conditions tested. At concentrations less than 5 wt% NH4HS, carbon steel corrosion rates increased
rapidly with increasing concentration but were relatively insensitive to velocity. At concentrations
greater than 5 wt% NH4HS, carbon steel corrosion rates increased rapidly with increasing velocity but
were rather insensitive to NH4HS concentration up to 25 wt%. Interestingly, the maximum carbon steel
corrosion rates observed were generally in the same range for all three levels of PNH3 tested, indicating
little influence of PNH3 in this range. Figure 1 shows the baseline isocorrosion diagram for carbon steel
at PNH3 = 90 psia (620 kPa absolute). Although this isocorrosion diagram represents the corrosion
behavior of carbon steel at the highest level of PNH3 tested, it is also generally indicative of the behavior
of carbon steel at the lower levels of PNH3 tested. The main difference observed at this very high PNH3
was the tendency for the isocorrosion curves to trend upward at high NH4HS concentration, indicating
somewhat decreased corrosion at these very NH3-rich conditions.
The isocorrosion diagrams for Type 316L SS show substantially different corrosion behavior than that
indicated previously for carbon steel. Type 316L SS corrosion rates were < 1 mpy (0.03 mm/y) at low
NH4HS concentration and velocity and steadily increase with increasing NH4HS concentration and
velocity. Figure 2 shows the baseline isocorrosion diagram for Type 316L SS at PNH3 = 90 psia (620
kPa absolute). The corrosion rate of Type 316L SS at 25 wt% NH4HS and 80 ft/s (24 m/s) exceeded
40 mpy (1 mm/y), which is approximately twice the corrosion rate of carbon steel at the same test
conditions.
The isocorrosion diagrams for Alloys 2205 and 2507 show the same general behavior as Type 316L
SS. However, the maximum corrosion rates of Alloys 2205 and 2507 at the most severe conditions of
25 wt% NH4HS concentration, 80 ft/s (24 m/s) velocity, and PNH3 = 90 psia (620 kPa absolute)
exceeded 60 mpy (1.5 mm/y), or 50 percent greater than observed for Type 316L SS.
The isocorrosion diagrams for Alloys 825 and C-276 also show the same trend of increasing corrosion
rate with increasing NH4HS concentration and velocity at all three levels of PNH3 tested. However, the
maximum corrosion rates of Alloys 825 and C-276 at the most severe conditions of 25 wt% NH4HS
concentration, 80 ft/s (24 m/s) velocity, and PNH3 = 90 psia (620 kPa absolute) were less than 2 mpy
(0.05 mm/y). These nickel-based alloys demonstrated very good corrosion resistance in these highly
alkaline NH4HS solutions.

Carbon Steel
PNH3 = 90 psia (620 kPa absolute); Temperature = 130 oF (55 oC)
90
80
70

Velocity, ft/s

60
50
>20 mpy

40
30
15-20 mpy
20

10-15 mpy

10

5-10 mpy
<5 mpy

10

15

20

25

30

NH4HS Concentration, wt%

1 mpy = 0.0254 mm/y


1 ft/s = 0.3048 m/s

Figure 1: Isocorrosion Diagram for Carbon Steel

Type 316L SS
PNH3 = 90 psia (620 kPa absolute); Temperature = 130 oF (55 oC)
90
>40 mpy

80
70

Velocity, ft/s

60
20-40 mpy
50
40

10-20 mpy
30
1-5 mpy

5-10 mpy

20
10
<1 mpy
0

0
1 mpy = 0.0254 mm/y
1 ft/s = 0.3048 m/s

10

15

20

25

30

NH4HS Concentration, wt%

Figure 2: Isocorrosion Diagram for Type 316L SS


When using these data, it is important to note that the velocity plotted on the isocorrosion diagrams
corresponds to the NH4HS solution velocity through the 0.15 in (3.8 mm) ID bore of the flow-through
coupons. The corrosion rate at this velocity does not equate to the corrosion rate of the multiphase
fluids passing through typical refinery sour water systems at the same velocity. In order to make a

rigorous connection between the laboratory test results and flow conditions in actual process unit
systems, the wall shear stress for the system in service must be calculated using hydrodynamic
modeling and equated to a corresponding laboratory test velocity that produces the same value of wall
shear stress.
Effect of Alloy Content. The corrosion behavior described here, with stainless steels corroding
at higher rates than carbon steel, and higher alloy stainless steels (Alloys 2205 and 2507) corroding at
higher rates than leaner alloy stainless steels (Type 316L SS), is not commonly observed in most
service environments. In fact, it did not occur in the H2S-dominated environments included in the
Phase I tests. This corrosion behavior appears to be the result of the corrosion process postulated by
Damin and McCoy. At the highly alkaline NH3-dominated sour water conditions, the normally protective
corrosion films on these SS alloys appear to be removed from the metal surface by the combined
effects of metal-ammonium complex formation and the high wall shear stress produced by the fluid
flowing at high velocity. The interesting aspect of the corrosion behavior observed in this first task was
that the surface corrosion films on the SS alloyswhich include higher levels of chromium (Cr) and
molybdenum (Mo) than carbon steelappear to be more prone to attack than the iron-rich sulfide films
on carbon steel, thus resulting in the higher corrosion rates for the stainless steels. At the most severe
test conditions, this behavior resulted in increasing corrosion rates with increasing Cr + Mo content in
the stainless steels evaluated in Phase II.
Although the nickel-based alloys (Alloys 825 and C-276) have Cr + Mo contents comparable to the
duplex stainless steels (Alloys 2205 and 2507), these two nickel-based alloys have much higher nickel
content than the duplex stainless steels. The observed corrosion rates of Alloys 825 and C-276 were
quite low even at the most severe test conditions in this first task. Therefore, it appears that their high
nickel contents imparted sufficient corrosion resistance to these alloys despite their relatively high Cr +
Mo contents.
H2S Tie-In Plots. As the analysis of the baseline data obtained in the first task progressed, it
was realized that correlating the Phase II data to the Phase I data would be quite challenging. The main
issue was that the two data sets (Phase I and Phase II) appeared to have greatly varying
characteristics. However, the overall goal of the Phase II program was to provide an integrated
corrosion prediction capability that spanned the full range of H2S-dominated and NH3-dominated
conditions included in the Phase I and Phase II data sets.
Development of H2S tie-in plots based on the H2S partial pressure proved to be the best means to
achieve the goal of linking these Phase II baseline data with the baseline data from Phase I. Ionic
modeling of the NH3-dominated conditions included in the Phase II first task data sets provided the H2S
partial pressures. Ionic modeling of the H2S-dominated conditions included in the Phase I baseline
data sets provided the PNH3. The span of H2S partial pressures encompassed approximately five orders
of magnitude to cover the combined Phase I and Phase II data sets. Because of this large span of H2S
partial pressure, the H2S tie-in plots were constructed with the H2S partial pressure on the x-axis using
a logarithmic scale. The corrosion rate was shown on the left y-axis, and the corresponding PNH3 was
shown for information on the right y-axis. A set of H2S tie-in plots was developed for each material at
three levels of NH4HS concentration.
Figure 3 shows the H2S tie-in plot for Type 316L SS at 25 wt% NH4HS. The data from Phase I for H2Sdominated conditions are located generally on the right side of the plot and the data from Phase II for
NH3-dominated conditions are located on the left side of the plot. The general trend on the H2S tie-in
plots for all materials was for the corrosion rates at each velocity level plotted to decrease from high
values on the right side of the plot (high H2S partial pressure) to much lower values on the left side of
the plot (low H2S partial pressure). However, as indicated on the far left side of this figure for Type
316L SS, corrosion rates increased markedly as a result of strong NH3 dominance. This behavior was
also evident on H2S tie-in plots for Alloys 2205 and 2507.

Type 316L SS Corrosion Rate vs. H2S Partial Pressure


Temperature = 130 oF (55 oC); NH4HS Concentration = 25 wt%
100
0 ft/s (0 m/s)

90

90

10 ft/s (3.0 m/s)


20 ft/s (6.1 m/s)

80

80

80 ft/s (24 m/s)

70

70

60

60

50

50

40

40

30

30

20

20

10

10

0.1
1 mpy = 0.0254 mm/y
1 psia = 6.895 kPa absolute

10

100

NH3 Partial Pressure, psia

Corrosion Rate, mpy

pp NH3

0
1000

H2S Partial Pressure, psia

Figure 3: H2S Tie-In Plot for Type 316L SS


The left side of this H2S tie-in plot shows graphic evidence of the effect of the metal-ammonium
complex formation postulated by Damin and McCoy. However, this behavior was not based simply on
pH as assumed in the original postulation. Although the highest corrosion rates measured occurred at
high pH (9.4), much lower corrosion rates were measured in many other tests at higher pH (up to 11.1).
The nature of this corrosion behavior is more likely based on the interrelationship between H2S partial
pressure, NH3 partial pressure, and NH4HS concentration that occurs in alkaline sour water
environments. It appears that the large increase in corrosion rate does not occur until the H2S partial
pressure is so low that a stable sulfide film cannot be maintained, and rapid metal-ammonium complex
formation occurs.
One important learning from the first task of Phase II involved extrapolation of the corrosion rate
prediction to H2S partial pressures lower than those tested in Phase I. At the end of the Phase I
program, the extrapolations made based on the best available understanding at that time indicated that
corrosion rates would approach zero as the H2S partial pressure approached zero. This was the basis
used for programming the corrosion prediction software tool developed in Phase I. These new data
obtained in the Phase II program suggested something differentcorrosion rates for the materials
tested in Phase II actually reached a low level (but not zero) at low H2S partial pressure (high PNH3)
conditions. And in fact, corrosion rates for the SS materials tested actually showed marked increases at
very low H2S partial pressure (very high PNH3) conditions. This learning established a firm technical
basis to replace the low H2S partial pressure extrapolations in the Phase I corrosion prediction software
tool with these new relationships observed in the Phase II data.
Effect of Temperature
The test matrix for the second task to investigate the effect of temperature involved tests with 25 wt%
NH4HS at all three levels of PNH3 and the flow loop velocities used in the first task. A series of tests
were conducted at 110 F (43 C) and at 190 F (88 C), and the results of these tests were compared
with the results of the first task at the baseline temperature of 130 F (55 C). The results of these tests
were captured on 18 plots covering all six materials at the three levels of PNH3.

For all six materials at all three levels of PNH3, the plots of corrosion rate versus temperature show an
increase in corrosion rate when the temperature increases from 110 F (43 C) to 130 F (55 C). The
magnitude of the corrosion rate increase varied considerably for the different materials. For carbon
steel, the corrosion rate at 130 F (55 C) varied from only marginal to as much as three times the
corrosion rate at 110 F (43 C) at the different levels of PNH3. For the SS alloys, the corrosion rate at
130 F (55 C) varied from approximately 5 to 10 times the corrosion rate at 110 F (43 C) at the two
lower levels of PNH3. However, at PNH3 = 90 psia (620 kPa absolute), the corrosion rates of both duplex
stainless steels at 130 F (55 C) were approximately 50 times their respective corrosion rates at 110
F (43 C) at the highest test velocity. For the nickel-based alloys, corrosion rates increased only
slightly in this temperature range.
The observed effect of temperatureincreasing corrosion rate with increasing temperaturewas not
unexpected, but the extreme magnitude of the corrosion rate increase in such a small range of
temperature increase was quite surprising. However, the effect of temperature observed with the
increase in temperature from the baseline temperature of 130 F (55 C) to 190 F (88 C) was equally
surprising and much more complex. There was no consistent trend evident for the effect of
temperature on the corrosion rate of all materials in this temperature range. For carbon steel, the effect
of the increased temperature varied at the three levels of PNH3, from a moderate decrease in corrosion
rate with increasing temperature to a significant increase in the corrosion rate with increasing
temperature. For the stainless steels, the effect of this temperature increase was (at all but one set of
test conditions) a drastic decrease in the corrosion rate. For the nickel-based alloys, the effect of this
temperature increase was a moderate decrease in the corrosion rate.
One likely explanation for this unusual behavior was found by examining the differences in the ionic
modeling results at the various temperatures relative to the equilibrium H2S partial pressure at the
imposed conditions of PNH3 used in these tests. The NH4HS concentration and PNH3 were held constant
to study the effect of temperature. Unfortunately, when these two parameters were forced to remain
constant, ionic equilibria required that the H2S partial pressure change to achieve these conditions.
When increasing the temperature from 110 F (43 C) to 130 F (55 C), the H2S partial pressure
increased marginally but was still at a relatively low level. The result was that the test conditions would
obviously be characterized as NH3-dominated. However, when increasing the temperature from 130 F
(55 C) to 190 F (88 C), the H2S partial pressure increased drastically. At one set of test conditions,
the H2S partial pressure increased to 97 psia (670 kPa absolute), which suggested that these test
conditions were H2S-dominated rather than NH3-dominated.
The effect of temperature on corrosion was obviously most pronounced for the stainless steels. The
increase in corrosion rate with temperature in the 110 F (43 C) to 130 F (55 C) range may be
associated with two possible effectsincreased thermal activation of the corrosion process and the
onset of the metal-ammonium complex formation postulated by Damin and McCoy. However, at
temperatures above 130 F (55 C), there appears to be another overriding factor that caused the
drastic reduction in the corrosion rates of the stainless steels. The significant increase in H2S partial
pressure with increasing temperature above 130 F (55 C) may counteract or interfere with the metalammonium complex formation associated with the NH3-dominated conditions. Increasing H2S partial
pressure would favor enhanced stability of the sulfide corrosion film on the stainless steel surface,
thereby reducing the corrosion rates with increasing temperature. It should also be noted that the
maximum corrosion rate of the stainless steels tested in these NH3-dominated conditions may not occur
at 130 F (55 C), as might be construed from these test results, but may actually occur at some other
intermediate temperature in the 110 F (43 C) to 190 F (88 C) range.
Effect of Free Cyanide Concentration
The test matrix for the third task to investigate the effect of free cyanide concentration used a set of test
conditions that investigated two levels of cyanide addition to be compared with the test results at the
baseline conditions with no cyanide in the first task. The two levels of cyanide addition were 100 ppm

and 500 ppm in the test solution added as NaCN. Because cyanide is a reactive species in alkaline
sour waters, an effort was made to measure the actual concentration of free cyanide in the test
environments at these two levels of cyanide addition. Test solution samples were taken using sample
cylinders under pressure at test initiation, midway through the test period, and at test conclusion. The
free cyanide concentration was determined from test solution analyses.
The relationship between the two levels of cyanide addition and the resulting free cyanide
concentrations in the test solutions was based on an average of four tests at each level of cyanide
addition. Based on cyanide additions of 100 ppm (low level) and 500 ppm (high level), the average
concentration of free cyanide attained in the test environments were actually 17 ppm and 40 ppm,
respectively. The free cyanide concentration varied somewhat with time, but in general appeared to be
fairly stable over the test duration. One concern at the start of this task was that the free cyanide
concentration would continually decrease during the 48 hour test duration, thus making this value a
moving target. Despite some nominal variations, a continuing decrease in the free cyanide
concentration was not observed. This gave some degree of assurance that the test facility and
procedures were both credible and reliable especially in terms of their ability to exclude oxygen ingress
during the test period, which could have resulted in rapid reaction and depletion of the free cyanide in
the test solution.
Furthermore, the two levels of free cyanide concentration achieved in this task were in a range that is
relevant to refinery process unit operations. Many investigators have identified that 20 ppm free cyanide
in refinery sour waters is a concentration at which major changes in corrosion behavior and/or
hydrogen charging of steel occur. Therefore, the two levels of free cyanide concentration (17 ppm and
40 ppm) attained in this task nicely bound this important refining industry benchmark value for free
cyanide.
A series of corrosion rate plots were developed that spanned the range of test conditions included in
this third task. A total of 18 plots were developed for each material. Half of these were direct plots of
corrosion rate as a function of free cyanide concentration at each combination of NH 4HS concentration
and PNH3. The other half included cross-plots of corrosion rate as a function of either NH4HS
concentration or PNH3, while holding the other parameters constant. The cross-plotting of corrosion
rates as a function of multiple variables allowed for more complete assessment of the actual test data
and evaluation and/or resolution of test data scatter. This process led to the identification of several
important parametric relationships for use in development of the corrosion prediction software tool.
For carbon steel, the effect of free cyanide concentration on NH4HS corrosion was far more
pronounced between 17 and 40 ppm than it was between 0 and 17 ppm. Increasing the free cyanide
concentration from 0 to 17 ppm increased the corrosion rate marginally. Only at the most severe
conditions of 25 wt% NH4HS, 80 ft/s (24 m/s) velocity, and PNH3 = 60 to 90 psia (410 to 620 kPa
absolute) did the corrosion rate increase by a factor of approximately two. However, increasing the free
cyanide concentration from 17 and 40 ppm further increased the corrosion rate by a factor of two to four
at most of the conditions tested. Corrosion rates with 40 ppm free cyanide were as much as six to eight
times the corrosion rate with no free cyanide present. These data and observations regarding the
significant increase in corrosion when the NH4HS solution contained greater than 17 ppm free cyanide
correlates well with the industry benchmark of 20 ppm free cyanide.
By comparison, the effect of the free cyanide concentration on the corrosion rate of the stainless steels
was found to be quite different than was observed for carbon steel. The effect of free cyanide
concentration on NH4HS corrosion of the stainless steels was far more pronounced between 0 and 17
ppm than it was between 17 and 40 ppm. Increasing the free cyanide concentration from 0 to 17 ppm
typically increased the corrosion rate of Type 316L SS by an order of magnitude, and increased the
corrosion rate of the duplex stainless steels in many cases by more than two orders of magnitude.
However, increasing the free cyanide concentration from 17 to 40 ppm further increased the corrosion
rate, but only marginally (less than a factor of two). These large increases in corrosion rate of the

stainless steels with even low concentrations of free cyanide are in part caused by their very low
corrosion rates with no free cyanide present. However, the maximum corrosion rate observed for Type
316L SS was comparable to that for carbon steel. The maximum corrosion rates for the duplex
stainless steels were approximately 240 mpy (6 mm/y), which was almost twice as high as for carbon
steel. These data indicate that even low levels of free cyanide (17 ppm or less) can produce very large
increases (an order of magnitude or more) in the corrosion rate of stainless steels. Free cyanide
concentrations less than 20 ppm appear to have a far greater impact on the performance of stainless
steels than carbon steel.
The effect of the free cyanide concentration on the corrosion rate of Alloy 825 was found to be quite
similar to that observed for the stainless steels, but the corrosion rates were somewhat lower. The
effect of free cyanide concentration on NH4HS corrosion of Alloy 825 was far more pronounced
between 0 and 17 ppm than it was between 17 and 40 ppm. Increasing the free cyanide concentration
from 0 to 17 ppm typically increased the corrosion rate of Alloy 825 by a factor of approximately 50 at
PNH3 = 60 to 90 psia (410 to 620 kPa absolute). Increasing the free cyanide concentration from 17 to
40 ppm further increased the corrosion rate, but only marginally (less than a factor of two). At P NH3 =
15 psia (100 kPa absolute), the corrosion rate increase was much less. The maximum corrosion rate
for Alloy 825 was approximately 100 mpy (2.5 mm/y), approaching that for carbon steel. These data
indicate that even low levels of free cyanide (17 ppm or less) can produce very large increases (an
order of magnitude or more) in the corrosion rate of Alloy 825.
The effect of the free cyanide concentration on the corrosion rate of Alloy C-276 was found to be very
slight compared to all the other materials tested. As with the stainless steels and Alloy 825, the
increase in corrosion rate between 0 and 17 ppm free cyanide was greater than increase in corrosion
between 17 and 40 ppm free cyanide. However, even at the most severe conditions tested, the
corrosion rate of Alloy C-276 was less than 3 mpy (0.1 mm/y).
From the cross plots, two trends were observed. At the free cyanide concentrations tested (17 ppm
and 40 ppm), the corrosion rate of all materials tested generally increased with increasing NH 4HS
concentration. Also, at the free cyanide concentrations tested, the corrosion rate of the alloys generally
increased with increasing PNH3. Carbon steel did not follow this general trend.
NH4HS Corrosion Prediction Software Tool
In the fourth task of Phase II, data collected from the first three experimental tasks were used to
develop a new user friendly corrosion prediction software tool called Predict -SWII.(6) This new
software tool uses the isocorrosion diagrams developed in the first task, along with rule sets to adjust
for the effects of temperature and free cyanide concentration observed in the second and third tasks, to
predict corrosion rates of the six materials in NH3-dominated alkaline sour water conditions. The
software tool provides an easy-to-use interface to input data related to environment, application, and
process stream variables in a manner similar to the software tool developed for Phase I of the Sour
Water JIP. The software tool includes a multiphase flow modeling module that calculates the wall
shear stress taking into account system throughput and phase mix, fluid properties, pipe sizes and flow
geometries. Alternatively, user-determined values of wall shear stress from other software modules or
computational flow dynamic routines can be input directly. The calculated wall shear stress for the
process flow conditions is in turn related to the laboratory flow loop velocity for linkage with the
corrosion rates on the isocorrosion diagrams and parametric relationships. This information is further
used with the environment variables to predict corrosion rates of the materials evaluated in Phase II.
The new NH4HS corrosion prediction software tool was developed as an extension of the corrosion
prediction software tool developed in the Phase I program. In addition to the rule-based prediction of
corrosion rates for NH3-dominated alkaline sour water environments developed in this Phase II
(6)

Predict is a registered trademark and Predict-SWII is a software product of Honeywell International, Inc.

program, it includes the rule-based prediction of corrosion rates in H2S-dominated alkaline sour water
environments developed in Phase I. It also incorporates appropriate decision methodology to
determine which set of rules (Phase I or Phase II) apply and a methodology for predicting corrosion
rates when the alkaline sour water conditions lie within the transition region between the H2S-dominant
regime (Phase I) and the NH3-dominant regime (Phase II).
Corrosion Prediction for Case Histories. This new corrosion prediction software tool was used
to predict the corrosion rate for Type 316L SS at the conditions given for the case histories involving the
NH3 stripper column overhead system discussed in the Introduction. The predicted corrosion rates
were in relatively close agreement with the actual corrosion rates of the Type 316 SS reflux piping.
Although much higher corrosion rates were predicted for the control valves and pump components,
these somewhat underpredicted the actual corrosion rates reported in the actual process unit
equipment. This corrosion rate underprediction is most likely the result of difficulties in determining the
actual wall shear stress present in these complex equipment geometries, but may be associated with
the differences in corrosion performance of the actual alloy grades and product forms (e.g., cast versus
wrought material) or possible inaccuracies in the reported service conditions. The severe corrosion
suffered by a Type 316 SS control valve body and trim in this service is shown in Figure 4.

Figure 4: Corroded Type 316 SS control valve body and trim NH3 stripper reflux line
CONCLUSIONS
The following conclusions were drawn based on the results of this program.
1. PNH3, especially in the 15 to 90 psia (100 to 620 kPa absolute) range, had a significant effect on the
corrosion of carbon steel, stainless steels and nickel-based alloys in refinery alkaline sour water
environments.
2. Carbon steel corrosion rates under conditions of high PNH3 at 130 F (55 C) were generally less
than approximately 25 mpy (0.64 mm/y) in the absence of free cyanide. Carbon steel corrosion
rates increased with increasing test velocity (wall shear stress) but were relatively insensitive to
PNH3 and NH4HS concentration within the ranges of the test environments.
3. Stainless steel corrosion rates under conditions of high PNH3 at 130 F (55 C) were low at low
NH4HS concentration and velocity and steadily increased with increasing NH4HS concentration and
velocity. The stainless steel alloys corroded at much higher rates than carbon steel at the most
severe conditions tested.
4. Under highly alkaline NH3-dominated sour water conditions, the normally protective corrosion films
on stainless steels appear to be compromised by the combined effects of metal-ammonium

complex formation and high wall shear stress produced by high fluid velocity, resulting in very high
corrosion rates.
5. Nickel-based alloys evaluated under conditions of high PNH3 at 130 F (55 C) showed the same
trend of increased corrosion with increasing NH4HS concentration and velocity but exhibited very
good corrosion resistance even at the most severe conditions tested (in the absence of free
cyanide).
6. The corrosion rates of the materials evaluated did not approach zero as the H2S partial pressure
approached zero, an assumption used when extrapolating the Phase I results. As the H2S partial
pressure decreased to very low levels, the increasing PNH3 influenced the corrosion rates of all
materials evaluated. In fact, the corrosion rates of the stainless steels actually increased with
decreasing H2S partial pressure in Phase II tests.
7. For all materials evaluated at all three levels of PNH3, corrosion rates increased with increasing
temperature from 110 F (43 C) to 130 F (55 C), but the magnitude of the increase varied
considerably among the different materials. The extreme magnitude of the stainless steel corrosion
rate increase for a small change in temperature was quite surprising. This may be attributable to
metal-ammonium complex formation.
8. The effect of temperature was not consistent when temperature was increased from 130 F (55 C)
to 190 F (88 C). A drastic decrease observed in stainless steel corrosion rates appears to be
attributable to enhanced stability of the sulfide corrosion film produced by increased H2S partial
pressure at the higher temperature.
9. The effect of free cyanide concentration on corrosion rates of all materials evaluated was
significant, but varied with different materials.
10. For carbon steel, the effect of free cyanide concentration on NH4HS corrosion was far more
pronounced between 17 and 40 ppm than it was between 0 and 17 ppm. This finding correlates
well with the industry benchmark of 20 ppm free cyanide for accelerated corrosion and cracking of
steels.
11. For the stainless steels and Alloy 825, the effect of free cyanide concentration on NH4HS corrosion
was far more pronounced between 0 and 17 ppm than it was between 17 and 40 ppm, indicating
greater sensitivity of stainless steels to low levels of free cyanide than was observed for carbon
steel. Increasing the free cyanide concentration from 0 to 17 ppm increased the corrosion rates of
these alloys by as much as one or two orders of magnitude. Although Alloy 825 was very resistant
to corrosion in highly alkaline sour water environments in the absence of free cyanide, the presence
of 17 to 40 ppm free cyanide caused Alloy 825 corrosion rates to approach that of carbon steel.
12. For Alloy C-276, the effect of free cyanide concentration was slight. Even at the most severe
conditions tested, Alloy C-276 exhibited very good corrosion resistance. Of the materials evaluated
in Phase II, Alloy C-276 was clearly the best performer.
13. A new corrosion prediction software tool was developed that successfully incorporated the data
gathered from tests in the NH3-dominated environments included Phase II of the Sour Water JIP.
This new software tool is an extension of the software tool developed in Phase I of the Sour Water
JIP that integrates data and results from both experimental programs to facilitate the prediction of
corrosion rates in alkaline sour water environments that cover the full range of NH3-dominated and
H2S-dominated conditions.

ACKNOWLEDGMENTS
The authors would like to acknowledge the support and contributions by the representatives of the
sponsor companies for Phase II of the Sour Water JIP. Special appreciation is due Michael Cayard for
his leadership and contributions to this program while serving as President of InterCorr International,
Inc. The authors would also like to specifically acknowledge Ashok Dewan and Paul Petkovsky of
Shell Global Solutions (US) Inc. for their ionic modeling work, and Lou Hajdik of Honeywell
International, Inc. for his skill and dedicated efforts in safely conducting these very challenging
laboratory tests.
REFERENCES
1. R.J. Horvath, M.S. Cayard, R.D. Kane, Prediction and Assessment of Ammonium Bisulfide
Corrosion Under Refinery Sour Water Service Conditions, CORROSION/2006, paper no. 576
(Houston, TX: NACE, 2006).
2. M.S. Cayard, W.G. Giesbrecht, R.J. Horvath, R.D. Kane, V.V. Lagad, Prediction of Ammonium
Bisulfide Corrosion and Validation with Refinery Plant Experience, CORROSION/2006, paper no. 577
(Houston, TX: NACE, 2006).
3. R.D. Kane, R.J. Horvath, M.S. Cayard, Major improvements in reactor effluent air cooler reliability,
Hydrocarbon Processing September (2006): pp. 99111.
4. D.G. Damin, J. D. McCoy, Prevention of Corrosion in Hydrodesulfurizer Air Coolers and
Condensers Materials Performance 17, 12 (1978): pp. 23-26 (see also NACE CORROSION/78, paper
no. 131).
5. Private Communication: Russell D. Kane and Vishal Lagad, Honeywell International, Inc., and
Richard J. Horvath, Consultant retired from Shell Global Solutions (US) Inc., Final Report on
Prediction and Assessment of Ammonium Bisulfide Corrosion Under Refinery Sour Water Service
Conditions Phase II (NH3-Dominated Conditions), Issued by Honeywell International, Inc. to the Sour
Water JIP Phase II Sponsors, March 2007.