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 16th Nordic Corrosion Congress – 2015

Sour Top of Line Corrosion: An Overview

Gaute Svenningsen

Institute for Energy Technology,

NO-2027 Kjeller, Norway
gaute.svenningsen@ife.no

Abstract
This paper provides a state-of-the-art overview of sour top of line corrosion (TLC) in
open literature. The findings indicate that sour TLC is different from sweet TLC in
many ways. In particular, the impact of condensation rate is less pronounced for sour
TLC than for sweet TLC. Sour TLC field failures were always related to areas with low
temperature and low condensation rates. Research indicates that this can be related
to the formation of a less protective iron sulphide film at low temperatures. It was also
suggested that the presence of methanol, frequently saturated with oxygen before
injection, could destabilise or reduce the protectiveness of iron sulphide films.

A large number of papers have been published on top of line corrosion (TLC) under
sweet conditions (dominated by CO2 corrosion), but significantly fewer papers have
been published on sour TLC (dominated by H2S corrosion), although such field
failures have been reported as far back as the late 1950s. Nevertheless, the number
of field failures is low compared to the large number of sour pipelines that have been
operated during the last 50-60 years.

Keywords: Top of line corrosion, TLC, sour corrosion, H2S

1 Introduction
Internal condensation in wet gas pipeline can cause top of line corrosion (TLC). The
condensed water is very corrosive since it contains acid species like CO2, H2S and organic
acids. Top of line corrosion in sweet conditions has been studied for several decades and the
mechanisms are well understood [1] and several predictive TLC models exist [2-9].

An approach for predicting areas of risk was proposed by Gunaltun and co-workers [10-13].
Several occurrences of TLC were reported for sweet pipelines in Borneo. Severe TLC (up to
5 mm/y) was observed at river crossings where the pipeline was in direct contact with flowing
river water. Modelling work was used to predict condensation rates along the whole pipelines’
length [11]. The authors showed a clear correlation between high condensation rates and
TLC rates, and it was claimed that there is a critical water condensation rate of 0.15 –
0.25 g/m²s beyond which TLC takes place [12]. At lower condensation rates no TLC is
expected.

Nyborg and Dugstad [2] suggested that the TLC rate was limited by the amount of iron that
can be released in the condensing water. This means that the TLC rate is proportional to both
the condensation rate and the iron solubility [3]. Iron solubility must be calculated using a
chemical equilibrium software. Although these TLC-models are significantly different in
nature, the practical results may not necessarily be very different. With Nyborg and Dugstad’s
model the TLC rate varies with the condensation rate, while Gunaltun’s approach gives an on-
off situation.

It is generally accepted that the presence of organic acids increases the TLC rates [14-18]
since they will condense together with the water and make the condensed water even more
acid. This increases the iron solubility and thus the TLC rate. Mono ethylene glycol (MEG) is
commonly used for hydrate prevention in wet gas pipelines. Significant amounts of organic
acids (i.e. carboxylates) may accumulate in the MEG loop, which may give a significant
contribution to the total iron solubility in the condensed water.
Sour TLC failures have been reported as far back as to the 1950s, but only a limited number
of papers have been published on this topic [19]. The available literature suggests that the
condensation rate is of less importance for the TLC rate in sour conditions [20-24]. This is in
contrast to sweet TLC where the corrosion rate is proportional to the condensation rate [2],
and it indicates that other mechanisms are dominating sour TLC.

The author is currently involved in a joint industry project (JIP) on sour corrosion on carbon
steel (Kjeller Localised Internal Corrosion - KLIC). Sour TLC testing is currently being carried
out as a sub task of this JIP. As part of this task, a large literature survey was carried out. This
paper will give a summary of the publicly available literature on H2S - dominated TLC.

2 Sour TLC field cases

At least seven field cases of sour TLC have been documented in the literature [19-21,25-40].
In addition TLC-related attacks have been reported for a pig launcher and a heat exchanger
operated under sour conditions. A summary of these cases is shown in Table 1. Only a short
description of each case is given here as it will be too tedious to go into the detail of all cases.

Lacq gas gathering system, France (Total)

The Lacq sour gas field is located in the south west of France [25-27]. Sulphide stress
cracking was initially a problem for the well tubing/casing, but it was mitigated by using the
correct steel type and corrosion inhibition. The gas gathering system consisted of a network
with many pipelines of many sizes (4 – 8 inch inner diameter) that were insulated with coal tar
and fiberglass, and buried at least 0.75 m below ground. In August 1959, after just 9 months
of operation, several severe TLC attacks (1 - 4 mm deep) were detected in a 6 inch pipeline,
and later similar damages were found in many other pipelines in the same field. The corrosion
attacks occurred in pipeline sections with gas flow velocities as low as 3 m/s, thus giving rise
to a local wavy (stratified) flow regime. There was no corrosion in areas with liquid hold-ups or
in thinner pipes which had annular/slug flow. The gas contained 15 % H2S, 9 % CO2 and
70 % methane at a pressure up to 103 bar. Corrosion inhibitor (content only 30 ppm) was
injected to prevent general corrosion and diethylene glycol/methanol was used for hydrate
prevention. The diethylene glycol concentration was 30-60 wt.%. The temperature was 50 °C
after the separator and it dropped along the pipeline to 35 °C at the gas plant. The gathering
system was made of Martin Grade B seamless drawn steel [25].

The problem was mitigated using a pipeline operation mode that promoted non-stratified flow
(i.e. keeping the flow higher than a minimum rate). In addition several inspection and
monitoring points were installed. Corrosion inhibitors were developed, but later taken out of
use. It should also be mentioned that no TLC problems were detected on the flow lines
between the wellhead and the separators or in the separators where the temperature was
higher and probably with a turbulent flow regime.

Scarsee, Canada (Shell)

The Scarsee pipeline (8 inch, 22 km long) is located within the Jumping Pond West field in
Canada, approximately 50 km west of Calgary [28]. The pipeline was transporting sour
natural gas from 1966 to 1985. The gas composition was 4.4 mol% H2S and 5.5 mol% CO2,
and the pressure was 20 and 58 bar respectively upstream or downstream the compressor
unit. A dehydration unit was destroyed by a fire in 1972 after which methanol injection was
used for hydrate prevention and a water dispersible corrosion inhibitor was used for corrosion
control. An inspection in 1978 revealed severe TLC attacks in the first 8 km of the pipeline
and two failures occurred shortly after. Up to 25% wall thickness loss was discovered. The
corrosion attacks were always confined to the top of the line (“vapour phase attack”) and the
affected areas were mainly located downstream crests of hills where the flow was stratified.
Totally 310 m of the pipeline was replaced at 15 separate locations. The wall thickness was
not reported so it is not possible to give exact TLC rates, but if one assumes ½ inch wall
thickness the corrosion rate would be at least 0.26 mm/y (for 12 years of operation) or
0.5 mm/y for 6 years of operation (assuming no TLC prior to methanol injection). The
temperature was not reported but TLC was not observed for the first part of the pipeline
where the temperature was highest. Interestingly there was no sign of TLC in a similar 6 inch
pipeline connected to the neighbouring well transporting the same type of gas and liquids at

Page 2 of 18
the same flow velocity, but without methanol injection. Thus it was claimed that methanol
injection was the main cause of the TLC in this pipeline because methanol diluted the
condensing water and thus interrupted the formation of a protective iron sulphide layer.
Possible oxygen contamination of the methanol was not mentioned, but it is reasonable to
believe that the methanol contained some dissolved oxygen.

The sour TLC problem was mitigated by injection of a corrosion inhibitor containing a large
fraction (13%) of a volatile component, and from 1982, monthly batch treatment with a heavily
film-forming corrosion inhibitor was also carried out. In 1985 a new 4 inch pipeline was used
for transporting the Scarsee gas and the old 8 inch pipeline was converted to fuel gas
transport to a compressor station.

Crossfield, Canada (Shell)

The 6 inch “Rundle F” gathering pipeline is located in the Crossfield gas field near Calgary in
Canada [28]. It has been operated since the early 1960ies, and regular corrosion monitoring
showed gradual increasing - but still acceptable - corrosion rates [29]. The pipeline ruptured in
1985 due to severe sour TLC [30-32]. Corrosion attacks with up to 64 % wall thickness loss
were detected, although 22 % loss was most common. The attacks were confined to the top
of the line (from 7 o’clock to 5 o’clock) while the bottom of the line was essentially unattacked.
The wall thickness was 4.78 mm so the average TLC rate would be 0.05-0.15 mm/y (22-68 %
wall thickness loss) for a 22 year time of operation. The corrosion attacks were deeper in the
splash zone at the gas/liquid interface. The attacked areas were located in downhill sections
of the pipeline where the flow was stratified [28]. Uphill slopes had slug flow and no corrosion
problems. The gas composition varied with time due to different production rates from several
wells, but the H2S content was 0.01- 1.4 mol% and the CO2 content 5.2-8.9 mol%. At the time
of failure the H2S:CO2 ratio was around 1:20 (0.3 mol% H2S and 5.9 mol% CO2) and the
operating pressure was 70 bar giving 0.21 bar H2S and 4.1 bar CO2, i.e. significantly lower
H2S than CO2 partial pressure. The temperature was not reported directly but 40°C was used
for de Waard Milliams’ corrosion model. The TLC occurred downstream a well tie-in. Most
likely the tied-in gas was warmer, which increased the likelihood of water condensation
downstream the tie-in. The TLC was relatively low (2-10 % wall thickness loss) in the first
0.5 km length downstream the tie-in where the temperature and condensation rates were
highest, while it was much more severe (5 – 50 % wall thickness loss) along the rest of the
pipeline [30]. Condensate was claimed to reduce corrosion where it was in contact with the
pipe wall, possibly explaining the higher corrosion rate in the splash zone (above condensate
level) and negligible corrosion in locations with liquid hold-up. The corrosion product on the
failed pipe section contained mackinawite but not iron carbonate (XRD-analysis), indicating
that sour corrosion was dominating. The failure investigations claimed the TLC failure was a
result of several factors:
• Termination of an inhibitor program due to incompatibility problems. Thus there was
no corrosion inhibitor in the system.
• Pigging was not possible.
• Declining production rates during the last 10 years, which resulted in less condensate
(which had shown inhibiting properties), 60% increased water production and 50%
reduced gas velocity. The H2S and CO2 content increased also.
• Reduction in the gas velocity changed the flow regime to stratified flow for many
downhill pipe sections.

Several mitigation actions were initiated. A continuous and batch corrosion inhibitor program
was started and the pipeline system was modified to allow for pigging. A simple corrosion
model was developed for predicting areas at high risk. 21 locations were inspected and cut-
outs made to confirm the model. The model gave high TLC probability if two criteria were met:
(1) Water condensation on pipe wall and (2) Stratified flow [31]. Some of the pipeline was
replaced with a smaller diameter pipe to increase the flow velocity (avoid stratified flow).

Tioga gas gathering system, North Dakota (Amerada Hess Corporation)

The Tioga Gas Gathering system is located in North Dakota [33]. Two TLC incidences (1994
and 1998), each on different pipelines, have been reported for this system [34].

Page 3 of 18
The 1994 incidence (line 1) occurred in a 10 inch ID pipeline with 16.4 mol% H2S and
2.6 mol% CO2 and 34.4 – 20.7 bar pressure. The gas temperature was 37 – 4 °C. Modelling
showed that most of the cooling occurred during the first 400 m downstream the compressor
and the pipeline fluid reached ground temperature after about 4800 m. Corrosion inhibitor was
continuously injected and the pipeline was in addition treated with batch corrosion inhibitor
th
every 5 day. Methanol injection was used for hydrate prevention (usually 189 liters/day). The
failure was TLC located in a downhill section at the crest of a hill with low flow rate (0.3-
0.8 m/s) and segregated flow regime. Corrosion coupons that were installed flush to the top of
the line revealed high corrosion rates (0.25 mm/y) without mitigation while batch treatment
reduced the TLC rates to < 0.05 mm/y. The condensation rates were not given directly but it
was possible to estimate a rate of about 0.008 g/m²s from the modelling results (water only,
not including methanol).

The 1998 incidence (line 2) occurred in a 6¾ inch pipeline and the failure (blowout) was
located about 457 m downstream a compressor. The investigation showed that TLC caused
the failure. No sign of corrosion was observed downstream the failure. The gas temperature
was 42 °C at the exit of the compressor, after 610 m it had dropped to 25°C and after 4825 m
the gas reached the soil temperature of 10 °C. Thus most of the condensation occurred within
the first 800 m. The flow was stratified. Methanol was usually injected at a rate of
130 liters/day but was 71 liters/day at the time of failure. The condensation rate was
estimated from modelling results to be about 0.004 g/m²s. Corrosion inhibitor was
continuously injected.

For both pipelines the problem was mitigated by batch corrosion inhibitor treatment and more
frequent pigging (line 1 only). In addition, temperature and pressure profiles were used to
predict sites with high TLC risk. It was assumed that methanol injection contributed to the
TLC, possibly assisted by oxygen contamination of the methanol [34]. The effect of methanol
by “washing off” batch corrosion inhibitor was demonstrated in a glass cell experiment. The
corrosion rate dropped sharply after batch treatment but increased steadily again to
uninhibited levels as more and more batch corrosion inhibitor was removed by condensing
methanol.

Sour gas gathering pipeline with oxygen contamination

A 16 km long 12 inch pipeline was part of a sour gas gathering system carrying 0.5 mol%
H2S, 1.3 mol% CO2 and volatile organic acids at a pressure of 49.6 bar [35,36]. The location
was not reported. The pipeline was periodically treated with methanol that was oxygen
saturated. TLC occurred a few hundred feet downstream the compressor station. The
temperature or condensation rate in the affected area was not reported, but most likely the
temperature was increased by the compression. Flush-mounted coupons inside the pipeline
were used to measure the corrosion rate. The measured TLC rates (12 o’clock coupon) were
initially 0.4 – 0.5 mm/y while the bottom of line rate was about 0.25 mm/y. The TLC rates
decreased to less than 0.033 mm/y after a new improved inhibitor formulation was used. The
new inhibitor was more tolerant against oxygen contamination (originating from the methanol)
and contained also active volatile components to prevent TLC.

Wet gas subsea pipeline

Pugh and co-workers [20,21] reported TLC for a wet gas sour pipeline. Very few details are
given on this case, but it is clear that it is a 95 km long large diameter subsea pipeline going
from a platform to shore. The temperature is not directly stated, but the fluid temperature was
most likely in the 43 – 15 °C range since this is the temperature of a flow modelling result in
the same paper. Intelligent pigging (magnetic flux leakage) detected TLC at a distance 17 –
32 km from the platform, at a location where the temperature/condensation rate was very low
(most likely the fluid temperature was 25-15 °C in the affected area). No TLC was detected
before or after the 17-35 km section. This is in strong contrast to sweet TLC where the
corrosion rate is usually highest where the temperature/condensation rate is highest (i.e. near
the platform or pipeline inlet). The gas contained approximately 1 mol% H2S, 2.4 mol% CO2
and organic acids. The TLC appeared at time with extended periods of low flow, facilitating
stratified flow and no supply of corrosion inhibitor to the top section of the pipeline. The
problem was mitigated by implementation of corrosion inhibitor and “minimum flow rate”

Page 4 of 18
guideline (to avoid stratified flow). Measures were also taken to prevent residual organic acids
after well stimulation.

Alaska Highway pipeline pig launcher, Canada (Westcoast Energy Inc.)

th
A pig sending barrel connected to the 18 inch Alaska Highway pipeline ruptured the 20 of
February 2009 near Wonowon in British Columbia [37]. The sending barrel had a wall
thickness of 9.5 mm. The gas contained approximately 2 % H2S and 4 % CO2. The
temperature was not reported but the barrel was located above ground without insulation and
would therefore be significantly affected by the local air temperature. Since this was a pig
launcher the pressure varied from ambient to 55 bar. It was common to pressurize the barrel
a day or so before the pig was launched. The investigation following the accident revealed
significant top of line corrosion (acid vapor phase attack) on the upper quadrant of the
sending barrel. There was no internal coating on the corroded areas. It was discovered that a
broken valve had caused wet sour gas to constantly flow into the sending barrel for a period
of more than 8 months, and this likely caused continuous water condensation inside the
barrel. Methanol was used together with the pig to avoid hydrate formation. Contamination
with oxygen was therefore possible, both from the methanol and remnants from the air when
the pigs were loaded into the sending barrel. It was also suggested that the presence of
methanol may have dissolved/diluted corrosion inhibitors and thereby further promoted
corrosion. Following the accident several preventive steps were taken: Use of vapor phase
corrosion inhibitor to all barrels after receiving/sending pigs, prohibited pre-loading of sending
barrels with methanol, and applying internal coating on sending barrels.

The 16-16 Vulcan pipeline, Canada

The 16-16 Vulcan 6.6 inch OD pipeline is situated near Alberta, Canada [38]. The pipeline
was insulated and buried about 2 meters underground. The pipeline was installed in 2000 and
put into service in 2001. In 2009, after about 8 years of service, the pipeline ruptured about
1.9 km downstream compressor station no. 4. The outlet temperature of the compressor
station was 25 – 30 °C and the average soil temperature was around 10°C. The pipeline
transported wet natural gas containing up to 0.28 - 0.53 mol% H2S and 5.5 - 13.4 mol% CO2.
Condensate was also present in the pipeline. The condensed water contained no organic
acids. The dehydration unit was operated intermittently from 2001 to 2006 and permanently
bypassed after 2006. The pipeline was pigged weekly and batch corrosion inhibitor was
th
applied every 6 week. Methanol was added at a rate of 50-60 liters/day. The subsequent
investigation revealed significant wall loss in the upper part of the pipeline (from 8 – 4 o’clock)
while the bottom segment was intact. The wall loss was 60 – 85% (5.6 mm wall thickness) at
the rupture site, corresponding to a TLC rate of about 0.56 mm/y. Intelligent pigging (MFL)
was carried out on the entire pipeline length and revealed significant wall loss. Although metal
loss was found all along the pipeline length, all the deepest attacks (> 40% wall thickness)
were confined to the first 3 km downstream the compressor station. This is also where the
temperature drop (and consequently condensation rate) was highest. However, the
condensation rate was low in absolute values, around 0.003 – 0.0015 g/m²s. The corrosion
products contained iron sulfide and most likely elemental sulfur. Corrosion modelling was
carried out and gave TLC rates of 0.6 – 0.9 mm/y depending on operational conditions. Due
to the severe corrosion attacks the pipeline was abandoned.

Sour corrosion survey

Bonis and co-workers in Total carried out a sour corrosion survey on 125 distinct
cases [19,39,40], which included both public literature and unpublished cases inside Total.
The main focus of the survey was on general sour corrosion, but sour TLC was also
commented on. Although most of the sour TLC cases were from the open literature
(summarized in this chapter), it is at least indirectly suggested that several sour TLC cases
has been identified within Total. All field cases of sour TLC were observed for onshore buried
pipelines with moderate temperatures (less than 40 – 50 °C) and moderate condensation
rates. A case of “iso-TLC” inside a cooler tube in a heat exchanger is mentioned but no
details are given except that the maximum flow rate was less than 6-7 m/s and that the
temperature was likely less than 50 °C.

The authors point out that the sour TLC mechanism has not yet been fully understood and a
possible explanation could be that iron sulfides formed at low temperatures offers less

Page 5 of 18
protection. Flow regime (stratified vs slug/annular flow) and temperature seems to be the
most important factors for this type of corrosion. The presence of organic acids is expected to
have a negative effect. Furthermore, the authors clearly state that sour TLC is a relatively rare
phenomenon since only 10 field cases are known - despite the very high number of sour wet
gas pipelines that has been operated without problems for 30 – 50 years. (When including the
“iso-TLC” case and pig launcher case, nine individual field cases have been documented in
the present review, indicating that possibly another sour TLC is known inside Total).

3 Sour wet pipelines without TLC

Gunaltun and Larrey [10-13] carried out a corrosion survey for two 8 inch pipelines for the
Abu Al Bukhoosh (ABK) field located outside Abu Dhabi (United Arab Emirates). The flow
regime was stratified except for in the risers which had annular flow. The gas contained CO2
and H2S, but no compositions were given. However, in a different paper on the same
pipeline [41] the H2S content is reported to be approximately 2.5 mol%. The pipeline pressure
was 116-107 bar and thus the H2S partial pressure was about 2.8 bar. The temperature was
70-41 ° for the first pipeline and 63-29 ° for the second pipeline. Both pipelines were
externally coated with coal tar epoxy and concrete resulting in condensation rates below
0.1 g/m²s for most of the pipeline lengths. No TLC was detected for any parts of the pipelines.

4 Sour TLC laboratory experiments

Martin (1997)
Martin [42] tested vapor phase inhibitors in glass cells at room temperature. The test coupons
were vertically mounted carbon steel (UNS G 10200) cylinders (4.4 cm long, 0.6 cm
diameter). The glass cells were continuously purged with pure H2S at ambient pressure.
There were, however, no external cooling of the corrosion coupons and no condensation
rates were measured. The corrosion rate varied from 0.5-2 mm/y depending on exposure time
(1-6 days) and sample height over the liquid. It was shown that the additional presence of
oxygen increased the corrosion rate by about 4 times (from 0.5 to 4.1 mm/y). Although no
direct negative effect of methanol was shown, it was suggested that it would dilute any
protective hydrocarbon phase, thus increasing the corrosion rate. Furthermore, methanol
could be contaminated with oxygen.

Schmitt (2001)
Schmitt and co-workers [43] tested TLC of X65 carbon steel pipes with 2 bar H2S. The
corrosion rate was 1.3 mm/y for a condensation rate of 3.82 g/m²s and a steel surface
temperature of 35 - 37.9 °C. Localized corrosion (pitting) was observed on the exposed
coupons.

Pugh (2009)
Following sour TLC in a field pipeline, Pugh and co-workers [20] carried out TLC experiments
in purpose built autoclaves where the sample temperature could be controlled. The gas
contained 1 mol % H2S + 2.5 mol % CO2 (the total pressure was not reported) with varying
amounts of acetic acid. Samples with a surface temperature of 25 °C had a corrosion rate of
0.38 mm/y and 65 µm deep localised attacks despite a low condensation rate of 0.002 g/m²s.
The samples with 55 °C surface temperature had a much lower corrosion rate of 0.051 mm/y
(0.1 g/m²s condensation rate). The presence of organic acids further increased the TLC rate
for the low temperature (25°C) coupons, and with 650 ppm formic acid + 650 ppm acetic acid
in the bulk aqueous phase the TLC rate was more than doubled (0.84 mm/y). The corrosion
product was characterised as “fluffy polycrystalline” and it was identified by XRD as
mackinawite for both sample temperatures. The mackinawite grain size was markedly smaller
for the low temperature coupons (~0.5 µm) compared to high temperature coupons (~10µm).
The authors claimed that the temperature affected the protective properties of the
mackinawite, thus explaining the strong effect of surface temperature on TLC rates. The
same authors [21] also carried out flow loop experiments under the same conditions. The TLC
rates in the flow loop (0.62 mm/y) were comparable to the autoclave experiments (0.39 mm/y)
at 25 °C, and the difference was most likely related to different exposure time (7 vs. 3 weeks).
The flow rate did not have a direct effect on the TLC rate or corrosion product, but it may have
an effect on droplet entrainment which could transport corrosion inhibitors to the top section of
the pipeline.

Page 6 of 18
 Table 1: Summary of sour TLC field failures reported in literature.
Field/Pipeline and H2S CO2 H2S (bar) CO2 Fluid Pipe Cond. rate TLC Max Inhib- Org. Meth- Remark
references (mol%) (mol%) (bar) temp. wall (g/m²s) rate corr. tor acids anol?
(°C) temp. (mm/y) depth #?
(°C) (mm)
Lacq [25-27] 15 9 ≤ 15.5 ≤9 50-35 N/A N/A 1.4-5.4 1 - 4 CI N/A Yes Onshore buried, Glycol
Scarsee [28] 4.4 5.5 2.6 3.2 N/A N/A N/A (0.2-0.5) (3) CI N/A Yes Onshore
Crossfields [28,30,32] ≤ 1.2 ≤6 ≤ 0.21 ≤ 4.1 (<40) N/A N/A (> 0.2) (8) BCI N/A No Onshore
Tioga 1 [33,34] 16.4 2.6 ≤ 5.6 ≤ 0.89 37-4 N/A (0.0008) 0.25 N/A CI+BCI N/A Yes Onshore buried
Tioga 2 [33,34] 16.4 2.6 ≤ 5.6 ≤ 0.89 ~27 N/A (0.004) N/A N/A CI N/A Yes Onshore buried
Unknown1 [35,36] 0.5 1.3 0.2 0.6 N/A N/A N/A 0.5 N/A CI Yes Yes Onshore buried
Unknown2 [20,21] 0.5-1 2.5 N/A N/A (25-15) (43-15) (0.002-0.1) N/A N/A CI Yes No Subsea
Alaska Hwy. [37] 2 4 ≤ 1.1 ≤ 2.2 N/A N/A N/A N/A N/A BCI N/A Yes Pig launcher
Vulkan pipeline [38] 0.28-0.5 5.5-13 0.17-0.33 3.4-8.3 ~22 (10-15) 0.0015-0.003 0.56 4.8 BCI No Yes Buried onshore
“iso-TLC” [19] N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A Heat exchanger
Values in parenthesis are estimates based on available published information and should therefore be considered as less accurate.
# BI = Batch inhibitor, CI = Continuous inhibitor injection, VCI = vapour phase corrosion inhibitor

Page 7 of 18
Singer (2010, 2011, 2012)
Singer and co-workers [22,44,45] carried out sour TLC testing in a flow loop with 4 bar H2S and 10 bar
CO2 and 280 ppm acetic acid in the aqueous bulk phase. The gas temperature was 55 °C and the
sample surface temperature was 25 °C or 50 °C with a corresponding condensation rate of 0.12 or
0.02 g/m²s. The TLC rate was 0.13 mm/y for the low temperature sample and 0.07 mm/y for the high
temperature sample. The exposed coupons were covered with iron sulphide corrosion products, and
no localised corrosion was observed. The high temperature sample had a dense and adherent inner
layer (thickness ~10 µm) and an outer layer with a varying thickness and individual crystals. The
corrosion products were mackinawite with some troilite (identified by XRD). The low temperature
sample had a similar dual layer structure with a dense inner adherent layer (thickness ~10 µm) and a
porous outer layer with small crystallites (thickness 25- 30µm). The corrosion product was only
mackinawite. The authors indicated that the protectiveness of the iron sulphide surface film depends
on the temperature at which it forms.

Singer et al. [46] carried out sour TLC testing of X65 carbon steel for the Karan sour gas field in the
Arabian Gulf. The experiments were carried out in flow loop (0.1 bar H2S + 0.5 bar CO2) and in
autoclaves (up to 4 bar H2S + up to 10 bar CO2) with about 350 ppm acetic acid in the aqueous bulk
phase. The temperature of the corrosion coupons was varied from 17 – 50 °C and the gas
temperature was varied from 40 – 50 °C, which resulted in condensation rates from 0.02 – 0.14 g/m²s.
TLC rates in the flow loop varied from 0.38 mm/y (0.05 g/m²s) to 0.18 mm/y (0.25 g/m²s). The
autoclave testing gave results comparable to the flow loop for similar conditions. Autoclave testing
gave TLC rates ranging from 0.06 to 0.3 mm/y. The TLC rate did not show the same dependency on
condensation rate as for sweet TLC. The corrosion products had a two-layer morphology: a dense
adherent inner layer (thickness 5 – 20 µm) and a more porous outer layer (20 – 40 µm) with individual
crystals with poor adherence. The data indicated a trend of decreasing TLC rate when the H2S partial
pressure increased. Furthermore the TLC rate was highest for the lowest gas temperatures (40 °C)
and it decreased as the gas temperature increased (50 °C). The highest TLC rates were associated
with corrosion products of cubic FeS and mackinawite.

Singer and Yaakob (2013)

Singer and co-workers reported that the sour TLC rate was not much affected by the condensation
rate [23]. They also reported that the metal surface temperature was important for the TLC rate and
the type of iron sulphide that formed [24]. The highest TLC rates (0.2 - 0.3 mm/y) were observed for a
surface temperature of 15 - 25 °C where the corrosion product was a mixture of cubic iron sulphide
and mackinawite. Lower corrosion rates (0.002 - 0.08 mm/y) were observed for a surface temperature
of 55 and 75 °C where the product consisted of mackinawite, cubic FeS and troilite.

Asher (2012)
Asher et al. [6,47] compared a corrosion model with experimental data for sour TLC. The experimental
TLC rate was 0.23 mm/y (25 °C, 0.002 g/m²s) and 0.15 mm/y (55 °C, 0.1 g/m²s). The CorrCast model
predicted 0.25 and 0.18 mm/y respectively for 25 and 55 °C, i.e. a relatively good match between
1
model and experimental data. CorrCast uses a “H2S–threshold” method; if the supersaturation of iron
sulphide (Mackinawite) is less than 1, the normal sweet TLC model is used. If the saturation is higher
than 1, the sour TLC model is used [47]. This model includes a mechanistic model of mackinawite
+ +
scale formation, and it includes the effect of H2S, H3O (H ) and organic acids. The protectiveness is
described in terms of porosity and tortuosity.

Kvarekvål (2014)
Kvarekvål et al. [48] reported corrosion rates in the range of 0.7 – 1.2 mm/y for vertically mounted
“cold finger” probes exposed to 5 bar CO2 and 0.5 bar H2S with 50 wt.% MEG in the aqueous phase.
For purely sweet conditions (5 bar CO2) the corrosion rate was 0.27 mm/y. The gas temperature was
60 °C and the condensation rate was approximately 0.6 g/m²s. The surface temperature was not
measured. The same authors also reported results with flat coupons that were mounted in a sample
holder that exposed one side (facing down) to the autoclave environment while the other side was
exposed to cooling liquid. The gas contained 5.4 bar H2S and 10.8 bar CO2 and the gas phase
temperature was 70 °C and the condensation rate was in the range of 1 – 1.5 g/m²s. The aqueous
phase was 50 wt.% MEG with 350 ppm organic acids and no buffering agents. The TLC rate was
1
ExxonMobil's CorrCast™ corrosion prediction.

Page 8 of 18
0.42 mm/y, but the rate was reduced to 0.29 mm/y when the sample was sprayed with the aqueous
phase right after the experiment started up (simulating a spray pig). Localized attacks with 70 – 80 µm
depth were recorded for both conditions. The coupon surface temperature was not reported, but it is
estimated to be in the range 40 – 55 °C.

Miksig (2013)
Miksig [49] tested vapour corrosion inhibitors in a flow loop at a remarkably high temperature of
177 °C. The gas contained H2S (0.72 bar), CO2 (0.59 bar) and 25 ppm oxygen. The TLC rate was
1.4 mm/y without inhibitor and 0.41 mm/y with inhibitor. It should be noted, however, that the test
duration was very short, only 8 hours. There were no information on the steel (sample) temperature or
condensation rate. The same authors also carried out autoclave experiments but without H2S.

5 Slightly sour TLC laboratory experiments

Camacho (2008) and Singer (2010)
Camacho [50], Singer [45] and co-workers carried out slightly sour TLC experiments on X-65 carbon
steel in a flow loop with 2 bar CO2 and low amounts (0 – 0.13 bar) of H2S. The gas temperature was
70 °C and organic acids (100 – 1000 ppm) were present in some tests. The corrosion coupons were
cylindrical pipes with 4 inch inner diameter and the condensation rate was 0.25 g/m²s. The
experiments with only CO2 (no H2S) had the highest TLC rate, starting at 1.2 mm/y and gradually
dropping down to 0.5 mm/y after 21 days. The additional presence of acetic acid increased the TLC
rate to 1.5 mm/y (21 days exposure). In the tests with CO2 and H2S the TLC rate was lower and
relatively stable with time: 0.35 mm/y (0.004 bar H2S) and 0.05 mm/y (0.13 bar H2S). The additional
presence of 1000 ppm acetic acid increased the TLC rates: 1.6 mm/y (0.004 bar H2S) and 0.6 mm/y
(0.13 bar H2S). No localised corrosion occurred in the presence of CO2 +H2S but localised corrosion
(up to 250 µm) was observed when also acetic acid was present. Up to 500 µm deep attacks were
observed for tests with only CO2 and acetic acid (no H2S). The corrosion products were FeCO3
(crystals) in the tests without H2S, and FeS (amorphous) in all tests with H2S present. Both H2S and
acetic acid affected the morphology of the corrosion products.

Li (2012)
Li and co-workers [51] tested TLC under slightly sour conditions (6.7 bar CO2 with 0.00007 – 0.007 bar
H2S). SEM/EDS investigations revealed mixed corrosion products of FeCO3 and FeS, and they were
confirmed by XRD to be siderite and mackinawite. A “normalized” corrosion rate was reported,
meaning that the absolute corrosion rates were not published. Nevertheless, it was shown that for
these slightly sour conditions the TLC rate was proportional to the condensation rate (0.1 –
0.45 g/m²s). The metal surface temperature (25 – 55°C) had insignificant effect on the TLC rate and
there were no clear effect of variations of H2S partial pressure (< 0.007 bar).

Nyborg (2009)
Nyborg and co-workers carried out TLC experiments in a flow loop with 10 bar CO2, 0.002 bar H2S
and acetic acid at 25°C. It was estimated that the condensed water contained 300 ppm acetic acid.
The TLC rate varied with the condensation rate and was 0.17 mm/y (0.006 g/m²s condensation rate)
and 0.10 mm/y (0.003 g/m²s condensation rate). The corrosion products formed a thin inner layer of
protective FeCO3 while the thicker outer layer (50 – 100 µm) consisted of porous iron sulphide. The
surface films spalled and cracked during drying after exposure.

Page 9 of 18
 Table 2: Summary of sour TLC rates experiments (without inhibitor)reported in the literature.
No. Author H2S CO2 H2S CO2 Fluid Steel Cond. rate Sum of all TLC Max Remark
content content partial partial temp. temp. (g/m²s) organic rate corrosion
(mol%) (mol%) pressure pressure (°C) (°C) acids (mm/y) depth (µm)
(bar) (bar) (mmol/kg)
1 Martin [42] 100 0 1 0 25 ~25 N/A 0 0.51
2 100 0 1 0 25 ~25 N/A 0 2.0
3 100 0 1 0 25 ~25 N/A 0 2.2 Methanol
4 100 0 1 0 25 ~25 N/A 0 4.1 Methanol+oxygen
5 Schmitt [43] 100 0 2 0 40 36.5 3.82 0 1.3
6 Pugh [20] 1.0 2.4 1.0 2.4 (30) 25 0.002 0 0.39 64
7 1.0 2.4 1.0 2.4 (60) 55 0.1 0 0.051 13
8 1.0 2.4 1.0 2.4 (30) 25 0.002 10.8 0.43 20
9 1.0 2.4 1.0 2.4 (60 25 0.002 13 0.62
10 1.0 2.4 1.0 2.4 (30) 25 0.002 24.9 0.84
11 1.0 2.4 1.0 2.4 (60) 25 0.002 10.8 0.09
12 Pugh [21] 1.0 2.4 1.0 2.4 (30) 25 0.002 0 0.39 66
13 1.0 2.4 1.0 2.4 (30) 25 0.002 13 0.62 66
14 1.0 2.4 1.0 2.4 (60) 55 0.1 13 0.089
15 1.0 2.4 1.0 2.4 (30) 25 0.002 13 0.58
16 1.0 2.4 1.0 2.4 (60) 55 0.1 13 0.18
17 Singer [45,46] 66.7 0.1 2 0.004 70 50 0.25 0 0.35 Flow loop
18 66.7 2.3 2 0.07 70 50 0.25 0 0.025 Flow loop
19 66.7 4.3 2 0.13 70 50 0.25 0 0.05 Flow loop
20 66.7 0.1 2 0.004 70 50 0.25 16.7 1.7 Flow loop
21 66.7 4.3 2 0.13 70 50 0.25 16.7 0.55 Flow loop
22 Asher [6] N/A N/A N/A N/A 25 N/A 0.002 0.25 0.23
23 N/A N/A N/A N/A 55 N/A 0.1 0.18 0.15
24 Singer [22] 35.7 14.3 10 4 55 50 0.02 4.7 0.075
25 35.7 14.3 10 4 55 24.4 0.12 4.7 0.13
Values in parenthesis are estimates based on available published information and should therefore be considered as less accurate.

Page 10 of 18
 Table 3: Summary of sour TLC rates experiments reported in the literature.
No. Author H2S CO2 H2S CO2 Gas Steel Cond. rate Sum of all TLC Max Remark
content content partial partial temp. temp. (g/m²s) organic rate corrosion
(mol%) (mol%) pressure pressure (°C) (°C) acids (mm/y) depth (µm)
(bar) (bar) (mmol/kg)
26 Kvarekvål [48] 34.9 65.1 5.8 10.8 70 (47) 1.25 3.0 0.42 70 50wt% MEG
27 34.9 65.1 5.8 10.8 70 (47) 1.25 3.0 0.29 80 50wt% MEG
28 9.1 90.9 0.5 5 60 (35) 0.6 0 0.78 50wt% MEG
29 9.1 90.9 0.5 5 60 (35) 0.6 0 1.22 50wt% MEG
30 9.1 90.9 0.5 5 60 (35) 0.6 0 0.76 50wt% MEG
31 9.1 90.9 0.5 5 60 (35) 0.6 0 0.73 50wt% MEG
32 9.1 90.9 0.5 5 60 (35) 0.6 0 1.17 50wt% MEG
33 9.1 90.9 0.5 5 60 (35) 0.6 16.7 0.67 15 50wt% MEG
34 Singer [23,46] 3.3 16.7 0.10 0.50 55 25 0.25 4.2 0.18 Flow loop
35 3.3 16.7 0.10 0.50 55 50 0.05 5.8 0.38 Flow loop
36 21.2 78.8 0.11 0.41 40 17 0.14 0.0 0.30
37 19.0 81.0 1.90 8.10 45 38.1 0.02 0.0 0.25
38 11.7 88.3 1.24 9.40 55 21.4 0.12 5.8 0.08
39 30.2 69.8 4.29 9.90 55 50 0.02 0.0 0.07
40 30.2 69.8 4.29 9.90 55 24.4 0.14 0 0.13
41 Yaakob [24] 8.0 40.0 2 10 25 (15) 0.012 0 0.19
42 8.0 40.0 2 10 60 (19) 0.21 0 0.31
43 8.0 40.0 2 10 25 20 0.005 0 0.24
44 8.0 40.0 2 10 40 (22) 0.04 0 0.13
45 8.0 40.0 2 10 80 (34) 0.51 0 0.13
46 8.0 40.0 2 10 40 35 0.01 0 0.07
47 8.0 40.0 2 10 60 55 0.02 0 0.08
48 8.0 40.0 2 10 80 75 0.02 0 0.022
49 Miksig [49] 1.7 1.4 0.72 0.59 177 N/A N/A N/A 1.4 Flow loop,
only 8h exposure.
25ppm oxygen
Values in parenthesis are estimates based on available published information. Large uncertainties may be expected.

Page 11 of 18
 3.0
Field case (Reported)

2.5 Field case (Estimated)

Lab experiment (Reported)
Lab experiment (Estimated)
TLC rate (mm/y)

2.0

1.5

1.0

0.5

0.0
0 20 40 60 80 100
Gas temperature (°C)

Figure 1: Summary of TLC rates as a function of gas temperature. Open markers

indicate that the gas temperature is estimated based on information in the paper.
The figure includes results from significantly different field/test conditions.

1.4
Steel temp ≤ 20 °C
1.2 20 °C < Steel temp ≤ 40 °C
Steel temp > 40 °C
1.0
TLC rate (mm/y)

0.8

0.6

0.4

0.2

0.0
0.001 0.01 0.1 1 10
Cond. rate (g/m²s)
Figure 2: Summary of TLC rates from the open literature as a function of condensation rate.
Only cases without organic acids are shown. Where not directly reported in the source
paper, the condensation rates are estimated.

Page 12 of 18
 0.7
Pugh CORROSION/2009
0.6 Pugh IPTC2009
Pugh IPTC2009
0.5 Yaakob 2014
TLC rate (mm/y)

Singer 18ICC
0.4

0.3

0.2

0.1

0.0
0 20 40 60 80
Steel temperature (°C)

Figure 3: Summary of TLC rates as a function of steel temperature for

several experimental series each carried out under similar conditions.

1.8
Pugh CORROSION/2009
1.6 Singer NACE/2010
1.4 Pugh CORROSION/2009
TLC rate (mm/y)

1.2

1.0

0.8

0.6

0.4

0.2

0.0
0 5 10 15 20 25
Organic acids in bulk (mmol/kg)
Figure 4: Summary of TLC rates as a function of total organic acid content in the
bulk phase for several experimental series each carried out under similar conditions.

Page 13 of 18
6 Summary
A summary of the literature findings is shown in Figure 1 through Figure 4, and in Table 1 through
Table 3. Important parameters like gas temperature, steel temperature and condensation rates were
not always reported but for the purpose of parametric study it was sometimes possible to make
estimates of these values, indicated as open markers in the graphs or numbers in parenthesis in the
tables. These numbers should therefore be considered with caution.

Several sour TLC field cases have been found in open literature. Seven of them were onshore
pipelines, one was a subsea pipeline, one was a pig launcher and one was in a heat exchanger. All
cases occurred at low to moderate fluid temperatures (all ≤ 42 °C) and low condensation rates. The
TLC rates in field were in most cases moderately high, from 0.1 – 0.6 mm/y (see blue markers in
Figure 1). Factors that promoted stratified flow, i.e. declining pipeline slope and low flow rates were
always observed at the failure location. It was further shown that non-stratified flow regime prevented
TLC, since the aqueous phase containing corrosion inhibitors and buffering agents will then reach the
top sector of the pipelines. In addition many failures were located downstream a compressor station,
which most likely increased the temperature enough to cause condensation inside the pipeline.

Methanol injection was applied in seven of ten reported field cases of sour TLC, and several authors
claimed that TLC is directly related to methanol since its presence in the condensing phase disturbs
the formation of a protective iron sulphide layer. Experiments have shown that methanol affect the
corrosion rate and type of iron sulphides that form [52]. Others claimed that methanol condensation
washed off corrosion inhibitors or diluted the condensate phase (which may inhibit corrosion) from the
pipe wall, thus removing corrosion protection [34,42]. It was also suggested that methanol introduced
oxygen to the system since the methanol frequently was not deoxygenated [28,34]. Oxygen
contamination is known to accelerate H2S corrosion, as demonstrated by Song et al. [53]. The
presence of oxygen may affect the type of iron sulphide which forms. For example at 40 °C
mackinawite and pyrite formed with only H2S present, while troilite, mackinawite, pyrite, gregite,
hematite and magnetite formed when also traces of oxygen was present. Although these experiments
with oxygen contamination were carried out as conventional corrosion experiments in glass cells,
there is no reason to believe that the trends would be different for sour TLC. Another important aspect
in this regard is that oxygen also may form elemental sulphur which is known to cause corrosion. It is
not unlikely that oxygen could condense together with water and form elemental sulphur on the top of
the line.

The field and experimental TLC rates reported here (Figure 1 and Figure 2) covers many significantly
different experimental/operational conditions, and comparing them may therefore not be
straightforward, as shown with the large spread of data in Figure 1. Therefore it is clear that
comparison should be done only for data acquired within relatively similar conditions. Figure 2 shows
the TLC rate as a function of condensation rate and steel temperature for cases without organic acid.
There is no clear trend of the condensation rate, opposite to what is expected for sweet TLC. Even for
very low condensation rates the sour TLC rates are very high (> 0.1 mm/y). Thus it can be claimed
that the condensation rate is a much less important factor for sour TLC than for sweet TLC, as also
suggested by several papers [20,21,24].

The effect of steel temperature on sour TLC seems is shown in Figure 3. For easy comparison the
figure shows only experimental series that were carried out under similar conditions. The general
trend is that TLC rates increase with decreasing steel temperature, and the highest TLC rates occur in
the temperature range of 20 – 30 °C. Field reports [13] of two sour wet gas pipelines that were
operated for 12 years with a gas temperature of 41-29 °C without TLC supports this. The importance
of steel surface temperature for sour TLC has been suggested by several papers. Most likely the
temperature affects the morphology (and possibly polymorph type) of the iron sulphide film that forms,
and hence it also affects the protectiveness of the inner layer [20,21,24]. Others have suggested that
the gas temperature may be the most important factor [23,46], but these parameters are anyhow
closely connected although they are not the same.

The presence of organic acids increases the sour TLC rates, particularly at low temperatures, as
shown in Figure 4. This is most likely related to the organic acids condensing together with water and
making the condensed water even more acid. A similar trend is known for sweet TLC [1]. According to
Pugh et al. [20] the presence of organic acids resulted in higher general corrosion rates and did
therefore cause a more uniform (less localised) corrosion morphology.

Page 14 of 18
Precipitation of iron sulphide is fast even at low temperature [23], opposite to iron carbonate
precipitation which is known to be slow, particularly at low temperatures [54]. This may, at least partly,
explain the much less dependency of condensation rate for sour TLC, since there will be little or no
supersaturation iron of the condensed water. It has also been indicated that the pH of the condensed
water may be important since it may affect the type (or morphology) of iron sulphide that forms [23]. It
should also be mentioned that fast precipitation kinetics will give higher removal rate of alkaline
- 2-
species (HS , S ) and consequently a lower pH than slow precipitation kinetics. A “two step”
mechanism for iron sulphide precipitation has been suggested [7,55], where a thin mackinawite layer
forms rapidly on the steel surface with another layer forming on top of this. The type of iron sulphide in
the second layer depends on the experimental conditions.

Only a limited number of papers have studied TLC under slightly sour conditions [45,50,51,56]. The
results indicate that the presence of H2S reduces TLC since it forms a more protective layer on the
corroding surface than iron carbonate alone. However, the iron sulphide layer offers only partial
protection so that TLC is just reduced, not completely avoided. The resulting corrosion product is a
combination of iron carbonate and iron sulphide depending on the conditions (i.e. H2S:CO2 ratio and
temperature). Slightly sour TLC seems to be mechanistically closer to sweet TLC, so the corrosion
rate is proportional to the condensation rate.

Mitigation of sour TLC follows largely the principles of sweet TLC. A common mitigation method has
been to implement pipeline operation procedures that prevent stratified flow. These procedures are
frequently combined to the injection of corrosion inhibitor or pigging with batch corrosion inhibitor.
Many operators also carried out a multiphase flow study on the whole pipeline system, including
topographic data, to identify areas at risk and intensified inspection of the most susceptible areas.
Volatile inhibitors (gas phase inhibitors) have been developed but it is not known how much they are
used.

The number of published sour TLC cases is remarkably low compared to the high number of sour
pipelines that have been operated for the last 50 – 60 years [19]. As an example, totally 39 sour gas
pipeline failures were reported for Canada in 2004, and 15 were related to internal corrosion, but none
were related to sour TLC [57]. This indicates that sour TLC is not a common problem in practice.
However, the experimental results show a relatively high TLC rates over a relatively wide temperature
range. It was even claimed that sour TLC is usually so low that no mitigation is needed [58].
Nevertheless several field failures have been documented and the problem cannot be neglected from
a pipeline safety perspective.

Since relatively few sour TLC failures have been observed in the field it indicates that the TLC rates in
the field must be even lower than in the lab, possibly due to a gradual reduction corrosion rate with
time, for which the laboratory experiments are too short to show. It is also, likely that the early reports
of sour TLC and mitigation methods have made a general awareness in the early years of sour
pipeline operation and thus made it possible for operators to implement preventive measures.

7 Conclusions
• Sour TLC is mechanistically different from sweet TLC.
• Condensation rate is a much less important parameter for sour TLC than for sweet TLC
• The TLC rate is strongly affected by the steel temperature, most likely because it affects the
protectiveness of the iron sulphide films that forms. Apparently steel temperatures around 20 -
30°C gives the highest TLC rates.
• The presence of organic acids can further increase the sour TLC rate
• When considering the large amount of sour gas pipelines that are and have been in operation
during the last 50 – 60 years, sour TLC is a relatively rare phenomenon. However, field
failures with TLC do occur and from a safety point it is important to understand the
mechanisms.

Page 15 of 18
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