CORROSION ENGINEERING
About the Correlation Between Crude Oil
Corrosiveness and Results From Corrosion
Monitoring in an Oil Refinery
Philipp Schempp,‡,* Karsten Preuß,* and Micha Tröger*
ABSTRACT
Corrosion monitoring is an important tool to control and
predict corrosion in piping, vessels, furnace tubes, etc. of
chemical plants. This study shows results from ultrasonic
wall thickness measurements in crude oil and high vacuum
distillation units of a German crude oil refinery. Wireless
ultrasonic sensors were installed on the external surface of
selected piping to continuously monitor internal corrosion. The
focus was on high-temperature corrosion (>220°C), which is
mainly caused by sulfur and acid components that are
present in crude oil and its fractions. Two corrosion parameters
were calculated: corrosion rates (from wall thickness over
time) and the change in shape of the ultrasonic back wall
reflection over time (PSI). This latter parameter is derived from
the ultrasonic waveform measured by each sensor. Both cor-
rosion parameters showed different results regarding corro-
sion activity over time. This was explained by variations in
process temperature that significantly influence wall thick-
ness readings but not PSI. Furthermore, only limited correlation
was found between corrosion and flow velocity/internal
pressure. Finally, three crude parameters (total sulfur content,
total acid number, and mercaptan content) were obtained
from crude run history and compared to measuring data. Sig-
nificant correlations between shape change and crude
parameters were found, dependent upon sensor location/
corrosion loop.
Submitted for publication: October 14, 2015. Revised and accepted:
April 6, 2016. Preprint available online: April 6, 2016, http://dx.
doi.org/10.5006/1940.
‡
Corresponding author. E-mail: p.schempp@shell.com.
*
Rheinland Refinery, Shell Deutschland Oil GmbH, Godorfer
Hauptstraße 150, 50997 Cologne, Germany.
ISSN 0010-9312 (print), 1938-159X (online)
CORROSION—Vol. 72, No. 6 16/0000123/$5.00+$0.50/0 © 2016, NACE International
KEY WORDS: corrosion monitoring, corrosion rate, high-
temperature corrosion, mercaptans, naphthenic acid corrosion,
oil and gas, sulfidation, ultrasonic testing
INTRODUCTION
During the last decades, cost pressure on oil refin-
eries has grown continuously, particularly in Europe,
where consumption of crude oil products is de-
creasing more and more.1 As a consequence, oil refin-
eries are looking for ways to increase their margin,
and reducing crude oil costs is an important key factor.
These costs can account for about 80% of the total
refinery expenditures.2 One possible way to cope with
this challenge is to purchase cheaper crudes on the
global markets, such as crudes with elevated sulfur
content and/or acidity. These “opportunity crudes”
are, however, often difficult to process owing to their
increased tendency for corrosion, fouling, coking, and
unfavorable boiling point ranges. Furthermore, one
corrosion issue per week worldwide occurs statisti-
cally that leads to a severe incident such as sudden
leakages, e.g., resulting from pipe ruptures.3 These
facts emphasize the need for corrosion control in pet-
rochemistry, where corrosion monitoring is one im-
portant approach to maximize equipment integrity.
Other than traditional techniques such as, e.g., in-
trusive weight loss coupons, new wireless sensors were
developed in the last years. They monitor pipe or
vessel wall thickness and, thus, corrosion online by
ultrasonic testing (UT). There is, however, little ex-
perience with this new monitoring approach. Open
literature provides few articles about the general
843
CORROSION ENGINEERING
sensor technique, its advantages, and typical measur-
ing data.4-8 This study aims to discuss not only
advantages and challenges of this new technique by
focusing on measuring data but also its correlation to
empirical data and crude run history of an oil refinery.
One important question is, for instance, if measured
corrosion can be linked to crude oil parameters that
represent the corrosion potential such as total sulfur
content or total acid number (TAN). If the UT sensor data
can be used to predict corrosion for a certain crude oil
diet, this would be an important step forward to reduce
inspection and maintenance costs. Also, opportunity
crudes could be processed by a safer and more eco-
nomic manner.
BACKGROUND
High-Temperature Corrosion in Crude Distillation
Unit and High Vacuum Unit
The first units of each oil refinery are crude
distillation unit (CDU) and high vacuum unit (HVU)
where crude oil is distilled in two steps (at atmo-
spheric pressure and at vacuum) into its major frac-
tions. There are a variety of corrosion mechanisms
that play a role in these units and that usually have a
very different appearance at different locations. This
study focuses on the following main high-temperature
corrosion mechanisms in CDU and HVU hydrocarbon
streams.
Sulfidation — Sulfidation or sulfidic corrosion is the
reaction of steel and other alloys with reactive sulfur
compounds such as H2S from the fluid (e.g., crude oil) in
high-temperature environments.9 Being observed at
temperatures above approximately 260°C, sulfidation
corrosion rates increase with temperature, peaking at
approximately 450°C. Both carbon steel/low-alloyed
steel and stainless steel can be affected by this
mechanism, which usually results in general wall
thickness reduction. The modified McConomy curves
predict the influence of temperature, disclosing that
increasing Cr and Ni alloying contents in the bulk
material can reduce corrosion rates significantly.10-11
This relation was extended to hydrogen/H2S-
containing environments by the modified Couper-
Gorman curves.11-12
Dependent upon bulk material, flow conditions,
and chemical composition of the fluid, the reaction
product iron sulfide (FeS) can form a stable, protective
sulfide scale eventually reducing the corrosion rate. But
this passive layer can be damaged or even removed
completely, which is influenced by flow conditions,
temperature, content/type of sulfur compounds and
naphthenic acids, and hydrogen/H2S content, etc.
Moreover, a further influencing factor is the flow
regime (e.g., two-phase and/or turbulent flow) that can
cause localized sulfidation.
Influence of Mercaptans — In addition to H2S,
mercaptans (or “thiols”) are considered to be some of
844
the most reactive and, hence, most corrosive sulfur
species. Their concentration depends strongly upon
crude oil and boiling point range. Experiments showed
that mercaptans are most reactive somewhere be-
tween 235°C and 300°C where they can accelerate
sulfidation. Thus, particularly middle distillate loops,
such as light and heavy gas oil, are susceptible to
mercaptan corrosion. A minimum mercaptan con-
centration of 100 ppm to 200 ppm was found to be
necessary to enable mercaptan corrosion.13 Fur-
thermore, it was suggested that corrosion rates depend
upon mercaptan type and that mercaptans start to
decompose at temperatures between 300°C and
400°C.13-14
Naphthenic Acid Corrosion — Each crude oil con-
tains naphthenic acids, where TAN is a common
measure of general acidity. Increasing TAN, tempera-
ture, and flow velocity/turbulences and decreasing
alloy contents of the bulk material accelerate
naphthenic acid corrosion (NAC), which is often found
to be very localized.9 This corrosion mechanism usually
occurs at temperatures > 220°C and TAN > 0.5.15 The
limit can be reduced to TAN > 0.1 for sweet, low sulfur
crudes that have too little sulfur available to form a
stable FeS scale.16 As a consequence, it was stated that
TAN (and thus the overall acid content) is far too
rough to evaluate the crude oil’s tendency to cause
NAC.17-18 Molybdenum contents > 2% in the bulk
metal may restrict NAC corrosion rates,9 and it is ar-
gued that increasing sulfur contents can inhibit NAC
as a result of FeS scale formation.19 Furthermore, the
reactivity of each naphthenic acid, its distribution
over boiling point range, and the influence of its mo-
lecular weight on its corrosion behavior are still under
discussion.18-19 For instance, experiments showed that
naphthenic acids start to decompose at temperatures
> 350°C.2 As a result, NAC is difficult to predict and thus
observed frequently in CDU and HVU, particularly in
furnace tubes and transfer lines between furnace and
distillation column.16 Several pipe ruptures in CDU
or HVU furnaces, for instance, were caused in the past
by localized NAC. Those incidents can easily result in
production losses of tens of million dollars.
The above chemical corrosion mechanisms can
be further increased by erosion (by solid particles) or
erosion-corrosion (e.g., for very high flow velocities
and/or droplet impingement). Both mechanisms impair
the FeS protective scale and accelerate sulfidation
and naphthenic acid corrosion, in many cases very
locally. Particularly, transfer lines are susceptible to
these effects because of the presence of high flow ve-
locities and two-phase flow. To control and limit high-
temperature corrosion, materials and corrosion engi-
neers usually consider one or several of the following
approaches:
• Materials selection (by applying, e.g., corrosion
resistant alloys [CRAs])
• Coatings (to protect the bulk material from the
corrosive attack)
CORROSION—JUNE 2016

• Corrosion allowance (by increasing nominal
wall thickness to allow a certain degree of
corrosion)
• Corrosion inhibition (by injecting chemicals
that, e.g., neutralize corrosive fluids)
• Process adjustments (by limiting parameters
such as sulfur content, TAN, or temperature)
• Corrosion monitoring (by applying, e.g., non-
destructive testing [NDT] to control the remaining
wall thickness)
This paper focuses on the latter approach (cor-
rosion monitoring).
Corrosion Monitoring
There are different approaches in the petro-
chemical industry to monitor these corrosion mechan-
isms, where the most important ones are the
following:
Weight Loss Coupons — The use of corrosion cou-
pons is the oldest and simplest method to estimate
wall losses from corrosion.20 A metallic corrosion cou-
pon is weighed and introduced to the corrosive en-
vironment (e.g., inside of a pipe) where it remains for a
certain time (e.g., some weeks) before being removed
and re-weighed. From the difference in weight, an av-
erage corrosion rate can be calculated to obtain an
estimate of the corrosion rate for the surrounding pipe/
vessel.21 As a result of its simplicity, the method can
be applied to many corrosion mechanisms and, thus, to
different units of an oil refinery.22
Electrical Resistance Probes — Electrical resistance
(ER) probes are also introduced into the process
stream where they start to corrode. The resulting
thickness reduction of the probe’s cross section is
proportional to an increase in its electrical resistance,
which is measured by an instrument outside of the
pipe/vessel. This allows calculation of corrosion rates
that are usually monitored online, which is a clear
advantage in comparison to only a few values per year
from weight loss coupons. Furthermore, ER probes
can be applied to almost all corrosion environments23
and they can have a high resolution down to tenths of
nanometers.24 They can be used, for instance, to eval-
uate the effectiveness of a chemical corrosion inhib-
itor in the atmospheric distillation overhead system.3,25
The limits of the ER technique are, however, that they
are intrusive and that the measurements are very
local.24 Also, ER probes have to be replaced when the
maximum corrosion depth is exceeded (usually between
0.05 mm and 0.6 mm, dependent upon probe
geometry23).
Linear Polarization Resistance Probes — Linear po-
larization resistance (LPR) is an electrochemical
technique that allows determining corrosion rates in
real time. Such intrusive probes usually consist of
three electrodes that measure the electrochemical cor-
rosion potential in corrosive environments. For this
reason, the method can only be applied if an electrolyte
CORROSION—Vol. 72, No. 6
CORROSION ENGINEERING
(such as, e.g., water) is present, being restricted to
electrochemical corrosion.26 Hence, LPR cannot be used
for corrosion monitoring in hydrocarbon streams in
CDU and HVU where temperature is above the water
boiling point.
Pulsed Eddy Current Method — Pulsed eddy current
(PEC) probes were introduced in 200127 and are
attached to the pipe’s external surface where they use a
pulsed magnetic field. This generates eddy currents
in the wall, which again induce voltages in the receiver
coil of the PEC probe. This signal is used to calculate
the remaining wall thickness, which is used as an
indicator of corrosion, but it is not as accurate as, e.g.,
UT wall thickness measurements. PEC probes are
portable and can thus be used at several corrosion
monitoring locations (CMLs);28 however, good accessi-
bility for manual data collection is needed. The
measuring system withstands metal temperatures up to
550°C but is restricted to conductive metals (carbon
and low-alloyed steel)29 and cannot be used as an online
monitoring system.
Field Signature Measurements — Field signature
measurements (FSM) involve a network of sensing
pins or electrodes that are mounted on the external
surface of a pipe or vessel producing an electrical field
in the wall.24 After an initial voltage measurement,
subsequent changes in electrical field pattern are
detected and compared against the initial measurement
to detect local changes in wall thickness (accuracy:
±0.01 mm24). The comparably large measuring
area of FSM (e.g., an entire pipe elbow) allows
detecting both general wall loss and localized corrosion.
Owing to its complexity and thus elevated installation
and operational costs, such measurements are
usually restricted to a few locations within a
chemical plant where corrosion hot spots are
expected.24
Ultrasonic Testing — Non-intrusive UT measure-
ments are the fastest method to reliably measure wall
thickness and thus to monitor general wall loss. The
wall thickness is calculated from the reflection of the
ultrasonic signal at both external and internal surface.
But the exact measuring location usually varies
during periodic manual inspection, which limits
accuracy of corrosion rates. To reduce this uncer-
tainty, some systems monitor both measurement and
location.30 A further approach to increase the accu-
racy of several measurements at one location is to
install permanent UT sensors that remain at the
corresponding CML for a longer period such as
months or even years.5,8 In comparison to FSM, UT
sensors provide local measurements as a result of
their comparably low measuring area (usually some
cm2), which makes detection of local corrosion
phenomena difficult. An important advantage of UT
sensors is that many more CMLs can be monitored
by simple UT sensors for the same cost as
by FSM.6
845
CORROSION ENGINEERING

TABLE 1 With increasing pipe diameter (from 150 mm to

Pros and Cons of Corrosion Monitoring Techniques 800 mm), sensors were also attached at elbow inlet
Online Costs (10° position) and apex (45° position). As a result, many
Technique Intrusive Resolution Measurement per CML pipe elbows and some T-pieces of this CDU/HVU
complex are now monitored continuously for corrosion.
Weight loss Yes Low No Low
coupons
The pipe material was carbon steel at CMLs in loops 2,
ER probes Yes High Yes Low 3, and 4 and 5%Cr-0.5%Mo steel (ASTM A355, P5/
LPR probes Yes High Yes Medium X12CrMo5) at CMLs in loops 1, 5, and 6 (see Table 2).
PEC method No Medium No Medium To protect the electronics in the orange sensor head
FSM No High Yes High
from the heat of the near pipe, heat shield plates were
UT No High Yes Medium
positioned on the sensor guide waves, which were at-
tached afterward to the insulation. The measuring
frequency of all sensors was chosen to be twice a day to
Table 1 summarizes pros and cons of the dis- allow increased battery life, also taking into account
cussed corrosion monitoring methods, disclosing that that such wall thickness measurements are usually
UT sensors provide important advantages for corro- mid- to long-term analyses.
sion monitoring in an oil refinery. The UT signal travels from the sensor head
through two stainless steel guide waves to the sensor
PROCEDURES foot where it enters the pipe wall. It is then reflected
particularly on both external (first echo) and internal
Refinery Setup (second echo) pipe surface. The corresponding UT
waveform (or “A-scan”) is shown in Figure 2, empha-
As a result of their suitability and flexibility, an
sizing two important parameters that are recorded by
increased number of ultrasonic sensors were installed
the software for each sensor:
to monitor high-temperature corrosion in CDU and
HVU. All sensor locations were selected on the basis of • Wall thickness
○ Calculated by time-of-flight analysis from
three parameters:
• Inspection history, particularly regarding for- the interval between both main echoes that are
mer UT and radiographic testing (RT) measure- detected by the “EP” (envelope peaks)
ments at the corresponding CMLs (to focus on approach;
○ Used to calculate corrosion rates (by
corrosion hot spots);
• Corrosion rates, calculated by a simulation trending wall thickness over time) as a mea-
tool that predicts high-temperature corrosion on sure of general wall loss at the corre-
the basis of pipe/vessel geometry, fluid, pro- sponding CML.
cess conditions, and crude run history; and • Shape of back wall reflection
○ Compared to the back wall echo shape from
• Accessibility of each CML (to reduce installa-
tion and maintenance efforts). previous and subsequent measurements
As a result, pipe of the CDU and HVU systems (= change in shape of back wall reflection)
discussed next were selected for the installation of such and interpreted as a measure of change in
sensors. roughness of the internal surface;
○ Used to calculate “PSI” (Permasense† shape

indicator) at the corresponding CML.

Online Wall Thickness Measurements
Permasense† UT sensors were mounted with
their H-shaped foot on a pair of threaded studs that had
been welded on the pipe’s external surface by a
drawn-arc stud welding process (see Figure 1[a]). The
challenge here was to do this while the pipe was in
service at temperatures between 250°C and 410°C.
Preceding welding procedure qualification report,
welding procedure specification and selection and ex-
amination of specialized welders ensured maximum
safety. This eventually allowed minimization of the
turnaround scope. Furthermore, manual NDT mea-
surements (UT + RT) were executed at each sensor
location to check the actual wall thickness prior to
welding. Ultrasonic sensors were installed, particularly
at pipe elbow outlets (in the 80° position in Figure 1[b]).
†
Trade name.
It is important to understand the difference be-
tween both parameters. Note that sulfidation usually
leads first to a slight increase in surface roughness.
This effects initiates at a very low order of magnitude
such as micrometers or even nanometers. After some
time, surface roughening accumulates and results in
measurable wall thinning, from which one can cal-
culate corrosion rates. The dimensionless parameter
PSI was designed to describe the first stage (surface
roughening) by focusing on the second echo of the UT
waveform (see Figures 2 and 3). Accordingly, the
sensor software analyzes the shape of this echo over
time. Figure 3 shows an example of one sensor,
revealing how significantly the echo’s shape can change
(here: during 75 d). Remember that this second peak
represents the appearance of the measuring area on the
pipe’s internal surface (such as the first peak

846 CORROSION—JUNE 2016

 CORROSION ENGINEERING

(a) (b)

Heat H-shaped
shield foot
80°

Sensor head
(electronics)

45°

50 mm
10°

FIGURE 1. Ultrasonic wall thickness sensor (a) and CMLs (corrosion monitoring locations) where such sensors were
attached (b, black arrow indicates flow).

represents the external surface). Even small degrees of sensitive to detection of even low degrees of corrosion,
corrosion roughen the internal surface and change and wall thickness can indicate elevated corrosion
the shape of the second UT echo. Moreover, Figure 3 activity.
shows that wall thickness did not change in this Each PSI value was calculated by the UT software by
example, which is shown by the distance between both analyzing 60 different UT measurements/waveforms.
main peaks that remained constant during 75 d. The With a measuring frequency of twice a day, all PSI values
shape of the back wall reflection is thus a parameter were thus based on data from 30 d. Furthermore,
each PSI value was calculated from 30 preceding and 30
subsequent UT waveforms. This means that PSI data
TABLE 2 were always first available with a “delay” of 15 d (for a
Corrosion Loops in CDU/HVU Where Ultrasonic Sensors measuring frequency of twice a day). The exact al-
Were Installed(A) gorithm used to compare the back wall reflection for
Boiling Process
different UT waveforms in order to calculate PSI was
Point Range Temperature developed experimentally by the company in the last few
Loop (°C) at CML (°C) Material years. It is unknown to the end-user and is thus not
subject of this publication.
1) Crude oil 143-FBP 360 5%Cr-0.5%Mo
steel (P5) High PSI values are related to high changes in
2) Kerosene 123-210 250 Carbon steel roughness indicating elevated corrosion on the internal
3) Gas oil (refl.) 272-291 317 Carbon steel pipe surface and vice-versa. Note that PSI is not
4) Gas oil 210-330 275-285 Carbon steel influenced by process temperature because tempera-
5) LR 340-FBP 410 5%Cr-0.5%Mo
steel (P5)
ture does not influence the back wall signal’s shape.
6) HVGO 473-484 275-300 5%Cr-0.5%Mo In contrast, wall thickness is influenced by temperature
steel (P5) because the distance between both main peaks of the
(A)
FBP: final boiling point; refl.: circulating reflux; LR: long (atmo- UT waveform increases with increasing temperature.
spheric) residue; HVGO: heavy vacuum gas oil. This makes PSI an additional, very sensitive

UT 1st information:
amplitude wall thickness

2nd information:
shape of back wall reflection (2nd echo)

Signal envelope

Time
1st echo:
external surface 2nd echo:
internal surface

FIGURE 2. Typical UT (ultrasonic testing) waveform (= A-scan).

CORROSION—Vol. 72, No. 6 847

CORROSION ENGINEERING

UT flexibility during the last years (recall Introduction).

amplitude In many cases, crude diets and thus parameters such
Waveform on day 1 as chemical composition, viscosity, flow conditions, or
yields (in % per boiling point range) can change sig-
nificantly within days or even hours. As a consequence,
high-temperature corrosion phenomena in CDU and
Time
HVU vary over time and “corrosion hot spots” can
change their severity and location. Hence, it is im-
portant to monitor crude parameters that contribute to
high-temperature corrosion. In this study, the fol-
lowing crude parameters were obtained from the com-
pany’s crude assay database for the corrosion loops
Waveform on day 75 listed in Table 2:
• Total sulfur content (determined according to
ASTM D2622);
Time • TAN (determined according to ASTM D974);
• Mercaptan content (determined according to
ASTM UOP163).

FIGURE 3. Change of UT waveform appearance over time (for one RESULTS AND DISCUSSION
sensor). Note the change in shape of the second peak.
Crude Parameters
Figure 4(a) shows average values (9 month) of
measuring value that complements conventional wall total sulfur content and TAN for six different CDU and
thickness readings.
It is of note that the sensor’s “footprint” (mea-
suring area) is approximately 1 cm2, which emphasizes (a) 1.5 1.5
that localized corrosion such as pitting cannot be Total sulfur content
detected reliably with such sensors. In other words, the TAN

TAN (mg KOH/g)

S Content (wt%)

sensor network should have a sufficient amount of 1.0 1.0

sensors to allow reliable and repeatable measurements
that show the potential for high-temperature corro-
sion in the whole pipe. Local effects owing to, e.g.,
0.5 0.5
turbulent flow or droplet impingement might only be
evaluated with a very high number of sensors, which
increases costs. On the other hand, only a few sensors
0.0 0.0
are needed to monitor general wall loss in a comparably
l l
oi e oi LR O
)

large area of a petrochemical plant. en

fl.

G
e as 5.
re

ud os HV
l(

After installation, the sensors automatically r er G

4. 6.
oi

1.C .K
as

build a self-healing wifi network and connect to gateway 2

G
3.

(wifi antenna) and server. Software records UT

waveform and wall thickness of each sensor, allowing
(b) 30 1. Crude oil
further data processing to calculate corrosion rates
2. Kerosene
Mercaptan Content (ppm)

and PSI. Thus, corrosion engineers can check these 25 3. Gas oil (refl.)
corrosion parameters at their office computers at any 4. Gas oil
5. LR
time, which makes the UT sensors a smart online cor- 20 6. HVGO
rosion monitoring tool. Furthermore, it should be
noted that all sensors are wireless. Their intrinsically 15
safe batteries can last for up to 7 y, dependent upon
10
measuring frequency and stability of the sensor net-
work. Also, these sensors withstand metal surface 5
temperatures up to 600°C, which again highlights the
flexibility of the measuring system. 0
1 2 3 4 5 6 7 8 9 10
Time (month)
Crude Parameters
Today, it is common practice that crude oil diets FIGURE 4. Mean values (9 month) of total sulfur content vs. TAN (a)
processed in oil refineries vary in very short time and mercaptan content over time in different loops of CDU and
HVU (b).
intervals as a result of the increasing need for crude

848 CORROSION—JUNE 2016

 CORROSION ENGINEERING

HVU loops. Accordingly, sulfur content (0.82 wt%) (a) 22.1 Corrosion rate: 0.07 mm/y 280
and TAN (0.28 mg KOH/g) of the crude oil diet were
comparably low. Both parameters can reach levels of

Wall Thickness (mm)

several wt% (S content) or several mg KOH/g (TAN). This 22.0 265

Temperature (°C)
suggests that particularly sweet, low TAN crudes were
processed during this period of 9 months. Furthermore,
the diagram reveals a correlation between sulfur 21.9 250
content and TAN. The mean sulfur/TAN ratio was
measured to be > 2.0, except for kerosene (1.2) and
heavy vacuum gas oil (HVGO, 1.7). Low ratios, < 1.0, can 21.8 235
be interpreted as an indication of an increased sus- Wall thickness
ceptibility to NAC.16 Accordingly, increased NAC was Temperature
found elsewhere in CDU and HVU of an oil refinery 21.7 220
0 20 40 60 80 100
while processing very sweet, low TAN crude oils such as
Time (d)
WAF (West African) crudes that can have sulfur/TAN
ratios even below 0.5.16 As a result (from Figure 4[a]), (b) 22.1 Corrosion rate: 0.07 mm/y 200
sulfidation is expected to be the dominating corrosion
mechanism (compared to NAC).

Wall Thickness (mm)

To give an overview of how such crude parameters 22.0 150
vary over time, Figure 4(b) shows the mercaptan
content during 10 months for the same CDU and HVU

loops. In accordance with the total sulfur content (see
Figure 4[a]), the mercaptan content was also found to be
comparably low (< 25 ppm), indicating a low risk for
mercaptan corrosion.13 It should be noted that there is a
strong variation of mercaptans over time, but not for
the total sulfur content. This emphasizes that each
crude oil usually has a very different mercaptan
concentration, independent of total sulfur. As known
from experiments,13 Figure 4(b) shows elevated
mercaptan contents for middle-distillates (such as gas
oil) and low mercaptan contents for higher tempera-
tures (here: LR [long (atmospheric) residue] and HVGO).
This is a result of the boiling point range distribution
of mercaptans and likely also a result of their decom-
position at temperatures > 300°C.13-14
Wall Thickness, Corrosion Rates, and PSI
A typical plot of wall thickness vs. time (110 d) is
shown by Figure 5(a) for one sensor that was installed in
the kerosene system. The corresponding graph
reveals very low wall thickness data scattering of
±0.01 mm. This is very accurate in comparison to
manual UT thickness measurements where it is usually
almost impossible to repeatedly measure at exactly
the same position. Consequently, inaccuracy can in-
crease by 1 to 2 magnitudes. The other curve in
Figure 5(a) is temperature data that was measured with
a nearby temperature sensor. It is obvious that both
curves have a very similar shape, disclosing a strong
dependence of measured wall thickness on process
temperature. Accordingly, changes in temperature of
only 3 K influence wall thickness readings signifi-
cantly. This makes calculation of corrosion rates inac-
curate, particularly if they are low. The corrosion rate
indicated in Figure 5(a) (0.07 mm/y) corresponds to the
slope of the linear fit of the wall thickness–time curve
and was not compensated for temperature.
PSI (-)
21.9 100
21.8 50
Wall thickness
PSI
21.7 0
0 20 40 60 80 100
Time (d)
FIGURE 5. Influence of process temperature on UT wall thickness
readings (a) and relationship between wall thickness and PSI (b) for
sensor in kerosene loop.
The propagation velocity of the UT signal depends
upon metal temperature. Increasing temperatures
reduce this velocity, increasing the distance between
both main peaks in Figure 2. This is interpreted by the
software as increasing wall thickness, which is, of
course, not realistic. Furthermore, parameters such
as insulation conditions, surrounding temperature,
etc., are different at each sensor location, resulting in
a different susceptibility of each sensor to temperature
variations. As a consequence, “manual” or automatic
compensation for temperature by the sensor software
(by applying, e.g., a general correction factor) is dif-
ficult. Therefore, the sensor producer recently released a
new sensor generation that includes a thermocouple.
The software then compensates all wall thickness
readings for temperature, which is intended for in-
creasing the measuring system’s accuracy. The sensors
of this study do not have such a thermocouple be-
cause they had been installed earlier.
Figure 5(b) shows the comparison between wall
thickness and PSI for the same UT sensor. Interestingly,
PSI data scatter very little. Furthermore, wall thick-
ness and PSI developed very differently over time. Ac-
cordingly, PSI indicates a strong increase in

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CORROSION ENGINEERING

corrosiveness between days 40 and 60, while the real (a) 100 150
wall thickness likely did not change significantly if ∅ Corrosion rate UT
∅ Corrosion rate McConomy
one considers the temperature influence from Figure 5(a).

∅ CR (normalized, %)
80 ∅ PSI 120
A possible reason for this behavior (change in crude
corrosiveness) is discussed in detail in the Correlation

∅ PSI (-)
60 90
Between PSI and Crude Parameters section.
It should be noted here that changes in internal 40 60
roughness (that are actually used to calculate PSI) can
also slightly influence wall thickness readings. This 20 30
was observed in a few cases where a small but sharp
change in wall thickness by up to 0.1 mm was 0 0
l l
measured. This observation could not be explained by a oi ne oi LR O

)
fl.
de e as 5. VG

(re
change in temperature but by PSI, which was at u os G H
Cr er 4. 6.

l
oi
maximum at that moment. Strong and sudden changes 1. .K

as
2

G
in internal roughness (high PSI) can smear the shape

3.
of the second UT echo, which modifies the exact peak
(b) 8 120
location of this echo (recall Figure 3). This is inter- ∅ Corrosion rate UT ∅ PSI
preted by the software as slight but sharp change in wall
20% of all 39% of all 41% of all
thickness, which again affects overall corrosion rate.

∅ CR (normalized, %)
6 sensors sensors sensors 90
The extent of this effect was determined to be very
low (< 5%) by comparing all wall thickness data to 84

process temperature. Affected data was excluded
and not considered for the calculation of corro-
sion rates.
The two main effects can be summarized as
follows:
• Process temperature (on wall thickness read-
ings but not on PSI),
• Internal roughness (on wall thickness readings
and PSI).
Accordingly, PSI can be used as a first, very
sensitive indicator of corrosion (in the form of changes in
internal roughness), where wall thickness/corrosion
rates indicate subsequent wall thinning restricted by
temperature and, to some degree, by roughness. Also,
data trending over time is more accurate for PSI than for
corrosion rates.
Mean Values for Corrosion Rates and PSI
In a second step, average values for corrosion rate
and PSI data from 9 months were calculated and
compared for six different corrosion loops (see
Figure 6[a]). Note that all measured average corrosion
rates (UT) were generally found to be low in com-
parison to rates that are typically observed in these
CDU/HVU corrosion loops of an oil refinery. For gas
oil reflux and long residue, the corrosion was even
measured to be zero. The diagram compares mea-
suring values to theoretical corrosion rates that were
calculated from modified McConomy curves on the
basis of Table 3. Therefore, temperature and material
(recall Table 2) were used to determine corrosion rates
for 0.5 wt% sulfur content, which was adjusted by
a multiplier to obtain a theoretical corrosion rate for
the corresponding sulfur content. Note that all corro-
sion rates in Figure 6(a) and Table 3 are normalized
values, which means that absolute values (in mm/y)
were transformed into relative values (in %).
∅ PSI (-)
4 66 60
3.5%
2 2.4% 30
2.1%
20
0
0
10 45 80
CML (degree)
FIGURE 6. Mean values (9 month) for normalized corrosion rate (CR)
and PSI in different loops of CDU and HVU (a) and at different pipe
elbow CMLs for all sensors (b).
As a result, no correlation was found between
measurement (UT) and prediction (McConomy), see
Figure 6(a). To explain this, it should be noted that
hydrogen or H2S were assumed to be absent
(McConomy curves). Furthermore, this comparison
points out that parameters such as type and distri-
bution of sulfur compounds/naphthenic acids or flow
conditions, etc., influence high-temperature sulfida-
tion significantly. They are, however, not considered by
the McConomy approach. This challenges the com-
parison of measured to theoretical corrosion rates.
Moreover, it appears from Figure 6(a) that theoretical
McConomy corrosion rates may be overly conservative
for the corrosion observed in this study.
Figure 6(a) also shows PSI values that can range
by definition from 255 (highest corrosion) to 0 (no cor-
rosion). Hence, the presented PSI values are compa-
rably low (< 100), which matches with the (low) level for
UT corrosion rates in the same diagram. Further-
more, PSI correlates to the pipe material in Figure 6(a):
PSI is lowest for loops 1, 5, and 6 in which 5 wt% Cr
steel was used instead of carbon steel as in the other
loops. As both PSI and UT corrosion rates are based

850 CORROSION—JUNE 2016

 CORROSION ENGINEERING

TABLE 3
Data for Determination of McConomy Corrosion Rates on the Basis of McConomy10 and Gutzeit11
Mean Process Corrosion Rate for McConomy
Temperature Total Sulfur 0.5 wt% Sulfur(A) Corrosion Rate Corrosion Rate(A)
Loop at CML (°C) Content (wt%) (normalized) Multiplier (normalized)

1) Crude oil 360 0.82 4.3% 1.13 4.8%

2) Kerosene 250 0.02 9.6% 0.20 1.9%
3) Gas oil (refl.) 317 0.22 60.7% 0.72 43.7%
4) Gas oil 280 0.21 23.9% 0.71 17.0%
5) LR 410 1.31 67.9% 1.37 93.0%
6) HVGO 288 1.02 10.0% 1.25 12.5%
(A)
Dependent upon temperature and material according to McConomy10 and Gutzeit.11

on data from a large number of sensors, one can con-
clude that the crude oil diet processed in this period of
time was not very corrosive in the high-temperature
areas of CDU and HVU. Moreover, Figure 6(a) reveals
significant differences between UT corrosion rates and
PSI, although both are measuring data from UT
sensors. It is probable that temperature (which influ-
ences wall thickness and thus corrosion rate, but not
PSI) is the main reason behind this discrepancy. In
other words, PSI values seem to show again a higher
sensitivity to corrosion and thus an increased signifi-
cance compared to corrosion rates.
An interesting comparison is given in Figure 6(b)
that shows average UT corrosion rates and PSI for three
different CML positions on pipe elbows (recall Figure 1
[b]). It is a common belief that the elbow back side (45°
the UT sensors used here collect local measurements on
the one hand, which likely do not fully represent the
corrosion in the whole pipe. On the other hand, the flow
regime usually affects corrosion locally. Examples are
elbow back sides resulting from flow impingement or
locations downstream of reinforced welds that cause
local turbulences. In other words, flow velocity is a key
factor but its effects on high-temperature corrosion
cannot be detected reliably by local measurements.
Interestingly, pressure was observed to correlate to
some degree to corrosion rate (see Figure 7[b]).
(a) 120 24
∅ PSI
100 ∅ Velocity 20

∅ Velocity (m/s)
position) is subject to the highest corrosive attack in 80 16
∅ PSI (-)

each elbow because shear stresses resulting from flow

60 12
impingement are expected to be the highest here.
Figure 6(b) suggests a maximum in corrosion some- 40 8
where between 45° and 80° (elbow outlet). The lowest
corrosion rates and PSI values were measured on the 20 4
10° position, which sounds reasonable. At this point,
0 0
it should be highlighted that, e.g., computational fluid l l
dynamics simulation can give a “corrosion profile” for oi ne oi LR O
)
fl.

de e as 5. VG
re

u os H
l(

er G
such an elbow. This way, corrosion hot spots resulting Cr 4. 6.
oi

1. .K
as

from high local shear stresses that impair the passive 2

G
3.

FeS layer can be found.

(b) 8 24
∅ Corrosion rate
Influence of Flow Velocity and Pressure 7 20
∅ CR (normalized, %)

∅ Pressure
∅ Pressure (bar [g])

As outlined earlier, important key factors for 6

high-temperature corrosion in CDU/HVU are further 16
5
process parameters such as flow velocity and pres-
4 12
sure. An increase in these parameters can result in
increased corrosion, owing to the increase of shear 3
8
stresses at the internal pipe surface. This impairs the 2
FeS protective layer, which facilitates corrosion of the 4
1
bulk metal. Figure 7(a) discloses that no correlation was
0 0
found between average values for flow velocity and l l
oi ne oi LR O
)
fl.

corresponding PSI values. While PSI was highest in e as VG

de 5.
re

u os H
l(

corrosion loops 2, 3, and 4, the corresponding flow er G

Cr 4. 6.
oi

1. .K
as

velocity was very low (and vice-versa for the other loops). 2
G
3.

Similar results were found for the comparison of

mean flow velocity with mean corrosion rates (not FIGURE 7. Mean values (9 month) for PSI and flow velocity (a) and
corrosion rates and pressure (b) in different loops of CDU and HVU.
shown in Figure 7). This observation confirms that

CORROSION—Vol. 72, No. 6 851

CORROSION ENGINEERING

Accordingly, corrosion rates were highest in loops with
elevated pressure, such as the HVGO system. This
suggests that pressure might be a key factor in sulfi-
dation behavior, although, on the other hand, PSI did
not show a clear influence by pressure (not shown in
Figure 7).
Summarizing Figures 7(a) and (b), it should be
pointed out that the UT sensors used here collect local
measurements that have been averaged. Conse-
quently, “local” influencing factors (such as flow veloc-
ity) seem to be dominated by “global” factors such as
metallurgy, chemical composition (e.g., sulfur content),
or pressure.
Correlation Between PSI and Crude Parameters
A very important question is if the UT measuring
data correlates to crude parameters that are related to
sulfidation and naphthenic acid corrosion. Therefore,
measuring data was compared to crude parameters
dependent upon time. As a result of the influence of
temperature and roughness on corrosion rates (recall
the Wall Thickness, Corrosion Rates, and PSI section),
it was impossible to determine accurate corrosion rates
over a small period of time, such as one month. The
dependence on temperature variations and the result-
ing data scattering was simply too high. It was,
however, possible to accurately average PSI values for
each month. These mean values were compared to
monthly mean values for the total sulfur content during
the same 10 months period (see Figure 8). According
to these six graphs (one per corrosion loop), there seems
to exist a clear correlation between PSI and sulfur
content. While both variables were found to have a
minimum somewhere between months 4 and 5,
there was a higher corrosion activity/sulfur content
before and afterward (maximum in months 2
and 9).
Note that, for purposes of clarity, the vertical sulfur
content axis of these six diagrams have different
scales as a result of very different sulfur levels in each
loop (recall Figure 4[a]). This makes the correlation
between PSI and sulfur content quite significant, par-
ticularly for the kerosene loop (Figure 8[b]). Here, the
total sulfur content was just some hundredths of wt%.
The clear correlation of both curves thus emphasizes
(1) the high sensitivity of the UT measuring system and
(2) the relevance of PSI.
The crude oil’s total sulfur content covers many
different sulfur species with very different tendencies for
high-temperature corrosion. For this reason, it was
often stated that such a “general” parameter would not
be appropriate to predict sulfidation. This is
challenged by the results in Figure 8. One should re-
member here that the total sulfur content is com-
parably easy to determine and to monitor in an oil
refinery.
Two other influencing crude parameters (TAN
and mercaptan content) are compared to PSI in different
diagrams (see Figures 9 and 10). Note that the PSI
curves in these two figures are consequently the same,
as shown in Figure 8. Furthermore, the scales of all
TAN axes in Figure 9 were adjusted to different typical

(a) 250 1.5 (b) 250 0.05 (c) 250 0.5

PSI PSI PSI
200 S content 1.2 200 S content 0.04 200 S content 0.4
S Content (wt%)

S Content (wt%)
S Content (wt%)
PSI (-)

0.9 150 0.3

PSI (-)

PSI (-)

150 0.03 150

100 0.6 100 0.02 100 0.2

50 0.3 50 0.01 50 0.1

0 0.0 0 0.00 0 0.0

1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
Time (month) Time (month) Time (month)

(d) 250 0.5 (e) 250 2.0 (f) 250 2.0

PSI PSI PSI
200 S content 0.4 200 S content 1.6 200 S content 1.6
S Content (wt%)

S Content (wt%)
S Content (wt%)

PSI (-)

1.2 150
PSI (-)

150 1.2
PSI (-)

150 0.3

100 0.2 100 0.8 100 0.8

50 0.1 50 0.4 50 0.4

0 0.0 0 0.0 0 0.0

1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
Time (month) Time (month) Time (month)
FIGURE 8. Monthly mean values of total sulfur content and PSI in (a) crude oil, (b) kerosene, (c) gas oil reflux, (d) gas oil, (e)
LR, and (f) HVGO.

852 CORROSION—JUNE 2016

 CORROSION ENGINEERING

(a) 250 0.5 (b) 250 0.03 (c) 250 0.12

PSI PSI PSI

TAN (mg KOH/g)

TAN (mg KOH/g)
200 TAN 0.4 200 TAN 200 TAN

TAN (mg KOH/g)

0.09
0.02
150 150 150

PSI (-)

PSI (-)
0.3
PSI (-)

0.06
100 0.2 100 100
0.01
0.03
50 0.1 50 50

0 0.0 0 0.00 0 0.00

1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
Time (month) Time (month) Time (month)

(d) 250 0.12 (e) 250 1.0 (f) 250 1.0

PSI PSI PSI
TAN
TAN (mg KOH/g)

200 200 TAN 0.8

TAN (mg KOH/g)

200 TAN 0.8

TAN (mg KOH/g)

0.09
150 150 150 0.6
PSI (-)

PSI (-)
0.6
PSI (-)

0.06
100 100 0.4 100 0.4
0.03
50 50 0.2 50 0.2

0 0.00 0 0.0 0 0.0

1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
Time (month) Time (month) Time (month)
FIGURE 9. Monthly mean values of TAN and PSI in (a) crude oil, (b) kerosene, (c) gas oil reflux, (d) gas oil, (e) LR, and (f)
HVGO.

TAN levels of each stream to improve clarity (as also not be used as an appropriate parameter to predict
done in Figure 8). As a result, no clear correlation was NAC.9,16-18
found between monthly TAN and PSI values for all Some correlation was found between mercaptan
systems (see Figure 9), but to some degree for the content and PSI (see Figure 10) that shows mercaptan
kerosene and gas oil loops (Figures 9[b] through [d]). data from Figure 4(b). Interestingly, the highest corre-
As TAN is also a mixture of many acids with very lation was observed for rather “cool” kerosene on the
different properties, it was suggested that TAN could one hand, and high-temperature streams (crude oil, LR,

(a) 250 25 (b) 250 25 (c) 250 25

Mercaptan Content (ppm)

Mercaptan Content (ppm)

Mercaptan Content (ppm)

PSI PSI PSI
200 Mercaptan content 20 200 Mercaptan content 20 Mercaptan content
200 20
PSI (-)

PSI (-)

15 15
PSI (-)

150 150 150 15

100 10 100 10 100 10

50 5 50 5 50 5

0 0 0 0 0 0
1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
Time (month) Time (month) Time (month)

(d) 250 25 (e) 250 25 (f) 250 25

Mercaptan Content (ppm)
Mercaptan Content (ppm)

Mercaptan Content (ppm)

PSI PSI PSI

200 Mercaptan content 20 200 Mercaptan content 20 200 Mercaptan content 20

15
PSI (-)

PSI (-)

15 15
PSI (-)

150 150 150

100 10 100 10 100 10

50 5 50 5 50 5

0 0 0 0 0 0
1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
Time (month) Time (month) Time (month)
FIGURE 10. Monthly mean values of mercaptan content and PSI in (a) crude oil, (b) kerosene, (c) gas oil reflux, (d) gas oil, (e)
LR, and (f) HVGO.

CORROSION—Vol. 72, No. 6 853

CORROSION ENGINEERING

TABLE 4 six different corrosion loops of an oil refinery’s CDU

Correlation Between PSI and Crude Parameters: Percen- and HVU:
tage of Gradients Between Two Months Where Both PSI and • Corrosion rates (as a measure of general wall
Corresponding Crude Parameter Increased (positive gradi- thinning, derived from wall thickness);
ent) or Decreased (negative gradient)(A),(B),(C) • PSI (change in shape of UT back wall signal as
Correlation Between PSI and a measure of change in internal roughness).
Sulfur Mercaptan v The results revealed two particular influencing
Loop Content TAN Content factors:
• Temperature (that influences wall thickness
1. Crude oil, 360°C 75% 38% 75%
2. Kerosene, 250°C 71% 57% 71%
and corrosion rates, but not PSI);
3. Gas oil (CL), 317°C 71% 67% 43% • Internal roughness (that can, when changing
4. Gas oil, 275-285°C 57% 86% 57% significantly, reduce wall thickness measuring
5. LR, 410°C 56% 33% 67% accuracy).
6. HVGO, 275-300°C 56% 22% 67%
v Furthermore, the following results were observed:
Average 64% 63% 50% • PSI seems to provide more accuracy in corro-
59% sion monitoring than wall thickness/corrosion
(A)
Recall Figures 8 through 10. rates, mainly because of uncertainty caused by
(B)
High correlation: 67% to 100%; medium correlation: 34% to 66%; temperature influence;
(C)
and low correlation: 0% to 33%. • No correlation between (measured) UT corro-
CL: circulating reflux; LR: long (atmospheric) residue; HVGO:
heavy vacuum gas oil. sion rates and (theoretical) McConomy corro-
sion rates;
• Clear correlation between pipe material and
corrosion parameter PSI (low PSI for
and HVGO) on the other hand, where the mercaptan P5 material and elevated PSI for carbon steel
content was low (< 16 ppm). Mercaptans are commonly piping);
expected to decompose at temperatures between • No correlation between measuring data and
300°C and 400°C,13-14 which makes this observation flow velocity but increased correlation between
even more interesting. measuring data and process pressure.
Table 4 summarizes the correlation between PSI v Measuring data was compared to three crude
and crude parameters (Figures 8 through 10) by com- parameters from crude run history: total sulfur content,
paring both curves of each diagram. The percentage of TAN, and mercaptan content. The most important
cases where both curves have a positive or negative results from this analysis are as follows:
slope between two neighbored months is given. From • Corrosion rates are too inaccurate to compare
this overview, it becomes clear that both total sulfur them to crude parameters for short periods of
content and TAN seem to be suitable to predict the time such as, e.g., one month;
corrosion that was measured with UT sensors used in • Good correlation between PSI and crude
this study, although the UT corrosion rates were parameters for comparably short periods of time
found to be very low (recall Figure 6[a]). Accordingly, the (1 month), particularly regarding total sulfur
total sulfur content correlates well with high- content and TAN;
temperature corrosion in crude oil and middle distillates • Significant dependence of this correlation
where TAN correlates well with corrosion in gas oil. upon CDU/HVU corrosion loop.
The very low correlation of TAN with PSI values at high v Thus, one important result from this study is the
temperatures (LR and HVGO) is surprising, as TAN observation of correlations between measuring data
was measured here to be highest of all corrosion loops. (PSI) and crude parameters that represent the crude
Naphthenic acids are just some of many different oil diet’s potential for high-temperature corrosion in
acids that are considered in TAN calculation. It is dif- CDU/HVU. This allows improved corrosion prediction
ficult to predict which loop naphthenic acids con- based on measuring data, which is an important step
centrate in but they were already found to cause severe toward safer and more economic processing of op-
corrosion in HVUs.2 Furthermore, good correlation portunity crude oils.
was found between mercaptan content and UT wall
thickness measurements for crude oil, kerosene, LR, ACKNOWLEDGMENTS
and HVGO pipe.
The authors would like to thank the sensor producer
CONCLUSIONS and partner companies for their outstanding support
during commissioning and subsequent service of the UT
v Two parameters were determined from continuous sensors. Furthermore, they appreciate the support of all
wall thickness measurements by wireless UT colleagues from Shell Rheinland Refinery and further
sensors that are installed permanently on piping in Shell sites who contributed to this work.

854 CORROSION—JUNE 2016


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