CORROSION ENGINEERING

About the Correlation Between Crude Oil

Corrosiveness and Results From Corrosion
Monitoring in an Oil Refinery
Do
wn
lo
ad
Philipp Schempp,‡,* Karsten Preuß,* and Micha Tröger* ed
fro
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eri
di
an
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en
pr
es
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o
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ABSTRACT KEY WORDS: corrosion monitoring, corrosion rate, high-
co
rro
temperature corrosion, mercaptans, naphthenic acid corrosion, sio
Corrosion monitoring is an important tool to control and n/
oil and gas, sulfidation, ultrasonic testing
predict corrosion in piping, vessels, furnace tubes, etc. of art
icl
chemical plants. This study shows results from ultrasonic e-
wall thickness measurements in crude oil and high vacuum INTRODUCTION pd
f/7
distillation units of a German crude oil refinery. Wireless 2/
ultrasonic sensors were installed on the external surface of During the last decades, cost pressure on oil refin-
6/
84
selected piping to continuously monitor internal corrosion. The
eries has grown continuously, particularly in Europe, 3/
focus was on high-temperature corrosion (>220°C), which is 23
where consumption of crude oil products is de- 12
mainly caused by sulfur and acid components that are 71
present in crude oil and its fractions. Two corrosion
creasing more and more.1 As a consequence, oil refin- 5/

parameters were calculated: corrosion rates (from wall eries are looking for ways to increase their margin, 19
40
thickness over time) and the change in shape of the ultrasonic and reducing crude oil costs is an important key .p
df
back wall reflection over time (PSI). This latter parameter is factor. These costs can account for about 80% of the by
derived from the ultrasonic waveform measured by each total refinery expenditures.2 One possible way to cope gu
es
sensor. Both cor- rosion parameters showed different results with this challenge is to purchase cheaper crudes on t
regarding corro- sion activity over time. This was explained on
the global markets, such as crudes with elevated 03
by variations in process temperature that significantly sulfur content and/or acidity. These “opportunity Se
influence wall thick- ness readings but not PSI. Furthermore, pt
crudes” are, however, often difficult to process owing e
only limited correlation was found between corrosion and m
to their increased tendency for corrosion, fouling,
flow velocity/internal pressure. Finally, three crude
coking, and unfavorable boiling point ranges.
parameters (total sulfur content, total acid number, and
mercaptan content) were obtained from crude run history and Furthermore, one corrosion issue per week worldwide
compared to measuring data. Sig- nificant correlations occurs statisti- cally that leads to a severe incident
between shape change and crude parameters were found, such as sudden leakages, e.g., resulting from pipe
dependent upon sensor location/ corrosion loop. 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-
Submitted for publication: October 14, 2015. Revised and trusive weight loss coupons, new wireless sensors
accepted: April 6, 2016. Preprint available online: April 6, 2016,
http://dx. doi.org/10.5006/1940.
were developed in the last years. They monitor pipe or
‡
Corresponding author. E-mail: p.schempp@shell.com. vessel wall thickness and, thus, corrosion online by
*
Rheinland Refinery, Shell Deutschland Oil GmbH, Godorfer ultrasonic testing (UT). There is, however, little ex-
Hauptstraße 150, 50997 Cologne, Germany.
perience with this new monitoring approach. Open
literature provides few articles about the general
CORROSION ENGINEERING

CORROSION—Vol. 72, No. 6 ISSN 0010-9312 (print), 1938-159X (online)

16/0000123/$5.00+$0.50/0 © 2016, NACE International 843
sensor technique, its advantages, and typical the most reactive and, hence, most corrosive sulfur
measur- ing data.4-8 This study aims to discuss not species. Their concentration depends strongly upon
only advantages and challenges of this new technique crude oil and boiling point range. Experiments showed
by focusing on measuring data but also its that mercaptans are most reactive somewhere be-
correlation to empirical data and crude run history of tween 235°C and 300°C where they can accelerate
an oil refinery. One important question is, for sulfidation. Thus, particularly middle distillate loops,
instance, if measured corrosion can be linked to such as light and heavy gas oil, are susceptible to
crude oil parameters that represent the corrosion mercaptan corrosion. A minimum mercaptan con-
potential such as total sulfur content or total acid centration of 100 ppm to 200 ppm was found to be
number (TAN). If the UT sensor data can be used to necessary to enable mercaptan corrosion. 13 Fur-
predict corrosion for a certain crude oil diet, this thermore, it was suggested that corrosion rates
would be an important step forward to reduce depend upon mercaptan type and that mercaptans
inspection and maintenance costs. Also, opportunity start to decompose at temperatures between 300°C
crudes could be processed by a safer and more eco- and 400°C.13-14
Do
nomic manner. Naphthenic Acid Corrosion — Each crude oil con- wn
tains naphthenic acids, where TAN is a common lo
ad
measure of general acidity. Increasing TAN, tempera- ed
BACKGROUND ture, and flow velocity/turbulences and decreasing fro
m
alloy contents of the bulk material accelerate htt
High-Temperature Corrosion in Crude Distillation naphthenic acid corrosion (NAC), which is often
p:/
/m
Unit and High Vacuum Unit found to be very localized.9 This corrosion mechanism eri
di
The first units of each oil refinery are crude usually an
.all
distillation unit (CDU) and high vacuum unit (HVU) occurs at temperatures > 220°C and TAN > 0.5.15 The en
where crude oil is distilled in two steps (at atmo- limit can be reduced to TAN > 0.1 for sweet, low sulfur pr
crudes that have too little sulfur available to form a es
spheric pressure and at vacuum) into its major frac- s.c
stable FeS scale.16 As a consequence, it was stated
tions. There are a variety of corrosion mechanisms o
that TAN (and thus the overall acid content) is far too m/
that play a role in these units and that usually have a co
rough to evaluate the crude oil’s tendency to cause rro
very different appearance at different locations. This NAC.17-18 Molybdenum contents > 2% in the bulk sio
study focuses on the following main high-temperature metal may restrict NAC corrosion rates,9 and it is ar- n/
art
corrosion mechanisms in CDU and HVU hydrocarbon gued that increasing sulfur contents can inhibit NAC icl
e-
streams. as a result of FeS scale formation. 19 Furthermore, the pd
Sulfidation — Sulfidation or sulfidic corrosion is reactivity of each naphthenic acid, its distribution f/7
2/
the reaction of steel and other alloys with reactive over boiling point range, and the influence of its mo- 6/
84
sulfur compounds such as H2S from the fluid (e.g., lecular weight on its corrosion behavior are still 3/
crude oil) in high-temperature environments. 9 Being under discussion.18-19 For instance, experiments 23
12
observed at temperatures above approximately 260°C, showed that naphthenic acids start to decompose at 71
5/
sulfidation corrosion rates increase with temperature, temperatures 19
peaking at approximately 450°C. Both carbon > 350°C.2 As a result, NAC is difficult to predict and 40
.p
steel/low-alloyed steel and stainless steel can be thus observed frequently in CDU and HVU, df
affected by this mechanism, which usually results in particularly in by
gu
general wall thickness reduction. The modified furnace tubes and transfer lines between furnace and es

McConomy curves predict the influence of distillation column.16 Several pipe ruptures in CDU t
on
temperature, disclosing that increasing Cr and Ni or HVU furnaces, for instance, were caused in the past 03
Se
alloying contents in the bulk material can reduce by localized NAC. Those incidents can easily result in pt
corrosion rates significantly.10-11 This relation was production losses of tens of million dollars. e
m
extended to hydrogen/H2S- containing environments The above chemical corrosion mechanisms can
by the modified Couper- Gorman curves.11-12 be further increased by erosion (by solid particles) or
Dependent upon bulk material, flow conditions, erosion-corrosion (e.g., for very high flow velocities
and/or droplet impingement). Both mechanisms
and chemical composition of the fluid, the reaction
impair the FeS protective scale and accelerate
product iron sulfide (FeS) can form a stable,
sulfidation and naphthenic acid corrosion, in many
protective sulfide scale eventually reducing the
cases very locally. Particularly, transfer lines are
corrosion rate. But this passive layer can be damaged
susceptible to these effects because of the presence of
or even removed completely, which is influenced by
high flow ve- locities and two-phase flow. To control
flow conditions, temperature, content/type of sulfur
and limit high- temperature corrosion, materials and
compounds and naphthenic acids, and hydrogen/H 2S
corrosion engi- neers usually consider one or several
content, etc.
of the following approaches:
Moreover, a further influencing factor is the flow
• Materials selection (by applying, e.g., corrosion
regime (e.g., two-phase and/or turbulent flow) that
resistant alloys [CRAs])
can cause localized sulfidation. • Coatings (to protect the bulk material from
Influence of Mercaptans — In addition to H2S, the corrosive attack)
mercaptans (or “thiols”) are considered to be some of
84 CORROSION—JUNE 2016
 CORROSION ENGINEERING

rosion potential in corrosive environments. For this

• Corrosion allowance (by increasing
reason, the method can only be applied if an electrolyte
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-
CORROSION ENGINEERING

(usually some cm2), which makes detection of local

(such as, e.g., water) is present, being restricted to
corrosion phenomena difficult. An important
electrochemical corrosion.26 Hence, LPR cannot be
advantage of UT sensors is that many more CMLs can
used for corrosion monitoring in hydrocarbon
be monitored
streams in CDU and HVU where temperature is
by simple UT sensors for the same cost as
above the water boiling point.
by FSM.6
Pulsed Eddy Current Method — Pulsed eddy
current (PEC) probes were introduced in 2001 27 and TABLE 1 tool that predicts
are attached to the pipe’s external surface where they Pros and Cons of high-temperature
use a pulsed magnetic field. This generates eddy Corrosion corrosion on the
currents Monitoring basis of pipe/vessel
Techniques geometry, fluid, pro-
in the wall, which again induce voltages in the
receiver coil of the PEC probe. This signal is used to cess conditions,
calculate the remaining wall thickness, which is Technique Intrusive Resolution and crude run
used as an indicator of corrosion, but it is not as Weight loss Yes Low history; and
accurate as, e.g., UT wall thickness measurements. coupons • Accessibility of each Do
ER probes Yes High CML (to reduce
PEC probes are portable and can thus be used at wn
LPR probes Yes High lo
several corrosion monitoring locations (CMLs); 28 installa- ad
PEC method No Medium
however, good accessi- bility for manual data FSM No High tion and ed
fro
collection is needed. The measuring system UT No High maintenance m

withstands metal temperatures up to 550°C but is efforts). htt

p:/
restricted to conductive metals (carbon and low- As a result, pipe of the /m
eri
CDU and HVU systems
alloyed steel)29 and cannot be used as an online di
Table 1 summarizes discussed next were an
monitoring system. .all
pros and cons of the dis- selected for the en
Field Signature Measurements — Field signature cussed corrosion pr
installation of such
measurements (FSM) involve a network of sensing monitoring methods,
es
sensors. s.c
pins or electrodes that are mounted on the external disclosing that UT
o
m/
surface of a pipe or vessel producing an electrical sensors provide co
field in the wall.24 After an initial voltage Online Wall Thickness rro
important advantages for sio
measurement, subsequent changes in electrical field corro- sion monitoring in
Measurements n/
art
pattern are detected and compared against the initial an oil refinery. Permasense† UT icl
measurement to detect local changes in wall sensors were mounted e-
pd
thickness (accuracy: with f/7
PROCEDURES their H-shaped foot on a 2/
±0.01 mm24). The comparably large 6/
measuring area of FSM (e.g., an entire pipe pair of threaded studs 84
Refinery Setup that had been welded on 3/
elbow) allows 23
As a result of their the pipe’s external surface 12
detecting both general wall loss and localized 71
suitability and flexibility, by a 5/
corrosion. Owing to its complexity and thus elevated
an increased number of drawn-arc stud welding 19
installation and operational costs, such 40
ultrasonic sensors were process (see Figure 1[a]). .p
measurements are usually restricted to a few df
installed to monitor high- The challenge here was to by
locations within a temperature corrosion in gu
do this while the pipe was
chemical plant where corrosion hot spots are CDU and HVU. All
es
in service at temperatures t
expected.24 sensor locations were on
between 250°C and 03
Ultrasonic Testing — Non-intrusive UT measure- selected on the basis of Se
410°C. Preceding welding
ments are the fastest method to reliably measure three parameters:
pt
procedure qualification e
wall thickness and thus to monitor general wall loss. • Inspection history, m
report, welding procedure
The wall thickness is calculated from the reflection of particularly specification and selection
the ultrasonic signal at both external and internal regarding for- and ex- amination of
surface. But the exact measuring location usually mer UT and specialized welders
varies during periodic manual inspection, which radiographic ensured maximum safety.
limits accuracy of corrosion rates. To reduce this testing (RT) This eventually allowed
uncer- tainty, some systems monitor both measure- ments at minimization of the
measurement and location.30 A further approach to the corresponding turnaround scope.
increase the accu- racy of several measurements at CMLs (to focus on Furthermore, manual NDT
one location is to install permanent UT sensors that corrosion hot mea- surements (UT + RT)
remain at the corresponding CML for a longer period spots); were executed at each
such as months or even years.5,8 In comparison to • Corrosion rates, sensor location to check
FSM, UT sensors provide local measurements as a calculated by a the actual wall thickness
result of their comparably low measuring area simulation prior to welding.
 CORROSION ENGINEERING

Ultrasonic sensors were recorded by the internal

With increasing
installed, particularly at software for each surface;
pipe diameter (from
pipe elbow outlets (in sensor: ○ Used to
150 mm to 800
the 80° position in • Wall thickness calculate
mm), sensors were
Figure 1[b]). ○ Calculated “PSI”
also attached at
by time-of- (Permasens
†
Trade name. elbow inlet
flight e† shape
(10° position) and
apex (45° position). As analysis indicator)
a result, many pipe from the at the
elbows and some T- interval correspond
pieces of this between ing CML.
CDU/HVU complex both main It is important to
are now monitored echoes that understand the
continuously for are detected difference be- tween
corrosion. The pipe by the “EP” both parameters. Note
material was carbon (envelope that sulfidation
steel at CMLs in loops peaks) usually leads first to a
2, 3, and 4 and 5%Cr- approach; slight increase in
0.5%Mo steel (ASTM ○ Used to surface roughness.
A355, P5/ X12CrMo5) calculate This effects initiates at
at CMLs in loops 1, 5, corrosion a very low order of
and 6 (see Table 2). rates (by magnitude such as
To protect the trending micrometers or even
electronics in the wall nanometers. After
orange sensor head thickness some time, surface
from the heat of the over time) roughening
near pipe, heat shield as a mea- accumulates and
plates were positioned sure of results in measurable
Do
on the sensor guide general wall thinning, from wn
lo
waves, which were at- wall loss at which one can cal- ad
tached afterward to the corre- culate corrosion rates. ed
fro
the insulation. The sponding The dimensionless m
measuring frequency CML. parameter PSI was htt
p:/
of all sensors was • Shape of back wall designed to describe /m
eri
chosen to be twice a reflection the first stage (surface di
day to allow increased ○ Compare roughening) by an
.all
battery life, also taking d to the focusing on the second en
pr
into account that such echo of the UT
back wall es
wall thickness waveform (see Figures s.c
echo o
measurements are 2 and 3). Accordingly, m/
shape co
usually mid- to long- the sensor software
from rro
term analyses. analyzes the shape of sio
previous n/
The UT signal this echo over time. art
and icl
travels from the Figure 3 shows an
subseque e-
sensor head through example of one sensor, pd
nt f/7
two stainless steel revealing how 2/
measure
guide waves to the significantly the echo’s 6/
ments (= 84
sensor foot where it shape can change 3/
change in (here: during 75 d).
23
enters the pipe wall. 12
shape of Remember that this 71
It is then reflected
back wall second peak
5/
particularly on both 19
reflection) represents the 40
external (first echo) .p
and appearance of the df
and internal (second by
interprete measuring area on the
echo) pipe surface. gu

The corresponding d as a pipe’s internal surface es

t
UT waveform (or “A- measure (such as the first peak on
03
scan”) is shown in of change Se
Figure 2, empha- in pt
e
sizing two important roughnes m

parameters that are s of the

 (a) (b)

Heat shield H-shaped foot

80°

Sensor head (electronics)

45°

50 mm
10°
Do
wn
FIGURE 1. Ultrasonic wall thickness sensor (a) and CMLs (corrosion monitoring locations) where such sensors were lo
ad
attached (b, black arrow indicates flow). ed
fro
m
htt
represents the external surface). Even small degrees p:/
sensitive to detection of even low degrees of /m
of corrosion roughen the internal surface and change
corrosion, and wall thickness can indicate elevated eri
the shape of the second UT echo. Moreover, Figure 3 di
corrosion activity. an
shows that wall thickness did not change in this .all
Each PSI value was calculated by the UT software
example, which is shown by the distance between en
by analyzing 60 different UT pr
both main peaks that remained constant during 75 d. es
measurements/waveforms. s.c
The shape of the back wall reflection is thus a o
With a measuring frequency of twice a day, all PSI
parameter m/
values were thus based on data from 30 d. co
rro
Furthermore, each PSI value was calculated from 30 sio
n/
preceding and 30 subsequent UT waveforms. This art
TABLE 2 means that PSI data were always first available with a icl
Corrosion Loops in CDU/HVU Where Ultrasonic Sensors e-
“delay” of 15 d (for a measuring frequency of twice a pd
Were Installed(A) f/7
day). The exact al- gorithm used to compare the back 2/
wall reflection for 6/
84
Boiling Process
different UT waveforms in order to calculate PSI was 3/
23
Point Range Temperature developed experimentally by the company in the last 12
Loop (°C) at CML (°C) Material few years. It is unknown to the end-user and is thus 71
5/
not 19
40
subject of this publication. .p
1) Crude oil 143-FBP 360 5%Cr-0.5%Mo
steel (P5) High PSI values are related to high changes in df
by
2) Kerosene 123-210 250 Carbon steel roughness indicating elevated corrosion on the gu
es
internal t
3) Gas oil (refl.)
4) 272-291
210-330 317
275-285 Carbon steel pipe surface and vice-versa. Note that PSI is not on
5) LR 340-FBP 410 5%Cr-0.5%Mo influenced by process temperature because tempera- 03
Se
steel (P5) ture does not influence the back wall signal’s shape. pt
6) HVGO 473-484 275-300 5%Cr-0.5%Mo In contrast, wall thickness is influenced by e
m
steel (P5)
temperature because the distance between both main
(A)
FBP: final boiling point; refl.: circulating reflux; LR: long (atmo- peaks of the UT waveform increases with increasing
spheric) residue; HVGO: heavy vacuum gas oil.
temperature. This makes PSI an additional, very
sensitive
 UT 1st information: wall thickness
amplitude

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

Signal envelope

Time
1st echo:
external surface2nd echo:
internal surface

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

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
Time
in CDU and 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
Waveform on day 75 corrosion loops listed in Table 2:
• Total sulfur content (determined according to Do
ASTM D2622); wn
lo
Time • TAN (determined according to ASTM D974); ad
• Mercaptan content (determined according ed
fro
to ASTM UOP163). m
htt
p:/
FIGURE 3. Change of UT waveform appearance over time (for one RESULTS AND DISCUSSION /m
eri
sensor). Note the change in shape of the second peak. di
Crude Parameters an
.all
Figure 4(a) shows average values (9 month) of en
pr
measuring value that complements conventional wall total sulfur content and TAN for six different CDU es
s.c
thickness readings. and o
It is of note that the sensor’s “footprint” (mea- m/
co
suring area) is approximately 1 cm2, which compute wireless. Their (a) 1.5
rro
Total sulfur content TAN sio
emphasizes that localized corrosion such as pitting rs at any intrinsically safe 15 n/
art
cannot be detected reliably with such sensors. In time, batteries can icl
10
S Content (wt%)

other words, the sensor network should have a which last for up to 7 e-
1.0 pd
sufficient amount of sensors to allow reliable and makes y, dependent f/7
5 2/
repeatable measurements that show the potential for the UT upon measuring 6/
high-temperature corro- sion in the whole pipe. Local sensors frequency and 0
84
0.5 3/
effects owing to, e.g., turbulent flow or droplet a smart stability of the 1 23
12
impingement might only be evaluated with a very online sensor net- 71
high number of sensors, which increases costs. On cor- work. Also, 5/
19
the other hand, only a few sensors are needed to rosion these sensors 0.0 40
.p
monitor general wall loss in a comparably large area monitori withstand metal df
of a petrochemical plant. ng tool. surface by
gu
After installation, the sensors automatically Further temperatures up es
t
build a self-healing wifi network and connect to more, it to 600°C, which on
gateway (wifi antenna) and server. Software records should again highlights 03
Mercaptan Content (ppm)

Crudeofoil (b) 30 Se
UT waveform and wall thickness of each sensor, be noted the flexibility pt
Kerosene e
allowing further data processing to calculate that all the measuringGas oil (refl.) 25 m
corrosion rates and PSI. Thus, corrosion engineers sensors system. Gas oil
LR
can check these corrosion parameters at their office are HVGO 20
 2 3 4 7 8 9
1.5
5 6

TAN (mg KOH/g)

1.0

0.5

0.0

10
Crude Parameters Time (month)
Today, it is common practice that crude oil FIGURE 4. Mean values (9 month) of total sulfur content vs. TAN
diets processed in oil refineries vary in very short (a) and mercaptan content over time in different loops of CDU and
time intervals as a result of the increasing need for HVU (b).
crude
HVU loops. Accordingly, sulfur content (0.82 wt%) merca content. This
and TAN (0.28 mg KOH/g) of the crude oil diet were ptan (a) 22.1
corros emphasizes that
comparably low. Both parameters can reach levels of ion.13 each
several wt% (S content) or several mg KOH/g (TAN). It
Wall Thickness (mm)

This suggests that particularly sweet, low TAN crudes shoul 22.0
d be
were processed during this period of 9 months. noted
Furthermore, the diagram reveals a correlation that
21.9
between sulfur content and TAN. The mean there
sulfur/TAN ratio was is a
measured to be > 2.0, except for kerosene (1.2) and stro
heavy vacuum gas oil (HVGO, 1.7). Low ratios, < 1.0, ng 21.8
can be interpreted as an indication of an increased
sus- varia
ceptibility to NAC.16 Accordingly, increased NAC was tion
of 21.7
found elsewhere in CDU and HVU of an oil refinery 0 20 40
while processing very sweet, low TAN crude oils such merc 60
as WAF (West African) crudes that can have apta Time
sulfur/TAN ratios even below 0.5.16 As a result (from ns (b) 22.1 (d)
Figure 4[a]), sulfidation is expected to be the over
dominating corrosion mechanism (compared to NAC). time
, but
Wall Thickness (mm)

To give an overview of how such crude 22.0

parameters vary over time, Figure 4(b) shows the not
mercaptan content during 10 months for the same for
CDU and HVU loops. In accordance with the total the 21.9
sulfur content (see Figure 4[a]), the mercaptan total
content was also found to be sulf
comparably low (< 25 ppm), indicating a low risk for ur 21.8
 280
Corrosion rate: 0.07 mm/y 235
150

265
220

PSI(°C)
(-)
80 100 100

Temperature
Do
250 wn
lo
200 ad
Corrosion rate: 0.07 mm/y 50 ed
21.7 0
crude oil usually has a very different mercaptan 0 20
60 40
80 100
fro
m
concentration, independent of total sulfur. As known Time (d) htt
Wall thickness p:/
from experiments,13 Figure 4(b) shows elevated Temperature /m
mercaptan contents for middle-distillates (such as FIGURE 5. Influence of process temperature on UT wall thickness eri
readings (a) and relationship between wall thickness and PSI (b) di
gas oil) and low mercaptan contents for higher an
for sensor in kerosene loop. .all
tempera- tures (here: LR [long (atmospheric) residue] en
and HVGO). This is a result of the boiling point range pr
es
distribution of mercaptans and likely also a result of s.c
The propagation velocity of the UT signal o
their decom- Wall thickness
depends upon metal temperature. Increasing m/
co
position at temperatures > 300°C.13-14 PSI
temperatures reduce this velocity, increasing the rro
sio
distance between both main peaks in Figure 2. This n/
Wall Thickness, Corrosion Rates, and PSI is interpreted by the software as increasing wall art
icl
A typical plot of wall thickness vs. time (110 d) is thickness, which is, of course, not realistic. e-
pd
shown by Figure 5(a) for one sensor that was installed Furthermore, parameters such as insulation f/7
in the kerosene system. The corresponding graph conditions, surrounding temperature, etc., are 2/
6/
reveals very low wall thickness data scattering of different at each sensor location, resulting in 84
3/
±0.01 mm. This is very accurate in comparison to a different susceptibility of each sensor to 23
manual UT thickness measurements where it is temperature variations. As a consequence, “manual” 12
71
usually almost impossible to repeatedly measure at or automatic compensation for temperature by the 5/
exactly the same position. Consequently, inaccuracy sensor software (by applying, e.g., a general 19
40
can in- crease by 1 to 2 magnitudes. The other curve correction factor) is dif- ficult. Therefore, the sensor .p
df
in Figure 5(a) is temperature data that was measured producer recently released a new sensor generation by
with a nearby temperature sensor. It is obvious that that includes a thermocouple. gu
es
both curves have a very similar shape, disclosing a The software then compensates all wall thickness t
on
strong dependence of measured wall thickness on readings for temperature, which is intended for in- 03
process temperature. Accordingly, changes in creasing the measuring system’s accuracy. The Se
pt
temperature of only 3 K influence wall thickness sensors of this study do not have such a e
m
readings signifi- cantly. This makes calculation of thermocouple be- cause they had been installed
corrosion rates inac- curate, particularly if they are earlier.
low. The corrosion rate indicated in Figure 5(a) (0.07 Figure 5(b) shows the comparison between wall
mm/y) corresponds to the slope of the linear fit of the thickness and PSI for the same UT sensor.
wall thickness–time curve and was not compensated Interestingly, PSI data scatter very little.
for temperature. Furthermore, wall thick- ness and PSI developed very
differently over time. Ac- cordingly, PSI indicates a
strong increase in
corrosiveness between days 40 and 60, while the real chang
wall thickness likely did not change significantly if es in  Corrosion rate UT (a) 100
one considers the temperature influence from Figure intern  Corrosion rate McConomy
 PSI
 CR (normalized, %)

5(a). A possible reason for this behavior (change in al 80

crude corrosiveness) is discussed in detail in the rough
Correlation Between PSI and Crude Parameters ness 60
section. (high
It should be noted here that changes in internal PSI) 40
roughness (that are actually used to calculate PSI) can
can also slightly influence wall thickness readings. smear 20
This was observed in a few cases where a small but the
sharp change in wall thickness by up to 0.1 mm was shape 0
measured. This observation could not be explained by
a change in temperature but by PSI, which was at
maximum at that moment. Strong and sudden
150
90

 PSI (-)
30
120 Do
60 0 wn
lo
of the second UT echo, which modifies the exact peak ad
(b) 8
 Corrosion rate UT PSI 120 ed
location of this echo (recall Figure 3). This is inter- fro
20% of all39% of all41% of all sensorssensorssensors
preted by the software as slight but sharp change in 84
m
htt
wall thickness, which again affects overall corrosion

 CR (normalized, %)
6 p:/
90
rate. 66
/m
eri
The extent of this effect was determined to be very di
low (< 5%) by comparing all wall thickness data to

 PSI (-)
an
4 3.5% .all
process temperature. Affected data was excluded 60 en
and not considered for the calculation of pr
es
corro- sion rates. s.c
The two main effects can be summarized as 2 2.4%
30
o
2.1% m/
follows: 20
co
rro
• Process temperature (on wall thickness sio
0 n/
read- ings but not on PSI), 0 art
• Internal roughness (on wall thickness readings icl
e-
and PSI). CML (degree) pd
f/7
Accordingly, PSI can be used as a first, very FIGURE 6. Mean values (9 month) for normalized corrosion rate 2/
sensitive indicator of corrosion (in the form of (CR) and PSI in different loops of CDU and HVU (a) and at different
6/
84
changes in internal roughness), where wall pipe elbow CMLs for all sensors (b). 3/
23
thickness/corrosion rates indicate subsequent wall 12
thinning restricted by temperature and, to some 71
5/
degree, by roughness. Also, data trending over time is As a result, no correlation was found between 19
more accurate for PSI than for corrosion rates. measurement (UT) and prediction (McConomy), see 40
.p
Figure 6(a). To explain this, it should be noted that df
by
Mean Values for Corrosion Rates and PSI hydrogen or H2S were assumed to be absent gu
es
In a second step, average values for corrosion (McConomy curves). Furthermore, this comparison t

rate and PSI data from 9 months were calculated points out that parameters such as type and distri- on
03
and compared for six different corrosion loops (see bution of sulfur compounds/naphthenic acids or flow Se
pt
Figure 6[a]). Note that all measured average corrosion conditions, etc., influence high-temperature sulfida- e
rates (UT) were generally found to be low in com- tion significantly. They are, however, not considered by m

parison to rates that are typically observed in these the McConomy approach. This challenges the com-
CDU/HVU corrosion loops of an oil refinery. For gas parison of measured to theoretical corrosion rates.
oil reflux and long residue, the corrosion was even Moreover, it appears from Figure 6(a) that theoretical
measured to be zero. The diagram compares mea- McConomy corrosion rates may be overly conservative
suring values to theoretical corrosion rates that were for the corrosion observed in this study.
calculated from modified McConomy curves on the Figure 6(a) also shows PSI values that can range
basis of Table 3. Therefore, temperature and material by definition from 255 (highest corrosion) to 0 (no cor-
(recall Table 2) were used to determine corrosion rates rosion). Hence, the presented PSI values are compa-
for 0.5 wt% sulfur content, which was adjusted by rably low (< 100), which matches with the (low) level
for UT corrosion rates in the same diagram. Further-
a multiplier to obtain a theoretical corrosion rate for
the corresponding sulfur content. Note that all corro- more, PSI correlates to the pipe material in Figure 6(a):
sion rates in Figure 6(a) and Table 3 are normalized PSI is lowest for loops 1, 5, and 6 in which 5 wt% Cr
values, which means that absolute values (in mm/y) steel was used instead of carbon steel as in the other
were transformed into relative values (in %). loops. As both PSI and UT corrosion rates are based
 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 McConomy 10 and Gutzeit.11

on data from a large number of sensors, one can con-

the UT sensors used here collect local measurements
clude that the crude oil diet processed in this period
on the one hand, which likely do not fully represent Do
of time was not very corrosive in the high- wn
the corrosion in the whole pipe. On the other hand,
temperature areas of CDU and HVU. Moreover, lo
the flow regime usually affects corrosion locally. ad
Figure 6(a) reveals significant differences between UT ed
corrosion rates and PSI, although both are measuring Examples are elbow back sides resulting from flow fro
m
data from UT sensors. It is probable that temperature impingement or locations downstream of reinforced htt
p:/
(which influ- ences wall thickness and thus corrosion welds that cause local turbulences. In other words, /m
rate, but not PSI) is the main reason behind this flow velocity is a key factor but its effects on high- eri
di
discrepancy. In other words, PSI values seem to show temperature corrosion cannot be detected reliably by an
.all
again a higher sensitivity to corrosion and thus an local measurements. en
increased signifi- cance compared to corrosion rates. Interestingly, pressure was observed to correlate to pr
es
An interesting comparison is given in Figure 6(b) some degree to corrosion rate (see Figure 7[b]). s.c
o
that shows average UT corrosion rates and PSI for m/
co
three different CML positions on pipe elbows (recall 24
(a) 120  PSI
rro
Figure 1 [b]). It is a common belief that the elbow sio
n/
back side (45° position) is subject to the highest 100  Velocity 20 art
icl
corrosive attack in each elbow because shear stresses

 Velocity (m/s)
80 16 e-
resulting from flow impingement are expected to be pd
 PSI (-)

f/7
the highest here. 60 12 2/
Figure 6(b) suggests a maximum in corrosion some- 6/
84
where between 45° and 80° (elbow outlet). The lowest 40 8 3/
23
corrosion rates and PSI values were measured on the 12
20 4
10° position, which sounds reasonable. At this point, 71
5/
it should be highlighted that, e.g., computational fluid 0 0 19
40
dynamics simulation can give a “corrosion profile” for .p
such an elbow. This way, corrosion hot spots df
by
resulting from high local shear stresses that impair gu
es
the passive FeS layer can be found. t
on
03
Influence of Flow Velocity and Pressure (b) 8  Corrosion rate 24 Se
pt
As outlined earlier, important key factors for 7  Pressure e
20
 CR (normalized, %)

 Pressure (bar [g])

m
high-temperature corrosion in CDU/HVU are further 6
process parameters such as flow velocity and pres- 16
sure. An increase in these parameters can result in 5
4 12
increased corrosion, owing to the increase of shear
stresses at the internal pipe surface. This impairs the 3
8
FeS protective layer, which facilitates corrosion of the 2
bulk metal. Figure 7(a) discloses that no correlation 4
was found between average values for flow velocity 1
0 0
and corresponding PSI values. While PSI was highest
in corrosion loops 2, 3, and 4, the corresponding flow
velocity was very low (and vice-versa for the other
loops). Similar results were found for the comparison
of mean flow velocity with mean corrosion rates (not
shown in Figure 7). This observation confirms that 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.

Accordingly, corrosion rates were highest in loops with

to exist a clear correlation between PSI and sulfur
elevated pressure, such as the HVGO system. This
content. While both variables were found to have a
suggests that pressure might be a key factor in sulfi-
minimum somewhere between months 4 and 5,
dation behavior, although, on the other hand, PSI did
there was a higher corrosion activity/sulfur content
not show a clear influence by pressure (not shown in
before and afterward (maximum in months 2
Figure 7).
and 9).
Summarizing Figures 7(a) and (b), it should be
Note that, for purposes of clarity, the vertical
pointed out that the UT sensors used here collect
sulfur content axis of these six diagrams have
local measurements that have been averaged. Conse-
different scales as a result of very different sulfur
quently, “local” influencing factors (such as flow veloc-
levels in each loop (recall Figure 4[a]). This makes the
ity) seem to be dominated by “global” factors such as
correlation between PSI and sulfur content quite
metallurgy, chemical composition (e.g., sulfur
significant, par- ticularly for the kerosene loop (Figure
content), or pressure.
8[b]). Here, the total sulfur content was just some
hundredths of wt%. The clear correlation of both Do
Correlation Between PSI and Crude Parameters curves thus emphasizes wn
lo
A very important question is if the UT measuring (1) the high sensitivity of the UT measuring system and ad
data correlates to crude parameters that are related to (2) the relevance of PSI.
ed
fro
sulfidation and naphthenic acid corrosion. Therefore, The crude oil’s total sulfur content covers many m
htt
measuring data was compared to crude parameters different sulfur species with very different tendencies p:/
dependent upon time. As a result of the influence of for high-temperature corrosion. For this reason, it
/m
eri
temperature and roughness on corrosion rates (recall was often stated that such a “general” parameter di
an
the Wall Thickness, Corrosion Rates, and PSI section), would not be appropriate to predict sulfidation. This .all
en
it was impossible to determine accurate corrosion is challenged by the results in Figure 8. One should pr
rates over a small period of time, such as one month. re- member here that the total sulfur content is com- es
s.c
The dependence on temperature variations and the parably easy to determine and to monitor in an oil o
m/
result- ing data scattering was simply too high. It refinery. co
was, however, possible to accurately average PSI Two other influencing crude parameters (TAN rro
sio
values for each month. These mean values were and mercaptan content) are compared to PSI in n/
art
compared to monthly mean values for the total sulfur different diagrams (see Figures 9 and 10). Note that icl
content during the same 10 months period (see Figure the PSI curves in these two figures are consequently e-
pd
8). According to these six graphs (one per corrosion the same, as shown in Figure 8. Furthermore, the f/7
2/
loop), there seems scales of all TAN axes in Figure 9 were adjusted to 6/
84
different typical 3/
23
12
71
5/
19
(a) 250 40
PSI 1.5 (b) 250 PSI
0.05 (c) 250 PSI
0.5 .p
S content S content S content df
200 by
1.2 200 0.04 200 0.4
S Content (wt%)
S Content (wt%)

S Content (wt%)

gu
150 es
PSI (-)

0.9 150 0.03 150 0.3 t

PSI (-)
PSI (-)

on
100 03
0.6 100 0.02 100 0.2 Se
pt
50
0.3 50 0.01 50 0.1 e
m

0 0.0 0 0.00 0 0.0

123 456 7 8 9 10 1 2 3 4 5 6 7 8 9 10 123456 7 8 9 10
Time (month) Time (month) Time (month)

(d) 250 0.5 2.0 2.0

PSI (e) 250 PSI (f) 250 PSI
S content S content S content
200 0.4 200 1.6 200 1.6
S Content (wt%)
S Content (wt%)

S Content (wt%)

150 0.3 150 1.2 150 1.2

PSI (-)
PSI (-)

PSI (-)

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

123456 7 8 9 10 1 2 3 4 5 6 7 8 9 10 123456 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.

(a)
250 0.5 (b) 0.03 (c) 0.12
PSI PSI PSI
TAN
250 TAN
250 TAN
0.4

TAN (mg KOH/g)

200 0.09
200 200

TAN (mg KOH/g)

TAN (mg KOH/g)
0.02
150 0.3
PSI (-)

150 150 0.06

PSI (-)

PSI (-)
100 0.2
100 0.01 100
0.03
50 0.1
50 50
0 0.0 0.00 0.00
123456 7 8 9 10 0 123456 7 8 9 10 0 123456 7 8 9 10
Time (month) Time (month) Time (month)

0.12 (e) 250 1.0 1.0

(d) 250 PSI (f) 250
PSI PSI
TAN TAN TAN
200 200 0.8 200 0.8

TAN (mg KOH/g)

TAN (mg KOH/g)

TAN (mg KOH/g)

0.09 Do
wn
150 150 0.6 150 0.6 lo
PSI (-)

PSI (-)

PSI (-)
0.06 ad
ed
100 100 0.4 100 0.4 fro
m
0.03
50 50 0.2 50 0.2 htt
p:/
/m
0 0.00 0 0.0 0 0.0 eri
123456 7 8 9 10 123456 7 8 9 10 12345 6 7 8 9 10 di
an
Time (month) Time (month) Time (month) .all
en
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 pr
es
(f) HVGO. s.c
o
m/
co
TAN levels of each stream to improve clarity (as also rro
not be used as an appropriate parameter to predict sio
done in Figure 8). As a result, no clear correlation was n/
NAC.9,16-18
found between monthly TAN and PSI values for all art
Some correlation was found between mercaptan icl
systems (see Figure 9), but to some degree for the e-
content and PSI (see Figure 10) that shows pd
kerosene and gas oil loops (Figures 9[b] through [d]). f/7
mercaptan data from Figure 4(b). Interestingly, the 2/
As TAN is also a mixture of many acids with very 6/
highest corre- lation was observed for rather “cool”
different properties, it was suggested that TAN could 84
kerosene on the one hand, and high-temperature 3/
23
streams (crude oil, LR, 12
71
5/
19
40
(a) 250 25 (c) 250
25 (b) 250 25 .p
Mercaptan Content (ppm)

PSI
Mercaptan Content (ppm)
PSI
Mercaptan Content (ppm)

PSI df
Mercaptan content Mercaptan content Mercaptan content
200 by
20 200 20 200 20 gu
es
150
PSI (-)

15 150 15 t
15 150
PSI (-)
PSI (-)

on
100 03
10 100 10 100 10 Se
pt
50 e
5 50 5 50 5 m

0 0 0 0 0 0
123456 7 8 9 10 123456 7 8 9 10 12345 6 7 8 9 10
Time (month) Time (month)
0 0
(d) 25 25
250 (e) 250
Mercaptan Content (ppm)

PSI PSI
Mercaptan content Mercaptan content
200 20 200 20

150 15 150 15
PSI (-)
PSI (-)

100 10 100 10

50 5 50 5
 150 Time (month) 15 0

PSI (-)
0
100 25 10
(f) 250

Mercaptan Content (ppm)

PSI

Mercaptan Content (ppm)

Mercaptan content
200 50 20 5

0
123456 7 8 9 10 12345 6 7 8 9 10 123456 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.

TABLE 4 correlation was found between mercaptan content and

Correlation Between PSI and Crude Parameters: Percen- UT wall thickness measurements for crude oil, kerosene,
tage of Gradients Between Two Months Where Both PSI LR, and HVGO pipe.
and Corresponding Crude Parameter Increased (positive
gradi- ent) or Decreased (negative gradient)(A),(B),(C)
CONCLUSIONS
Correlation Between PSI and
Sulfur Mercaptan v Two parameters were determined from continuous
Loop Content TAN Content wall thickness measurements by wireless UT
sensors that are installed permanently on piping in
1. Crude oil, 360°C 75% 38% 75%
2. Kerosene, 250°C 71% 57% 71%
3. Gas oil (CL), 317°C 71% 67% 43%
4. Gas oil, 275-285°C 57% 86% 57%
5. LR, 410°C 56% 33% 67%
6. HVGO, 275-300°C 56% 22% 67%
Average 64% 63% 50%
59%
(A)
Recall Figures 8 through 10.
(B)
High correlation: 67% to 100%; medium correlation: 34% to 66%;
and low correlation: 0% to 33%.
(C)
CL: circulating reflux; LR: long (atmospheric) residue; HVGO:
heavy vacuum gas oil.

and HVGO) on the other hand, where the mercaptan

content was low (< 16 ppm). Mercaptans are commonly
expected to decompose at temperatures between
300°C and 400°C,13-14 which makes this observation
even more interesting.
Table 4 summarizes the correlation between PSI
and crude parameters (Figures 8 through 10) by com-
paring both curves of each diagram. The percentage
of cases where both curves have a positive or negative
slope between two neighbored months is given. From
this overview, it becomes clear that both total sulfur
content and TAN seem to be suitable to predict the
corrosion that was measured with UT sensors used in
this study, although the UT corrosion rates were
found to be very low (recall Figure 6[a]). Accordingly,
the total sulfur content correlates well with high-
temperature corrosion in crude oil and middle
distillates where TAN correlates well with corrosion in
gas oil.
The very low correlation of TAN with PSI values at
high temperatures (LR and HVGO) is surprising, as
TAN was measured here to be highest of all corrosion
loops. Naphthenic acids are just some of many
different acids that are considered in TAN calculation.
It is dif- ficult to predict which loop naphthenic acids
con- centrate in but they were already found to cause
severe corrosion in HVUs.2 Furthermore, good
six different corrosion loops of an oil refinery’s CDU between measuring data and process
and HVU: pressure.
• Corrosion rates (as a measure of general v Measuring data was compared to three crude
wall thinning, derived from wall parameters from crude run history: total sulfur
thickness); content, TAN, and mercaptan content. The most
• PSI (change in shape of UT back wall important results from this analysis are as follows:
signal as a measure of change in internal • Corrosion rates are too inaccurate to compare
roughness). them to crude parameters for short periods of
v The results revealed two particular time such as, e.g., one month;
influencing factors: • Good correlation between PSI and crude
• Temperature (that influences wall parameters for comparably short periods of
thickness and corrosion rates, but not time (1 month), particularly regarding total
PSI); sulfur content and TAN;
• Internal roughness (that can, when • Significant dependence of this
changing significantly, reduce wall correlation upon CDU/HVU corrosion
thickness measuring accuracy). loop.
v Furthermore, the following results were v Thus, one important result from this study is the Do
observed: observation of correlations between measuring data wn
lo
• PSI seems to provide more accuracy in (PSI) and crude parameters that represent the crude ad
corro- sion monitoring than wall oil diet’s potential for high-temperature corrosion in ed
fro
thickness/corrosion rates, mainly because CDU/HVU. This allows improved corrosion prediction m
htt
of uncertainty caused by temperature based on measuring data, which is an important step p:/
influence; toward safer and more economic processing of op- /m
eri
• No correlation between (measured) UT portunity crude oils. di
an
corro- sion rates and (theoretical) .all
McConomy corro- sion rates; ACKNOWLEDGMENTS en
pr
• Clear correlation between pipe material es
and corrosion parameter PSI (low PSI The authors would like to thank the sensor s.c
o
for producer and partner companies for their outstanding m/
co
P5 material and elevated PSI for carbon support during commissioning and subsequent rro
steel piping); service of the UT sensors. Furthermore, they sio
n/
• No correlation between measuring data appreciate the support of all colleagues from Shell art
icl
and flow velocity but increased correlation Rheinland Refinery and further Shell sites who e-
contributed to this work. pd
f/7
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on
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http:// www.alspi.com/ERMonitoring.pdf. Do
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