Development of a naphthenic acid
corrosion model
A model has been developed to predict and help prevent corrosion when
processing high TAN crudes
ERIC VETTERS
ProCorr Consulting Services
H
igh total acid number
(TAN) crudes often sell
at a significant discount
due to concerns about naph-
thenic acid corrosion (NAC)
– both real and perceived. In
some systems, high corrosion
rates are experienced with rel-
atively low TAN feedstocks,
while other systems without
extensive alloy upgrades seem
to handle high TAN feeds with
few problems. This unpredict-
ability, as well as the localised
nature of NAC, has created an
air of mystery around NAC
and has caused many refin-
ers to take a very conservative
approach towards processing
high TAN crudes. The chal-
lenges of predicting naphthenic
acid corrosion along with new
developments in understand-
ing the mechanism led ProCorr
Consulting Services to analyse
the available literature corro-
sion data and to turn that data
into the Tancorr naphthenic
acid corrosion model.
NAC is generally under-
stood to occur in parts of the
crude and vacuum unit operat-
ing above 450°F (232°C) when
the TAN value exceeds some
threshold value without the
www.digitalrefining.com/article/1002331
presence of a high molybde-
num alloy such as 316 or 317L
stainless steel. TAN, which
is a measure of the acid con-
tent, is used as an indicator
of NAC potential; however,
it not considered to be a relia-
ble predictor of NAC by itself.
This temperature range also
coincides with that of high
temperature sulphur corro-
sion, meaning that at least two
simultaneous corrosion mech-
anisms can be occurring simul-
taneously with the potential for
significant interaction between
mechanisms.
The basic NAC corrosion
reaction is shown in Equation
1. Because the iron naphthen-
ate corrosion product is oil sol-
uble, it has not been thought to
form a protective scale like the
sulphidation corrosion reac-
tion depicted in Equation 2,
which is illustrated using H2S
as the reactive sulphur com-
pound. Sulphidation occurs at
similar temperatures to NAC
and is more generalised in
nature with less susceptibility
to high shear stress. The iron
sulphides formed from sulphi-
dation corrosion are not oil sol-
uble and tend to form a scale
on the metal surface, which
has been shown to provide
some level of inhibition against
NAC. Equation 3 shows how
naphthenic acids can also react
directly with iron sulphide,
potentially reducing the inhib-
itive effects of iron sulphide
scales against direct naphthenic
acid attack on the metal surface:
2RCOOH + Fe → Fe(OOCR)2 + H2 (1)
H2S + Fe→ FeS + H2 (2)
2RCOOH + FeS ⇒ Fe(OOCR)2 + H2S (3)
Many theories exist to explain
why TAN alone is not a good
predictor of corrosion. The
most commonly promoted the-
ories are related to the compo-
sition of the naphthenic acids
and the presence of sulphur in
the system. The acid composi-
tion claims are usually either
that the TAN test is non- spe-
cific and detects things other
than naphthenic acids or that
some acids are non-corrosive
or may even inhibit corro-
sion. While there is a limited
amount of testing on specific
molecules that seems to indi-
cate that different individual
PTQ Q2 2019 1

Fluid flow
(HC, RCOOH, RS)
Figure 1 Combined NAC and sulphidation corrosion mechanism
S
dominated
Inhibition, %
Inhibition
Potential corrosion
TAN
Figure 2 Theoretical corrosion inhibition in systems with both sulphur and
naphthenic acid
acids cause corrosion at differ-
ent rates, there is nothing that
definitively links differences in
crude oil corrosivity to differ-
ences in the nature of the actual
acid species present, and there
is certainly no way to measure
the parameters likely to make
a difference in the corrosivity
of individual acid molecules
found in crude oil.
There is actually good evi-
dence to support the inhibitive
effect of sulphur on NAC. The
idea has been that the iron sul-
phide corrosion product layer
formed from sulphidation cor-
rosion, which usually occurs
in the same locations as NAC,
inhibits diffusion of naphthenic
acids to the metal surface,
which thus reduces the corro-
sion rate due to NAC. In work
by Craig,1 the presence of H2S
reduced the overall corrosion
rate of mineral oil and naph-
2 PTQ Q2 2019
Metal surface
Corrosion products
(FE3O4 inner and
R-S FeS RCOOH Fe(RCOO)2 FeS outer)
Combined
Potential corrosion
S & NAC NAC
dominated
thenic acid mixtures by approx-
imately 80-90% compared to
similar systems without H2S.
This interaction between NAC
and sulphidation is compli-
cated by the fact that naph-
thenic acids can also react with
iron sulphide scales to dissolve
the scale.
More recently, a joint indus-
try programme (JIP) at Ohio
University discovered the pres-
ence of a thin iron oxide layer
under an outer iron sulphide
layer. This iron oxide layer
provided additional corrosion
protection and was determined
to result from the thermal deg-
radation of iron naphthenate
corrosion products. Iron naph-
thenates are not thermally sta-
ble and have been shown to
break down to form a separate
iron oxide layer under the outer
iron sulphide layer.2 It is likely
that the size of the iron naph-
thenate molecule (Fe(OOCR)2)
hinders diffusion out of the iron
sulphide scale enough to allow
some thermal decomposition.
This formation of an iron
oxide scale adds yet another
layer of complexity to the
mechanism by adding at
least two new reactions to the
mechanism:
Fe(RCOO)2 → FeO + CO2 + RCOR (4)
4FeO → Fe3O4 + α-Fe (5)
The net result is that a com-
plex set of interacting scale
forming and scale destroying
reactions are simultaneously
occurring. This complex cor-
rosion mechanism is depicted
in Figure 1, which shows the
development of a dual layer
protective scale. Alloying ele-
ments, such as chromium, add
still more complexity as the
resulting Cr containing corro-
sion products are incorporated
into the scale. The overall cor-
rosion rate depends on the rel-
ative rates of these different
reactions, which in turn depend
on the fluid composition, the
process conditions and the
metallurgy.
With this mechanism, a
number of distinct corrosion
regimes can be expected. At
low TAN values, the formation
of any oxide scales will be mini-
mal and sulphidation corrosion
will dominate. At some level of
TAN, the interactions between
NAC and sulphidation become
significant and a maximum
inhibition level is reached. As
TAN increases relative to the
sulphur level, at some point
NAC and the attack of iron
sulphide scales by naphthenic
acids begins to dominate. Figure
2 depicts how this scale inhibi-
www.digitalrefining.com/article/1002331
tion might look as a function
of TAN at a constant sulphur 8
level. 7
R2 = 0.7735
The percentage inhibition Source 10
6
in Figure 2 is based on the fol- Source 14
lowing overall corrosion rate 5 Source 15
equation: 4 Source 3
Source 6
3
CRoverall = [CRS + CRNAC](100-%I)/100 (6) Source 9
2

CRS and CRNAC are the sul-
phidation and naphthenic acid
corrosion rates independent of
any interactions between the
mechanisms, and %I repre-
sents the interaction between
the two mechanisms expressed
as a % inhibition. The iron sul-
phide scale formed from sul-
phidation corrosion naturally
limits the steady state corrosion
rate, and that effect is already
incorporated into the Modified
McConomy curve, which is
the most widely used method
of predicting sulphidation
corrosion.
At low TAN, there is limited
oxide layer formation, so inhi-
bition levels are low. As the
TAN increases, the formation
of oxide scale increases, which
increases inhibition until a
maximum is reached. Beyond
some TAN level, the negative
impact of TAN on the scale
starts to outweigh the benefit of
the oxide layer and inhibition
starts to decrease. If the TAN
relative to the sulphur level
in the stream is high enough
to disrupt the iron sulphide
ln(CR/TAN)
1
0
−1
−2
8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 13.0
1/T, ºR ×10−4
Figure 3 Corrosion data for carbon steel from multiple test programmes can be
fitted into a single correlation for NAC
inhibition factor is also chang- develop a corrosion model for
ing at the same time as the fluid combined NAC and sulphida-
corrosivity is changing, which tion. This analysis resulted in
would be expected to result in the development of the Tancorr
a complex relationship between corrosion model, which pre-
the sulphur and acid concentra- dicts the combined effects of
tions and actual corrosion rates. sulphur and naphthenic acids
in high temperature refinery
Model development systems.
Based on this corrosion mech- The first step in the model’s
anism and the expected corro- development was to develop
sion behaviour, the data from a correlation for pure NAC in
a number of corrosion stud- the absence of sulphur. Figure
ies presented in the literature 3 shows that pure NAC can be
was analysed in an attempt to predicted with an Arrhenius
100
R2 = 0.84
80 R2 = 0.53
60
Inhibition, %

scale formation, the actual cor- 40

rosion rate can be higher than 20
the sum of the predicted NAC
0
and sulphidation rates (that is, Blue line is fit without this data point
percentage inhibition becomes −20
0 10 20 30 40 50
negative).
Correlating parameter
It should also be noted that
at a constant sulphur level,
increasing TAN increases the Figure 4 Percent inhibition shows correlation when the proper correlating
corrosivity of the fluid. The parameter is used

www.digitalrefining.com/article/1002331 PTQ Q2 2019 3

 highlighted point appears to
200
be an anomalous result based
180 Fractions on comparison with results for
160 Crude oil +20% other metallurgies at the same
140 test conditions. When it is left
120
−20% out of the analysis, the correla-
tion does not change much, but
Predicted mpy

100
80 the data fit improves signifi-
60
9Cr CR > CS in lab
cantly. The correlating param-
40 eter is easily calculated from
20 readily available crude oil assay
0 properties.
0 20 40 60 80 100 120 140 160 180 200
Figure 5 shows a compari-
Measured mpy
son of Tancorr predictions vs
measured corrosion rates for
Figure 5 Good correlation for fractions with much more data scatter for crude oil all of the available test data,
which includes both crude oil
type equation of the form: 9% chrome, 410 stainless steel, and fractions. Ideally, all of the
and 304 stainless steel were all data would fall along the line
CRNAC = TAN * A e –Ea/RT (7) evaluated. Figure 4 shows an where the predicted corrosion
example of the results of that rate equals the measured rate.
Using the correlation for analysis for 9Cr. As expected, the data predic-
NAC based on Figure 3 and the A correlating parameter tions were much better for frac-
Modified McConomy curve for based on the competing scale tions than for crude oil. Crude
sulphidation, it was possible to forming and attacking reac- oil predictions did generally
solve Equation 7 to calculate an tions inherent in the mecha- increase along with measured
experimental inhibition factor nism was used to analyse the corrosion rates but the data was
using experimental corrosion inhibition data. As Figure 4 more scattered and tended to
results for the overall corrosion shows, this correlating param- under-predict measured rates
rate. Based on an understand- eter generated a good fit with at corrosion rates greater than
ing of the corrosion mechanism, the experimental inhibition 100 mils per year.
the experimental inhibition data for petroleum fractions on Correlations for the other
data was then analysed to see if 9Cr. Crude oil data was very common metallurgies found
it could be correlated with any- noisy and was only used as part in crude units (CS, 5Cr, 410SS,
thing. Carbon steel 5% chrome, of the model validation. The and 304SS) were also developed
in a similar fashion to the 9Cr
model. Figure 6 shows a series
30
CS
of hypothetical corrosion rate
5CR calculations for CS, 5Cr, and
25
9CR 9Cr using Tancorr. In Figure
20
6, corrosion rate as a function
of TAN is plotted for a system
15 with a constant high level of
sulphur.
10 This new model appears to
shed some light on reported
CR, mpy

5 industry experience. Over the

years, a number of refiners
0 have reported being able to
TAN process high TAN, high sul-
phur crudes without significant
Figure 6 Impact of TAN on corrosion rates for a high sulphur system corrosion problems in units that

4 PTQ Q2 2019 www.digitalrefining.com/article/1002331

were not upgraded specifically
for high TAN (no 316/317SS).
Figure 6 indicates a fairly wide
range of TAN values where
the corrosion rate is stable and
there is little difference in pre-
dicted corrosion rates for any
of the three metallurgies. The
model predictions are consist-
ent with an iron oxide layer
providing additional corrosion
resistance against both NAC
and sulphidation, thus limit-
ing the actual corrosion in high
sulphur, high TAN systems. At
some point, the TAN becomes
high enough that corrosion
begins to increase. Figure 6
shows that starting to happen
for CS and 5Cr, while the 9Cr
corrosion rate is still flat.
Quantitative data show-
ing the effect of sheer stress
on NAC is very limited in the
published literature. Tancorr,
therefore, does not attempt to
incorporate sheer stress effects
into its predictions. The model
does however allow actual
sheer stresses based on normal
piping configurations to be esti-
mated. Sheer stress limits can
be set by the user, which allows
estimation of the actual sheer
stress expected, including the
effect of standard fittings on
sheer stress.
Model application
The input data required to run
the Tancorr model is normally
readily available at the refin-
ery, making the model easy to
use. Table 1 shows the input
data requirements for both
corrosion rate and sheer stress
predictions.
The Tancorr model’s cor-
rosion prediction capabili-
ties can be used in a variety of
ways to help improve refinery
operation:
www.digitalrefining.com/article/1002331
Inputs for corrosion rate and sheer
stress predictions
Corrosion rate Sheer stress
predictions predictions*
Sulphur Flow rate
TAN Line size
Temperature Temperature
Metallurgy API gravity
*Optional inputs of specific fitting types
can also be used
Table 1
• To validate or expand a refin-
ery’s operating window for sul-
phur and TAN
• Linked to linear program
(LP) outputs to make corrosion
predictions on planned refinery
crude slates
• Historical data can be used
to make predictions of actual
corrosion so that inspectors
can decide whether inspection
intervals should be adjusted
based on actual past operation.
• Model predictions in conjunc-
tion with piping condition data
can be used to set limits which
ensure that minimum targets
on remaining piping life are
met.
12
11
10
9 LCL S
8
Predicted CR, mpy
7
6
5
4
3
Avg TAN UCL TAN
2
1
0
0 1 2 3
TAN
Figure 7 Expected corrosion rates over current and future TAN and sulphur
ranges in a HVGO circuit
Most refineries operate over
a range of TAN and sulphur,
depending on the actual crude
slates being processed at any
given time. By analysing histor-
ical crude slate information, the
actual range of operating con-
ditions can be determined. By
making a number of corrosion
rate predictions over a range of
sulphur and TAN that includes
the actual operating range, it
is possible to get a clear pic-
ture of expected corrosion rates
and how much those corro-
sion rates would change if the
sulphur and TAN range was
expanded. Figure 7 shows the
results of one such analysis car-
ried out for a refinery that saw
high value in allowing a mod-
est increase in crude slate TAN.
This type of analysis should be
carried out at the maximum
temperature for each metal-
lurgy/stream combination to
find out the location of the max-
imum predicted corrosion rate
in the system, which will set the
ultimate boundaries on crude
slate TAN and sulphur.
This refinery saw significant
economic incentives in making
UCL S
AVG S
4 5
PTQ Q2 2019 5
 a modest 0.1 TAN increase to
its maximum crude oil TAN.
The purpose of this analysis
was to understand how that
increase would be expected
to impact corrosion. Average
values for crude and side cut
sulphur and TAN were deter-
mined from historical data.
Upper (UCL) and lower (LCL)
control limits were assumed
to be +/-2 standard deviations
from the average. Tancorr pre-
dictions were then made over
a range of TAN values at LCL,
average, and UCL sulphur
concentrations.
The solid vertical lines going
from left to right in Figure 7
represent the average historical
HVGO TAN, the HVGO TAN
at current maximum crude
TAN, and the HVGO TAN at
new target crude TAN. The
dashed lines to the right rep-
resent the upper control limits
for each of the previous num-
bers. This analysis indicates
that increasing crude TAN by
0.1 should have little effect on
corrosion rates and that corro-
sion rates might even decrease.
Caution should be used in
reading too much into small
changes up or down in corro-
sion predictions. Between the
inherent accuracy limits of the
model and limited ability to
accurately measure corrosion in
the field, actually seeing small
differences in corrosion rate
will normally be very hard to
do.
Another way Tancorr can be
used is to check the corrosiv-
ity of actual crude blends that
come out of the refinery’s LP
model. If appropriate sulphur
6 PTQ Q2 2019
and TAN ranges have been
developed and those ranges
have been built into the LP
model, then this use of Tancorr
may have little value. If rigor-
ous analysis has not been done
to set sulphur and TAN ranges,
then this approach can be an
easy check to ensure that spe-
cific crude blends will not cause
excessive corrosion. Tancorr
can be easily linked with LP
output data to automate the cal-
culation process.
Tancorr can also be used
to support risk based inspec-
tion (RBI) efforts at the refin-
ery. Actual refinery operating
data (temperatures and stream
compositions) can be used to
estimate past corrosion. By
comparing the expected actual
corrosion rates with the basis
used to set the inspection inter-
vals, decisions can be made on
whether inspection intervals
should be shortened or can be
increased. This capability is
particularly useful when crude
slates vary widely or the refin-
ery has made a step change
shift in crude sulphur and
TAN.
Finally, Tancorr predictions
can be used in conjunction
with actual piping condition
data to develop allowable sul-
phur and TAN ranges which
ensure that minimum desired
piping life targets are achieved.
This approach can also be used
when a refinery is looking to
process increasing amounts of
opportunity crudes over time
without initiating a major met-
allurgy upgrade project. This
approach has previously been
described in more detail.3
Conclusion
By analysing literature data
using knowledge about
the mechanism, ProCorr
Consulting Services has been
able to develop a useful model
for naphthenic acid corrosion.
Because the Tancorr model
is also easy to use and only
requires readily available input
data, there are a number of
ways it can be used to help
refineries optimise their high
TAN crude processing capabili-
ties. This model is a critical new
tool for refineries seeking to
improve profitability through
processing increasing amounts
of opportunity crudes.
References
1 Craig H L Jr, Temperature and velocity
effects in naphthenic acid corrosion,
Corrosion 96, Paper No. 603.
2 Jin P, et al, Mechanism of high
temperature corrosion by model
naphthenic acids, Corrosion 2016, Paper
7302.
3 Vetters E, Clarida D, Maintaining
reliability when processing opportunity
crudes, PTQ, Q4 2013.
Eric Vetters is President of ProCorr
Consulting Services LLC in Owasso,
Oklahoma. He has over 35 years of
experience in process engineering
and corrosion at Phillips 66 and as a
consultant.
Email: ewvetters@yahoo.com
LINKS
More articles from the following
categories:
Corrosion and Fouling Control
Heavy and Sour Feedstocks
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