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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 presence of a high molybde- on the metal surface, which
(TAN) crudes often sell num alloy such as 316 or 317L has been shown to provide
at a significant discount stainless steel. TAN, which some level of inhibition against
due to concerns about naph- is a measure of the acid con- NAC. Equation 3 shows how
thenic acid corrosion (NAC) tent, is used as an indicator naphthenic acids can also react
– both real and perceived. In of NAC potential; however, directly with iron sulphide,
some systems, high corrosion it not considered to be a relia- potentially reducing the inhib-
rates are experienced with rel- ble predictor of NAC by itself. itive effects of iron sulphide
atively low TAN feedstocks, This temperature range also scales against direct naphthenic
while other systems without coincides with that of high acid attack on the metal surface:
extensive alloy upgrades seem temperature sulphur corro-
to handle high TAN feeds with sion, meaning that at least two 2RCOOH + Fe → Fe(OOCR)2 + H2 (1)
few problems. This unpredict- simultaneous corrosion mech-
ability, as well as the localised anisms can be occurring simul- H2S + Fe→ FeS + H2 (2)
nature of NAC, has created an taneously with the potential for
2RCOOH + FeS ⇒ Fe(OOCR)2 + H2S (3)
air of mystery around NAC significant interaction between
and has caused many refin- mechanisms.
ers to take a very conservative The basic NAC corrosion Many theories exist to explain
approach towards processing reaction is shown in Equation why TAN alone is not a good
high TAN crudes. The chal- 1. Because the iron naphthen- predictor of corrosion. The
lenges of predicting naphthenic ate corrosion product is oil sol- most commonly promoted the-
acid corrosion along with new uble, it has not been thought to ories are related to the compo-
developments in understand- form a protective scale like the sition of the naphthenic acids
ing the mechanism led ProCorr sulphidation corrosion reac- and the presence of sulphur in
Consulting Services to analyse tion depicted in Equation 2, the system. The acid composi-
the available literature corro- which is illustrated using H2S tion claims are usually either
sion data and to turn that data as the reactive sulphur com- that the TAN test is non- spe-
into the Tancorr naphthenic pound. Sulphidation occurs at cific and detects things other
acid corrosion model. similar temperatures to NAC than naphthenic acids or that
NAC is generally under- and is more generalised in some acids are non-corrosive
stood to occur in parts of the nature with less susceptibility or may even inhibit corro-
crude and vacuum unit operat- to high shear stress. The iron sion. While there is a limited
ing above 450°F (232°C) when sulphides formed from sulphi- amount of testing on specific
the TAN value exceeds some dation corrosion are not oil sol- molecules that seems to indi-
threshold value without the uble and tend to form a scale cate that different individual

www.digitalrefining.com/article/1002331 PTQ Q2 2019 1


thenate molecule (Fe(OOCR)2)
Metal surface
hinders diffusion out of the iron
Fluid flow
Corrosion products sulphide scale enough to allow
(FE3O4 inner and
(HC, RCOOH, RS) R-S FeS RCOOH Fe(RCOO)2 FeS outer) some thermal decomposition.
This formation of an iron
Figure 1 Combined NAC and sulphidation corrosion mechanism oxide scale adds yet another
layer of complexity to the
mechanism by adding at
least two new reactions to the
mechanism:
S
dominated Combined Fe(RCOO)2 → FeO + CO2 + RCOR (4)

Potential corrosion
S & NAC NAC
Inhibition, %

dominated 4FeO → Fe3O4 + α-Fe (5)

The net result is that a com-


plex set of interacting scale
forming and scale destroying
Inhibition
reactions are simultaneously
Potential corrosion occurring. This complex cor-
rosion mechanism is depicted
TAN in Figure 1, which shows the
development of a dual layer
Figure 2 Theoretical corrosion inhibition in systems with both sulphur and protective scale. Alloying ele-
naphthenic acid ments, such as chromium, add
still more complexity as the
acids cause corrosion at differ- thenic acid mixtures by approx- resulting Cr containing corro-
ent rates, there is nothing that imately 80-90% compared to sion products are incorporated
definitively links differences in similar systems without H2S. into the scale. The overall cor-
crude oil corrosivity to differ- This interaction between NAC rosion rate depends on the rel-
ences in the nature of the actual and sulphidation is compli- ative rates of these different
acid species present, and there cated by the fact that naph- reactions, which in turn depend
is certainly no way to measure thenic acids can also react with on the fluid composition, the
the parameters likely to make iron sulphide scales to dissolve process conditions and the
a difference in the corrosivity the scale. metallurgy.
of individual acid molecules More recently, a joint indus- With this mechanism, a
found in crude oil. try programme (JIP) at Ohio number of distinct corrosion
There is actually good evi- University discovered the pres- regimes can be expected. At
dence to support the inhibitive ence of a thin iron oxide layer low TAN values, the formation
effect of sulphur on NAC. The under an outer iron sulphide of any oxide scales will be mini-
idea has been that the iron sul- layer. This iron oxide layer mal and sulphidation corrosion
phide corrosion product layer provided additional corrosion will dominate. At some level of
formed from sulphidation cor- protection and was determined TAN, the interactions between
rosion, which usually occurs to result from the thermal deg- NAC and sulphidation become
in the same locations as NAC, radation of iron naphthenate significant and a maximum
inhibits diffusion of naphthenic corrosion products. Iron naph- inhibition level is reached. As
acids to the metal surface, thenates are not thermally sta- TAN increases relative to the
which thus reduces the corro- ble and have been shown to sulphur level, at some point
sion rate due to NAC. In work break down to form a separate NAC and the attack of iron
by Craig,1 the presence of H2S iron oxide layer under the outer sulphide scales by naphthenic
reduced the overall corrosion iron sulphide layer.2 It is likely acids begins to dominate. Figure
rate of mineral oil and naph- that the size of the iron naph- 2 depicts how this scale inhibi-

2 PTQ Q2 2019 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

ln(CR/TAN)
1
CRS and CRNAC are the sul-
0
phidation and naphthenic acid
corrosion rates independent of −1
any interactions between the −2
8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 13.0
mechanisms, and %I repre-
sents the interaction between 1/T, ºR ×10−4
the two mechanisms expressed
as a % inhibition. The iron sul- Figure 3 Corrosion data for carbon steel from multiple test programmes can be
phide scale formed from sul- fitted into a single correlation for NAC
phidation corrosion naturally
limits the steady state corrosion inhibition factor is also chang- develop a corrosion model for
rate, and that effect is already ing at the same time as the fluid combined NAC and sulphida-
incorporated into the Modified corrosivity is changing, which tion. This analysis resulted in
McConomy curve, which is would be expected to result in the development of the Tancorr
the most widely used method a complex relationship between corrosion model, which pre-
of predicting sulphidation the sulphur and acid concentra- dicts the combined effects of
corrosion. tions and actual corrosion rates. sulphur and naphthenic acids
At low TAN, there is limited in high temperature refinery
oxide layer formation, so inhi- Model development systems.
bition levels are low. As the Based on this corrosion mech- The first step in the model’s
TAN increases, the formation anism and the expected corro- development was to develop
of oxide scale increases, which sion behaviour, the data from a correlation for pure NAC in
increases inhibition until a a number of corrosion stud- the absence of sulphur. Figure
maximum is reached. Beyond ies presented in the literature 3 shows that pure NAC can be
some TAN level, the negative was analysed in an attempt to predicted with an Arrhenius
impact of TAN on the scale
starts to outweigh the benefit of
the oxide layer and inhibition
100
starts to decrease. If the TAN R2 = 0.84
relative to the sulphur level 80 R2 = 0.53
in the stream is high enough 60
to disrupt the iron sulphide
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 Most refineries operate over
Inputs for corrosion rate and sheer
for high TAN (no 316/317SS). stress predictions a range of TAN and sulphur,
Figure 6 indicates a fairly wide depending on the actual crude
range of TAN values where Corrosion rate Sheer stress
slates being processed at any
the corrosion rate is stable and predictions predictions* given time. By analysing histor-
there is little difference in pre- Sulphur Flow rate ical crude slate information, the
dicted corrosion rates for any TAN Line size actual range of operating con-
Temperature Temperature
of the three metallurgies. The Metallurgy API gravity
ditions can be determined. By
model predictions are consist- making a number of corrosion
ent with an iron oxide layer *Optional inputs of specific fitting types rate predictions over a range of
providing additional corrosion can also be used
sulphur and TAN that includes
resistance against both NAC the actual operating range, it
and sulphidation, thus limit- Table 1 is possible to get a clear pic-
ing the actual corrosion in high ture of expected corrosion rates
sulphur, high TAN systems. At • To validate or expand a refin- and how much those corro-
some point, the TAN becomes ery’s operating window for sul- sion rates would change if the
high enough that corrosion phur and TAN sulphur and TAN range was
begins to increase. Figure 6 • Linked to linear program expanded. Figure 7 shows the
shows that starting to happen (LP) outputs to make corrosion results of one such analysis car-
for CS and 5Cr, while the 9Cr predictions on planned refinery ried out for a refinery that saw
corrosion rate is still flat. crude slates high value in allowing a mod-
Quantitative data show- • Historical data can be used est increase in crude slate TAN.
ing the effect of sheer stress to make predictions of actual This type of analysis should be
on NAC is very limited in the corrosion so that inspectors carried out at the maximum
published literature. Tancorr, can decide whether inspection temperature for each metal-
therefore, does not attempt to intervals should be adjusted lurgy/stream combination to
incorporate sheer stress effects based on actual past operation. find out the location of the max-
into its predictions. The model • Model predictions in conjunc- imum predicted corrosion rate
does however allow actual tion with piping condition data in the system, which will set the
sheer stresses based on normal can be used to set limits which ultimate boundaries on crude
piping configurations to be esti- ensure that minimum targets slate TAN and sulphur.
mated. Sheer stress limits can on remaining piping life are This refinery saw significant
be set by the user, which allows met. economic incentives in making
estimation of the actual sheer
stress expected, including the
12
effect of standard fittings on UCL S
11
sheer stress. AVG S
10
9 LCL S
Model application
8
The input data required to run
Predicted CR, mpy

7
the Tancorr model is normally 6
readily available at the refin- 5
ery, making the model easy to 4
use. Table 1 shows the input 3
Avg TAN UCL TAN
data requirements for both 2
corrosion rate and sheer stress 1
predictions. 0
0 1 2 3 4 5
The Tancorr model’s cor-
TAN
rosion prediction capabili-
ties can be used in a variety of
ways to help improve refinery Figure 7 Expected corrosion rates over current and future TAN and sulphur
operation: ranges in a HVGO circuit

www.digitalrefining.com/article/1002331 PTQ Q2 2019 5


a modest 0.1 TAN increase to and TAN ranges have been Conclusion
its maximum crude oil TAN. developed and those ranges By analysing literature data
The purpose of this analysis have been built into the LP using knowledge about
was to understand how that model, then this use of Tancorr the mechanism, ProCorr
increase would be expected may have little value. If rigor- Consulting Services has been
to impact corrosion. Average ous analysis has not been done able to develop a useful model
values for crude and side cut to set sulphur and TAN ranges, for naphthenic acid corrosion.
sulphur and TAN were deter- then this approach can be an Because the Tancorr model
mined from historical data. easy check to ensure that spe- is also easy to use and only
Upper (UCL) and lower (LCL) cific crude blends will not cause requires readily available input
control limits were assumed excessive corrosion. Tancorr data, there are a number of
to be +/-2 standard deviations can be easily linked with LP ways it can be used to help
from the average. Tancorr pre- output data to automate the cal- refineries optimise their high
dictions were then made over culation process. TAN crude processing capabili-
a range of TAN values at LCL, Tancorr can also be used ties. This model is a critical new
average, and UCL sulphur to support risk based inspec- tool for refineries seeking to
concentrations. tion (RBI) efforts at the refin- improve profitability through
The solid vertical lines going ery. Actual refinery operating processing increasing amounts
from left to right in Figure 7 data (temperatures and stream of opportunity crudes.
represent the average historical compositions) can be used to
HVGO TAN, the HVGO TAN estimate past corrosion. By References
at current maximum crude comparing the expected actual 1 Craig H L Jr, Temperature and velocity
TAN, and the HVGO TAN at corrosion rates with the basis effects in naphthenic acid corrosion,
new target crude TAN. The used to set the inspection inter- Corrosion 96, Paper No. 603.
2 Jin P, et al, Mechanism of high
dashed lines to the right rep- vals, decisions can be made on
temperature corrosion by model
resent the upper control limits whether inspection intervals
naphthenic acids, Corrosion 2016, Paper
for each of the previous num- should be shortened or can be 7302.
bers. This analysis indicates increased. This capability is 3 Vetters E, Clarida D, Maintaining
that increasing crude TAN by particularly useful when crude reliability when processing opportunity
0.1 should have little effect on slates vary widely or the refin- crudes, PTQ, Q4 2013.
corrosion rates and that corro- ery has made a step change
sion rates might even decrease. shift in crude sulphur and
Eric Vetters is President of ProCorr
Caution should be used in TAN. Consulting Services LLC in Owasso,
reading too much into small Finally, Tancorr predictions Oklahoma. He has over 35 years of
changes up or down in corro- can be used in conjunction experience in process engineering
sion predictions. Between the with actual piping condition and corrosion at Phillips 66 and as a
inherent accuracy limits of the data to develop allowable sul- consultant.
model and limited ability to phur and TAN ranges which Email: ewvetters@yahoo.com
accurately measure corrosion in ensure that minimum desired
the field, actually seeing small piping life targets are achieved.
differences in corrosion rate This approach can also be used
will normally be very hard to when a refinery is looking to
do. process increasing amounts of LINKS
Another way Tancorr can be opportunity crudes over time
used is to check the corrosiv- without initiating a major met- More articles from the following
ity of actual crude blends that allurgy upgrade project. This categories:
come out of the refinery’s LP approach has previously been Corrosion and Fouling Control
model. If appropriate sulphur described in more detail.3 Heavy and Sour Feedstocks

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