Review of naphthenic acid corrosion in

oil refining
E. SLAVCHEVA Naphthenic acid corrosion is a major concern for the oil refinery business. W hile much is
B. SHONE now known about the phenomenon, it is still not completely understood because of the
complex influences on corrosion of the type of acid and other constituents in the crude oil
A. TURNBULL and the eVects of both temperature and fluid flow. A review of this form of corrosion has
been undertaken with respect to the role of crude oil composition, temperature, fluid velocity,
physical state (vapour or liquid), pressure, and materials of construction. Simple measures
of corrosivity based on the total acid or neutralisation number are insuYcient. T he sulphur
content of the crude is important but the extent to which the various sulphur containing
compounds act as inhibitors or corrodents is not understood. T here is little knowledge also
of the nature of films formed on the steel surfaces under operating conditions and the role of
natural inhibitors that may be present in crudes requires more attention.
Mr Slavcheva is at the Bulgarian Academy of Sciences, Akad. G. Bonchev St, 1113 Sofia,
Bulgaria, Mr Shone is a consultant, T y Isa, Mold CH7 5BQ, UK, and Dr T urnbull is at
the National Physical L aboratory, T eddington, Middx T W 11 0L W, UK. Manuscript
received 11 September 1998; accepted 19 November 1998.
© 1999 IoM Communications L td.

INTRODUCTION
Crude oils from many parts of the world, including China,
India, Venezuela, Eastern Europe, Russia, and the USA,
are often said to be naphthenic. Such oils have been found
to contain organic acids with saturated ring structures and
one or more carboxylic groups. While the acids varied
considerably in molecular weight, their general formula,
like that of all naphthenic acids, could be written as
R[CH ] COOH, where R is usually a cyclopentane or
2 n
cyclohexane ring. Table 1 is illustrative of the range of
species in a heavy vacuum gas oil (HVGO), determined by
fast atom bombardment mass spectrometry. In this table,
the carbon number is simply the number of carbon atoms
in the molecule. At the operating temperatures relevant to
crude oil refining, these acids can be corrosive and the
form of attack is appropriately called ‘naphthenic acid
corrosion’. Crude oils are complex and sulphur species and
chlorides may be present also which in different ways can
influence the nature and extent of corrosion.
The crude oil refining process is illustrated schematically
in Fig. 1. The oil is preheated by heat exchange using, 1 Schematic illustration of crude oil refinery process
for example, hot product streams from the process. It is
then passed through the furnace tubes which supply the
remaining heat requirement by direct firing before being lines, tower packing, pump internals, valves, and fittings
transferred to the atmospheric distillation column. Here are all potentially susceptible. Metal thinning can occur
the lighter products are distilled over. The heavy hydro- on the underside of trays and downcomers, where high
carbon residue is transferred to the vacuum distillation concentrations of acid condense from the vapour, and on
column via another preheater and further distillates are the walls of the column owing to condensate rundown.
drawn off. More localised attack may occur in regions of sulphide
The nature of the corrosion process depends upon the film formation, although such films can be beneficial.
location in the refinery system. Furnace tubes, transfer Corrosion–erosion can occur, e.g. owing to high velocities
in the transfer lines.
Damage due to naphthenic acid corrosion was first
Table 1 Proportions of acids (%) in heavy vacuum observed in the 1920s.1 In recent years, interest in
gas oil naphthenic acid corrosion has increased for several reasons.
It has become apparent that if low cost ‘opportunity crude
Carbon number oils’ could be processed in plants constructed from con-
Number ventional inexpensive steels, then considerable savings
of rings 16 17 18 19 20 21 22 Total could be made. Opportunity crude oils are readily available
but their processing in those conventional refineries con-
2 2·0 2·1 2·4 3·8 2·9 3·4 ... 16·6 structed from plain carbon steels is regarded as risky as
3 2·3 5·1 5·4 5·3 4·1 2·9 ... 25·1 many of these crudes are naphthenic and potentially
4 1·9 3·0 3·3 5·0 4·8 3·7 3·4 25·1 corrosive. If corrosion occurred then refinery outages and
5 ... ... 3·4 4·1 4·6 3·8 2·9 18·8
6 ... ... ... 3·5 3·7 4·4 2·8 14·4 expensive repairs could be anticipated. In principle, a better
Total 6·2 10·2 14·5 21·7 20·1 18·2 9·1 100 understanding of the fundamentals of naphthenic acid
corrosion should lead to the identification of the potentially

ISSN 0007–0599 British Corrosion Journal 1999 Vol. 34 No. 2 125

126 Slavcheva et al. Naphthenic acid corrosion in oil refining

corrosive crude oils and enable selected opportunity crudes

to be processed in the units constructed from inexpensive
materials without fear of corrosion. Such information
would also enable the most cost effective materials to be
used in the constructions of new plants and the prevention
of in-service failures. Additionally, the judicious selection
of materials could prevent corrosion and the subsequent
contamination of oil feedstocks by ferrous corrosion
products. The presence of such contaminants in the
feedstock used in complex modern refineries may result in
the poisoning of process catalysts and expensive stoppages.
In a review article in 1987, Piehl2,3 summarised some of
the key papers, including case histories,1,4,5 attempts to
develop corrosion correlations based on laboratory test
data,6,7 and industry surveys.8–10 Blanco et al.5 listed the
main factors that influence naphthenic acid corrosion as:
neutralisation number (amount of KOH to neutralise acid,
as described below), temperature of operation, velocity and
turbulence, physical state of the crude oil (liquid or vapour),
and materials of construction. The work of Derungs1 and
Craig11,12 suggests that the influence of pressure and the
crude oil should also be accounted for.
In the present paper an assessment will be made of the
significance of the varied factors influencing corrosion, a
critical review of available literature will be given, and the
work that is required to develop a fuller understanding of
this form of corrosion will be outlined.
CORROSION MECHANISM
The corrosion reaction processes are described typically by
Fe+2RCOOH=Fe(RCOO) +H
2 2
Fe+H S=FeS+H
2 2
Fe(RCOO) +H S=FeS+2RCOOH
2 2
The iron naphthenates are soluble in oil and the surface is
relatively film free. In the presence of H S a sulphide film
2 and cathodes on the same surface with the cathodic current
is formed which can offer some protection depending on
the acid concentration.
The net reaction processes described by the above
equations could apply equally to chemical or electrochemi-
cal reactions. The distinction with respect to the latter is
that there are separate anodic and cathodic reaction
processes with movement of ions through the solution and
electrons through the metal. To distinguish the relative
contributions of electrochemical and chemical processes to
the corrosion rate, the ideal approach would be to apply
a sufficiently high anodic current to the specimen and
compare the mass loss with that predicted from Faraday’s
law. Alternatively, apply a cathodic current to retard dis-
solution and compare with the mass loss rate. The use of
the linear polarisation method is thwarted somewhat by
uncertainty in measurement of potential in these fluids at
the operating temperatures.
The requirement for current transfer implies some degree
of fluid conductivity, although the separation of anodic
and cathodic areas on the metal under open circuit
conditions can be small. Measurement13 of conductivity of
a 1M solution of a commercial naphthenic acid mixture in
mineral oil at ambient temperatures indicated a value of
less than 0·01 mS cm−1. To put this in context, theoretically
pure water has a conductivity of about 0·05 mS cm−1. In
an effort to resolve the issue of chemical versus electrochemi-
cal reaction processes, Francis and Turnbull13 inserted a
carbon steel rod inside a stainless steel tube with PTFE
used to electrically insulate the two metals. The distance
between the electrodes was about 1 mm. The assembly was
immersed in a 1M cyclohexane carboxylic acid (CHCA) in
mineral oil (with the PTFE above the liquid level ) and
50 V applied with the carbon steel acting as anode and the
stainless steel as cathode. The current was measured as
the temperature of the fluid was increased to 275°C. The
2 Dependence of current on temperature (time) for applied
voltage of 50 V between carbon steel anode and stainless
steel cathode
nominal area of exposed carbon steel was about 2 cm2.
The results are shown in Fig. 2.
It is evident that passage of current is only significant
above about 150°C, and at 275°C the current density is
about 0·6 mA cm−2. To put this measurement in perspective,
the mass loss at this concentration of naphthenic acid
(separate measurement) was equivalent to 22 mm/year,
which on a Faradaic basis would represent a current
density of about 9·2 mA cm−2. Since the displacement of
potential is unknown, it can be argued that such currents
could arise at open circuit by virtue of close proximity of
the anodes and cathodes. Certainly, this cannot be refuted
but it seems unlikely.
A more definitive conclusion can be deduced in relation
to the observation of pitting. An electrochemical mechanism
for pitting requires more significant separation of anodes
spread over a reasonable area (otherwise the electrode
potential would be reduced and the pit growth stifled). In
view of the above results, an electrochemical basis for
pitting is not tenable unless there are water and salts in
the crude to increase the conductivity. Pitting is most
probably associated with local chemical reaction induced
by local variations in turbulent flow and film breakdown.
LABORATORY TESTING
Laboratory test methods have been reviewed by Tebbal
and Kane.14 A primary challenge is how best to maintain
the chemistry of service conditions at temperature and, in
that context, whether to use a sealed autoclave system or
an open system. In an open system with a condenser,
evolved gases such as H S are inevitably lost with time,
2
although light fractions will recondense. It is necessary to
pass an inert gas–H S mix to account for the effects of
2
H S. However, defining the appropriate concentration
2
relative to service conditions is uncertain since the latter is
usually unknown. Sealing of the system can lead to
unrealistically high concentrations of H S at temperature
2
and is not satisfactory. Tebbal and Kane claim that a
pressure relief valve and condenser can generate corrosion
data close to those determined in plant but recognise that
there is a certain arbitrariness in the pressure level setting.
However, this is not helpful if such plant data are not
available and may not apply to different crudes. Indeed,
the approach is really no different from a test in an open
system through which an inert gas–H S mix is passed, with
2
the corrosion rate in plant used to define the appropriate
levels. An improved basis for predicting the effective
concentration of H S in the oil in plant conditions is the
2
primary requirement so that relevant simulation can be
attempted.

British Corrosion Journal 1999 Vol. 34 No. 2

 Slavcheva et al. Naphthenic acid corrosion in oil refining 127

3 Dependence of total acid number on exposure time of 1018

carbon steel in mineral oil with 0·25M CHCA at 275°C

Decomposition of the acids at temperature is also a

concern with respect to laboratory simulation.12,13 In 4 Naphthenic acid corrosion of carbon steel:3 mpy=mils/year
where 1 mil=0·001 in
laboratory testing of a single ring acid (CHCA), Turnbull
and Francis observed13 very marked decomposition of the
acid at 275°C, evidenced by a rapid decay in the total acid
number (TAN) with exposure time (Fig. 3). Use of double
condensers demonstrated that this was not simply a loss of
volatile species, which was confirmed by the observation
that the decay in TAN value was significant only in the
presence of corroding metal. In the absence of the metal
the TAN value decreased only from 18 to about 16 over
the same period. Simple calculations from mass loss rate
indicated that the consumption of acid by corrosion was
over an order of magnitude too small to explain the
decrease in TAN value. In a commercial naphthenic acid
mixture the TAN value decreased from 18 to about 9,
suggesting that the decomposition was more significant for
the lighter acids.
The key issue is whether such decomposition would
occur in the presence of a corrosion resistant alloy as used
in autoclaves or requires the steel to be corroding for some
reason. Further work needs to be done, but the implication 5 Corrosion rate of 1018 carbon steel in mineral oil with
is that more consideration should be given to testing under 0·25M acid (initial TAN 17/18)
conditions in which there is a gradual flow (to waste)
of liquid through the cell to maintain constancy of
environment. corrosivity, as indicated for carbon steel in Fig. 4.3
Nevertheless, significant variations in corrosivity can be
obtained at the same TAN value depending on the nature
CRUDE OIL COMPOSITION of the naphthenic acids,15 as illustrated in Fig. 5. The
Neutralisation number carbon number referred to in this figure is simply the
Naphthenic acids are present in crude oils in small number of carbon atoms in the molecule. Babaian-Kibala
quantities, generally less than 3%, and their concentration et al.16,17 suggested that there may be a poor correlation
in an oil is expressed as the amount of KOH in milligrams between the TAN value of a number of oils and the weight
required to neutralise the acidity in one gram of oil. This percentage of naphthenic acid found in a given oil, the
measure of acidity is called the total acid number (TAN) latter being determined by the combination of acid
of the oil. Two of the standard tests used frequently to separation by liquid phase chromatography followed by IR
determine the level of acidity of oils are ASTM method absorption. However, laboratory measurement of the TAN
D974, a colorimetric procedure, and ASTM D664, a value for varying molar concentrations of a single acid and
potentiometric method. Piehl3 pointed out that the two a commercial acid mix suggests a linear correlation, with
methods may yield results that are different by up to 80%. TAN values being similar for the same concentration of
The ASTM D664 method is more commonly used, single acid or acid mixture.15 Babaian-Kibala et al. did not
the colorimetric method being considered less reliable. explain the origin of the discrepancy between TAN value
However, results produced using ASTM D664 are influ- and weight per cent concentration, but this may simply
enced by the presence of acid gases, e.g. H S and CO , and reflect the use of weight percentage as a parameter for
2 2
salts such as MgCl and CaCl that may hydrolyse. The defining concentration, which would seem inappropriate
2 2
ASTM D974 method yields an end point pH which is for molecules of varying molecular weight. A more likely
generally less alkaline than that measured using the ASTM explanation is that the TAN value measures an acidity, not
D664 test. just that of the naphthenic acids.
Several workers have attempted to correlate TAN values Field surveys6–8,16,17 have indicated that the likelihood
of crude oils and their fractions with corrosion rates. of significant naphthenic acid corrosion occurring increases
Increasing TAN values are usually indicative of increasing when the crude oil has a TAN value greater than 0·5 mg

British Corrosion Journal 1999 Vol. 34 No. 2

128 Slavcheva et al. Naphthenic acid corrosion in oil refining
KOH g−1 crude and distillation temperatures are between
220 and 400°C. Other field studies2,18 have found that the
threshold TAN value for the initiation of corrosion is
between 1·5 and 2·0 mg KOH g−1 crude. Corrosion has
also been reported when a light Indonesian crude with a
TAN value well below 0·5 mg KOH g−1 crude was pro-
cessed. The observation of a cutoff below some apparently
critical acid number is indicative of a protective film being
formed. This will depend on the material and on the
composition of the crude. The stability of that film will
also be dependent on flow, particularly wall shear stress,
and on temperature. Thus, generalisation with respect to
the value of the threshold for corrosion would seem, from
a fundamental viewpoint, inappropriate.
Crude oil type
The influence of the crude oil type on naphthenic acid
corrosion is complex and not well understood. It is
generally acknowledged that the TAN value of the crude
oil is important and that both the sulphur content and
the presence of hydrogen sulphide are also of import-
ance. Crude oils can have sulphur contents ranging from
∏1 wt-% (sweet crudes) to about 6 wt-% (sour crudes).
Piehl2,3 suggested that in crude distillation the acids will
partition themselves along with other hydrocarbons of the
same boiling point and that a knowledge of the distribution
of acids in a crude as a function of the true boiling point
will enable prediction to be made of where high acid
concentrations will occur in a process unit. Unfortunately,
this information may still be inadequate for predictive
purposes for, as he suggested, crude oil seems to have some
inhibiting qualities that result in less corrosion occurring
than would be expected. Also, information on the aggressiv-
ity of the particular acids will be required as different acids
may have different corrosivities.
It has been recognised for some time that various sulphur
compounds that originate from crude oils, and include
polysulphides, mercaptans, aliphatic sulphides, disulphides,
and thiophenes, may react with metal surfaces to form
metallic sulphides, organic complexes, and hydrogen sul-
phide. The thiophenes are regarded as non-corrosive.
Decomposition of certain sulphide compounds can occur
at temperatures above about 260°C to produce H S,
2
although direct reaction with the metal to produce sulphides
can also occur. Reaction with H S is considered to be the
2
dominant corrosion process and, indeed, correlations of
corrosion rate with the quantity of H S evolved have been
2
obtained. It is proposed that naphthenic acid and hydrogen
sulphide corrosion may be proceeding simultaneously and
that the former produces soluble corrosion products while
the latter forms an insoluble product. When both are
present he suggested that one form of corrosion may
proceed at the expense of the other and that this is possibly
why distillation units handling low sulphur crude oils
appear to be more prone to naphthenic acid corrosion
than units handling high sulphur crude oils. The compara-
tive inhibiting effect of H S is illustrated in Fig. 6.12
2
The possibility of other compounds in a crude oil having
similar inhibiting effects has not been given sufficient
consideration. Piehl’s analysis of the surface films formed
is superficial and the identification of FeS as the main
corrosion product and H S as the corrodent must be
2
treated with caution. Considerably more work is required
to understand the nature of the films that form on the
metal surfaces in the presence of hot crude oils and the
role that the various sulphur containing compounds that
may be present have before their value as either inhibitors
or corrodent can be ascertained.
From the above it is apparent that there is only limited
understanding of the relationship that exists between the
crude oil types and their corrosion characteristics. The
British Corrosion Journal 1999 Vol. 34 No. 2
D D D K1+H S; CC acid (K1); V HVGO (var); 1 HVGO-AT;
2
^ HVGO+acid
6 Effect of H S on naphthenic acid corrosion of carbon steel:12
2
K1 represents neutral, sulphur free oil to which naphthenic
acid was added; HVGO-AT represents tests in heavy vacuum
gas oil after utilisation in hot oil impingement tests;
HVGO+acid represents tests with HVGO before utilisation;
test temperature 260°C
concept that crude oil may contain natural inhibitors has
been suggested but only superficially explored. The use of
TAN values to describe the corrosion characteristics of
crude oils has significant limitations if used in isolation.
More emphasis on laboratory tests with carefully controlled
chemistry is required.
TEMPERATURE OF OPERATION
There appears to be little doubt that naphthenic acid
corrosion occurs over the temperature range of about
220–400°C.2,4,11,12,16–21 It is suggested that at higher
temperatures the naphthenic acids decompose and that at
lower temperatures the corrosion rate is not high enough
to cause problems. Gutzeit6,7 reported the results of field
surveys which indicate that naphthenic acid corrosion is
greatest at the condensation point where the vapour stream
draws liquid over the metal. It seems probable that the
temperature he refers to is the condensation temperature
for specific naphthenic acids. In the laboratory experimental
work he undertook, corrosion coupons were exposed in
both liquid and vapour phases and he found that the
corrosion of most steels approximately triples with each
55 K increase in temperature and, at a given temperature,
is directly related to the naphthenic acid content of the
hydrocarbon stream. He also suggested that at about 230°C
the corrosion rate of plain carbon steels and of AISI 410
type alloys is parabolic and claims that corrosion is
controlled by a chemisorption mechanism. In the absence
of data to the contrary he tentatively concluded that
naphthenic acid corrosion continues to increase up to at
least 385°C if the acids are not lost through evaporation.
While the exact value of the corrosion isotherms he presents
may be challenged in view of the considerable scatter
observed, there is little doubt that the trends he observed
are real. At the conclusion of his work he suggests that the
corrosion kinetics can be represented by an Arrhenius type
equation at temperatures above 288°C (and probably at
lower temperatures).
The type of naphthenic acids present in the hydrocarbon
stream was not considered in detail and would be expected
to influence the corrosion rate and magnitude of the
activation energy. This is demonstrated in Fig. 7 (Ref. 15)
in which the temperature dependence of the corrosion rate

7 Corrosion rate of 1018 carbon steel in mineral oil with
0·25M acid (TAN 17/18): CHCA=cyclohexane carboxylic
acid; NAs=commercial naphthenic acid mixture
8 Modified McConomy curve 22
of a carbon steel in both a single acid and acid mixture are
compared. The lines shown represent the best fit by the
linear regression method. The activation energy was 31·8
and 23·8 kJ mol−1 for the single acid and acid mixture
respectively. This is considerably lower than the value
of 68·5 kJ mol−1 suggested by Gutzeit7 for carbon steel.
However, the former results were obtained in the temper-
ature range 210–300°C. Guitzeit showed a significant
decrease in the temperature sensitivity of corrosion in this
temperature region, but his data are insufficient to estimate
an activation energy. The possible influence of exposure
time on the corrosion rate and its temperature dependence
cannot be discounted as an explanation for the different
activation energies.
The temperature dependence of the corrosion rate for
different alloys had been investigated by McConomy22 and
by Heler8 from field studies. The former study gave rise to
the modified McConomy curve (Fig. 8) with the proposed
correction factor for sulphur content (Fig. 9). The
McConomy curves are based essentially around sulphur
species as the predominant corrodent. As pointed out by
Tebbal and Kane,14 there are a number of inconsistencies
with known behaviour when different levels of naphthenic
acid are present. The lower corrosion rate indicated for
4–6Cr steel relative to carbon steel does not correspond to
many field or more recent laboratory studies.
Slavcheva et al. Naphthenic acid corrosion in oil refining 129
9 Correction factor for sulphur content 22
An interesting feature of Fig. 8 is the broad similarity
in activation energy for the different materials (about
50–67 kJ mol−1). Gutzeit7 also noted the similarity of
activation energy for AISI 410 and carbon steel in
naphthenic acid corrosion. However, no such concurrence
in activation energy was apparent in the work of Heler.8
The activation energy would be expected to be a sensitive
function of the composition of the crude oil as this will
determine the controlling kinetics through film formation
and rates of adsorption. As such, the compilation of data
from field studies may be somewhat misleading and greater
emphasis should be placed on controlled laboratory studies.
VELOCITY AND TURBULENCE
Blanco et al.5 showed that velocity and turbulence are
important parameters and suggested that corrosion is
always increased by a high linear velocity situation.
Additionally, they presented corrosion data that had been
collected from transfer lines handling crude oils at about
360°C, which indicated that the corrosion rate of plain
carbon steel is considerably higher than that of 5Cr–0·5Mo
containing steel when the crude oil flows at high velocities.
In practice, the influence of velocity and turbulence on
corrosion is demonstrated by the observation that naph-
thenic acid corrosion is most severe in areas of highest
turbulence, i.e. T pieces, elbows, and pumps.19 Gutzeit7
showed that in white oil–naphthenic acid blends at 280°C,
with velocities up to 4 m s−1 in the liquid phase, the
influence of velocity on corrosion was quite small. In
contrast, he found a drastic increase in vapour phase
(condensate) corrosion as the velocity increased from 0 to
0·12 m s−1. He also showed that further increases in
velocity, up to 4·0 m s−1, resulted in reduced corrosion.
This effect is attributed to centrifugal forces in the system
preventing the condensate film from forming at the higher
velocities. It is reported2 that high velocities or turbulence
can accelerate naphthenic acid corrosion but that the
effect is not usually pronounced in distillation columns,
exchangers, and piping when the latter are liquid packed.
Fluid flow can have a very strong effect on corrosion of
furnace tubes and transfer lines owing to the combination
of both high velocity and two phase flow.
Tebbal and Kane23 emphasised the importance of wall
shear stress in assessing the impact of flow on corrosion
and observed that the magnitude of the shear stress is
strongly dependent on the degree of vaporisation. Certainly,
wall shear stress is normally the most effective approach to
relating laboratory data to service applications.
Laboratory measurements of corrosion rate by these
authors suggest general rates of the order of 20–25 mil/year
British Corrosion Journal 1999 Vol. 34 No. 2
130 Slavcheva et al. Naphthenic acid corrosion in oil refining
(0·51–0·64 mm/year) for both 5Cr and 9Cr steels with little
impact of increasing velocity, although pitting attack was
significantly enhanced. At the high velocities (61 m s−1)
corresponding to the latter, this pitting attack represents
presumably local variations in wall shear stress at the
surface.
PHYSICAL STATE, VAPOUR OR
LIQUID PHASE
Blanco5 noted that the severity of corrosion appeared to
be higher when the physical state of the acids was changing,
for instance in a vaporisation situation such as a transfer
line or in a condensing situation such as the vacuum tower.
This presumably means that corrosion will be highest just
below the boiling point or condensation temperature of the
acid. However, since naphthenic acids is the term given to
a collection of organic acids with boiling points ranging
from about 200 to about 400°C, it is difficult to quantify
the extent of corrosion that can be anticipated at a given
temperature. Scattergood et al.24 have reported that the
observed corrosion is most severe at the liquid/vapour
interface where the vapour forms a liquid film over the
metal surface. Gutzeit6 suggests that if condensates form
then the corrosion associated with them is directly related
to their acid content. There seems to be little doubt that
for corrosion to proceed the acids must be present in
the liquid state. However, little consideration appears to
have been given either to the possibility that dilution of
the acids by hydrocarbons with a similar boiling point
will significantly modify the rate of corrosion or to the
possibility that different naphthenic acids will have different
corrosion rates (see Fig. 5, for example).
PRESSURE
From the literature available1,11 it appears that the direct
influence that pressure has on the kinetics of naphthenic
acid corrosion is small and of little significance. Its indirect
influence on corrosion would appear to be more import-
ant as it will affect condensation and vaporisation of the
naphthenic acids.
MATERIALS OF CONSTRUCTION
In practice, naphthenic acid corrosion is controlled usually
by the appropriate selection of materials of construction.
Blanco et al.5,19 stated that:
(i) carbon steels are not attacked at temperatures
below 230°C and can also be used at higher
temperatures if the flowrates are low
(ii) 5Cr–0·5Mo steels are more resistant to naphthenic
acid corrosion than carbon steels and can be used
satisfactorily at higher flowrates
(iii) ferritic and martensitic stainless steels, AISI 405 and
AISI 410, can have a higher resistance to corrosion
by naphthenic acids than carbon steel under some
conditions but may corrode in a catastrophic
manner in others
(iv) austenitic stainless steels containing molybdenum
are regarded as having the most resistance to
naphthenic acid corrosion
(v) other materials, such as aluminised steels and the
alloys Inconel 600 and Incoloy 800, have been used
with success, but operating experience with these
alloys is limited.
The paper by Piehl3 presents the results of materials
performance assessments carried out on test coupons
exposed in refineries, together with refinery inspection data.
This work showed that carbon steels and AISI 410 steels
both corrode rapidly when exposed in a crude unit vacuum
column. Under these conditions the alloys AISI 430, AISI
304, Incoloy 800, and Inconel 600 also corrode at similar
but somewhat lower rates. However, AISI 316 and other
British Corrosion Journal 1999 Vol. 34 No. 2
highly alloyed stainless steels were not prone to any
significant corrosion. In other comparative performance
tests he undertook on coupons made from AISI 410, AISI
304, and AISI 316 steels, the superior corrosion resistance
of the AISI 316 alloy was also demonstrated. The corrosion
resistance of the AISI 410 alloy was extremely variable and
no attempt was made to explain this observation. Piehl
suggested that the AISI 316 type alloys will corrode if their
molybdenum content falls below a critical level which
McHie25 suggested is 2·3%. He supports this claim in
relation to corrosion failure of AISI 316 SS thermowells in
a furnace transfer line. A subsequent examination showed
that the molybdenum content of the thermowells was 2·1%,
i.e. below the minimum required. Piehl2,3 also suggested
that the corrosion of AISI 316 alloy in naphthenic acid
service is rare when its molybdenum content is within the
specified limits. However, he suggests that the critical
molybdenum content required to prevent corrosion may
vary as a function of the service conditions and that it may
not be the same in all parts of a plant.
Perhaps the most informative work on materials for
use in a naphthenic acid environment is presented by
Gutzeit.6,7 In the ‘controlled studies’ he carried out on
eight alloys he looked at the influence that selected heat
and surface treatments had on their corrosion character-
istics. The corrosion characteristics of AISI 410 and carbon
steel were compared and it was found that at temperatures
below 232°C the corrosion rate of both materials was quite
low (less than 3 mil/year, 0·076 mm/year) with essentially
no significant difference. At high temperatures he found
that the AISI 410 alloy corroded at about half the rate of
carbon steel. Additionally, he showed that the corrosion
rate of carbon steel and 7Cr–0·5Mo and 9Cr–1Mo steels
increased by a factor of about 2·5 when the TAN value
was doubled. Under similar conditions the corrosion rate
of an AISI 410 alloy increased by a factor of nearly 4·6
when the TAN was doubled. He suggested that this may
have been due to the localised nature of the attack but
believed that he had insufficient data to allow definite
conclusions to be drawn. However, his work does indicate
that AISI 410 alloy appears to be little more corrosion
resistant than carbon and low chromium containing
steels, as had been suggested by Derungs.1 The corrosion
isotherms produced by Gutzeit7 appear to be the best
available for predicting the rates of corrosion of materials
in naphthenic acid environments. However, the scatter in
the data he produced reduces the level of confidence that
can be placed in these plots. In his work on the influence
of heat treatment on the corrosion of stainless steels the
damage observed was always low on the solution annealed
material and the AISI 317 alloy appeared to be the most
corrosion resistant. It is interesting to note that all of the
materials he tested corroded to some extent albeit at very
low rates (solution annealed AISI 317 corroded at a rate
of 0·3 mil/year (7·6×10−3 mm/year) in a white oil–naph-
thenic mixture with a TAN value of 36·6 mg KOH g−1
at 293°C).
To make his work more complete, Gutzeit reported the
results of corrosion surveys that he had undertaken in
crude distillation units processing feedstocks with TAN
values averaging about 0·6 but occasionally reaching 1·0
and higher. He reported that carbon steel and 5Cr–0·5Mo
and AISI 410 steels corroded at similar rates. Addition-
ally, he observed that severe pitting occurred in vacuum
distillation tower trays operating at between 304 and 338°C
and made from the alloys AISI 316 and AISI 317. An AISI
316 woven wire mesh demister that had operated at a
temperature of about 290°C was also severely corroded,
with about 40% of the pad having been completely
dissolved. AISI 410 tray valves operating at about 220°C
were reported to be badly corroded and it was suggested
that impingement attack had contributed to this damage.

A reduction cap made from AISI 317 alloy that had
operated at about 300°C was reported to be 35% severely
pitted. Many of these observations appear to conflict with
the experimental results previously reported and suggest
that his results must be treated with some caution.
Laboratory studies of the relative corrosion rate of
carbon steel and a 5Cr–0·5Mo steel15 have indicated that
the latter can corrode at a higher rate in a naphthenic acid
mixture and in a HVGO at 275°C. This was also true when
0·1%H S was bubbled through.
2
In a recent study,11 Craig investigated the influence of
molybdenum on resistance to naphthenic acid corrosion
using the alloys 5Cr–0·5Mo and 9Cr–1Mo as well as
stainless steels 317L and 317LM for which the molybdenum
content is between 3 and 4·5%. He demonstrated that a
fivefold increase in molybdenum content appears to increase
the corrosion resistance of alloys by about one decade.
Under high velocity conditions the effect of molybdenum
is even stronger. There was no discussion of the role of
molybdenum and other alloying elements other than that
the net effect is a more resistant protective film.
SUMMARY AND CONCLUSION
Predictions relating to the extent of corrosion that can be
anticipated when crude oils containing naphthenic acids
are processed are based upon previous experience rather
than a real understanding of the problem. If the problems
that are being encountered by the oil industry are to be
solved then it would appear a more systematic approach is
required. There is a need to establish the extent of corrosion
that can be anticipated when crude oils containing various
types of naphthenic acid are processed. Additionally, the
influence that turbulence and velocity have on corrosion
needs to be quantified. While there appears to be little
doubt that for corrosion to proceed the acid must be in
the liquid state, inadequate information is available relating
to the influence that both dilution by other hydrocarbons
and the type of naphthenic acid have on the corrosion rate.
The operative corrosion mechanism does not appear to
have been identified conclusively, although the evidence
suggests a chemical process. Many of the observations of
corrosion made by workers in this field appear to conflict
and there is a need for definitive work to clarify this
situation. There is little understanding of the nature of the
films that form on steel surfaces when they are in contact
with hot naphthenic acid containing crude oils, and the
Slavcheva et al. Naphthenic acid corrosion in oil refining 131
role of various natural inhibitors that may be present in
crudes has received little attention.
ACKNOWLEDGEMENT
One of the authors (ES) gratefully acknowledges the award
of a UK Royal Society Fellowship.
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