CORROSION ENGINEERING SECTION

Factors Controlling Naphthenic Acid Corrosion

A. Turnbull,* E. Slavcheva,** and B. Shone***

ABSTRACT KEY WORDS: carbon steel, corrosion rate, crude oil refining,
heavy vacuum gas oil, hydrogen sulfide, mineral oil,
A laboratory study was conducted to elucidate the influence naphthenic acid, total acid number
of chemical and physical parameters on corrosion of type
1018 carbon steel (CS, UNS G10180) and 5% Cr-0.5% Mo INTRODUCTION
steel in oils containing naphthenic acids (NAs) for application
to crude oil refinery systems. Effects of test duration, tem- Crude oils from many parts of the world often are
perature, and acid concentration were assessed for a range referred to as naphthenic acid (NA) crudes (i.e., they
of single acids of varying carbon numbers and for NA mix-
contain organic acids with saturated ring structures
tures in mineral oil (MO) and in heavy vacuum gas oil
and one or more carboxylic groups). When such
(HGVO). In addition, a limited study of the effect of hydrogen
sulfide (H2S) addition to the acid-oil mixture was conducted.
crude oils are processed in refineries, corrosion may
Use of the total acid number (TAN) as a measure of corrosive- occur. This form of attack is called appropriately
ness of a crude oil was discredited further. For the same TAN “naphthenic acid corrosion.” NA corrosion is not a
value, molecular size and structure of the acid were shown new problem for the petroleum industry. This type of
to have an important influence. Tests conducted in HGVO damage was identified first in the 1920s. Most of the
showed lower corrosion rates than in MO, suggesting inhibi- existing research has dealt with case histories, at-
tion caused by S species in the oil or the steric hindrance of tempts to correlate results of simple laboratory tests
naphtheno-aromatic acids. In oil containing the mixture of with service performance, or industry surveys.1 Cur-
NAs, the corrosion rate of type 1018 CS was lower than that rently, there is a renewed interest in the problem
for 5% Cr-0.5% Mo steel. The 0.1% H2S that passed through
because of the variable quality and cost of crude oils
the acid-oil mixtures had an inhibiting effect on corrosion.
and the potential savings (several dollars a barrel) if
Predicting corrosiveness of a crude oil from the measurement
of TAN, distribution of NA composition, and S content and
the corrosiveness of the crudes could be defined
form was particularly challenging. The simple tests used properly. The fundamental problem is the complexity
were informative, but further work will be required to estab- of the factors affecting corrosiveness. There is no
lish a standard test method that can provide an adequate clear measure of corrosiveness, and simple measures
ranking of crudes. used previously, such as the total acid number
(TAN), commonly are believed to be insufficient.1
The objective of the present work was to clarify
Submitted for publication August 1997; in revised form, further the factors controlling NA corrosion. To
December 1997. Presented as paper no. 579 at CORROSION/98, achieve this, model NA-oil mixtures with single and
March 1998, San Diego, CA.
* National Physical Laboratory, Teddington, Middlesex, TW11 0LW, mixed acids were used to limit the influence of un-
U.K. controlled variables. The ultimate goal was to provide
** Bulgarian Academy of Sciences, Akad. G. Bonchev St., 1113 Sofia,
Bulgaria.
a basis for processors to identify potentially corrosive
*** Ty Isa, Nr Mold, Flintshire, CH7 5BQ, U.K. crudes and to be able to process low-cost “opportu-

0010-9312/98/000193/$5.00+$0.50/0
922 © 1998, NACE International CORROSION–NOVEMBER 1998
 CORROSION ENGINEERING SECTION

nity” crude oils with confidence in refineries con- ment of the test specimens included polishing with
structed from inexpensive conventional steels. emery paper (nos. 400,600, 800, and 1,200),
degreasing in acetone, rinsing in distilled water, and
EXPERIMENTAL drying, following the ASTM G 31-72 test method.2
Three samples were tested in parallel. The corrosion
The apparatus consisted of a round-bottomed rate (in mm/y) was evaluated by weight loss after any
glass cell containing ~ 0.25 L of an oil sample rich in corrosion product film that may have been present
NA. The cell was equipped with an upper chamber had been removed in Clark’s solution. The reported
isolated by a glass valve. The purpose of this upper values of corrosion rate were, in all cases, the aver-
chamber was to retain the samples (20 mm by age of at least three coupons.
10 mm by 1 mm) in an Ar atmosphere while the oil TAN of the oil samples was determined by color
was being preheated. Each sample had a small hole indicator titration according to ASTM D 974.3
(2-mm diameter) at one end to enable attachment to
the glass holder. The bore of the glass valve was large RESULTS AND DISCUSSION
(25-mm diameter), which permitted the samples to be
lowered into the fluid when the operating tempera- Effect of Test Duration
ture was attained without exposing the system to the In considering the test duration for measuring
external atmosphere. A mantle heater, controlled by NA corrosion, two main factors had to be taken into
a thermocouple located in the fluid, and a tempera- account: time for the corrosion process to attain
ture controller were used to maintain the test steady state and susceptibility of NA to thermal
temperature constant to ± 5°C. Mixing of the solution decomposition at the test temperature.4 NA corrosion
was induced by the bubbling of Ar and thermal con- occurs primarily in the range from 200°C to 400°C
vection. A magnetic stirrer was used initially to with an onset at ~ 200°C to 220°C and a maximum
assess the effect of enhanced flow, but no difference rate at ~ 370°C. However, NA can decompose at these
in corrosion rate was observed up to the limit of stir- temperatures, producing carbon dioxide (CO2),4
ring practically achievable. A condenser was used to which results in a change of the oil corrosiveness
limit evaporation losses. with time. To determine an optimum exposure time,
Synthetic solutions were prepared by adding preliminary tests with exposure periods of 1.5 h, 3 h,
commercially available NAs to a pure paraffin oil 6 h, 16 h, 24 h, 48 h, and 72 h were carried out. The
(Fluka† mineral oil [MO]) or to a heavy vacuum gas oil corrosion rate of CS in 0.25 mol/L cyclohexane-
([HVGO], Shell fraction-ERL Vacuum Distillate†. To carboxylic acid (CHCA) dissolved in MO was mea-
prevent oxidation, all tests were carried out in an sured at two characteristic temperatures, 210°C and
Ar atmosphere. Ar was bubbled into the solution 275°C, for which the minimum and the maximum
(40 cm3/min) for a minimum of 1 h prior to immer- rates of the process were expected, respectively.
sion of the test coupons, and bubbling was continued Results are plotted in Figure 1. The values shown
for the duration of the test. In some cases, 0.1% were the mean of the corrosion rates measured on
hydrogen sulfide (H2S in Ar) was used to saturate the the three specimens. The variability in corrosion
acid-bearing oil. The gas outlet for all tests was via rates was < ± 1.5%, which included not only variabil-
the condenser. Concentration of H2S in the oil was ity between specimens in one test but also in repeat
not measured but reasonably could be assumed to be tests. TAN was determined before and after each test
at its equilibrium value. The off-gas was passed via to follow the decomposition/vaporization of the acid.
an empty trap bottle to a vessel containing sodium The TAN value initially was 18.
hypochlorite (NaOCl) solution and finally to a caustic At the lower temperature, the corrosion rate was
scrubber. low and reached steady state in a relatively short
The specific NAs studied were selected on the time. At this temperature, evaporation losses and
basis of their chemical structures, molecular sizes, decomposition of the acid with time were minimal.
and boiling points (Table 1). The TAN value of the oil sample remained nearly
All corrosion tests were carried out on type 1018 unchanged even after 72 h. At higher temperature,
carbon steel (CS, UNS G10180)(1) and on a 5% Cr- the acid progressively decomposed or was lost by
0.5% Mo low-alloy steel that is used commonly as a evaporation (although the condenser should have
construction material (i.e., in furnace tubes and limited the latter), and the TAN value decreased
transfer lines). The 5% Cr-0.5% Mo low-alloy steel exponentially over the test period (Figure 2). A test
samples were machined from a section of furnace without specimens also showed this decay in TAN
tube that had been removed from service. Pretreat- value, thus demonstrating that it was not simply
consumption of acid by reaction with the metal.
†
Trade name. Decay in TAN value for the NA mixture was less
(1)
UNS numbers are listed in Metals and Alloys in the Unified
Numbering System, published by the Society of Automotive marked, decreasing from 17.2 to ~ 9.1. The corrosion
Engineers (SAE) and cosponsored by ASTM. rate initially was large but then decreased, and after

CORROSION–Vol. 54, No. 11 923

CORROSION ENGINEERING SECTION

TABLE 1
NAs Studied
Structural Boiling Point Molar Carbon
Designation Formula (°C) Mass Number Abbreviation

O
Cylopentane C 216 114 6 CPCA
carboxylic acid
OH

O
Cyclohexane 232 128 7 CHCA
C
carboxylic acid
OH

O
Cyclohexane 242 142 8 CHAA
CH2 C
acetic acid
OH

O
Cyclohexane 276 156 9 CHPA
CH2CH2 C
propionic acid
OH

O
Cyclohexane CH2CH2CH2 C – 170 10 CHBA
butyric acid
OH

Commercial mixture 270 to 324 244 10 to 18 NAs

of naphthenic acid

16 h, remained comparatively constant. No film of rosion rate for the 5% Cr-0.5% Mo steel was consis-
corrosion product was seen on the surface of the type tently higher.
1018 specimens after the 3-h tests. After 24 h, the These preliminary results were directed primarily
metal surface was covered with a thin loose film of at optimizing the duration of the corrosion tests.
corrosion product (assumed to be iron naphthenates) Using these results as a guide, it was decided that
that could be wiped off easily. Although film forma- evaluation of the influence of operational variables
tion could be invoked to rationalize the trend in (temperature, concentration of the acid, and TAN of
corrosion rate with exposure time, it appeared more the oil sample, presence of H2S, and type of steel) on
likely that the decrease in corrosion rate was associ- the rate of NA corrosion as well as the corrosiveness
ated with the decrease in acidity of the test solution. of different NA should be made at exposure times of
Dependence of corrosion rate on the test dura- 3 h and 24 h (quasi-steady-state process).
tion at 275°C was evaluated for the low-alloy 5%
Cr-0.5% Mo steel in the 0.25 mol/L CHCA solution Effect of Acid Concentration
but also in MO containing the mixture of different One of the goals was to compare the corrosive-
NAs at the same concentration. Results together with ness of different NAs under well-defined conditions
those for the CS are shown in Figure 3. Dependence (i.e., using synthetic solution of particular acids in
of corrosion rate on test duration showed the same pure MO). The common practice in oil refineries is to
characteristic trend for all cases. This tended to sup- use TAN as a measure of the acidity of the oil. How-
port the hypothesis that the decrease in rate was ever, experience has shown that NAs vary in their
associated with the decrease in acidity since the film structures and concentrations from one crude to
characteristics and formation kinetics were expected another, even if the TAN value is the same. The lack
to be different for the two steels. The corrosion rate of correlation between concentration of NA and TAN
depended critically on the acid type with the NA mix- values of crude oils has been reported previously.5-7
ture showing much reduced corrosion of type 1018 For purposes of the present study, the concentration
with respect to the single acid. The corrosion rate of of the acid in mol/L was used as a measure of oil
5% Cr-0.5% Mo steel was lower than that for type corrosiveness, but with the TAN value of each solu-
1018 in the single acid. For the NA mixture, the cor- tion determined also for comparison. Table 2 shows

924 CORROSION–NOVEMBER 1998

 CORROSION ENGINEERING SECTION

FIGURE 1. Influence of test duration on the rate of NA (0.25 M CHCA

in MO) corrosion of CS at different temperatures.
FIGURE 2. Time dependence of TAN value of 0.25 M CHCA in MO
during corrosion of CS at 275°C.

there was a linear relationship between TAN and acid

concentration, which was expected in the case of
model solutions.
The dependence of corrosion rate of type 1018 on
the concentration of acid is shown in Figure 4. Re-
sults indicate a linear dependence of corrosion rate
on acid concentration for both the single acid (CHCA)
and the mixture of NAs and further demonstrated the
greater aggressiveness of the single acid (i.e., TAN
value is not a sufficient indicator).

Effect of Temperature
In addition to the concentration of corrosive acid,
the temperature of the fluid has a great influence on
the corrosion rate. There is little debate concerning
the range of temperatures at which NA attack occurs,
but the specific relationship between corrosion rate FIGURE 3. Influence of test duration on the NA corrosion of CS and
and temperature is not clarified fully. Gutzeit re- low-alloy 5% Cr-0.5% Mo steel in MO containing 0.25 mol/L of single
ported the results of field surveys that indicated that acid (CHCA) or mixture of NA at 275°C.
the corrosion of most steels approximately triples
with each 55°C.7 He suggested that the corrosion
kinetics can be represented by an Arrhenius-type The corrosion rate of type 1018 in MO containing
equation at temperatures > 288°C (and probably at single CHCA and mixture of acids (NAs) in the tem-
lower temperatures) with an activation energy of perature range from 210°C to 300°C was evaluated.
68.5 kJ/mol and proposed that the process is con- Results are plotted in Figure 5. Data supported the
trolled by chemisorption. field study in that the kinetics of the process obeyed

TABLE 2
Dependence of Corrosion Rate of Type 1018 CS on Concentration
of NA and Corresponding TAN Factors of Oil Samples (t = 3 h, T = 275°C)
Concentration Corrosion Rate TAN in CHCA Corrosion Rate TAN in NA
(mol/L) in CHCA (mm/y) (mg KOH/g oil)(A) in NA (mm/y) (mg KOH/g oil)

0.05 5.32 3.07 0.92 2.79

0.10 11.83 6.93 2.39 4.25
0.25 28.60 18.14 5.55 17.23
0.50 56.51 35.46 11.44 34.76
1.00 112.67 69.33 23.08 68.68

(A)
KOH, potassium hydroxide.

CORROSION–Vol. 54, No. 11 925

CORROSION ENGINEERING SECTION

FIGURE 4. Influence of acid concentration on the corrosion rate of

CS in MO containing single acid (CHCA) and mixture of NA (T = FIGURE 5. Arrhenius plot for corrosion of CS in MO containing single
275°C, t = 3 h). acid (CHCA) and mixture of NA (T = 275°C, t = 3 h).

TABLE 3
m/z Values of Detected Carboxylate Anions in Commercial Mixture of NA
Number Carbon Number
of Rings 10 11 12 13 14 15 16 17 18

0 171 185 199 213 227 241 255 269 283

1 169 183 197 211 225 239 253 297 281
2 – 181 195 209 223 237 251 264 279
3 – – – 207 221 235 249 263 277

TABLE 4
Proportion of Acids in Commercial Mixture of NA (%)

Number Carbon Number

of Rings 10 11 12 13 14 15 16 17 18 Total

0 0.31 0.96 1.95 8.14 5.38 6.13 1.49 2.69 1.72 28.8
1 0.76 2.01 4.07 8.64 9.73 6.97 2.42 1.23 1.04 36.9
2 – 1.07 3.69 8.20 8.13 5.62 1.82 0.26 0.54 29.3
3 – – – 1.23 1.80 1.01 0.47 0.32 0.23 5.06
Total 1.07 4.04 9.71 26.2 25.0 19.7 6.20 4.50 3.53 100

the Arrhenius equation. However, the calculated To study the effect of this factor, the corrosive-
values of activation energy (viz. 31.8 kJ/mol and ness of several single NAs with increasing carbon
23.8 kJ/mol for CHCA and NA, respectively) were numbers, molecular weights, and boiling points, as
lower than those reported by Gutzeit. Clearly, the well as a mixture of NA were compared. Composition
type of acid had an impact and much could have of this commercial mixture of NA was analyzed by
depended on the detailed composition of the crude. fast atom bombardment mass spectroscopy (FABMS).
This method is known for its ability to analyze polar,
Effect of Acid Type nonvolatile, and high-molecular weight components,
NA refers to saturated acids based upon single including NAs. The FAB composite mass spectrum
and multiple five- and six-membered rings. Although provides an envelope that follows the molecular
all NAs contain a carboxylic group that determines weight distribution of the mixture. The method has
their acidity, it is logical to expect that the rest of the been described in detail elsewhere.8-9 Results from
molecule will influence corrosiveness of the acid, at FABMS analysis of the commercial mixture of NA
least through its effect on adsorbability on the metal used are presented in Tables 3 and 4, where m
surface. There are no data on the impact of acid type indicates mass of the carboxylate ion, and z is the
on the rate and mechanism of the corrosion process. charge. Results showed that the mixture contained

926 CORROSION–NOVEMBER 1998

 CORROSION ENGINEERING SECTION

FIGURE 7. Corrosion rate of low-alloy steel 5% Cr-0.5% Mo in MO

FIGURE 6. Corrosion rate of CS in MO containing different NAs. containing different NAs.

TABLE 5
Influence of Acid Type and Test Duration on Corrosion Rate
of Type 1018 CS and Cr-Mo in MO at 275°C and Cacid = 0.25 mol/L

Corr. Rate Corr. Rate Corr. Rate Corr. Rate

MW Carbon (mm/y) (mm/y) (mm/y) (mm/y)
Acid Type (BP) Number TAN Type 1018, 3 h Type 1018, 24 h Cr-Mo, 3 h Cr-Mo, 24 h

CPCA (cyclopentane- 114 6 18 23.25 7.9 2.86 1.57

carboxylic acid) (216)

CHCA (cyclohexane- 128 7 18 28.60 9.40 4.31 2.00

carboxylic acid) (232)

CHAA (cyclohexane- 142 8 17 30.34 12.26 4.44 2.39

acetic acid) (242)

CHPA (cyclohexane- 156 9 17 34.64 16.73 4.71 2.58

propionic acid) (276)

CHBA (cyclohexane- 170 10 17 31.02 15.14 2.93 1.13

butyric acid) (—)

NA (mixture of NA) 244 10-18 17 5.55 2.56 7.28 4.03

(270 to 324)

28.8% acyclic acids, 36.9% one-ringed acids, 29.3% 1018 in the presence of cyclohexanepropionic acid
two-ringed acids, and 5.06% three-ringed acids. (C9), and then decreased. This relationship could be
Corrosiveness of acids selected was evaluated in explained perhaps by the assumption that the corro-
MO for the following conditions: acid concentration = sion rate was controlled by the adsorption of the acid
0.25 mol/L (TAN = 18); temperature = 275°C; materi- on the metal surface. It is well known that the in-
als = type 1018 and 5% Cr-0.5% low-alloy steels; and crease in number of (CH2)n groups in C chains, up to
test duration = 3 h and 24 h. n = 3 to 4, increases the adsorbability in a given re-
The relationship between the rate of corrosion action series of organic compounds. After that, the
process and carbon number of the NA for CS and Cr- steric hindrance between organic molecules causes a
Mo steel is illustrated in Figures 6 and 7, decrease in adsorbability.
respectively. Results are summarized in Table 5. As shown in Figures 6 and 7, the low-alloy Cr-
The chemical structure of the acids had a signifi- Mo steel was much more resistant to the attack of
cant influence on the corrosion rate of both single NA than CS. Experiments carried out with Cr-
materials, although the details differed. The rate of Mo steel showed that, even after 3 h of exposure in
the process increased with the increase in molar the corrosive media, the metal surface was covered
mass of the single acid, reached a maximum for type with an adherent film of corrosion products. This film

CORROSION–Vol. 54, No. 11 927

CORROSION ENGINEERING SECTION

TABLE 6
m/z Values of Detected Carboxylate Anions in HVGO
Carbon Number
Number
of Rings 16 17 18 19 20 21 22

2 245 259 273 287 301 315 –

3 243 257 271 285 299 313 –
4 241 255 269 283 297 311 325
5 – – 267 281 295 309 323
6 – – – 279 293 307 321

TABLE 7
Proportion of Acids in HVGO (%)
Number Carbon Number
of Rings 16 17 18 19 20 21 22 Total

2 2.0 2.1 2.4 3.8 2.9 3.4 – 16.6

3 2.3 5.1 5.4 5.3 4.1 2.9 – 25.1
4 1.9 3.0 3.3 5.0 4.8 3.7 3.4 25.1
5 – – 3.4 4.1 4.6 3.8 2.9 18.8
6 – – – 3.5 3.7 4.4 2.8 14.4
Total 6.2 10.2 14.5 21.7 20.1 18.2 9.1 100

pirical deduction. The precise mechanism was

unclear.

Experiments in HVGO
In crude oils, NA span a wide boiling range and
tend to concentrate during crude distillation, most
commonly reaching a maximum concentration in the
heavy gas oil. To correlate the results obtained in
model solutions with the process in real environ-
ments, a series of tests were run in HVGO. A TAN
value of 6 for this oil was measured using the ASTM
D 974 test. Total S content of the oil determined by
x-ray fluorescence analysis (XRF) using the standard
Institute of Petroleum (IP) 366 method was 2.27% m/
m (i.e., relative mass). To distinguish the molecular
structures of organic acids, the HVGO was analyzed
by FABMS. The sample showed a complex series of
peaks over the mass range from 230 to 330. The
main series appeared to comprise two-, three-, four-,
five-, and six-ringed acids with one of the rings in
FIGURE 8. Some examples of possible structures of naphtheno- each case being aromatic (Table 6). Therefore, these
aromatic acids in HVGO. ion peaks were assigned as naphtheno-aromatic ac-
ids.10 Some possible structures are shown in Figure
8. Approximate proportions of each acid type were
protected the metal surface to some extent, which estimated by normalizing the intensity of the ob-
resulted in a decrease of corrosion rate in the pres- served ions (Table 7). On the basis of these results,
ence of the single acid by a factor of 8 to 10 relative NAs in the sample of HVGO appeared to comprise
to type 1018 CS. 16.6% two-ringed, 25.1% three- and four-ringed,
Corrosion of the 5% Cr-0.5% Mo steel in single 18.8% five-ringed, and 14.4% six-ringed naphtheno-
acids appeared to follow the same trend as for type aromatic acids, with the distribution maximizing at
1018 CS up to a carbon number of 10 but then in- carbon number of 19.
creased for the NA mixture. A possible explanation is Corrosion tests on type 1018 CS and 5% Cr-
that certain acids in the mixture adsorbed and inter- 0.5% Mo steel at 275°C were carried out in HVGO,
acted preferentially with the alloying elements to as-received, and in two synthetic samples prepared
form soluble naphthenates. This is a somewhat em- by adding 0.25 mol/L CHCA or 0.25 mol/L commer-

928 CORROSION–NOVEMBER 1998

 CORROSION ENGINEERING SECTION

TABLE 8
Corrosion Data in HVGO (T = 275°C)
Corrosion Rate (mm/y)
Type 1018 CS Cr-Mo
Oil Sample TAN 3h 24 h 3h 24 h

HVGO 6 0.032 0.31 0.039 0.43

0.25 M CHCA in HVGO 22 3.83 (28.60)(A) 1.96 (9.40) 6.24 (4.31) 3.29 (2.00)
0.25 M NAs in HVGO 22 4.26 (5.55) 2.57 (2.56) 6.73 (7.28) 3.59 (4.03)

(A)
Results from tests in MO (Table 5) are shown in brackets.

TABLE 9
Effect of H2S on Corrosion Rates (t = 24h, T = 275°C)
Oil Corrosion Rate (mm/y) I (%)(B)
Sample Type 1018 Cr-Mo Type 1018 Cr-Mo

CHCA in MO 7.38 (9.40)(A) 1.92 (2.00) 21.5 4.0

NAs in MO 1.62 (2.56) 2.52 (4.03) 36.7 37.4
CHCA in HVGO 0.91 (1.96) 1.53 (3.29) 53.5 53.4
NAs in HVGO 1.31 (2.57) 2.27 (3.59) 49.0 26.7

(A)
Values in absence of H2S are shown in brackets.
(B)
I is the inhibition parameter.

cial mixture of NA to the HVGO. The TAN value of the explained also by the presence of S (2.7% according
oil samples and the measured rate of the corrosion to XRF analysis) in different forms in the HVGO.
process are presented in Table 8. These results Certain organic S-containing substances are well
should be compared with those obtained for MO. For known as good inhibitors against corrosion of iron
ease of comparison, the relevant results from Table 5 and steel in acid solutions.11 As XRF analysis gives
are incorporated into Table 8. The corrosion rate of only the total S content, other analytical methods
both steels in HVGO itself was an order of magnitude would have to be used to distinguish the different
greater after 24 h than after 3 h. Speculations about forms of S present in the oil.
the presence of S-containing compounds and surface These explanations of the inhibiting ability of
changes with time would not be meaningful because HVGO to type 1018 CS, although feasible, require
of the low level of current understanding. validation by further experimental studies. The role
Corrosion rates of the two steels in the HVGO of alloying elements (Cr and Mo) needs resolution.
were not markedly different and, as with the NA mix-
ture in MO, were lower for type 1018 CS. The sample Effect of H2S
of 0.25 M CHCA in HVGO with a TAN value of 22 was The fact that some oils possess inhibiting quali-
~ 7 times less corrosive to type 1018 CS than the ties, shown to an extent by the HVGO tests, also has
sample with the same concentration of this acid dis- been noted by other authors.6 They proposed that the
solved in pure MO whose TAN value was 18. The inhibition is a result of the S present in oil as H2S or
inhibiting effect of the HVGO, although much less as compounds that form H2S because the usual cor-
significant, was found in oil samples containing the rosion product of H2S corrosion is an oil-insoluble
mixture of NA as well. iron sulfide (FeS), while NAs form soluble iron
Table 8 shows that the corrosion rates of 5% Cr- naphthenates. It is postulated that there is a compe-
0.5% Mo coupons in model solutions and in HVGO tition between both processes and as a result, the
were close for the NA mixture but with the CHCA rate of NA corrosion decreases when sulfides form. At
being slightly more corrosive for the HVGO. However, the same time, the possibility that other compounds
TAN values for the HVGO tests were higher. that originate in crude oils could have a similar in-
Results could be explained by the effect of hibiting effect largely has been ignored.
naphtheno-aromatic acids present in HVGO acting as To verify the inhibitive effect of H2S for the test
corrosion inhibitors. The presence of π-electron rings conditions and to compare it with the inhibiting ef-
in the molecules of aromatic acids could act as ad- fect of HVGO, tests were conducted with 0.1% H2S (in
sorption centers and determine planar adsorption, Ar) bubbled through MO and HVGO containing
thus decreasing the number of iron atoms free for CHCA and the mixture of NA. Results for the two
reaction with the carboxylic group of the acids. The steels are presented in Table 9. The concentration of
inhibiting effect on the corrosion process could be the acids was 0.25 mol/L. There was no evidence of

CORROSION–Vol. 54, No. 11 929

CORROSION ENGINEERING SECTION

localized corrosion on the specimen surface. Included edly different. With addition of either a single acid or
in Table 9 are results obtained in the absence of H2S. NA mixture to the HVGO, the rate was lower for type
H2S in test solutions decreased the rate of NA 1018 CS.
corrosion. Defining an inhibition parameter (I) = ❖ Addition of 0.1% H2S to the acid-oil mixtures
(C – CH2S)/C x 100%, where C and CH2S represent the tended to decrease the corrosion rate, most likely
corrosion rates in the absence and presence of H2S, from the formation of stable iron sulfides in competi-
respectively, it was evident that the inhibiting effect tion with the soluble iron naphthenates.
was greatest in the case of CHCA dissolved in HVGO ❖ In comparison with MO, the HVGO itself had some
for type 1018 CS and 5% Cr-0.5% Mo steel (I = 53%). degree of inhibition. The presence of S compounds,
At the same time, comparison of the corrosion perhaps generating H2S, was a possible factor. The
rates in MO and HVGO in the presence of CHCA and other relevant substances were naphtheno-aromatic
the NA mixture indicates that the impact of H2S de- acids or S-containing organic compounds with large
pended on the type of acid itself and the carrier fluid molecules and good adsorbability on iron and steel.
(i.e., MO or HVGO). These may have been present in the crude oil or may
These observations confirm that the influence of have been produced during its processing.
oil constituents on NA corrosion is very complex. The ❖ To find a reliable quantitative correlation between
effect of large organic molecules with benzene π-rings chemical composition of crude oils and their corro-
or S-containing compounds on the rate and mecha- siveness, further corrosion studies with more
nism of the process, previously not considered, would powerful analytical methods for identification of oil
appear significant and limit simple interpretations of constituents are required. In the meantime, simple
the impact of individual constituents. corrosion studies of the type described herein and
designed to rank severity of particular crudes could
CONCLUSIONS be utilized. However, further understanding of the
nature of films formed in the alloyed material is nec-
❖ In reporting corrosion rates in NA-containing oils, essary to explain the results of this study and to
it is necessary to define the exposure period and have confidence in extrapolating to service conditions.
initial and final TAN values because of possible ❖ For a more accurate quantitative prediction, the
evaporation losses or decomposition of the NA at the effect of flow velocity and two-phase chemistry must
elevated temperatures of practical relevance. A re- be considered.
freshment system with a continuous slow outflow of
test solution to waste is advisable. ACKNOWLEDGMENTS
❖ At a given temperature, the corrosion rate in-
creased linearly with increase in acid concentration, E. Slavcheva acknowledges the award of a U.K.
albeit in model acid-MO mixtures. Royal Society Fellowship. FABMS analyses were con-
❖ Corrosion rates in MO depended critically on the ducted at M-Scan Ltd., Ascot, U.K.
acid type, with the NA mixture showing reduced cor-
rosion of type 1018 CS compared to a single acid for REFERENCES
the same TAN value. This was in accord with the
hypothesis of reduced corrosion rates caused by the 1. E. Slavcheva, B. Shone, A. Turnbull, “Review of Naphthenic
Acid Corrosion,” Brit. Corros. J., in press.
steric hindrance between molecules of different acids 2. ASTM G 31-72, “Standard Practice for Laboratory Immersion
and demonstrated the limitations of defining corro- Corrosion Testing,” in Annual Book of Standards, vol. 03.02
(West Conshohocken, PA: ASTM, 1995), p. 89.
siveness simply in terms of the TAN value. The 3. ASTM D 974-95, “Standard Test Method for Acid and Base
corrosion rate of 5% Cr-0.5% Mo steel was lower Numbers by Color-Indicator Titration,” in Annual Book of
than that for type 1018 CS in the single acid, but the Standards, vol. 02.06 (West Conshohocken, PA: ASTM, 1995),
p. 310.
reverse was true of the differences in the NA mixture. 4. H. Craig, “Temperature and Velocity Effects in Naphthenic Acid
❖ An increase in the number of –(CH2)n groups, up to Corrosion,” CORROSION/96, paper no. 603 (Houston, TX:
n = 3, in the series of individual NA studied led to an NACE, 1996).
5. R. Piehl, MP 27, 1 (1988): p. 37.
increase in corrosion rate. At higher values of n, the 6. E. Babaian-Kibala, H.L. Craig, G.L. Rusk, K.V. Blanchard, T.J.
corrosion rate of type 1018 CS decreased, probably Rose, B.L. Uehlein, R.C. Quinter, M.A. Summers, MP 32, 4
resulting from steric hindrance between long C (1993): p. 50.
7. J. Gutzeit, MP 16, 10 (1977): p. 24.
chains of acid molecules restricting adsorption, 8. R. Large, P.J.C. Tibbetts, A.J. Holland, Petroanalysis ’87, ed.
which in turn slowed the formation of soluble iron G.B. Crump (London, U.K.: John Wiley and Sons, Ltd., 1988).
9. T.-P. Fan, Energy Fuels 5 (1991): p. 371.
naphthenate and the rate of corrosion. However, this 10. R. Large, M-Scan Ltd., Ascot, U.K., private communication to E.
explanation was not fully consistent with the behav- Slavcheva, National Physical Laboratory, Middlesek, U.K., 1996.
ior of 5% Cr-0.5% Mo steel. 11. G. Trabanelli, V. Carassiti, “Mechanisms and Phenomenology of
Organic Inhibitors,” in Advances in Corrosion Science and
❖ In HVGO, as-received, the corrosion rates of type Technology, vol. 1, eds. M.G. Fontana, R.W. Staehle (New York,
1018 CS and 5% Cr-0.5% Mo steel were not mark- NY: Plenum Press, 1970), p. 147.

930 CORROSION–NOVEMBER 1998