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Corrosion Science 58 (2012) 1–11

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Review

Corrosion of carbon steel pipes and tanks by concentrated sulfuric acid: A review
Zehbour Panossian a,b,⇑, Neusvaldo Lira de Almeida a, Raquel Maria Ferreira de Sousa a,
Gutemberg de Souza Pimenta c, Leandro Bordalo Schmidt Marques c
a
Corrosion and Protection Laboratory, Institute for Technological Research of São Paulo State, Av. Prof. Almeida Prado, No. 532, 05508-901 São Paulo, Brazil
b
Polytechnic School of São Paulo University, Av. Prof. Mello Moraes, No. 2463, 05508-900 São Paulo, Brazil
c
PETROBRAS, Av. Horácio Macedo, 950-prédio 20, 21941-598, Cidade Universitária – Ilha do Fundão, Rio de Janeiro, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The corrosion of carbon steel storage tanks and pipes by concentrated sulfuric acid is a great concern. The
Received 12 July 2011 contact of carbon steel with concentrated sulfuric acid generates an immediate acid attack with the for-
Accepted 24 January 2012 mation of hydrogen gas and ferrous ions, which, in turn, form a protective layer of FeSO4 on the metallic
Available online 2 February 2012
surface. This work presents a review of carbon steel corrosion in concentrated sulfuric acid. The corrosion
mechanism of carbon steel in sulfuric acid, accelerating factors, types of carbon steel corrosion and the
Keywords: preventive methods against this corrosion are outlined.
A. Carbon steel
Ó 2012 Elsevier Ltd. All rights reserved.
A. Sulfuric acid
C. Anodic protection
C. Acid corrosion

1. Introduction fossil fuels, in the form of oil and natural gas, correspond to
approximately 60% of the global energy demand [8]. Currently,
Although sulfuric acid, in concentrated form, is the most pro- the challenge for all oil and natural gas companies is to meet the
duced reagent worldwide, corrosion by concentrated sulfuric acid growing industrial needs without inducing changes in the stability
has received little attention from researchers dedicated to the of the global climate.
study of corrosion. An extensive literature review showed that Sulfuric acid is a strong oxidizer and dehydrator. It may ignite
the majority of published papers deal with dilute sulfuric acid other materials (wood, paper, oil, etc.) and reacts violently with
and that a substantial number of papers report the selection of cor- water. Therefore, it is considered to be a dangerous product that re-
rosion inhibitors in sulfuric-acid pickling operations. Few studies quires safe storage and transport to avoid possible accidents.
related to the corrosivity of concentrated sulfuric acid were found Sulfuric acid, being very aggressive, attacks the metallic materi-
in the literature. In addition, most of them were published prior to als used for the construction of storage tanks and pipes. Depending
the 1980s. The recent published papers are mainly related to on the sulfuric acid concentration range, many types of metallic
highly corrosion-resistant steels, including stainless steels [1–7]. materials can be used to construct tanks and pipes, as shown in
Market research among some local sulfuric acid producers (São Table 1.
Paulo, Brazil) showed that the aggressiveness of the sulfuric acid The most widely used alloys for handling sulfuric acid are car-
is managed through an effective industrial plant maintenance pol- bon steel and UNS S304 and UNS S316 austenitic stainless steels.
icy rather than the adoption of corrosion prevention practices. Each material exhibits a different behavior in concentrated sulfuric
In Brazil, the concern for corrosion by sulfuric acid has acid. Table 2 shows some corrosion-rate values of these alloys in
increased in the oil and gas industry because of the recent policy concentrated sulfuric acid.
concerning the transformation of H2S and SOx produced during The data in Table 2 demonstrate that carbon steel has higher
oil extraction and refining into concentrated sulfuric acid. This pol- corrosion rates than the UNS S304 and S316 austenitic stainless
icy is being adopted to reduce the negative impact of the release of steels. However, the cost of carbon steel is much lower than the
these gases into the atmosphere because the burning of fuels is a abovementioned stainless steels. Fig. 1 shows the values in US$/
major cause of global warming because of the production of green- ton of metal [11]. The price difference between carbon steels and
house gases. According to the International Energy Agency (IEA), the UNS S304 and S316 austenitic stainless steels is substantial.
For this reason, carbon steel is preferred by many industries as a
⇑ Corresponding author at: Corrosion and Protection Laboratory, Institute for construction material for concentrated sulfuric acid storage tanks.
Technological Research of São Paulo State, Av. Prof. Almeida Prado, No. 532, 05508- However, the success of this choice will significantly depend on the
901 São Paulo, Brazil. adoption of appropriate corrosion prevention measures.
E-mail address: zep@ipt.br (Z. Panossian).

0010-938X/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2012.01.025
2 Z. Panossian et al. / Corrosion Science 58 (2012) 1–11

Table 1
Resistant alloys for different concentration ranges of sulfuric acid at 25 °C. Adapted
from Ref. [9] (Table B1).

H2SO4 (%, mass) Alloy (UNS number)


70–100.5 S31254, N10276, N08367, N08024, N08026, N08825,
N08028, N08904, N06022, N06030, N06455, N08926,
N06625, N06686, N06985, N08020, N09925, N06059
88–95.5 Carbon steel, S31600, S30400
90–100.5 S31600, S31603
93–100.5 S30400, S30403, N06693

Table 2
Corrosion rates (mm y1) of carbon steel and of UNS S304 and S316 austenitic
stainless steels in H2SO4. Data from Ref. [10] (Table 2.B.5.2M, 2.B.5.3M and
2.B.5.4M).

Carbon steel Austenitic stainless


Fig. 2. Corrosion rate of carbon steel as a function of carbon content in 6.5 mol L1
(33 °C and 2.0 m s-1 flow) steel (30 °C and 2.1 m s1 flow)
H2SO4. Test temperature: (25 ± 2) °C. Test duration: 24 h (except for tests in which
93.5% (H2SO4) 98% (H2SO4) UNS 92.5% (H2SO4) 98% (H2SO4) the corrosion rate was so high that steel specimen would have completely
1.91 1.02 S304 1.52 0.38 corroded). Adapted from Ref. [14].
S316 0.76 0.38

Fig. 1. Price in US$/ton in 2010 and 2011 of carbon steel and austenitic stainless
steel type UNS S304 and S316. Adapted from Ref. [11].

Awareness of the necessity of the mentioned prevention mea-


sures requires understanding the corrosion behavior of carbon
steel in concentrated sulfuric acid. Thus, the goal of this work is
to describe the corrosion mechanisms of carbon steel in concen-
trated sulfuric acid and to present a summary of preventive meth-
ods against this process.

2. Corrosion mechanisms of carbon steel in sulfuric acid

When carbon steel contacts dilute sulfuric acid, an immediate


attack on the metal takes place with the formation of hydrogen Fig. 3. Corrosion rate as a function of H2SO4 concentration for carbon steel with
gas and ferrous ions, as shown in reactions (1) and (2). different amounts of carbon. Test temperature: (25 ± 2) °C. Test duration: 24 h
(except for tests in which the corrosion rate was so high that steel specimen would
have completely corroded). Adapted from Ref. [14].
(a) Anodic reaction

Fe ! Fe2þ þ 2e ð1Þ


curs on the cementite phase [13]. These reactions explain the
(b) Cathodic reaction important role of the carbon content on the steel corrosion rates
[12] and are shown in Fig. 2. This figure shows the corrosion rate
2Hþ þ 2e ! H2 ð2Þ
of carbon steels in 6.5 mol L1 (corresponding to almost 50%)
According to Dean and Grab [12], the rate of corrosion of carbon H2SO4 as a function of the carbon content. The steel with 0.19% car-
steels in dilute acids depends strongly on steel chemical composi- bon exhibited the lowest corrosion rate. According to Damon [14],
tions, especially the carbon content. Accordingly, the oxidation the reasons for this unusual experimental result are not clear.
reaction of iron (Fe ? Fe2+ + 2e) occurs on the ferrite phase, and Fig. 3 shows the dependence of the corrosion rate on the
the cathodic reduction reaction of hydrogen (2H+ + 2e ? H2) oc- concentration of H2SO4. Up to concentrations within the range of
Z. Panossian et al. / Corrosion Science 58 (2012) 1–11 3

Fig. 4. Carbon steel ring in 96% reagent-grade H2SO4 under static conditions at 25 °C [15].

(5–6) mol L1 (corresponding to (40–46.5%)), the corrosion rate of oxidant (in this case, the sulfuric acid) to the metal surface through
carbon steels tends to increase with different intensities depending the corrosion product layer (FeSO4 in the case of carbon steel); the
on their carbon content. corrosion reaction rate; or the diffusion rate of the corrosion prod-
Fig. 3 also shows that, at concentrations greater than (5– ucts from the metal surface toward the bulk solution. The slowest
6) mol L1 H2SO4, the corrosion rate decreases in the same way step determines the metal corrosion rate. Thus, any factor that
for all steels, and above a concentration of approximately 9 mol L1 causes acceleration of these steps will result in an increase in the
(which corresponds to 63%) H2SO4, the corrosion rate becomes low corrosion rate. In the case of carbon steel in sulfuric acid, the most
and assumes almost the same value for all tested steels. These re- important factors that cause an increase in the corrosion rate are
sults suggest that, in high acid concentrations, the rate of corrosion the FeSO4 solubility in the acid, the temperature and the relative
no longer depends on the carbon content, which means that an- movement between the metal and the acid [10,16,17]. The follow-
other corrosion mechanism is occurring. ing paragraphs discuss each of these factors.
When carbon steel contacts concentrated sulfuric acid, the for-
mer is in fact reduced to form H2 and the iron oxidizes with the for-
3.1. Solubility of FeSO4
mation of ferrous sulfate (FeSO4), as shown in reaction (3):

H2 SO4 þ Fe ! FeSO4 þ H2 ð3Þ The solubility of FeSO4 depends on the acid concentration as
shown in Fig. 5. As evident from this figure, for concentrated sulfu-
The FeSO4 adheres to the steel surface and forms a protective ric acid (concentration greater than 90%), the solubility of the
layer. This layer prevents the metal against further attack by con- FeSO4 decreases with increasing acid concentration.
centrated sulfuric acid. Therefore, the durability of tanks made of
carbon steel depends on the preservation of the FeSO4 layer.
According to Dean and Grab [12], the mass transfer of FeSO4 is
the controlling step in the corrosion mechanism for acid concen-
tration between 50% and 99% for steel at ambient temperature.
At concentrations less than 50%, corrosion rates are lower and
are influenced by the carbon content of the carbon steel, as already
shown in Figs. 2 and 3. In this latter case, the hydrogen iron reduc-
tion process (reaction (2)) is the rate-limiting factor rather than the
dissolution of FeSO4.
Fig. 4 shows images of a carbon steel ring in concentrated 96%
reagent-grade H2SO4 at 25 °C at various immersion times [15].
Immediately after the immersion, the formation of a large amount
of H2 can be observed. After 24 h of immersion, a strong decrease of
the metal attack is observed because of the presence of a dark pro-
tective layer of FeSO4 on the metallic surface.

3. Accelerating factors for concentrated sulfuric acid corrosion

When the corrosion of a metal is accompanied by the formation


of a protective layer of corrosion products, the corrosion rate is
determined by one of the following stages: the diffusion of the Fig. 5. Solubility of FeSO4 in concentrated H2SO4. Adapted from Ref. [12].
4 Z. Panossian et al. / Corrosion Science 58 (2012) 1–11

absorbed water are sufficient to dilute the acid. However, for re-
tained acid concentrations greater than 25 g m2, the amount of
absorbed water must be very large so that the dilution reaches crit-
ical levels.
The acceleration of corrosion caused by water absorption is
greater for 70% H2SO4 than for 98% H2SO4 for two reasons: first,
the amount of water that 98% H2SO4 needs to absorb to become
corrosive is two to three times higher than the amount necessary
for 70% H2SO4 to reach a level of dilution capable of causing strong
acceleration of corrosion; second, and even more important, is that,
at room temperature, the FeSO4 in equilibrium with acid concen-
trations of 90% or greater contains no hydration water, but the
FeSO4 contains one molecule of hydration water when in equilib-
rium with (15–90%) H2SO4. Thus, with more concentrated acids,
part of the absorbed water is primarily intended for incorporation
by FeSO4 in the form of hydration water, and only after that incor-
poration can the acid be diluted to less than 90% and become cor-
rosive [19].
For concentrated acid (>90%) and for normal storage-tank oper-
ating conditions, water absorption is generally not sufficiently high
to cause corrosion acceleration. However, for out-of-service tanks,
especially for those out of service for long periods, severe localized
corrosion may be observed. One example cited by Dean and Grab
[19] is related to an acid storage tank taken out of service for
Fig. 6. Corrosion rate of carbon steel as a function of H2SO4 concentration at 20 °C.
two months that exhibited a localized corrosion rate as high as
Adapted from Ref. [18].
30 mm y1. This tank was left open to the atmosphere. Total hydra-
tion of the FeSO4 layer and oxidation of ferrous ions to ferric ions
The relationship between the solubility of FeSO4 and the rate of by atmospheric oxygen were observed. Furthermore, water drop-
corrosion can be observed by comparison of Fig. 5 with Fig. 6. De- lets along the horizontal welds were observed. According to the
spite the differences in the temperatures of the tests conducted for authors, ferric sulfate solutions corrode carbon steel at rates up
the construction of Figs. 5 and 6, both show the same trend: to 35 mm y1 at room temperature, which explains the previously
discussed high corrosion rate.
(1) at concentrations up to 70%, an increase in the acid concen- From the above discussion, preventive measures against water
tration causes a decrease in both the FeSO4 solubility and the intake are not required for normally operated tanks that contain
corrosion rate of carbon steel; sulfuric acid with a concentration of 90% or greater. However, vent
(2) at concentrations greater than 70%, an increase in the acid dryers are desirable for sulfuric acid tanks out of service for ex-
concentration causes an increase in both the FeSO4 solubility tended periods.
and the corrosion rate of carbon steel;
(3) at concentrations between 90% and 100%, an increase in acid 3.2. Temperature
concentration again causes a decrease in both the FeSO4 sol-
ubility and the corrosion rate of carbon steel; The corrosion rate increases with an increase in temperature.
(4) at concentrations between 80% and 90%, all curves exhibit a This behavior can be observed in Fig. 7. From this figure, for 90%
maximum. However, the concentration at which this maxi- H2SO4, the corrosion rate is slightly higher than 0.5 mm y1 at
mum occurs is different, probably because of differences in 24 °C, whereas the rate increases approximately 10-fold
temperature and in other test conditions not outlined by (5 mm y1) when the temperature is increased to 107 °C. For 98%
the authors. sulfuric acid, the corrosion rate is approximately 0.13 mm y1 at
24 °C and almost 5 mm y1 at 79 °C.
From the above discussion, it is clear that, for concentrated sul-
furic acid, dilution should be avoided. If an accidental water intake
occurs in a level high enough to cause an acid dilution, the protec-
tive layer starts to dissolve in the acid, which causes an accelera-
tion of the metal corrosion.
In acid storage tanks, water absorption especially occurs during
loading/unloading operations because of exposure to atmospheric
air, which is usually humid. The stored acid absorbs the water va-
por from the humid atmosphere and becomes more corrosive [19].
Water–vapor absorption can also occur by the protective layer
of FeSO4 (which undergoes hydration) or by the acid entrapped
in the FeSO4 layer, both of which are exposed to atmospheric air
at the empty space of the tank. In the case of acid entrapped in
the FeSO4 layer, all the acid retained by the sulfate layer, may react
with the steel after dilution and may induce a higher corrosion rate
of the tank walls in contact with the empty space [19]. The degree
of corrosion acceleration will depend on the amount of acid re-
tained on the walls of the tank: If it is less than 25 g m2, an accel- Fig. 7. Corrosion rate of carbon steel tanks at different temperatures and sulfuric
eration of corrosion is expected because small amounts of acid concentrations under static conditions. Adapted from Ref. [9] (Fig. B1).
Z. Panossian et al. / Corrosion Science 58 (2012) 1–11 5

3.3. Relative movement between the metal and acid

The agitation caused by the acid flow through pipes or by load-


ing/unloading operations of tanks accelerates the mass transport of
FeSO4 from the metallic surface toward the bulk acid. Conse-
quently, the corrosion rate of the carbon steel increases. The main
factors that cause an increase in the mass transport are as follows:

(A) Diffusivity: This factor is related to the difference in concen-


tration between the interface and the bulk solution. The
coefficient of diffusion of FeSO4 in sulfuric acid is dependent
on the temperature and the viscosity, as shown by the
extrapolation equation [12,16]:

1:68  109 T
D¼ ð4Þ
l
where: D = diffusion coefficient of FeSO4 in m2 s1; T = tem- Fig. 8. Viscosity as a function of H2SO4 concentration for different temperatures.
Adapted from Ref. [12].
perature in K; l = viscosity of H2SO4 in kg m1 s1
This equation was proposed originally by Ellison and
Schmeal [16]. These authors obtained experimentally the
diffusion coefficient for ferrous ion using a rotating platinum
disk electrode. The mass transfer limited current density for
the oxidation of ferrous ion to ferric ion was determined in
an acid of a known ferrous concentration. This current
density was then related to the diffusion coefficient for
ferrous ion using Levich’s equation. Using this procedure,
these authors measured the diffusion coefficient of ferrous
ion in 68% and in 78% H2SO4 at 24 °C and 30 °C, respectively.
To compute the diffusion coefficient at other temperatures,
the authors adopted the extrapolation technique to Wilke’s
following relationship:

T
D1 ð5Þ
l Fig. 9. Thermal convection in a H2SO4 storage tank [15].

Viscosity values were obtained from the literature. Eq. (4) is


the equation obtained by the described technique. According are coated with insulating or reflective products. Further-
to Ellison and Schmeal [16], although this extrapolation is more, if only certain regions of the tanks are exposed to sun-
not ideal, its use did lead to results which were consistent light, these areas exhibit higher corrosion rates. The
with experimental data. influence of exposure to the sun on the corrosion rate can
On the basis of Eq. (4), higher viscosity values result in de- be verified in a practical case of a 9-year-old carbon steel
creased diffusivity of FeSO4, and the corrosion rates are tank for H2SO4 storage [19]. The corrosion rate on the sunny
therefore lower. In addition, the diffusion coefficient exhibits side was 0.84 mm y1 and on the shaded side was
a linear relationship with the temperature, which means 0.53 mm y1. To reduce the natural convection countermea-
that the corrosion rates increase with the temperature as ex- sures such as the application of a coat of white-colored
pected. The viscosity of H2SO4, in turn, varies with the acid paint, the application of insulation to the external tank
concentration in a manner shown in Fig. 8. walls, or the installation of sun screens on the sunny side
(B) Thermal (or natural) convection: Thermal convection accel- of the tank may be considered.
erates the removal by erosion of the FeSO4 surface layer, (C) Forced convection: Forced convection is provoked by
which exposes carbon steel to the aggressive environment mechanical stirring, such as the stirring that occurs because
and thus decreases the rate of corrosion. This convection oc- of flow through pipes, tank loading/unloading operations,
curs because of the temperature difference between the turbulence from the change of direction of flow caused by
external and internal environments of the storage tanks. elbows and joints in pipes, the presence of valves, the
During the day, the outside temperature is higher, which roughness in welds, or the lack of alignment of pipes. This
determines the heating of the tank walls. Therefore, the acid agitation also causes the removal of the FeSO4 layer by
in the vicinity of the heated tank walls exhibits a tempera- erosion. However, in this case, the FeSO4 layer removal is
ture higher than that found in the center of the tanks. The greater than that caused by thermal convection because
temperature increase is accompanied by the expansion of the agitation is more severe. According to Dean and Grab
the acid volume, which, in turn, determines a decrease in [12], the corrosion rate is proportional to the flow velocity.
the acid density. Thus, the acid along the walls tends to When the speed of flow is doubled, the corrosion rate is
move upward, and the acid in the central region of the tank almost doubled. Fig. 10 shows the corrosion rate of a carbon
tends to move downward. Fig. 9 represents the mechanism steel pipeline as a function of the flow velocity at three
of thermal convection. Tanks directly exposed to sunlight different temperatures. The concentration of transported
exhibit a higher thermal convection and thus higher corro- acid was 75%. As evident from the figure, the corrosion rate
sion rates than tanks that are protected from sunlight or increased as the velocity increased.
6 Z. Panossian et al. / Corrosion Science 58 (2012) 1–11

4. Types of carbon steel corrosion in concentrated sulfuric acid

Under stagnant or low-flow conditions, concentrated sulfuric


acid causes a general thinning of carbon steel, i.e., generalized cor-
rosion. However, depending on exposure conditions, carbon steel
may present other types of corrosion, such as hydrogen grooving,
blistering and preferential weld attack.

4.1. Hydrogen grooving

Hydrogen grooving is a type of corrosion that can be observed


on surfaces exposed to H2SO4 in the upper portion of horizontal
tanks, the top half of horizontal manways and nozzles and the
top half of horizontal pipe runs [9,19,21,22]. Such corrosion is
caused by bubbles of H2 formed by H2 molecules derived from
the actual corrosion of carbon steel in sulfuric acid (see reaction
(2). These bubbles can detach from the metal surface and can rise
along the pipe or tank walls because of their buoyancy in the acid.
The rise of hydrogen bubbles creates turbulence, increases the
mass transfer and removes the protective layer of FeSO4, which
continually exposes the metal to acid. The disruption of the film
is not uniform, but rather occurs along preferential paths that are
generally parallel to each other. The condition that determines
the occurrence of this type of corrosion is the geometry of the sur-
face on which corrosion occurs. On flat surfaces or on surfaces that
form angles greater than 90° to the horizontal, the bubbles of
hydrogen rise through the sulfuric acid solution and cause no dam-
age to the metal surface. However, on vertical surfaces and on sur-
faces that form an angle smaller than 90° to the horizontal, the
bubbles rise along the walls, which causes the formation of vertical
grooves (Fig. 11a). The formation of grooves on cylindrical surfaces
running circumferentially from the 9-o’clock to the 12-o’clock po-
sition is observed (Fig. 11b and c).
In manholes, deep grooves that run along the 12-o’clock axis are
observed from the accumulation of hydrogen bubbles from the
cylindrical walls, as illustrated in Fig. 12a. In addition, the vertical
walls located over the manhole may also exhibit grooves because
of hydrogen bubbles that escape from the 12-o’clock axis (Fig. 12b).
Any factor that accelerates the rate of corrosion of carbon steel
by concentrated sulfuric acid will cause increased amounts of
hydrogen gas and will therefore increase the incidence of grooves
caused by hydrogen. In tanks, these grooves may appear on the
walls of the tank located below the inlet nozzles (Fig. 13) and
above the outlet nozzles.
To avoid hydrogen grooving in areas of the tank walls that are
susceptible to this type of corrosion, corrosion-resistant alloys or
corrosion-resistant alloy-cladding should be used instead of carbon

Fig. 11. Schematic illustration showing hydrogen grooving: (a) vertical wall of
tanks; (b) and (c) cylindrical surfaces [15].

steel, together with modifications of the tank geometry. The top in-
let nozzles should lie far from the tank walls. For example, for ver-
tical tanks, the standard NACE SP0294 [9] recommends that these
nozzles should be placed at least 1.8 m away from the sidewall of
the tank, closer to the center of the roof of the tank, if possible, as
shown in Fig. 14a. The same procedures should be applied to
bottom outlet nozzles (Fig. 14a). In addition, flow deflectors can
be placed on the nozzle entrance to direct the flow of the acid away
from the tank walls, as is shown in Fig. 14b. Deflectors can be used
also on the upper side of manholes (Fig. 14c). The use of highly cor-
rosion resistant alloys is advisable for the deflectors to extend their
Fig. 10. Corrosion rate of a carbon steel pipeline at different temperatures and flow lifetime [19]. However, the choice of the deflector material should
velocities in 75% H2SO4. Adapted from Ref. [20]. be made with caution to avoid galvanic couples with carbon steel,
Z. Panossian et al. / Corrosion Science 58 (2012) 1–11 7

Fig. 13. Pattern of side-wall grooving due to inadequate location of the top inlet
nozzle. Adapted from Ref. [21].

H þ H ! H2 ð7Þ
Reaction (6) occurs at different sites on the metal surface. The
formed hydrogen atoms remain adsorbed and move randomly on
the metal surface until they meet another hydrogen atom and form
hydrogen gas (H2). Some of the hydrogen atoms, however, do not
combine to form hydrogen gas, but rather diffuse into the steel,
mainly toward discontinuities (dislocation, pores around inclu-
sions, lamination, etc.) and combine there to form hydrogen gas.
This gas is trapped within the discontinuities. Pressures of several
thousand atmospheres may build up at such locations because of
the continued formation of hydrogen gas, which leads to blister for-
mation and growth and, eventually, rupture [21,23]. In ductile
steels, such as the walls of sulfuric acid storage tanks, a deformation
will occur, and blisters will appear on the metal surface, if this strain
is significant and occurs along the outer surface of the metal [21,23].
Figs. 15 and 16 illustrate the formation of hydrogen blistering.

4.3. Preferential weld attack

According to studies by Dean and Grab [19], acid holdup occurs


in the roughened area of welds; this acid is subsequently diluted
by absorption of water from the air during unloading operations.
This dilution causes the acceleration of the corrosion on roughed
weld areas. Therefore, welds should be lightly ground and repaired,
if necessary, to remove flaws such as strikes, pits, gouges and
Fig. 12. Schematic illustration showing hydrogen grooving: (a) manhole; (b) undercuts.
vertical walls over manhole [15].

which will accelerate corrosion. Detailed information about tank 5. Corrosion rate of carbon steel in concentrated sulfuric acid
geometry can be found in NACE SP024 [9].
As mentioned before, although sulfuric acid corrodes carbon
4.2. Blistering steel, it is widely used for tank storage and piping that handles
concentrated sulfuric acid at near-ambient temperatures. There-
Blistering is a type of damage caused by atomic hydrogen. fore, knowledge of the order of magnitude of the corrosion rate
When the cathodic reaction responsible for the corrosion of carbon of carbon steel in different concentrations, at different tempera-
steel is the reduction of hydrogen ions, blistering may occur. This tures and under different flow conditions is important.
cathodic reaction occurs in two steps. Hydrogen is first produced The corrosion-rate values for carbon steel pipes can be esti-
in atomic form. Two atoms then combine to form hydrogen gas mated using a well-established mathematical equation proposed
molecules, as shown by the following reactions: by Dean and Grab [12]. This equation was formulated based on
the following assumption: the corrosion rate of carbon steel in con-
Hþ þ e ! H ð6Þ
centrated H2SO4 is equal to the mass transfer of the ferrous ion
8 Z. Panossian et al. / Corrosion Science 58 (2012) 1–11

Fig. 15. Schematic illustration of atomic hydrogen diffusion into steel during wall
corrosion of a sulfuric acid storage tank [23].

Fig. 16. Schematic illustration of hydrogen blistering: (a) atomic hydrogen trapping
in steel discontinuities; (b) formation of molecular hydrogen and blistering[15].

from the FeSO4 film – H2SO4 interface to the bulk acid. According to
the authors, the steel surface in this condition is covered with a
layer of FeSO4 whose mass remains constant with time so that
any mass loss of this layer is made up of corrosion of the metal.
Thus, the corrosion rate is proportional to the mass transfer rate
and can be calculated by the following equation [12,16]:
mcorr ¼ AkðW ¼ W bulk Þ ð8Þ
where: mcorr = corrosion rate A = conversion factor (it depends on the
adopted units for mcorr , k, W and W bulk ) k = mass transfer coefficient
Fig. 14. Schematic illustration showing the prevention of hydrogen grooving: (a) W = solubility of FeSO4 in H2SO4 (or concentration of FeSO4 at the
vertical tank with the top inlet nozzle placed near the center of the tank roof; (b) vicinity of the FeSO4 protective layer) in mass fraction % W bulk =
with the top inlet nozzle with deflectors; (c) manhole with deflectors [15]. concentration of FeSO4 in the bulk acid.
Z. Panossian et al. / Corrosion Science 58 (2012) 1–11 9

Table 3
Estimated corrosion rates (mm y1) for carbon steel. Data from Ref. [10].

H2SO4 (%, mass) Temperature (°C) Acid velocity (m s1)


0 1 2 3 4.5 6.5 8.5 11.5 12
100 6 0.13 0.18 0.23 0.3 1.14 1.52 1.91 2.41 2.05
15 0.3 0.38 0.43 0.51 1.65 2.16 2.79 3.56 4.32
33 1.27 1.4 1.52 1.78 6.86 9.14 11.43 14.73 18.29
50 2.54 3.81 5.08 7.62 25.37 25.37 25.37 25.37 25.37

Dean and Grab [12] used three dimensionless parameters from (c) the flow velocity of sulfuric acid in carbon steel tanks and in
fluid mechanics (Sherwood number, Reynolds number and Schmidt pipelines should be limited to 0.9 m s1 [10,25] and the tem-
number), an empirical equation proposed by Harriott and Hamilton perature to 50 °C;
[24] for the mass transfer factor for solid pipes dissolving in liquids (d) a corrosion allowance for tanks, pipes and nozzle surfaces
and Eq. (4) to obtain the corrosion rate defined by Eq. (8) as a func- wetted by sulfuric acid should be between 3.2 mm and
tion of parameters related to the H2SO4 properties (density and vis- 6.4 mm [9] depending on the acid concentration, as shown
cosity); the flow condition parameters (velocity, temperature and in Table 4. Corrosion allowance is defined as metal thickness
pipe diameter) and the FeSO4 solubility and concentration in acid. above the design minimum thickness that may be consumed
These authors presented a detailed mathematical proof of the cal- or otherwise removed without performing fitness-for-
culations made to obtain the following equation: service evaluations;
(e) corrosion test coupons installed in critical tank locations is
0:0001427T 0:654 V 0:913 q1:567 ðW  W bulk Þ
mcorr ¼ ð9Þ advisable because they can provide valuable quantitative
0:087
ð0:001lÞ1:221 d data on the prevalent types of attack in the specific locations
at which the coupons are installed [9];
where: mcorr = corrosion rate in mm y1 T = temperature in K V = acid
(f) precautions should be taken to avoid the ingress of water
flow velocity in m s1 q = density in kg m3 W = solubility of FeSO4
during loading/unloading operations [9,25];
in H2SO4 (or concentration of FeSO4 at the vicinity of the FeSO4 pro-
(g) to avoid acid dilution, the entry of moisture from the outside
tective layer) in mass fraction% W bulk = concentration of FeSO4 in the
should be controlled by proper venting and the minimiza-
bulk acid. Commercial acid contains about 0.01% (mass fraction) of
tion of air movement caused by natural convection. Taking
ferrous sulfate because it is produced and handled in carbon steel
measures to dry the air entering the tank reduces the risks
equipment. l = viscosity of H2SO4 in kg m1 s1, d = pipe diameter
of sulfuric acid dilution. Desiccant systems used for drying
in m.
incoming air should be properly maintained to ensure that
According to Dean and Grab [12], corrosion rates calculated
vents are not inadvertently obstructed and that the desic-
from this equation are in agreement with actual corrosion rates re-
cant is not saturated. Vent obstruction can result in serious
ported in the literature.
damage to a tank. When the local atmospheric humidity is
API Recommended Practice 581 [10] presents estimated corro-
normally high, a dry nitrogen or dry air pad should be con-
sion rates of carbon steel pipes based on Eq. (9) for pure sulfuric
sidered [9];
acid with no ferrous sulfate at different temperatures and at differ-
(h) the mechanical properties of the carbon steel plates, welds
ent flow velocities. According to this Practice, for turbulent flow in
and heat-affected zones (HAZ) must comply with applicable
straight pipes, the obtained corrosion rates were multiplied by a
codes (e.g., ASME BPVC, Section VIII, Division 1) or standards
factor of 3 to account for the enhanced localized corrosion at el-
(e.g., API650, Section 2, Materials or API 620 Section 4, Mate-
bows, tees, valves and areas of internal surface roughness such as
rials). A maximum tensile strength that exceeds 620 MPa
protuberances at welded joints. These adjustments provide the
should not be used because of the potential risk for hydro-
maximum estimated corrosion rates. Actual corrosion rates could
gen damage. The hardness of heat-affected zones of the weld
be 20–50% of these estimated maximum values. Table 3 presents
metal and base metal should be limited to 22 HRC [9];
estimated corrosion-rate values for carbon steel for different acid
(i) mill scales, as well as other types of impurities, should be
concentrations, different temperatures and different acid velocities.
removed from the steel surface to be exposed to the sulfuric
acid before the tank is put into service [9]. For this purpose,
6. Preventive measures for carbon steel corrosion control in
grit blasting should be considered [9]. This practice
concentrated sulfuric acid
improves the effectiveness of the protective FeSO4 layer
formed on the carbon steel surfaces;
To increase the useful life of tanks and pipelines made of carbon
steel, all of the countermeasures cited in Sections 3 and 4 should be
considered, and a detailed study of appropriate standards should Table 4
be performed. Among these standards, NACE SP0294 [9] and NACE New construction corrosion allowance for carbon steel at ambient temperature.
Adapted from Ref. [9] (Table 1).
RP0391 [25] can be cited.
Some of the recommended practices reported in standards for H2SO4 Minimum Typical corrosion allowance (mm)
the use of sulfuric acid are as follows: (%, mass) corrosion
allowance (mm)

(a) the concentration of sulfuric acid should be maintained >88–99.5 3.2 6.4
>93–99.5 1.6 3.2
between 88.0% and 99.5% [9], and preferably between
anodically
98.0% and 98.5%, where corrosion rates are lower; protected
(b) with (99–100.5)% H2SO4, the increased corrosion rate may >99.5–100.5 3.2 The increased corrosion rate may limit
limit the use of carbon steel. In this case, the stainless steel the use of carbon steel. Therefore, the
use of corrosion-resistant alloys
type UNS S304 and UNS S316 have been used successfully
should be considered.
in (90.0–100.5)% H2SO4 [9];
10 Z. Panossian et al. / Corrosion Science 58 (2012) 1–11

j) coatings should be applied to external surfaces of uninsu-


lated tanks to minimize radiant heating from the sun and
to keep the metal temperature as low as possible [9].

In cases where carbon steel exhibits low performance, lined car-


bon steel pipes may be considered. Fluorinated plastics such as
polytetrafluoroethylene (PTFE); perfluoroalkoxy (PFA); ethylene
chlorotrifluoroethylene (ECTFE); fluorinated ethylene propylene
(FEP) and ethylene trifluoroethylene (ETFE) are resistant to concen-
trated sulfuric acid at temperatures up to 50 °C [25].
Polyethylene (PE) and polypropylene (PP) are subject to envi-
ronmental cracking. Cracking probability increases with increasing
acid concentration and temperature, and a careful review of long-
term performance of these materials should be performed prior to
their application [25].
Polyvinylchloride (PVC) and polyvinylidene chloride (PVDC)
have been used successfully as piping for concentrated sulfuric
acid at concentration less than 96%. Polyvinylidene fluoride (PVDF)
may be used for concentrations up to 98% [25].
High-temperature-baked phenolic and epoxy novolac linings
are normally used to protect small tanks that store sulfuric acid
with a concentration of (90–98%). At acid concentrations greater
than 98%, some types of baked phenolic coatings that have been
slowly carbonized may be used [25].
The most common protection method for reducing the corro-
sion rate of carbon steel in concentrated sulfuric acid is anodic pro-
tection [26–31]. This method also guarantees the quality of the
acid in terms of iron content, which is an important feature where
high acid purity is required, such as in the production of sulfonated
products, where sulfuric acid is used as a raw material. For large
tanks (greater than 190 m3), anodic protection is a suitable method
to extend the useful life of the tanks [9]. Fig. 17. (a) Polarization curve of a metal in acid solution presenting a stable passive
The essential condition for the use of anodic protection is that film. Adapted from Ref. [23]. (b) Polarization curve of carbon steel in 96% H2SO4.
the metal must exhibit an active/passive behavior in a specific Adapted from Ref. [27].
media, such as carbon steel in sulfuric acid. Anodic protection is
again, and a second peak is observed (point R). According to Wil-
obtained by the application of an anodic current to put the metal
liamson and Hines [18], this step is called the activation step. How-
under consideration in the passivity domain [26].
ever, it is believed that it is more suitable to refer to it as the
Fig. 17a depicts a typical polarization curve of an active/passive
reactivation stage as long as the sulfation stage is also an activation
metal/ environment combination. As a positive potential is applied
process.
from the corrosion potential (Ecorr), the current density increases up
During this stage, the FeSO4 film becomes unstable because of
to a maximum value that is called the critical current density (icrit).
the oxidation of Fe2+ ions to Fe3+ ions, as observed by Banks and
The corresponding potential is called the Flade potential (EF). The
Sudbury [28]. This oxidation makes the film more porous and
potential range from Ecorr to EF concerns the active stage of the cor-
therefore less protective. This transformation is accompanied by
rosion process with the evolution of H2 from the reduction of water.
a change in the film color: the dark color due to the FeSO4 film dis-
From point P, a range of potentials (EP to EO) is reached. This range is
appears, and a white-colored film begins to form, which indicates
characterized by low corrosion rates and is known as the passive re-
the formation of Fe3+ ions.
gion of the polarization curve. At point O, the evolution of oxygen
According to Williamson and Hines [18], at the second current
becomes possible, and the current density again increases.
density peak (icrit at point R of Fig. 17b), a process of nucleation
In the case of carbon steel in sulfuric acid, the anodic polariza-
and growth of a passive film occurs. This film is constituted by a
tion curves show two peaks of current density, as shown in Fig. 17b
crystalline layer of Fe2O3 mixed with Fe2(SO4)35H2SO4 and FeS-
[18,27].
O43H2SO4. This stage is called the passivation stage, which is
In Fig. 17b, the first peak (point S) occurs as soon as the appli-
accompanied by a sharp reduction in the current density. The
cation of anodic potential from the corrosion potential begins.
range of potentials of the passivation stage is that in which carbon
The range from Ecorr to ES is a typical activation process, known
steel is maintained during anodic protection.
as the sulfation stage. This stage involves the reduction of water
In sulfuric acid, the water oxidation reaction (2H2O ? O2 +
to hydrogen and the formation of a supersaturated FeSO4 solution
4H+ + 4e) occurs at a much higher potential—almost 5 V vs. SHE
at the metal surface, which leads to nucleation and growth of
(standard hydrogen electrode) [29]. This high value is a conse-
FeSO4 crystals. This nucleation and growth is followed by the for-
quence of the low pH and the low concentration of water in the
mation of a FeSO4 protective film [27]. At this point (S in
acid.
Fig. 17b), a sharp decrease in the current density is observed. The
described sulfation process occurs naturally on the surface of the
carbon steel when it is brought into contact with a concentrated 7. Conclusion
solution of sulfuric acid.
After the formation of the sulfate film, a potential increase will The corrosion resistance of carbon steel in sulfuric acid is a con-
not determine an increase in the current density up to point A sequence of the formation of a protective FeSO4 layer and does not
(Fig. 17b). However, at this point, the current starts to increase depend on the steel composition. Thus, preventive measures
Z. Panossian et al. / Corrosion Science 58 (2012) 1–11 11

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Standard practice – Design, fabrication, and inspection of storage tank systems
will cause an increase in the corrosion rate of carbon steel in con- for concentrated fresh and process sulfuric acid and oleum at ambient
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