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Engineering Failure Analysis 17 (2010) 906912

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Engineering Failure Analysis


journal homepage: www.elsevier.com/locate/engfailanal

Corrosion failure analysis of stainless steel components for maleic


anhydride plant
Wei Wu a, Guangxu Cheng a,*, Wensheng Zhu b, Congmin Xu c, Heping Cai d
a

School of Energy and Power Engineering, Xian Jiaotong University, Xian 710049, PR China
Research Institute of Lanzhou Petrochemical Corporation, Lanzhou 730060, PR China
c
School of Material Science and Engineering, Xian Shiyou University, Xian 710065, PR China
d
School of Material Science and Engineering, Xian Jiaotong University, Xian 710049, PR China
b

a r t i c l e

i n f o

Article history:
Received 25 September 2009
Received in revised form 1 November 2009
Accepted 2 November 2009
Available online 10 November 2009
Keywords:
Erosioncorrosion
Pitting corrosion
Austenitic stainless steel
Sulphuric acid
Chloride

a b s t r a c t
Failures of a owmeter oater and a spherical valve installed at a pipe transporting maleic
acid aqueous solution in a maleic anhydride plant were investigated by means of macroscopic and microscopic examinations, chemical composition analysis, and weight loss
tests. The investigation results indicated that the components were made of AISI type
316L stainless steel. The damages of both the oater and the inner surface of the valve were
caused by an extensive erosioncorrosion in maleic acid aqueous solution contaminated
with sulphuric acid and chlorides, which originated from the feed blending coking benzene
and the recycled process water, while that of the back surface of the oater as well as the
outer surface of the valve was induced by general and pitting corrosion as a result of formation of a stagnation zone where the acidic chloride-containing solution collected. It was
recommended to use a dechlorination device by resin adsorption technique for reducing
the content of chloride ions in the maleic acid aqueous solution.
2009 Elsevier Ltd. All rights reserved.

1. Introduction
Maleic anhydride (C2H2(CO)2O) is an important industrial raw material and ne chemical product, which is normally
manufactured by oxidation of benzene or n-butane. The production process of maleic anhydride from benzene includes three
main steps: benzene reacts with oxygen in air over V2O5 catalyst to form maleic anhydride; the anhydride is adsorbed in
water to convert into maleic acid (cis-HO2CCH@CHCO2H); the acid is dehydrated and puried to form nal product (Fig. 1).
The intermediate product, maleic acid, tends to cause serious corrosion of carbon steel at relatively high temperatures, so
most of the equipment and components under maleic acid environment in the maleic anhydride plant have been made of
stainless steels to stand up to this acid corrosion. Nevertheless, several corrosion phenomena were still claimed but not severe. Recently, for the purpose of reducing production cost, petroleum benzene as feed was blended with coking benzene
which had more impurities, such as sulphur compounds and chlorides. A few months later, some equipment and pipelines
frequently suffered extensive corrosion, in particular the components involving owmeters and valves. For instance, a valve
located at a pipe transporting maleic acid has been replaced as many as three times during 12 months. In the present work,
the typical failures of metal tube oater owmeter and spherical valve, which failed after 4 months service, are investigated
for founding out the reason for corrosion failures of the components.

* Corresponding author. Fax: +86 29 83234781.


E-mail address: gxcheng@mail.xjtu.edu.cn (G. Cheng).
1350-6307/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.engfailanal.2009.11.001

W. Wu et al. / Engineering Failure Analysis 17 (2010) 906912

907

Fig. 1. Schematic diagram of the production process for maleic anhydride.

2. Failure location and environment


The failed metal tube oater owmeter and spherical valve belonged to a pipe transporting maleic acid aqueous solution
from the maleic acid tank to the rening unit (Fig. 1). The solution had an average concentration of 20 wt.% and a temperature
of 70 C. The ow rate through the straight pipe was about 1.4 m/s. According to chemical analysis of the solution and recycled
process water samples, it is known that there were, besides maleic acid, small quantities of chloride ions (50 mg/L), sulphate
ions (13,500 mg/L) and a few of solid particles of fumaric acid, which is the isomer of maleic acid, in the solution, and smaller
quantities of chloride ions (48 mg/L) and sulphate ions (5000 mg/L) in the recycled process water. The chloride ions mainly derived from the recycled process water and the feed blended with coking benzene, and sulphate ions from the reaction between
water and sulphur trioxide as a result of oxidation of sulphur compounds present in the feed at reaction unit.
3. Failure examination and results
3.1. Visual observation
The failed owmeter oater and two samples which were cut from both inner and outer surfaces of the failed valve body
were carefully observed. The observations are presented below.
The macroscopic photos of the failed oater are shown in Fig. 2. Its overall surface was grayish in colour without metallic
luster. The straight beam exhibited slight general thinning and no pits (Fig. 2a), whereas the back surface existed large

Fig. 2. Macroscopic feature of the failed oater: (a) the general feature; (b) enlargement of the back surface with many cavities; (c) enlargement of the
convex part with many grooves along the direction of the uid ow.

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W. Wu et al. / Engineering Failure Analysis 17 (2010) 906912

amounts of pits with different sizes and depths, the biggest size up to 2.0 mm (Fig. 2b), and the convex part had a lot of
grooves along the direction of uid ow (Fig. 2c).
As shown in Fig. 3, it is clearly found that the features of the two surfaces from the valve body made a great different. The
inner surface contacting the uid exhibited several parallel shallow striations (Fig. 3a), but on the outer surface connecting
with the inner surface of the pipe, some cavities and many pits were just observed (Fig. 3b).
3.2. Chemical composition and metallographic structure analysis of materials
The chemical compositions of the component materials were determined using standard techniques. The same are listed
in Table 1. From the results of the chemical analysis, it is evident that the chemical composition of the components complies
with that of AISI type 316L austenitic stainless steel [1]. The small difference in carbon content and molybdenum content of
the oater is basically tolerable.
The metallurgical examinations were also conducted using optical microscope. Microstructure of the oater revealed austenite grains and a large number of deformation twins (Fig. 4a), and that of valve exhibited polygonal austenite grains, a minor amount of ferrite and some twins (Fig. 4b).
3.3. Chemical composition analysis of surface deposits
The samples cut from the failed components were examined under a scanning electron microscope (SEM), using the energy dispersive spectroscopy analysis (EDS) for major elements contained in the deposits.
In the deposits on the sample from the oater, EDS analysis shows that carbon (52.89 wt.%), oxygen (19.54 wt.%) and iron
(18.29 wt.%) were the main elements, and there were smaller quantities of sulphur and sodium at 0.14 and 0.85 wt.%, respectively. In the deposits on the sample from the valve, besides the presence of carbon (15.05 wt.%), oxygen (8.16 wt.%) and iron
(51.41 wt.%), EDS analysis indicates small amounts of sulphur and magnesium at 0.50 wt.% and 0.50 wt.%, respectively.
Based on the above analysis, it can be ensured that the large amounts of carbon and oxygen mainly originated from the
products of oxidation reactions at the reaction unit, and sodium and magnesium from chlorides present in the feed and the
recycled process water. Although chlorine was not detected on account of too low content on the surfaces, it had a signicant
inuence on the corrosion problems of the components.
3.4. Microscopic examinations
Some samples used for visual observation were also examined using scanning electron microscopy. Fig. 5 shows the
microscopic morphology of the sample cut from the convex part. Corrosion exfoliation along twin boundaries and deforma-

Fig. 3. Macroscopic features of the different parts of the failed spherical valve body: (a) the inner surface and (b) the outer surface.

Table 1
Chemical compositions of the different components (wt.%).
Item

Mn

Si

Cr

Ni

Mo

Floater
Valve
AISI 316L SS

0.035
0.026
60.030

1.53
1.65
62.0

0.46
0.87
61.00

17.91
17.86
16.018.0

10.42
10.02
10.014.0

0.025
0.023
60.045

0.022
0.026
60.03

1.68
2.00
2.03.0

W. Wu et al. / Engineering Failure Analysis 17 (2010) 906912

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Fig. 4. Metallographic structures of the components: (a) the owmeter oater (400) and (b) the spherical valve body (400).

Fig. 5. SEM micrograph showing surface morphology of the oater.

tion steps was apparently seen. Fig. 6 shows details of two surfaces of the valve body. The erosive traces were clearly observed on the inner surface (Fig. 6a), while general loss of thickness and several corrosion pits were observed on the outer
surface (Fig. 6b).

Fig. 6. SEM micrographs showing surface morphologies of the valve: (a) the inner surface and (b) the outer surface.

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W. Wu et al. / Engineering Failure Analysis 17 (2010) 906912

3.5. Weight loss tests in laboratory


Weight loss tests have been conducted in laboratory for determining the effect of maleic acid aqueous solutions in the
presence of chlorides and sulphuric acid on corrosion of 316L stainless steel. The specimens used for the tests were cut from
a 316L stainless steel sheet. The nominal elemental composition (wt.%) of the specimens for the tests is: C 0.029, Cr 16.69, Ni
10.11, Mo 2.04, Mn 1.38, Si 0.39, P 0.031, S 0.005 and Fe balance, which is similar to that of the failed components. The specimens were exposed to test solutions for 7 days at 70 C. They were weighted before and after each test using electronic balance. After weight loss tests, the specimens were examined for their corrosion morphologies using scanning electron
microscopy. The results and SEM graphs are shown in Figs. 79, respectively.
4. Discussion
Austenitic stainless steels, as the biggest family of stainless steels, have been applied in a variety of industries due to their
good corrosion resistance in both mild and severe corrosive conditions, which depends on the formation of a thin and adherent chromium-rich oxide surface passive lm that can separate the metal from the surrounding environment. In general, the
passive lm can be formed or restored if broken in the presence of oxygen or other oxidizing agents, such as nitric acid
(HNO3) and chromic acid (H2CrO4).
316L stainless steel is a molybdenum-bearing austenitic stainless steel and has lower carbon allowed. As it has higher
corrosion resistance owing to adding molybdenum, this type of steel is usable in almost all of organic acids, even at relatively
high temperatures. There is no exception in maleic acid [1]. As far as sulphuric acid is concerned, 316L stainless steel is well
resistant to low concentrations of this acid at room temperature, but on increasing the temperature the corrosion rate of
316L stainless steel rises gradually. For instance, the rate is not more than 0.1 mm/year at low concentration, up to
22 wt.% at 20 C but to 3 wt.% maximum at 70 C [2,3]. As mentioned above, selection of 316L stainless steel to manufacture
the components contacting maleic acid solutions in the maleic anhydride plant is acceptable, even in the presence of small
amounts of sulphuric acid.
However, under certain conditions, in particular presence of chlorides in a wet environment, the passive lm of austenitic
stainless steel may subject to attack at vulnerable area (e.g., inclusions, twin boundaries, second phase precipitates, and slip
steps) and not be permitted healing after damaged. The chloride ions can result in the formation of a pit by preferential
adsorption on the passive lm and chemical reaction with metal atoms to form metal chlorides. Subsequently, the metal
chlorides generate hydroxide of the metal and hydrochloric acid by hydrolysis. Finally, the hydrolysates induce decrease
in pH at the pit site and further metal dissolution enhancing the growth of pits [2,4,5].
If chloride ions and some acids, like sulphuric acid, are present simultaneously, the metal dissolution rate can be significantly accelerated since the acid is easier to attack the metal due to the breakdown of the passive lm by chloride ions [6],
which has been also veried by the loss weight tests. As shown in Fig. 7, the corrosion rate of 316L stainless steel exposed to
the acid solutions (i.e., maleic acid and sulphuric acid) without chloride ions was less than 0.1 mm/year at 70 C and there
was no corrosion to be found except few small pits on the samples (Fig. 9a and b). However, once sodium chloride was added
into the solutions, the rate drastically increased and general and pitting corrosion occurred on the specimens (Fig. 9c and d),
and moreover, with the increase in concentration of chloride ions, the corrosion rate increased. On the other hand, if there

Fig. 7. Corrosion rate of 316L stainless steel exposed to 20 wt.% maleic acid solutions with different concentrations of sodium chloride and sulphuric acid at
70 C.

W. Wu et al. / Engineering Failure Analysis 17 (2010) 906912

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Fig. 8. Corrosion rate of 316L stainless steel exposed to the mixed aqueous solutions of sodium chloride and sulphuric acid at 70 C.

Fig. 9. SEM micrographs showing surface morphologies of 316L stainless steel specimens exposed to different solutions at 70 C after 7 days: (a) 20 wt.%
maleic acid; (b) 20 wt.% maleic acid + 3.0 wt.% H2SO4; (c) 20 wt.% maleic acid + 3.0 wt.% H2SO4 + 0.5 wt.% NaCl; (d) 20 wt.% maleic acid + 3.0 wt.%
H2SO4 + 1.0 wt.% NaCl.

was not maleic acid in the solutions, the corrosion rate of the steel could decrease to some extent, as shown in Fig. 8, which
indicates that maleic acid can enhance the corrosion effect of the mixed solutions of sulphuric acid and chloride ions on 316L
stainless steel. So it is certain that the corrosion failures of the components were associated with the synergistic effects of
maleic acid, sulphuric acid and chloride ions.

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W. Wu et al. / Engineering Failure Analysis 17 (2010) 906912

Besides chloride ions and acids, ow conditions of the process uid also had an important effect on damages of the components. The ow rate through the pipe (approximately 1.4 m/s) was not high to 316L stainless steel, since there was only
general thinning and a few pits to be observed at the straight pipe. However, when the corrosive uid containing suspended
solid particles of fumaric acid owed through the owmeter and the valve, the disturbed turbulent ow would take place
due to a sudden change in the ow system geometry [7]. This excessive turbulence and solid particles could impinge, erode
and remove the passive lm by imposing disruptive shear stresses and pressure variations on the metal surfaces, which resulted in that new active surfaces continuously exposed to the strong corrosive uid, and then accelerated metal dissolution
by chemical reaction on the active surfaces. Finally the phenomenon of erosioncorrosion took place on the oater and the
inter surface of the valve. In addition, the ow of uid is able to decrease pitting attack [8], so no pits were observed at the
straight beam of the oater.
Different from the inner surface of the valve, the damage on the outer surface was caused by general and pitting corrosion
in a relative stationary corrosive environment due to the formation of a stagnation zone in the gap between the outer surface
of the valve and the inner surface of the pipe, where the aggressive contaminants collected, resulting in a stronger corrosivity. Likewise, the back surface of the oater failed due to the same reason.
The corrosion problems of the components can be mitigated by reducing the contents of strong aggressive contaminants
in the process uid, particularly chloride ions. Since addition of inhibitors may contaminate the process uid and reduce the
quality of the product, it is recommended to use physical removal methods in steady of chemical methods. The installation of
a dechlorination device by resin adsorption technique at the outlet of the recycled process water tank is one of the feasible
countermeasures to avoid accumulation of chloride ions. Furthermore, solid particles of fumaric acid in the process uid
should be decreased by strictly controlling process parameters at the reaction unit. To avoid such failures, the most effective
solution is the substitution of duplex stainless steel for 316L austenitic stainless steel to manufacture the components, but it
requires a high price.
5. Conclusions
(1) The failed owmeter oater and spherical valve installed at a pipe supplying maleic acid to rening unit of a maleic
anhydride plant were made of AISI type 316L austenitic stainless steel. The investigation of the oater and the inner
surface of the valve found that the failure has been caused by extensive erosioncorrosion in maleic acid contaminated
with small quantities of chlorides and sulphuric acid.
(2) The failure of the outer surface of the valve as well as the back surface of the oater has taken place by general thinning and pitting corrosion as a result of formation of a stagnation zone of the acidic chloride-containing uid ow.
(3) The corrosion attack may be mitigated by installing a dechlorination device by resin adsorption technique to decrease
the content of chloride ions from the feed and the recycled process water.

Acknowledgements
The Project nancially supported by the National Natural Science Foundation of China (Grant No. 20676109). The authors
greatly acknowledge Sheng Gang, engineer in Research Institute of Lanzhou Petrochemical Corporation, CNPC, for his assistance in analysis of solution and water samples.
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