Engineering Failure Analysis 44 (2014) 6673

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Engineering Failure Analysis

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

Corrosion analysis and inhibition studies in the process

of natural gas wet desulfurization
Zhihong Wang, Chaoyue Yang, Lin Zhu
School of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, PR China

a r t i c l e

i n f o

Article history:
Received 24 December 2013
Received in revised form 1 April 2014
Accepted 20 April 2014
Available online 28 April 2014
Keywords:
Corrosion analysis
Inhibition study
Wet desulfurization
Natural gas

a b s t r a c t
The present work investigates the corrosion on FeAl alloy steel in the process of the wet
desulfurizing of Sichuan natural gas purication master plant. The morphology and composition of the corrosion scale are characterized by scanning electron microscopy, X-ray
power diffraction and energy-dispersive spectroscopy. Results show that corrosion scale
mainly consists of FeS. Electrochemical methods such as polarization curve and electrochemical impedance spectroscopy were used to analyze the effects of alcohol amine
concentration and temperature on the corrosion. It can be found that the strongest corrosion occurs at the temperature of 50 C and the concentration of 40% alcoholic solution. In
addition, the electrochemical experiments demonstrate that the corrosion rate can be
apparently reduced by adding corrosion inhibitors such as diethanol amine and
triethanolamine.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Natural gas plays an important role in the national economy, and it is a kind of clean, convenient, efcient, high quality
fuel, and also an important raw material for chemical industry [1]. Generally, there are some impurities such as hydrogen
sulde (H2S) in the natural gas which may cause many unwished problems including air pollution and corrosion. Therefore,
the purication of natural gas becomes very important. Desulfurization process can be divided into dry or wet technology.
Wet desulfurization in which the liquid solution usually contains some alkaline substances to strengthen purication quality
of gas is one of the most promising processes in natural gas desulfurization. The alcohol amine method, one kind of wet technology, is the most widely used process because of large capacity, stability and operation reliability [2]. However, it should
be noted that some serious corrosion problems have been found in the process of alcohol amine desulfurization [3]. In the
process of purication natural gas, corrosion can cause signicant losses in property and human lives. In addition, amine
solution pollution and loss due to corrosion will increase the production cost [4]. According to relevant statistics, about
60% of the chemical equipment was damaged by the corrosion [5].
Fig. 1 shows the process ow diagram of the natural gas wet desulfurization unit in Sichuan natural gas purication master plant, and the insert presents two kinds of corrosion morphologies which demonstrate that both severe pitting and uniform corrosion have taken place on the surface of the metal inside the absorption tower. As shown in Fig. 1, the sour natural
gas after inlet preliminary treatment contacted counter-currently with the lean amine solvent ranging from 30 C to 80 C in

Corresponding author. Address: School of Chemistry and Chemical Engineering, Southwest Petroleum University, No. 8 Xindu Road, Chengdu 610500,
PR China. Tel.: +86 02883037323; fax: +86 02883037305.
E-mail address: zhulinswpi65@gmail.com (L. Zhu).
http://dx.doi.org/10.1016/j.engfailanal.2014.04.030
1350-6307/ 2014 Elsevier Ltd. All rights reserved.

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Z. Wang et al. / Engineering Failure Analysis 44 (2014) 6673

Fig. 1. Process ow diagram of the wet desulfurization.

Table 1
Chemical composition of natural gas.
Component

H2

N2

CO2

H2S

COS

H2O

CH4

C2H6

Others

wt%

0.02

0.55

9.99

17.98

0.02

0.09

71.20

0.12

0.03

Table 2
Chemical composition (wt%) of FeAl alloy steel.
Element

Al

Si

Ca

Cr

Fe

Nb

wt%

28.06

12.45

1.73

0.08

2.34

6.43

43.72

5.21

the absorber. The puried gas which contains only a very small amount of hydrogen sulde will leave overhead from the
column. The rich amine solution loaded with H2S is heated again with the hot lean amine solution returning from the regeneration tower in a heat exchanger. The H2S is stripped off from the rich amine in the regenerator at a low pressure. The sour
gas and some water leave the regenerator through an overhead condenser. The lean amine leaving the bottom of the regenerator passes through the lean/rich amine heat exchanger to lower the temperature and mixes with the make-up water and
make-up amine to compensate the degraded amine solution and escaping water. The lean amine is further cooled at the second heat exchanger by cooling water, and then sent back to the absorber. The chemical composition of natural gas was listed
in Table 1.
The corrosion, which occurred in the wet desulfurization process of nature gas, can be affected by many factors, such as
amine concentration, temperature, pressure and uid velocity [6]. However, the alcohol amine concentration and temperature can be regarded as the main factors. The aim of the present work is to investigate the corrosion and the corrosion inhibition of the FeAl alloy steel that is used in the natural gas purication master plant. Table 2 presents the chemical
composition of this FeAl alloy steel. The microstructure and composition of the corrosion scale were investigated by scanning electron microscope (SEM), X-ray power diffraction (XRD) and energy-dispersive spectroscopy (EDS). Additionally, the
factors affecting the corrosion such as temperature and concentrations of alcohol amine were also described by electrochemical methods such as polarization curve and electrochemical impedance spectroscopy (EIS).
2. Theory: corrosion mechanism of hydrogen sulde
H2S aqueous solution can be dissociated to H+, HS and S2. It is a process of depolarization when it corrodes the metal
[7].

H2 S
HS H

HS
S2 H

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Z. Wang et al. / Engineering Failure Analysis 44 (2014) 6673

First, H2S is absorbed on the iron surface in the solution. Then, a series of reactions about anion adsorption and desorption
on iron happened [8]. At last, Fe2+ or FeS was produced through anodic oxidation and hydrolysis process [9]. The processes
could be summarized into four sub-reactions Eqs. (3)(6), where the subscript ad referred to the adsorption state.

Fe H2 S H2 O ! FeHSad H3 O

Fe HSad ! FeHSad 2e

FeHSad H3 O ! Fe2 H2 S H2 O

Fe2 HS ! FeS H

6
+

FeHS
ad

In weak acid solution, after the desorption of H ,

directly changes into FeS which is produced by anodic electrochemical reaction [10]. This FeS makes a certain function to slow down the corrosion if it is compacted and has good adhesion
to the substrate. However, when the generated FeS is not dense, it will form a strong galvanic with the potential difference from
0.2 V to 0.4 V, so that it can promote corrosion of the base metal. In addition, when sulfur presents in the solution or on the
metal substrate, it prevents the hydrogen atoms from transforming into the hydrogen molecule in a certain extent. The hydrogen atom combined into hydrogen molecules in the surface layer of the defective portion of the steel, and expanded to produce
the hydrogen pressure. It leads to sulde stress cracking (SSCC) in the effect of steel service superposition and synergistic.
3. Material and methods
3.1. Materials preparation
The FeAl alloy steel coupons with dimension of 10 mm  10 mm  5 mm were used for electrochemical measurements.
The H2S used in this study was obtained with phosphoric acid and sodium sulde in the laboratory, according to the reaction
(7). The different concentration solutions of alcohol amine was prepared by dilution of industrial grade, and the deionized
water was used for preparing test solutions for all experiments.

2H3 PO4 Na2 S H2 S 2NaH2 PO4

3.2. Characterization
The chemical composition of the FeAl alloy steel was analyzed by using a direct reading spectrometer (ARL 4460, Beijing)
on the basis of ASTM A751-2008.
To identify the chemical composition of the corrosion scale, EDS (Oxford Inca 300, England) was employed at 10KV accelerating voltage. XRD was carried out by X-ray diffractometer (XPert Pro MPD, Hlland) using Cu Ka X-ray at 40 kV and 40 mA,
and the XRD diffractogram was recorded in the angle range between 15and 60 at a step size of 0.03.
The surface morphology of the corrosion scale was observed with SEM (Phlips-XL30, Holland).
3.3. Electrochemical test
The electrochemical test was evaluated by a CHI604D electrochemical workstation. The classic three-electrode system
was used in the tests, where the FeAl alloy steel sealed with epoxy was used as the working electrode (WE, electrode contact area of 1 cm  1 cm); carbon rod was used as the counter electrode (CE); the saturated calomel electrode was used as
the reference electrode (RE), and the saturated calomel electrode with a Lukin capillary was used as the bridge to connect
with service substance.
Before the experiment, the emery paper (240 mesh, 360 mesh, 800 mesh) were used to polish the working electrode. The
working electrode was rinsed with distilled water after its surface being polished to a mirror bright, and then cleaned by
anhydrous ethanol and acetone, nally cold and dry it.
Alternating current amplitude in the test of impedance spectra was 5 mV vs. o.c (natural corrosion potential), and its
frequency was at the range of 25 mHz100 kHz. Scanning speed in the test of polarization curve was 1.0 mv s1.
4. Results and discussion
4.1. SEM, XRD and EDS analysis of corrosion morphology
To gure out the adsorption state of the corrosion scale on the FeAl alloy steel, Fig. 2 shows the XRD spectrum of the
corrosion scale on FeAl alloy steel. It can be seen that the characteristic diffraction peaks of FeS appeared at the 2h of
21.8, 27.9, 33.9, 35.9, 40.4, 44.4 and 53.7. In addition, the bands at 38.1 and 49.2 were assigned to the diffraction peal

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Z. Wang et al. / Engineering Failure Analysis 44 (2014) 6673

Fig. 2. XRD spectrum of the corrosion scale on FeAl alloy steel.

of FeCO3. In order to further clarify the composition of the corrosion scale, SEM and EDS depth proles were acquired, and the
results were presented in Fig. 3.
Fig. 3 (the left) shows SEM surface morphologies of corrosion scales. It was found that a layer of occulent corrosion product lm occurred on the surface of FeAl alloy steel in the process of natural gas desulfurization. The corrosion scale was not
tight and the distribution was also nonuniform. Some parts of the corrosion scale have fallen and some parts have formed in
bulk. The corrosion scale was easily exfoliated from the matrix that would expose the fresh steel surface to the corrosive
medium. In order to further clarify the composition of the corrosion scale, EDS depth proles were acquired, and the results
were presented in Fig. 3 (the right). Two points of different regions were selected to analyze the composition of the corrosion
scale. The element of the corrosion scale on the surface of FeAl alloy steel was listed in Table 3. It can be found that the
element such as Fe, S, C, O, Al, Si, Cr and Ca appeared in the survey spectrum of the corrosion scale surface. The atomic ratio
of Fe, S, C and O was approximately 3:2:1:3, indicating that the composition of the corrosion scale was mainly FeS, followed
by FeCO3 and a small amount of Al(OH)3, Cr2O3, Al2O3, CaCO3.

Fig. 3. SEM surface morphologies and EDS analysis of corrosion scales on FeAl alloy steel.

Table 3
Elemental analysis of corrosion scales on FeAl alloy steel.
Element (wt%)

Al

Si

Ca

Cr

Fe

Nb

1
2

11.98
10.30

31.55
38.98

5.62
4.86

0.12
0.11

0.07

27.36
14.86

0.11

2.06
6.83

30.28
15.28

4.00

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Z. Wang et al. / Engineering Failure Analysis 44 (2014) 6673

4.2. Effect of alcohol amine concentration on corrosion

H2S supplied by the reaction of Na2S and H3PO4 was used to countercurrent ow through MDEA solutions of different
concentrations (30%, 40% and 50%). The concentration of the acid gas loaded by the three amine solutions was maintained
at 0.5 mol acid gas/1 mol amine. Then impedance spectra and polarization curves were measured at 25 C. The results were
illustrated in Figs. 4 and 5.
From Fig. 4, it can be seen that the measured electrochemical impedance spectra were approximately semicircular, and
the diameter of the semicircle changed with the amine concentration. This suggested that the corrosion behavior of FeAl
alloy steel was inuenced by the alcohol amine concentration in the process of using alcohol amine solution to removal acid
gas. As shown in Fig. 4, the diameter of capacitive arc decreased at rst and then increased with the increasing alcohol amine
concentration, which indicated the corrosion of FeAl alloy steel rstly increased and then decreased in the process of acid
gas removal. Various electro-chemical corrosion parameters such as corrosion potential (Ecorr), corrosion current density
(Icorr), anodic and cathodic Tafel slopes (ba and bc) obtained by extrapolation of Tafel lines are presented in Table 4. The value
of Icorr which has a direct relationship with the corrosion rate of FeAl alloy steel also rst decreased and then increased with
the increasing alcohol amine concentration. These phenomena can be understood by the following reasons. The higher the
concentration of amine was, the greater amount of H2S was absorbed by the unit volume amine under the same acid gas
load, which led to the increase of the corrosion rate. However, the higher concentration of MDEA (such as the concentration
was 50%), would result in a higher pH value, which was less conductive to the anodic reaction.
As illustrated in Fig. 5 and Table 4, the corrosion process was controlled by the anode in these experiments for the reason
that the value of ba is generally larger than that of bc. In the polarization curve, corrosion potential of MDEA solution whose

Fig. 4. EIS of alcohol amine acidic solutions at different concentrations at 25 C.

Fig. 5. Polarization curves of alcohol amine acidic solutions at different concentrations at 25 C.

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Z. Wang et al. / Engineering Failure Analysis 44 (2014) 6673

Table 4
Electrochemical polarization parameters for the corrosion of the FeAl alloy steel in alcohol amine acidic solutions at different concentrations at 25 C.
Alcohol amine concentration (%)

ba

bc

Icorr (A)

Ecorr (V)

Corrosion rate (lm a1)

30
40
50

8.364
8.762
8.528

5.600
5.561
6.395

2.398  105
2.576  105
2.489  105

0.708
0.706
0.719

2.7718  104
2.9776  104
2.8770  104

concentration was 40% moved to the positive polarization potential direction. This indicated that the MDEA solution was
more effective on the anode electrode, namely it was more corrosive.
4.3. Effect of temperature on corrosion
H2S supplied by the reaction of Na2S and H3PO4 was used to countercurrent ow through MDEA solutions of 40% concentration. The concentration of the acid gas loaded was maintained at 0.5 mol acid gas/1 mol amine. Then, impedance spectra
and polarization curves were measured at 30 C, 40 C, 50 C and 55 C. The results were illustrated in Figs. 6 and 7.
From Fig. 6, the measured electrochemical impedance spectra were approximately semi-circular and the diameter changed with the temperature. The specic performs as the diameter rst decreased and then increased with the increase of the
temperature. Various electro-chemical corrosion parameters obtained from the Tafel curve were presented in Table 5. In
addition, the change trend of Icorr was as the same as that of the diameter in EIS when the temperature ranged from

Fig. 6. EIS of 40% alcohol amine acidic solution at different temperatures.

Fig. 7. Polarization curves of 40% alcohol amine acidic solution at different temperatures.

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Z. Wang et al. / Engineering Failure Analysis 44 (2014) 6673

Table 5
Electrochemical polarization parameters for the corrosion of the FeAl alloy steel in 40% alcohol amine acidic solution at different temperatures.
Temperature (C)

ba

bc

Icorr (A)

Ecorr (V)

Corrosion rate (lm a1)

30
40
50
55

9.308
10.268
9.917
8.680

6.549
8.167
5.998
8.415

2.614  105
2.882  105
8.396  105
6.163  105

0.723
0.718
0.721
0.745

3.0215  104
3.3313  104
9.7048  104
7.1237  104

30 C to 55 C. It showed that the corrosion of FeAl alloy steel in alcohol amine solution of acid gas rst increased and then
decreased with the increasing temperature. The maximum value appeared at 50 C, which meant the solution was the most
corrosive at this temperature.
During the transfer process, the kinetics of electrode reaction was sped up with the increasing temperature, thus the
response speed was improved and the corrosion rate of steel was enhanced. However, when the temperature was higher
than 50 C, a dense and strong adhesion lm was produced on the surface of steel, so that the lm can prevent the corrosion
of steel. On the other hand, the results may be explained by that increasing temperature can exacerbate corrosion in the
dynamics while increasing temperature also contributed corrosive acid gas to be desorbed, which can effectively slow down
the corrosion at the same time.
As presented in Fig. 7, the corrosion process of 40% alcoholic solution was controlled by the anode. The amine solution has
the strongest corrosive at the temperature of 50 C.

4.4. Effect of corrosion inhibitor on corrosion

H2S supplied by the reaction of Na2S and H3PO4 was used to countercurrent ow through 40% alcoholic solution, and then
the 1 wt% ethylene glycol, diethanol amine and triethanolamine were added respectively. Impedance spectrum and polarization curve were measured under 50 C. The results were showed in Figs. 8 and 9. The corrosion kinetic parameters
obtained from the Tafel analysis method were list in Table 6.
As illustrated in Fig. 8, the corrosion behavior of FeAl alloy steel in the acid gas removal process was affected by the corrosion inhibitor. Among them, the radius of capacitive arc with ethylene glycol solution was smaller than the blank solution.
This indicated that the corrosion of ethylene glycol solution was larger than the blank solution. That is to say, ethylene glycol
has a promotive effect on corrosion.
The capacitive arc radius of both the diethanol amine solution and triethanolamine were larger than that of the blank
solution, moreover, the radius of the triethanolamine solution was the largest. In addition, the polarization curves of amine
solution adding TEA and DEA were on the left side of blank solution curve while the curve of amine solution adding glycol
was on the right. Thus, it can be concluded that the corrosion of the triethanolamine solution was the minimum. Because the
glycol was active and acidic in oxygen, it was propitious to the anode reaction and increased the corrosive of solution. However, diethanol amine and triethanolamine were two of corrosion inhibitors in the industry. After adding corrosion inhibitor
to the amine solution, the metal electrode surface absorbed inhibitors molecules to form a protective lm. Thus, the protective lm prevented the corrosive ion absorbed on the metal surface and also prevented the oxygen atom spreading in the
solution, which protected the metal electrode. Therefore, they can suppress anodic reaction to inhibit the corrosion.

Fig. 8. EIS of 40% alcohol amine acidic solution with corrosion inhibitor at 50 C.

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Z. Wang et al. / Engineering Failure Analysis 44 (2014) 6673

Fig. 9. Polarization curves of 40% alcohol amine acidic solution with corrosion inhibitor at 50 C.

Table 6
Electrochemical polarization parameters for the corrosion of the FeAl alloy steel in 40% alcohol amine acidic solution with different corrosion inhibitor at
50 C.
Alcohol amine
Blank
TEA
DEA
Glycol

ba
9.917
4.136
2.937
10.954

bc
5.998
7.163
5.754
5.724

Icorr (A)
5

8.396  10
7.688  105
4.920  105
8.583  105

Ecorr (V)

Corrosion rate (lm a1)

0.721
0.697
0.705
0.710

9.7045  104
8.8633  104
5.6869  104
9.9209  104

5. Conclusion
In the paper, the corrosion analysis of FeAl alloy steel in the process of natural gas wet desulfurization was investigated.
It can be concluded from the experiments.
(1) The morphology and chemical composition of the formed corrosion scales were characterized by SEM, XRD and EDS
analysis, indicating that the corrosion scale of FeAl alloy steel was mainly FeS.
(2) The concentration of 40% amine solution was the most corrosive for FeAl alloy steel.
(3) Corrosion on FeAl alloy steel in the process of wet desulfurization was rst increased and then decreased with the
increasing of temperature, and the solution was the most corrosive at 50 C.
(4) Corrosion inhibitors such as diethanol amine and triethanolamine can reduce the corrosion rate.

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