Corrosion of Carbon Steels in Monoethylene Glycol (51300-00498-Sg)

Paper No.
00498
2000
CORROSION
CORROSION OF CARBON STEELS IN M O N O E T H Y L E N E GLYCOL

J.J. Gonzfilez, M.E. Afonso
PDVSA INTEVEP S.A.
Material Technology Department
PO Box 76343, Caracas 1070 A, Venezuela
G. Pellegrino
PDVSA E&P Occidente, Maracaibo, Venezuela
ABSTRACT
The dehydration of natural gas consists of water removal that is associated with the natural gas in
form of vapor. The removal of water prevents the formation of gas hydrates and reduces corrosion in
pipelines and components. The present study addresses the aggressiveness of the environment and the
possible prevention methods in a corrosive environment containing MEG (Monoethylene Glycol) in
presence of a neutralizer (Monoethanolamine MEA). The materials used were ASTM A106 gr. B and
A285 gr. C, steels that are extensively used by the oil industry in the construction of pipelines and
pressure vessels. Corrosion rate measurements were carried out through weight loss (in situ)
measurements, under normal operating conditions at different steps of the process: rich glycol-chiller (6C), rich glycol filter (60C) and lean glycol-reboiler (95C). The laboratory tests were performed by
means of linear polarization resistance (Rp) under the presence of MEG, MEG/H20 and MEG/MEA
ratios at 25, 60 and 93C using a nitrogen atmosphere. For rich glycol at high temperatures, both steels
showed a relatively high corrosion rate (0.45 ram/y) and internal pitting. This investigation suggested
that the presence of rich MEG at low pH increases the corrosion rate and may affect the susceptibility of
pitting of the steel. An optimal neutralizer dosage is an important factor to prevent the corrosion of the
components. The morphology of the corrosion products and the characteristics of pitting were studied
employing SEM-EDS techniques and optical microscopy.
INTRODUCTION
Natural gas usually, contains between 20 to 100 pounds of water by MMSCF of gas, depending on
the saturated point at the operation conditions. This water could be removed by passing the gas through
separators. Nevertheless, it is impossible to remove 100% of liquid, in addition to the partial
condensation of vapor that takes place by effect of changes in gas pressure and temperature. The
presence of this liquid can induce different problems in dehydration plants, such as: pipeline corrosion,
reduced gas transmission capacity and hydrate formation I~I
Copyright
2000 by NACE International.Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE
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In order to avoid corrosion problems, it is necessary either to remove water or carbon dioxide, or
both from the natural gas streams to desirable levels. For this reason, glycol solutions are used in natural
gas dehydration processes. After the absorption, the solution has a low pH (-5) and a high water content
(30-35%) in a relatively high temperature environment, this conditions are favorable to induce corrosion
of carbon steel [21
PDVSA Exploration and Production has established a program of internal corrosion control
methods to suppress or reduce it to a desirable level. As part of this effort, weight loss coupons have
been installed in situ to measure the extent of damage from a morphological point of view and the
effectiveness of chemical treatment (neutralizer of rich glycol) injected up stream of the measuring
locations. The product used for this purpose in this system has been Monoethanolamine (MEA) and a
neutralizing/film amine based complex (commercial product) injected in the glycol regeneration step in
Lamarliquido dehydration plant (Figure 1). Due to the failures reported above, an effort was made to
determine the effectiveness of the current treatment (MEA) and to evaluate alternative ones in the
dosage and neutralization capacity 13.41
Lamarliquido dehydration plant, a unit for treatment of natural gas at Lake Maracaibo in
northwest Venezuela, extract liquids from natural gas by a cooling process with propane, through an
heat exchanger. Natural gas is cooled, from 52 to -37C (125 to -35F), and some liquids condensed
including water steam with the formation of hydrates (crystals formed from liquid water, light
hydrocarbons, CO2 and H2S) that could clog valves and pipelines. To avoid such problems an aqueous
solution of (78% MEG) is injected [31
The present study addresses this problem with the purpose of determining the corrosion rate of
carbon steel, and provides a laboratory approach to evaluate the performance of using commercially
products to neutralize glycol solutions. Some practical considerations are discussed in order to
recommend better operational practices.
EXPERIMENTAL METHODOLOGY
Field corrosion evaluation
Tests were performed on critical sites at the operating conditions at different stages of the
Lamarliquido dehydration plant, according to the availability of sampling facilities to draw glycol with
the following characteristics: water content, temperature and pH. The autoclave connection to the pipe
was attained by performing a "by pass" to the line or component between two ~A" nipples. A pressure
gradient was obtained to guarantee glycol flow through this device. Within the autoclave 2 sets of 3
weight loss coupons of both materials were placed as shown in Fig. 2 in order to obtain an average
corrosion rate and a standard deviation for the statistical analysis of results.
The materials used in the present study were commercial carbon steel having ASTM specifications
AI06 grade B and A285 grade C. Table 1 shows the chemical composition of both materials. Figure 34 depicts the microstructure of the steels used in this work. Both steels showed alternate grains of
pearlite (~ + Fe,C) and ferrite (c~) and the presence of inclusions. The AI06 (Fig. 3) is elongated
product of the cold work while A285 (Fig. 4) carbon steel has no-particular orientation because of a
thermal treatment for grain size homogenization. The grain size was determinated by ASTM El 12-96 151
test method. The grains of A106 gr. B are smaller than A285 (N 9 and N 8, respectively).
The corrosion rate was determined by means of the weight-loss technique using 30x15x3 mm
specimens, which were placed for about 10 weeks inside a static autoclave containing the corrosive
medium. The coupons were polished to 600 grit and degreased with acetone prior to assembly.
After testing, the autoclave was taken down and the coupons retrieved for weight loss
measurements and for surface inspection with a scanning electron microscope (SEM). The corrosion
products were characterized by energy dispersive X-ray spectroscopy (EDX). Visual examination of the
surface of the coupons was conducted in order to identify the morphology and corrosion characteristics
of the layers [63
The samples of glycol taken were characterized by chemical analysis in order to determinate these
properties: pH, water content (Karl-Fisher methods), hydrocarbon content, iron content in water, solids
and specific gravity.
Laboratory evaluation
In order to estimate corrosion rates of carbon steels in the presence of glycol and solutions treated
with neutralizer, a coupon 15-mm in diameter and 2-mm thick (electrochemical technique) was also
used. The solution was prepared before the test in a cell with the coupon and the electrodes just to attain
the experimental condition.
Polarization resistance (Rp) tests were done at different conditions, equivalent to such indicated in
field evaluation using Nitrogen (N2) atmosphere. A volume of 400 mL of fresh MEG solution from
different parts of the plant were used for each experiment. Linear polarization resistance measurements
were taken every five minutes for a total time of 3 hours, then a potentiodynamic sweep was performed
in order to obtain the anodic and cathodic Tafel's slopes in a + 300 mV range at a 0.2 mV/s. All
conditions were tested twice at 25 and 60C. Finally, the average corrosion rate was determined for
both materials in each condition. The tests were performed with glycol solutions bubbled with dry
nitrogen for 30 minutes, and then maintaining light flow of this gas during the heating just to the
temperature of the experiment. The pH of the solutions was determined before and after the tests.
The solutions used were fresh fluids from different steps of the process: lean glycol (before the
absorber after the chiller), and rich glycol filters and rich glycol from a surge tank. In addition, some
tests were performed with 100% MEG with a pH around 10. The tests were carried out using different
concentration of neutralizer (MEA pH= 14.0 and a commercial product, pH=l 3.51)just to obtain a pH in
a range 8.5 to 9.0. Table X shows the dosages used for neutralizer. A reference test was performed with
a glycol solution (not neutralized) at 60C saturated with CO2.
RESULTS AND DISCUSSION

Glycol solutions
Table 2 shows the chemical composition of the glycol solutions used. Comparing lean and rich
glycol chemical composition (pH, water, Fe, etc.), it indicates that the rich solution has a high water
content, less iron content and more acidity. Those characteristics would increase the corrosion rate of
the steels. The difference between each sample is probably due to operational practice associated with
the neutralization with MEA. An acceptable value of pH to prevent the corrosion process ranges
between 7.0 to 8.5 with optimal control for all conditions tTl.
The relative high iron content (over 400 ppm) corresponds to corrosion products (oxide or sulfur)
generated during the process. The formation of these compounds could be associated to corrosion
including a deficient filtration of the solid particules.
The heavy hydrocarbon content (>C12) in the glycol solution was 0.48%, for lean MEG) and
0.31%, for rich glycol. Normally, in dehydration plant using MEG, a recommended value should be
lower than 0.30% [8]
Corrosion Rate (in situ tests)
The average corrosion rate of A106 and A285 carbon steel obtained in the experiences performed
at Lamarliquido dehydration plant and relevant morphological observations are shown in Table 3. Both
materials show a comparable average corrosion rate for each environment and condition tested. The
highest corrosion rate (-0.5 mrrdyear) was obtained in the presence of lean MEG in cooler inlet (@60C,
650 psi.
Morphology analysis performed by SEM of the corroded surfaces of the coupons tested revealed
abundant pitting activity and an important damage as shown in Figures 5 and 6. The corrosion products
formed on the samples were analyzed by SEM-EDX, in all the cases; the elements found were: oxygen,
iron, sulfur, and carbon. This result should be associated with the existence of a corrosion mechanism,
probably due to the presence of water in an alkaline environment, with the formation of iron oxide and
other species like sulfur or carbonate. The coupons tested in the rich MEG filter present similar
characteristics. Nevertheless, in the case of the samples placed in rich MEG separator outlet, slight
general corrosion was detected and no corrosion products were identified, the sample surface was found
virtually intact, probably due because almost the compounds of the fluid are in liquefied in this condition
(@-6.7C, 400 psi). Figures 7 and 8 shows the surface corrosion aspect after removal the corrosion
products for both steel in two different conditions.
Corrosion Rate (laboratory tests)
Table 4 shows the results obtained during the polarization resistance tests in different conditions
for the A106 and A285 carbon steel. As shown, the results obtained for those experiments are very
similar to the ones obtained with the other technique (lost weight technique). In all conditions tested, the
average corrosion rate obtained for each steel were practically equivalent comparable. The highest
corrosion rate for A285 was 0.73 mm/y (29.2 mpy) and 0.53 mm/y (21.3 mpy) for A106, in the presence
of rich MEG at 60C. The corrosion rate of A106 carbon steel in virgin MEG with 5% of water at 23C
bubble with slow flux of N2 was practically negligible (0.004 mm/y), and this fluid not increase the
corrosivity of carbon steel.
Since one of the main objectives of the present study was to address the dosage optimization and
selection of an efficient neutralizer, the products, MEA and one commercial inhibitor package, were
evaluated using A285 carbon steel in fresh rich glycol solution at 60C. The initial pH of the gycol
solution was 7.0, and the water content was 30%. Corrosion rates were measured for different
concentrations of MEA and inhibitor (see Figures 9 and 10).
Figure 9 shows the corrosion rate measurements obtained for different dosages of MEA and
product 1. As it can readily be seen, MEA exhibit a strong dependency on the dosage and in some
instances, corrosion rates increased as opposed to an expected decrease. When the dosage of MEA
increased, the corrosion rate decreased, just to a minimal value (0.2 ram/y) when the MEA concentration
was 0.05%. At this condition, the pH of the solution after the neutralization was 9.0. With product 1, a
slight dosage of 0.15% is sufficient to reduce the corrosion rate near zero (0.004 ram/y). For higher
dosages (concentrations 2.5 and 5%), the corrosion rate was practically undetectable. This product is an
inhibitor (film) constitued of nitrite that protects the surface of the environment (pH= 12.5)tgl.
As a reference, the condition without inhibitor presents a general
mpy) with rich MEG at 60C. This value is considered very high,
corrosion process occurs, probably due to an inadequate neutralization.
rate in the plant is necesary to implant an optimal control of pH and a
the glycol solution.
corrosion rate of 0.93 mm/y (37

and suggests that an important
In order to reduce the corrosion
chemical treatment to neutralize
CONCLUSIONS
ASTM A I06 gr. B and A285 gr. C carbon steel showed comparable corrosion rate for the same
condition tested in the operational conditions of Lamarliquido dehydration plant. At 60C, the
corrosion rate obtained was between 0.440 and 0.475 mm/y.
The coupons placed in the plant presents evidence of localized atack. In the presence of the solution
of rich glycol coming from the filters at 60C and in the cooler inlet presents an important damage
with pits coalescence and severe uniform corrosion. Under all the tests the formation of a thick
corrosive products was also observed.
The highest corrosion rate of carbon steels coupons evaluated with the electrochemical tests was
found in the presence of the solution of rich glycol comming from the filters at 60C (140F). For
AI06 was 0.534 mm/y and for A285 was 0.731 ram/y, while, at environment temperature (25C),
the corrosion rate was smaller (0.16 - 0.2 ram/y). This solution has a high water content (about 30%)
and a relative acid pH (-5).
The tests performed in order to determine an optimal dosage of neutralizer to reduce the corrosion
rate of carbon steel, shows that 0.15% of MEA reduce the corrosion rate to 0.004 mm/y. The
corrosion rate without product (blank tests o1" reference) was 100 times higher. The coupon surface
remained intact after the test because the corrosion rate was almost undectectable.
REFERENCES
1. J.L. Gonz~ilez; J.A. Morales; M. Gonz~lez, Report M-00090,92, PDVSA INTEVEP, July (1992).
2. J.J. Gonz~ilez; M.E.Afonso; I. Martfnez, Report INT-5526,98, PDVSA INTEVEP, December (1998).
3. N.G. Hon, Report IDTR-928, Ancilisis de fallas condensador de reflujo E-41.6 Lamarl[quido,
Maraven S.A., Maracaibo ( 1991 ).
4. F. Torres; M. Niazoa; G. Severeyn, Report MSPT, Evaluaci6n sistema defiltraci6n de glicol. Planta
Lamarliquido, Maraven S.A., Maracaibo, may (1997).
5. ASTM E112, Standard Test Methods for Determining Average Grain Size, USA, (1996).
6. ASTM G1, Standard Practice.for Preparing, Cleaning and Evaluating Corrosion Test Specimens.
7. Ballard Don, The Fundamental oJ Gas Dehydration. Gas Conditioning Conference. Norman,
Oklahoma: B 1-B34, March 6-7, (1979).
8. B. Stefl; S. Bosen, Buffering and inhibition of glycol in gas dehydration applications: alternative to
amines, Corrosion/95, Paper no. 573, NACE International USA (1995).
TABLE i
CHEMICAL COMPOSITION OF ASTM A106 GR. B AND A 285 GR. C CARBON STEEL
Material
Mn
Si
Fe
ASTM A106
0.18
1.00
0.25
0.15
0.002
Bal.
ASTM A 285
0.13
0.53
0,14
0.019
0.015
Bal.
TABLE 2
CHEMICAL ANALISYS OF THE GLYCOL SOLUTIONS SAMPLES
Sample 2
Sample 1
Analysis
Rich M E G
Lean M E G
Rich M E G
Lean MEG
pH (23oc)
7.19
6.66
7,66
7.08
Fe in water [ppm]
466_+ 14
413_+ 13
590 + 8
528 _+ 10
Water content [%]

(Karl-Fisher Method)
23,7
32.5
26.2
30.0
Specific Gravity
(60/60F)
1.0940
1.0890
1.0977
1.0927
38
12
0.48
0.31
Solid content [ppm]

Hydrocarbon >nC 12
[%wt.]
TABLE 3
AVERAGE CORROSION RATE FOR THE MATERIALS (A106 B AND A285 CARBON STEEL) AT THE
DIFFERENT CONDITIONS EVALUATED (LAMARLIQUIDO DEHYDRATION PLANT)
Material
A I 0 6 gr. B
Environment
T [C]
Corrosion
Rate [mm/y]
Observations
Lean MEG cooler inlet
60
0.475
High corrosion with scale formation of

corrosion products and cracks
Rich M E G Separator outlet
-6.7
0.045
Slight general corrosion. No relevant

observations
76.7
0.300
Severe corrosion with a not adherent

thick layer of corrosion products
Lean M E G cooler inlet
60
0.440
High corrosion with scale formation of

corrosion products
Rich M E G Separator outlet
-6,7
0.048
No relevant observations
Rich M E G filters
76.7
0.283
Rich M E G filters i
I
A285 gr. C
! Severe corrosion with a thick layer of

i
corrosion products
TABLE 4
AVERAGE CORROSION RATE FOR THE MATERIALS (A 106 B AND A285 CARBON STEEL) AT THE
DIFFERENT CONDITIONS PERFORMED BY LPR (LINEAR POLARIZATON RESISTANCE)
Average Corrosion Rate [mm/y]
Solution
25C
60C
A106
A285
A106
A285
Lean M E G
0.173
0.161
0.389
0.418
Rich M E G
0.203
0.194
0.534
0.731
TABLE 5
AVERAGE CORROSION RATE FOR A285 CARBON STEEL IN THE PRESENCE OF GLYCOL SOLUTION
AT 60C WITH DIFERENT DOSAGE OF MEA AND COMMERCIAL PRODUCT
Concentration [%]
Initial pH
Final pH
Corrosion Rate [mm/y]
7.00
7.32
0.658
0.0160
7.00
7.60
0.515
0.0317
7.00
8.36
0.398
0.0476
7.00
9.01
0.207
0.0713
7.00
8.86
0.213
0.3170
7.00
9.55
0.320
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FIGURE 1 - Schematic diagram of the dehydration plant unit "Lamarliquido" [~1
LOW
~G~
P~ESSORE
iND;CATO~
PRESSURE
INDICATOR
.......
IN ~
OUT
FIGURE 2 - Schematic diagram of the conection of the reactor for the loss weigth (in situ test)
FIGURE 3 - Microstructure of ASTM A 106 gr. B carbon steel used for the corrosion tests (x400)
FIGURE 4 - Microstructure of ASTM A285 gr. C carbon steel used for the corrosion tests (x400)
(a)
0
20
131 ~
Real :
k~.
',,"I;~ II~,1
i
J,e-'rct;
'
~r
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~,eU
ch
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1 O, 3 7;
73
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(b)
:til
:t il
~"
;T>"'-
e,
J I
~"= ~'
,,~
d
,
11].7
........................ ....................
FIGURE 5 - SEM microphotographs of the corrosion products and EDX spectrum for the coupons steels
tested in the plant at the cooler inlet (lean MEG at 60C, 650psi) ' (a) ASTM A I 0 6 gr. B and (b) ASTM
A285 gr. C carbon steel
(a)
I ;wel
I..'~^ 1 ;
1lI(I~ l-'ra.~et.:
1 21:'~ ~
22.~
lOOs
Dea.d
F..'c:ma~ :". " : :
J
FS- 8K
I'IEH I ; :Ii'~:Ji~$.~3~J:L ~
eh
~7"I-
(b)
,)( I,.'1I',+II
Jc!;;,
i
l'l
.I
,2h
270-
' ~2
,:~.5
FIGURE 6 - SEM microphotographs of the corrosion products and EDX spectrum for the coupons steels
tested in the plant at the rich glycol filters (77C, 200 psi): (a) ASTM AI06 gr. B and (b) A285 gr. C
(a)
(b)
FIGURE 7 - Morphological aspect of the surface specimens after picking, tested at the inlet cooler (lean
glycol) at 60C, 650 psi: (a) ASTM A106 gr. B and (b) ASTM A285 gr. C
(a)
(b)
!
FIGURE 8 - Morphological aspect of the surface specimens after picking, tested at the rich glycol filter at
77C, 200 psi: (a) ASTM A106 gr. B and (b) ASTM A285 gr. C
0.7
"~
0.6
MEA
0.5
" Product 1
0.4
=
0.3
._o
0.2
O
0.1
0
0.05
0.1
111111
0.15
0.2
0.25
0.3
0.35
0.4
Dosage of Product [%]

FIGURE 9 - Average corrosion rates for the A285 carbon steel in rich glycol solution for diferent
dosages of neutralizer
1
O.9
Rich
MEG
0.8
n Lean MEG
0.7
0.6
0.5
81
0.4
o
0.3
0.2
18
0.1
0
4
pH
FIGURE
10 -
Average corrosion rates for the A285 carbon steel vs.the pH of the glycol solution used

Corrosion of Carbon Steels in Monoethylene Glycol (51300-00498-Sg)

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Paper No.

CORROSION OF CARBON STEELS IN M O N O E T H Y L E N E GLYCOL

RESULTS AND DISCUSSION

corrosion rate of 0.93 mm/y (37

Water content [%]

Solid content [ppm]

Lean MEG cooler inlet

High corrosion with scale formation of

Rich M E G Separator outlet

Slight general corrosion. No relevant

Severe corrosion with a not adherent

Lean M E G cooler inlet

High corrosion with scale formation of

Rich M E G Separator outlet

! Severe corrosion with a thick layer of

Corrosion Rate [mm/y]

FIGURE 1 - Schematic diagram of the dehydration plant unit "Lamarliquido" [~1

F..'c:ma~ :". " : :

Dosage of Product [%]

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