Corrosion of Steel Alloys in CO2 Environments

Abstract:
This report describes an experimental program to evaluate corrosion of carbon steels
in CO2 environment. Coupon exposure and electrochemical tests were conducted as a
part of the program. The objective of the test program was to determine the corrosion
rate of steel exposed to wet CO2 conditions. Test variables were brine chemistry, CO2
partial pressure, temperature, metal alloy and exposure duration.
Introduction
This report describes an experimental program to evaluate corrosion of carbon steels
in CO2 environment. Coupon exposure and electrochemical tests were conducted as a
part of the program. The objective of the test program was to determine the corrosion
rate of steel exposed to wet CO2 conditions. Test variables were brine chemistry, CO2
partial pressure, temperature, metal alloy and exposure duration.
The test program was performed in an effort to determine corrosion of metal alloys
used in the transportation, injection and withdrawal of wet natural gas from a storage
facility. Stored gas when retrieved would contain CO2 and reservoir brine over a
range of temperatures and pressures.
Background
CO2 corrosion is a complex phenomenon that depends on numerous experimental
variables. The key factor affecting iron dissolution in carbonic acid solutions
(containing chloride) is the formation (or lack thereof) of an iron carbonate surface
layer. Iron carbonate scales can be "protective" to provide low corrosion rates or "nonprotective" meaning poor coverage, poor adhesion, porosity or solubility that provide
higher iron dissolution rates.
The corrosion rate of iron in a CO2 environment is not constant, especially in
laboratory studies in which the starting point is a bare metal surface on a test
specimen. Steel, when initially exposed to a carbonic acid solution, corrodes rapidly
at first and then the rate decreases as the carbonate scale forms. The final or "steady
state" corrosion rate can remain high (if scaling does not occur), or it can
asymptotically approach a limit that reflects ferrous ion (Fe2+) transport through the
surface scale and other factors.
The dominant influence to the steady state corrosion rate of steel in CO2
environments is the aqueous phase chemistry and temperature. Low rates are
promoted by conditions that favor film formation. Such conditions are not intuitive in
the sense that several kinetic processes compete to produce either protective or nonprotective scales. In brines, higher CO2 partial pressure, higher pH, higher
temperature and low convection promote scale formation and low rates.
There is a temperature at which the CO2 corrosion rate is a maximum. The
temperature at which the rate is a maximum depends on aqueous phase chemistry.
When the brine phase is similar to seawater, the maximum is in the range of 60 to 150
F. Brine anions that favor scale formation and low rates are CO32-, SO42-, PO43-,
NO3-, and SiO3-. Cations that favor scale formation are Ca2+, Mg2+ and Fe2+.
Experimental
The test program consisted of autoclave exposures of coupons to provide weight loss
corrosion data and electrochemical corrosion rate measurements.

Apparatus
A set of eight hastelloy lined autoclave vessels with a pressure rating of 10,000 psig
and a temperature rating of 550 F were employed for the 30 day coupon corrosion
tests. These vessels were placed into an oven equipped with a rotisserie and were
rotated end over end to determine effects of fluid velocity and to mix multiphase
solutions. Illustrations of the autoclave system are provided in Figures 1and 2.
Electrochemical testing was performed in a three liter hastelloy lined autoclave with a
pressure rating of 5000 psig and temperature rating of 550 F. The autoclave was
equipped with pressure ports into which were mounted the electrode holders. The
vessel was also equipped with a pressure balanced silver/silver chloride reference
electrode system that contacted the test solution by means of a Luggin probe.
Materials
Coupons of X-42 carbon steel had dimensions of approximately 1.0 inches X 0.5
inches X 0.125 inches with two mounting holes located at one end of the coupon (See
Figure 3). A section of J-55 carbon steel tubular and machined additional coupons are
procured for testing. Electrochemical tests employed cylindrical electrodes machined
from X-42 stock as shown in Figure 4. Two electrodes of X-42 and J-55 with
dimensions of 0.250 inch diameter X 3.5 inches with one end drilled and tapped were
machined for electrochemical linear polarization tests (See Figure 4). Material
chemistries are listed in Table 1.

Figure 1 - Rotating Autoclave Apparatus

Figure - 2 Autoclave Configuration

Figure 3 - Coupon Dimensions

Figure 4 - Electrochemical Test Specimen
A - 0.25" ?? 0.01" Dia.
B - 3.50" ?? ; 0.01"
C - 0.50" ?? 0.05"
Note: The specimen is finished to surface roughness of 32 Micro-inch or finer
Table 1
Material Chemistry
Grade

Carbon, max

Manganese

Phosphorous

min

max

min

max

Sulfur, max

Cb, min

Ti, min

X-42

0.29

--

1.25

--

0.04

0.05

--

--

J-55

--

--

--

--

0.03

0.03

--

--

Corrosion of Steel Alloys in CO2 Environments

Environments
The environments for the autoclave exposures and electrochemical test were identical. The
brine solutions consisted of two concentrations that were laboratory formulated to simulate
field conditions. Table 2 provides the chemical composition of the laboratory formulations. A
third brine used in testing was provided by a third party company.
The gas phase of the tests consisted of carbon dioxide at partial pressures of 25, 140, and
250 psia respectively. Test temperature was 80 F with the exception of the final test which
was 125 F. A total test pressure of 3500 psig at room temperature was obtained with
methane. The test matrix for the autoclave and electrochemical exposures are provided in
Tables 3 and 4.
Some tests (see Tables 3 and 4) included 10 percent by volume of jet fuel (similar to diesel).
The hydrocarbon composition is provided in Table 4. Jet fuel was chosen because it most
closely matched the paraffin content of hydrocarbon phase in the reservoir.
Autoclave Test Procedure
Duplicate coupons of carbon steel X-42 were used in tests 1-11 and duplicate carbon steel
coupons of J-55 were used in tests 12-13. Prior to testing the coupons were cleaned in
solvent, dried with acetone and weighed to the nearest 0.1 mg. The coupons were fastened to
one end of a teflon rod with nylon nuts and bolts. A teflon liner was inserted into each
autoclave to provide galvanic isolation (See >Figure 2).
Brine solutions "A" and "B" were laboratory formulated according to the specifications
previously mentioned (See Table 2). Prior to testing, the batch solutions were dearated with
nitrogen and analyzed for alkalinity and pH. A sample of the brines were analysed.
The coupons and 550 ml of brine was added to each autoclave, sealed and a vacuum was
pulled. Each vessel was pressure tested to 4000 psig and the pressure was bled off slowly.
When the vessel reached ambient pressure another vacuum was pulled.
Carbon dioxide gas was added to each vessel to the corresponding partial pressure (See Test
Matrix Table 3) and allowed to equilibrate. Each vessel was brought to a total pressure, at
room temperature, of 3500 psig with methane. The vessels were placed into the rotisserie
oven and heated to test temperature by means of electrical resistance heaters and
maintained with a digital proportional temperature controller. Test durations were 15 and 30
days respectively.
At the completion of the test exposure, the vessels were allowed to cool and the pressure was
bled off slowly. The vessels were opened sequentially and immediately analyzed for alkalinity
and pH.
Corrosion data were determined from the following equation:
534 W
R=
DAT
where:
534 = constant
W = weight loss (mg)
D = density (g/cm3)
A = area (in2)
T = time (hours)
Data generated from these tests were weight loss values and visual observations.
Surface analysis of the scale corrosion was also performed.
Electrochemical Test Procedure
A total of 13 linear polarization tests were performed in a 3 liter Hastelloy C-276
lined autoclave equipped for high pressure electrochemical studies (See Figure 3).
A pressure balanced silver/silver chloride reference system using 0.1 N potassium
chloride as a bridge was utilized.
For each experiment, two electrodes were tested. One electrode was tested in the

as machined condition and the second was coated with a heat shrink teflon sleeve
over the upper two thirds of the electrode surface to mask the solution/vapor
interface.
Solutions were formulated and dearated with nitrogen and subsequently analyzed
for alkalinity and pH prior to the addition to the autoclave. Solution was added to
provide a known surface area. The autoclave was sealed and a vacuum was
pulled. The vessel was pressure tested to 4000 psig and the pressure was bled off
slowly. When the vessel reached ambient pressure, another vacuum was pulled.
Carbon dioxide gas was added to the autoclave to the corresponding partial
pressure (See Matrix Table 4) and allowed to equilibrate. The vessel was brought
to a total room temperature pressure of 3500 psig with methane. The vessel was
brought to test temperature and maintained with a digital proportional
temperature controller.
Linear polarization tests were performed on each electrode at intervals of
approximately 1, 6, 24, and 48 hours and corrosion rates determined. Parameters
for the linear polarization tests were as follows:
Scan rate = 0.2 mv/sec
Scan region = 20 mv ?? Ecorr
Equivalent weight = 28 for Fe
Density = 7.8 g/cm3
Tafel constant A = 120
Tafel constant B = 120
At the completion of each test, the solution was analyzed for alkalinity and pH.
Table 2
Chemical Analysis of Brines used in the Tests
Component Brine Form. "A", (mg/l)

Brine Form. "B",

(mg/l)

Actual Brine, (mg/l)

Na+

10090

10090

17,895

K+

5042

5042

15,509

Ca2+

80581

803

77,545

Mg2+

9907

99

10,021

Sr2+

2522

2522

2,028

Cl-

190914

22696

221,898

SO42-

396

396

60

CO3--

500

500

--

Table 3
Test Matrix and Test Data
Autoclave Exposures
Test(1)

Start

Finish

Duration
(days)

Temperature (F)

CO2
(psia)

Brine

Alki
(mg/l)

Alkf
(mg/l)

pHi pHf

Corrosion Rate
(mpy)

1-31

2/5 (6:30pm)

3/8 (1:00
pm)

31

80

25

140

8.8 5.2 5.16

2-31

2/5 (6:30 pm)

3/8 (1:00
pm)

31

80

25

240

1400

9.0 6.4 2.15

3-31

2/5 (6:30 pm)

3/8 (1:00
pm)

31

80

250

140

8.8 5.0 10.13

4-31

2/5 (6:30 pm)

3/8 (1:00
pm)

31

80

250

240

2000

9.0 6.1 3.78

1-14

2/5 (6:30 pm)

2/19 (1:00
pm)

14

80

25

140

8.8 5.2 3.15

2-14

2/5 (6:30 pm)

2/19 (1:00
pm)

14

80

25

240

1160

9.0 6.4 1.89

3-14

2/5 (6:30 pm)

2/19 (1:00
pm)

14

80

250

140

8.8 4.9 6.95

4-14

2/5 (6:30 pm)

2/19 (1:00
pm)

14

80

250

240

1140

9.0 6.2 7.51

5-15-H

2/22 (4:00
pm)

3/9 (1:00
pm)

15

80

25

160

8.8 5.2 --

6-15-H

2/22 (4:00
pm)

3/9 (1:00
pm)

15

80

25

>400

1800

8.9 6.4 --

7-15-H

2/22 (4:00
pm)

3/9 (1:00
pm)

15

80

250

160

8.8 4.9 --

8-15-H

2/22 (4:00
pm)

3/9 (1:00
pm)

15

80

250

>400

2000

8.9 5.9 --

5-30-H

3/12 (4:00
pm)

4/12 (2:00
pm)

31

80

25

180

9.1 4.5 5.93

6-30-H

3/12 (4:00
pm)

4/12 (2:00
pm)

31

80

25

840

2000

8.9 6.1 2.44

7-30-H

3/12 (4:00
pm)

4/12 (2:00
pm)

31

80

250

180

9.1 4.4 12.8

8-30-H

3/12 (4:00
pm)

4/12 (2:00
pm)

31

80

250

840

2100

8.9 5.8 5.5

9-30-A

3/12 (4:00
pm)

4/12 (2:00
pm)

31

80

25

Act

360

720

5.7 5.1 3.19

10-30-A

3/12 (4:00
pm)

4/12 (2:00
pm)

31

80

250

Act

360

640

5.7 4.6 2.13

11-30-A

3/12 (4:00
pm)

4/12 (2:00
pm)

31

80

140

Act

360

760

5.7 4.4 1.27

12-30-A

3/12 (4:00
pm)

4/12 (2:00
pm)

31

80

250

Act

360

1200

5.7 4.7 1.62

13-30-A

4/16 (4:00
pm)

5/17 (2:00
pm)

31

125

250

Act

246

840

5.5 4.9 10.19

(1)

H indicates tests with hydrocarbon

Corrosion of Steel Alloys in CO2 Environments

Results and Discussion

The two brines that were used in testing were distinguished by their scaling tendency with brine A
having a high scaling tendency and high chloride and brine B having a low scaling tendency (also low
chloride). It was postulated that corrosion rates would be lower in the brine (A) that possessed the
higher scaling tendency.
The time dependence of corrosion rate must be considered when viewing the rate data generated by
autoclave (weight loss) methods and electrochemical methods. As illustrated in Figure 5, the general
(theoretical) form of the corrosion function is logarithmic with time reaching a limiting value
asymptotically. Electrochemical data points fall on the initial steep portion of the curve and are

instantaneous, i.e. the rate at the instant measure. The normal variation in electrochemical rates is
approximately 20 percent. Autoclave corrosion rates, on the other hand, are averages of the rate over
the time period measured. These points aid rationalization of the corrosion data provided in Tables 3
and 4.
Autoclave Test Data
Brine
Higher corrosion rates (See Table 3) were obtained for (high scaling) Brine A in autoclave exposures
suggesting that the postulate of low scaling brines being more corrosive may not always be true. This
result may have been due to the higher content of aggressive ions such as chloride in Brine A.
Hydrocarbon
Hydrocarbon in equilibrium with the brine had little effect on test outcome.
Test Duration
No major difference in rate was measured in autoclave tests with duration of 14 days as opposed to
tests with a 30 day duration.
CO2 Partial Pressure
Brines in equilibrium with 250 psi CO2 are approximately twice as corrosive as brines in equilibrium with
25 psia CO2.
Corrosion Rates
Generally, corrosion rates in this system were not excessive. All rates measured in autoclave tests were
less than 12 mpy. Actual brines produced corrosion rates less than 4 mpy at 80 F and approximately 10
mpy at 125 F (on J-55).
Electrochemical Data
Brine
Electrochemical corrosion rates measured for low scaling brine (B) were generally larger than for the
high scaling brine which is opposite to the trend measured in autoclave tests. These higher initial rates
indicate that scale formation is aided by a high initial rate. Similar trends have been measured for CO2
corrosion. A high initial rate produces saturation of the interfacial region (metal/solution) with ferrous ion
giving rise to a high degree of scale surface coverage that eventually (t > 2 - 3 days) results in low rates.
Hydrocarbon
Hydrocarbon did not have a major influence on corrosion rate.
Test Duration
Tests were conducted at 1, 6, 24 and 48 hours (approximately). Electrochemical corrosion rates are
plotted versus time in Figures6, 7 and 8 for tests without hydrocarbon, with hydrocarbon and with field
brine, respectively.
In general, the trends (of rate vs. time) are downward as expected. The high scaling brine (A) reached
much lower rates in 48 hours than did the low scaling brine (B). This observation is in line with
expectation and is likely due to the faster rate of scale formation for brine A.
CO2 Partial Pressure
No trend of rate vs. partial pressure of CO2 was apparent.
Corrosion Rates
Corrosion rates for the field brine (C) and high scaling brine (A) measured electrochemically are less
than 10 mpy and correlate reasonably well with the autoclave test data. The higher rates measured for
brine B indicate scaling is slower.
Conclusions
In the system examined, CO2 corrosion of X-42 steel was measured as less than 10 mpy in autoclave
and electrochemical tests. Of the test variables examined, CO2 partial pressure and brine chemistry
(scaling tendency) have the greatest influence on rate.
The initial corrosion rate (less than 48 hours) as measured by electrochemical methods is significantly
higher for the low scaling brine (B), however, the steady state rate, as measured by autoclave tests was
lower. This observation is consistent with the known mechanism of CO2 corrosion. Autoclave
experiments in which the rate is obtained from mass loss over a 30 day period indicate that the high
scaling brine A will produce the higher metal dissolution rates. The field brine which is similar in
composition to brine A, produced low rates (less than 5 mpy).
Test parameters that were insignificant were metal alloy and presence of hydrocarbon. The J-55 alloy
produced a corrosion rate similar to X-42 at 80 F (2 mpy) and 10 mpy at 125 F.
Table 4
Test Matrix and Test Data

Electrochemical Exposures
Test(1) Start

Finish

Duration
(days)

Temp
(F)

CO2
(psia)

Brine

Alki
(mg/l)

Alkf
(mg/l)

pHi pHf

Initial Corr Rate Final Corr Ratef

(mpy)
(mpy)

2/3 (11:00
am)

2/5 (10:00am) 2

80

25

100

8.2 5.3 4.78

3.20

2/8 (10:00
am)

2/10 (9:00
am)

80

25

>400

>400

8.6 5.9 68.57

24.35

2/10 (12:00
pm)

2/12 (11:00
am)

80

250

120

8.2 4.6 21.57

8.90

2/16 (10:00
am)

2/18 (9:00
am)

80

250

>400

>400

8.6 5.9 57.77

13.02

5-H

2/18 (12:00
pm)

2/20
(11:00am)

80

25

120

8.2 4.0 22.02

6.94

6-H

2/22 (10:00
am)

2/24 (9:00
am)

80

25

1000

1000

8.6 6.2 30.10

37.06

7-H

2/24 (12:00
am)

2/26 (11:00
am)

80

250

100

8.2 4.8 18.77

4.11

8-H

3/1 (10:00
am)

3/3 (9:00 am) 2

80

250

1000

1600

8.6 6.1 35.08

15.84

3/15 (11:00
am)

3/17 (10:00
am)

80

25

Act

360

480

5.5 5.0 7.13

1.47

10

3/22 (11:00
am)

3/24 (10:00
am)

80

140

Act

240

360

4.9 4.4 20.57

1.61

11

3/24 (2:00
pm)

3/26 (1:00
pm)

80

250

Act

360

400

5.2 4.4 3.93

1.74

*12

3/29 (11:00
am)

3/31 (10:00
am)

80

250

Act

240

240

5.2 4.4 4.66

3.19

*13

3/31 (2:00
pm)

4/2 (1:00 pm) 2

125

250

Act

240

240

5.0 4.4 24.55

6.52

(1)

H indicates tests with hydrocarbon

Table 5
Hydrocarbon Analysis
Identification: Jet Fuel "A" (Los Angeles)
Composition
P
O
A
N
24.8 55.1 18.6 1.2

P = Paraffins
O = Olefin-Cyclics
A = Aromatics
N = Napthalenes