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Overview
This hot topic series describes a test program and the results targeted towards evaluating corrosion inhibitor performance in CO 2/H2S
environments. After preliminary screening of the inhibition characteristics and performance of 5 corrosion inhibitors (designated A, B, C, D, &
E) under simulated CO2/H2S environment in a high temperature, high pressure flowing autoclave, the best two corrosion inhibitors (corrosion
inhibitors A & B) were selected for further flow loop testing under simulated North Sea pipeline service conditions.
The worst case pipeline service conditions (90% synthetic field brine/10% hydrocarbon (depolarized kerosene) environment with H 2S (partial
pressure 0.075 psia [0.5 KPa]) and CO2 (partial pressure 75 psia [0.5 MPa]) were simulated at 300 F. (149 C.) in a laboratory flowloop and the
performance of the selected corrosion inhibitor formulations A & B on API 5L X-65 carbon steel and 0.5 percent Cr X-65 steel were evaluated
at two concentrations (100 ppm and 250 ppm by volume).
The corrosion rates were monitored at stirred (reservoir), laminar and turbulent flow regimes at wall shear stresses corresponding to a range of
velocities (4.2, 5.3, 6.3, 7.0, 7.9, 13.1, 15.4, 17.4 and 21.1 ft/sec) using linear polarization (LPR) and weight loss techniques.
The test results indicated the following:
Provided the proper concentration of corrosion inhibitor is applied continuously, carbon steel can be satisfactorily inhibited under
laboratory test conditions that simulate pipeline worst case corrosion conditions.
Corrosion inhibitor "B" was not as effective as corrosion inhibitor "A" requiring about 2.5 times as much "B" as "A" to accomplish the
same level of corrosion control under these simulated laboratory test conditions.
The results of this corrosion inhibitor evaluation program do not support the use of 0.5 Cr X-65 material over X-65.
The flowloop test data obtained at higher wall shear stresses indicated, within the limits of the wall shear stress parameters, there was
little or no effect on the corrosion inhibitor film being laid down continuously on the metal surface.
Introduction
The results presented in this hot topic are the second phase of a study performed to evaluate the feasibility of using inhibited carbon steel
rather than duplex steel as a major material of construction in a proposed North Sea pipeline.
In the first phase of this study, the results of high temperature-high pressure flowing autoclave tests established that it was possible for
commercially available corrosion inhibitors to be thermally stable at 300 F. (149 C.) as well as provide >90 percent corrosion inhibition to
carbon steels (X-65 and 0.5% Cr enhanced X-65) under laboratory test conditions simulating conditions predicted for the proposed North Sea
pipeline (see Tables 1 and 2).
In this hot topic the results of the Phase 2 studies are reported. In this study, the two best performing corrosion inhibitors from Phase 1 were
tested in a flow loop apparatus to evaluate their performance under varying conditions of flow over a longer period of time. The performance of
these two corrosion inhibitors was determined on both X-65 and 0.5% Cr enhanced X-65 specimens at inhibitor concentrations of 250 and 100
ppm. Data was measured for static, laminar and impingement flow conditions.
Maximum flow conditions for the flowloop tests were established at 10 ft/sec based on a flow regime calculated using the Briggs and Brill (BB)1, as well as the Taitel-Dukler (T-D) models. The Briggs and Brill model predicted the occurrence of intermittent slugs with a liquid film
velocity of 6.2 ft/sec. On the other hand, the Taitler-Dukler model, which is considered by the authors to be more representative, indicated
annular flow and no slug flow in the pipeline. A velocity of 10 ft/sec liquid velocity was selected as a very conservative flow rate parameter for
the flow loop tests. The wall shear stress () due to a liquid flow velocity, v, in the field pipeline was calculated as follows:
= f /2
2
their laboratory. The test parameters used were: 180 F. (82 C.); pp CO 2 of 70 psia; X-65 carbon steel specimens; 70% synthetic North Sea
pipeline brine; 30% depolarized kerosene; flowrate - 2.2 ft/sec. These flowloop test conditions were less rigorous than the Phase 2 flowloop
test conditions. However, the test results were in line with the performance indicated in the Phase 1 tests.
Both the BP Protocol Calibration Test results and the chemical supplier's flowloop test results tend to add support and credibility to the results
reported in study.
Table 1
HT-HP Autoclave Tests
Corrosion Inhibitors Evaluations
Table 2
HT-HP Autoclave Tests
Corrosion Inhibitors Evaluations
Table 3
North Sea Pipeline Flowloop Test
Corrosion Inhibitor Evaluation - Flow Regime Data
I.D.
[cm]
Velocity
[m/s]
MU
[poise]
Reynolds
No
Roughness
e/D
Friction
factor
[f]
Tau
Pa
Tau
Lbs/sq ft
0.00014
0.013
41.78
0.872
Re
691.04
36.2
3.05
0.001626
4692357
Note: Tau [wall shear stress} value calculations based on a velocity of 10 ft/sec
Calculated Data - Flowloop Apparatus
Percent
TAU
TAU
Pa
TAU
Lbs/sq/ft
RHO
[Kg/cu.m.]
I.D.
[cm]
Velocity
[m/s]
MU
[poise]
Reynolds
No. Re
Friction
factor [f]
Velocity
[ft/sec]
Flow
Rate
[gpm]
100
41.78
0.872
967.61
1.27
2.13
0.002825
92738
0.019
6.99
4.28
40
16.71
0.349
967.61
1.27
1.28
0.002825
55790
0.021
4.21
2.58
60
25.07
0.523
967.71
1.27
1.61
0.002825
70016
0.02
5.28
3.23
80
33.42
0.698
967.71
1.27
1.91
0.002825
82947
0.019
6.26
3.83
120
50.14
1.047
967.71
1.27
2.4
0.002825
104373
0.018
7.87
4.82
Table 4
SYNTHETIC BRINE COMPOSITION
North Sea Synthetic Brine Composition
Constituent
Sodium - Na
20,000
20,835.30
Calcium - Ca
2,000
2,000.00
Magnesium - Mg
1,500
1500.4
Barium - Ba
50
50
Chloride - Cl
40,000
39,994.90
Sulfate - SO4
20
20
Bicarbonate - HCO3
100
100.3
ALLOY
HEAT
5lx65
d134
5L0.5CrX6
0
a-50
Al
Cr
0.07
0.035
0.07
0.55
Cu
Fe
Mn
Mo
Ni
Si
Ti
1.26
0.014
0.011
0.24
Cb-0.033; V0.04
1. 27
0.012
0.010
0.24
Cb-0.033
other
Corrosion
Inhibitors
The two corrosion inhibitors (designated "A" and "B") selected for flowloop testing were evaluated at concentrations of 100 and 250 ppm by
volume.
Corrosion inhibitor "A" was a proprietary formulation of sulfonated fatty acid alkyl amide polyamine alkylate and isopropanol in hydrocarbon
solvent. The hydrocarbon solvent system contained the following: heavy aromatic solvent,, ethylbenzene, naphthalene and xylene.
Physical
characteristics
of
corrosion
inhibitor
"A"
include:
Form:
Liquid
Color:
Opaque
to
amber
Solubility
in
Water:
Insoluble
Water
dispersibility:
Highly
water
dispersible
Specific
Gravity:
0.93
@
60
F.
(15.60
C.)
Viscosity
(ASTM
D-445):
43
cst
@
75
F.
(23.90
C.)
Pour
Point
(ASTM
D-97):
<-30
F.
(<-34.40
C.)
PMCC
Flash
Point
(ASTM
D-93):
59
F.
(150
C.)
Vapor
Pressure
(ASTM
D-323):
61
mm
Hg
(1.036
psi)
@
100
F.
(37.80
C.)
Corrosion Inhibitor "B" was a proprietary "green" formulation. Green formulated production chemicals are formulated to be more environmentally
friendly.
Corrosion
inhibitor
"B"
is
an
aqueous
blend
containing
an
alkyl
amino
acid
and
ethylene
glycol.
Physical
characteristics
of
corrosion
inhibitor
"B"
include*:
Form:
Liquid
Color:
Clear,
brown
liquid
Odor:
Geranium
Water
Solubility:
Water
soluble
pH
(@100%):
4.8
@
20
C.
(68
F.)
Boiling
Point
Range:
100
C.
(212
F.)
Freezing/Melting
Point:
<-10
C.
(14
F.)
Density:
1.056
gms/cm3
@
15
C.
(59
F.)
Viscosity
(Cannon-Fenske):
66.30
cst
@
0
C.
(32
F.)
28.40
cst
@
20
C.
(68
F.)
Flash
Point
(PMCC):
>105
C.
(221
F.)
Vapor
Pressure:
<0.85
mm
Hg
(<0.0165
psi)
@
100
F.
(37.8
C.)
*
These
are
only
indicative
values
supplied
on
the
MSDS
sheets
by
the
chemical
supplier.
Test
Procedures
The test specimens were polished to a 600 grit finish, degreased and dimensions and weights were recorded. The degreased specimens were
mounted carefully in the flow loop test apparatus. The deaeration of the test fluids were carried out in separate reservoir containers. The autoclave
and the flow loop were also deaerated with ultra high purity nitroben prior to starting the test. The test solution (synthetic seawater or
brine/kerosene mixture) was introduced into the autoclave by pumping. Once the autoclave was 80 percent full (approximately 4 liters of fluid)
stirring in the autoclave and flowing in the loop was started. The gassing and measurement procedures for calibration test and for inhibitor
evaluation
tests
are
given
below.
The
Calibration
Test
At room temperature, CO2 was introduced slowly into the autoclave and stabilized at 25 psig. The autoclave was then heated to test temperature,
50 C. (122 F.) The pressure was adjusted to psig at 50 C. (122 F.) The liquid flow in the loop was adjusted to give a flow rate of 1.5 gpm which
produced a wall shear stress of 7 Pa (0.146 lbs/ft 2). The corrosion rates of 1018 steel specimens were measured in the reservoir and laminar
regions employing linear polarization resistance (LPR) technique per ASTM G-59. The measurements were continued for a duration of three days
(65
hours).
The
Inhibitor
Evaluation
Tests
The autoclave was heated to test temperature of 150 C. (302 F.) and the test gas was flowed into the autoclave to achieve the test conditions:
0.075 psia (0.5 kPa) H2S; 75 psia (0.54 MPa) CO2. The pressure and liquid flow through the autoclave ( 30 ml/min) were maintained using a back
pressure regulator on the outlet of the autoclave and metering pumps at the inlet. During the last three test series (100 ppm corrosion inhibitor "A",
250 ppm and 100 ppm corrosion inhibitor "B", the deaerated brine/kerosene mixture was saturated with the test gas (0.1 percent H 2S and the
balance
CO2)
before
pumping
into
the
autoclave.
Once the environment was established, the flow rate in the loop was adjusted to produce a wall shear stress value that corresponded to 10 ft/sec
(3.05 m/sec) liquid flow in the 14.25 inch (36.2 cm) pipe in the field based on flow modelling performed (see Table 3). The corrosion rates in the
uninhibited environment were measured on specimens (X-65 and 0.5 percent Cr enhanced X-65) in the reservoir and laminar flow regimes and on
X-65
in
the
impingement
regime
using
the
LPR
technique.
Once the corrosion rates were stable, the inhibitor was pumped into the autoclave to give a concentration of (1) Test 1 - 250 ppm, (2) Test 2 - 100
ppm (Corrosion Inhibitor "A"), (3) Test 3 - 100 ppm and (4) Test 4 - 250 ppm (Corrosion Inhibitor "B") based on total liquid volume. The pumping
rate of the inhibitor was then adjusted to maintain a constant inhibitor concentration during the test. The corrosion rates for the inhibited
environment were measured at the above mentioned locations at five different flow rates in the flow loop.
The flow rates were selected to simulate 40, 60, 80, 100 and 120 percent of wall shear stress. Higher wall shear stresses were measured later on
during the study. At each flow rate corrosion rates were monitored until stable values were reached. After completing the initial sequence of
measurements, the flow rate was brought down to represent 100 percent of wall shear stress value and corrosion monitoring was continued for a
total
of
2.8
days.
During the initial inhibitor evaluation test (Test 1 - 250 ppm corrosion inhibitor "A"), the baseline corrosion rates were monitored for 20 hours.
However, it was noticed that there was a tendency for iron carbonate filming and electrode passivation after prolonged exposure to the noninhibiting
test
environment
which
interfered
subsequently
with
the
measurement
of
inhibitor
efficiency.
This effect was also noted in the earlier HP-HT Flowing Autoclave Test work. Therefore, the procedure was changed for the second flowloop test to
monitor the corrosivity of the non-inhibited environment for a shorter duration (one hour) and proceed with the LPR measurements in the inhibited
environment (Test 2 - 100 ppm corrosion inhibitor "A", Test 3 - 100 ppm corrosion inhibitor "B" and Test 4 - 250 ppm corrosion inhibitor "B".)
Corrosion rate measurements were taken at flow rates which corresponded to 40, 60, 100 and 120 percent of wall shear stress value (velocity =
10 ft/sec for 100 percent ). The flow rate was then adjusted to represent 100 percent of wall shear stress value and the corrosion monitoring was
continued for 40 hours. The corrosion rate measurements were continued further at higher flow rates which corresponded to 1-- - 865 percent of
wall
shear
stress
value.
The
test
was
terminated
after
2.8
days.
The test specimens were visually examined, cleaned with non abrasive pads and weights were recorded.
Table 3
North Sea Pipeline Flow Tests
Corrosion Inhibitor Evaluation - Flow Regime Data
Input Data - Field
RHO
[kg/cu.m.]
I.D.
[cm]
Velocity
[m/s]
MU
[poise]
Reynolds
No
Roughness
e/D
Friction
factor
[f]
Tau
Pa
Tau
Lbs/sq ft
0.00014
0.013
41.78
0.872
Re
691.04
36.2
3.05
0.001626
4692357
Note: Tau [wall shear stress} value calculations based on a velocity of 10 ft/sec
Calculated Data - Flowloop Apparatus
Percent
TAU
TAU
Pa
TAU
Lbs/sq/ft
RHO
[Kg/cu.m.]
I.D.
[cm]
Velocity
[m/s]
MU
[poise]
Reynolds
No. Re
Friction
factor [f]
Velocity
[ft/sec]
Flow
Rate
[gpm]
100
41.78
0.872
967.61
1.27
2.13
0.002825
92738
0.019
6.99
4.28
40
16.71
0.349
967.61
1.27
1.28
0.002825
55790
0.021
4.21
2.58
60
25.07
0.523
967.71
1.27
1.61
0.002825
70016
0.02
5.28
3.23
80
33.42
0.698
967.71
1.27
1.91
0.002825
82947
0.019
6.26
3.83
120
50.14
1.047
967.71
1.27
2.4
0.002825
104373
0.018
7.87
4.82