Prediction of Corrosion Inhibitor Performance Using Simulated CO2/H2S

Environmental Autoclave and Flowloop Tests - I

Abstract:

The hot topic series describes a test program and the result targeted towards evaluating corrosion inhibitor performance in

CO2/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.

Overview
This hot topic series describes a test program and the results targeted towards evaluating corrosion inhibitor performance in CO2/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 H2S (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 (B-
B)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

where = density of the liquid and f = friction factor

The liquid flow rate in the laboratory flow loop corresponding to the above shear stress value was calculated using the above equation and
Moody diagrams which provide relationships between pipe diameter (D) and roughness factor (e/D) and f, e/D, and Reynolds number (Re =
D/??; ??= viscosity of the liquid.)
The effect of flow rate on the inhibitor film was studied using the flow loop apparatus at up to nine (9) flow rates corresponding to 40%, 60%,
80%, 100%, 120%, 330%, 456%, 660% and 865% of the maximum (100%) anticipated North Sea pipeline wall shear stress value using a
velocity of 10 ft/sec (Table 3). Other flowloop test parameters included were: 300 F. (149 C.); pp CO 2 of 75 psia; pp H2S of 0.075 psia; 90%
Synthetic North Sea Pipeline brine (Table 4); 10% depolarized kerosene. These test parameters represented worst case senario for the
proposed North Sea pipeline.
Prior to initiation of the Phase 2 study, flow loop apparatus performance was tested using the BP Protocol Calibration Test. The flow loop test
apparatus encountered no problems passing the require calibration test criteria.
The chemical supplier of the two corrosion inhibitors to be evaluated in the flow loop test, provided preliminary flowloop test data developed in
their laboratory. The test parameters used were: 180 F. (82 C.); pp CO2 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

Input Data - Field

RHO I.D. Velocity MU Reynolds Roughness Friction Tau Tau

[kg/cu.m.] [cm] [m/s] [poise] No e/D factor Pa Lbs/sq ft
Re [f]

691.04 36.2 3.05 0.001626 4692357 0.00014 0.013 41.78 0.872

Note: Tau [wall shear stress} value calculations based on a velocity of 10 ft/sec
Calculated Data - Flowloop Apparatus

Percent TAU TAU RHO I.D. Velocity MU Reynolds Friction Velocity Flow
TAU Pa Lbs/sq/ft [Kg/cu.m.] [cm] [m/s] [poise] No. Re factor [f] [ft/sec] 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 Desired Mixture - mg/L Actual Mixture -
mg/L

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

Flowloop Test Apparatus
As a result of budget and personnel restraints, it was necessary and more economically attractive to contract the flowloop testing to an outside
laboratory than to design and construct the flowloop test apparatus required as well as commit the number of personnel necessary to perform the
testing. The consulting laboratory that did our earlier high pressure-high temperature flowing autoclave testing was selected to perform the
flowloop testing. The apparatus used was theirs and is diagramed in Figure 1. The apparatus test parameters included: 300 F. (149 C.); pp CO 2 of
75 psia (0.5 Mpa); pp H2S of 0.075 psia (0.5 Kpa); 10 percent depolarized kerosene; 90 percent Synthetic Brine.
The flowloop was designed to produce the same magnitude of wall shear stress in the pipeline due to laminar flow and in the turbulent flow region
of the impingement electrode for a given liquid flow rate in the pipeline. Additionally, it provides for simulation of complex mixed brine fluids and the
effects of dissolved acid gas at partial pressures similar to those in the pipeline.
The diagram indicates the location of the test electrodes in the flowloop apparatus. In all cases linear polarization resistance (LPR) probes were
used and instantaneous corrosion rates were determined using electrochemical techniques (ASTM G59) and the average corrosion rate using
weight loss techniques (ASTM G). The type and metallurgy of the LPR are located in the apparatus as indicated in Figure 1:
Location LPR Probe Description Metallurgy
1. Laminar Flow Electrode X-65
2. Laminar Flow Electrode 0.5 CrX-65
3. Impingement Electrode X-65
4. Reservoir Electrode X-65
5. Reservoir Electrode 0.5CrX-65
Alloy analyses of the LPR probe electrode materials are shown in Table 5. The test electrodes in the reservoir were standard 0.25 inch (0.64 cm)
diameter and 1 inch (2.54 cm) long rods. In the laminar region, tubular specimens of 0.5 inch (1.27 cm) I.D. were used. The target specimen in the
turbulent region was a cross-section of a tubular specimen (0.202 inch I.D. and 0.404 inch O.D.) press fit into the peek specimen holder. All the
specimen surfaces were polished to 600 grit finish with SiC paper and degreased before mounting in the apparatus.
The test for calibration of the experimental set-up was performed using AISI 1018 carbon steel in a synthetic sea water environment.
 Figure 1 Consulting Laboratory Flow Loop Apparatus

Table 5
Alloy Analyses of LPR Electrode Materials for Flow Loop Test
Chemical Properties
ALLOY HEAT Al C Cr Cu Fe Mn Mo Ni P S Si Ti other

5lx65 d134 0.07 1.26 0.014 0.011 0.24 Cb-0.033; V-

0.04

5L0.5CrX60 a-50 0.035 0.07 0.55 1. 27 0.012 0.010 0.24 Cb-0.033

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/ft2). 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 non-inhibiting
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 I.D. Velocity MU Reynolds Roughness Friction Tau Tau
[kg/cu.m.] [cm] [m/s] [poise] No e/D factor Pa Lbs/sq ft
Re [f]

691.04 36.2 3.05 0.001626 4692357 0.00014 0.013 41.78 0.872

Note: Tau [wall shear stress} value calculations based on a velocity of 10 ft/sec
Calculated Data - Flowloop Apparatus

Percent TAU TAU RHO I.D. Velocity MU Reynolds Friction Velocity Flow
TAU Pa Lbs/sq/ft [Kg/cu.m.] [cm] [m/s] [poise] No. Re factor [f] [ft/sec] 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