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Prediction of Corrosion Inhibitor Performance Using Simulated CO2/H2S

Environmental Autoclave and Flowloop Tests - I

Prediction of Corrosion Inhibitor Performance Using Simulated CO2/H2S Environmental Autoclave and Flowloop Tests - I Abstract:

Abstract:

The hot topic series describes a test program and the result targeted towards evaluating corrosion inhibitor
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 CO 2 /H 2 S environments. After preliminary screening of the inhibition characteristics and performance of 5 corrosion inhibitors (designated A, B, C, D, & E) under simulated CO 2 /H 2 S 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 2 S (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:

= f2 /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 H 2 S 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 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 2

HT-HP Autoclave Tests

Corrosion Inhibitors Evaluations

Table 3 North Sea Pipeline Flowloop Test Corrosion Inhibitor Evaluation - Flow Regime Data

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 - SO 4

20

20

Bicarbonate - HCO 3

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

Flowloop Test Apparatus As a result of budget and personnel restraints, it was necessary and moreFigure 1 . The apparatus test parameters included: 300 F. (149 C.); pp CO of 75 psia (0.5 Mpa); pp H S 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 Location LPR Probe Description Metallurgy Figure 1 : 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. " id="pdf-obj-7-8" src="pdf-obj-7-8.jpg">

Figure 1. The apparatus test parameters included: 300 F. (149 C.); pp CO 2

of

75 psia (0.5 Mpa); pp H 2 S 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 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

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

5L0.5CrX6

a-50

0.035

0.07

0.55

1. 27

0.012

0.010

0.24

Cb-0.033

0

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, CO 2 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) H 2 S; 75 psia (0.54 MPa) CO 2 . 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 2 S and the

balance

CO 2 )

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

RHO I.D. Velocity MU Reynolds Roughness Friction Tau Tau [kg/cu.m.] [cm] [m/s] [poise] No e/D factor