SPE 117951

Challenges in Highly Sour Gas Environment Containing Elemental

Sulphur
Magdy Girgis, Shell Global Solutions

Copyright 2008, Society of Petroleum Engineers

This paper was prepared for presentation at the 2008 Abu Dhabi International Petroleum Exhibition and Conference held in Abu Dhabi, UAE, 36 November 2008.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
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BACKGROUND

To compete with more conventionally produced gas, wet sour gas is transported from the well
head to the gas sweetening units in carbon steel pipelines. Sour gas corrosion can lead to
pipeline pinhole leaks which pose hazardous consequences to people, wild life and pollution to
the environment. Corrosion is usually controlled through chemical inhibition in combination with
frequent batching and pigging programs.
In the presence of elemental sulphur corrosion rate can exceed 30 mm/y. Most of the mitigation
methods designed to manage and maintain the integrity of carbon steel downhole tubing and
pipelines present in itself some of the toughest technical challenges.
This paper outlines specific corrosion challenges related to the use of sulphur solvents; frequent
pigging and inspection programs; corrosion monitoring, the use of lined carbon steel materials
and some case histories. The paper also addresses the challenges associated with well
acidizing on sulphur corrosion in surface and subsurface operations

CORROSION MANAGEMENT IN SOUR ENVIRONMENT

In sour environment, in the absence of elemental sulphur, corrosion mitigation for carbon and
low alloy steels is controlled by applying appropriate inhibition program. In most cases
continuous injection of inhibitors and pigging activities are considered to be adequate for
mitigating corrosion. Several factors are considered important; inhibitor availability (residual);
pigging frequency, effective corrosion monitoring protocol and rigorous inspection program.
Corrosion monitoring tools are located in high risk areas (low flow regimes) . These locations
are determined by appropriate flow modelling programs.

In the presence of elemental sulphur the predicted uninhibited corrosion rates could be as high
as 30 mm/y (1). The system becomes complicated in several ways:

1. Continuous corrosion inhibitors may not be efficient on their own to provide adequate
protection. Batch inhibition is often required in this environment.
2. Sulphur deposition requires addition of sulphur solvents to minimize sulphur corrosion by
keeping sulphur particles moving.
2 SPE 117951

3. Rigorous pigging program is also required to ensure pipeline is clean of sulphur deposits.
4. Ensure that frequent pigging and batching would not result in process upsets in the
downstream units such as slug catcher and gas sweetening units.
5. Selection of proper corrosion monitoring tool is critical. Field experiences have shown
that In-situ corrosion monitoring tools are not reliable when under deposit corrosion
dominates. Corrosion monitoring devices measure fluid corrosivity, but often miss
corrosion related to sulphur deposition.

SULPHURE DEPOSITION IN SOUR GAS ENVIRONMENT

Several studies by ASRL showed that elemental sulphur is likely to drop out from sour gas in
the areas where temperature and pressure drop. According to Harris (2) sulphur solubility in
sour gas can be expressed as:

S sol = f (T) (P) (H2S) CO2

Condensate
Water Secondary factors
(Primary factors) CH4

Sulphur Solubility Curves - Devonian Production

Solubility profile in the reservoir with declining pressure
(assumes gas is saturated - note different reservoir temperatures)
0.7

Carbondale 19% H2S - 85C

0.6
Limestone - 21% H2S - 90C

Carbondale W - 15% H2S - 85C

0.5
Sulphur Saturation (kg/e3m3)

Castle River Miss - 26%H2S 80C

0.4

0.3

0.2

0.1

0.0
15 20 25 30 35 40
Reservoir pressure (kPa)

FIGURE 1: SULPHUR SOLUBILITY CURVES IN DIFFERENT SOUR CONDITIONS

SPE 117951 3

According to the paper, not all sour gas is saturated with elemental sulphur; the author quoted
ASRL Rules of Thumb for sulphur drop out:

If hydrocarbon liquid is present problems are unlikely

H2S>5% and no C2+ = deposition sooner or later
H2S>20% and no C2+ = deposition sooner than later

CHALLENGES WITH SULPHUR DEPOSITION

Deposition of elemental sulphur in pipelines results in significant impacts on the pipeline

integrity. The followings are examples of some challenges associated with sulphur deposition.

A) CHALLENGES WITH CORROSION INHIBITION

Field experience showed that effective corrosion inhibition program may require applying batch
inhibitor in addition to continuous inhibitor injection. Selection of batch inhibitors is dependent
on the batch volumes and the frequency of applying it. For many years, the industry adopted a
rule of thumb for batch volume calculations. The traditional method for calculating the volume of
batch corrosion inhibitor is based on a desired film thickness (typically 1 to 3 mils - 0.0254mm to
0.0762 mm) and the length and inside diameter of the pipe. This method of determining batch
corrosion inhibitor required has become an industry "Rule of Thumb". Following several
pipelines integrity issues, a comprehensive research program was developed and conducted at
Shell Canadas Calgary Research Center to investigate the factors that affect the performance
of batch inhibitors. Both lab and field findings supported the use of contact time as criteria for
batch inhibitor selection instead of relying on film thickness calculations.

CASE HISTORY

As reported earlier (3), the volume of batch inhibitor required for one of the wells (Panther River
Well #5) was based on a theoretical film thickness of 0.102 mm (4 mils). Batch inhibition
programs have included 30 litres batch inhibitor and 60 litres condensate to 100 litres batch
inhibitor diluted with 200 litres condensate. The batch frequency since start-up has been every
28 days and the flow line was pigged to remove stagnant liquid and the build-up of solids on a
7-day frequency. The well produce sour gas (8%H2S and 12% CO2), no condensate and
formation brine varied since start-up from 2.1 to 5.3 M3/day and contains 40,000 to 50,000 ppm
chlorides. In 1998, an inspection of PA-5 to PAJCT-3 was completed with a magnetic flux
leakage tool. When the pipe spool was cut out of the flow line both ends were taped and the
section of pipe was purged with nitrogen to remove oxygen. When the pipe was received at the
laboratory, the entire internal surface of the pipe was oxidized suggesting that no batch
corrosion inhibitor was present. A section of this pipe was further analyzed (solvent rinse
followed by Fourier Transform Infrared spectroscopy, FTIR, and comparison with a standard
spectrum) to establish if any batch inhibitor was present on the internal pipe surface. The FTIR
could not detect any batch corrosion inhibitor. Detailed studies showed that Inhibitor films
deposited on the field and lab spool pieces were typically 1 to 2 orders of magnitude lower than
the target film thickness of 0.102 mm (4 mils). This work promoted Shell Canada to focus on the
effectiveness of batch inhibitors based on contact time rather than on film thickness. It is
believed that this approach has been applied by other companies including the chemical
vendors.
4 SPE 117951

FACTORS AFFECTING BATCH INHIBITION

In addition to the film thickness issues discussed above, sulphur deposition could be
detrimental to the performance of the batch film. It becomes imperative to test the performance
of the inhibitor under field conditions with emphasis on including sulphur particles into the test
matrix. Shell Canada developed test protocol for batch inhibitor selection. As summarized in
earlier publication (4) , the set up contains a specially designed flat, washer-like coupon (
C1018 carbon steel) is employed and is fitted in a custom-made holder (see FIGURES 2&3).
Prior to filming the coupon with the batch inhibitor, a 12 hour pre-corrode step in the autoclave
is performed to establish an iron sulphide scale similar to the scale present in a field pipeline.
After the 12-hour pre-corrode step, the coupon is removed from the autoclave and dipped in the
inhibitor solution for the prescribed contact time and is then allowed to drip dry for 15 minutes. A
known amount of sulphur particles is added on the coupon surface. The quantity is based on
the field production data .The filmed coupons are then returned to the autoclaves containing
fresh brine for the duration of the exposure period to assess the protection afforded by the
inhibitor film.

FIGURE 2: Coupon Set-Up Used For Sulphur Deposition Corrosion Tests

(Electrochemical Measurements)
SPE 117951 5

FIGURE 3: Coupon Holder for Sulphur Deposition Corrosion tests (Weight Loss
Measurement)

B) EFFECT OF ELEMENTAL SULPHUR ON CORROSION

Both field and laboratory studies showed that uninhibited corrosion rates could increase by
several orders of magnitude in the presence of elemental sulphur. FIGURE 4 demonstrates an
example of the effect of sulphur on corrosion rates (1). The results also showed that sulphur
corrosion is dependent on chloride ion concentrations. This finding agrees with the work
conducted by Alberta Sulphur Research Limited (ASRL) that sulphur corrosion is characterized
by incubation period. The incubation period is reduced or even eliminated by the addition of
chloride ions (5) as shown in FIGURE 5.
6 SPE 117951

Corrosion rate as a function of Cl-

No S Elemental S
M axim um pitting rate in m m /y

40
35
30
25
20
15
10
5
0
2 3 4 5 6
log (ppm Cl-)
FIGURE 4: Effect of Elemental Sulphur on Corrosion
SPE 117951 7

FIGURE 5: ASRL Data on the Effect of Sulphur on Corrosion

On a paper by Schaschl (6); the comparison between sulphur and oxygen corrosion
mechanisms was described (Figure 6). It was found that dissolved sulphur parallels the action
of dissolved oxygen in aerated solutions.
8 SPE 117951

FIGURE 6: Comparison of Oxygen and Sulphur Corrosion Mechanisms

DOWNHOLE CORROSION CHALLENGES

For the wells that produce elemental sulphur, it is recommended to inject sulphur solvents
followed by applying batch inhibition. Failure to comply with these steps, serious tubing
corrosion is expected. For one of our wells, the procedure was changed to a monthly batch
application, regardless of the frequency of sulphur solvent treatments. The existing tubing
string was found to be corroded virtually over its entire length. The only non-corroded portion
was above the SSSV, where 600 liters/day diesel injection was applied.

If the volume of sulphur solvents was not adequate, sulphur may drop out in the tubing and in
the wellbore. This would cause production and corrosion problems. In the case of production
problems, the wells are often stimulated with strong acids such as hydrochloric acid. Acids do
not spend on sulphur particles; thus when the well is back produced; acids may return with its
full strength live and would cause severe corrosion to the tubing.

C) EFFECT OF SULPHUR ON IRON SULPHIDE SCALES

Extensive studies on Old Jumping Pound Line pipe failure (Shell Canadas sour gas field)
revealed the followings:

1) The failure was primarily due to Stress Oriented Hydrogen Induced Cracking (SOHIC)
phenomenon ( FIGURES 6&7 )
2) Analysis of scales and deposits by X-ray diffraction showed the presence of
Mackinawite (Fe9S8) and Greigite (Fe3S4). The presence of Greigite may indicate the
(past) presence of elemental sulphur:

Fe9S8 + 1/2S8 = 3Fe3S4.

SPE 117951 9

It is assumed that this reaction is preceded by the consumption of S8 molecules in the

following reaction:

S8 + 16e- = 8S2-
Presence of sulphur depolarizes (speeds up) the cathodic reaction - greater anodic
reaction rate.

3) Greigite scale is poorly protective; flaky (poorly adherent) and porous. The scale permits
higher general (weight loss) and localized corrosion rates. It favors hydrogen atom entry
and hydrogen damage in susceptible materials.
4) Identification of Marcasite (FeS2) may also indicate presence of sulphur at high (~100
o
C) temperature

FIGURE 6: Scale Build Up in a Section of the Failed Pipe

10 SPE 117951

FIGURE 7: Cross Section through Leak Locations

A review on the nature of sulphides and their corrosive effect (7) referred to a work by Stumper
( 8) who reported a 230% increase in the corrosion rate of mild steel when in physical contact
with iron sulphide. The review also reported corrosion data (FIGURES 8&9) by Sheppard ( 9 )
and Treseder (10 ). They found that certain of the sulphides, and also sulphur itself were highly
corrosive when placed on a mild steel surface.
SPE 117951 11

Effect of Sulphide Scales on Corrosion Rate

140
120
100
C R (m m / y )

80
60
40
20
0
H2S FeS FeS2 Fe3S4
Sulphide Scales
FIGURE 8: Corrosion Rates In the Presence of Different Sulphide Scales

Effect of Sulphide Scales on Corrosion Rate

1200
1000
C R (m m /y )

800
600
400
200
0
H2S FeS FeS2 Fe3S4 So
Sulphide Scales

FIGURE 9: Comparison of Data in Figure 7 with Elemental Sulphur

12 SPE 117951

D) CORROSIVITY OF SULPHUR SOLVENTS

Because of the consequences of sulphur deposition on pipeline integrity, sulphur solvents are
used to minimize the direct contact of sulphur on the pipeline surface and help keep sulphur
moving. The solvents such as Di Methyl Di Sulphides (DMDS) or Di Aryl Di Sulphides (DADS)
are known to be very efficient in dissolving elemental sulphur. When saturated with sour gas
and elemental sulphur; the new mixtures (Di Methyl PolySulphide, DMPS, or Di Aryl
Polysulphide, DAPS) become very corrosive (Table 1).

TABLE 1: Corrosion Data of Sulphur Solvents (10)

H2S Temp, C DADS Brine Sulphur CR (mpy)

( Pressure, Added
psi)
30%(4800) 140 No Yes No 14
30%(4800) yes yes No 421
30%(4800) yes yes yes 921
30%(4800) 100 212
30%(4800) 60 110

Similar results were obtained when DMDS was tested under same conditions. The results
indicate the followings:

In the absence of DADS, sour brine is corrosive; the degree of corrosivity depends on
H2S partial pressure and chloride concentrations. This type of corrosion rates could be
mitigated by applying proper inhibition program.
In the presence of DADS, corrosion rate has increased significantly and almost
increased 80 times in the presence of elemental sulphur. These high corrosion rates
require rigours mitigation program that include frequent pigging and batching program. It
is important to know that some pigs (e.g. wire brush pigs) can damage the protective iron
sulphide and may create crevices along the pipe surface (FIGURES 10&11). It is
recommended to batch inhibit the pipelines following pigging activities.
Corrosion rates are still significantly high even at low temperatures.
SPE 117951 13

FIGURE 10: A Track on a Section of Pipeline As A Result of Wire Brush Pigging

(Corrosion is Initiated)

Internal Pitting Corrosion Damage Example

Track Left by Internal Corrosion Inspection Tool

(Smart Pig) - Did it initiate the corrosion damage?

FIGURE 11: Track Left By Inspection Tool

14 SPE 117951

E) CHALLENGE WITH NON METALLIC LINERS

To mitigate sulphur corrosion, an alternative method is to apply non metallic liners inside the
carbon steel pipelines. The use of these liners such as poly amides (Rilsan) or High Density
Poly Ethylene (HDPE) should reduce the cost of chemical programs and may eliminate pigging
activities.. Few problems are associated with liners (12):

1) Linear breach as result of improper liner design (lose fit) ; inversions leading to tears
(e.g. FIGURE 12 )
2) Chemical degradation with water and methanol at higher temperatures
3) Modulus and strength lowered by some chemicals (e.g. methanol and DMDS)
4) greater than expected gas permeation

All of the above can lead to significant corrosion issues behind the liners. The annulus
corrosion could be mitigated by proper gas venting program and maintain controlled
environment inside the pipelines.

FIGURE 12: Liner Inversion and Elongation (Note damage from LBV gate)

FIGURE 13: Close-up view of thinning and tearing from line-break valve closure
SPE 117951 15

CONCLUSION

In 1612 Martin Rulando (German Scientist), expressed a powerful view about the behavior of
sulphur as it gives life but is and remains an enemy of all metals.

To manage corrosion in sulphur containing environment; the following controls

should be considered:

1) Detailed study on sulphur solubility under well operating conditions is the

first step to be considered.
2) Develop program for applying appropriate sulphur solvents.
3) Corrosion program should consider the use of batch inhibitors in addition to
continuous inhibitors. Frequency of pigging and batching is determined
based on field inspection data; corrosion monitoring data and lab
experiments.
4) Liners can be considered with proper annulus gas venting practices and
adequate installation. It is recommended to test the physical and chemical
properties of the liners prior to using it.
5) Determine appropriate corrosion monitoring tools and appropriate locations
to installing it.
6) Study the impact of batch inhibitors on gas sweetening units.

REFERENCES

1) M. Girgis, Presentation at Sulphur Bearing Sour Gas Pipeline Corrosion Workshop

Organized by Shell Canada Ltd., Oct 23-25, 2002.
2) R. Harris; Presentation at Sulphur Bearing Sour Gas Pipeline Corrosion Workshop
Organized by Shell Canada Ltd., Oct 23-25, 2002
3) J.Bojes, M. Maddison, H. Fear, M.Girgis, NACE Paper 01028, 2001
4) J.Bojes; M. Girgis; K. Goerz and I. Rippon ; NACE Paper No 02289, 2002
5) N.I. Dowling , Presentation at Sulphur Bearing Sour Gas Pipeline Corrosion Workshop
Organized by Shell Canada Ltd., Oct 23-25, 2002.
6) E. Schaschl; NACE Paper No 0094; 1980
7) P. D. Clark, E.Fitzpatrick, C.Lau and J. Simion; ASRL Chalk Talk; January 1995
8) J.S.Smith and J.D.A. Miller ; Br.Corrosion.J. Vol 10, No 3, 1975
9) R. Stumper; C.R.Acad.Sci; Vol 176, 1316; 1923
10) L.R.Sheppard; Corrosion; Vol 6, 27 (1950)
11) R.S. Treseder; San Francisco Western Region; NACE Meeting; 1955
12) K. Goerz, Presentation at Sulphur Bearing Sour Gas Pipeline Corrosion Workshop
Organized by Shell Canada Ltd., Oct 23-25, 2002.