Managing Corrosion Challenges in

Amine Treating Units at Gas Plants

Mohamed A. Saleem
Saudi Aramco
Uthmaniyah Gas Plant Department
Box 755, Udhailiyah, Saudi Arabia
Fax: 966-3-577-5445
E-mail: saleemmx@aramco.com.sa

Faisal A. Al-Odah
Saudi Aramco
Uthmaniyah Gas Plant Department
Box 755, Udhailiyah, Saudi Arabia
Fax: 966-3-577-5445
E-mail: odahfa@aramco.com.sa

ABSTRACT

Diglycol amine (DGA) is widely used in Saudi Aramco’s gas treating units to absorb hydrogen sulfide
(H2S) and carbon dioxide (CO2) from sour gas. More than two decades of operational experience in low
pressure gas treating units’ demonstrated carbon steel (CS) material to provide optimum performance in
DGA environment under normal operating conditions.

However, DGA can lead to accelerated corrosion of CS material with unique damage mechanisms such
as erosion corrosion, preferential weld attack and localized corrosion with distinct pit morphology. Due
to localized corrosion, conventional corrosion monitoring techniques are of limited value.

While these corrosion issues can be efficiently addressed in new plants with appropriate design and
material upgrade, cost effective control of accelerated corrosion in existing plants remains a challenging
task for proactive corrosion management.

Due to limitations with some corrosion protection options such as coatings and chemical treatment,
other approaches were adopted. This paper outlines an overview of specific integrity issues due to
various forms of corrosion and several innovative approaches adopted for corrosion management.

Investigation of H2S containing DGA solutions in gas sweetening environment indicated that
conventional ASTM A516-70 carbon steel material is not susceptible to hydrogen induced cracking
(HIC) or stress oriented hydrogen induced cracking (SOHIC). Ongoing Amine (DGA) stress corrosion
cracking (SCC) study at elevated temperatures revealed that PWHT could be exempted even beyond the
existing temperature limit of 280ºF for CS material.
 1. INTRODUCTION

1.1 Background

Uthmaniyah Gas Plant (UGP) is one of the largest sour gas processing facilities in the world. UGP was
commissioned in 1981 as part of a Master Gas System (MGS) to process the associated gas from oil
wells. Initial design capacity was 1.4 billion SCFD (standard cubic feet per day) with three low pressure
(LP) gas treating units; each LP gas treating unit designed to process 491 million SCFD of sour gas. The
feed rate was 1.2 billion SCFD until mid 1980’s. It was increased to 1.8 billion SCFD when the gas
demand increased during 1984. The additional 600 million SCFD was from non-associated (Khuff) gas
stream. After major expansion with one high pressure (HP) DGA unit and two Sulfur Recovery Units in
2000, the feed rate was increased to 2.4 billion SCFD by processing additional 600 million SCFD of
Khuff gas. Continuous efforts are in progress to increase the processing capacity to 2.6 billion SCFD.

1.1.1. Present and Future Situation Gas processing plants operated by Saudi Aramco produce
sales gas, NGL and sulfur as the end products. The domestic average sales gas demand is expected to
get doubled within the next five years. As a result, all the gas plants will be expected to operate at or
near their full capacities to meet the demand.

1.1.2. Process Description In the gas plants, with the exception of one gas plant, DGA is used
as a sweetening solvent to recover both hydrogen sulfide (H2S) and carbon dioxide (CO2) from the sour
gas. These units have carbon steel as the predominant metallurgy in almost all the process equipment
and piping systems. The sour gas goes through feed gas filter separators to remove entrained
hydrocarbon liquids and particulates before going to the bottom of contactor (Figure 1).

The sour gas is primarily treated in the contactor where DGA absorbs H2S and CO2. The rich DGA is
then processed in the regenerator where the acidic components are removed resulting in the formation of
sweet gas and acid gas. Sweet gas from the three LP DGA units is compressed prior to transferring to
NGL recovery modules and the acid gas processed further in sulfur recovery units. The lean amine
solution leaving the bottom of the regenerator pumped through DGA circulation pumps to lean solution
cooler prior to recycling to the contactor.

The Rich DGA solution (containing absorbed H2S and CO2) flows from the bottom of the contactor to
the DGA flash drum. The pressure in the flash drum is reduced from 200 psig to about 75-80 psig to
flash out absorbed hydrocarbon gases. Flashed gases are used as fuel gas in the Utilities Plant. The rich
DGA solution stream then flows to the top of the Stripper at a pressure of 12-14 psig. The DGA is
heated in the stripper reboilers to approximately 260-280 ºF. At this temperature, H2S and CO2 gases are
released or stripped from the DGA solution.

The overhead stream from the stripping column, containing H2S, CO2, DGA and water vapor is cooled
in the overhead condenser. Condensed liquids flow to the reflux drum and returned as reflux to the
stripping column. The resulting acid gas consisting of H2S, CO2 and water vapor is sent to the sulfur
recovery units to recover sulfur. A small amount of lean DGA is fed to the reclaimer to convert
degradation products back to DGA at high temperatures. These degradation products are formed due to
side reactions of DGA with carbon dioxide (CO2), carbonyl sulfide (COS) and carbon disulfide (CS2 ).
 2. CAUSES OF CORROSION

2.1 General

More than two decades of operational experience demonstrated CS material to provide optimum
performance in DGA streams operating within the design envelope. However, several factors such as
design, improper fabrication, poor operating practices, amine degradation, etc. can lead to significant
corrosion concerns. In general, the problems in amine treating units can be broadly classified into two
distinct categories, corrosion and environmental cracking.

2.1.1 Corrosion The corrosion concerns observed in amine treating units are basically due to
absorbed acid gases (H2S and CO2) and amine degradation products. There are several contributing
factors for the accelerated corrosion such as process parameters, process chemistry, design, etc. As the
process control is complex due to different variables such as velocity, temperature, pressure,
concentration of corrosive species, dissolved oxygen, amine concentration, acid gas loadings, H2S
stripping, filtration and fouling, greater emphasis is required in managing the corrosion challenges to
ensure a safe and reliable operation. While these corrosion issues can be efficiently addressed in new
plants with appropriate design and material upgrade, cost effective control of accelerated corrosion in
existing units remains a challenging task for proactive corrosion management.

2.1.1.1 Rich Amine Flashing Acid gas flashing from the amine solution is a concern
because this results in significantly low pH condensate. Flashing can occur at a pressure and temperature
lower than the boiling point of the solution. Flashing is caused by an increase in the temperature or
reduction in the pressure affecting acid gas-amine equilibrium reaction. The areas of highest corrosion
potential are the reboiler, hot lean amine piping, lean/rich cross exchanger, hot rich amine piping,
stripper and stripper overhead.

2.1.1.2 Velocity and Suspended Solids Velocity has a significant impact on corrosion.
An increase in velocity results in erosion corrosion due to damage of the protective iron sulfide (FeS)
film. Presence of high suspended solids at high velocities will lead to accelerated localized corrosion
due to rapid destruction of FeS protective film. In reference to API RP 945, fluid velocities should not
exceed 1.5 m/sec for CS piping in DGA streams and per governing company piping standard the
velocity should not exceed 2 m/sec. However, this velocity limitation is not well clarified for rich and
lean DGA streams.

Indirectly, increasing velocity creates areas of higher and lower local pressure caused by flow. Local
changes in pressure, differential pressure, create the environment for acids to flash from the bulk
aqueous solution. Collapsing of the vapor phase in piping, pumps, and exchangers contributes to the
physical damage by flow in the form of cavitation or impingement.

2.1.1.3 Amine Degradation Various undesirable compounds including gaseous

degradation products as well as heat-stable amine salts are generated as a result of the thermal
degradation and oxidation of DGA. Degradation can have a significant impact on plant operations as it
results in a loss of active amine as well as an increase in corrosion due to the acidic nature of the
degradation products. The accumulation of these acids combined with high acid gas concentrations, high
temperatures or velocities can lead to accelerated corrosion. Corrosion is most common in the hot areas
of the units such as the re-boiler, regenerator column, regenerator overhead, and in hot amine piping and
exchangers.

(i) Reactions with CO2: Most corrosion in an amine system is acidic in nature. CO2 dissolves in amine
solution and forms carbonic acid. In addition, reactions with CO2 can lead to chelating compounds.

(ii) Oxygen: Oxygen can react with DGA resulting in the formation of formic acid, oxalic acid, and
ammonia. High concentrations of oxygen in the amine can also lead to the formation of iron oxide and
iron hydroxide. Presence of oxygen in the feed gas stream can also enable the reaction with H2S to form
several byproducts including elemental sulfur.

(iii) Ammonia: In amine systems, ammonia can be generated due to thermal degradation of the amine.
Ammonia is soluble in the amine solution and regenerated in the stripper. The ammoniacal condensate
absorbs CO2 to form ammonium carbamate or bicarbonate, which can cause plugging of the condenser.
The ammoniacal condensate also absorbs H2S forming ammonium bisulfide, which is corrosive

2.1.1.4 Chlorides Chlorides can enter the system mostly from chloride-containing make-
up water and can also enter from the incoming feed gas. Chloride ions can cause pitting, crevice
corrosion and stress corrosion cracking of stainless steel and general corrosion of carbon steels.
Chlorides can be minimized in the amine solution by ensuring adequate inlet separation and use of good
quality make-up water.

2.1.1.5 Heat Stable Amine Salts (HSAS) Impurities accumulate due to inefficient and
unstable amine unit operation. These contaminants include metal ions, specific ions that interfere with
the absorption, amine degradation products and amine by products in the form of heat stable salts. These
HSAS in the solution increase the amine loss and affect unit’s productivity. HSAS also cause corrosion
problems and can cause foaming tendency. Foaming in the absorber columns, higher amine losses, heat
exchanger fouling, shortened amine filter life, and overall unit instability can be the most common
problems associated with HSAS accumulation.

2.1.1.6 Other Corrosive Species Hydrogen cyanide (HCN) and Carbon monoxide (CO)
can both increase the corrosivity of the amine solution through the formation of formic acid. CO reacts
with water to form formic acid by using iron, iron oxide, or iron sulfides as catalysts. HCN hydrolyses
in water to form formic acid.

2.1.2 Environmental Cracking Environmental cracking can occur in amine treating units
when CS materials are in regions of high hardness, high residual stress or both. However, as far as DGA
is concerned, available data did not indicate any major environmental cracking concerns in DGA
streams.

2.1.2.1 Amine Stress Corrosion Cracking: Research studies conducted by Saudi

Aramco during 1984 at South West Research Institute concluded that CS is not susceptible to amine
SCC in DGA environment up to 280 ºF. As a result, the governing company standards were revised to
exempt post weld heat treatment up to 280 ºF. At the request of UGP, further research is in progress to
determine the SCC tendency at elevated temperatures.
 2.1.2.2 HIC and SOHIC Saudi Aramco conducted a research project in coordination
with Fontanna Corrosion Center and CC Technologies Lan, Inc. to determine the HIC and SOHIC
susceptibility of conventional ASTM A516-70 CS in H2S containing DGA solutions. The study
involved characterization of cracks in terms of crack length ratio (CLR), crack thickness ration (CTR)
and crack sensitivity ratio (CSR). Results indicate that conventional ASTM A516-70 CS material is not
susceptible to HIC or SOHIC in various H2S containing DGA solutions at the temperatures studied.

3. CORROSION MANAGEMENT

3.1 Philosophy

As the corrosion protection options are very limited and the objective of any option elected shall provide
a life of not less than the equipment inspection schedule (EIS) interval of five years, only reliable
options were adopted.

3.1.1 In-kind Replacement In-kind replacement of the affected CS sections with heavier wall
thickness often appeared to be a reliable and cost effective option, which provided a life of at least two-
five year T&I cycles.

3.1.2 In-Kind Replacement with Improved Design For the piping circuits in the hot lean
DGA streams, which experienced significant erosion-corrosion, in-kind replacement with configuration
change identified as the cost effective option than replacing with larger diameter piping.

3.1.3 Material Upgrade Process equipment such as stripper reboiler top heads that experienced
severe localized attack on the shell and welds were upgraded by strip lining with 316L in a local facility.
This was highly cost effective option than new CS fabrication with 316L cladding on internals.

3.1.4 Use of Tube Inserts SS tube inserts were installed on the lean solution cooler fin fan tubs
to alleviate the tube end erosion-corrosion problems. This approach was identified as the most cost
effective option than the conventional option of retubing.

3.1.5 Coatings The option of coating has limitations in withstanding the effects of erosion-
corrosion and higher operating temperatures. However, one of the equipment, reflux drum, (which
experienced under deposit corrosion at the bottom head and general corrosion on the shell at the
submerged sections), was restored by a suitable coating system. However, this coating system was not
available in sprayable grade and did not provide a satisfactory life of at least five years due to issues
mostly related to application. Prior to further widespread application, this option is being pursued for
field trial on pipe spools by applying other candid products with sprayable grade.

3.1.6 Corrosion Inhibition: Though this option can be of some assistance, the effectiveness in
controlling flow related impingement attack is questionable. However, some areas of the process
streams such as overhead condensers can be the ideal candidates for this option.
 3.1.7 Oxygen Control Oxygen is one of the corrosion promoters and corrective measures such
as nitrogen blanketing will be required to eliminate or minimize the oxygen ingress. Sources of oxygen
ingress can be: DGA storage tanks, Sump, make-up water, feed gas stream, packing glands of pumps,
etc.
3.1.8 Task Force and Investigation A task force was formed with multi-disciplines to identify
the root causes and develop suitable action plan to mitigate accelerated corrosion. Though the task force
managed to tackle several issues, however, further efforts are required to deal with the unique
anomalous corrosion trend observed in specific streams (Table 1) and preferential weld attack.

4. PROACTIVE CORROSION MANGEMENT CHALLENGES

As these operating units are under five years turn-around cycle, suitable non-intrusive techniques
become an integral part of monitoring to predict the corrosion trend and develop appropriate action plan
for timely corrective action. Erosion/corrosion (Figure 2), preferential weld attack (Figure 3), pitting, etc
are the predominant damage mechanisms. NDT techniques used shall be of appropriate combinations.

4.1 Limitations with Nondestructive Testing (NDT)

Advanced NDT techniques such as P-scan monitoring can be used only up to 140ºF. The multiple UT
transducers, Rightrax, can be of assistance only up to 230ºF. However, as he operating temperature of
most of the locations that require extensive monitoring is operating at or above 260ºF, these techniques
are of little or no use. Furthermore, these techniques are beyond the scope of application on elbows,
where extensive scanning is required to determine the extent of damage. Conventional radiography is of
limited support in predicting localized damages because of the high operating temperature and the
viscous nature of DGA. Eventually, these conditions limit the options of NDT to manual UT, which is
not only slow but also highly subjective.

4.2 Corrosion Monitoring

Due to the nature of localized damage mechanisms (erosion-corrosion, preferential weld attack, pitting),
monitoring with coupons and probes are not cost effective and the monitoring data are of limited value.
An effective monitoring program should include combination of techniques and amine solution analysis.

5. ACTION PLAN WITH INNOVATIVE APPROACHES

5.1 Enhancement of Corrosion Monitoring

In order to corrosion monitoring, further efforts are in progress to utilize the most suitable innovative
techniques including the state-of-the art technologies. Some of the techniques planned or under
validation are: High Temperature Scanner – fast method to quantify the damaged areas/sections, Field
Signature Method (FSM) – high sensitive multiple ER probe specifically designed for monitoring
preferential weld attack and Time-of-Flight Diffraction – sensitive technique to detect weld attack and
cracking.
5.2 Partnering with Amine Joint Industry Program (JIP)

UGP is to partner with the Amine JIP program which will be of great assistance to support the on-going
investigation. The objectives of the Amine JIP are:

• Develop database for amine corrosion

• Parametric evaluation of temperature, CO2/H2S ratio, HSAS, organic acids
• Develop software corrosion prediction tool

5.3 Study on DGA SCC Tendency at Elevated Temperatures

Due to increased localized attack on CS and the need to repair/replace these sections, PWHT is often
required. However, such requirements led to extensive delays in the repair and extending the duration
of the shutdown. To overcome these concerns, at the request of UGP, a study is in progress to determine
the SCC tendency of DGA at elevated temperatures beyond 280ºF. Based on the study completed at the
present time, SCC was not detected until 330ºF.

5. 4 Explore Suitable Corrosion Protection Options

In a continuous effort, suitable corrosion protection options are explored for timely application. Some of
the options pursued/applied are:

• Thermal sprayed coatings

• Strip lining rather than new clad fabrication
• Use of tube inserts than retubing
• Corrosion inhibition program for specific application

6. CONCLUSIONS

• CS material provided optimum performance in DGA environment under normal operating

conditions.
• Accelerated corrosion occurred within the last seven years. One of the root causes identified for
this accelerated corrosion is the 25% increase in the feed rate.
• Corrosion trend can be generic but can also be plant specific, which requires a thorough
evaluation. Anomalous corrosion trend shall be identified and addressed immediately.
• DGA is largely used in Saudi Aramco than other industries. Considering the future gas demand,
follow-up work is required to develop specific guidelines for each facility for safe and reliable
operation.
• Severe localized corrosion occurred in lean DGA streams than rich DGA streams.
• Demothballing of side coolers and installation of lean/rich exchangers will help to minimize the
concerns significantly.
• Preferential weld attack required further evaluation.
• Piping standard needs to reflect velocity limitations for lean and rich amines
• Proactive corrosion management remains a challenging task due to limitations with most of the
monitoring techniques.

REFERENCES

1. National Association of Corrosion Engineers (NACE) Recommended Practice, NACE Standard

RP-01-70, 1985 Revision.
2. T. R. Bacon, “Amine Solution Quality Control Through Design, Operation and Correction,”
1987 Gas Conditioning Conference.
3. K. P. Butwell, L. Kroop, “ Fundamentals of Gas Sweetening,” 1983 Gas Conditioning
Conference.
4. David Owen, “Corrosion Control in Amine Treating Units”, 2001 Ninth Middle East Corrosion
Conference.
5. F. F. Lyle Jr., “Stress Corrosion Cracking of Steels in Amine Solutions Used in Natural Gas
Treatment Plants,” NACE Corrosion 1988, St. Louis, paper 158.
6. C. M. Schillmoller, “Amine Stress Cracking: Causes and Cures”, Hydrocarbon Processing, June
1986.
7. J. Gutzeit, J. M. Johnson, “Stress Corrosion Cracking of Carbon Steel Welds in Amine Service,”
NACE Corrosion 1986, paper 206.
8. API Recommended Practice 945, “Avoiding Environmental Cracking in Amine Unit”, Second
edition, October 1997.
9. M. A. Al-Anezi, G. S. Frankel, A. K. Agarwal, “Investigation of the susceptibility of
conventional ASTM- A516-70 Pressure Vessel steel to HIC and SOHIC in H2S-containing
DGA solutions”
10. M. K. Seubert, G. D. Wallace Jr., “Corrosion in DGA Gas Treating Units”, NACE Corrosion
1985, Boston Paper 159.
11. H. H. Uhilg, “ The Corrosion Handbook,” John Wiley & Sons, 1948, pp. 545-559.
12. C. M. Schillmoller, “Amine Stress Cracking: Causes and Cures”, Hydrocarbon Processing, June
1986.
13. B. J. Moniz, W. I. Pollock (editors) and J. Gutzeit, “Refinery Corrosion Overview” p171-189 in
“Process Industries Corrosion”, NACE 1986.
14. H. T. Ball, “Design and Operation of Amine Units”, Petroenergy 1989.
15. T. R. Bacon, “Amine Solution Quality Control Through Design, Operation and Correction”,
1987 Gas Conditioning Conference.
16. L. R. White, “Corrosion in Amine Units”, 1994 Gulf Coast Corrosion Control Seminar, NACE
Houston, Texas.
 Table 1 - ANOMALOUS CORROSION TREND IN GAS TREATING MODULES

SYSTEM MODULE #1 MODULE #2 MODULE #3

Reboiler Top Head Concerns on all the four No Major Concerns. Concerns on two heads
(1997-98) Reboiler heads. from Reboilers, A&B.
Reboiler Outlet Piping Concerns on Outlet (O/L) No Major Concerns. Concerns on Outlet
(1997-98) Piping from all the four Piping from two
Reboilers. Reboilers, A&B.
Life cycle: ~ 16 years. Life cycle: ~ 16 years.
All the four O/L Piping Replaced Two O/L
replaced. Piping from A&B.
Reboiler Outlet Piping Different trend: No Major Concerns. Due for T&I in 1st
(2003) Quarter of 2004.
Reboiler A: 32 mpy
Reboiler B: 1.5 mpy
Reboiler C: 34 mpy
Reboiler D: 16 mpy

Replaced two O/L Piping

from A&C.
Lean DGA Piping Concerns led to failures. Concerns and failures. No major concerns on the
Header (1999) common header.
 To Feed Gas CompressionTo 3
F dG C i 2
Module 3
To Sulfur Plant
Module 2
1 To S Plant
Guard Filter E-103 D-
113F
10 Reflux Drum
Water from D-011 Precoat Filter 3
330# Cond. A
D-104
G-106A/B

DGA Contactor 250#,140F,7.5MGPM

DGA Stripper
G-104/404A/B
216F,3MGPM Flash Gas
Side Cooler to Utilities G-105A/B 375# Steam
E-106 170F C-101 C-102
E101A/B
220#,110F,480
Lean DGA Cooler
From Inlet Area Reclaimer

75# Steam
D 101
A/B Cond.
D-102
Re-boiler
80# G-101A/C
Circulation
Pumps Cond.
Filter Separator 3
2%
To Module 2
To Module 1

Figure 1 - LP GAS TREATING UNIT PROCESS FLOW DIAGRAM

 Figure 2 - Erosion/Corrosion

Figure 3 - Preferential Weld Attack