Maintenance

and Reliability
J. DAUGHTRY and E. TELETZKE,
INEOS GAS/SPEC Technology Group, Freeport, Texas

Case histories of amine plant equipment

corrosion problems–Part 2
Past corrosion incidents provide insight into the causes of
corrosion and the preventive actions required to protect plant
equipment and reduce costly plant downtime. Part 1, which
was featured in the November issue of Hydrocarbon Process-
ing, provided three case studies that demonstrated how cor-
rosion in alkanolamine systems can be identified, minimized
and controlled with a multidisciplinary approach that takes
into account chemistry, engineering design, metallurgy and
computer simulations. Part 2 provides an in-depth analysis on
three additional case studies, and focuses on centrifugal pump
cavitation corrosion, stress and fatigue failure, and pump bear-
ing fouling and seizure.
CASE STUDY 4: CENTRIFUGAL PUMP
CAVITATION CORROSION
Problem. As a result of corrosion, a lean amine booster pump seal
failed just months after the startup of an amine system in Texas.
With cavitation suspected as a possible cause of the corrosion
and the subsequent failure, the pump design curve (FIG. 11) was
consulted to determine if the pump had been operating within
an acceptable range. Trend data collected from the plant control
room showed the pump had been operating with a flowrate of
620 gpm. Suction-side cavitation is commonly associated with
a drop in the available net positive suction head (NPSH) below
the required NPSH specified on the pump curve. In this case,
the available NPSH was above the 5 ft of NPSH required at the
620 gpm circulation rate. However, the pump data sheet speci-
fies a minimum circulation rate of 660 gpm for this pump.
The minimum circulation rate for centrifugal pumps is speci-
fied by the pump manufacturer to prevent vapor formation and

Background. A gas processing plant in the Eagle Ford Shale

play was designed to treat approximately 200 MMsft3d of nat-
ural gas with 2 mol% carbon dioxide (CO2 ). On startup, the
plant was running at reduced capacity, and was treating only
75 MMsft3d, with 0.7 mol% CO2. Consequently, the operators
decided to reduce the amine circulation rate in accordance with
the rich loading requirements.
Two months after starting up the amine system with fresh FIG. 9. Corrosion observed on the lean amine booster pump casing.11
amine, a centrifugal lean amine booster pump began to leak.
When the leak was noticed, operations took the pump out of
service for inspection. Upon inspection, corrosion was discov-
ered (FIGS. 9 and 10).

Observations. During a walkthrough of the plant, operators

noticed vibrations and a rattling noise emitted from an identical
pump on an identical train in the same facility. The sounds that
were emitted from the pump were consistent with the sounds of
pump cavitation. Cavitation occurs when vapor bubbles form
in the low-pressure areas surrounding the impeller of the pump.
The collapse of those bubbles creates the rattling sound charac-
teristic of cavitation, and is associated with pitting corrosion to
FIG. 10. Corrosion observed on the lean amine booster pump seal.11
the pump impeller and housing.12
Hydrocarbon Processing | DECEMBER 2017 71
 Maintenance and Reliability

vibrations, which can cause catastrophic pump failures. Main- Corrections. The following corrections were made:
taining flow above the minimum specified flowrate prevents re- 1. The amine flowrate was increased above 660 gpm,
circulation of the fluid in the pump, which can lead to bubble in both trains, in accordance with the minimum
formation and cavitation. Low liquid flowrates can also cause flowrate required by the pump data sheets.
cavitation if the temperature increase in the liquid across the 2. Equipment limitations, in addition to the chemistry
pump results in vaporization. Typically, the minimum circula- and loading limits of the amine, are now considered
tion rate for a given pump is 50% of the best efficiency point when adjusting the amine circulation rate and other
(BEP)—the operating point at which the pump is most effi- process variables.
cient.14 For this pump, the BEP is 1,270 gpm, more than double 3. In subsequent years of operation, no additional leaks
the 620 gpm flowrate at which the pump had been operating. or failures of the lean amine booster pumps have
The pump curve confirmed that operating below the mini- occurred at this facility.
mum flowrate was resulting in discharge cavitation corrosion.
Upon increasing the circulation rate of the pump above the 660 CASE HISTORY 5: BROKEN PUMP
gpm required by the pump design curve, the rattling sound in- SHAFT—STRESS AND FATIGUE FAILURE
dicative of pump cavitation ceased.
Problem. In 1985, a gas processing plant in Texas treating gas-
Conclusions. After the investigation was completed, the fol- eous-phase ethane and propane experienced an amine pump
lowing conclusions were drawn: failure. The multistage pump shaft experienced a clean and in-
1. The lean amine booster pump was operating below the stantaneous break. While the root cause analysis for the first
minimum flowrate specified on the pump design curve. pump failure was being conducted, a second pump shaft expe-
2. The resulting cavitation caused a pump failure rienced a clean and instantaneous break for an unknown reason.
two months after the pump was put into service.
Background. This facility was using a formulated methyldieth-
Data point 175 13 in. 65 70 anolamine (MDEA) solvent to treat an inlet ethane and propane
Flow: 1,270 US gpm 75
Head: 146 ft 78
78.6
gas stream from 10 mol% CO2 to a pipeline specification of less
Eff.: 79% 150
Power: 59.6 hp 56 pw ~133 ft 78
75
than 2 mol%. The feed to this facility included seven different
NPSHr: 9.74 ft
Design curve
125 70 pipelines with varying CO2 compositions. The amine circula-
Shutoff head:
Shutoff dP:
179 ft
77.5 psi 100 tion rate was fixed to handle the highest possible inlet CO2 com-
9 in.
Head, ft

Min. flow:
SEP:
660 US gpm
79% at 75 position of 10 mol%. Prior to the pump failures, a reduction had
NOL power:
1,270 US gpm
69.8 hp at
65 occurred in the inlet flowrate to the plant, and operations had
50
1,688 US gpm
Max. curve decided to reduce the amine circulation rate in accordance with
Max. power: 69.6 hp at 25 200 400 600 800 1,000 1,200 1,400 1,600 1,800 the rich loading requirements for the formulated MDEA solvent.
1,688 US gpm 15
10 The amine at this gas processing plant was on a routine ana-
5 lytical program, and the sample history was consulted to identify
0 any unusual trends that could be responsible for the pump fail-
200 400 600 800 1,000 1,200 1,400 1,600 1,800
ure. The amine analytical history did not show significant levels
FIG. 11. Pump data sheet for the centrifugal lean amine booster pump.13 of oxygen degradation products or any other contaminants that
would increase the corrosivity of the amine solution. The rich
and lean amine loadings were within the recommended range
for the formulated MDEA solvent.
An unusual light lavender color was observed in the transpar-
ent amine solution. A purple tint to the amine solution indicates
the presence of chromium (Cr), a component of 300 and 400
series stainless steel. The presence of Cr dissolved in the amine
solution suggested corrosion to stainless steel equipment in the
plant. Interestingly, the amine was analyzed for soluble metals
using inductively coupled plasma mass spectrometry (ICP-
MS). Less than 1 ppmw of dissolved Cr was detected. It was later
discovered that strips of denim blue jeans had been used in a
filter canister, and the indigo dye had leached into the amine,
resulting in the light lavender color.

Observation. With no corrosion risks discovered in the amine

chemistry, the focus turned to the pump operation and guide-
lines. Multistage pumps use multiple impellers and volutes in
series to achieve pressure. The pumped fluid is discharged from
an impeller and volute (called a stage) and immediately enters
the next impeller and volute. The amount of pressure devel-
FIG. 12. Stress failure on a pump shaft. Photo courtesy of Gates Corp.
oped in a multistage pump depends on the diameter of the im-
72 DECEMBER 2017 | HydrocarbonProcessing.com
 Maintenance and Reliability

pellers, the number of stages used and the speed at which the While the issues with the RO H2O system were being inves-
impellers are turning. The diameter of the impellers is usually tigated, the amine solvent began to form degradation products,
not trimmed to achieve the required conditions. resulting from oxygen (O2 ) contamination. These degradation
The appearance of the damaged or broken shaft can be used products—known as heat-stable amine salts (HSAS)—bind
to speculate the cause of failure. A clean break indicates an “in- with the amine in a reaction that cannot be reversed in the re-
stantaneous” fracture caused by sudden overload or imbalance generator. As these salts were formed, the concentration quickly
(FIG. 12). If the broken shaft is discolored (usually blue), the increased to 9 wt% in the amine solvent, with acetate, formate
damage was gradual, indicating excessive heat buildup before and oxalate accounting for most of the HSAS.
the shaft broke (FIG. 13). Six months after startup, a pump failed unexpectedly. The
The failure in FIG. 11 between where the shaft diameter changed operations team began investigating the cause of the failure.
is the exact location of the actual failure. With an instantaneous When the pump was taken apart, a solid, salt-like material was
pump shaft failure suspected, the next course of action was to de- found coating the bearing surface (FIG. 14). While the plant was
termine why the instantaneous break in the pump shaft occurred. shut down for inspection, similar deposits were found plug-
An instantaneous break indicates the pump shaft was overloaded ging 40% of the reboiler tubes. Samples of the solids from both
with unbalanced forces. Pumps are designed to be balanced when the pump and the reboiler were collected and were identified
operating within a safe range of their BEP. As the pump flowrate as calcium oxalate (C2CaO4 ). This event was the first instance
moves farther from the BEP, the pounds of unbalanced thrust on of fouling resulting from calcium oxide that operations had ob-
the pump increase. Further review of the pump operations re- served in any of the company’s plants.
vealed that the pump was operating at less than 50% of the BEP. The cause of the fouling and pump failure was two-fold.
First, the RO unit allowed Na, K and Ca salts to enter the amine
Conclusions. The following conclusions were observed: system. Second, the O2 contamination in the inlet natural gas
1. The clean break indicates an instantaneous fracture resulted in degradation of the amine solvent to form oxalate.
caused by a sudden overload or imbalance on the When strong base cations like Na, K and Ca are present in the
pump shafts that experienced failures. amine solution, they will replace the amine molecule in the
2. Operating the pumps too far from the BEP specified HSAS and form an inorganic heat-stable salt (IHSS). TABLE 2
for each pump resulted in unbalanced thrust being
applied to the pump shafts. TABLE 1. H2O quality standards for amine systems14
Property Specific values ASTM test method
Corrections. The following corrections were made:
1. The multi-stage pumps that experienced failures Total solids, ppmw 100 max. D1888
were replaced. Total hardness, ppmw 50 max. D1126
2. Flowrates were maintained within a safe operating Chloride (CL), ppmw 2 max. D512, D4327
range of the BEP for each pump. No additional pump
Sulfate (SO4 ), ppmw 3 max. D516, D4327
shaft failures have occurred since the operating range
was adjusted. Sodium (Na), ppmw 3 max. D516, D4327
Potassium (K), ppmw 3 max. D516, D4327
CASE HISTORY 6: PUMP BEARING FOULING Iron (Fe), ppmw 10 max. D516, D4327
AND SEIZURE—HARD WATER (H2O) DEPOSITS pH 7–7.7 D1293

Problem. As a result of hard H2O deposits, a pump bearing

seized a few months after being placed into service.

Background. In 2013, a plant was commissioned using an

amine solvent to remove CO2 and hydrogen sulfide (H2S) from
rich Eagle Ford Shale gas. The gas was dehydrated with trieth-
yhlene glycol (TEG) and a molecular sieve before being sent
to a cryogenic tower to separate the ethane and propane. The
inlet gas contained more than 25 ppmv of oxygen, which was
expected to degrade the amine.

Observations. Shortly after startup, the reverse osmosis (RO)

H2O treating system at this facility experienced problems
with meeting the required H2O quality standards for makeup
H2O in amine systems (TABLE 1). Analysis of the H2O quality
revealed that hardness—a measure of the calcium (Ca) and
magnesium salts in solution—exceeded the recommended 50-
ppmw threshold. Ca, along with sodium (Na) and potassium
(K), were observed increasing in the amine solution propor- FIG. 13. Fatigue failure on the pump shaft. Photo courtesy of Thomas
Davidson.
tionate to H2O usage.
Hydrocarbon Processing | DECEMBER 2017 73
 Maintenance and Reliability
FIG. 14. Bearing hard H2O deposits.
1,800
Ca
1,600 Na
Oxalate
1,400
1,200
Concentration, ppmw
1,000
800
600
400
200
0
1 2 3 4 5 6 7 8
Months after startup
FIG. 15. Cation and anion levels in solution.
lists the solubility limit of the salts formed, with C2CaO4 having
a much lower solubility than the K or sodium oxalate salts.
Analysis of the plant amine solvent showed a decrease in the
concentration of Ca and oxalate after approximately 6 mos of
operation. The speculation was that either a pH threshold or
solubility concentration was reached and resulted in accelerated
precipitation of C2CaO4 . FIG. 15 shows the levels of Ca, Na and
oxalate in solution in the months following startup of the plant.
A plant shutdown resulted from the pump failure. The amine
system was boiled out with hot H2O, which solubilized the
C2CaO4 solids. The amine was returned to the process and the
plant was restarted. Two months later, the solvent was replaced
with a formulated MDEA solvent to address the high levels of
contamination and to increase the capacity of the amine system.
Conclusions. The following conclusions were observed:
1. The pump failure and reboiler tube plugging were
caused by the precipitation of C2CaO4 salts.
2. An issue with the RO H2O system allowed alkaline earth
metals to enter the circulating amine solvent.
3. Additionally, 25 ppm of O2 contamination in the inlet
gas stream resulted in degradation of the amine solvent.
74 DECEMBER 2017 | HydrocarbonProcessing.com
TABLE 2. Alkaline metal oxalate solubility/hot H2O, °C
Potassium oxalate 33 grams/100 cc hot H2O at 16°C
Sodium oxalate 6.33 g/100 cc hot H2O at 96°C
C2CaO4 0.0014 g/100 cc hot H2O at 96°C
Corrections. The following corrections were made:
1. The RO unit was repaired during the plant’s turnaround
to provide H2O quality within the recommended
guidelines for amine systems.
2. O2 contamination will result in amine degradation
and corrosion. No corrosion problems due to O2
degradation products were observed in this case study.
If the system had been allowed to continue operating
with high levels of oxalate and other O2 degradation
products, corrosion would have likely occurred.
The industry-recommended standard for O2 is less
than 3 ppmv of the inlet gas stream to the amine unit.
Takeaways. The six case histories presented in Parts 1 and
2 demonstrate that corrosion in alkanolamine systems can be
identified, minimized and controlled with a multidisciplinary
approach. This approach takes into account chemistry, engi-
neering design, metallurgy and computer simulations. The real-
world examples of amine plant problems demonstrated seven
types of corrosion that have been observed in amine plants:
Pitting, erosion, galvanic, selective leaching, stress and fatigue
failure, cavitation and fouling.
Preventing corrosion begins in the design phase with the
selection of an amine solvent, equipment sizing and metal-
lurgy decisions. An emphasis must be placed on ensuring inlet
9 filtration and separation devices to protect the amine solution
against contamination from hydrocarbon, O2 and other pipeline
chemicals. During operations, the amine system must be oper-
ated within the loading and temperature ranges specified by the
amine supplier. All amine plants should conduct routine amine
analysis to identify potential corrosion risks before they result in
an equipment failure. Learning from past corrosion experiences
allows corrosion risks to be quickly diagnosed and resolved.
REFERENCES
Complete references are available online at HydrocarbonProcessing.com.
JAMES DAUGHTRY is a retired Regional Commercial Manager
in the GAS/SPEC Technology Group of INEOS. He has a wide
range of experience in gas processing, from corrosion inhibitor
research to process optimization of amine plants and amine
sales. Prior to joining INEOS GAS/SPEC in 2000, he worked
for Dow Chemical USA for 32 yr, specializing in epoxy
manufacturing, research, technical service and development.
While at Dow, he was a founding member of the GAS/SPEC Technology Group
in 1983. Mr. Daughtry has coauthored several papers on gas processing and one
paper on vinyl ester corrosion for the Society of the Plastics Industry. He holds
a BS degree in chemistry from the University of Houston in Clear Lake, Texas.
ERIC TELETZKE is a Territory Manager and Technical Service
Engineer with the INEOS GAS/SPEC Technology Group. He has
extensive experience with the design, operation and optimization
of amine systems in a range of applications, including natural gas
processing, LNG, refining, tail gas, acid gas enrichment, syngas,
ammonia and carbon capture. Mr. Teletzke graduated from the
University of Texas at Austin with a BS degree in chemical
engineering, and joined the INEOS GAS/SPEC Technology Group in 2011.