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Amine Unit Materials and Corrosion (Updated)
Amine Unit Materials and Corrosion (Updated)
Materials
Materials and
and Corrosion
Corrosion Issues
Issues In
In
Amine
Amine Plants
Plants (ADIP,
(ADIP, MDEA)
MDEA)
Sergio Kapusta
Shell Global Solutions International
Materials Engineering
Outline
Outline
z Degradation Mechanisms
Ö Corrosion
Ö Lean amine
Ö Rich amine
Ö NH4HS
Ö Heat stable salts
CO2 + H2O ←
→H2CO3
O O
R R R - + R
N C OH + H N N C O + H2N
R R R R
OH
OH H3C CH CH 2
O - O
H3C CH CH 2 - HO
NC N C
H 2C - DIPA-ox
O H 2C O
HO CH
CH
CH3
CH3
Shell Global Solutions
Reactions of ADIP with H2S
+
((CH3)2 COH )2 NH + H2S ←→ ((CH3)2COH)2NH2 + HS -
O O
|| ||
Glycolic Acid HO-CH2-COOH HO-C--C-OH Oxalic Acid
O O
|| ||
CH3-C-OH H-C-OH
10.8 12 71 17 0 0 153
11.1 0 53 11 0 0 133
7.5 0 59 13 0 0 10
234 1059 51 17 0 59
10.7 0 28 46 0 0 23
11.4 52 168 81 0 0 52
10.0 11 96 15 0 0 42
O O
|| ||
HO-CH2-CH2--NH2 + HO-CH2-COOH CH3-C-OH H-C-OH
O O O
|| || ||
NH3 + HO-CH2-COOH HO-C--C-OH H-C-OH
Glycolate Oxalate
14 12
12 10
No. of Samples
10
No. of Samples
8
8
6
6
4 4
2 2
0
0
0 50 100 150 200 300 500
0 30 100 300 600 900 1500 More
Oxalate, ppmw Glycolate
Exposed to Stress
Yes Lean Amine? No Relieved? Yes Not Susceptible
No
Not Susceptible
Exposed to
No Exposed to No
MEA or
DIPA? DEA?
Yes Yes
Temp Temp
Yes Yes
> 80°C? > 80°C?
High Medium
No Susceptibility No
Susceptibility
No No No
No No No
No No No
z Mechanism
z Material Susceptibility
z Preventative Measures
Ö Materials selection
Ö Precautions during shut-downs
z Vibration/fatigue
z Others
Steamed out? Determine whether the equipment/piping has been steamed out
(Yes or No) prior to water flushing to remove residual amine.
Stress Relieved? Determine whether the equipment/piping has been properly stress
(Yes or No) relieved after welding and cold forming.
Tail Gas to
Incinerator
FRC Carbon Bed c.w. LIC
lean/rich
exchangers
Solvent Purge
3
6 Treated Gas
3
FRC 3 FRC
FRC
5 5 3
5
Carbon
5
Beds
2
2
SW Purge
A
B Filters
S
S
O
4
T
R
5
solvent
1
R
1
B coolers I
2
E
P
R 50 psig
Feed P
E 4 Steam
LRC
R
4
c.w.
5
Vent Gas
4
Amine 2
1
Lean/rich
4
Flash/Skim exchangers
1
Drum
1
4
Hydrocarbon
KO drum
T2 to overhead
system
Ch1
feed
T1 T4
UT1
regenerator
UT2 T3
lean/rich amine exchangers
UT3
UT4
P1
H2S/CO2
T2
T1
regenerator
reflux drum
UT4 UT3
regenerator
reboiler
T1
UT3
P1
UT2
LP steam
T2
UT1 Ch1
lean amine to
lean/rich heat
exchanger
Shell Global Solutions
Corrosion Loop 4 = Lean Amine
treated gas
absorber amine
makeup
UT3
filter
regenerator
T3
lean UT2
amine
pump
lean reboiler
amine
cooler
T1
T2
Ch1 UT1
lean/rich amine exchangers
• Corrosion by lean amine in the reboiler shell, reboiler vapor return line,
lower part of the stripper column.
• Wet H2S cracking/HIC blistering in the upper part of the stripper
column.
• Amine SCC, especially in the hottest equipment
• Cl- SCC of stainless steel equipment if Cl- in amine exceeds 1000 ppm
• FeS fouling in the stripper column, reboiler, and lean/rich exchangers