Shell Global Solutions

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

ÖStress corrosion cracking

z Other M&C Issues To Be Considered
z Resource Documents

Shell Global Solutions

Shell Global Solutions
Property DIPA MDEA
Formula (CH3CH(OH)CH2)2-NH CH-N(CH2CH2OH)2
Dissociation
Constant, Ka 8.9 8.5
Formula Weight 133.2 119.16
Density 1.004 1.038
Boiling point °C 270 248
Vapor pressure 20°C 0.002 mmHg
Freezing point, °C 48
Solubility in water Miscible Miscible
Viscosity, at 100 °C 6.5 cp

Shell Global Solutions

 Reaction of MDEA with H2S

(HOC 2 H 4 ) 2 NCH 3 + H 2 S ←→(HOC 2 H 4 ) 2 NCH 3 H + + HS -

Reaction of MDEA with CO2

CO2 + H2O ←
→H2CO3

(HOC 2H4 )2 NCH3 + H2CO 3 ←→ (HOC 2H4 )2 NCH3H+ + HCO 3−

Shell Global Solutions

Reactions of secondary amine (DIPA) with CO2
O O
R R
NH + C N C OH
R R
O
Secondary Amine Carbamic Acid

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 -

Shell Global Solutions

 Decomposition of DIPA
DIPA MIPA O
CH3-CH(OH)-CH2 ||

NH CH3-CH(OH)-CH2-NH2 + CH3-CH2-C-OH Propionic Acid

CH3-CH(OH)-CH2
O OH O
|| ||
Propionic Acid CH3-CH2-C-OH + NH3 CH3-CH-C-OH Lactic Acid

O O
|| ||
Glycolic Acid HO-CH2-COOH HO-C--C-OH Oxalic Acid

O O
|| ||
CH3-C-OH H-C-OH

Acetic Acid Formic Acid

Shell Global Solutions

 Distribution of DIPA decomposition products
pH FORMATE ACETA PROPRIONATE GLYCOLAT OXALATE LACTATE
TE

10.8 12 71 17 0 0 153

11.1 0 53 11 0 0 133

7.5 0 59 13 0 0 10

10.7 302 1413 12 0 0 92

234 1059 51 17 0 59

10.6 176 230 46 0 0 103

10.7 0 28 46 0 0 23

9.5 21 1528 100 0 0 40

11.4 52 168 81 0 0 52

10.0 11 96 15 0 0 42

Shell Global Solutions

Regeneration of DIPA

Shell Global Solutions

Regeneration of MDEA

Shell Global Solutions

 Decomposition of MDEA

MDEA DEA Formate

HO-CH2-CH2 HO-CH2-CH2 O
||
N--CH3
N-H + H-C-OH CO2 + H2O
HO-CH2-CH2
HO-CH2-CH2

O O
|| ||
HO-CH2-CH2--NH2 + HO-CH2-COOH CH3-C-OH H-C-OH

MEA Glycolate Acetate

CO2 + H2O

O O O
|| || ||
NH3 + HO-CH2-COOH HO-C--C-OH H-C-OH
Glycolate Oxalate

Shell Global Solutions

 MDEA degradation products
14 16
12 14
10 12
8
10
8
6 6
4 4
2 2
0 0
50 500 1000 1500 2000 2500 3000 0 50 250 500 1000 2000 2500 3000
Formate, ppmw Acetate, ppmw

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

Shell Global Solutions

Corrosion modes
z The pure, lean amines are not corrosive
Ö pH > 10
z Corrosivity depends on acid gas loading
Ö pH < 8.5
Ö H2S loading > 0.3 to 0.4 m/m
Ö Velocity > 1.5 m/s in MDEA, 1 m/s in DIPA
Ö Temperature > 100 oC
z Lean amine corrosion depends on
Ö Stripping
Ö HSAS (> 2 %)
R 2NH + CH3 Ac 
→ R 2NCH3 + HAc
+
(R 2NH CH 3 ) 2 Cl 
→ 2R 2NCH3 + HCl

Shell Global Solutions

Stress corrosion cracking

z Sulphide Stress Corrosion Cracking (SSCC)

z Hydrogen Induced Cracking (HIC)
z Amine Stress Corrosion Cracking (ASCC)
z Chloride Stress Corrosion Cracking (ClSCC)

Shell Global Solutions

Amine SCC

z High and low temperatures (> 60 oC limit not valid)

z Pure amines do not cause ASCC
z Susceptibility MEA > DEA > DIPA, MDEA
z H2S protects against ASCC, CO2 promotes ASCC
z More prevalent in lean amine
z PWHT prevents ASCC
z Care during shut-downs (steaming)

Shell Global Solutions

D e te r m in a tio n o f S u s c e p tib ility to
A m in e C r a c k in g
Start

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

Temp 37- Temp 60- Yes Yes Temp

Yes
80°C? 80°C? > 80°C?

No No No

Heat traced? Yes Heat traced? Yes Yes Heat traced?

No No No

Steamed out? Yes Steamed out? Yes Yes Steamed out?

No No No

Low Medium Not Low Not

17
Susceptibility Susceptibility Shell Global Solutions
Susceptible Susceptibility Susceptible
Hydrogen induced cracking (HIC)

Shell Global Solutions

Chloride
Chloride SCC
SCC

z Mechanism
z Material Susceptibility
z Preventative Measures
Ö Materials selection
Ö Precautions during shut-downs

Shell Global Solutions

Materials selection & corrosion control
z PWHT’d Carbon steel to 100 oC, velocity < 1.5 m/s
z 12 Cr can be used for trays but not for piping
z 321 SS for lean/rich heat exchanger, velocity < 3 m/s
z Prevent flashing of gas in the heat exchanger and piping
z Reboiler tubes should be fully immersed
z Reboiler steam temperature below 160 oC
z Pressure let down valve 316 SS
z Prevent oxygen entry
z Maintain clean solvent

Shell Global Solutions

Solvent hygiene

z Chlorides below 1000 (5000?)ppmw

z Heat stable salts below 2 %
z Amine derivatives below 3 %
z Filter solids out

Shell Global Solutions

Non Process Related Corrosion

z Chloride SCC (Can be both!!)

z Corrosion under Insulation

z Vibration/fatigue

z Others

Shell Global Solutions

Shell Global Solutions
 Basic Data Comments
Material of Construction Determine the material of construction of equipment/piping.
(CS or SS)
Amine Concentration (wt%) Determine the amine concentration in the equipment/piping. Due
to vaporization of water, a local increase in amine concentration
may need to be considered in evaluating the corrosion of some
reboilers and reclaimers.
Maximum Process Temperature Determine the maximum process temperature. In reboilers and
(°C) reclaimers, tube metal temperatures may be higher than the bulk
process temperature.
Acid Gas Loading Determine the acid gas loading in the amine. If analytical results
are not available, it should be estimated by a knowledgeable
(mole acid gas/mole active amine)
process engineer.
Velocity (m/s) Determine the maximum velocity of the amine in this
equipment/piping.
Heat Stable Amine Salt (HSAS)
Concentration:
MEA and DEA In MEA and DEA, “HSAS” represents the normal family of
amine degradation products
(= 2 wt%, 2-4 wt%, > 4 wt%)
MDEA In MDEA “HSAS” refers to organic acid contaminants, mainly
formate, oxalate, and acetate
(< 500, 500-4000, > 4000,
wpmm)

Shell Global Solutions

 Corrosion rates in MDEA
Corrosion Rate (mm/year)
Acid Temperature (°C)
Gas < 88 88-99 99-110 110-121 121-132 > 132
Loading HSAS Velocity (m/s)
(mol/mol) (wt%) ≤ > ≤ > ≤ > ≤ > ≤ > ≤ >
6.1 6.1 6.1 6.1 6.1 6.1 6.1 6.1 6.1 6.1 6.1 6.1
< 0.1 = 0.5 0.03 0.08 0.03 0.08 0.08 0.25 0.13 0.38 0.25 0.64 0.38 1.02
0.51-4.0 0.05 0.15 0.05 0.15 0.15 0.51 0.38 1.02 0.51 1.14 0.76 2.03
> 4.0 0.13 0.25 0.13 0.38 0.38 1.02 0.76 1.52 1.02 2.29 1.52 3.05
Velocity (m/s)
≤ > 1.5 ≤ > 1.5 ≤ > 1.5 ≤ > 1.5 ≤ > 1.5 ≤ > 1.5
1.5 1.5 1.5 1.5 1.5 1.5
0.1-0.2 = 0.5 0.03 0.08 0.05 0.15 0.13 0.38 0.25 0.76 0.38 1.14 0.51 1.52
0.51-4.0 0.05 0.15 0.10 0.30 0.25 0.76 0.51 1.52 0.76 2.29 1.02 2.03
> 4.0 0.13 0.38 0.20 0.64 0.51 1.52 1.02 2.03 1.52 3.05 3.05 3.81

Shell Global Solutions

Stainless steel corrosion rates
Acid Gas Loading Temperature (°C)
(mol/mol) ≤ 149

< 0.1 0.03

0.1-0.2 0.03
0.21-0.3 0.03
0.31-0.4 0.05
0.41-0.5 0.05
0.51-0.6 0.08
0.61-0.7 0.1
> 0.7 0.13

Shell Global Solutions

 Amine SCC Basic Data for Susceptibility
Basic Data Comments
Type of Amine Determine what type of amine is being handled in this
equipment/piping.
Amine Solution Composition Determine what amine solution composition is being handled in this
equipment/piping. Fresh amine has not been exposed to H2S or CO2.
Lean amine contains low levels of H2S or CO2. Rich amine contains
high levels of H2S or CO2. For equipment exposed to both lean and
rich amine solutions (i.e., amine contractors and regenerators), indicate
lean.
aximum Process Temperature (°C) Determine the maximum process temperature in this equipment/piping.
Heat traced? Determine whether the equipment/piping is steam-traced or
(Yes or No) electric-traced (e.g., for freeze protection).

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.

Shell Global Solutions

 Typical amine process
H2S to
Claus

Tail Gas to
Incinerator
FRC Carbon Bed c.w. LIC

A Filters S S.W. Purge

B T
S R
O I
R P
B solvent
E
c.w. coolers
E R
Feed Gas from
R
Quench Col. Steam
LRC

lean/rich
exchangers

Solvent Purge

Shell Global Solutions

 Claus

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

Shell Global Solutions

Corrosion Loop 1 = Rich Amine
treated product

KO drum
T2 to overhead
system

absorber from overhead

lean solvent system
UT5

Ch1
feed
T1 T4
UT1

regenerator
UT2 T3
lean/rich amine exchangers

UT3
UT4

P1

Shell Global Solutions

 Corrosion loop 1

• Wet H2S cracking/HIC blistering

• Rich amine corrosion due to erosion, gas flashing, turbulence, high
solids loading, especially downstream of the pressure letdown valve
• Chloride SCC of stainless steel
• Corrosion due to H2S/CO2 in cooled areas where water vapor might
condense, especially in the flash/skim drum vapor phase space where
the benefits of high pH amine are not realized.
• Fatigue to vibration around the pressure letdown valve
• Fouling by iron sulfide and coke fines in the flash/skim drum
• Fouling in the lean/rich exchanger bundles by FeS deposits

Shell Global Solutions

Corrosion Loop 2: Regenerator overhead
regenerator
condensor

UT1 UT2 UT5

H2S/CO2
T2
T1

regenerator
reflux drum

rich solvent P1 Ch1

UT4 UT3

regenerator

Shell Global Solutions

Corrosion loop 2

• Wet CO2 corrosion - predominantly in the overhead vapor line and in

the condensers (at dew point). Corrosion in the condenser outlet
piping. reflux drum and reflux piping is further reduced because the
carbonic acid concentration is diluted by condensation of large
quantities of water.
• Wet H2S cracking/HIC blistering - all
• NH4HS corrosion - if ammonia is allowed to build up in the overhead
system, NH4HS corrosion will occur in the condenser outlets and outlet
piping as well as in turbulent zones in the reflux drum, e.g. near control
valves, check valves, pumps, etc.

Shell Global Solutions

Corrosion Loop 3 = Regenerator Reboiler
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

Shell Global Solutions

Corrosion loop 4

• 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

Shell Global Solutions