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Degradation of amines

in CO
2
Capture
Gary T. Rochelle, Stephanie Freeman, Alex Voice,
Fred Closmann
Luminant Carbon Management Program
The University of Texas at Austin
Presented at
TCCS-6
June, 2011
Messages
• Stripper energy use is constrained by the max
T permitted by thermal degradation
– T
MEA
< T
MDEA
<T
AMP
< T
PZ
• As amines become more resistant, oxidation
shifts from the absorber to the heat exchanger
– MEA > Tertiary > Piperazine
• Amine degradation must be minimized to
manage secondary environmental impact.
– Volatile Products can leave with flue gas
– Nonvolatile products make up reclaimer waste
Where is degradation most likely to occur?
Flue Gas
10% CO
2
5-10% O
2
Purified Gas
1% CO
2
30% MEA
α = 0.4-0.5
1 mM Fe
+3
CO
2
H
2
O
(O
2
)
30% MEA
α = 0.3-0.4
Reboiler
Absorber
40 -70
o
C
1 atm
Stripper
120
o
C
1 atm
Cross
Exchanger
Oxidative
Degradation
Thermal Degradation
Thermal Degradation
180
240
300
360
5 10 15 20 25 30 35
W
t
o
t
a
l
(
k
W
h
/
t
o
n
n
e

C
O
2
)
(∆H
CO2
-∆H
H20
)∆(1/T) (kJ/gmol-K)
∆H
CO2
=60 kJ/mole
70
80
Thermal Degradation limits stripper
performance because
Greater T
strip
& ∆H
CO2
reduce W
eq
MEA 120 C
PZ
Single stage flash at 90-150°C
Compression to 150 bar
Lean P
CO2
= 0.5 kPa at 40°C
90 C
150 C
5 Mechanisms for Thermal Degradation
• 1. Carbamate Polymerization - MEA
• 2. Cyclic Urea - Ethylenediamine
• 3. Arm Switching/Elimination - Tertiary Amine
• 4. SN2 Ring Opening – Piperazine
• 5. Blend Synergism – Piperazine/MEA
Carbamate Polymerization
• ↔
MEA Carbamate Oxazolidone

MEA HEEDA
NH
O H CO
2
-
NH
O
O
+ O
-
H
NH
O
O
O H
NH
2
+
O H
NH
NH
2 +
O
O
Primary & Secondary Alkanolamines Deg T
Amine k
1
= 2.91 × 10
-8
s
-1
Structure
T (
o
C)
2-methyl-aminoethanol 103
Monoethanolamine 120
3-amino-propanol 126
2-piperidine ethanol 127
Diglycolamine
®
133
2-methyl-2-amino-propanol 137
Cyclic urea
N H
2
NH
2
+
O
O
O
NH
N H
1
o
& 2
o
Diamines = cyclic ureas Deg T
Amine Structure T (
o
C)
Dimethylethylenediamine 100
Diethylenetriamine 105
Methylaminopropanolamine 114
Hydroxyethylethylenediamine 114
Ethylenediamine 121
Hexamethylenediamine 156
C H
3
NH
NH
CH
3
2 Tertiary ↔ Quaternary + Secondary
+
CH
3
O H
N
OH
CH
3
O H
NH
+
OH
+
O H
NH
OH
C H
3
CH
3
O H
N
+
OH
Tertiary
1
+ Secondary
2
↔ Tertiary
2
+ Secondary
1
Tertiary
1
+ Quaternary
2
↔ Tertiary
2
+ Quaternary
1
Elimination
C H
3
CH
3
O H
N
+
OH +
+
CH
3
CH
3
O H
NH
+
O H
OH
O H
2
3
o
amines→2
o
amines + other 3
o
amines
Amine Structure T (
o
C)
Dimethylmonoethanolamine 122
Tetramethylethylenediamine 125
Methyldiethanolamine 128
N-(2-Hydroxyethyl)PZ 132
N,N’-Dimethylpiperazine 139
1-methyl-piperazine 148
C H
3
N N CH
3
C H
3
CH
3
N
CH
3
CH
3
N
Ring Opening
N H NH
2
+
NH
N H
N NH
3
+
N H NH
+
N H
2
O
OH
N H O
+
O H
2
Ring Closing
Cyclic ↔ Linear
Amine Structure T (
o
C)
Diglycolamine
®
133
Homopiperazine
133
Pyrrolidine
135
2-Methyl-Piperazine
152
Hexamethylenediamine
156
Piperazine
162
Morpholine
169
CH
3
NH
NH
N H NH
Interactive Blends
• Carbamate Polymerization
NH N H
NH
O
O
+
N
N H
NH
O H
O
+
+
O H
NH
2
+
OH
NH N H
NH
+
O H OH
N N H
Secondary
2
+ Tertiary
1
↔ Tertiary
2
+ Secondary
1
Total Amine Loss in Blends
Amine (m) Structure T (
o
C)
MEA/PZ
104
MEA/AMP
123
4 AMP/6 PZ
135
7 MDEA/2 PZ
138
4 PZ/4 2MPZ
155
3.9 PZ/3.9 1MPZ/
0.2 14DMPZ
160
Oxidation
O
2
solubility & Mass Transfer
0,E+0
2,E-5
4,E-5
6,E-5
2,E-04 2,E-03 2,E-02
A
m
i
n
e

O
x
i
d
a
t
i
o
n

(
m
o
l
/
m
o
l
C
O
2
)
Oxygen Rate Constant (s
-1
)
Total
Absorber
Exchanger
Sump
PZ
MEA
MDEA
Degradation Products and
Environmental Impact
7 m MDEA/2 m PZ Oxidized at 120
o
C
Products (CO
2
carrying)
C-Loss
(%)
Diethanolamine/Methylaminoethanol 40
1-methyl PZ 8.4
1,4-Dimethyl PZ 0.9
Aminoethyl PZ 3.5
N-formyl PZ (amide) 8.3
Formate & other acids 2.5
Bicine 5.3
Hydroxyethyl sarcosine 10.5
~79.5
Message on Thermal Degradation
• Stripper energy is constrained by the max T
permitted by Degradation
–Linear alkanolamines and diamines degrade
by polymerization & urea formation at 100-
130
o
C
–Tertiary amines degrade by arm switching &
elimination at 120-140
o
C
–Piperazine and related cyclic amines degrade
by ring opening at 150-165
o
C.

Message on Oxidation
• As amines become more resistant, oxidation
shifts from the absorber to the heat exchanger
–MEA & alkanolamines readily oxidize in the
absorber unless inhibited by radical or
peroxide scavengers
–Tertiary amines inhibit self oxidation,
probably by scavenging peroxides
–Piperazine oxidizes only at the higher T of
the heat exchanger exit
Message on Environmental Impact
• Amine degradation must be minimized to
manage secondary environmental impact.
–Volatile Products can leave with flue gas
• Aldehydes, formate, ammonia, volatile amines,
amides
–Nonvolatile products make up reclaimer
waste
• Polyamines, Cyclic urea, amino acids
A review of previous Work
• University of Texas
– Thermal: Austgen, Freeman, Closmann
– Oxidation: Goff, Sexton, Voice
• IFP – Thermal, Oxidation
– Lepaumier, Carrette, et al.
• NTNU – Thermal, oxidation
– Lepaumier, Eide-Haugm, et al.