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
= 0.4-0.5
1 mM Fe
+3
CO
2
H
2
O
(O
2
)
30% MEA
= 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 90-150C
Compression to 150 bar
Lean P
CO2
= 0.5 kPa at 40C
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
amines2
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.