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com

Thermal degradation of amines for CO2 capture

Gary T Rochelle
Amine scrubbing will be an important technology for CO2
capture and storage. The degradation of the amine at 100
150 8C limits the maximum T/P and therefore the energy
performance of the solvent regeneration. This is a review of the
rate, products, and mechanisms of thermal degradation.
Primary and secondary ethanolamines and ethylenediamines
degrade at 100130 8C as they form cyclic oxazolidinones and
ureas. Tertiary amines can be more resistant to degradation if
they do not include methyl and ethanol groups. Piperazine
structures and long chain diamines such as
hexamethylenediamine degrade by ring opening and closing
and can be used at 150160 8C. Thermal degradation can
produce products that are more volatile than the parent
amines.
Address
Luminant Carbon Management Program, Department of Chemical
Engineering, The University of Texas at Austin, 1 University Station,
C0400, Austin, TX 78712, United States
Corresponding author: Rochelle, Gary T (gtr@che.utexas.edu)

Current Opinion in Chemical Engineering 2012, 1:183190

This review comes from a themed issue on
Separation engineering
Edited by W.S. Winston Ho and K. Li

2211-3398/$ see front matter

# 2012 Elsevier Ltd. All rights reserved.
DOI 10.1016/j.coche.2012.02.004

Introduction
Amine scrubbing with thermal regeneration will be an
important technology for CO2 capture from fossil fuel
combustion to manage global climate change [1]. In this
process (Figure 1), CO2 is absorbed in a countercurrent
contactor at 4070 8C. The solvent is heated to 100
150 8C and stripped with steam to produce pure CO2.
For geologic storage the CO2 is further compressed to
150 bar.
To minimize energy consumption, the amine solvent
should have a large operating CO2 capacity, fast CO2
absorption kinetics, and a high heat of CO2 absorption
[2]. If the amine is resistant to thermal degradation, the
stripper can be operated at greater temperature and
pressure to further reduce compression work and capital
costs. Excessive thermal degradation must be avoided to
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minimize the economic loss of amine and the environmental impact of the degradation products.
In CO2 capture from coal-fired power plants by amine
absorption/stripping, amine losses can occur by five
mechanisms [3]. Nonionic amines with a finite vapor
pressure can vaporize into the flue gas. Flue gas typically
contains 35% oxygen that can oxidize the amine in the
absorber packing or absorber sump at 4070 8C or at 100
145 8C in the hot solution leaving the crossexchanger.
Oxygen is rapidly removed at the top of the stripper and
should not cause oxidation there. Thermal degradation
occurs at the greatest rate at 120150 8C in the liquid
hold-up of the stripper sump and reboiler.
This paper will review work published from 2009 to 2011
on the thermal degradation of amines in this process. A
previous review of this topic was prepared in 2001 [4].

Thermal degradation limits the maximum T/P

and therefore the energy performance of the
stripper
Thermal degradation of amines is easily managed by
reducing the temperature and liquid holdup at the stripper bottom. However, greater heat of CO2 absorption and
greater stripper temperature reduce the overall energy
requirement of the stripper [2,5]. A condition of higher
stripper temperature (T) and pressure (P) is energetically
preferred because thermal compression is more efficient
than mechanical compression. Greater stripper pressure
will also reduce the size and capital cost of the stripper
and compressor. Increasing the temperature of a single
stage heated flash from 90 to 150 8C reduced the equivalent work required by as much as 30% [2]. This equivalent work (Weq) includes reboiler heat duty (Qi),
compression work (Wcomps) and pump work (Wpumps)
and depends upon the reboiler temperature (Ti) and
the ambient temperature (Tsink).


nX
reboilers
T i 5K  T sink
W eq
0:75  Qi
W pum ps
T i 5K
i1
W com ps
Therefore the maximum and optimum operating
temperature of the amine regenerator is determined by
thermal degradation. It should be expected that stripper
systems will be optimized to the temperature at which
thermal degradation affects economic makeup of the
amine and environmental impact of the degradation
products. Davis [6] estimated that the optimum
temperature for 7 m monoethanolamine (MEA) should
Current Opinion in Chemical Engineering 2012, 1:183190

184 Separation engineering

Figure 1

Amine
volatility

Oxidation
dissolved oxygen
solubility
lean amine
CO2

Flue Gas Out

Oxidation oxygen
mass transfer

100 150 C
1 10 atm

Heat X

ABS

STR

40 65 C

Flue Gas In
~5 % O2

Reb

12 % CO2
rich amine

Oxidation kinetics

Thermal
degradation
Current Opinion in Chemical Engineering

Amine losses in the CO2 capture process [3].

be about 132 8C with an operating pressure of 3 bar.

However, most MEA systems have been designed with
a maximum temperature of 120 8C. The maximum
temperature of the stripper could be further reduced
by innovative equipment design that minimizes liquid
hold-up at the high temperature in the bottom of the
stripper.

Four mechanisms of thermal degradation are evident

Table 1 gives selected results from the literature on the

thermal degradation of amine solvents loaded with CO2.
Freeman [7] has interpreted the literature measurement
to report the temperature where the apparent first order
rate constant for the degradation of total amine is
2.9e8 s1. This rate is approximately that of MEA at
120 8C. It is known that MEA has been commercially
used at 120 8C with a tolerable level of thermal degradation. If rate measurements at multiple temperatures are
available, the Arrhenius expression was used to interpolate or extrapolate the data. If the measurement is
available only at one temperature the rate was extrapolated using the activation energy for the degradation of
MEA (157 kJ/mol) or piperazine (PZ) (184 kJ/mol). Most
Current Opinion in Chemical Engineering 2012, 1:183190

of the measurements in Table 1 were made at greater

CO2 loading (0.30.5 mol/equiv. amine).

Principal authors working on thermal

degradation
Most of the measurements reported in Table 1 were
made by Davis, Lepaumier, Freeman and Eide-Haugmo.
Davis (University of Texas at Austin [6,8]) degraded 18
amines in 10 ml cylinders placed in convection ovens at
100150 8C for 116 weeks. He analyzed samples primarily by cation chromatography with and without mass
spectrometry. His primary focus and contribution was a
comprehensive study of MEA. He also studied a number
of MEA analogs, MEA blends with other amines, and a
few other amines. Most of his screening studies degraded
amines at 7 m alkalinity with 0.4 mol CO2/equiv. N for 4
weeks at 135 8C.
Freeman (2011) [7,9] continued to use the methods of
Davis at 100175 8C with a primary focus on PZ. She
added the use of anion chromatography, HPLC, acid
titration for total alkalinity, and acid evolution for total
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Thermal degradation of amines for CO2 capture Rochelle 185

Table 1
Degradation temperature giving k1 = 2.9  10S8 sS1 of selected amines.
Abbrev

Amine

Structure(s)

Stripper T (8C)

Ref.

Diamines that degrade to cyclic ureas

N,N0 -Dimethylethylenediamine

N,N0 -diMEDA

104

[11]

Diethylenetriamine

DETA

108, 118

[6,15]

N-(2-Hydroxyethyl)ethylenediamine

HEEDA

114

[15]

3-(Methylamino)propylamine

MAPA

114

[6,11]

Ethylenediamine

EDA

117128

[7,15,23]

Alkanolamines that degrade through an oxazolidinone

Diethanolamine
DEA

103, 105

[11,15]

N-Methylethanolamine

MAE

102, 105

[6,11,14]

2-Piperidinemethanol

2-PM

109

[6]

Monoethanolamine

MEA

111125

[6]

2-Piperidineethanol

2-PE

127

[7]

3-Amino-1-propanol

3a1p

126,127

[6,15]

2-Amino-2-methyl-1-propanol

AMP

123, 137, 140

[6,11,15]

Tertiary amines that degrade by elimination and transalkylation

N,N-Dimethylethylenediamine
N,N-diMEDA

115

[11]

N,N-Dimethylethanolamine

DMAE

118

[11]

N-(2-Aminoethyl)piperazine

AEP

121

[6]

N,N-Dimethylethanolamine

DMMEA

122

[15]

N-Methyldiethanolamine

MDEA

119129

[3,6,11,15,22]

N-(2-Hydroxyethyl)piperazine

HEP

130

[6]

1-Methylpiperazine

1-MPZ

150

[7]

132

[6]

Amines that degrade by ring opening and closing

Diglycolamine1
DGA
2-Methylpiperazine

2-MPZ

151

[7]

Hexamethylenediamine

HMDA

160

[7]

Piperazine

PZ

162

[7]

104

[6]

Amine blends, degradation rate of total amine

Monoethanolamine/piperazine
MEA/PZ

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186 Separation engineering

Table 1 (Continued )
Abbrev

Amine

Structure(s)

Stripper T (8C)

Ref.

Monoethanolamine/DGA1

MEA/DGA1

112

[6]

N-Methyldiethanolamine/PZ

MDEA/PZ

120, 143

[3]

Monoethanolamine/AMP

MEA/AMP

123

[6]

Piperazine/AMP

PZ/AMP

134

[7]

Piperazine/1,4-dimethylpiperazine/1-MPZ PZ/1,4-DMPZ/1-MPZ

156160

[7]

Piperazine/2-methylpiperazine

155

[7]

PZ/2-MPZ

CO2. She also measured degradation of PZ analogs and a

few additional amines.
Lepaumier [10,11,12] degraded 17 amines with 4 mol
amine/kg in 100 ml batch reactors at 135 8C for 15 days.
She conducted experiments with and without CO2 and
oxygen. Table 1 includes her results with CO2 and without oxygen. Lepaumier analyzed her samples primarily
by gas chromatography with mass spectrometry. As a
postdoc, Lepaumier also conducted thorough studies of
MEA [13] and methylaminoethanol (MAE) [14] degradation.
Eide-Haugmo (NTNU) [15,16] adapted the methods
of Lepaumier and Davis including the use of LCMS and
GCMS. She measured 33 amines, primarily at 135 8C for
5 weeks without CO2 and with 0.5 mol CO2/mol amine.
She reports results on 11 amines in one paper and gives
results for 22 additional amines in her dissertation.

Cyclic urea is rapidly produced from

ethanediamines or propanediamines
Diamine structures where two secondary or primary Ns
are separated by two or three carbons readily degrade at
lower T in the presence of CO2 to produce cyclic ureas
(imidazolidinone), such as the production of hydroxyethylimidazolidinone (HEI) from hydroxyethylethylenediamine (HEEDA):

HO

NH

NH2 + CO2
HO

Current Opinion in Chemical Engineering 2012, 1:183190

This reaction is reversible, especially at greater temperature [7] (S Freeman, GT Rochelle, Thermal degradation
of aqueous piperazine for CO2 capture: 2: Product types and
generation rates, IECR, unpublished data). However, the
equilibrium concentration of the cyclic urea is substantial
and represents an unacceptable loss of active amine.
Structures containing secondary N degrade to the urea at
lower T (methylaminopropanolamine (MAPA), dietheylenetriamine (DETA), HEEDA).
It is possible that the cyclic ureas act as intermediates in
further oligomerization with the production of ammonia
and other fragments. For example, HEEDA may react with
HEI to produce ammonia and hydroxyethyldiethylenetriamine.
Simple ureas are also produced reversibly from amines
that are resistant to other degradation mechanisms. Diglycolamine1 (DGA1) is known to produce the urea, which
can be reversibly decomposed by reclaiming at elevated
temperature with low CO2 loading [17]. It is possible this
urea is an intermediate in the thermal degradation of
DGA to produce morpholine.

Carbamate polymerization
Primary and secondary alkanolamines with two or three
carbons between the N and oxygen degrade by reversibly

NH + H2O
O

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Thermal degradation of amines for CO2 capture Rochelle 187

forming a cyclic oxazolidinone from the carbamate, which

then reacts with another amine to form a dimer of the
starting amine [6,8,18].

O
HO

NH2

NH

HO

NH

SN2 reactions are catalyzed by CO2 or acid loading to

protonate the tertiary amine [3,11,20]. Bedell [21]
shows that addition of a quaternary amine catalyzes this

NH2

Because the equilibrium concentration of the oxazolidinone will be greater, greater CO2 loading accelerates
carbamate polymerization. Table 1 shows that secondary
amines degrade most readily (diethanolamine (DEA),
105 8C; MAE, 102 8C). Even the hindered alkanolamines
are not resistant to this mechanism. Both aminomethylpropanol (AMP) (126 8C) and 2-PE degrade (127 8C) with
the production of the expected dimer. The severely
hindered N-tertbutylethanolamine still degrades about
half as fast as AMP [15]. If the alkanolamine has more
than 3 carbons between the alcohol and the amine, it will
degrade by another, usually more resistant, mechanism.
DGA (with 5 atoms between the amine and the alcohol)
degrades at 132 8C.

CO2

process. Tertiary amines react even more readily with a

quaternary amine.

HO

HO

N
H3C

NH

OH + HO

HO

OH + HO

H3C

+
OH H2O

Lepaumier [14] conducted a similar study with MAE,

which degrades much faster, but produces similar types of
products by a comparable mechanism.

Tertiary amines degrade by transalkylation

and elimination
Tertiary amines appear to degrade by two mechanisms.
All of the tertiary amines participate in transalkylation,
especially in the presence of secondary Ns in the parent
molecule or from other degradation mechanisms. These

NH

OH

OH

Elimination from the quatenary amine will result in the net

production of the secondary amine. Elimination may be
faster with ethyl alcohol or ethyl amine attached to the
tertiary N.

CH3

Davis [6] developed a rate model for MEA with six

reactions and completed a material balance for reactions
at 100150 8C. He found that the apparent activation
energy of the individual rate steps is about 138 kJ/mol.
Lepaumier [13] and Strazisar [19] identified degradation
products found in a flue gas treating unit. The initial
product is HEEDA which rapidly degrades to produce
the cyclic urea, HEIA. These dimers react by the same
mechanisms to produce the cyclic urea of the trimer, 1-[2[(2-hydroxyethyl)amino]ethyl]-2-imidazolidone and other oligomers such as N-(2-hydroxyethyl)triethylenetetramine, and the corresponding cyclic urea, 1-[2-[2-[(2hydroxyethyl)amino]ethyl]amino)ethyl]-2-imidazolidone.

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CH3

CH3

CH3
+

CH3

HO

NH CH3 +

HO

OH

Methyldiethanolamine (MDEA) thermally degrades to

DEA, dimethylmonoethanolamine (DMMEA), MAE,
and other related molecules [3]. Since secondary alkanolamines are produced, further degradation occurs by
carbamate polymerization. Table 1 shows that tertiary
amines with ethyl amino or ethyl alcohol arms such as
MDEA degrade at lower T.
Since the degradation rate of tertiary amines is proportional to the CO2 loading there can be wide variations
of the reported rate with CO2 loading. It is also possible to
strip tertiary amines to very low CO2 loading if there is no
primary or secondary amine promoter.
A BASF patent application reports degradation rate for six
simple substituted tertiary amines saturated with CO2
and H2O at 162 8C and 6.3 bar for 300 hours [22]. These
conditions would provide exceptionally low CO2 loading.
The two tertiary amines including both methyl groups
and ethanol groups had 6% (MDEA) and 4% degradation
(dimethylethanolamine). The four other tertiary amines
had 1% (or less) degradation (3-dimethylamine-1-propanol, N,N-diethylethanolamine, N-ethyldiethanolamine,
and 3-diethylaminopropanol). The results from EideHaugmo confirm this effect with 0.5 mol CO2/mol amine,
Current Opinion in Chemical Engineering 2012, 1:183190

188 Separation engineering

the degradation rate at 135 8C for MDEA and DMMEA

(dimethylethanolamine) is 23 times faster than that for
diethylethanolamine and triethanolamine [15]. This
would suggest that the methyl group on a tertiary nitrogen
with an ethanol group is more subject to transalkylation
and/or elimination.

PZ disappears at about one mole for every mole of MDEA

that degrades [3].

Lepaumier [12] shows that tertiary diamines can also

participate in ring closing and other more complicated
reactions.

HN

Piperazines and long chain diamines degrade

by ring closing or opening
Freeman [7] (S Freeman, GT Rochelle, Thermal degradation of aqueous piperazine for CO2 capture: 2: Product
types and generation rates, IECR, unpublished data)
established that PZ degrades by ring opening catalyzed
by protonation in loaded CO2 solutions or in solutions
with added acid. The initial product, aminoethylaminoethylpiperazine (AEAEPZ) is subject to further degradation by cyclic urea formation. The cyclic urea reacts
with PZ to produce oligomers and fragments such as
ethylenediamine (EDA) and ammonia. The most stable
final product is aminoethylpiperazine (AEP).

H
H

HN

NH

NH

N
HN

NH

AEAEPZ

Hexamethylenediamine (HMDA) is resistant to degradation and degrades by ring closing to make piperidine
and ammonia [7,15].

Blends with alkanolamines degrade faster

than either amine
Blends of MEA with other amines always degrade faster
than either amine. The blend of MEA with PZ
degrades at 104 8C because the reactive PZ reacts with
the MEA oxazolidinone to produce the cross dimer
[6].
HN

NH +

O
NH

HN

HO
N

NH O

Blends of tertiary amines with secondary or primary

amines usually degrade faster [3,21]. A reactive secondary amine can pick up arms from the tertiary amine. PZ
will react with MDEA to produce N-methylpiperazine
and DEA. When MDEA/PZ is thermally degraded, the
Current Opinion in Chemical Engineering 2012, 1:183190

NH + HO

HN
N

+ HO

NH

+
NH2

OH
OH

Some blends may degrade to an equilibrium mixture of

useful amines. The blend of N-methylpiperazine with PZ
disproportionates at 150 8C to an equilibrium mixture of
PZ, 1-methylpiperazine (1-MPZ), and 1,4-dimethyl
piperazine [7] (SA Freeman et al., Piperazine/N-methylpiperazine/N,N0 -dimethylpiperazine as an aqueous solvent for carbon dioxide capture, Oil Gas Sci Technol,
unpublished data). 1-MPZ by itself degrades to a similar
equilibrium mixture.

Formate production at stripper conditions

Freeman [7] observed significant production of formate and its amide with PZ at 150 8C. She used NMR
with C13O2 to demonstrate that the formate is produced

NH2
+ H+

from the CO2 and not from C in the PZ. Closmann [3]
also observed formate/formamide formation in the thermal degradation of MDEA and MDEA/PZ. The mechanism is not understood but probably requires oxidation
of a C on the amine and reduction of the CO2 in a
carbamate to the respective amide or formate. The
analytical methods for oxidation products of PZ are
known to be incomplete and could easily miss an
important oxidation product.
Freeman [7] also established that the formate and its
respective amide are in equilibrium at 150 8C in less than
a week. The equilibrium in loaded PZ provides about
equal amount of formate and amide.

Thermal degradation may be avoided by

stripping to very low CO2 loading
The four principal mechanisms for thermal degradation of
useful amines require the amine carbamate or protonated
amine as an important reactant. Therefore CO2 loading or
an amine salt such as sulfate or formate will increase the
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Thermal degradation of amines for CO2 capture Rochelle 189

rate of amine degradation. It should be possible to avoid

thermal degradation by overstripping to very low CO2
loading. This is possible with tertiary or hindered amines
that make only bicarbonate. However, it is difficult to
strip to low loading with primary or secondary amines that
produce carbamates. Furthermore Van Wagener [5] has
established that minimum energy use is achieved in
systems that strip the CO2 only to the level required to
achieve adequate CO2 removal.

Alkanolamines thermally degrade by carbamate polymerization at a rate that limits stripper operation to 100
130 8C.

A few amines degrade in the absence of CO2. EideHaugmo [15] found three propanediamines with
>20% degradation at 135 8C for 5 weeks without CO2:
(MAPA),
N-[33-amino-1-methylaminopropane
(dimethylamino)propyl]-N,N-dimethyl-1,3-propanediamine (TMBPA), and 3-aminopropanol. It may be that
these molecules participate in reversible addition to a
heteroconjugated double bond.

PZs, HMDA, and related structures degrade by ring

closing or opening at 150160 8C.

Eide-Haugmo [15] also observed significant loss with

four amino acids. It is probable that these molecules
participate in the reversible formation of the respective
amides.

Internal urea formation limits ethane and propane diamines to 100120 8C.
Tertiary amines thermally degrade by transalkylation and
elimination at 120140 8C.

Blends of alkanolamines with reactive amines such as PZ

degrade more rapidly as the reactive amine participates in
carbamate polymerization.
Formate and formamides are thermal degradation products at greater T.
Thermal degradation can produce products that are more
volatile that the parent amines.

Acknowledgements
LePaumier [14] observed significant loss of 2-methylaminoethanol in the absence of CO2, with more loss in a
metal reactor than in a glass reactor.

This review is based in large part on the work of former PhD students
supported by the Luminant Carbon Management Program at the University
of Texas at Austin: Jason Davis, Stephanie Freeman, and Fred Closmann.

References and recommended reading

Degradation products may be more volatile
than parent amines
Ammonia has been observed in the thermal degradation
of PZ, probably with PZ addition to a cyclic urea [7].
Methylated amines are typically more volatile than
their parent amines. Methyl piperazine and dimethylpiperazine can be significant products in the thermal
degradation of PZ and blends of PZ with other amines
[3,7]. The volatility of the DMPZ makes this an
unacceptable blend for commercial practice [7] (SA
Freeman et al., Piperazine/N-methylpiperazine/N,N0 dimethylpiperazine as an aqueous solvent for carbon
dioxide capture, Oil Gas Sci Technol, unpublished
data).

Papers of particular interest, published within the period of review,

have been highlighted as:
 of special interest
 of outstanding interest
1.

Rochelle GT: Amine scrubbing for CO2 capture. Science 2009,

325:1652-1654.

2.


Rochelle GT, Chen E, Freeman S, VanWagener D, Xu Q, Voice A:

Aqueous piperazine as the new standard for CO2 capture
technology. Chem Eng J 2011, 171:725-733 http://dx.doi.org/
10.1016/j.cej.2011.02.011.
This work provides a basis for the importance of elevated stripper T.

3.


Closmann F: Oxidation and thermal degradation of

methyldiethanolamine/piperazine in CO2 capture, PhD
dissertation, The University of Texas at Austin, December 2011
http://research.engr.utexas.edu/rochelle/images/stories/
publications/closmann_dissertation_20119.pdf
This comprehensive work on MDEA/PZ degradation includes data at
cyclic absorber and stripper T.

4.

Transalkylation with MDEA can produce DMMEA and

other amines more volatile than MDEA itself [3].

Rochelle GT: Research needs for CO2 capture from flue gas by
aqueous absorption/stripping. DE-AF26-99FT01029; 2011.

5.

Other impurities in the flue gas may react with amines in

the stripper. Sulfite will react with MEA to produce
specific sulfo-amine products, possibly identified as N(2-hydroxyethyl)-amidosulfurous acid to N-(2-hydroxyethyl)-sulfamic acid [22].

Van Wagener D: Stripper modeling for CO2 removal using

monoethanolamine and piperazine solvents, PhD dissertation,
The University of Texas at Austin, 2011, http://
repositories.lib.utexas.edu/bitstream/handle/2152/ETD-UT-201108-4302/VAN-WAGENER-DISSERTATION.pdf.

6.


Conclusions
Thermal degradation limits the maximum T/P and therefore the energy performance of the stripper.
www.sciencedirect.com

Davis J: Thermal degradation of aqueous amines used for

carbon dioxide capture, Ph.D. dissertation, The University of
Texas at Austin; 2009, http://repositories.lib.utexas.edu/handle/
2152/6581
This work develops a comprehensive model of MEA thermal degradation
and provides rate data on 17 other amines.

7.


Freeman S: Thermal degradation and oxidation of aqueous

piperazine for carbon dioxide capture, PhD dissertation, The
University of Texas at Austin, May 2011, http://hdl.handle.net/
2152/ETD-UT-2011-05-3290, May 2011
Current Opinion in Chemical Engineering 2012, 1:183190

190 Separation engineering

This is a comprehensive study of piperazine degradation. It includes data

for a number of piperazine derivatives. It summarizes all of the rate data
from the literature.
8.

Davis J, Rochelle GT: Thermal degradation of

monoethanolamine at stripper conditions. Energy Procedia
2009, 1:327-333.

9.

Freeman SA, Davis J, Rochelle GT: Degradation of aqueous

piperazine in carbon dioxide capture. Int J Greenhouse Gas
Control 2010, 4:756-761.

10. Lepaumier H: Etude des mecanismes de degradation des

amines utilisees pour le captage du CO2 dans les fumees.
Sciences Pour lIngenieur, Ph.D. thesis, University of Savoie,
France, October 2008.

15. Eide-Haugmo I: Environmental impacts and aspects of

 absorbents used for CO2 capture, PhD thesis, Norwegian
University of Science and Technology, ISBN 978-82-471-3046-9,
2011
Chapter 4 provides data on rates and degradation products for 33
amines.
16. Eide-Haugmo I, Lepaumier H, Einbu A, Vernstad K, da Silva EF,

Svendsen HF: Chemical stability and biodegradability of new
solvents for CO2 capture. Energy Procedia 2011,
4:1631-1636.
Provides measured thermal degradation rates for 11 amines.
17. Al-juaied MA: Carbon dioxide removal from natural gas by
membranes in the presence
W of heavy hydrocarbons and by
aqueous Diglycolamine /Morpholine, PhD dissertation, The
University of Texas at Austin, May 2004.

11. Lepaumier H, Picq D, Carrette P-L: New amines for CO2 capture.
 I. Mechanisms of amine degradation in the presence of CO2.
Ind Eng Chem Res 2009, 48:9061-9067.
Lepaumier presents results on thermal degradation of 12 amines, including a series of substituted ethylenediamines and several consistent
mechanisms/pathways to describe expected products.

18. Polderman LD, Dillon CP, Steele AB: Why MEA solution breaks
down in gas-treating service. Oil Gas J 1955, 54:180-183.

12. Lepaumier H, Martin S, Picq D, Delfort B, Carrette PL: New


amines for CO2 capture. III. Effect of alkyl chain length
between amine functions on polyamines degradation. Ind Eng
Chem Res 2010, 49:4553-4560.
This work provides data and interpretations for several tertiary polyamines.

20. Chakma A, Meisen A: Methyl-diethanolamine degradation

mechanism and kinetics. Can J Chem Eng 1997, 75:861-871.

13. Lepaumier H, da Silva EF, Einbu A, Grimstvedt A, Knudsen JN,


Zahlsen N, Svendsen HF: Comparison of MEA degradation in
pilot-scale with lab-scale experiments. Energy Procedia 2011,
4:1652-1659.
This work gives bench-scale and pilot-scale results on MEA oxidation and
thermal degradation.

22. Lichtfers U, Asprion N, Claessen M, Umino H, Tanaka K: Process

 for the recovery of carbon dioxide. PCT Int. Appl. (2007), WO
2007068695 A1 20070621.

14. Lepaumier H, Grimstvedt A, Vernstad K, Zahlsen K, Svendsen HF:

Degradation of MMEA at absorber and stripper conditions.
Chem Eng Sci 2011, 66:3491-3498.

Current Opinion in Chemical Engineering 2012, 1:183190

19. Strazisar BR, Anderson RR, White CM: Degradation pathways

for monoethanolamine in a CO2 capture facility. Energy Fuels
2003, 17:1034-1039.

21. Bedell SA, Worley CM, Al-Horr RS, McCrery DA: Quaternaries as
intermediates in the thermal and oxidative degradation of
alkanolamines. Ind Eng Chem Res 2011, 49:7147-7151.

23. Zhou S, Chen X, Nguyen T, Voice Alexander K, Rochelle GT:

Aqueous ethylenediamine for CO2 capture. ChemSusChem
2010, 3:913-918.

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