International Journal of Greenhouse Gas Control 12 (2013) 472–477

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International Journal of Greenhouse Gas Control

journal homepage: www.elsevier.com/locate/ijggc

Products and process variables in oxidation of monoethanolamine for CO2

capture
Alexander K. Voice, Gary T. Rochelle ∗
University of Texas, 1 University Station, C0400, Austin, TX 78712, USA

a r t i c l e i n f o a b s t r a c t

Article history: Oxidative degradation of monoethanolamine (MEA) in CO2 capture systems was studied using two dif-
Received 17 April 2012 ferent apparatuses and a variety of experimental conditions. Dissolved iron, manganese, and copper were
Received in revised form 2 November 2012 all potent catalysts, increasing the oxidation rate by up to a factor of ten. The activation energy of the
Accepted 13 November 2012
oxidation rate was 68–70 kJ/mol. Addition of 2% CO2 to the gas increased oxidation by a factor of five. The
Available online 9 January 2013
oxidation rate was found to be approximately first-order in oxygen partial pressure. Addition of 50 ppm
NO2 • or SO2 to the reactor gas had a minimal effect on the degradation rate. The mass balance was closed
Keywords:
within 5% at high gas flow and within 20% at low gas flow. Two-thirds of the degraded MEA in both
Monoethanolamine (MEA)
Oxidation
systems was converted to ammonia. Other major products were 1-(2-hydroxyethyl)-formamide (HEF)
Degradation and 1-(2-hydroxyethyl)-imidazole (HEI).
Ammonia production © 2012 Elsevier Ltd. All rights reserved.
Process variables

1. Introduction 2. Previous work

Oxidative degradation of amine solutions for CO2 capture is
caused by the presence of excess oxygen for combustion in the
flue gas entering the amine scrubber. Oxygen dissolves into the
liquid phase and reacts irreversibly with the amine in the absorber
packing, absorber sump, and cross-exchanger. Monoethanolamine
(MEA), a common amine for CO2 capture, was first observed by
Kindrick to be particularly susceptible to oxidation (Kindrick et al.,
1950).
Solvent oxidation causes several problems for plant operators.
Degraded solutions have reduced CO2 capacity and may have
slower reaction rates compared with fresh solutions. In addition,
heat stable salts resulting from oxidative degradation can increase
corrosion. Make-up solvent must be added to replace degraded sol-
vent, and reclaiming processes must be used to remove degradation
products as they accumulate. Most importantly, many oxidation
products belong to chemical classes known to cause environmental
and health problems (Jackson and Attalla, 2010). One way to miti-
gate these problems is to limit the amount of oxidative degradation
occurring in the process and thus minimize the costs associated
with degradation.
∗ Corresponding author at: Department of Chemical Engineering, University of
Texas at Austin, 1 University Station, C0400, Austin, TX 78712, USA.
Tel.: +1 512 471 7230; fax: +1 512 471 7060.
E-mail addresses: voice@che.utexas.edu (A.K. Voice), gtr@che.utexas.edu
(G.T. Rochelle).
The presence of oxygen in gas-treating systems has long been
recognized as a cause of degradation of MEA (and other amines),
as well as production of corrosive degradation products (Hofmeyer
et al., 1956; Lloyd and Taylor, 1954; Blanc et al., 1982; Dupart et al.,
1993; Rooney et al., 1998; Blachly and Ravner, 1966, 1962). Previous
work has also established evidence of the chemical mechanism and
oxidative fragmentation products of MEA oxidation (Petrayev et al.,
1984; Denisov, 1996; Dennis et al., 1967; Russell, 1962; Rosenblatt
et al., 1963) and how these mechanisms apply to CO2 capture
(Rochelle and Chi, 2001). Later work focused specifically on rates
of ammonia production and other oxidation products from MEA
solutions at absorber conditions (Chi, 2000; Chi and Rochelle, 2002;
Goff, 2005; Goff and Rochelle, 2004, 2006; Sexton, 2008; Sexton and
Rochelle, 2011).
Blachly and Ravner (1966, 1962) first observed the catalytic
effect of dissolved metals present in MEA solutions on the oxida-
tion rate. Recent work has further explored this effect by analyzing
for ammonia production as an indicator of MEA oxidation in a
semi-batch laboratory system. Chi and Rochelle (Chi, 2000; Chi and
Rochelle, 2002) demonstrated the role of iron as an oxidation cata-
lyst. Goff and Rochelle (Goff, 2005; Goff and Rochelle, 2004, 2006)
showed that copper alone or with iron was a more potent catalyst
than iron only.
Sexton and Rochelle (Sexton, 2008; Sexton and Rochelle, 2011)
confirmed that copper was a potent catalyst by analyzing for
MEA loss and degradation product rates during prolonged solvent
oxidation. Sexton also identified several new oxidation products

1750-5836/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijggc.2012.11.017
 A.K. Voice, G.T. Rochelle / International Journal of Greenhouse Gas Control 12 (2013) 472–477 473

of MEA and discovered that ammonia, 1-(2-hydroxyethyl)-

imidazole (HEI) and 1-(2-hydroxyethyl)-formamide (HEF) were
the most prevalent products. Other likely products, which
have been reported in industrial systems and laboratory
experiments include 1-(2-hydroxyethyl)-oxalamide, N,N -bis(2-
hydroxyethyl)oxalamide, 4-(2-hydroxyethyl)-piperazin-2-one,
1-(2-hydroxyethyl) glycine and its corresponding amide N-(2-
hydroxyethyl)-2-(2-hydroxyethylamino)acetamide (Strazisar
et al., 2003; Lepaumier et al., 2009, 2011).
The effects of some process variables on MEA oxidation have also
been studied. Goff (2005) showed that the ammonia production
rate was higher in a lean (˛ = 0.15) solution than in a rich solution
(˛ = 0.40), and lowest in the absence of CO2 . Goff and Rochelle (Goff,
2005; Goff and Rochelle, 2004) also demonstrated that ammonia
production was first-order in oxygen concentration.
Supap et al. (2001) conducted oxidation of MEA at various Fig. 1. Anion chromatogram for a typical sample of oxidized MEA at absorber con-
concentrations in a batch reactor at high oxygen partial pressure ditions.
(241–345 kPa) and high temperature (120–170 ◦ C). The activation
energy of MEA oxidation was 66 kJ/mol, and the reaction was first- Program (SRP) Pilot Plant (PP) in Austin, TX (which was ana-
order in MEA and 1.5-order in oxygen. However, these results are lyzed and found to contain 0.5 mM Fe). Some experiments were
likely oxygen mass-transfer controlled, are confounded by changes also performed with 7 m MEA prepared from reagent-grade MEA
in oxygen pressure during the experiment, and contained unknown (Huntsman) with added dissolved metals. In addition, a high rate of
amounts of dissolved metal catalyst. gas sparged through the solution (HGF) or vigorous agitation (LGF)
This work has quantified the effects of process conditions, was used to increase oxygen mass transfer to the liquid.
as well as various gas- and liquid-phase contaminants, on MEA
oxidation—using a semi-batch system and representative condi-
tions. 4. Analytical methods

Samples taken from the liquid phase in the LGF and HGF reactors
3. Experimental methods were analyzed using a variety of methods, including anion chro-
matography, cation chromatography, HPLC–UV and total nitrogen.
This work used two semi-batch reactors designed to simulate Gas exiting the HGF was analyzed by hot-gas FTIR.
oxidation in the absorber packing in an MEA scrubbing system. The
low gas flow (LGF) system used 100 mL/min of 2% CO2 in oxygen 4.1. Anion chromatography
with reactor agitation at 1440 RPM. The high gas flow (HGF) used
2% CO2 in air sparged from the bottom of the reactor at a rate of Samples were prepared in two ways: dilution of the neat sample
7.65 L/min (dry basis). In the LGF, the water balance was controlled to 100× in water, and treatment of the sample with two volume-
by adding water daily to the marked level on the reactor; in the equivalents of 5 N sodium hydroxide, followed by 100× dilution
HGF the condenser and saturator were tuned to maintain the water in water after letting stand for 48 h at room temperature. NaOH
balance. treated samples allowed for recovery of organic acids (namely
The HGF experiment is similar to that described by Sexton formic acid and oxalic acid) from their respective amides via base-
(2008) and Goff (2005), with the exception that a higher reac- catalyzed hydrolysis (Figs. 1 and 2). This method was first used
tor temperature (70 ◦ C instead of 55 ◦ C) and oxygen concentration by Koike et al. (1987) for analysis of N-formyl-diethanolamine in
(21 kPa) was used to accelerate degradation. A condenser was also a 20% diethanolamine solution, and later by Sexton and Rochelle
used to reduce volatile amine loss from the reactor at 70 ◦ C. The (Sexton, 2008; Sexton and Rochelle, 2011) for analysis of various
low gas system used was the same as that described by Sexton and amide-degradation products in oxidized MEA solutions.
Rochelle (Sexton and Rochelle, 2011). The instrument was a Dionex ICS-3000 with IonPac AS15 ana-
The HGF was typically run for a period of one or two days to lytical column and mobile phase 2–45 mM aqueous potassium
achieve steady-state; NH3 production was used as an indication of
the relative amount of oxidation occurring. The LGF was run for
two weeks to achieve observable loss of MEA in the liquid-phase
and accumulation of liquid-phase degradation products.
It was initially assumed that ammonia accounted for a fixed per-
centage of degraded MEA; this percentage was later shown to be
roughly the same in the LGF and HGF. Since changes in the liquid-
phase MEA concentration require long experiment times, the major
advantage of using ammonia rates (in the HGF system) is that
changes in ammonia production rates can be observed instanta-
neously, thus significantly shortening the amount of time required
for an experiment.
Real process conditions were simulated by using low tempera-
tures (40–70 ◦ C) similar to those encountered in the absorber and
by using a continuous gas phase and batch liquid phase (to provide
a continuous supply of oxygen at roughly atmospheric pressure).
Most experiments were performed with 9 m MEA (PP), a sam- Fig. 2. Post-NaOH treatment anion chromatogram for a typical sample of MEA oxi-
ple (received in November 2010) from the Separations Research dized at absorber conditions.
474 A.K. Voice, G.T. Rochelle / International Journal of Greenhouse Gas Control 12 (2013) 472–477

Table 1
Analysis regions for FTIR.

Compound Range 1 (cm−1 ) Range 2 (cm−1 ) Range 3 (cm−1 )

Water 3157–3477 Fig. 3. Logistic equation.

CO2 910–1003 3425–3616 2165–2251
MEA 2416–3150
NH3 915–988 2423–2560
N2 O 2123–2224 2505–2628

Fig. 4. Derivative evaluated at t = 0.

hydroxide at 1.6 mL/min. Chromatograms for a typical sample are
shown below.
Table 2
Summary of NH3 rates from 7 m MEA (Huntsman) with metal additions. HGF con-
4.2. Cation chromatography ditions: 98 kPa air, 2 kPa CO2 , 70 ◦ C.

Metals added NH3 rate (mmol/kg/h)

Cation chromatography was used to determine liquid MEA, as
None (<1 ␮ Fe) 0.33
well as dissolved ammonia. Samples were diluted 10,000× in water 0.1 mM Fe 2.5
to reduce the MEA concentration to a manageable level. The instru- 0.1 mM Fe2+ + 0.01 mM Mn2+ 8.6
ment was a Dionex ICS-2100 with IonPac CS17 analytical column 0.1 mM Fe2+ + 0.25 mM Mn2+ 9.7
and aqueous methane sulfonic acid eluent (0–36 mM). This method 0.1 mM Fe2+ + 0. 50 mM Mn2+ 11.6
0.1 mM Fe2+ + 1.00 mM Mn2+ 12.6
allowed for fast separation of MEA from sodium and ammonium 1.0 mM Fe2+ + 1.00 mM Cu2+ 6.6
cations. 1.0 mM Fe2+ + 1.00 mM Mn2+ + 1.00 mM Cu2+ 11.6

4.3. HPLC–UV
HPLC with a UV detector was used for determination of 1-(2-
hydroxyethyl)-imidazole in degraded MEA solutions. Samples were
diluted 100× in water prior to injection on the HPLC. The instru-
ment was a Dionex U3000 with Dionex Polar Advantage 2 analytical
column and UV detector set to 210 nm. The mobile phase was ace-
tonitrile, methanol, and 10 mM aqueous ammonium carbonate. The
program started with 95% acetonitrile in 5% methanol and ended
with 50% acetonitrile in 50% aqueous ammonium carbonate. HEI
was eluted after approximately 13.5 min.
4.4. Total nitrogen analysis
Total nitrogen analysis was performed using an Aurora 1030
Combustion TOC analyzer with total bound nitrogen (TNb ) module
manufactured by OI Analytical. The sample was diluted to 3000×
in water; the injection volume was 0.2 mL. The sample is burned in
a catalytic combustion tube before passing to a NOx converter that
reduces NO2 to NO, which passes through an electrochemical NO
detector. Total nitrogen response decreases as MEA is oxidized to
ammonia, most of which exits the reactor with the gas.
4.5. FTIR analysis
5. Results
5.1. Effect of metals
Aqueous metal sulfate salts were added to neat 7 m MEA in the
HGF at 70 ◦ C with 98 kPa air and 2 kPa CO2 (Table 2 and Fig. 5). Rel-
ative ammonia rates were used to determine the catalyst potency.
Addition of 0.1 mM Fe2+ increased the ammonia production rate
by more than a factor of six relative to the neat solution received
from Huntsman, Inc. (certified to contain less than 50 ppb of Fe) to
2.5 mmol/kg/h. Addition of 0.01 mM Mn2+ to this solution increased
the oxidation rate by 2.5× to 8.6 mmol/kg/h relative to iron only;
further additions of Mn2+ up to 1 mM increased the ammonia rate
to 12.6 mmol/kg/h. Addition of 1 mM Cu2+ to a MEA solution at
the same conditions resulted in an ammonia rate of 6.6 mmol/kg/h,
whereas 1 mM each of Fe2+ , Cu2+ , and Mn2+ resulted in an ammonia
rate of 11.6 mmol/kg/h.
The results concerning the catalytic effects of iron and cop-
per concur with previous work (Blachly and Ravner, 1966, 1962;
Chi, 2000; Chi and Rochelle, 2002; Goff, 2005; Goff and Rochelle,
2004, 2006; Sexton, 2008; Sexton and Rochelle, 2011). In this work,
manganese was found to be a catalyst of MEA oxidation of greater
potency than copper.

Gas exiting the HGF was analyzed using a Temet-Gasmet hot-gas

FTIR (DX-4000). Gas exiting the condenser on top of the HGF reac-
tor was pumped through a heated Teflon line maintained at 180 ◦ C 8
through a heated pump (also maintained at 180 ◦ C) to the anal-
NH3 Rate (mmol/kg/hr)

yser. The major components observed were water, CO2 , MEA, and 6
NH3 . A small amount of a fifth component, possibly N2 O, was also
observed in small quantities although this could not be confirmed.
No statistically significant amounts of NO, NO2 , formaldehyde, or 4
acetaldehyde were observed. A summary of the spectrum regions +0.01 mM Mn2+
used for each component is given in Table 1. 2

+0.1 mM Fe2+
4.6. Data analysis 0
0 5 10 15 20
Initial oxidation rates were determined by fitting the MEA con- Time (hrs)
centration as a function of time with an empirical fit (Fig. 3) and
Fig. 5. Oxidation of 7 m MEA with 98 kPa air and 2 kPa CO2 in the HGF at 70 ◦ C with
evaluating the derivative at time zero (Fig. 4). additions of Fe2+ and Mn2+ .
 A.K. Voice, G.T. Rochelle / International Journal of Greenhouse Gas Control 12 (2013) 472–477
Fig. 6. Oxidation of 9 m MEA (PP) in the LGF with 98 kPa O2 , 2 kPa CO2 at 55 ◦ C.
5.2. SO2 and NO2
The effect of NO2 and SO2 were studied by adding 50 ppm of
each contaminant separately to the LGF with 98 kPa oxygen and
2 kPa CO2 at 55 ◦ C. The 9 m MEA (PP) solution containing 0.5 mM
Fe was used; MEA losses in the presence of SO2 and NO2 are com-
pared with that in the presence of oxygen and CO2 only (Fig. 6).
Neither SO2 nor NO2 had a significant effect on the loss of MEA.
These three experiments demonstrate the reproducibility of the
LGF experiment. The regressed initial rate of MEA loss in 9 m MEA
from the SRP pilot plant is 29 ± 3 mmol/kg/h. This rate is signifi-
cantly higher than rates reported previously, and may be due to
the presence of certain dissolved metals in the solution (Kindrick
et al., 1950; Blachly and Ravner, 1966, 1962; Chi, 2000; Chi and
Rochelle, 2002; Goff, 2005; Goff and Rochelle, 2004, 2006; Sexton,
2008; Sexton and Rochelle, 2011).
5.3. CO2 dependence
The effect of CO2 on the ammonia evolution rate was studied
by sparging unloaded, 7 m MEA with 2% CO2 in air in the pres-
ence of 0.1 mM Fe at 70 ◦ C. Addition of CO2 to the reactor increased
the NH3 rate from 0.54 mmol/kg/h to a maximum of 2.6 mmol/kg/h
(at 0.30 loading) before falling to 2.3 mmol/kg/h at the final load-
ing (0.36) (Fig. 7). The loading was determined over the course of
the experiment by integrating the difference between the outlet
CO2 concentration and the equilibrium outlet CO2 concentration
Fig. 7. Oxidation of 7 m MEA with 98 kPa air and 2 kPa CO2 in the HGF with 0.1 mM
Fe at 70 ◦ C.
475
Fig. 8. Oxidation of 9 m MEA (PP) in the LGF with air and oxygen at 55 ◦ C and 70 ◦ C.
2% CO2 .
(after no more CO2 was being absorbed into the solution). Qual-
itatively, this result concurs with Goff’s observation (2005), that
ammonia production was lowest in the presence of no CO2 , and
higher at a lean-loaded condition that a rich-loaded condition. This
complex effect is likely due to two factors: at zero loading metals
are insoluble in the high pH MEA solution; at higher loading only
the “free” MEA oxidizes (and not the MEA-carbamate or protonated
MEA). This explains the initial increase and subsequent decrease in
ammonia production with respect to CO2 loading. In an industrial
process, the percentage of free MEA could range from 13% to 70%
(at 0.45 and 0.15 loading, respectively).
5.4. Oxygen dependence
MEA was oxidized in the LGF with air (98 kPa air dry = 17.9 kPa
O2 wet) and oxygen (98 kPa O2 dry = 83.3 kPa wet) at 55 ◦ C with 2%
CO2 . MEA concentration is shown for both experiments in Fig. 8.
The initial rate of MEA loss (regressed) was 4.0 mmol/kg/h with air
and 25 mmol/kg/h with oxygen, indicating that the rate of MEA loss
is approximately first order in oxygen. This generally concurs with
observations by Goff and Rochelle (Goff, 2005; Goff and Rochelle,
2004) (who measured NH3 production rather than MEA loss) and
Supap et al. (2001) that MEA oxidation was around first-order in
oxygen partial pressure. This also indicates that NH3 production is
a good indicator of relative degradation rates.
Goff and Rochelle (Goff, 2005; Goff and Rochelle, 2004) sug-
gested that MEA oxidation could be controlled by the absorption
rate of oxygen, based on weak effect of agitation with catalysis by
dissolved iron. However this observed activation energy is signif-
icantly greater than what might be expected for a mass transfer
controlled reaction.
5.5. Temperature dependence
The temperature dependence of MEA oxidation was determined
first by observing ammonia production rates at three tempera-
tures in the HGF and second by observing MEA loss over two
weeks in the LGF system at two temperatures and regressing the
initial rate (Fig. 8). In the first case, the activation energy was
70 kJ/mol, whereas in the second case it was 68 kJ/mol. All of the
rates observed in these experiments are shown in Fig. 9, where the
rates have been normalized by oxygen partial pressure.
The result is somewhat confounded by the fact that 2% CO2 was
used in all experiments, thus the loading was lower at the higher
temperature. Based on the above data on the effect of CO2 , a change
476 A.K. Voice, G.T. Rochelle / International Journal of Greenhouse Gas Control 12 (2013) 472–477
Fig. 9. Oxidation of 9 m MEA (PP) in the LGF and HGF at 55–70 ◦ C with 2% CO2 in
oxygen and air.
Fig. 10. Equations for the ammonia ratio in the LGF reactor (top), where TN(i) is the
(initial) total nitrogen concentration, and HGF (bottom).
in loading from 0.40 to 0.35 at constant temperature could increase
the oxidation rate by 20%.
5.6. Material balance
The material balance was closed to 100 ± 5% in the HGF and to
100 ± 20% in the LGF. Greater error is expected in the LGF because
ammonia could not be analyzed directly. Control of the water bal-
ance in the LGF reactor may have also contributed to greater error.
The ratio of ammonia products to lost MEA in the LGF and HGF
was calculated using the equations shown in Fig. 10. These equa-
tions assume that disappearance of total nitrogen in the LGF is
primarily ammonia, that nitrate and nitrite are products of ammo-
nia oxidation, and that one ammonia equivalent is used to produce
one equivalent of 1-(2-hydroxyethyl)-imidazole HEI (Speranza and
Wei-Yang, 1990).
In the final sample, the percent of oxidized MEA recovered as
ammonia was 68% in the HGF and 71% LGF reactor (Figs. 10–12).
For the LGF, it was assumed that the difference in total nitrogen
represented ammonia loss from the solution. Besides ammonia,
the two other major products are 1-(2-hydroxyethyl)-formamide
(HEF) and HEI. Both of these products result from secondary
Fig. 11. Products and material balance for oxidation of 9 m MEA (PP) in the HGF
(98 kPa air, 2 kPa CO2 , 70 ◦ C).
Fig. 12. Products and material balance for oxidation of 9 m MEA (PP) in the LGF
(98 kPa O2 , 2 kPa CO2 , 70 ◦ C).
reactions between MEA and aldehydes. HEF is likely formed by
reaction of MEA with formaldehyde, followed by oxidation. HEI is
likely formed by reaction of ammonia, glyoxal, and formaldehyde
with MEA (Speranza and Wei-Yang, 1990). Significantly more HEI
was formed in the LGF reactor due to the fact that more of the
ammonia remains in the solution rather than being continuously
stripped out (as with the HGF). The relative amounts of some prod-
ucts may change in a real system that exposes the solvent to high
temperature in the stripper (Voice and Rochelle, 2012). However,
because ammonia always seems to represent more than 50% of the
nitrogen loss from MEA oxidation, it is a good surrogate to quantify
the rate of MEA oxidation.
6. Conclusions
In conclusion, dissolved metals and temperature are the two
most important factors to consider in oxidation of MEA. Contami-
nation by Fe and Mn from corrosion, fly ash, or other sources could
cause up to a 38× increase in the oxidation rate of MEA in the
absorber, thus this is the most important factor to control. Based on
the regressed activation energy of 70 kJ/mol, the temperature bulge
in the absorber (which can range from 40 to 80 ◦ C) could increase
the oxidation rate by a factor of 19×. Decreasing the temperature
bulge can provide significant benefit in reducing oxidation. Oxygen
concentration is set by the amount of excess air used for combus-
tion to optimize power plant efficiency and therefore could not be
changed for purposes of degradation. Low loadings may increase
oxidation by 6× compared with high loadings, however the load-
ing is typically set to optimize energy performance of the capture
plant. In addition, although higher loadings may benefit oxidation
by decreasing the free MEA, they would increase thermal degrada-
tion (Davis, 2009). The presence of SO2 and NO2 in the gas (up to
50 ppmv ) had no discernible effect on the oxidation rate of MEA.
The main oxidation products formed in the absorber (at low tem-
perature) are ammonia, HEI, and HEF with ammonia accounting
for about two-thirds of the degraded MEA. HEI production in an
industrial system is expected to be low (similar to the HGF system)
because ammonia is continuously stripped out.
Acknowledgement
This work was supported by the Luminant Carbon Management
Program.
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