International Journal of Greenhouse Gas Control 34 (2015) 129–140

Contents lists available at ScienceDirect

International Journal of Greenhouse Gas Control

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

An overview of solvent management and emissions of amine-based

CO2 capture technology
Shaukat A. Mazari, Brahim Si Ali ∗ , Badrul M. Jan, Idris Mohamed Saeed, S. Nizamuddin
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia

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

Article history: Increasing global carbon dioxide (CO2 ) emissions are a rising concern for the global climate change.
Received 13 September 2014 Amine-based post-combustion CO2 capture (PCC) technology is one of the mature options to contribute
Received in revised form to the mitigation of these emissions. The technology is approaching toward its commercialization. How-
17 November 2014
ever, there are two important problems, which should properly be addressed, solvent management and
Accepted 29 December 2014
the amine-based PCC emissions. Major losses in amines are due to the oxidative and thermal degrada-
Available online 17 February 2015
tion. Concentration of oxygen (O2 ) is the driving force for the oxidation. Temperature, CO2 loading and
amine concentration affect both thermal and oxidative degradation. This manuscript reviews solvent
Keywords:
Amines
selection, thermal and oxidative degradation of amines used for CO2 capture. Furthermore, amine-based
CO2 capture PCC emissions have also been highlighted, with some of their concerns. Based on literature reviewed and
Solvent management discussions provided, conclusions are made. In addition, some of the future work is also directed in form
Photo-oxidation of suggestions.
Nitrosamine © 2015 Elsevier Ltd. All rights reserved.
Nitramines

1. Introduction be necessary to mitigate CO2 emissions up to 50%, based on the

emissions of 2005 (IPCC, 2013).
1.1. Carbon dioxide emissions and environment
1.2. Technologies of choice for CO2 capture
Global warming is a well-known, worldwide concern, most
probably caused by increasing concentrations of CO2 and other
Carbon dioxide capture technologies are a valuable way to
greenhouse gases in the earth’s atmosphere, due to human activi-
achieve an important reduction in CO2 emissions. There are a num-
ties. Power sector, mainly relies on coal, gas and heavy oil. Coal is
ber of technologies which are being evaluated for the capture of
widely known as the most intensives of the fossil fuels, and hence
industrial CO2 emissions. Generally, three technology choices are
is amplifying its share in the global warming. The report of inter-
widely known as viable for large scale development in coming
national energy agency (IEA) revealed that the highest rate of CO2
times, like post-combustion CO2 capture using amine solvents,
emissions of 71.5% has been observed in electricity and heat sec-
oxyfuel combustion and calcium looping technologies (MacDowell
tor for last two decades, from 1990 to 2010 (IEA, 2012). Global
et al., 2010). Amine scrubbing may be a more feasible technology
CO2 emissions can raise up to 29% by the year 2035, which are
of for CO2 capture from coal-fired power plants due to its retrofit
nearly double to that of, which were in 1990 (BP, 2014). Another
approach for capturing CO2 from existing power plants (Rao and
report claimed that the global energy-related CO2 emissions have
Rubin, 2002). The estimated energy requisite for an advanced amine
been predicted to increase up to 46% by 2040, approaching 45 bil-
scrubbing process may be up to 2.6 MJ/tons CO2 , with an overall
lion metric tons (Sieminski, 2013). As a result, ecosystems may fail
thermodynamic efficiency of 50% (Rochelle et al., 2011).
and about 15–40% of all of the species may get destroyed (Shao
and Stangeland, 2009). In order to limit long-term global average
temperature rise between 2 and 2.4 ◦ C by the year 2050, it would 1.3. CO2 capture through amine scrubbing technology

Carbon dioxide absorption by chemical technology refers to the

counter-current, gas–liquid contact, in a separating column known
as absorber. Stripper in parallel is configured with absorber for
∗ Corresponding author. Tel.: +60 3 7967 6896; fax: +60 3 7967 5319. the regeneration of the solvent, which is later on recycled to the
E-mail address: [email protected] (B. Si Ali). absorber. Additional amine is added to the absorber as solvent make

http://dx.doi.org/10.1016/j.ijggc.2014.12.017
1750-5836/© 2015 Elsevier Ltd. All rights reserved.
130 S.A. Mazari et al. / International Journal of Greenhouse Gas Control 34 (2015) 129–140

Fig. 1. Schematic of basic chemical absorption/stripping process for amine-based CO2 capture.

up, because of the degradation of solvent. A detailed flow diagram et al., 2005; Namjoshi et al., 2013). PZ is a newly established sol-
of amine-based absorption/stripping technology is illustrated in vent which has shown promising CO2 capture properties and higher
Fig. 1. stability under process operating conditions compared to others
CO2 capture through post-combustion capture technology, (Dugas and Rochelle, 2009; Freeman, 2011; Freeman and Rochelle,
using amine solvents is a well-known technology to date. It is 2011, 2012b; Li et al., 2013b; Namjoshi et al., 2013; Rochelle et al.,
unlikely that any major innovation in design of either process or 2011). In addition to PZ, morpholine (Mor), and piperidine (PD)
columns to minimize the cost may be discovered. However, eco- have also been categorized to be the stable solvents up to 150 ◦ C
nomical approach through solvent management is a possibility (De (Freeman et al., 2010a; Freeman, 2011; Freeman and Rochelle,
Brito et al., 1994). There are a number of criteria for an economical 2011, 2012b). PZ has limited solubility, due to which precipitation
solvent. One of an essential property for an efficient solvent consid- occurs with both higher and lower CO2 loading (˛) (Li et al., 2013b).
ered to be is the capacity and absorption rate of CO2 (Puxty et al., To avoid precipitation, PZ may be used as blended forms with other
2009). Higher the CO2 solubility and CO2 absorption rate, better the amines (Closmann et al., 2009; Closmann, 2011; Freeman et al.,
solvent. Apart that stability of the solvent is a critical property for 2013).
its choice, as these amines undergo irreversible reactions. Stabil-
ity of the solvent can minimize the solvent makeup and disposal
1.5. Environmental concerns of amine-based CO2 capture
costs.
technology

1.4. Amines used for CO2 capture One of the foremost complications associated with amine-based
CO2 capture technology is the emissions from the plant into the
The common amines tested in this technology are mono- atmosphere and its waste handing (Shao and Stangeland, 2009).
ethanolamine (MEA), methyldiethanolamine (MDEA), diethano- The harming pollutant emissions may originate mainly from the
lamine (DEA), and aminomethylpropanolamine (AMP) (Dumée two sources, the point of discharge of flue gases and the reclaimer.
et al., 2012; Lowe et al., 2009; MacDowell et al., 2010). These amines Other emissions such as fugitive emissions and accidental release
experience irreversible reactions resulting deterioration of the sol- may also be dangerous and uncontrolled (Thitakamol et al., 2007).
vent by reacting with acidic gases, (CO2 , H2 S, COS, CO, SOx and NOx ), One of the emissions of PCC is the nitrosamine and nitramines.
higher temperature and oxidation (Freeman et al., 2010a; Goff and Their adulteration to air and drinking water supplies, downwind
Rochelle, 2006; Islam et al., 2010, 2011; Lepaumier et al., 2009c; of amine-based CO2 capture plants may pose considerable dam-
Wang et al., 2011). A number of new amines are under investi- ages (Fostås et al., 2011). In addition, nitroamines are carcinogenic,
gation for the sake of a promising amine that should have good toxic and mutagenic compounds (Bartsch and Montesano, 1984;
CO2 capture properties and higher stability (Hilliard, 2008; Idem Lijinsky and Epstein, 1970).
 S.A. Mazari et al. / International Journal of Greenhouse Gas Control 34 (2015) 129–140 131

2. Solvent management 2012; Lepaumier et al., 2009a; Rochelle, 2012; Zoannou et al., 2013).
Main contributions in the thermal degradation of various amines
2.1. Solvent selection have been added by Davis, Freeman, Closmann, Lepaumier and
Eide-Haugmo (Closmann and Rochelle, 2011; Davis, 2009; Eide-
Solvent selection is a critical stage for the amine-based CO2 Haugmo et al., 2011; Freeman, 2011; Lepaumier et al., 2009a). Davis
capture technology. Common tested amines like MEA, MDEA, DEA (2009) conducted thermal degradation study of about 18 amines in
and AMP are suspected to degrade under process operating con- stainless steel thermal cylinders with Swagelok endcaps. Cylinders
ditions producing hazardous compounds. Solvent selection cannot were kept in convection ovens, up to 150 ◦ C for the duration of 1–6
be underestimated due to two main reasons; economics and envi- weeks. Davis mainly focused on the degradation of MEA. He found
ronment. Studies have brought to light that the solvent makeup that besides temperature, increasing the concentration of amine
accounts around up to 10% of the total operating cost of the CO2 or CO2 loading increases the thermal degradation. In screening
capture technology using monoethanolamine (MEA) as a standard experiments of various amines, degradation rate investigation was
solvent (Rao and Rubin, 2002). A continuous research is underway based on 7 m alkalinity with 0.4 mole CO2 per mole alkalinity
to develop an amine system (single or blend) that should be stable (mol CO2 /mol alkalinity) at 135 ◦ C for 28 days. The amines degra-
under process operating conditions and should have higher CO2 dation in Davis study has been ranked as follows: cyclic amines
capture capacity with favorable thermodynamic properties (Aronu with no side chains < long chain alkanolamines < alkanolamines
et al., 2009; Ma’mun et al., 2007; Mangalapally et al., 2009; Notz with steric hindrance < tertiary amines < MEA < straight chain di-
et al., 2007). and triamines. Furthermore, study exhibited that the PZ and Mor
A number of amines have been tested to date; Table 1 provides were found as stable solvents, however, they degraded significantly
a detailed list of common amines tested for CO2 capture. when blended with MEA.
Many of the tested amines have good CO2 capture capacity and Lepaumier et al. (2010, 2009a,c) conducted thermal degra-
rate of absorption of CO2 under absorber operating conditions; dation study of 17 different amines including: alkanolamines,
however search for the best is still ongoing. Two new solvents have diamines, and triamines without alcohol function with a con-
shown better CO2 capture capacity with feasible physical character- centration of 4.0 mol/kg. Experiments were conducted in 100 ml
istics and thermal stability, like PZ and Mor under process operating stainless steel batch reactors, with and without CO2 and O2 pres-
conditions (Bishnoi and Rochelle, 2000; Freeman, 2011; Freeman ence up to 140 ◦ C for a period of 15 days. CO2 loading increased
et al., 2010a; Liu et al., 2013; Matin et al., 2013; Nielsen et al., the rate of degradation of amines. Study provided some of the
2013). However, further research on these solvents as alternatives conclusions as: the stability of the ethanolamines is an order of,
to the MEA is necessary. Degradation products formed through PZ III > hindered I > I > II (I, II, III represents primary, secondary and ter-
and Mor are not yet quantified and identified completely. Stud- tiary amine respectively). Thermal stability of ethylenediamines is
ies have reported that the significant quantities of nitrosamine as: III–III > III–I > III–II > II–II. Thermal degradation of PZ has been
and nitramine are formed through the degradation of PZ and Mor broadly investigated by Freeman, (Freeman (2011), Freeman et al.
(Chandan et al., 2013; Dai et al., 2012; Fine et al., 2014). In addition, (2010a), and Freeman and Rochelle (2011, 2012a,b)). Experiments
PZ and Mor are well-known for their limited solubility as being were carried out using 5-inches (in.) long 316 stainless steel (316SS)
ring structured. It has been speculated that the limited solubility of cylinders with Swagelok endcaps and cylinders were kept in ovens
PZ and Mor may be addressed through their blending with other for thermal degradation. Concentration of PZ was as 4, 8, 12 and
amines (Ali et al., 2010; Bishnoi and Rochelle, 2002; Derks et al., 20 m and experimental duration was up to 72 weeks. CO2 load-
2010; Dubois and Thomas, 2009; Zhang et al., 2003). However, at ing ranged from 0 to 0.47 mol CO2 /mol alkalinity at temperatures
present, any of the systems cannot be reported as a perfect system ranging from 135 to 175 ◦ C. Thermal degradation of PZ is spec-
until a comprehensive study of the system is conducted. ulated to follow first and second order kinetics (Freeman and
Rochelle, 2012b). The rate of degradation seemed to increase with
2.2. Degradation of amines the increase in all the three parameters: temperature, PZ concen-
tration and CO2 loading. On the one hand degradation of 8 m PZ is
The degradation of amines not only causes operating problems observed to increase linearly with CO2 loading, from 0 to 0.3 moles
like corrosion and fouling but may also increase the operating cost CO2 per mole alkalinity at temperatures of 150–175 ◦ C. On the other
and environmental concerns (Chen et al., 2011; Kittel et al., 2012; hand rate declined when CO2 loading was above 0.4 mol CO2 /mol
Veltman et al., 2010). Amines mainly degrade in two ways, ther- alkalinity under the same conditions. Additionally, the author car-
mally and through oxidation. The thermal degradation occurs due ried out some screening tests to check the thermal stability of CO2
to the high temperature, while the oxidative degradation is induced loaded structural analogs of PZ and diamines. Concentrations of
by the presence of oxygen, CO2 , and metal ions in the system. Degra- amines were kept 8 m each with a CO2 loading of 0.3 mol CO2 /mol
dation products of amines and mechanism of their formation are alkalinity. Results brought to light that the Mor is even more stable
not listed or highlighted in details in this manuscript as these are than PZ, followed by PD.
already discussed briefly by some other reviews (Gouedard et al., Eide-Haugmo et al. (2011) used methods of Lepaumier and Davis
2012). to degrade various amines at 135 ◦ C, without and with CO2 loading
of 0.5 mol CO2 /mol amine. Results exhibited that thermal degra-
2.2.1. Thermal degradation of amines dation is directly affected by CO2 loading. In the presence of CO2 ,
Stripper operates at about 120–150 ◦ C, depending upon its hindered amine AMP had the highest stability and the secondary
configuration, where there are maximum chances of thermal amines degraded faster. Zoannou et al. (2013) experimented MEA
degradation, and it may also occur in cross heat exchanger and the thermally at 160 ◦ C for 2–8 weeks, with a CO2 loading of 0.19
reclaimer. Due to the degradation products, capacity of the solvent and 0.37 mol CO2 /mol alkalinity to determine CO2 removal capac-
to capture CO2 , decreases. To maintain CO2 capture capacity level, ity. Solvent seemed to degrade up to 95% for the maximum time
ultimately the solution is discarded and fresh solvent is added as mentioned. Bougie and Iliuta (2014) thermally degraded five sin-
makeup. A number of studies on thermal degradation of amines gle amines namely: 2-amino-2-hydroxymethyl-1,3-propanediol
have been conducted under various conditions to investigate the (AHPD), PZ, 2-amino-1,3-propanediol (serinol), AMP and MEA up
stability of the solvents (Bougie and Iliuta, 2014; Davis and Rochelle, to 130 ◦ C for fourteen days in thermal cylinders. The initial concen-
2009; Freeman, 2011; Freeman and Rochelle, 2011; Gouedard et al., trations of the amines were as following: 30 wt% for MEA (4.95 M),
132 S.A. Mazari et al. / International Journal of Greenhouse Gas Control 34 (2015) 129–140

Table 1
List of the common amines tested to date.

Amine Abbreviation Reference

Monoethanolamine MEA Bello and Idem (2005b), da Silva et al. (2012), Lepaumier et al. (2009a), Strazisar et al. (2003),
and Supap et al. (2001).
Diethanolamine DEA Hsu and Kim (1985), Jamal and Meisen (2001), Kim and Sartori (1984), Lepaumier et al.
(2009a), Tontiwachwuthikul and Idem (2013), and Tontiwachwuthikul et al. (2011).
Piperazine PZ Freeman et al. (2009), Freeman et al. (2010b), and Rochelle et al. (2011).
Morpholine Mor Alper (1990), Freeman and Rochelle (2011), and Liu et al. (2013).
1-Methylpiperazine 1-MPZ Freeman et al. (2013) and Freeman and Rochelle (2011).
2-Methylpiperazine 2-DMPZ Freeman et al. (2013) and Freeman and Rochelle (2011)
Piperidine PD Freeman and Rochelle (2011)
Pyrrolidine Pyr Freeman and Rochelle (2011)
Hexamethylenediamine HMDA Freeman and Rochelle (2011)
Hexamethyleneimine HMI Freeman and Rochelle (2011)
Homopiperazine HomoPZ Freeman and Rochelle (2011)
Ddiglycolamine DGA Al-Juaied and Rochelle (2006) and Alper (1990)
Methyldiethanolamine MDEA Chakma and Meisen (1988), Chakma and Meisen (1997), Closmann and Rochelle (2011),
Closmann (2011) and Namjoshi et al. (2013).
N-(2-Aminoethyl)ethanolamine AEEA Bindwal et al. (2011) and Ma’mun et al. (2007).
Aminomethylpropanol AMP Lepaumier et al. (2009a), Li et al. (2013a), Wang and Jens (2012a) and Wang and Jens (2014).
Tetraethylenepentamine TEPA Aronu et al. (2009)
1,4-Diaminobutane DAB Namjoshi et al. (2013)
Bis(aminoethyl)ether BAE Namjoshi et al. (2013)
N,N-dimethylaminoethanol DMAE Lepaumier et al. (2009a)
N,N -dimethylpiperazine DMP Lepaumier et al. (2009a)
N-(2-hydroxyethyl)ethylenediamine HEEDA Lepaumier et al. (2009a)
N-methylaminoethanol MAE Lepaumier et al. (2009a)
N,N,N ,N ,N  -pentamethyldiethylenetriamine PMDETA Lepaumier et al. (2009a)
2-(Methylamino)ethanolamine MMEA Ma’mun et al. (2007)
Ethylenediamine EDA Zhou et al. (2010)
Diethylenetriamine DETA Freeman et al. (2010a)
N-(2-aminoethyl) piperazine AEP Du et al. (2013) and Davis (2009).

Table 2
Thermal degradation rates of different amines.

Solvent Concentration (m) Loading (mol CO2 /mol alkalinity k1 (×10−7 s−1 ) Reference

100 ◦ C 120 ◦ C 135 ◦ C 150 ◦ C 175 ◦ C

MEA 3.5 0.4 0.03 0.22 1.09 Davis (2009)

MEA 7 0.2 0.28 0.90 3.97 Davis (2009)
MEA 7 0.4 0.02 0.29 1.34 8.28 Davis (2009)
MEA 11 0.2 0.19 0.69 Davis (2009)
DEA 4.0 0.5 9.91 Eide-Haugmo et al. (2011)
DGA 7 0.4 0.39 Davis (2009)
PZ 8 0.47 0.24 Freeman (2011)
PZ 8 0.3 0.01 0.61 1.32 Freeman (2011)
PZ 8 0.2 0.79 Freeman (2011)
PZ 8 0.1 0.66 Freeman (2011)
PZ 8 0.0 0.001 0.07 Freeman (2011)
1-MPZ 8 0.3 0.36 Freeman (2011)
2-MPZ 8 0.3 0.25 Freeman (2011)
MDEA 7 0.2 0.42 4.38 Closmann (2011)
Mor 8 0.3 0.5 Freeman (2011)
Pyr 8 0.3 14.0 Freeman (2011)
HomoPZ 8 0.3 18.5 Freeman (2011)
(PD 8 0.3 0.84 Freeman (2011)
t2,5-DimethylPZ 2 0.3 0.09 Freeman (2011)
HMDA 8 0.3 1.9 Namjoshi et al. (2013)
BAE 8 0.4 2.0 Namjoshi et al. (2013)
DAB 8 0.4 27.2 Namjoshi et al. (2013)
PDA 5.0 0.4 4.08 Hatchell (2014)
Putrescine 5.0 0.4 2.69 Hatchell (2014)
EDA 5.0 0.4 7.97 Hatchell (2014)
HMI 8 0.3 59.30 Freeman (2011)
HEEDA 3.5 0.4 16.0 Freeman (2011)
AMP 7.0 0.4 0.21 0.86 Freeman et al. (2010a)
HEP 7.0 0.4 0.46 Freeman et al. (2010a)
DETA 7 0.4 9.91 Freeman et al. (2010a)
AEP 2.33 0.4 1.91 Davis (2009)

AMP (3.35 M), and serinol (3.46 M), 23 wt% for AHPD (1.98 M) and of PZ does not match with the literature as it is illustrated as a
7 wt% for PZ (0.76 M). The highest amine concentration loss was highly a stable amine compared to AMP. Vevelstad et al. (2013b)
noticed in serinol, followed by MEA and PZ. The lowest amine con- conducted thermal degradation study of already oxidized amine
centration loss was observed for AMP and AHPD. However, the loss solutions with CO2 in closed cylinders at a temperature of 135 ◦ C
 S.A. Mazari et al. / International Journal of Greenhouse Gas Control 34 (2015) 129–140 133

in both closed and open batch reactors. Amine losses after five 2.2.2. Oxidative degradation of amines in CO2 capture
weeks were found to be 50–56% for all MEA solutions. The results Oxidative degradation of amines is highly undesirable for
enlightened that there is no effect of oxidative degradation on the amine-based CO2 capture as this causes growing economic bur-
thermal degradation amine loss. Huang et al. (2013) established den and may also cause operating problems like fouling, corrosion
that the flue gas contaminants enhance the thermal degradation of and foaming (Chakma and Meisen, 1986). Driving force for the rate
amine (MEA). Results showed that the MEA degrade significantly in of oxidative degradation is the presence of O2 partial pressure,
the presence of nitrite (5000 ppm). However, the acidic impurities concentration of amine, and temperature. Furthermore, Goff and
seemed not to influence of the rate of thermal degradation of MEA. Rochelle (2004) reported that oxidative degradation is accelerated
Though, it may affect the product distribution (Zhou et al., 2011). by the presence of oxygen, and free metal ions. However, amine
Thermal degradation rates of different amines are listed in Table 2. oxidative degradation is more sensitive to O2 than the amine con-
Data from Table 2 shows that the highly stable amines tested centration (Supap et al., 2001; Vevelstad et al., 2013a), CO2 loading
to date are Mor, PD, PZ, BAE and, HMDA. Only PZ has been stud- has also a significant impact on the oxidative degradation of amine
ied in significant details up to now, however, other amines are not (Chi and Rochelle, 2002). The presence of acidic gases meanwhile
yet developed. Studies on PZ revealed that it is a stable solvent cannot be ignored as they have tendency to catalyze the oxidation
up to 150 ◦ C with favorable CO2 capture and absorption proper- of amine as SO2 has seemed to increase the rate of oxidation of
ties. However, it has lower CO2 solubility which is the hurdle for MEA on an increase of its concentration (Uyanga and Idem, 2007).
this solvent to be used as a single solvent. In addition, other afore- Oxidation of amines (e.g. MEA, MDEA and PZ), is more dependent
mentioned amines are also ring structure or diamines what makes on O2 concentration than that of CO2 (McDonald et al., 2014).
them more favorable for CO2 capture. Mor is also being investigated U.S. Army Chemical Research and Development Laborato-
by researcher for CO2 capture and its solubility and formation of ries have proposed fragmentation of amines through electron
nitrosamines (Chandan et al., 2013; Liu et al., 2013; Matin et al., abstraction. Oxidative degradation experiments, mainly focusing
2013). Results of the studies brought to light that Mor has higher on tertiary amines, were conducted in the presence of chlorine
CO2 capacity, and absorption rate compared to MEA but lower than dioxide (ClO2 ) and other oxidants (Dennis et al., 1967; Hull et al.,
PZ. However, other mentioned solvents are not yet investigated, 1967; Rosenblatt et al., 1963, 1967). Authors reported that the
this is a research gap that is needed to be undertaken to evalu- rate-limiting step is the electron abstraction, instead of hydrogen
ate their CO2 capture capacity, CO2 solubility and CO2 absorption abstraction. Pietsch et al. (2001) investigated oxidation of primary
rate. and secondary amines in the presence of ClO2 and chlorine while
A number of blended amines have been investigated under dif- studying the application of chlorine based water treatment process
ferent conditions to appreciate the stability of the solvent with for pharmaceutical agents. Study reported that the rate of oxidation
capable CO2 capture properties (Hilliard, 2008; Idem et al., 2005; of amines in presence of ClO2 mainly depend on their structure. A
Namjoshi et al., 2013). The blends of PZ have been reported as generalized order of rate of degradation is suggested as: tertiary
efficient and stable solvents as that of alkanolamines and other amines ≥ secondary amines ≥ primary amines. In addition, PZ has
amines (Dugas and Rochelle, 2009; Freeman, 2011; Freeman and been reported as highly degradable solvent in the presence of ClO2
Rochelle, 2011, 2012b; Li et al., 2013b; Namjoshi et al., 2013; compared to other tested primary and secondary amines, however,
Rochelle et al., 2011). Closmann (2009, 2011, 2013) examined it is resistant to chlorine. In another study, Wattanaphan (2012)
the combination of PZ and MDEA under different conditions. 7 m in order to investigate the effect of chlorides present in flue gas
MDEA/2 m PZ has been examined at temperatures and CO2 load- on the degradation of MEA, conducted oxidation experiments in
ing of 100–150 ◦ C and 0–0.43 mol CO2 /mol alkalinity respectively. presence of sodium chloride (NaCl), ferrous chloride (FeCl2 ), and
Experiments were executed in stainless steel cylinders, which hydrochloric acid (HCl). Study speculated that the chloride ion (Cl− )
were placed in a temperature-controlled oven for the duration while reacting with protonated MEA(R-NH3 + ) decreases the rate of
of nine weeks. Author reported that either degradation of the degradation of MEA.
blend was almost zero or immeasurable under prescribed condi- In the light of above statements, it may be summed up that
tions. The blend of AMP/PZ has also been investigated, showing amines are more sensitive to ClO2 than other chloride ions. How-
good CO2 capture characteristics (Brúder et al., 2011; Samanta ever, most of the studies conducted are not representing the
and Bandyopadhyay, 2009). Thermal degradation of 5 m PZ/2.3 m operating conditions of flue gas composition, absorber and strip-
AMP blend has been studied at 135 and 150 ◦ C with a CO2 load- per. It would be complementary to conduct a study that should
ing of 0.4 mol CO2 /mol alkalinity for up to 6 weeks (Li et al., represent the similar operating conditions of flue gas composition,
2013a). Two sets of experiments were run for AMP/PZ, and results absorber and stripper to know the more accurate reaction rate and
have been arranged in percentage range. In 6 weeks, 9–13% loss degradation mechanism of amines with chlorides.
for PZ and 19–22% for AMP was noticed at 135 ◦ C. Higher degra- Oxidative degradation of various amines, tested for post-
dation was observed at 150 ◦ C, which was around 20–28% for combustion CO2 capture has been widely studied by several
PZ and 56–60% for AMP. Results indicate that blending AMP scholars (Didas et al., 2014; Fredriksen and Jens, 2013; Kindrick
and PZ does not provide desired result as in the blended form, et al., 1950; Lepaumier et al., 2009b; Sexton and Rochelle, 2010;
AMP accelerated the rate of degradation of blend as that of Voice and Rochelle, 2011; Wang and Jens, 2013). Bello and
alone. Idem (2005a) studied the oxidative degradation of 5 and 7 m
Du et al. (2013) investigated thermal degradation of PZ with MEA at 55–120 ◦ C with a CO2 loading of 0–0.44 mol CO2 /mol
N-(2-aminoethyl) piperazine (AEP). Degradation experiments of MEA with and without corrosion inhibitor sodium meta-vanadate
the 5 m PZ/2 m AEP were conducted in stainless steel cylinders. (NaVO3 ). The experiments were conducted in a rotary-type auto-
Solutions were loaded with CO2 (0.2–0.3 mol CO2 /mol alkalinity), clave with an O2 pressure of 250 and 350 kPa. Results of the
and the experimentation duration was up to 20 weeks, at 150 and study brought to light that the presence of the corrosion inhibitor
175 ◦ C. Amine loss for PZ was up to 10% and 30% for AEP for 20 weeks NaVO3 , as well as amine concentration, temperature or presence
at 150 ◦ C. The blend did not sustain the temperature of 175 ◦ C where of O2 increased the rate of the degradation of MEA, however,
it lost all of its initial concentration for the same duration. Author increase in CO2 loading decreased the solvent degradation rate.
reported that loss of the blend followed first order kinetics with The degradation of MEA–H2 O–O2 and MEA–CO2 –O2 systems also
rate constants of 1.52 × 10−8 s−1 and 20.1 × 10−8 s−1 at 150 ◦ C and increased with increase in the temperature and O2 partial pres-
175 ◦ C respectively. sure but decreased with increasing amine concentration (Bello
134 S.A. Mazari et al. / International Journal of Greenhouse Gas Control 34 (2015) 129–140

and Idem, 2005b). Furthermore, when MDEA was blended with partial pressure. However, the degradation rate of MEA was found
MEA, it showed a decrease in the rate of degradation of MEA to be higher than that of AMP in the blend.
at elevated temperature (≥100 ◦ C) (Lawal et al., 2005). Sexton Freeman (2011) and Freeman et al. (2010a) conducted bench
and Rochelle (2009) studied oxidation of MEA in low gas flow scale oxidative degradation experiments of PZ in a low gas flow
(LGF) and high gas flow (HGF) reactors at 55 ◦ C. Metal ions (LGF) (100 ml/min) Teflon oxidation reactor (TOR) and an original
copper (Cu), chromium (Cr), iron (Fe) and vanadium (V) were oxidation reactor (OOR). Experiments of 8 to 10 m PZ, CO2 loaded
used as catalysts. The catalysts seemed to enhance the rate of with 0.2–0.4 mol CO2 /mol alkalinity at temperatures 55–70 ◦ C
oxidation. In the presence of Cu and Fe, MEA loss was twice, com- allowing 2% CO2 , and 98% O2 as input parameters for 3–5 weeks. In
pared to that of the solvent without Fe. In the HGF experiments, oxidation, metal salts like iron (1 mM Fe2+ ) stainless steel (0.4 mM
the potential of metals to degrade solvent was in an order of Fe2+ , 0.1 mM Cr3+ and 0.05 mM Ni2+ ) and copper (4 mM Cu2+ ) were
Cu > Cr/Ni > Fe > vanadium. used (Freeman, 2011). Oxidation of PZ in presence of metal ions
Goff and Rochelle (2004) studied the oxidative degradation and O2 followed first order kinetics. Oxidation of PZ seemed to
of MEA under typical CO2 capture process operating conditions. increase with the increase in partial pressure of O2 as well as tem-
Experiments were conducted in a jacketed semi batch glass reactor perature. An increase of 245% in O2 partial pressure from 40 to
at 55 ◦ C with a CO2 loading of 0.15 and 0.40 mol CO2 /mol MEA. 98 kPa, enhanced PZ loss by 240% at 55 ◦ C. The increase in temper-
Some of the experiments were also conducted in the presence ature from 55 to 70 ◦ C has increased oxidation by 230%. The increase
dissolved iron and copper to monitor the catalytic effect of these in CO2 loading from 0.2 to 0.3 mol CO2 /mol alkalinity increased oxi-
metals on MEA degradation process. The O2 mass transfer has been dation, even so, the effect was not well understood. 8 m PZ loss in
reported as the rate-limiting step for the oxidative degradation of presence of 1.0 mM Fe2+ was observed to be 8% of the original amine
MEA. The degradation rate of MEA also seemed to increase with the in 450 h. Higher degradation of 10 m PZ, accounted for 28% of the
increase in CO2 loading. The rate of degradation of loaded MEA is not original amine in 220 h when 4.0 mM Cu2+ was added as a catalyst
much affected in the presence of Fe and Cu, however, oxidation of (Freeman et al., 2010a). In the absence of any catalyst, a loss of 2–7%
unloaded MEA may be catalyzed by ferrous iron (Chi and Rochelle, of PZ was noticed for 350 h. Results exhibited that adding Cu2+ as a
2002). Under small concentrations of SO2 about 60 ppm the rate of catalyst for the oxidation of PZ, increased the rate of degradation.
MEA oxidation can decrease by scavenging the oxidative radicals,
however, degradation rate may increase if the concentration of SO2
is increased (Zhou et al., 2013). Furthermore, the oxidation of MEA 3. PCC emissions and their environmental concerns
is reported to decrease in the presence of oxidation inhibitors like
ethylenediaminetetraacetic acid (EDTA) and diethylene triamine Reduction in CO2 emissions is based on the expense of some
penta methylene phosphonic acid (DTPMP) at a temperature of other environmental pollutants (Schreiber et al., 2009). In amine-
60 ◦ C and under 98% O2 and 2% CO2 , the decrease may be in an based CO2 capture, some of the wastes in form of volatile
order of EDTA > DTPMP (Lee et al., 2013). organic compounds (VOCs), solid and liquid streams are emitted
Lepaumier et al. (2009b,c) studied the oxidative degradation of (Koornneef et al., 2010; Reynolds et al., 2012; Strazisar et al., 2003).
various ethanolamines and ethylenediamines. Experiments were Spent amine, degradation products and heavy-metal corrosion
conducted in a stainless steel reactor at 140 ◦ C under an air pressure inhibitors emitted from reclaimer can cause toxicity (Thitakamol
of 2 MPa for 15 days. Study found that the most stable alkanolamine et al., 2006). The volatile degradation products like 2-butanamine,
is AMP followed by dimethylethanolamine (DMAE), however, the ammonia, and ethylamine are toxic and can affect health through
least stable are DEA and MEA. Whereas in the ethylenediamines skin burns and irritation once they are vaporized with treated flue
(polyamines), the most stable is tetramethylenediamine (TMDA) gas (Thitakamol et al., 2007). Irrespective of the adverse impacts of
and the least stable is pentamethyldiethylenetriamine (PMDETA). gaseous emissions and traces of the metals to the human and health
A comprehensive study of oxidative degradation of AMP and does not contribute to a great extent to the environmental impacts
blends of AMP with other amines have been conducted by Wang caused by CO2 capture plants (Thitakamol et al., 2006). However,
and Jens (2012a,b, 2013, 2014) and Wang (2013). Experiments of the main concern is regarding the volatile emissions, which are
3–5 mol/kg AMP loaded and unloaded with CO2 were conducted mainly either amines or their degradation products. Solvent losses
at temperatures 100–140 ◦ C and O2 partial pressure ranging from are approximately about up to 0.01–0.8 kg/ton CO2 captured (Karl
250 to 350 kPa. They found that AMP degradation is influenced by et al., 2011). Ammonia being more volatile degradation product
varying the parameters such as temperature, amine concentration, found to have maximum concentration as the emissions of PCC
CO2 loading, and O2 partial pressure. Degradation rate was slightly while using MEA (Azzi et al., 2014b). In Norway, the strategies for
higher for 5 mol/kg AMP than 3 mol/kg AMP as well as for CO2 structuring a full scale CCS at the 420 MW gas power plant at Kårstø
loaded AMP samples than unloaded. Degradation rate increased may release amine emissions about up to 40–160 tones yearly (Shao
by the increase in temperature, however, oxidation was highly O2 and Stangeland, 2009). However, the exact amount of emissions
partial pressure dependent. In the comparative study with each may vary depending up on the size of the plant, flue gas compo-
5 mol/kg MEA, DEA and MDEA at 120 ◦ C and 350 kPa O2 , the oxi- sition and operating conditions of the plant. These emissions may
dation of AMP was lower than MEA and DEA but equivalent to further deteriorate into harmful products through photo oxidation
MDEA. Furthermore, the blend of AMP/PZ was tested at temper- and rain (Nielsen et al., 2011a,b). Amine emissions are not only
atures 80–120 ◦ C with an O2 partial pressure of 250 kPa for 13 harmful to the humans but also may damage ecosystem (Gjernes
days. Degradation of the blend increased with increase in tem- et al., 2013; Poste et al., 2014). The highly alarming degradation
perature as well as with the increase in PZ concentration from 0 products of amines are the nitrosamines and nitramines.
to 0.15 mol/kg as AMP concentration was fixed at 3.5 mol/kg. It is Fugitive emissions and accidental releases cannot be ignored.
observed from the results that the loss of AMP/PZ is near to that in Fugitive emissions are unintentional releases that are not emit-
the single AMP system; however, PZ loss rate is greater than that ted through the discharge point of the treated flue gases. This
of the single PZ system. This shows the catalytic effect of AMP to may happen due to the leakages caused by different reasons,
degrade PZ. AMP/MEA blends were examined at temperatures up working and breathing (Thitakamol et al., 2007). These are uncon-
to 100–140 ◦ C with different concentrations of AMP and MEA and trolled emissions and can occur at any part of the plant. These
O2 partial pressures of 250 and350 kPa. Rate of degradation of the emissions may include; treated and untreated flue gas, solvents,
blends increased with the increase in temperature as well as O2 corrosion inhibitors, degradation products, and chemical additives
 S.A. Mazari et al. / International Journal of Greenhouse Gas Control 34 (2015) 129–140 135

(Thitakamol et al., 2007). Accidental release is mostly in a larger Nitrite

quantity than fugitive release which may be caused by the process 1E-6 Total Nitrosamine
equipment upsets.

Formation Rates (M/s)

1E-7

3.1. Formation of nitrosamines and nitramines in process and

their concerns 1E-8

Nitrosamines and nitramines are the suspected carcinogen

1E-9
compounds (Bartsch and Montesano, 1984; Lijinsky and Epstein,
1970). Nitrosamines and nitramines are toxic and mutagenic,
the toxicity and mutagenicity of the nitrosamines is higher than 1E-10
nitramines (Marit Låg et al., 2009). They have high tendency for PZ MDEA AMP MEA
adsorption to soil, so nitrosamine may cause damage to the soil
Fig. 2. Formation rates of nitrite and total N-nitrosamines during purging of 2.5 M
dwelling organisms or in case of mobility to groundwater, they each: PZ, MDEA, AMP, and MEA solutions at 44 ◦ C and an initial pH of 12 with
may adulterate the sources of drinking water (Lisbet et al., 2013). 25 ppmv NO and NO2 each. Adapted with permission from Dai et al. (2012). Copy-
Nitrosamine and nitramines contamination of air and drinking right (2014) American Chemical Society.
water supplies downwind of amine-based CO2 plants can cause sig-
nificant damages (Fostås et al., 2011). Regulations aware that the
sum of concentration of nitrosamines and nitramines should not The effect nitrite, PZ carbamate species, and hydronium on
exceed 0.3 nano-gram (ng)/m3 for air concentrations and 4 ng/l for the formation of nitrosopiperazine were investigated through PZ
fresh water sources (Climate N., Pollution Agency, 2011). Strazisar (0.1–5 mol/kg) with 0.001–0.8 mol CO2 /PZ at 50–135 ◦ C (Goldman
et al. (2003) reported that the concentration of nitrosamines in et al., 2013). Results showed that the formation of MNPZ in the
a 800 tons per day CO2 capture plant is about 2.91 ␮mol/ml of presence of nitrate follows first order. Increase in CO2 decreases
lean solution. Another study reports that the emissions of both pH which causes more PZ carbamate species formation. PZ car-
nitrosamines and nitramines are about up to 5–47 ng/Nm3 under bamate species can enhance nitrosation since two groups on PZ
pilot plant conditions operating with MEA (da Silva et al., 2013). function semi-independently. Increase in temperature overcomes
In amine-based post-combustion CO2 capture amines degrade activation energy and lowers pH which also results an increase
to produce nitrosamines and nitramines (Fostås et al., 2011; Nielsen in rate of nitrosation. In a comparative study for the formation of
et al., 2011a,b; Poste et al., 2014). Partly these are produced during nitrosamines and nitramines in Mor, MDEA, PZ, AMP and AMP at
the CO2 capture process and the rest in the environment through 44 ◦ C in presence of each nitrous oxide (NO) and nitrogen dioxide
photochemical oxidation (Maree et al., 2013). The main reason (NO2 ), each at 25 ppmv conducted by Dai et al. (2012). The highest
for formation of nitrosamine and nitramines is the presence of accumulation rate of nitrosamine was found through the degra-
HONO, H2 ONO+ , NO2 *, NO*, N2 O4 , N2 O3 , etc., but the formation dation of PZ followed AMP and was the lowest for MEA. However,
of N2 O3 is regarded as the rate limiting step for secondary amines rate of accumulation of nitramine was almost similar for all amines.
nitrosation agent (Mitch, 2002). Nitrosamine and nitramines may The rate of formation of nitrosamines and nitramines is shown in
also be formed indirectly from the degradation products of pri- Fig. 2.
mary amines (MEA) and directly from secondary and tertiary
amine (PZ and MDEA) (da Silva and Booth, 2013). Studies have 3.2. Atmospheric degradation of amines
brought to light that MEA degrades into DEA which is nitrosated
to nitrosodiethanolamine (NDELA). In addition, nitrosodimethy- Volatility of amines and their degradation products is a well-
lamine (NDMA) is also detected as a degradation product of MEA known phenomenon in amine scrubbing technology. It contributes
which may be produced through the degradation of NDELA (Fostås to a major loss of amines and increasing concentrations in atmo-
et al., 2011). The presence of NO may not cause the formation sphere. Volatility of some common amines is reported in an
of NDELA through MEA but it would happen in the presence of order of MDEA < DGA < PZ < 2-MPZ < MAPA < EDA < MEA < DAP < 1-
NO2 (Knuutila et al., 2013). Driving force for the formation of N- MPZ < AMP (Nguyen et al., 2011). For the most tropospheric traces
nitrosomorpholine is the concentration of NO in wash water and of gas on a global scale, OH radical reactions are the main reason
in addition, the absence of CO2 may speed-up the rate of accu- for gas phase loss. NO3 radicals and Cl atoms are two other atmo-
mulation of N-nitrosomorpholine and N-nitromorpholine (Dai and spheric oxidants, however, NO3 may degrade into NO and NO2 in
Mitch, 2014). daytime. Whereas NO and NO2 may react with amines at night
In the dark, DEA promptly forms diethylnitrosamine (DEN), to continue the atmospheric degradation. A detailed report on the
when exposed to air containing 25–30% relative humidity (RH), photo-oxidation of ethylamine, diethylamine, triethylamine and PZ
ambient level NOx and small concentrations of HONO. In addi- is presented by Nielsen et al. (2011b). Study reports that the OH rad-
tion, tertiary amines like triethylamine can also form DEN at ical is the dominant oxidant for the atmospheric photo-oxidation.
ambient level of NOx in small concentrations (Pitts et al., 1978). Furthermore, study reveals that 9% of reactions between OH and
MDEA undergo alkylation to form secondary amines and aldehyde. ethylamine occurs at amino group ( NH2 ), which leads to the for-
Nitrosamines and nitramines formed from secondary amines are mation of (CH3 CH2 )2 NNO and (CH3 CH2 )2 NNO2 . For triethylamine,
chemically stable compared to primary (Mitch, 2002). Using PZ as about 35% of the reactions with OH has ability to form nitrosamine,
a solvent in a pilot plant study, the concentration of mononitro- (CH3 CH2 )2 NNO, and nitramine (CH3 CH2 )2 NNO2 . The expected
spiperazine (MNPZ) was found to be 0.09 mol/kg using a synthetic lifetimes for nitramines, (CH3 CH2 NHNO2 and (CH3 CH2 )2 NNO2
flue gas stream without additional NOx , however, a concentration of with respect to the OH have more than one day. However, for
0.9–1.2 mmol/kg solvent was observed using a real flue gas stream diethylamine, the study exhibits that 60% of the OH radicals reac-
under similar operating conditions (Nielsen et al., 2013). Under lab- tions occur at the amino group (>NH), whilst the nitrosamine
oratory conditions the formation of MNPZ is in first order (Fine et al., carcinogen, (CH3 CH2 )2 NNO, and potential carcinogen nitramine,
2013). Furthermore, it is speculated that MNPZ is thermally stable (CH3 CH2)2 NNO2 , are reported to be formed resulting from this reac-
up to 150 ◦ C (Jackson and Attalla, 2011). tion. It is also speculated that the quantification of photo-oxidation
136 S.A. Mazari et al. / International Journal of Greenhouse Gas Control 34 (2015) 129–140

Table 3
Initial amine, VOC and NOx mixing ratios for smog chamber experiments (Azzi et al., 2014a).

Experiment NO (ppbv) NO2 (ppbv) Amine (ppbv) Propene (ppbv) Isoprene (ppbv) m-Xylene (ppbv) i-Pentane (ppbv)

VOC low NOx

E729 45 9 – 87 24 25 69
E740 46 7 – 90 32 34 93

VOC high NOx

E742 142 19 – 78 52 23 97
E744 146 17 – 76 57 26 79

MEA low NOx

E755 44 9 ∼13 (5) 81 59 20 81
E757 46 8 ∼27 (10) 78 52 31 98
E764 45 8 ∼82 (50) 81 50 28 78
E771 43 7 106 86 52 30 85
E761 47 7 433 80 52 26 87

MEA high NOx

E769 153 16 ∼83 (50) 84 56 30 93
E766 146 12 480 83 51 32 99

PZ low NOx
E805 43 10 57 76 56 31 105

AMP low NOx

E809 42 7 ∼81 77 54 29 101
E811 43 6 ∼28 83 57 30 100

of PZ products, MNPZ and nitropiperazine was not in range, 4.1. Theme 1: solvent management
however, their formation is reported. In addition, the study
brought to light that the photolysis of N-nitrosodimethylamine, N- The concept is well established that the amine-based PCC tech-
nitrosodiethylamine, N-nitrosomorpholine, N-nitrosopiperazine, nology can be economized through proper management of the
N-nitrosopiperidine and N-nitrosopyrazine under sunlight is about solvent. Solvent makeup cost is around up to 10% of the total oper-
0.3–0.5 times to that of NO2 presence. At night concentrations of OH ating cost using MEA, as a solvent. The major concern in the solvent
are less and inactive, however, the concentrations of NO and NO2 management is the solvent selection. To date, none of the solvents
plays a vital role as an oxidant at that time (Lee and Wexler, 2013). have been found to have complete package of desired properties.
Lindley et al. (1979) studied the gas phase reactions of O2 , However, there are some amines like PZ and Mor that may be used
NO and NO2 with (CH3 )2 N radical. They perform identification as solvents of choice in future if their CO2 solubility and environ-
of methylmethanimine, CH3 NQCH2 , as being the major product mental concerns are controlled (Mazari et al., 2014). It should also
during dimethylamino radical reactions. Lee and Wexler (2013) be noted that detailed studies are required for the quantification of
reported that lifetime for amines with respect to the attack of the degradation products of these new amines. On one hand, the
OH radical is about 2–20 h, excluding triflouroethlamine (13 days) blends of PZ and Mor may also be solvents of choice as they miti-
and dimethylhydrazine (4.6 days). The photolysis of nitrosamine is gate the limited solubility problem of these solvents. However, on
rapid, and having an average lifetime of about 40 min in Mongstad the other hand, it cannot be ignored that blending PZ with other
area (day and night) (Nielsen et al., 2011a,b). amines has catalyzed its degradation rate.
CSIRO Australia is involved in the research of photo-oxidation Most of the amines have good CO2 capture capability but the pri-
of the amines used in PCC at Loy Yang Power Station (Angove et al., mary determination of solvent’s suitability is based on its stability.
2013; Aronu et al., 2009; Azzi et al., 2014a). The photo-oxidation Instability of the solvent will lead to many problems, like fouling,
studies of MEA, AMP and PZ have been conducted, in CSIRO smog foaming, corrosion and deactivation of the solvent. Thermal degra-
chamber, the initial temperature for all experiments was 23 ± 2 ◦ C. dation reported for most of the amines follow first order kinetics.
The volume of chamber is about up to 18.1 m3 and is lined with FEP Thermal degradation is a function of temperature, however, it is
Teflon film. The chamber has been illuminated with 80 black-light also influenced by the concentration of CO2 and amine. In addition,
tubes (Sylvania BLB 350, 36 W) which emit radiations, over the UVA composition of flue gases may play a substantial role in the ther-
range of 350–390 nm, with peak intensity occurring at 366 nm. The mal degradation. Amines with no chains, followed by long chain
total duration of each experiment including, injection preparations have the highest stability toward thermal degradation. Data from
and calibrations, was 10–12 h. The concentrations of additives and literature shows that PD, Mor and PZ are the most stable amines
other conditions used are listed in Tables 3 and 4. with favorable CO2 absorption rate. Some of the diamines like BAE
Results revealed that the photo-oxidation of MEA, PZ and AMP and HMDA are also stable at elevated temperatures. In one of the
in the presence of VOCs and NOx formed huge amounts of aerosol studies discussed in Section 2.1, speculates that AMP and AHPD
mass. However, ammonia was found as the main degradation prod- are more stable at 130 ◦ C than PZ. However, this seems to be an
uct of MEA in most of the experiments. PZ + NOx + VOC showed incomplete study or an error as most of the literature suggests PZ
the formation of ozone which is speculated to be formed either as stable solvent compared to AMP at elevated temperatures but
due to the lower reactivity of PZ or the reaction of PZ with AHPD is new a solvent.
ozone. Many studies have reported that the dominant part of the
degradation is oxidation. The oxidative degradation is highly
4. Discussion dependent on the concentration of O2 , however, temperature, CO2
and presence of metal ions also reported to catalyze the oxidation.
In this section, two main themes of post-combustion CO2 Not for all but in some cases, increase in concentration of amine
capture, solvent management and environmental impacts of and CO2 can minimize the rate of oxidation (Bello and Idem,
amine-based emissions are discussed. 2005b). In MEA–H2 O–CO2 system, Fe and Cu do not influence the
 S.A. Mazari et al. / International Journal of Greenhouse Gas Control 34 (2015) 129–140 137

Table 4
Summary of key product data for VOC, MEA, PZ and AMP experiments (Azzi et al., 2014a).

Expt Change from initial amount/concentration at ∼6 h

O3 (ppbv) NH3 (ppbv) Aerosol (␮g m−3 ) i-C3 H12 (% lost) H2 NCHO (ppbv) HCHO (ppbv) CO (ppbv)

VOC low NOx

729 308 – 1.3 38% – 77 81

VOC high NOx

742 198 – 0.3 31% – 91 51
744 201 – 1.3 26% – 89 52

MEA + VOC low NOx

755 293 – 13.0 30% <1 100 77
757 323 ∼3 22.9 31% <1 109 73
764 308 ∼5.5 88.8 30% ∼1.4 102 75
771 252 29 477 30% 6.0 106 58
761 172 95 888 16% 18.3 104 46

MEA + VOC high NOx

769 201 ∼4 148 26% ∼2.1 100 79
766 182 92 1237 27% 25.6 78 27

PZ + VOC Low NOX

805 231 10 248 31% NA 78 56

AMP + VOC low NOx

809 234 12 261 NA NA NA 52
811 323 7.5 30.6 36% NA NA 83

oxidation of MEA but Fe2+ can increase the oxidation. The same nitrosamines and nitramine vary from 2 to 20 h. Research work of
catalyst can accelerate the oxidation of the MEA system (if H2 O and CSIRO Australia at Loy Yang Power Station found that nitrosamines
CO2 are not present in the MEA system). In case of PZ, Fe does not and nitramines formation is not in that much quantity, which may
affect the oxidation, however, it is catalyzed by Cu. Under similar impart any effect on the environment. However, higher amounts
condition, the oxidation of some amines can be ranked as follows: of ammonia and aerosol mass were observed.
PZ < AMP < MDEA < DEA < MEA. Oxidation of amine may also be
affected by the blending it with another amine as oxidation of PZ 5. Suggestions
is enhanced if it is blended with AMP. Such cases make the solvent
selection even difficult if one problem is solved on the expense of MEA is known as one of the mature solvents, for post-
another problem created. combustion CO2 capture. However, there are some other solvents
like Mor, PZ, PD and BAE which should be focused for further inves-
4.2. Theme 2: PCC emissions and their concerns tigation in order to replace MEA due to its instability. Mor, PZ, PD
and BAE have shown thermal stability up to 150 ◦ C. Except PZ, none
One of the growing concerns of the amine-based CO2 capture of the solvents have been investigated, under either absorber or
technology is its emissions. Amines and some of their degradation stripper conditions. To mitigate limited CO2 solubility problem, PZ
products being volatile get vaporized through water-wash from has been investigated with some other amines in blended form,
absorber section which cause significant solvent losses. Some of what accelerated its rate of degradation except MDEA, however,
heavy metals in flue gas and as corrosion inhibitors are also emitted search should be continued in order to find the suitable blend. It
through the recalimer to the environment. Many of these prod- would be mandatory to identify and quantify the degradation prod-
ucts are not only toxic but are carcinogenic like nitrosamine and ucts of the new amines to be tested, as even degradation products
nitramines. There are certain chances that these emissions also of PZ has not yet been completely identified and quantified. Chlo-
have tendency to accumulate in the water resources including rides are speculated to be the oxidation promoters, a detailed study
underground water and may endanger the ecosystem. Emissions on primary, secondary and tertiary amines under post-combustion
of nitrosamines and nitramines reported in literature are under CO2 operating conditions and flue gas composition should be con-
control as per guidelines of environmental agencies. However, it ducted in order to understand the mechanism of the degradation of
must be noted that these emissions can vary depending upon a amines. Amine emissions contribute to the formation of hazardous
number of parameters, like plant size, flue gas composition and products through photo-oxidation. Besides degradation, MEA is
solvent, etc. A number of nitrosamines and nitramines have been understood as the more volatile amine, compared to MDEA, PZ,
reported in literature through the degradation of amines and more DGA, etc. which is another reason for its replacement with any
than 80% of them are suspected carcinogenic. Nitrosamines formed other system. Formation of nitrosamines and nitramines is a serious
from the secondary amines are the most stable. In addition, sec- issue, what should completely be explored for the amines like Mor,
ondary amines may form highest amount of nitrosamines as has PZ, PD and BAE. Post-combustion, pilot plant experiments should
been found for PZ in a comparative study with MDEA, AMP and be conducted for Mor, PD and BAE for understanding the relative
MEA. onsite behavior of the amines.
Photo-oxidation of amines is another serious concern. Forma-
tion of nitrosamine may be controlled within the process but cannot 6. Conclusion
be controlled in atmosphere. OH radical is the main culprit for
the photo-oxidation of amines. However, nitrite and Cl radicals Solvent selection is a complex task and multidisciplinary area,
may also play a significant role. The concerns of these emissions where a number of amines and amine systems are tested. None
mainly depends on the lifetime of these products, more the lifetime of the amine systems with a complete package of characteristics
higher the risk. Literature reports that generally lifetimes of the have been reported yet. Piperazine morpholine and piperidine have
138 S.A. Mazari et al. / International Journal of Greenhouse Gas Control 34 (2015) 129–140

been found to be the most stable amines. Thermal and oxidative Chakma, A., Meisen, A., 1988. Identification of methyl diethanolamine degradation
degradation of amines follows the first order kinetics. Oxidative products by gas chromatography and gas chromatography–mass spectrometry.
J. Chromatogr. A 457, 287–297.
degradation is heavily dependent on the concentration of oxygen. Chakma, A., Meisen, A., 1997. Methyl-diethanolamine degradation—mechanism and
However, some of the other oxidants present in flue gas may also kinetics. CJChE 75, 861–871.
accelerate the rate of oxidation. Temperature, CO2 loading, amine Chandan, P.A., Remias, J.E., Neathery, J.K., Liu, K., 2013. Morpholine nitrosation to bet-
ter understand potential solvent based CO2 capture process reactions. Environ.
concentration and presence of metal ions also catalyzes the rate of Sci. Technol. 47, 5481–5487.
thermal degradation. In terms of thermal stability, only few amines Chen, X., Freeman, S.A., Rochelle, G.T., 2011. Foaming of aqueous piperazine and
are stable above 150 ◦ C. Cyclic amines with no chains, followed by monoethanolamine for CO2 capture. Int. J. Greenh. Gas Control 5, 381–386.
Chi, S., Rochelle, G.T., 2002. Oxidative degradation of monoethanolamine. Ind. Eng.
long chain have the highest stability toward thermal degradation.
Chem. Res. 41, 4178–4186.
Volatile amines and degradation products like ammonia have Climate, N., 2011. Pollution Agency. Permit for Activities Pursuant to the Pollution
been reported as the emissions of the post combustion CO2 capture Control Act. CO2 Technology Centre, Mongstad, DA.
Closmann, F., Nguyen, T., Rochelle, G.T., 2009. MDEA/piperazine as a solvent for CO2
plant, which ultimately contaminate the atmosphere. Formation of
capture. Energy Procedia 1, 1351–1357.
nitrosamines and nitramines, have been reported in the literature. Closmann, F., Rochelle, G.T., 2011. Degradation of aqueous methyldiethanolamine
Nitrosamine quantities for MEA and PZ are provided for lab-scale by temperature and oxygen cycling. Energy Procedia 4, 23–28.
as well for pilot plants. The driving force for the photo-oxidation of Closmann, F.B., 2011. Oxidation and Thermal Degradation of Methyldithanolamine/
Piperazine in CO2 Capture. University of Texas, Austin, TX, pp. 1 online resource
amines is the presence of OH radical. Nitrite and Cl as well can cause [xxxi, 458 leaves].
the photo-oxidation. Amines with lower volatility and higher sta- da Silva, E.F., Booth, A.M., 2013. Emissions from post-combustion CO2 capture plants.
bility may release fewer quantities of emissions, ultimately which Environ. Sci. Technol. 47, 659–660.
da Silva, E.F., Kolderup, H., Goetheer, E., Hjarbo, K.W., Huizinga, A., Khakharia, P.,
may lead a minimal photo-oxidation of the amine. Tuinman, I., Mejdell, T., Zahlsen, K., Vernstad, K., Hyldbakk, A., Holten, T., Kvams-
dal, H.M., van Os, P., Einbu, A., 2013. Emission studies from a CO2 capture pilot
plant. Energy Procedia 37, 778–783.
Acknowledgement da Silva, E.F., Lepaumier, H., Grimstvedt, A., Vevelstad, S.J., Einbu, A., Vernstad, K.,
Svendsen, H.F., Zahlsen, K., 2012. Understanding 2-ethanolamine degradation
in post-combustion CO2 capture. Ind. Eng. Chem. Res. 51, 13329–13338.
This research is supported by High Impact Research Grant Dai, N., Mitch, W.A., 2014. Effects of flue gas compositions on nitrosamine and
UM.C/625/1/HIR/123, from University of Malaya, Kuala Lumpur nitramine formation in post-combustion CO2 capture systems. Environ. Sci.
Technol. 48, 7519–7526.
50603, Malaysia
Dai, N., Shah, A.D., Hu, L., Plewa, M.J., McKague, B., Mitch, W.A., 2012. Measurement
of nitrosamine and nitramine formation from NOx reactions with amines during
amine-based carbon dioxide capture for post-combustion carbon sequestration.
References Environ. Sci. Technol. 46, 9793–9801.
Davis, J., Rochelle, G., 2009. Thermal degradation of monoethanolamine at stripper
Al-Juaied, M., Rochelle, G.T., 2006. Absorption of in aqueous blends of diglycolamine conditions. Energy Procedia 1, 327–333.
and morpholine. Chem. Eng. Sci. 61, 3830–3837. Davis, J.D., 2009. Thermal Degradation of Aqueous Amines used for Carbon Dioxide
Ali, S.H., Al-Rashed, O., Merchant, S.Q., 2010. Opportunities for faster carbon diox- Capture. University of Texas Libraries, Austin, TX, pp. 1 online resource [xxix,
ide removal: a kinetic study on the blending of methyl monoethanolamine and 278 leaves].
morpholine with 2-amino-2-methyl-1-propanol. Sep. Purif. Technol. 74, 64–72. De Brito, M., Henriques von Stockar, U., Bangerter, A., Menendez Bomio, P.,
Alper, E., 1990. Kinetics of reactions of carbon dioxide with diglycolamine and mor- Laso, M., 1994. Effective mass-transfer area in a pilot plant column equipped
pholine. Chem. Eng. J. 44, 107–111. with structured packings and with ceramic rings. Ind. Eng. Chem. Res. 33,
Angove, D.E., Stephen, W.S., Tibbett, A.R., Campbell, I., Emmerson, K.M., Cope, M.E., 647–656.
Patterson, M.P., Feron, P.M.H., Azzi, M., 2013. Deliverable 4.2: Determination of Dennis, W.H., Hull, L.A., Rosenblatt, D.H., 1967. Oxidations of amines. IV. Oxidative
the Fate of PCC Emissions into the Atmosphere. Prepared for: ANLEC R&D. CSIRO, fragmentation. J. Org. Chem. 32 (12), 3783–3787.
Australia. Derks, P., Hogendoorn, J., Versteeg, G., 2010. Experimental and theoretical study
Aronu, U.E., Svendsen, H.F., Hoff, K.A., Juliussen, O., 2009. Solvent selection for carbon of the solubility of carbon dioxide in aqueous blends of piperazine and N-
dioxide absorption. Energy Procedia 1, 1051–1057. methyldiethanolamine. J. Chem. Thermodyn. 42, 151–163.
Azzi, M., Angrove, D., Campbell, I., Cope, M., Emmerson, K., Feron, P., Patterson, M., Didas, S.A., Zhu, R., Brunelli, N.A., Sholl, D.S., Jones, C.W., 2014. Thermal, oxidative
Tibbett, A., White, S., 2014a. Assessing Atmospheric Emissions from Amine based and CO2 induced degradation of primary amines used for CO2 capture: effect of
CO2 PCC Process and their Impacts on the Environment – A Case Study. Atmo- alkyl linker on stability. J. Phys. Chem. C 118, 12302–12311.
spheric Chemistry of MEA and 3D Air Quality Modelling of Emissions from the Du, Y., Li, L., Namjoshi, O., Voice, A.K., Fine, N.A., Rochelle, G.T., 2013. Aqueous
Loy Yang PCC Plant, vol. 2. CSIRO, Australia. piperazine/N-(2-aminoethyl) piperazine for CO2 capture. Energy Procedia 37,
Azzi, M., Tibbett, A., Halliburton, B., Element, A., Artanto, Y., Meuleman, E., Feron, 1621–1638.
P., 2014b. Assessing Atmospheric Emissions from Amine-based CO2 Post- Dubois, L., Thomas, D., 2009. CO2 absorption into aqueous solutions of
combustion Capture Processes and their Impacts on the Environment – A monoethanolamine, methyldiethanolamine, piperazine and their blends. Chem.
Case Study. Measurement of Emissions from a Monoethanolamine-based Post- Eng. Technol. 32, 710–718.
combustion CO2 Capture Pilot Plant, vol. 1. CSIRO, Australia. Dugas, R., Rochelle, G., 2009. Absorption and desorption rates of carbon dioxide with
Bartsch, H., Montesano, R., 1984. Relevance of nitrosamines to human cancer. Car- monoethanolamine and piperazine. Energy Procedia 1, 1163–1169.
cinogenesis 5, 1381–1393. Dumée, L., Scholes, C., Stevens, G., Kentish, S., 2012. Purification of aqueous amine
Bello, A., Idem, R.O., 2005a. Comprehensive study of the kinetics of the oxidative solvents used in post combustion CO2 capture: a review. Int. J. Greenh. Gas
degradation of CO2 loaded and concentrated aqueous monoethanolamine (MEA) Control 10, 443–455.
with and without sodium metavanadate during CO2 absorption from flue gases. Eide-Haugmo, I., Lepaumier, H., Einbu, A., Vernstad, K., da Silva, E.F., Svendsen, H.F.,
Ind. Eng. Chem. Res. 45, 2569–2579. 2011. Chemical stability and biodegradability of new solvents for CO2 capture.
Bello, A., Idem, R.O., 2005b. Pathways for the formation of products of the oxidative Energy Procedia 4, 1631–1636.
degradation of CO2 -loaded concentrated aqueous monoethanolamine solutions Fine, N.A., Goldman, M.J., Nielsen, P.T., Rochelle, G.T., 2013. Manag-
during CO2 absorption from flue gases. Ind. Eng. Chem. Res. 44, 945–969. ing n-nitrosopiperazine and dinitrosopiperazine. Energy Procedia 37,
Bindwal, A.B., Vaidya, P.D., Kenig, E.Y., 2011. Kinetics of carbon dioxide removal by 273–284.
aqueous diamines. Chem. Eng. J. 169, 144–150. Fine, N.A., Goldman, M.J., Rochelle, G.T., 2014. Nitrosamine formation in amine
Bishnoi, S., Rochelle, G.T., 2000. Absorption of carbon dioxide into aqueous piper- scrubbing at desorber temperatures. Environ. Sci. Technol. 48, 8777–8783.
azine: reaction kinetics, mass transfer and solubility. Chem. Eng. Sci. 55, Fostås, B., Gangstad, A., Nenseter, B., Pedersen, S., Sjøvoll, M., Sørensen, A.L., 2011.
5531–5543. Effects of NOx in the flue gas degradation of MEA. Energy Procedia 4, 1566–1573.
Bishnoi, S., Rochelle, G.T., 2002. Absorption of carbon dioxide in aqueous piper- Fredriksen, S.B., Jens, K.-J., 2013. Oxidative degradation of aqueous amine solutions
azine/methyldiethanolamine. AIChE J. 48, 2788–2799. of MEA, AMP, MDEA, Pz: a review. Energy Procedia 37, 1770–1777.
Bougie, F., Iliuta, M.C., 2014. Stability of aqueous amine solutions to thermal and Freeman, S.A., 2011. Thermal Degradation and Oxidation of Aqueous Piperazine for
oxidative degradation in the absence and the presence of CO2 . Int. J. Greenh. Gas Carbon Dioxide Capture, Chemical Engineering. University of Texas at Austin,
Control 29, 16–21. University of Texas at Austin.
BP, 2014. BP Energy Outlook 2035., pp. 96, www.bp.com/energyoutlook Freeman, S.A., Chen, X., Nguyen, T., Rafique, H., Xu, Q., Rochelle, G.T.,
Brúder, P., Grimstvedt, A., Mejdell, T., Svendsen, H.F., 2011. CO2 capture into aqueous 2013. Piperazine/N-methylpiperazine/N,N -dimethylpiperazine as an Aqueous
solutions of piperazine activated 2-amino-2-methyl-1-propanol. Chem. Eng. Sci. Solvent for Carbon Dioxide Capture. Oil & Gas Science and Technology – Revue
66, 6193–6198. d’IFP Energies nouvelles.
Chakma, A., Meisen, A., 1986. Corrosivity of diethanolamine solutions and their Freeman, S.A., Davis, J., Rochelle, G.T., 2010a. Degradation of aqueous piperazine in
degradation products. Ind. Eng. Chem. Prod. Res. Dev. 25, 627–630. carbon dioxide capture. Int. J. Greenh. Gas Control 4, 756–761.
 S.A. Mazari et al. / International Journal of Greenhouse Gas Control 34 (2015) 129–140 139

Freeman, S.A., Dugas, R., Van Wagener, D., Nguyen, T., Rochelle, G.T., 2009. Car- Lepaumier, H., Martin, S., Picq, D., Delfort, B., Carrette, P.-L., 2010. New amines for CO2
bon dioxide capture with concentrated, aqueous piperazine. Energy Procedia 1, capture. III. Effect of alkyl chain length between amine functions on polyamines
1489–1496. degradation. Ind. Eng. Chem. Res. 49, 4553–4560.
Freeman, S.A., Dugas, R., Van Wagener, D.H., Nguyen, T., Rochelle, G.T., 2010b. Car- Lepaumier, H., Picq, D., Carrette, P.-L., 2009a. New amines for CO2 capture. I. Mech-
bon dioxide capture with concentrated, aqueous piperazine. Int. J. Greenh. Gas anisms of amine degradation in the presence of CO2 . Ind. Eng. Chem. Res. 48,
Control 4, 119–124. 9061–9067.
Freeman, S.A., Rochelle, G.T., 2011. Thermal degradation of piperazine and its struc- Lepaumier, H., Picq, D., Carrette, P.-L., 2009b. New amines for CO2 capture. II. Oxida-
tural analogs. Energy Procedia 4, 43–50. tive degradation mechanisms. Ind. Eng. Chem. Res. 48, 9068–9075.
Freeman, S.A., Rochelle, G.T., 2012a. Thermal degradation of aqueous piperazine for Lepaumier, H., Picq, D., Carrette, P.L., 2009c. Degradation study of new solvents for
CO2 capture. 1. Effect of process conditions and comparison of thermal stability CO2 capture in post-combustion. Energy Procedia 1, 893–900.
of CO2 capture amines. Ind. Eng. Chem. Res. 51, 7719–7725. Li, H., Li, L., Nguyen, T., Rochelle, G.T., Chen, J., 2013a. Characterization of
Freeman, S.A., Rochelle, G.T., 2012b. Thermal degradation of aqueous piperazine for piperazine/2-aminomethylpropanol for carbon dioxide capture. Energy Proce-
CO2 capture. 2. Product types and generation rates. Ind. Eng. Chem. Res. 51, dia 37, 340–352.
7726–7735. Li, L., Voice, A.K., Li, H., Namjoshi, O., Nguyen, T., Du, Y., Rochelle, G.T., 2013b. Amine
Gjernes, E., Helgesen, L.I., Maree, Y., 2013. Health and environmental impact of amine blends using concentrated piperazine. Energy Procedia 37, 353–369.
based post combustion CO2 capture. Energy Procedia 37, 735–742. Lijinsky, W., EPSTEIN, S.S., 1970. Nitrosamines as environmental carcinogens. Nature
Goff, G.S., Rochelle, G.T., 2004. Monoethanolamine degradation: O2 mass transfer 225, 21–23.
effects under CO2 capture conditions. Ind. Eng. Chem. Res. 43, 6400–6408. Lindley, C.R., Calvert, J.G., Shaw, J.H., 1979. Rate studies of the reactions of the
Goff, G.S., Rochelle, G.T., 2006. Oxidation inhibitors for copper and iron catalyzed (CH3 )2 N radical with O2 , NO, and NO2 . Chem. Phys. Lett. 67, 57–62.
degradation of monoethanolamine in CO2 capture processes. Ind. Eng. Chem. Lisbet, S., Brakstad, O.G., Zahlsen, K., da Silva, E., Booth, A., 2013. Environmental
Res. 45, 2513–2521. fate of nitramines and nitrosamines released as degradation products from post
Goldman, M.J., Fine, N.A., Rochelle, G.T., 2013. Kinetics of N-nitrosopiperazine for- combustion CO2 -capture plants. Energy Procedia.
mation from nitrite and piperazine in CO2 capture. Environ. Sci. Technol. 47, Liu, K., Jinka, K.M., Remias, J.E., Liu, K., 2013. Absorption of carbon dioxide in aqueous
3528–3534. morpholine solutions. Ind. Eng. Chem. Res. 52, 15932–15938.
Gouedard, C., Picq, D., Launay, F., Carrette, P.-L., 2012. Amine degradation in CO2 Lowe, A., Beasley, B., Berly, T., 2009. Carbon Capture and Storage (CCS) in Australia,
capture. I. A review. Int. J. Greenh. Gas Control 10, 244–270. Carbon Capture: Sequestration and Storage. The Royal Society of Chemistry, pp.
Hatchell, D., Rochelle, G., 2014. Thermal Degradation of CO2 Loaded Linear Diamines. 65–101.
McKetta Department of Chemical Engineering 4th Quarterly. Ma’mun, S., Svendsen, H.F., Hoff, K.A., Juliussen, O., 2007. Selection of new absorbents
Hilliard, M.D., 2008. A Predictive Thermodynamic Model for an Aqueous Blend of for carbon dioxide capture. Energy Convers. Manage. 48, 251–258.
Potassium Carbonate, Piperazine, and Monoethanolamine for Carbon Dioxide MacDowell, N., Florin, N., Buchard, A., Hallett, J., Galindo, A., Jackson, G., Adjiman,
Capture from Flue Gas. University of Texas, Austin, TX, pp. 1 online resource C.S., Williams, C.K., Shah, N., Fennell, P., 2010. An overview of CO2 capture tech-
[lvii, 1004 leaves]. nologies. Energ. Environ. Sci. 3, 1645–1669.
Hsu, C.S., Kim, C.J., 1985. Diethanolamine (DEA) degradation under gas-treating Mangalapally, H.P., Notz, R., Hoch, S., Asprion, N., Sieder, G., Garcia, H., Hasse,
conditions. Ind. Eng. Chem. Prod. Res. Dev. 24, 630–635. H., 2009. Pilot plant experimental studies of post combustion CO2 cap-
Huang, Q., Thompson, J., Bhatnagar, S., Chandan, P., Remias, J.E., Selegue, J.P., Liu, K., ture by reactive absorption with MEA and new solvents. Energy Procedia 1,
2013. Impact of flue gas contaminants on monoethanolamine thermal degrada- 963–970.
tion. Ind. Eng. Chem. Res. 53, 553–563. Maree, Y., Nepstad, S., de Koeijer, G., 2013. Establishment of knowledge base for
Hull, L.A., Davis, G.T., Rosenblatt, D.H., Williams, H.K.R., Weglein, R.C., 1967. Oxida- emission regulation for the CO2 Technology Centre Mongstad. Energy Procedia
tions of amines. III. Duality of mechanism in the reaction of amines with chlorine 37, 6265–6272.
dioxide. J. Am. Chem. Soc. 89, 1163–1170. Marit Låg, Å.A., Instanes, C., Lindeman, B., 2009. Health Effects of Different Amines
Idem, R., Wilson, M., Tontiwachwuthikul, P., Chakma, A., Veawab, A., Aroonwilas, and Possible Degradation Products Relevant for CO2 Capture.
A., Gelowitz, D., 2005. Pilot plant studies of the CO2 capture performance of Matin, N.S., Remias, J.E., Neathery, J.K., Liu, K., 2013. The equilibrium solubility of
aqueous MEA and mixed MEA/MDEA solvents at the University of Regina CO2 carbon dioxide in aqueous solutions of morpholine: experimental data and
Capture Technology Development Plant and the Boundary Dam CO2 Capture thermodynamic modeling. Ind. Eng. Chem. Res. 52, 5221–5229.
Demonstration Plant. Ind. Eng. Chem. Res. 45, 2414–2420. Mazari, S.A., Ali, B.S., Jan, B.M., Saeed, M.I., 2014. Degradation study of piperazine,
IEA, 2012. CO2 Emissions from Fuel Combustion Highlights, 2012 edition. Interna- its blends and structural analogs for CO2 capture: a review. Int. J. Greenh. Gas
tional Energy Agency, pp. 124. Control 31C, 214–228.
IPCC, 2013. Climate change 2013. The physical science basis. Intergovernmental McDonald, J.D., Kracko, D., Doyle-Eisele, M., Garner, C.E., Wegerski, C., Senft, A.,
panel on climate change. In: Fifth Assessment Report of the Intergovernmental Knipping, E., Shaw, S., Rohr, A., 2014. Carbon capture and sequestration: an
Panel on Climate Change. exploratory inhalation toxicity assessment of amine-trapping solvents and their
Islam, M., Yusoff, R., Ali, B., 2010. Role of acid and heat stable salt in the degradation degradation products. Environ. Sci. Technol.
process of alkanolamine during sour gas sweetening process. Eng. e-Trans. 5, Mitch, W., 2002. Tasks 1 and 3 Report: Critical Literature Review of Nitrosa-
53–60 (ISSN 1823-6379). tion/Nitration Pathways. Yale University.
Islam, M., Yusoff, R., Ali, B., Islam, M., Chakrabarti, M., 2011. Degradation studies of Namjoshi, O., Li, L., Du, Y., Rochelle, G., 2013. Thermal degradation of piperazine
amines and alkanolamines during sour gas treatment process. Int. J. Phys. Sci. 6, blends with diamines. Energy Procedia 37, 1904–1911.
5883–5896. Nguyen, T., Hilliard, M., Rochelle, G., 2011. Volatility of aqueous amines in CO2
Jackson, P., Attalla, M., 2011. Environmental impacts of post-combustion capture – capture. Energy Procedia 4, 1624–1630.
new insights. Energy Procedia 4, 2277–2284. Nielsen, C.J., D’Anna, B., Dye, C., Graus, M., Karl, M., King, S., Maguto, M.M., Müller, M.,
Jamal, A., Meisen, A., 2001. Kinetics of CO induced degradation of aqueous Schmidbauer, N., Stenstrøm, Y., Wisthaler, A., Pedersen, S., 2011a. Atmospheric
diethanolamine. Chem. Eng. Sci. 56, 6743–6760. chemistry of 2-aminoethanol (MEA). Energy Procedia 4, 2245–2252.
Karl, M., Wright, R.F., Berglen, T.F., Denby, B., 2011. Worst case scenario study to Nielsen, C.J., D’Anna, B., Karl, M., Aursnes, M., Boreave, A., Bossi, R., Bunkan, A.J.C., Gla-
assess the environmental impact of amine emissions from a CO2 capture plant. sius, M., Hallquist, M., Hansen, A.M.K., Kristensen, K., Mikoviny, T., Maguta, M.M.,
Int. J. Greenh. Gas Control 5, 439–447. Müller, M., Nguyen, Q., Westerlund, J., Salo, K., Skov, H., Stenstrøm, Y., Wisthaler,
Kim, C., Sartori, G., 1984. Kinetics and mechanism of diethanolamine degradation in A., 2011b. Atmospheric Degradation of Amines (ADA): Summary Report: Photo-
aqueous solutions containing carbon dioxide. Int. J. Chem. Kinet. 16, 1257–1266. Oxidation of Methylamine, Dimethylamine and Trimethylamine. Norsk Institutt
Kindrick, R., Atwood, K., Arnold, M., 1950. The Relative Resistance to Oxidation of for Luftforskning, pp. 146.
Commercially Available Amines. Girdler Corp [Report 15-11]. Nielsen, P.T., Li, L., Rochelle, G.T., 2013. Piperazine degradation in pilot plants. Energy
Kittel, J., Fleury, E., Vuillemin, B., Gonzalez, S., Ropital, F., Oltra, R., 2012. Corrosion Procedia 37, 1912–1923.
in alkanolamine used for acid gas removal: from natural gas processing to CO2 Notz, R., Asprion, N., Clausen, I., Hasse, H., 2007. Selection and pilot plant tests of
capture. Mater. Corros. 63, 223–230. new absorbents for post-combustion carbon dioxide capture. Chem. Eng. Res.
Knuutila, H., Asif, N., Vevelstad, S.J., Svendsen, H.F., 2013. Formation and Des. 85, 510–515.
Destruction of NDELA in 30 wt% MEA (Monoethanolamine) and 50 wt% DEA Tontiwachwuthikul, P., Idem, R., 2013. Recent Progress and New Developments in
(Diethanolamine) Solutions. Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles. Post-Combustion Carbon-Capture Technology with Reactive Solvents. Future
Koornneef, J., Ramirez, A., van Harmelen, T., van Horssen, A., Turkenburg, W., Faaij, Science Ltd.
A., 2010. The impact of CO2 capture in the power and heat sector on the emis- Pitts, J.N., Grosjean, D., Van Cauwenberghe, K., Schmid, J.P., Fitz, D.R., 1978. Photoox-
sion of SO2 , NOx , particulate matter, volatile organic compounds and NH3 in the idation of aliphatic amines under simulated atmospheric conditions: formation
European Union. Atmos. Environ. 44, 1369–1385. of nitrosamines, nitramines, amides, and photochemical oxidant. Environ. Sci.
Lawal, O., Bello, A., Idem, R., 2005. The role of methyl diethanolamine (MDEA) in Technol. 12, 946–953.
preventing the oxidative degradation of CO2 loaded and concentrated aqueous Pietsch, J., Sacher, F., Schmidt, W., Brauch, H.J., 2001. Polar nitrogen compounds
monoethanolamine (MEA)–MDEA blends during CO2 absorption from flue gases. and their behavior in the drinking water treatment process. Water Res. 35 (15),
Ind. Eng. Chem. Res. 44, 1874–1896. 3537–3544.
Lee, D., Wexler, A.S., 2013. Atmospheric amines. Part III. Photochemistry and toxicity. Poste, A.E., Grung, M., Wright, R.F., 2014. Amines and amine-related compounds
Atmos. Environ. 71, 95–103. in surface waters: a review of sources, concentrations and aquatic toxicity. Sci.
Lee, I.-Y., Kwak, N.-S., Lee, J.-H., Jang, K.-R., Shim, J.-G., 2013. Oxidative degradation Total Environ. 481, 274–279.
of alkanolamines with inhibitors in CO2 capture process. Energy Procedia 37, Puxty, G., Rowland, R., Allport, A., Yang, Q., Bown, M., Burns, R., Maeder, M., Attalla,
1830–1835. M., 2009. Carbon dioxide post-combustion capture: a novel screening study of
140 S.A. Mazari et al. / International Journal of Greenhouse Gas Control 34 (2015) 129–140

the carbon dioxide absorption performance of 76 amines. Environ. Sci. Technol. Tontiwachwuthikul, P., Idem, R., Gelowitz, D., Liang, Z.H., Supap, T., Chan, C.W.,
43, 6427–6433. Sanpasertparnich, T., Saiwan, C., Smithson, H., 2011. Recent progress and new
Rao, A.B., Rubin, E.S., 2002. A technical, economic, and environmental assessment of development of post-combustion carbon-capture technology using reactive sol-
amine-based CO2 capture technology for power plant greenhouse gas control. vents. Carbon Manage. 2, 261–263.
Environ. Sci. Technol. 36, 4467–4475. Uyanga, I.J., Idem, R.O., 2007. Studies of SO2 - and O2 -induced degradation of aqueous
Reynolds, A.J., Verheyen, T.V., Adeloju, S.B., Meuleman, E., Feron, P., 2012. Towards MEA during CO2 capture from power plant flue gas streams. Ind. Eng. Chem. Res.
commercial scale post-combustion capture of CO2 with monoethanolamine sol- 46, 2558–2566.
vent: key considerations for solvent management and environmental impacts. Veltman, K., Singh, B., Hertwich, E.G., 2010. Human and environmental impact
Environ. Sci. Technol. 46, 3643–3654. assessment of post-combustion CO2 capture focusing on emissions from amine-
Rochelle, G., Chen, E., Freeman, S., Van Wagener, D., Xu, Q., Voice, A., 2011. Aqueous based scrubbing solvents to air. Environ. Sci. Technol. 44, 1496–1502.
piperazine as the new standard for CO2 capture technology. Chem. Eng. J. 171, Vevelstad, S.J., Grimstvedt, A., Elnan, J., da Silva, E.F., Svendsen, H.F., 2013a. Oxida-
725–733. tive degradation of 2-ethanolamine: the effect of oxygen concentration and
Rochelle, G.T., 2012. Thermal degradation of amines for CO2 capture. Curr. Opin. temperature on product formation. Int. J. Greenh. Gas Control 18, 88–100.
Chem. Eng. 1, 183–190. Vevelstad, S.J., Grimstvedt, A., Knuutila, H., Svendsen, H.F., 2013b. Thermal degrada-
Rosenblatt, D.H., Albert, J., Hayes, J., Harrison, B.L., Streaty, R.A., Moore, K.A., 1963. tion on already oxidatively degraded solutions. Energy Procedia 37, 2109–2117.
The reaction of chlorine dioxide with triethylamine in aqueous solution. J. Org. Voice, A.K., Rochelle, G.T., 2011. Oxidation of amines at absorber conditions for CO2
Chem. 28, 2790–2794. capture from flue gas. Energy Procedia 4, 171–178.
Rosenblatt, D.H., Hull, L.A., Deluca, D.C., Davis, G.T., Weglein, R.C., Williams, H.K., Wang, M., Lawal, A., Stephenson, P., Sidders, J., Ramshaw, C., 2011. Post-combustion
1967. Oxidations of amines. II. Substituent effects in chlorine dioxide oxidations. CO2 capture with chemical absorption: a state-of-the-art review. Chem. Eng.
J. Am. Chem. Soc. 89 (5), 1158–1163. Res. Des. 89, 1609–1624.
Samanta, A., Bandyopadhyay, S.S., 2009. Absorption of carbon dioxide into aqueous Wang, T., 2013. Degradation of Aqueous 2-Amino-2-methyl-1-propanol for Carbon
solutions of piperazine activated 2-amino-2-methyl-1-propanol. Chem. Eng. Sci. Dioxide Capture.
64, 1185–1194. Wang, T., Jens, K.-J., 2012a. Oxidative degradation of aqueous 2-amino-2-methyl-
Schreiber, A., Zapp, P., Kuckshinrichs, W., 2009. Environmental assessment of Ger- 1-propanol solvent for post-combustion CO2 capture. Ind. Eng. Chem. Res. 51,
man electricity generation from coal-fired power plants with amine-based 6529–6536.
carbon capture. Int. J. Life Cycle Assess. 14, 547–559. Wang, T., Jens, K.-J., 2012b. A study of oxidative degradation of AMP for post-
Sexton, A.J., Rochelle, G.T., 2009. Catalysts and inhibitors for MEA oxidation. Energy combustion CO2 capture. Energy Procedia 23, 102–110.
Procedia 1, 1179–1185. Wang, T., Jens, K.-J., 2013. Oxidative degradation of AMP/MEA blends for post-
Sexton, A.J., Rochelle, G.T., 2010. Reaction products from the oxidative degradation combustion CO2 capture. Energy Procedia 37, 306–313.
of monoethanolamine. Ind. Eng. Chem. Res. 50, 667–673. Wang, T., Jens, K.-J., 2014. Oxidative degradation of aqueous PZ solution and AMP/PZ
Shao, R., Stangeland, A., 2009. Amines used in CO2 Capture – Health and Environ- blends for post-combustion carbon dioxide capture. Int. J. Greenh. Gas Control
mental Impacts. Bellona Report 49. 24, 98–105.
Sieminski, A., 2013. International Energy Outlook 2013. U.S. Energy Information Wattanaphan, P., 2012. Studies and Prevention of Carbon Steel Corrosion and Sol-
Administration 33. vent Degradation during Amine-based CO2 Capture from Industrial Gas Streams.
Strazisar, B.R., Anderson, R.R., White, C.M., 2003. Degradation pathways for Faculty of Graduate Studies and Research, University of Regina.
monoethanolamine in a CO2 capture facility. Energy Fuels 17, 1034–1039. Zhang, X., Wang, J., Zhang, C.-F., Yang, Y.-H., Xu, J.-J., 2003. Absorption rate into
Supap, T., Idem, R., Veawab, A., Aroonwilas, A., Tontiwachwuthikul, P., Chakma, a MDEA aqueous solution blended with piperazine under a high CO2 partial
A., Kybett, B.D., 2001. Kinetics of the oxidative degradation of aqueous pressure. Ind. Eng. Chem. Res. 42, 118–122.
monoethanolamine in a flue gas treating unit. Ind. Eng. Chem. Res. 40, Zhou, S., Chen, X., Nguyen, T., Voice, A.K., Rochelle, G.T., 2010. Aqueous ethylenedi-
3445–3450. amine for CO2 capture. ChemSusChem 3, 913–918.
Thitakamol, B., Veawab, A., Aroonwilas, A., 2006. Environmental Assessment of Zhou, S., Wang, S., Chen, C., 2011. Thermal degradation of monoethanolamine in CO2
the Integration of Amine-based CO2 Capture Unit to Coal-fired Power Plants capture with acidic impurities in flue gas. Ind. Eng. Chem. Res. 51, 2539–2547.
for Greenhouse Gas Mitigation. EIC Climate Change Technology, 2006 IEEE, Zhou, S., Wang, S., Sun, C., Chen, C., 2013. SO2 effect on degradation of MEA and some
pp. 1–7. other amines. Energy Procedia 37, 896–904.
Thitakamol, B., Veawab, A., Aroonwilas, A., 2007. Environmental impacts of Zoannou, K.-S., Sapsford, D.J., Griffiths, A.J., 2013. Thermal degradation of
absorption-based CO2 capture unit for post-combustion treatment of flue gas monoethanolamine and its effect on CO2 capture capacity. Int. J. Greenh. Gas
from coal-fired power plant. Int. J. Greenh. Gas Control 1, 318–342. Control 17, 423–430.