Energy Procedia 23 ( 2012 ) 92 101

1876-6102 2012 The Authors. Published by Elsevier Ltd. Selection and/or peer-review under responsibility of SINTEF Energi AS
doi: 10.1016/j.egypro.2012.06.072
TCCS-6
Improvement of lipophilic-amine-based thermomorphic
biphasic solvent for energy-efficient carbon capture
Jiafei Zhang
a
*, Yu Qiao
a
, David W. Agar
a

a
Faculty of Biochemical and Chemical Engineering; Technical University of Dortmund, Dortmund, D-44227, Germany

Abstract
A series of novel lipophilic amine solvents have been studied for improving the energy efficiency of post-combustion
carbon capture (PCC). More than thirty lipophilic amines with varying molecular structures, for instance primary
amine Cycloheptylamine (CHpA), secondary amine Dibutylamine (DBA) and tertiary amine N-Ethylpiperidine
(EPD), with respect to their phase separation temperatures, loading capacities, reaction kinetics and regenerabilities
have been investigated by screening tests at temperatures between 25-90 C. The further solvent selection was
assessed by absorption at 30-40 C with 50-500 mbar CO
2
partial pressure and desorption at 75-85 C with
intensified regeneration measures in absence of steam stripping. Compared to monoethanolamine (MEA), selected
lipophilic amines have performed excellently in CO
2
loading, solvent regenerability and chemical stability. The low
temperature (80C) required for desorption also permits the use of waste heat for reducing the operating cost.

2010 Published by Elsevier Ltd. Selection and/or peer-review under responsibility of [name organizer]

Keywords: post-combustion capture, biphasic solvent, CO
2
absorption, novel technology
1. Introduction
Solvent regeneration with high energy consumption at temperatures of 120-150 C represents a
significant shortcoming in the alkanolamine-based CO
2
capture process. Development of novel
absorbents and technologies to reduce the operational expense is thus essential for improving the process
economics of PCC [1]. A chemical solvent with phase change potentially offers considerable advantages
[2]. Since the absorbent is resolved into one phase highly concentrated in CO
2
and another phase low in
CO
2
, only the concentrated phase need be sent to the stripper. This is equivalent to a system operated with

* Corresponding author. Tel.: +49-231-755-2582; fax: +49-231-755-2698.
E-mail address: jiafei.zhang@udo.edu.
Available online at www.sciencedirect.com
2012 The Authors. Published by Elsevier Ltd. Selection and/or peer-review under responsibility of SINTEF Energi AS
Jiafei Zhang et al. / Energy Procedia 23 ( 2012 ) 92 101 93
an extremely high CO
2
capacity. Concerning the advantages provided by phase change in desorption, a
new CO
2
capture technology DMX
TM
process has also been developed by IFP Energies nouvelles to
reduce the operating cost by phase splitting in decanter before steam stripping, but the activating solvents
are still undisclosed [3].
High temperature required for solvent regeneration not only leads to the high energy consumption but
also significant thermal degradation of conventional alkanolamines. Thermomorphic biphasic solvent
(TBS) systems, comprising lipophilic amines as absorbing and activating component, have been proposed
to meet this challenge [4]. The advantages of using TBS absorbent for CO
2
capture, especially for low
temperature regeneration at 80 C and their high cyclic CO
2
capacities, have already been demonstrated
[5,6]. The excellent performance of such TBS absorbent makes it one of the most promising solvent
systems for assessing technical viability in ongoing scale-up development work.
In the lipophilic amine systems, the secondary amine Dipropylamine (DPA) and tertiary amine N,N-
Dimethylcyclohexylamine (DMCA) were firstly disclosed and extensively studied with respect to their
absorption and desorption characteristics. However, the slow absorption rate of DMCA and precipitation
of protonated DPA ions and bicarbonate salts were the drawbacks for those solvents. Investigation on
searching new amines has therefore been carried out. The structure influence on the activity of amine-
based CO
2
absorption and desorption has also been studied by other researchers [7-11]. Those works have
demonstrated that the amino group attaching an alkyl group especially with an alpha branched carbon was
found to be the most potential molecular structure for enhancing the absorption and desorption rates as
well as loading capacity. However, those studies were limited to the aqueous single-phase system.
Screening investigation to identify new thermomorphic biphasic lipophilic amines was thus conducted
both theoretically and experimentally in this project.
2. Experiment
2.1. Chemicals
More than thirty lipophilic amines with varying molecular structures have been studied in the
screening experiments; some of them representatively are listed in Table 1. All the amines tested in this
work were purchased from Merck, Sigma Aldrich, Acros Organics, ALFA AESAR and ABCR with high
purity (97%).
2.2. Test tube screening experiments
The preliminary screening experiment was carried out in test tubes (Schott GL-18 with 18 mm O.D.
and 180 mm length) containing 6 mL aqueous amine solutions at varying concentrations from 0.9 to 4.2
M. PTFE tubules with 1 mm I.D. and 240 mm length were used as gas inlet pipe through the rubber seal.
Absorption was performed in water bath at 25 C with CO
2
gas flow rate at 20 mL/min, saturated with
water vapour in order to make up the vaporised water, under atmospheric pressure. The weight of the tube
is measured every 5 or 10 min to observe the amount of absorbed CO
2
, until the reaction is completely in
equilibrium. The final CO
2
rich loading was determined by the barium chloride method with titration.
Desorption was carried out by heating in thermal oil bath stepwise from 40 to 90 C with interval of 10
C. In order to limit solvent vaporisation, cotton sponge was applied as demister for condensing water and
volatile amine vapours. Magnetic stirrers were laid into each test tube to intensify CO
2
release and also in
oil bath bowl to homogenise the temperature in the heating system. The weight was also measured
stepwise for indicating the mass of desorbed CO
2
and the final lean loading was determined by barium
chloride method.
94 Jiafei Zhang et al. / Energy Procedia 23 ( 2012 ) 92 101
Table 1. List of studied lipophilic amines
No. Chemical Abbr. Type Sub. No. Chemical Abbr. Type Sub.
1 Hexylamine HxA I L 17 Cyclohexylamine CHA I O
2 Heptylamine HpA I L 18 Cycloheptylamine CHpA I O
3 Octylamine OtA I L 19 Cyclooctylamine COA I O
4 Di-n-propylamine DPA II L 20 N-Isopropyl cyclohexylamine IPCA II O
5 Diisopropylamine DIPA II B 21 N,N-Dimethyl Cyclohexyl amine DMCA III O
6 N-Ethylbutylamine EBA II L 22 N,N-Diethyl Cyclohexyl amine DECA III O
7 Di-n-butylamine DBA II L 23 Dicyclohexylamine DCHA II O
8 Diisobutylamine DIBA II B 24 2,6-Dimethyl piperidine 2,6-DMPD II P
9 N-sec-Butyl-n-propylamine SBPA II B 25 3,5-Dimethyl piperidine 3,5-DMPD II P
10 Triethylamine TEA III L 26 2,2,6,6-Tetramethyl piperidine TMPD II P
11 Tripropylamine TPA III L 27 N-Methyl piperidine MPD III P
12 Tributylamine TBA III L 28 N-Ethyl piperidine EPD III P
13 N,N-Diisopropyl methylamine DIMA III B 29 Benzylamine BzA I Z
14 N,N-Diisopropyl ethylamine DIEA III B 30 N-Methyl benzylamine MBzA II Z
15 N,N-Dimethyl butylamine DMBtA III L 31 N-Ethyl benzylamine EBzA II Z
16 N,N-Dimethyl octylamine DMOA III L 32 N,N-Dimethyl benzylamine DMBzA III Z
Type: I - primary amine, II - secondary amine, III - tertiary amine;
Substitute (Sub.): L - liner chain, B - branched chain, O - cycloalkane, P - piperidine, Z - benzyl group.
2.3. Bubble column screening experiments
The further screening experiments were conducted in a 100mL glass bubble column containing 40 mL
of the aqueous amine solution at 30 C. Various amines with concentrations from 3 to 5 M and CO
2

partial pressures of 5-50 kPa balanced with N
2
were employed over contact times of 2-5 hrs, to ensure
that equilibrium was achieved. Desorption was carried out by magnetic agitation (PTFE coated round stir
bar, 30 mm length & 9 mm diameter) 1000 rpm at 75-80 C, without gas tripping. The feed and reference
gas flows were saturated by water and regulated by mass flow controllers (Bronkhorst EL-FLOW) so as
to be constant in the absorption and desorption tests. During experiments, the outlet gas was monitored
online by gas chromatography (GC) Agilent HP 6890 with a GS-GasPro capillary column 30.0 m x 320
m and oven temperature 35 C. The detailed experimental setup is presented in a previous publication
[5]. After the reaction had been completed, the CO
2
loading was ascertained by barium chloride method,
total amine concentration was determined by acid-base titration and the blended amine compositions were
determined by GC (CP-Volamine capillary column 60.0 m x 320 m and oven step-heating procedure
with temperatures from 60 to 250 C) analysis.
3. Selection of lipophilic amines
The screening of lipophilic amine solvents initially focused on observing the miscibility of organic and
aqueous phases and temperature dependent phase transition behaviour. Based on the theoretical study and
experimental measure on the physical and chemical properties, amines with high melting point, low
boiling point, high viscosity or low chemical stability were excluded. In total over thirty available
lipophilic amines were preliminarily selected for test tube experiment. The overall screening among those
amines is based on the comprehensive performance in absorption and regeneration, including phase
separation temperature, CO
2
capacity, reaction rate and regenerability.
Jiafei Zhang et al. / Energy Procedia 23 ( 2012 ) 92 101 95
3.1. Phase transition
Phase change behaviours such as lower critical solution temperature (LCST) for lean solvent and
liquid-liquid phase separation (LLPS) for rich solvent, observed in absorption and desorption,
respectively, are the most important phenomena in this study. Due to restricted miscibility, the LCST
behaviour were found in mixtures of lipophilic amine and water [12,13], typically between 10 and 40 C.
The aqueous solubility of amine decreases with increasing temperature and thus a phase splitting occurs
above the LCST. The prepared lean solvent is desired homogeneous in absorption at 30-40 C and the
loaded solution should exhibit LLPS in regeneration at 75-85 C. The LCST of most lipophilic amines
measured in the experiment is found below 20 C, which are not suitable to be used as primary absorbent.
Only a few amines, for example HxA, CHpA, A1 (secondary alkylamine), MPD and EPD, have shown
approved phase change characteristics.
3.2. Reaction rate
The absorption rate can be influenced by aqueous solubility, surface tension and basicity of amine. In
this experiment, aqueous solubility is the key factor; because the fast reactions were found in the
lipophilic amine solutions which are completely or partially aqueous miscible at room temperature, while
the slow reactions were observed in those that are aqueous insoluble or slightly soluble. According to the
reaction mechanism, carbamate formation (CF, eq. 1) is the main reaction for primary and secondary
amines and takes place very fast [14]. Fig. 1 demonstrates the rapid reaction rate has been obtained in
amine solutions such as HxA, CHA, A1, DPA, DIPA, SBPA, DMPDs, etc. Therefore, the highly reactive
primary or secondary amines are typically considered as activators for absorption; while the moderate
reactive tertiary or secondary amines can be used as regeneration promoter due to their remarkable
regenerability enhanced by LLPS behaviour.









(a) (b)









(c) (d)
Fig. 1. Characteristics of CO
2
absorption in 2.7M chain amines (a & b), cycloalkylamines (c) and cyclic amines (d) solutions
0 20 40 60 80 100
0,0
0,2
0,4
0,6
0,8
1,0
C
O
2

l
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[
m
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/
m
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]
Time [min]
DPA
DIPA
DBA
DIBA
SBPA
0 20 40 60 80 100 120
0,0
0,2
0,4
0,6
0,8
1,0
C
O
2

l
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[
m
o
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/
m
o
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]
Time [min]
HxA
DMBA
B1
DIMA
DIEA
0 20 40 60 80 100 120
0,0
0,2
0,4
0,6
0,8
1,0
1,2
C
O
2

l
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[
m
o
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/
m
o
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]
Time [min]
A1
CHA
CHpA
IPCA
DMCA
DCHA
0 20 40 60 80 100
0,0
0,2
0,4
0,6
0,8
1,0
C
O
2

l
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[
m
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/
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]
Time [min]
2,6-DMPD
3,5-DMPD
MPD
EPD
96 Jiafei Zhang et al. / Energy Procedia 23 ( 2012 ) 92 101
3.3. Absorption capacity
CO
2
loading capacity theoretically depends on the reaction mechanism, such as tertiary amine is
typically able to achieve higher capacity than primary and secondary amines. Because tertiary amine can
react with equivalent mole of carbon dioxide and water, the direct formation of bicarbonate (BF, eq. 2) is
the only main reaction; while CF is the major and fast reaction in primary and secondary amine solutions,
and the loading capacity only can be enhanced, when more carbamates get accumulated and carbamate
reversion (CR, eq. 3) takes place, after CO
2
loading approaching 0.5 mol/mol. However, it is very
complicated in fact, due to the influences of sterically hindrance, aqueous solubility or insoluble salts
formation. The loading capacity can be reduced, since CR or BF is inhibited by insoluble composition; or
be enhanced if CR is promoted by aqueous environment. The high CO
2
loadings were found in primary
and secondary amine solutions for example CHpA, A1, DPA, 2,6-DMPD, etc.; while very low loadings
were detected in tertiary amine solutions such as DIEA, TPA and TBA. Besides, the amine concentration
also has negative influence on CO
2
loading (mol/mol). Most amines exhibit high CO
2
loading, >0.9
mol/mol, at 2 M; but it decrease to <0.8 mol/mol at 4 M (see Fig. 2). However, A1 is an exception, since
it still keeps high loading capacity, 0.95 mol/mol, even at 5 M.

Carbamate formation (CF)

RNHCOO RNH RNH CO
3 2 2
2

(1)
Bicarbonate formation (BF)


3 3 2 2 2
HCO RNH O H RNH CO

(2)
Carbamate reversion (CR)


3 3 2 2
2 2 HCO RNH O H RNHCOO CO

(3)











(a) (b)










(c) (d)
Fig. 2. CO
2
absorption into A1 (a), DBA (b), DMCA (c) and EPD (d) solutions
0 20 40 60 80 100 120 140 160
0,0
0,2
0,4
0,6
0,8
1,0
1,2
C
O
2

l
o
a
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g

/

a
m
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n
e

[
m
o
l
/
m
o
l
]
Time [min]
A1, 0.9 M
A1, 1.8 M
A1, 2.7 M
A1, 4.2 M
convert to 1 phase
0 20 40 60 80 100
0,0
0,2
0,4
0,6
0,8
1,0
1,2
C
O
2

l
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g

[
m
o
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/
m
o
l
]
Time [min]
DBA, 0.9 M
DBA, 1.8 M
DBA, 2.7 M
DBA, 4.2 M
convert to 1 phase
precipitation
0 80 160 240
0,0
0,2
0,4
0,6
0,8
1,0
C
O
2

L
o
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g

[
m
o
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/
m
o
l
]
Time [min]
DMCA, 0.9 M
DMCA, 1.8 M
DMCA, 2.7 M
DMCA, 4.2 M
convert to 1 phase
0 40 80 120 160
0,0
0,2
0,4
0,6
0,8
1,0
1,2
C
O
2

l
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[
m
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/
m
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]
Time [min]
EPD, 0.9 M
EPD, 1.8 M
EPD, 2.7 M
EPD, 4.2 M
convert to 1 phase
Jiafei Zhang et al. / Energy Procedia 23 ( 2012 ) 92 101 97
3.4. Regenerability
Solvent regeneration at high temperature is one of the most significant drawbacks in the alkanolamine-
based CO
2
capture process. However, lipophilic amine can solve this problem dramatically with
thermomorphic LLPS. According to the comparison of regenerability, B1 (sterically hindered alkylamine),
DMCA and EPD have performed the most remarkably and become the most considerable solvents as
regeneration promoter for further studies. The regenerability of DMOA and MPD was also outstanding,
unfortunately extremely slow absorption rate or high volatility, respectively, was observed. Fig. 3
illustrate that the regeneration rate became fast after the LLPS taking place and very high regenerability
was obtained in tertiary amine solutions such as DMCA and EPD. The major advantage of using
lipophilic amines with reaction involving LLPS to a multiphase system is that the regeneration can be
carried out at a modest temperature, i.e. 80 C or even lower, which is much less than the temperature
employed in conventional industrial process using alkanolamines. Together with the high cyclic loading
capacity of such amines, the TBS absorbents offer more degrees of freedom for cost reduction with
respect to the quality of energy requirement.










(a) (b)










(c) (d)
Fig. 3. Regeneration of loaded DBA (a), DMCA (b), B1 (c) and EPD (d) solutions
3.5. Detrimental phenomena
Various phenomena, for example LLPS, gel formation, viscosity increasing, insoluble carbamate salts
formation and precipitation of bicarbonates, were observed during the absorbents screening, however,
only the miscibility gap with LLPS was of interest in this work and the remaining features were
detrimental to performance. Those unfavourable phenomena such as gel and insoluble salts formations
20 30 40 50 60 70 80 90 100
0,0
0,2
0,4
0,6
0,8
F
r
a
c
t
i
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n

o
f

d
e
s
o
r
b
e
d

C
O
2

[
m
o
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/
m
o
l
]
Temperature [
o
C]
DBA, 0.9 M
DBA, 1.8 M
DBA, 2.7 M
DBA, 4.2 M
convert to 2 phases
20 30 40 50 60 70 80 90 100
0,0
0,2
0,4
0,6
0,8
1,0
F
r
a
c
t
i
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f

d
e
s
o
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b
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d

C
O
2

[
m
o
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/
m
o
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]
Temperature [
o
C]
DMCA, 0.9 M
DMCA, 1.8 M
DMCA, 2.7 M
DMCA, 4.2 M
convert to 2 phases
20 30 40 50 60 70 80 90 100
0,0
0,2
0,4
0,6
0,8
1,0
F
r
a
c
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io
n

o
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d
e
s
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b
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d

C
O
2

[
m
o
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/
m
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]
Temperature []
B1, 0.9 M
B1, 1.8 M
B1, 2.7 M
B1, 4.2 M
convert to 2 phases
20 30 40 50 60 70 80 90 100
0,0
0,2
0,4
0,6
0,8
1,0
F
r
a
c
t
i
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f

d
e
s
o
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b
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d

C
O
2

[
m
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/
m
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]
Temperature [
o
C]
EPD, 0.9 M
EPD, 1.8 M
EPD, 2.7 M
EPD, 4.2 M
convert to 2 phases
98 Jiafei Zhang et al. / Energy Procedia 23 ( 2012 ) 92 101
are undesired in absorption; since they reduce the CO
2
loading capacity by impediment of either reaction
rate or carbamate reversing to bicarbonate; and also can damage the equipment by fouling.
According to experimental observation, insoluble carbamate salts formation took place at the very
beginning of absorption, typically in 5-15 min, before achieving CO
2
loading of 0.5 mol/mol, because it is
caused by CF in organic phase, especially in the gas-liquid interface. The solid salts are self-associated at
the liquid surface or adhered on the wall of the reactor. In contrast, precipitation occurred close to the end
of absorption during CR, due to the limited aqueous solubility of bicarbonate salts. In secondary amines,
the isoalkyl group, for example DIPA, DIBA or IPCA, has shown high potential to induce insoluble
carbamate salts formation; while n-alkyl groups, for instance DPA, DBA and EBA, can cause bicarbonate
precipitation. However, some of the carbamate and bicarbonate solids can be dissolved in water by
elevating temperature to 50-60 C. Due to individual reaction mechanism of BF, precipitation and
insoluble salts formation are avoided in tertiary amine solutions.
4. Technical viability of TBS absorbents
Since a biphasic solvent would be inconvenient for absorption, the fine tuning of the phase transition
behaviour has been investigated. The protonated lipophilic amine species was found to be able to play the
role of a solubiliser for elevating the LCST. For example, the LCST of unloaded 5 M A1+B1 (4:1)
solution is normally 15 C, but can be increased to 40 C for the lean solution with a CO
2
loading 0.05
mol/mol, which demonstrates the technical feasibility for implementing the absorption with single phase
solvent. In place of the high-energy-consumption steam stripping column, a continuous stirred-tank
reactor (CSTR) has been employed for achieving the low temperature (80 C) regeneration with
remarkable performance, when appropriate process intensification measures are adopted.
4.1. Classification
After surveying more than thirty lipophilic amines in the test tube screening experiments; only less
than ten proved to be comparable with, if not better than, conventional alkanolamines. Lipophilic amines
such as DPA, 2,6-DMPD, A1, DMCA, MPD, EPD and B1 with their good performances were proposed
as the most potential candidates which survived the rigorous selection process. Novel absorbent A1, has
performed much better than the benchmark amines MEA and AMP (Fig. 4-a). Conversely, DMCA, EPD
and B1 with low LLPS temperature exhibit an outstanding regenerability (>96%) at 80 C.
According to the operational performance, lipophilic amines can be classified into two categories:
absorption activator, for instance, CHpA, MBzA and A1, with rapid reaction kinetics, and regeneration
promoters, such as B1, DMCA and DMBzA, exhibiting outstanding regenerabilities. Aliphatic amines
with various molecular structures have been studied for this purpose. Primary and secondary amines are
typically regarded as activators; an alpha-branch has a positive influence on reaction kinetics, while a
beta-branch can lead to unwanted precipitation. Tertiary amines are preferred for promoting regeneration
by virtue of their low dielectric constants and thermally induced LLPS behaviour.
4.2. Blending
The ideal chemical solvent for CO
2
absorption is desired to match the following criteria [2,15]:
Fast kinetics reduces height requirements for the absorber and/or solvent circulation flow rates;
High absorption capacity directly influences solvent circulation flow rate requirements;
Low regeneration costs cut energy consumption;
High thermal stability and low solvent degradation reduce solvent waste;
Jiafei Zhang et al. / Energy Procedia 23 ( 2012 ) 92 101 99
Low solvent expense should be easy and cheap to produce;
Low environmental impact;
Technical feasibility.
Due to the difficulties in obtaining a single lipophilic amine as a perfect solvent to fulfil all the
screening criteria, i.e. with both high reactivity and good regenerability, blended solvent of activator +
promoter, has been developed to overcome the drawbacks of the individual amines and combine the
advantages of several components. The blended solutions such as B1+A1, EPD+A1 and DMCA+A1 (3M,
3:1) were formulated for the investigation. Those blended lipophilic solvents have successfully achieved
both the rapid absorption rate thank to the activator and low residual loading due to the promoter. Fig. 4-b
indicates the superiority of the lipophilic amine solvent blend lies not only in the high loading capacity
but also in the good regenerability in comparison with the benchmark absorbents; where the cyclic
loading capacity of the newly developed solvent blend p-A1 (regeneration promoted A1) was 130%
higher than that for MDEA+MEA solution.














(a) (b)
Fig. 4. Characteristics of single (a) and blended (b) amine solutions in absorption at 19.4 kPa CO
2
& 30 C and desorption at 80 C
4.3. Solubilisation
Thermal-induced phase transition is a distinctive property of TBS system. The homogeneous solution
converts to heterogeneous upon heating after achieving LCST; contrarily, the regenerated biphasic
solution reverses to a single phase by cooling. Most of the aliphatic amines exhibit the phase transition
behaviour in the aqueous solutions, but very few of them can be employed as absorbent, because of the
and high volatile loss of lower alkylamines (C5-C7) due to low boiling point and low LCST of fatty
alkylamines (C8-C10) which is typically close to the freezing point of aqueous solutions. In order to
improve the solubility property of lipophilic amines, aqueous solubiliser was considered for the regulation
of phase transition behaviour. Varying organic solvents, for example alkanols, alkanolamines and
diamines, were hence studied by screening tests. The ideal solubiliser should meet the following criteria:
Effectively elevate the LCST of lipophilic amine solution with only small amount of additive;
No negative influence on absorption or desorption;
Highly chemical stability, no significant degradation;
Low volatile loss.
Among all the tested solubilisers, AMP has exhibited the best performance on the influence of LCST.
0 20 40 60 80 100 120 140
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
2: 88.1%
4: 46.4%
3: 85.6%
L
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[
m
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-
C
O
2
/
L
-
s
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n
]
Time [min]
1. A1, 5 M
2. AMP, 30 wt%
3. A1, 3 M
4. MEA, 30 wt% (~5 M)
1
2
3
4
Regenerability at 80 1: 87.8%
0 20 40 60 80 100 120 140
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
e: 87.6%
b: 98.1%
d: 99.2%
c: 97.3%
e
L
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[
m
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-
C
O
2
/
L
-
s
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n
]
Time [min]
a. p-A1, 4 M
b. DMCA+A1, 3 M
c. EPD+A1, 3 M
d. B1+A1, 3 M
e. MDEA+MEA, 3 M
a
b
c
d
Regenerability at 80 a: 96.5%
100 Jiafei Zhang et al. / Energy Procedia 23 ( 2012 ) 92 101
Fig. 5 proves AMP also has successfully elevated the LCST of the DMCA+A1 solutions at different
proportions. Fig. 6 demonstrated the limited influence was found on the absorption and desorption
performance of lipophilic amine solutions. However, increase the mass fraction of AMP has positive
influence on the LCST of the DMCA+A1 solution. But it is limited at 10 wt%, since the regenerability is
significantly depressed when over 20 wt% of AMP is added in the lipophilic amine solution.













Fig. 5. Influence of concentration, proportion and AMP
addition on phase transition
Fig.6. Influence of AMP on the ab-/desorption
characteristics of TBS solution
4.4. Solvent and process performance
Experiments for optimising solvent formulations were initially conducted in a bubble column. Blended
solvents such as A1+B1 with varying concentrations and proportions have been developed, possessing
rapid absorption rates, high loading capacities, low regeneration temperatures and good regenerabilities.
Fig. 7 illustrates that the net CO
2
loading capacity of the preferred A1+B1 solution is higher than for the
benchmark conventional 30wt% MEA and DMX-1 [3] solutions at varying CO
2
partial pressures. After
identifying the optimal parameters, this solvent was studied in a scaled-up 1 m high packed absorption
column. The regenerated TBS solution becomes homogeneous upon cooling to the LCST of ca. 40C, and
the loaded solution separates into two immiscible phases upon heating to 80 C. In the improved TBS
process (see Fig. 8), deep regeneration is enhanced by LLPS, which permits exploitation of the low value
heat at 90 C from the other processes and cutting the energy consumption by more than 35% [16]
compared to the conventional alkanolamine solvent systems.












Fig. 7. Vapour-Liquid Equilibrium of CO
2
in aqueous amine
solutions
Fig. 8. Simplified process flow sheet for TBS system
3M(2:1) 3M(1:1) 4M(2:1) 4M(1:1)
0
10
20
30
40
50
em
ulsion
T
e
m
p
e
r
a
t
u
r
e

(

)
Concentration (mol/L)
PTT of DMCA+A1 with 9wt% AMP
CST of DMCA+A1 with 9wt% AMP
PTT of DMCA+A1
CST of DMCA+A1
Two phases
Single phase
em
ulsion
PTT: phase transition temperature
CST: critical solution temperature

0 20 40 60 80 100 120 140 160
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
C
O
2

l
o
a
d
i
n
g

(
m
o
l
/
L
)
Time (min)
1,3. TBS
2,4. TBS + 9wt.% AMP
5. 30wt.% MEA
Primary TBS solution: 2M DMCA + 2M A1
CO
2
partial pressure: 19.6 kPa
1
2
4
3
Absorption at 40
Desorption at 75
1
2
3
4
5
5
A1+B1, 4+1M, 30
A1+B1, 4+1M, 80
DMX-1, 40 [3]
MEA 30wt%, 40
MEA 30wt%, 120
0 1 2 3 4 5
40
50
60
70
80
90
100
200
300
400
500
Loading (mol
-CO2
/kg
-sol.
)

P
C
O
2

(
m
b
a
r
)
Absorber Regenerator Rich Solvent
Aq.
Org.
Lean Solvent
Flue Gas
Treated Gas
80
30-40
CO2 (Transport / Storage)
Jiafei Zhang et al. / Energy Procedia 23 ( 2012 ) 92 101 101
5. Conclusions
Novel lipophilic amine has been introduced and proposed as an alternative solvent for PCC. According
to screening tests on the physicochemical properties and ab/desorption characteristics, outstanding
alkylamines were selected. The blended absorbents such as DMCA+A1 and A1+B1 have shown better
performance compared to conventional alkanolamines in various aspects, especially in loading capacity
and solvent regenerability. The technical feasibility of TBS system for CO
2
ab/desorption has also been
studied with respect to improvement of solvent formulation, regulation of phase change behaviour and
optimisation of operating conditions. The temperature induced LLPS potentially enables an extensive
regenerability at only 80 C, thus facilitating a more flexible and expedient thermal integration of the CO
2

capture process into existing heat recovery networks and reducing the dominant operating expenditure.
Acknowledgements
This work was supported by Shell Global Solutions International B.V.
References
[1] Wang M., Lawal A., Stephenson P., Sidders J., Ramshaw C. Post-combustion CO
2
capture with chemical absorption: A state-
of-the-art review. Chem. Eng. Res. Des., 2011, 89 (9): 1609-1624.
[2] Svendsen H.F., Hessen E.T., Mejdell T. Carbon dioxide capture by absorption; challenges and possibilities. Chem. Eng. J.,
2011, 171 (3): 718-724.
[3] Raynal L., Alix P., Bouilon P., et al. The DMX
TM
process: an original solution for lowering the cost of post-combustion carbon
capture. Energy Procedia 2011, 4: 779-786.
[4] Agar D.W., Tan Y., Zhang X. Separating CO
2
from gas mixtures. Patent WO/2008/015217.
[5] Zhang J., Nwani O., Tan Y., Agar D.W. Carbon dioxide absorption into biphasic amine solvent with solvent loss reduction.
Chem. Eng. Res. Des., 2011, 89 (8): 1190-1196.
[6] Zhang J., Agar D.W., Zhang X., Geuzebroek F. CO
2
absorption in biphasic solvents with enhanced low temperature solvent
regeneration. Energy Procedia 2011, 4: 67-74.
[7] Singh P., Niederer J.P.M., Versteeg G.F. Structure and activity relationships for amine-based CO
2
absorbents I. International
Journal of Greenhouse Gas Control, 2007, 1 (1): 5-10.
[8] Singh P., Versteeg G.F. Structure and activity relationships for CO
2
regeneration from aqueous amine-based absorbents.
Process Safety and Environmental Protection, 2008, 86 (5): 347-359.
[9] Singh P., Niederer J.P.M., Versteeg G.F. Structure and activity relationships for amine-based CO
2
absorbents II. Chem. Eng.
Res. Des., 2009, 87 (2): 135-144.
[10] Chowdhury, F.A., Okabe, H., Yamada, H., Onoda, M. Fujioka, Y. Synthesis and selection of hindered new amine absorbents
for CO
2
capture. Energy Procedia 2011, 4: 201-208.
[11] Robinson K., McCluskey A., Attalla M. The effect molecular structural variations has on the CO
2
absorption characteristics of
heterocyclic amines. Energy Procedia 2011, 4: 224-231.
[12] Yalkowski S.H. Solubility and Solubilization in Aqueous Media, American Chemical Society, Washington, DC; 1999.
[13] Zhang J., Misch R., Tan Y., Agar D.W. Novel thermomorphic biphasic amine solvents for CO
2
absorption and low-temperature
extractive regeneration. Chem. Eng. Technol. 2011, 34 (9): 1481-1489.
[14] Astarita G. Gas Treating with Chemical Solvents. Wiley-Interscience Publication, New York; 1983.
[15] Davidson R.M. Post-combustion Carbon Capture from Coal Fired Plants Solvent Scrubbing. IEA Clean Coal Centre,
CCC/125; 2007.
[16] Geuzebroek F., Schneider A., Last T., Zhang X. Benchmark study on the energy consumption of novel solvents for CO
2

capture, Presentated in TCCS-5 Conference, 16-17 June, 2009, Trondheim, Norway.