Available online at www.sciencedirect.

com

Energy Procedia 37 (2013) 2021 – 2046

GHGT-11

Energy Efficient Solvents for CO2 Absorption from Flue Gas:

Vapor Liquid Equilibrium and Pilot Plant Study
Prachi Singha*, W. P. M. Van Swaaijb, D.W.F. (Wim) Brilmanb
a
IEAGHG, The Orchard Business Centre, Stoke Orchard, Cheltenham, GLOS UK, GL52 7RZ, UK
b
Faculty of Science and Technology, University of Twente, PO Box 217, 7500 AE, Enschede, The Netherlands

Abstract

From solvent screening for new, amine based solvents for CO2 recovery from flue gas, two most promising solvent
formulations, a 51 wt% New Solvent (NS) and a 26.7% AMP-11.9% HMDA mixture were selected and tested in an
industrial pilot plant, mainly to identify the regeneration energy requirement. In the pilot plant tests CO2 absorption
was done at 40°C, 1.3 bar and regeneration at 120ºC, 2.0-2.2 bar, using both 5 and 10 vol% CO2 inlet concentration.
At 90% CO2 recovery and optimized solvent circulation, the NS solvent was the most energy efficient, requiring only
2.48 and 2.26 MJ/kg CO2 for 5 and 10 vol% CO2 inlet concentration respectively, whereas the AMP-HMDA solvent
required 3.62 and 3.41 MJ/kg CO2. Both solvents compare favorably to the 30wt% MEA reference measurements in
the same pilot plant (4.80 resp. 4.33 MJ/kg CO2) showing the potential of these energy-efficient solvents.

© 2013 The
TheAuthors.
Authors.Published
PublishedbybyElsevier
Elsevier Ltd.
Ltd.
Selection and/or
and/orpeer-review
peer-reviewunder
underresponsibility of of
responsibility GHGT
GHGT

Keywords: Vapour Liquid Equilibrium; VLE; Pilot Plant; CO

O2; Energy efficiency; Solvent Development; Amine; Absorption

1. Introduction

Carbon dioxide is a greenhouse gas that contributes to global warming and climate change. Post
combustion capture of carbon dioxide (CO2) is undoubtedly the most versatile technology for mitigating
greenhouse gas (GHG) emissions from existing fossil fuel-fired electric power plants. It is also one of the
technologies that can supply huge amounts of CO2 to be used as flooding agent in enhanced oil recovery.
Considering the cost and performance of post combustion capture technology for coal and natural gas
power plants is still high around 58 and 80 USD/tonneCO2 avoided respectively [1]. Figure 1, shows a
comparison of different CO2 capture technologies like post combustion capture, oxy combustion capture
and pre combustion capture on the basis of cost per tonne CO2 avoided at 89% CO2 capture rate. The
power plant net efficiency is reduced by around 25 and 15% for coal and natural gas power plant
respectively [1]. The operational cost based on overall CO2 avoided cost contributes approximately 76%
see Figure 2. In this figure 50% of operation cost comes from fuel consumption from post combustion

*Corresponding author, E-mail address: [email protected].

1876-6102 © 2013 The Authors. Published by Elsevier Ltd.

Selection and/or peer-review under responsibility of GHGT
doi:10.1016/j.egypro.2013.06.082
2022 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046

capture unit [2]. Fuel requirement is mainly from the heat required for solvent regeneration which is
accounted for around 55-70% [3]. The rest of the fuel is required for CO2 compression and solvent
circulation pumps.

Figure 2, Cost of CO2 ($/tonne CO2 avoided) for

post combustion capture unit, MEA solvent for
Figure 1, CO2 avoided cost from different CO2
400MWe Coal fired power plant at 90% CO2
capture technology, IEA 2011.
capture rate, Singh et al. 2003.

In order to make post combustion capture technology competitive, it is important to reduce the effect
of post combustion capture technology on the power plant efficiency and CO2 avoided cost. One of the
most attractive methods to remove CO2 from diluted, low-pressure gas streams is by absorption with
chemical reaction using aqueous alkanolamine solutions. The reference solvent for this type of process is
a 30 wt.% aqueous solution of Monoethanolamine (MEA) which, however, has the drawback of a high
energy requirement for solvent regeneration, leading to an efficiency penalty up to 15 percentage points
or more in the efficiency of fossil fuelled power plants.

The stripping of CO2 from MEA or DEA solutions requires significant more energy as compared to
MDEA solution. The heat duty for solvent regeneration can constitute up to 40% of the total operating
costs in a CO2 capture plant [3], including solvent heating up, water evaporation and CO2 release, which
on their turn are determined by cyclic loading capacity and carbamate (or bicarbonate) stability. Other
operating costs concerns are solvent corrosiveness and solvent chemical instability, which are suggested
by literature studies. For better process economics it is essential to find more efficient
f solvents, tailored
for CO2 post combustion capture.

A wide variety of solvents types like alkanolamines, amino acid and cyclic amines exists for CO2
absorption process e.g. Monoethanolamine (MEA) including Diethanolamine (DEA), Di-2-
 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046 2023

propanolamine (DIPA), Methyldiethanolamine (MDEA), 2-amino-2-methyl-1-propanol (AMP) and

Piperazine (Pz). Some of these amine based solvents are already applied in industry for many years.
These solvents show clear differences in their performance during CO2 absorption when using e.g. packed
columns for contacting the flue gas with the absorption liquid. Figure 3, shows the survey of reported
energy requirement for post combustion capture process from different solvents [4-19]. It should be
noticed that these presented values are dependent on the specific plant design and operating conditions.
Therefore, these values only give an orientation and should not be compared directly.

Figure 3, Energy consumption in the stripper from different literature sources [4-19]. The reported
numbers only give an orientation and should not be compared directly.

Mixed amines like AMP + Pz, DMMEA + MAPA or Sarcosine + Amine shown in Figure 3, are also
of an interest as these have been reported to maximize the desirable qualities of the individual amines.
Thus, the specific goal with respect to the use of mixed amines is to have a solution consisting of tertiary
and primary amines or tertiary plus secondary amines that, in comparison with single amine based
systems, retains much of the reactivity of primary or secondary amines at similar or reduced solvent
circulation rates and offers low regeneration costs similar to those of tertiary amines, due to enhanced
bicarbonate formation and a higher CO2 cyclic capacity. Consequently, by blending a primary or
secondary alkanolamine with a tertiary alkanolamine, bulk CO2 removal is easily accomplished while
regeneration energy costs are minimized. In addition, another degree of freedom (the amine
concentration) is gained. The amine concentration can be altered to achieve precisely the desired
separation for a given process configuration. Substantial reductions in energy requirements and modest
reduction in solvent circulation rates have been reported for amine blends relative to the corresponding
single amine system of similar total amine concentration [20].
2024 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046

1.1. Solvent Development

In order to develop new, energy efficient solvents for CO2 absorption process, [21-25] performed
solvent screening experiments for various amine based solvents for CO2 absorption and regeneration.
From this solvent screening, Hexamethylenediamine (HMDA) and New solvent showed a high CO2
absorption capacity, when compared to MEA and other solvents, in combination with a high initial
absorption rate and good regeneration characteristics during screening.

5
Pz
HMDA N,N'*
4 HMDA

3 EDA
ln k2

MEA
2 DEA

0
8 8.5 9 9.5 10 10.5 11 11.5 12
pKa
Figure 4, Brønsted plot for primary and secondary amine based solvents at 303K *pKa value is at 293K
estimated by ACD/pKa software [26].

Therefore, CO2 absorption kinetics experiments were performed by [26] to evaluate HMDA CO2
absorption kinetics. The second order reaction rate constant (k2) for 1 mole/L HMDA was found to be
4.2E+4 L mole-1 s-1 at 303K. This second order CO2 absorption rate constant is high, when compared to
that of 1 mole/L MEA of 6.3E+3 L mole-1 s-1. The Brønsted plot shown below in Figure 4, shows the
comparison of different solvents second order rate kinetics (k2) based on their basicity. In Figure 4, the
linear correlation between the logarithm of k2 (L mole-1 s-1) and pKa for temperatures up to 303K for
primary and secondary aqueous alkanolamine, as proposed by [27] (Eq.28) is presented as a straight line.

1.2. Corrosion Test

Before applying a new solvent on a pilot plant scale and an addition to CO2 capture/regeneration
characteristics in terms of capacity and kinetics, the corrosiveness of the solvent needs to be evaluated.
Therefore, an intrinsic corrosion test was performed for both the HMDA solvent and New Solvent. This
test is essentially an iron solubility test, performed at 130°C for 2 hours of contact time. The results from
this iron solubility test for Hexamethylenediamine, the New Solvent and MEA (for reference) are
presented below in Table 1.
 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046 2025

Table 1. Iron solubility test for MEA, Hexamethylenediamine (HMDA) and New Solvent.
Solvent Iron solubility
ppm
MEA 15.0
HMDA 3.5
New Solvent 2.5

Based on the pre-test solvent screening experiments and the corrosion test results, an aqueous solution
of 26.7 wt% AMP + 11.9 wt% HMDA and an aqueous solution of the 51 wt% New Solvent were found
to be suitable for pilot plant testing.

Short-cut approach; New Solvent

Solvent Screening Pilot Plant Test Develloppmentt off
Absorption capacity
Energy Efficient
Initial absorption rate Regeneration energy Sollvent
Regeneration capacity requirement
Preliminary corrosion Solvent circulation
test rate

Fundamental
Data Detailed approach; HMDA
Kinetics study
Vapour liquid
equilibrium study

Figure 5, Energy efficient solvent development approach.

For further evaluation of the applicability of these selected amines in post combustion CO2 capture
solvent systems more detailed vapour liquid equilibrium tests and pilot plant testing were considered a
valuable and necessary next step. The thermodynamic equilibrium data (VLE) for the carbon dioxide
solubility determine the most important process parameters in an absorption-desorption cyclic process,
like the solvent flow rate and energy requirement for regeneration. Obviously, these two numbers play an
important role in process economics and data for this thermodynamic equilibrium is therefore crucial. In
this work vapour liquid equilibrium (VLE) data have been determined experimentally for 1,6
Hexamethylenediamine (HMDA) and its AMP blend (AMP+HMDA).

Another main objective of this study is to carry out pilot plant tests to provide proof-
f of-
f principle runs
for the new solvents, including a first round optimization on solvent circulation rate, the evaluation of the
energy requirements for solvent regeneration and, simultaneously, a check on possible operational
hurdles. For this purpose and with the permission and support of the technical staff of Shell Technology
Centre Amsterdam, pilot plant experiments were performed with the absorption/desorption pilot plant unit
2026 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046

(ASAP). As mentioned above, the solvent (mixtures) selected were based on the results obtained during
the experimental solvent screening activities [25] and subsequently formulated into a blend of amines.
Two different approaches have been taken in order to develop energy efficient solvents, as shown in
Figure 5.

In this study, the New Solvent was investigated via the short approach where after solvent screening
results New Solvent was investigated directly by pilot plant tests. For HMDA, on the other hand, first
more detailed data for e.g. kinetics and VLE (which is part of this study) was produced, before going for
pilot plant tests.

2. Vapor Liquid Equilibrium (VLE)

2.1. Experimental

Vapor liquid equilibrium study was performed by doing experiments for Hexamethylenediamine
(HMDA) and its mixture with 2-Amino-2-Methyl 1-propanol (AMP) + Hexamethylenediamine (HMDA).
VLE experiment test were also performed for Monoethanolamine (MEA) for experiment set-up validation
purpose. All chemicals have been purchased from Sigma Aldrich with a purity of 99%. These solvents
were diluted with demineralized water to the desired concentrations.
Vacuum Liquid Inlet

CO2

P
P Equilibrium
T Reactor
CO2

Sample
Figure 6, Schematic diagram of solubility experiment set-up.

Experimental data for the CO2 solubility at various CO2 partial pressures was obtained using a stirred
cell reactor setup, which mainly consisted of a thermostatic vigorously stirred reactor (ca. 2L) connected
to a calibrated gas vessel (see Figure 6). Both reactor- and gas supply vessel were equipped with a
temperature and pressure indicator. In a typical experiment, a known amount of amine solution was
transferred to the reactor vessel, after which the liquid was degassed by applying vacuum for a short
while to remove all inert gases from the setup and dissolved gases from the amine solutions prior to the
experiment. Next, the solution was allowed to equilibrate at the desired temperature and the (vapor)
pressure was recorded. Then, the gas supply vessel was filled with pure carbon dioxide and the initial
pressure in this vessel was measured. Next, the stirrer was switched on and a sufficient amount of CO2
was fed from the gas supply vessel to the reactor. The gas supply to the reactor was closed and the content
 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046 2027

of the reactor was allowed to reach equilibrium - which was reached when the reactor pressure remained
constant. The actual CO2 partial pressure could be calculated from this final (equilibrium) reactor pressure
corrected for the vapor pressure of the lean solution, thereby assuming that the solution vapor pressure is
not influenced by the CO2 loading.

20.0 MEA, This work

18.0 MEA, VLE model
CO2 partial pressure (kPa)

Jou, 1995
16.0
Lee, 1976
14.0
12.0
10.0
8.0
6.0
4.0
2.0
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Loading (mole CO2 /mole amine)
Figure 7, Comparison of the CO2 solubility validation experiment for 2.5 mole/L aqueous solution of
MEA at 25 °C with literature [28 & 29] and model data.

The difference between initial and final pressure in the gas supply vessel, taking non-ideal behavior for
CO2 in the gas phase into account, was used to calculate the corresponding CO2 loading of the solution.
These solubility experiments have been carried out for HMDA concentrations of 0.5, 1 and 2.5 mole/L at
20, 30 and 40°C and mixture of 1.5mole/L AMP + 0.5mole/L HMDA and 3mole/L AMP + 1mole/L
HMDA at 40°C.

In order to determine the accuracy of the VLE experiment set-up, an experiment for the CO2 solubility
in a 2.5 molar aqueous solution of Monoethanolamine (MEA) at 25°C was performed. Figure 7, shows
experimental data together with literature data reported by [28 & 29]. The data is quite in line with
literature data. The model line from the concentration based equilibrium model for MEA model was
calculated using the reaction equilibria reported in the VLE model by [30], for which an absolute standard
deviation of about 12.5% is reported, still less than the typical uncertainty of VLE data (around 20%),
according to [30]. The reproducibility between various experiments was within ±5%. The experimental
error in the data points presented in this work is estimated at maximally 0.01 unit (in loading) and 5 mbar
(in CO2 partial pressure) respectively. Equilibrium partial pressures below 1 kPa of CO2 were considered
to be unreliable for this measurement technique and are not reported here.

2.2. VLE Results and Discussion

2028 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046

Table 2, Experimental VLE data of CO2 in a 0.5 mole/L aqueous solution of HMDA.
T = 20oC T = 30oC o
T = 40 C
Loading PCO2 Loading PCO2 Loading PCO2
mole CO2 mole CO2 mole CO2
kPa kPa kPa
/mole amine /mole amine /mole amine

1.29 2.64 1.22 2.50 1.21 2.16

1.37 3.82 1.31 3.61 1.29 3.79
1.46 5.77 1.38 5.67 1.36 5.95
1.54 8.85 1.46 8.36 1.43 9.10
1.62 13.72 1.53 12.64 1.50 13.88
1.69 20.98 1.59 18.18 1.56 20.16
1.75 32.16 1.65 26.06 1.62 28.10
1.80 46.77 1.70 35.95 1.66 37.13
1.74 46.66 1.70 47.49
1.77 59.45 1.74 58.44
1.79 70.99 1.76 71.65
1.81 80.50
Table 3, Experimental VLE data of CO2 in a 1 mole/L aqueous solution of HMDA.
o o o
T = 20 C T = 30 C T = 40 C
Loading PCO2 Loading PCO2 Loading PCO2
mole CO2 mole CO2 mole CO2
kPa kPa kPa
/mole amine /mole amine /mole amine

1.07 1.19 1.15 1.88 1.02 1.47

1.20 2.91 1.19 2.82 1.05 1.98
1.24 3.86 1.23 3.98 1.09 2.77
1.28 5.11 1.27 5.45 1.13 3.85
1.33 6.65 1.30 7.07 1.17 4.98
1.37 8.53 1.34 9.27 1.21 6.85
1.41 10.92 1.38 11.85 1.24 9.13
1.45 13.69 1.42 14.95 1.28 11.60
1.48 17.04 1.45 18.52 1.31 14.64
1.52 20.67 1.48 22.78 1.35 18.00
1.55 25.00 1.52 27.40 1.38 21.79
1.58 30.12 1.54 32.57 1.40 25.94
1.60 35.38 1.57 38.45 1.43 30.66
1.63 41.81 1.59 42.04 1.46 35.41
1.65 48.48 1.62 50.29 1.48 40.89
1.67 55.27
1.69 62.57
 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046 2029

All experimentally obtained data on CO2 solubility in aqueous solution of 0.5, 1 and 2.5 mole/L of 1,6
Hexamethylenediamine (HMDA) at 20, 30 and 40°C with corresponding partial pressures are listed in
Tables 2 to 4. To determine the effect of temperature at fixed concentrations of HMDA on the solubility
of CO2, the partial pressures of CO2 (PCO2) (kPa) were plotted by the equilibrium loading (mole
CO2/mole amine). These results are summarized in Figure 8 to 11.

Table 4, Experimental VLE data of CO2 in a 2.5 mole/L aqueous solution of HMDA.
T = 20oC T = 30oC T = 40oC
Loading PCO2 Loading PCO2 Loading PCO2
mole CO2 mole CO2 mole CO2
kPa kPa kPa
/mole amine /mole amine /mole amine
1.05 1.81 1.04 1.86 1.01 1.87
1.07 2.23 1.06 2.40 1.02 2.43
1.09 2.69 1.07 3.03
1.04 3.33
1.10 3.30 1.09 3.77
1.05 4.36
1.12 3.98 1.11 4.65
1.07 5.53
1.14 4.74 1.12 5.63
1.15 5.58 1.08 6.95
1.14 6.72
1.17 6.53 1.10 8.46
1.15 7.95
1.19 7.55 1.17 9.35 1.11 10.02
1.20 8.66 1.18 10.92 1.13 11.87
1.22 9.97 1.20 12.52 1.14 13.66
1.24 11.31 1.21 14.24 1.16 15.84
1.25 12.61 1.23 16.09 1.17 17.98
1.27 14.19 1.24 18.09 1.18 20.43
1.28 15.84 1.25 20.30 1.19 22.92
1.29 17.52 1.27 22.47 1.21 25.75
1.31 19.38 1.28 24.89 1.22 28.32
1.32 21.28 1.29 26.93 1.23 30.97
1.33 23.37 1.30 29.39 1.24 33.73
1.35 25.59 1.31 31.93 1.25 36.46
1.36 27.88 1.32 34.45 1.26 39.28
1.37 30.18 1.33 36.98 1.27 42.23
1.38 32.72 1.34 39.46
1.28 45.04
1.40 35.43 1.35 42.01
1.41 38.12 1.28 48.08
1.36 44.72
1.42 40.79 1.29 50.99
1.37 47.46
1.43 43.47 1.30 53.91
1.44 45.87 1.31 56.21
2030 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046

The effect of HMDA concentration on its CO2 absorption capacity is shown in Figure 11, where
absorption equilibrium of CO2 in three different concentrations of HMDA is presented. The observed
concentration dependency, the CO2 equilibrium loading per amine group decreases with an increase in
HMDA concentration at fixed temperature and -CO2 partial pressure, is similar to what is normally found
for aqueous MEA-solutions. Realizing that HMDA contains two primary amine groups, a comparison on
a per-amine-group basis seemed relevant. The concentration effect for MEA and HMDA at a temperature
of 40ºC and similar amine group concentrations is compared in Figure12.

80 80

CO2 Partial pressure (kPa)

20 °C 20 °C
CO2 Partial pressure (kPa)

30 °C 30 °C
60 60
40 °C 40 °C

40 40

20 20

0 0
0.0 0.5 1.0 1.5 2.0
0.0 0.5 1.0 1.5 2.0
Loading (mole CO2 /mole amine) Loading (mole CO2/mole amine)
Figure 8, Equilibrium solubility of CO2 in a 0.5 Figure 9, Equilibrium solubility of CO2 in a 1
moles/L aqueous solution of HMDA. moles/L aqueous solution of HMDA.
80 80
20 °C 0.5 mole/L
CO2 Partial pressure (kPa)

CO2 Partial pressure (kPa)

30 °C 1 mole/L
60 60 2.5 mole/L
40 °C

40 40

20 20

0 0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0
Loading (mole CO2 /mole amine) Loading (mole CO2 /mole amine)

Figure 10, Equilibrium solubility of CO2 in a 2.5 Figure 11, Equilibrium solubility of CO2 at 40°C in
moles/L aqueous solution of HMDA. an aqueous solution of HMDA.

It can be observed in Figure 12 that at similar amine group molar concentrations and at the same
partial pressure, that the CO2 solubility in HMDA solutions is significantly higher. This effect is stronger
at higher loadings (higher CO2 partial pressures). Alternatively, for a given amine loading, the
equilibrium partial pressure of CO2 for HMDA is a factor 3-8 lower than for MEA. Again, this effect
 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046 2031

changes somewhat with loading and (not shown here) with temperature. The similarity of the curves is
illustrated by Figure 12.

100
2.5 mole/L HMDA, 40 °C

CO2 partial pressure (kPa)

5 mole/L MEA Model,
40 °C
0.25 * P(CO2, MEA-
10 model)

1
0.20 0.30 0.40 0.50 0.60 0.70 0.80
Loading (mole CO2/amine-group)

Figure 12, Similarity of CO2 partial pressure-loading curve for 5 mole/L MEA with 2.5 mole/L HMDA at
40ºC. Solid model line represents 25% of the CO2-equilibrium pressure for 5mole/L MEA.

Considering its fast kinetics and high capacity, HMDA was considered to be a potential replacement
for piperazine as an ‘activator’ or ‘absorption rate enhancing compound’. From the VLE curve presented
in Figure 13, it can be seen that HMDA exhibits a favorable, less steep increase in CO2 partial pressure
(PCO2) with increasing CO2 loading and a higher CO2 capacity per mole of amine (and per N atom).

1000
0.5 HMDA, This work
1 HMDA, This work
0.6 Pz, Zih-Yi 2010
100
P CO2 (kPa)

10

0.1
0 0.2 0.4 0.6 0.8 1

CO2 Loading (mole CO2/mole N atoms)

Figure 13, CO2 partial pressure-loading curve for 0.5 and 1 mole/L HMDA compared with 0.6 mole/L
Piperazine (Pz) at 40°C.
2032 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046

1000
AMP + HMDA

AMP
+ Pz AMP
100
Pz HMDA
P CO2 (kPa)

10

1
AMP
AMP
+ Pz
Pz

0.1
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
CO2 Loading (mole CO2/mole amine)

1.5 AMP+0.5HMDA, 40C, This Work 3 AMP+1 HMDA, 40C, This work
1 HMDA, 40C, This work 3 AMP+1.5 Pz, 40C, Peter Bru´ der 2011
3 AMP+1 Pz, 40C, Zih-Yi Yang 2010 3 AMP+0.5 Pz, 40C, Zih-Yi Yang 2010
0.6 Pz, Zih-Yi 2010 3 AMP, 40C, Zih-Yi Yang 2010
3 AMP, 40C, B.E. Roberts 1988

Figure 14, VLE curves for 1.5 mole/L AMP + 0.5 mole/L HMDA, 3 mole/L AMP + 1 mole/L HMDA by
experiments and from literature data for AMP, Pz and their blend AMP+PZ at 40°C [31-33].

Regarding to the solvent development for CO2 absorption, a combination of secondary amine and
sterically hindered amine can be expected to have a high cyclic capacity combined with fast kinetics and
possibility low heat requirement for regeneration. A good example is ‘activated’ AMP by Piperazine (Pz)
addition. Therefore, a further evaluation was performed in this study to investigate the potential of
HMDA as an activator in combination with the sterically hindered amine AMP. In Figure 14, a collection
of literature data [31-33] for the single solvents AMP, Pz and blends AMP+Pz, together with
experimental data for 1.5 mole/L AMP+0.5 mole/L HMDA and 3mole/L AMP + 1.5HMDA is presented.

It can be noticed from above Figure 14, that the AMP + Pz blends, slope is indeed higher than that for
single solvent AMP (and is more similar to that of Pz single solvent VLE slope). The VLE data from this
work for both AMP+HMDA blends shows that the slope of the CO2 partial pressure vs. CO2 loading is
less steep. Similarities in the performance between Pz and HMDA can be noticed and further test of the
 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046 2033

AMP+HMDA blends to evaluate possible operational issues and to determine the regeneration energy
requirement in the pilot plant is the next step.

3. Pilot Plant Test

The pilot plant test was performed in the bench scale unit called ASAP unit (shortened for Amine
Screening Apparatus) located at Shell Technology Centre, Amsterdam. The solvents tested in this plant
were Monoethanolamine (MEA), 2-Amino-2-Methyl 1-propanol (AMP), Piperazine (Pz),
Hexamethylenediamine (HMDA) and New Solvent. These solvents were purchased from Sigma Aldrich
with a purity of 99%. These solvents were diluted with dematerialized water to the desired concentrations.

3.1. Solvent Formulation

In order to determine the optimal solvent formulation for pilot plant test, a pre-test to screen various
solvent combinations was performed in a solvent screening unit as presented in Singh et al. 2010. Main
focus of these pre-test solvent screening experiments was to identify the suitable solvent formulation on
the basis of solvent maximum concentration, rich CO2 loading, lean CO2 loading and cyclic CO2 loading.
Other solvent issue like e.g. foaming tendency, crystallization, viscosity changes etc. could also be
identified from these experiments.

Table 5, Solvent pre-test screening results from solvent screening experiments at 20 vol% CO2 inlet
Concentration.
Rich Lean Cyclic Abs.
No. Amine concentration
loading loading loading slope
mole mole mole CO2 mole CO2 mole CO2
wt% wt% min-1
/L /L /mole amine /mole amine /mole amine

AMP HMDA
1 3.0 26.7 1.0 11.6 0.94 0.16 0.78 3.39E-03
2 2.5 22.3 1.5 17.9 0.98 - - 4.31E-03
3 2.5 22.3 2.5 29.8 0.94 0.31 0.63 2.69E-03
New Solvent
1 3.0 51.1 - - 1.58 0.17 1.41 3.21E-03

In these solvent pre-test solvent screening experiments, CO2 absorption was done at 20°C and
atmospheric pressure with 20 vol% CO2 inlet feed concentration. Regeneration of the solvent tested was
carried out at 90°C and atmospheric pressure. AMP solution has been introduced as a commercially
attractive co-solvent for HMDA, since it has a loading capacity of up to 1 mole of CO2 per mole of AMP.
It showed an excellent absorption characteristic and is easy to regenerate, higher degradation resistance
and a lower corrosion rate in comparison with more conventional amines as MEA and MDEA [30].
Hence AMP was chosen in the present investigation as a base solvent in combination with HMDA for
solvent formulation in the pre-tests. Additionally, and based on the results obtained during earlier solvent
screening activities (Singh et al., 2010), selected amines were formulated into a propriety blend of amines
(called ‘New Solvent’) which exact composition cannot be disclosed here.
2034 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046

Table 5 shows the results from different AMP+HMDA combinations and the New Solvent
combination used during pre-test experiments. The importance of pretesting is illustrated by the reported
results for AMP 2.5 mole/L + HMDA 1.50 mole/L, where a reliable regeneration experiment could not be
obtained due to the high foam formation during experiment. Furthermore, it can be noticed that solvent
formulation Nr.1 has a higher cyclic capacity when compared to that of solvent No.3, see Table 5.

3.2. Shell Pilot Plant ASAP Unit (ID4001)

The ASAP unit (shortened for Amine Screening Apparatus) is a bench scale unit that is capable to test
different amine solutions to sweeten several kinds of sour gases under various conditions. The ASAP unit
consists of two columns; the Absorber (C200) and the Regenerator (C300) (see Figure 15). The length of
absorber and regenerator is 150 cm and the internal diameter is 28 mm.

Figure 15, Simplified process flow scheme of pilot plant unit ASAP.

These columns are packed with structured packing type ex. laboratory packing (Sulzer Chemtech
Ltd.). This packing has a surface area of 1735 m2/m3. This high surface area ensures good contacting
between gas and liquid. The diameter of this packing element is 28 mm, which is same as internal
diameter of the columns. The absorber column is filled up to 145 cm with this packing. The regenerator is
 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046 2035

filled up to 130 cm with this packing. The columns are insulated so that exothermic and endothermic heat
effects can be monitored.

Sour feed gas of a certain composition is fed into the bottom of the absorber. In the absorber, feed gas
will be brought into contact in counter current direction with the amine solvent, which is circulating
continually through the absorber-regenerator system. The sour components in the feed gas dissolve in the
amine solution by an exothermic reaction. The sweetened off gas is cooled in condenser (E200) to remove
vaporized water from the off gas stream. The amine solvent which is loaded in the absorber with sour
components from the feed gas stream must be regenerated by stripping before it can be used again in the
absorber. In the regenerator (C300) the loaded amine solvent was stripped from its sour components by
means of steam generated from the boiling amine solution in the reboiler (E310) of the regenerator.

Loaded or rich solvent is warmed up to 100°C and fed in the top of the Regenerator. In the bottom of
the regenerator the amine solvent is boiling at approximately at 124°C and at 2 bar. During the trip down
of the loaded solvent, the sour components will come out of the solvent and the solvent become unloaded
or lean again. The sour off gas will be cooled in condenser (E300) to remove vaporized water. There is a
possibility to improve the stripping by adding nitrogen strip gas in the boiling solvent at the bottom of the
regenerator. Liquid samples were taken at every experiment from absorber and regenerator to determine
CO2 rich and lean loading by doing separate gas chromatography analysis. The concentrations of
components in the feed- and off-gasses are continuously monitored using a Varian CP-4900 micro gas
chromatographic (GC). Honeywell process control software is used to run the ASAP unit unmanned and
continuously. The process data were stored in the computer.

3.3. Pilot Plant Experimental Procedure

In a typical experiment the inlet gas flow rate, temperature and pressure is already fixed. The absorber
and regenerator pressure and temperature are also fixed. In this study absorption was done at 40°C, 1.3bar
and regeneration at 120ºC, 2.0-2.2bar. The temperature of lean and rich solvent is known and kept
constant (at respectively 40 and 100°C). To find the optimum solvent flow rate first the over stripping
(higher then optimal reboiler duty (E310)) conditions were applied and CO2 recovery from top of
absorber is monitored. Once the CO2 recovery reached 100%, the solvent flow rate is lowered in order to
achieve CO2 recovery at top of the absorber of 99% to 97%. Typically, the minimization of solvent flow
rate should maximize CO2 loading (mole CO2/kg solvent) and reduce desorption energy requirements per
amount of CO2 captured. Once the solvent flow rate is obtained the energy requirement is further
minimized by reducing the energy input until 90% CO2 is recovered. Subsequently the solvent flow rate is
adjusted again by increasing or decreasing with maximally some 10%-15%. This solvent flow rate
optimization helps to identify if further improvement in CO2 recovery can be achieved at the lowest
energy requirement. In the situation that CO2 recovery increases with an increase in solvent flow rate it is
then desired to reduce energy requirement until 90% CO2 recovery is obtained.

3.4. Pilot Plant Results

In this study, some of the main parameters affecting the capture process were pre-determined by
extensive validation of the experiments (not reported here) in this pilot plant and prior to this study. These
parameters were adopted from existing operating procedures and are reported in Table 6.
2036 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046

Table 6, Process parameters which were kept constant in the pilot plant tests.

Parameter Experiment Value

CO2 at Inlet (vol%) 5 and 10
Flue gas flow rate (nL/h) 645 (5% CO2 inlet Conc.) and 400 (10% CO2 inlet Conc.)
Flue gas inlet temp.(°C) 37±1
Stripper pressure (bara) 2.00
Solvent concentration (wt%) 38.65 (AMP+HMDA) and 51 (New Solvent)
Lean solvent temerature (°C) 40±1

In this study as explained earlier, some of the main parameters affecting the capture process will be
varied as an initial step towards an optimization of the process. Starting from the baseline conditions the
following process parameters were varied:

The solvent circulation rate (kg/h).

Reboiler duty (Watt).

The energy requirement in the stripper (MJ/kg CO2 removed) was used as an indicator when
investigating the effect of the above parameters. The energy requirement was calculated from the heat
required in the reboiler, mass rate of CO2 regenerated and the system heat loss. The energy requirement
(MJ/kg CO2 removed) was chosen as the main parameter to evaluate different solvent performance in this
pilot plant tests, as it is an indicative for operating costs.

Experiments were performed in the ASAP unit for aqueous solution of 26.74 wt% AMP + 11.91 wt%
HMDA and the New Solvent-blend at 51 wt% concentration. Two different combinations of CO2 inlet
concentrations and inlet gas flow rate in the feed gas were chosen, a feed gas flow rate of 630 Nm3/h at 5
vol% CO2 and 400 Nm3/h at 10 vol% CO2.
Table 7, Summary of pilot plant tests for the 26.74 wt% AMP + 11.91 wt% HMDA solvent; main input and results.

Parameter

CO2 at Inlet (vol%) 5.01 5.01 5.01 10.02 10.03 10.03 10.03

Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046

Solvent flow rate (kg/h) 0.60 0.60 0.63 0.70 0.73 0.73 0.73
Input
Flue gas (nL/h) 644.46 644.74 644.68 399.66 399.69 399.74 399.56
Flue gas inlet temp.(°C) 36.66 36.68 36.63 36.98 37.22 37.06 37.16
Stripper pressure (bara) 2.11 2.16 2.10 2.11 2.21 2.20 2.22
CO2 at outlet regenerator (nL/h) 29.42 29.45 27.55 36.31 34.93 33.96 31.54
CO2 capture (mole CO2/kg amine) 2.19 2.19 1.94 2.32 2.14 2.08 1.93
CO2 recovery from absorber (%) 99.71 99.63 90.80 99.87 99.17 88.02 87.48
Solvent concentration (wt%) 38.65 38.65 38.65 38.65 38.65 38.65 38.65
Rich loading (mole CO2/mole amine) 0.48 0.51 0.47 0.48 0.49 0.50 0.51
Results

Lean loading (mole CO2/mole amine) 0.05 0.07 0.14 0.05 0.06 0.16 0.16
Cyclic loading (mole CO2/mole amine) 0.43 0.44 0.33 0.42 0.43 0.33 0.34
Rebolier duty (Watt) 87.84 71.37 76.86 87.84 76.86 79.61 81.25
Energy requirement (MJ/kg CO2) 5.44 4.07 3.62 4.41 3.43 3.08 3.41
Flue gas outlet temperature (°C) 63.50 48.24 47.01 54.97 49.68 47.12 47.22
Lean solvent temerature (°C) 40.57 40.66 40.79 40.92 41.08 41.02 40.95
Reboiler temperature (°C) 122.94 123.60 121.63 122.81 123.35 121.46 122.02

2037
 2038
Table 8, Summary of pilot plant tests for the 51 wt% New Solvent; main input and results.

Parameter

CO2 at Inlet (vol%) 5 5 5 5 5 10 10 10 10

Solvent flow rate (kg/h) 0.50 0.50 0.50 0.50 0.48 0.50 0.55 0.55 0.57
Input

Flue gas (nL/h) 644 645 644 645 645 400 400 400 400

Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046

Flue gas inlet temp.(°C) 37 37 37 37 37 37 37 37 37
Stripper pressure (bara) 2.06 2.07 2.07 2.07 2.06 2.05 2.06 2.08 2.13
CO2 at outlet regenerator (nL/h) 30.28 30.17 29.00 29.01 27.96 37.78 36.23 35.58 33.02
CO2 capture (mole CO2/kg amine) 2.70 2.69 2.60 2.58 2.60 3.38 2.95 2.87 2.59
CO2 recovery from absorber (%) 100 100 99 98 93 100 100 98 89
Solvent concentration (wt%) 51 51 51 51 51 51 51 51 51
Rich loading (mole CO2/mole amine) 0.84 0.82 0.82 0.89 0.91 0.93 0.90 0.97 0.95
Results

Lean loading (mole CO2/mole amine) 0.04 0.06 0.10 0.15 0.22 0.01 0.05 0.15 0.20
Cyclic loading (mole CO2/mole amine) 0.80 0.76 0.72 0.74 0.69 0.92 0.84 0.81 0.75
Reboiler duty (watt) 82.35 76.86 71.37 65.88 60.39 109.80 82.35 68.63 60.39
Energy requirement (MJ/kg CO2) 3.62 3.30 3.09 2.74 2.48 4.24 3.03 2.38 2.26
Flue gas outlet temerature (°C) 47 48 45 46 45 75 49 47 46
Lean solvent temerature (°C) 40 40 40 40 40 40 40 40 40
Reboiler temperature (°C) 121 121 120 119 117 122 121 119 117
 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046 2039

Table 7 and 8 shows the experimental input and results from each test. It should be noticed that the
approximate minimum solvent flow rate (kg/h) was already determined for each solvent before starting
the experiments (see experiment procedure). Hence, the solvent flow rate (kg/h) is not varied much during
the experiments.

3.5. CO2 Recovery and Energy Requirement

Figure 16, shows the energy requirement (MJ/kg CO2) variation on the CO2 lean loading (mole
CO2/mole amine) for 26.74 wt% AMP + 11.91 wt% HMDA and for 51 wt% New solvent. The results
indicate that the reboiler heat duty is inverse to the lean CO2 loading. For instance the energy requirement
reduces from 3.43 to 3.08 MJ/kg CO2 for AMP+HMDA as lean loading increases from 0.055 to 0.16
mole CO2 / mole amine. A similar effect was noticed for the New Solvent as its energy requirement
reduces from 4.23 to 2.55 MJ/kg CO2 as its lean loading increases from 0.006 to 0.19 mole CO2/mole
amine, illustrating that the reduction in solvent regeneration efficiency at lower energy input. Figure 16
also shows that energy requirement indicate a nonlinear correlation with the lean loading obtained.

0.25
Lean loading ( mole CO2/ mole amine)

0.2 89%CO2

88%CO2
0.15 98%CO2

0.1

0.05 100%CO2 99%CO2 99%CO2

100%CO2
0
2.0 2.5 3.0 3.5 4.0 4.5 5.0
Energy requirement (MJ/kg CO2)

Figure 16, Effect of energy requirement (MJ/kgCO2) on CO2 lean loading (mole CO2/mole amine) for
26.74 wt% AMP + 11.91 wt% HMDA and 51 wt% New Solvent at 10 vol% inlet CO2
concentration, CO2 recovery range approximate 89 to 99%.

It should be noticed that for the New Solvent the lean loading is more sensitive to the energy input at
lean loading lower than 0.05 mole CO2/mole amine. Nevertheless, a significant additional heat is required
to achieve a further reduction in lean loading below 0.05 mole CO2/mole amine. For AMP+HMDA the
addition of more heat did not result in a noticeable reduction of the lean loading below 0.05. Hence,
2040 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046

regenerating the solvent to these low loading represents an unfavorable operating region that consumes
excessive energy. For lean loadings above 0.05 mole CO2/mole amine the energy requirement is less
sensitive to the change in lean loading, implicating that only a small amount of additional heat duty is
required to achieve a substantial reduction in lean-CO2 loading, thus presenting a favorable operating
condition. This effect is directly related to the vapor liquid equilibrium data.

3.5
100%CO2
CO2 recovery ( mole CO2/ kg solvent)

3.0 98%CO2 100%CO2

89%CO2
2.5
99%CO2
99%CO2 88%CO2
2.0
96%CO2
91%CO2
99%CO2
88%CO2
1.5

1.0
55 75 95 115 135
Reboiler duty (Watt)

Figure 17, Effect of reboiler duty (Watt) on CO2 recovery (mole CO2/kg solvent) for 31 wt% MEA,
26.74 wt% AMP + 11.91 wt% HMDA and 51 wt% New Solvent at 10 vol% inlet CO2 concentration,
CO2 recovery range approximate 89 to 99%.

The operating CO2 partial pressure at the reboiler is limited to an extremely low equilibrium CO2
partial pressure for a very lean solution. The operating CO2 partial pressure cannot be easily reduced
further to achieve an even slight reduction in lean CO2 loading without a penalty of excessive energy
input, required to generate the required considerable increase in the amount of water vapor leaving the
regeneration column. Comparing the solvent energy requirement (MJ/kg CO2) with CO2 recovery shows
that New Solvent can reach much higher CO2 recovery (mole CO2/kg solvent) when compared to
AMP+HMDA and MEA (see Figure 17).
 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046 2041

Energy requirement (MJ/kg CO2)

5

0
86 88 90 92 94 96 98 100
CO2 recovery (%)
Figure 18, Effect of CO2 recovery (%) on energy requirement (MJ/kgCO2) for 31 wt% MEA, 26.74
wt% AMP + 11.91 wt% HMDA and 51 wt% New Solvent at 10 vol% inlet CO2 concentration, CO2
recovery range approximate 89 to 99%.

Figure 18, shows the effect of CO2 recovery (%) on energy requirement (MJ/kg CO2). It should be
noticed that the New Solvent can recover more CO2 (mole CO2/kg solvent) when compared to
AMP+HMDA and MEA at much lower energy input. It is interesting to notice that for New solvent the
energy requirement is only slightly increased 2.26 to 2.38 (MJ/kg CO2) for CO2 recovery from 89 to 99
%. Further increase in CO2 recovery from 98% to 100% increases the energy requirement up to 3.03
(MJ/kg CO2). Similar behavior can be noticed for AMP+HMDA where the energy requirement is only
slightly increased from 3.08 to 3.43 (MJ/kg CO2) for CO2 recovery increase from 88 to 99 %. Further
increase in energy requirement does not affect much on CO2 recovery for AMP+HMDA. It is clear from
the test results that both solvents are more energy efficient when compared to MEA and are suitable for
recovery levels as high as 99%.

3.6. Solvent Evaluation

A further evaluation of the solvents performance at both CO2 inlet concentration 5 and 10 vol% was done
by measuring the required solvent circulation rate for a fixed CO2 removal fraction of 99% recovery. It
should be noticed that the values presented in this evaluation are based on those tests which achieved the
lowest energy requirement for 99% CO2 recovery from the absorber. Figures 19 (a & b) show the
resulting solvent circulation rate (kg/h) and cyclic loading (mole CO2/mole amine) for the (26.74 wt%
AMP + 11.91 wt% HMDA) solvent and the 51 wt% New Solvent and, for comparison, the 31 wt% MEA
solvent at 5 and 10 vol% CO2 inlet concentration respectively. Figure 19 (a) illustrates clearly that the 51
wt% New Solvent can achieve much higher cyclic loadings of 0.7 mole CO2/mole amine at lowest solvent
circulation rate 0.5 kg/h.
2042 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046

1.0 1.0
Cyclic loading ( mole CO2/ mole amine)

Cyclic loading ( mole CO2/ mole amine)

0.9 0.9 New Solvent
0.8 0.8
New Solvent
0.7 0.7
0.6 0.6
0.5 AMP+HMDA 0.5 AMP+HMDA
0.4 0.4 MEA
MEA
0.3 0.3
0.2 0.2
0.1 0.1
0.0 0.0
0.50 0.60 0.89 0.55 0.70 0.94
Solvent flow rate (kg/h) Solvent flow rate (kg/h)

Figure 19 (a), 5 vol% inlet CO2 conc. Figure 19 (b), 10 vol% inlet CO2 conc.
Effect of solvent flow rate (kg/h) on cyclic loading (mole CO2/mole amine) for 31 wt% MEA, 26.74
wt% AMP + 11.91 wt% HMDA and 51 wt% New Solvent at 99% CO2 recovery.
3.5 3.5
CO2 recovery (mole CO2/kg solvent)

CO2 recovery (mole CO2/kg solvent)

New Solvent
3.0 3.0
New Solvent
2.5 2.5 AMP+HMDA
AMP+HMDA
2.0 2.0 MEA
MEA
1.5 1.5

1.0 1.0

0.5 0.5

0.0 0.0
0.50 0.60 0.89 0.55 0.70 0.94
Solvent flow rate (kg/h) Solvent flow rate (kg/h)
Figure 20 (a), 5 vol% inlet CO2 conc. Figure 20 (b), 10 vol% inlet CO2 conc.
Effect of solvent flow rate (kg/h) on CO2 recovery (mole CO2/kg solvent) for 31 wt% MEA, 26.74 wt%
AMP + 11.91 wt% HMDA and 51 wt% New Solvent at 99% CO2 recovery.
 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046 2043

From Figure 19(b) it can be noticed that the increase in CO2 inlet concentration to 10 vol% increases
the required cyclic loading for the New Solvent up to 0.84 mole CO2/mole amine with an optimum
solvent flow rate of 0.55 kg/h. For AMP+HMDA at 5 vol% CO2 inlet concentration a higher cyclic
loading of 0.44 mole CO2/mole amine was found when compared to that of MEA. Which can be
explained by the lower solvent circulation rate (0.6 kg/h) of AMP+HMDA was found in comparison with
MEA, see Figure 19(a). At 10 vol% CO2 inlet concentration an optimum solvent circulation rate of 0.70
kg/h was found for AMP+HMDA. Taking into account that the cyclic loadings are almost identical, this
is in line with the increased total CO2 recovery task (in mole/h) when comparing the 5 vol% CO2, 645
nL/h with the 10 vol% 400 nL/h conditions. For the New Solvent, however, the cyclic loading increased
significantly, when going from the 5 to 10 vol% CO2 inlet concentration, Therefore, only a small increase
in the required solvent circulation rate (from 0.50 to 0.55 kg/h) was observed.

6.0 6.0

Energy requirement (MJ/kg CO 2)

Energy requirement (MJ/kg CO 2)

5.0 5.0 MEA

MEA
AMP+HMDA
AMP+HMDA
4.0 4.0

New Solvent New Solvent

3.0 3.0

2.0 2.0

1.0 1.0

0.0 0.0
0.50 0.60 0.89 0.55 0.70 0.94
Solvent flow rate (kg/h) Solvent flow rate (kg/h)
Figure 21 (a), 5 vol% inlet CO2 conc. Figure 21 (b), 10 vol% inlet CO2 conc.
Effect of solvent flow rate (kg/h) on energy requirement (MJ/kg CO2) for 31 wt% MEA, 26.74 wt% AMP
+ 11.91 wt% HMDA and 51 wt% New Solvent at 99% CO2 recovery.

Figures 20 (a & b) show that the New Solvent obtains the highest CO2 recovery 2.6 and 2.95 mole
CO2/ kg solvent for 5 and 10 vol% CO2 inlet concentration. For AMP+HMDA solvent CO2 recovery of
2.19 and 2.32 mole CO2/ kg solvent was achieved at 5 and 10 vol% CO2 inlet concentration respectively.
New solvent and AMP+HMDA were found to have less energy requirement (MJ/Kg solvent) compared
to MEA, as can be seen from Figure 21 (a & b). It is interesting to notice that New solvent energy
requirement was found to be same of 3.09 and 3.03 MJ/Kg solvent at 5 and 10 vol% CO2 inlet
concentration respectively. Whereas, AMP+HMDA energy requirement was increased from 4.07 to 4.41
MJ/Kg solvent for 5 to 10 vol% CO2 inlet concentration respectively. This could be due to the higher lean
2044 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046

loading for AMP+HMDA at 5 vol% CO2 inlet concentration case. These results already suggest that the
benefit of the use of New Solvent as absorption liquid could be substantial.

Table 9, Comparison of solvents energy requirement at 90% (± 3 %) CO2 recovery.

CO2 inlet Flue gas Solvent CO2 Cyclic Energy
Solvent
Conc. flow rate flow rate recovery loading requirement
mole CO2
vol% nL/h kg/h % MJ/kg CO2
/mole amine
MEA 31 wt%(*) 5 645 0.90 91 0.29 4.80
AMP 30 wt% +
5 645 0.63 90 0.51 3.87
Pz 5 wt%(*)
New Solvent 51 wt% 5 645 0.48 93 0.84 2.48
AMP 26.7 wt% +
5 645 0.63 91 0.44 3.62
HMDA 11.9 wt%

MEA 31 wt%(*) 10 400 0.91 89 0.34 4.33

AMP 35.6 wt%(*) 10 400 1.07 90 0.37 3.91

New Solvent 51 wt% 10 400 0.57 89 0.80 2.26

AMP 26.7 wt% +
10 400 0.73 88 0.46 3.41
HMDA 11.9 wt%
(*) In-house data Shell Technology Centre, Amsterdam.

Table 9, shows the comparison of the energy requirement for the AMP+HMDA – solvent and the New
Solvent with the more conventional solvents as 31 wt% MEA and 30 wt% AMP + 5 wt% Pz for the gas
streams containing 5 vol% inlet CO2 concentration and at 90% (±3%) CO2 recovery. For 10 vol% inlet
CO2 concentration and at 90% (±3%) CO2 recovery 31 wt% MEA and 35.6 wt% AMP was chosen for
comparison with New Solvent and AMP+HMDA - solvent. The New Solvent clearly shows that it
requires the lowest energy requirement for both CO2 inlet concentrations, reducing the energy
requirement (according to the experimental results above) with almost 50% in comparison with the 31
wt% MEA solvent. Also the value obtained for the energy requirement for the New Solvent is not much
different for both CO2 inlet concentrations and not very sensitive to the CO2 recovery fraction (see Figure
18) in the range up to 99%. Furthermore, it is interesting to notice that the energy requirement for the
26.74 wt% AMP + 11.91 wt% HMDA solvent is comparable (and even slightly lower) with the same of
30 wt% AMP + 5 wt% Pz solvent at 5 vol% inlet CO2 concentration.

4. Conclusions

The absorption equilibrium data of CO2 in aqueous solution of 0.5, 1 and 2.5 mole/L 1,6
Hexamethylenediamine (HMDA) were measured at 20, 30 and 40°C for pressures in the range of 1 to 100
kPa. Also the absorption equilibrium data of CO2 in aqueous blend of AMP + HMDA at 40°C was
measured for 1 to 100 kPa. The equilibrium partial pressure of CO2 is considerably lower than for
 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046 2045

aqueous MEA, compared at the same temperature and same amine-group concentration and amine-group
loading. Vapor liquid equilibrium results shows that HMDA has potential to be used as an activator for
CO2 absorption and AMP+HMDA blend shows comparable results to that for AMP+PZ.

In this study two new promising amine based solvent systems were successfully tested in a
continuously operated pilot plant in order to prove the operability of the solvent system and to obtain
information on the required solvent flow rates and energy requirements for regeneration of the solvent. It
has been shown that the solvent formulations studied, which were identified as ‘promising’ during earlier
solvent screening, indeed have the potential to reduce the reboiler energy requirements by 20-50% in
comparison with a 31 wt% MEA solution as reference solvent. Since, additionally, corrosiveness and
evaporative losses compare favorably, these solvents may form attractive alternatives to existing
absorption systems.

Acknowledgements

This research is part of the CATO programme, the Dutch national research programme on CO2
Capture and Storage. CATO is financially supported by the Dutch Ministry of Economic Affairs (EZ) and
the consortium partners (www.co2-cato.nl).
The authors wish to thank to Nick Aldenkamp, Henkjan Moed and Benno Knaken from the University
of Twente for the experimental work and technical support in the VLE experiments and Bas Armin
Schneider for the excellent work in the pilot plant experiments. Special thanks to Frank Geuzebroek and
Xiahoui Zhang of the GSGT group at Shell Technology Centre Amsterdam for the help and support.

References

[1] IEA Paris, Cost and performance of Carbon Dioxide Capture from Power generation. 2011.
[2] Singh D, Croiset E, Douglas PL, Douglas MA. Techno-economic study of CO2 capture from an existing coal-fired power plant:
MEA scrubbing vs. O2/CO2 recycle combustion. Energy Conversion and Management 2003; 44 (19): 3073-3091.
[3] Zahra A M, Ph.D. Thesis. Delft University; 2009.
[4] Aronu UE, Svendsen HF, Hoff KA, Knuutila H. Pilot plant study of 3- (methylamino)propylamine sarcosine for post-
combustion CO2 capture. In: Proceedings of the 2nd Annual Gas Processing Symposium, Doha 2010; 339–348.
[5] Aronu UE, Hartono A, Hoff KA, Svendsen HF. Kinetics of carbon dioxide absorption into aqueous amino acid salt; potassium
salt of sarcosine. Industrial and Engineering Chemistry Research 2011; 50: 10465–10475.
[6] Knudsen JN, Jensen JN, Vilhelmsen P-J, Biede O. Experience with CO2 capture from coal flue gas in pilot-scale: testing of
different amine solvents. Energy Procedia 2009, 1: 783–790.
[7] Knudsen JN, Jensen JN, Andersen J, Biede O. Evaluation of process upgrades and novel solvents for CO2 post combustion
capture in pilot-scale, Energy Procedia 2011; 4: 1558–1565.
[8] Mangalapally HP, Notz R, Hoch S, Asprion N, Sieder G, Garcia H, Hasse H. Pilot plant experimental studies of post
combustion CO2 capture by reactive absorption with MEA and new solvents. Energy Procedia 2009; 1: 963–970.
[9] Mangalapally HP, Hasse H. Pilot plant study of post-combustion carbon dioxide capture by reactive absorption: methodology,
comparison of different structured packings, and comprehensive results for monoethanolamine. Chemical Engineering Research and
Design 2011a; 66 (22): 5512–5522.
[10] Mangalapally HP, Hasse H. Pilot plant experiments for post combustion carbon dioxide capture by reactive absorption with
novel solvents. Energy Procedia 2011b; 4: 1–8.
[11] Ogawaa T, Ohashia Y, u Yamanakaa S, Miyaikeb K. Development of carbon dioxide removal system from the flue gas of coal
fired power plant. Energy Procedia 2009; 1: 721–724.
[12] Ohashi Y, Ogawa T, Egami N. Development of carbon dioxide removal system from the flue gas of coal fired power plant.
Energy Procedia 2011; 4: 29–34.
2046 Prachi Singh et al. / Energy Procedia 37 (2013) 2021 – 2046

[13] Plaza JM, Rochelle GT. Modeling pilot plant results for CO2 capture by aqueous piperazine. Energy Procedia 2011; 4: 1593–
1600.
[14] Reddy S, Johnson D, Gilmartin J. Fluor's econamine FG plusSM technology for CO2 capture at coal-fired power plants, Power
Plant Air Pollutant Control Mega Symposium Baltimore; 2008.
[15] Mimura T, Shimijo S, Suda T, Iljima M, Mitsuoka S. Research and development on energy saving technology for flue gas
carbon dioxide recovery and steam system in power plant, Energy Conversion and Management1995; 36: 397–400.
[16] Mimura T, Simayoshi H, Suda T, Iijima M, Mitsuoka S. Developments of energy saving technology for flue gas carbon dioxide
recovery in power plant by chemical absorption method and steam system. Energy Conversion and Management1997; 38: S57–S62.
[17] Jockenhoevel T, Schneider R, Rode H. Validation of a second-generation post-combustion capture technology—results from
POSTCAP pilot plant operation, PowerGen Europe, 8–10 June 2010.
[18] Raynal L, Bouillon P-A, Gomez A, Broutin P. From MEA to demixing solvents and future steps, a roadmap for lowering the
cost of post-combustion carbon capture. Chemical Engineering Journal 2011; 171 (3): 742–752.
[19] Brúder P, Owrang F, Svendsen HF. Pilot study—CO2 capture into aqueous solutions of 3-methylaminopropylamine (MAPA)
activated dimethyl-monoethanolamine (DMMEA). International Journal of Greenhouse Gas Control 2012; 11: 98–109.
[20] Idem R, Wilson M, Tontiwachwuthikul P, Chakma A, Veawab A, Aroonwilas A. Pilot plant studies of the CO2 capture
performance of aqueous MEA and mixed MEA/MDEA solvents at the University of Regina CO2 capture technology development
plant and the boundary dam CO2 capture demonstration plant. Industrial Engineering Chemical Research 2006; 45: 2414-2420.
[21] Singh P, Niederer JPM, Versteeg GF, Structure and activity relationship for amine based CO2 absorbents—I. International
Journal of Greenhouse Gas Control 2007; 1: 5-10.
[22] Singh P, Versteeg GF. Structure and activity relationships for CO2 regeneration from aqueous amine based absorbents. Process
Safety and Environmental Protection 2008; 86: 347-359
[23] Singh P, Niederer JPM, Versteeg GF. Structure and activity relationships for amine based CO2 absorbents—II. Chemical
Engineering Research and Design 2009; 87: 135-144.
[24] Singh P, Brilman DWF(Wim), Groeneveld MJ. Solubility of CO2 in aqueous solution of newly developed absorbents. Energy
Procedia 2009; 1: 1257–1264.
[25] Singh P, Brilman DWF, Groeneveld MJ, Evaluation of CO2 Solubility in Potential Aqueous Amine based Solvents at Low CO2
Partial Pressure, International Journal of Greenhouse Gas Control 2011; 5(1): 61-68.
[26] Singh P, van Swaaij WPM, Brilman DWF, Kinetics study of carbon dioxide absorption in aqueous solutions of 1,6-
hexamethyldiamine (HMDA) and 1,6-hexamethyldiamine, N,N di-methyl (HMDA, N,N). Chemical Engineering Science 2011; 66
(20): 4521-4532.
[27] Versteeg GF. On the kinetics between CO2 and alkanolamines both in aqueous and non-aqueous solutions-II. Tertiary amines.
Chemical Engineering Scienece 1988; 43: 587-591.
[28] Jou F-Y, Mather AE and Otto FD. The solubility of CO2 in a 30 mass percent monoethanolamine Solution. Can. J. Chem. Eng.
1995; 73: 140-147.
[29] Lee JI, Otto FD, Mathera AE. Equilibrium Between Carbon Dioxide and Aqueous Monoethanolamine Solutions. Journal of
Applied Chemical Biotechnology 1976; 26: 541-549.
[30] Aboudheira A, Tontiwachwuthikul P, Idem R. Rigorous model for predicting the behaviour of CO2 absorption into AMP in
packed-bed absorption columns. Industrial Engineering Chemical Research 2006; 45: 2553-2557.
[31] Yang Z-Y, Soriano A N, Caparanga AR, Li M-H. Equilibrium solubility of carbon dioxide in (2-amino-2-methyl-1-propanol +
piperazine + water). J. Chem. Thermodynamics 2010; 42: 659–665
[32] Bru´ der P, Grimstvedt A, Mejdell T, Svendsen HF. CO2 capture into aqueous solutions of piperazine activated 2-amino-2-
methyl-1-propanol. Chemical Engineering Science 2011; 66: 6193–6198
[33] Roberts BE, Mather AE. Solubility of CO2 and H2S in a Hindered Amine Solution, Chemical Engineering Communications
1988; 64: 105–111.