Article

pubs.acs.org/est

Novel Shortcut Estimation Method for Regeneration Energy of

Amine Solvents in an Absorption-Based Carbon Capture Process
Huiyong Kim, Sung June Hwang, and Kwang Soon Lee*
Department of Chemical and Biomolecular Engineering, Sogang University, 35 Baekbeom-ro, Mapo-gu, Seoul 121-742, Korea

ABSTRACT: Among various CO2 capture processes, the

aqueous amine-based absorption process is considered the
most promising for near-term deployment. However, the
performance evaluation of newly developed solvents still
requires complex and time-consuming procedures, such as
Downloaded by INST OF CHEMICAL TECHNOLOGY at 02:51:08:164 on May 24, 2019

pilot plant tests or the development of a rigorous simulator.

Absence of accurate and simple calculation methods for the
energy performance at an early stage of process development has
lengthened and increased expense of the development of
economically feasible CO2 capture processes. In this paper, a
novel but simple method to reliably calculate the regeneration
from https://pubs.acs.org/doi/10.1021/es504684x.

energy in a standard amine-based carbon capture process is

proposed. Careful examination of stripper behaviors and
exploitation of energy balance equations around the stripper
allowed for calculation of the regeneration energy using only vapor−liquid equilibrium and caloric data. Reliability of the
proposed method was confirmed by comparing to rigorous simulations for two well-known solvents, monoethanolamine (MEA)
and piperazine (PZ). The proposed method can predict the regeneration energy at various operating conditions with greater
simplicity, greater speed, and higher accuracy than those proposed in previous studies. This enables faster and more precise
screening of various solvents and faster optimization of process variables and can eventually accelerate the development of
economically deployable CO2 capture processes.

1. INTRODUCTION used in the industry.5,9−11 However, the immediate deployment

Preventing anthropogenic climate change by reducing
emissions of CO2 without decreasing fossil fuel usage is a
critical issue worldwide.1,2 Global energy usage is continuously
increasing, and the International Energy Agency (IEA) predicts
that the reliance on fossil fuels will account for 80% of the
energy supply in 2050.3 With the increase in the consumption
of fossil fuels, greenhouse gas emissions, which are thought to
bring about severe climate change, are also expected to increase.
Efforts to solve this problem have led to numerous initiatives
concerning the reduction of CO2 emissions.
Carbon capture and sequestration (CCS) technology is
considered to be a promising means of addressing the CO2
emission problem. This technology includes the capture (and
compression) of CO2 from fixed-point sources, its trans-
portation, and its storage. According to the IEA Blue Map
Scenario, the amount of CO2 emitted in 2050 could be reduced
by 48 billion tons from the projected total CO2 emissions
through the use of all possible efforts, and CCS is predicted to
be responsible for 19% of this reduction.3
A large portion of carbon capture research is focused on
absorption-based post-combustion CO2 capture technol-
ogy.2,4−8 Other technologies, such as adsorption, solid
sorbent-based absorption, membrane separation, oxy-fuel
combustion, and pre-combustion capture, are not expected
for near-term use because of their technical immaturity
compared to the absorption process, which has long been
of the current absorption-based technology has been delayed
because of the large amount of energy required to run the
process,5,10,12 while a lot of research is being carried out to
develop advanced energy-efficient solvents and processes. The
adoption of any of the present absorption-based capture
processes in a power plant is expected to result in an energy
penalty of 20−30%,13−15 where the energy is consumed mostly
for regeneration of absorbed CO2.
With various absorbent candidates being competitively
developed in many institutions worldwide, the performance
(i.e., total required work including the regeneration energy)
evaluation of developed solvents remains time-consuming and
challenging. Typically, candidate solvents are pre-screened by
comparing the absorption rate, absorption capacity, heat of
absorption, degradation, viscosity, solvent cost, etc.16,17
However, the energy performance is not evaluated quantita-
tively at this stage, and only solvent characteristics are listed
without having a clear selection guideline for the best candidate
solvent. After pre-screening, pilot plant tests and rigorous
modeling studies are usually conducted to observe solvent
performance. Pilot plant testing is essential in the process
Received: September 24, 2014
Revised: December 9, 2014
Accepted: December 11, 2014
Published: January 20, 2015

© 2015 American Chemical Society 1478 DOI: 10.1021/es504684x

Environ. Sci. Technol. 2015, 49, 1478−1485
Environmental Science & Technology
development but is labor-intensive and costly. In addition,
further scale-up is required to obtain an accurate energy
assessment because of the heat loss problem in small-scale
plants. Rigorous modeling is another labor-intensive job,
demanding a lot of experimental work for thermodynamic
and kinetic modeling. Thus, developing a method that can
reliably estimate the regeneration energy at the pre-screening
stage can reduce trial and error and act as an important agent
that can accelerate carbon capture research.
The total required work of a CO2 capture process is
composed of the regeneration energy (i.e., reboiler duty of the
stripper), compression energy to 150 bar, solvent pumping
energy, and flue gas blowing energy, as in eq 1.18 The
regeneration energy, Qregen, can be further decomposed into
energies required for solvent heating (sensible heat, Qsens),
water and amine evaporation (latent heat, Qlatent), and CO2
desorption (heat of reaction, Qrxn), as shown in eq 219 and also
in Figure 2a. In this study, we restricted ourselves to amines
that have much lower volatility than water, and the amine
evaporation was neglected.
Wtotal = Wcomp + Wpump + Wblower + 0.75Q regen
Treboiler + 10 − Tambient
(GJelec /tCO2 )
Treboiler + 10 (1)
Q regen = Q sens + Q latent + Q rxn (GJth /tCO2 )
(2)
Individual energy terms in eqs 1 and 2 can be easily calculated,
except Qlatent, the latent heat for water vaporization. Required
works for compression, pumping, and blowing can be easily and
reliably estimated from the respective performance equations.
Among the three energy terms comprising Qregen, Qrxn can be
predicted quite accurately using the Gibbs−Helmholtz
equation19,20 and a small number of vapor−liquid equilibrium
(VLE) data. Consistency of evaluating Qrxn using the Gibbs−
Helmholtz equation with VLE data was confirmed by Mathias
and O’Connell.20 Qsens can also be estimated from a simple
enthalpy balance relation. The most troublesome part of the
energy assessment is the latent heat for water evaporation,
Qlatent.
There have been some studies dedicated to the estimation of
Qlatent. Rochelle et al. proposed a method to calculate Qlatent
when regeneration is conducted in a flash drum instead of a
stripper.21 Notz et al. proposed a shortcut method to estimate
Qregen in a stripper using a modified Kremser equation.22 This
method can estimate Qregen for various solvent flow rates when
VLE data at absorber and stripper temperatures and caloric data
are available. The method can yield reasonable results in limited
situations only because of underlying assumptions, such as
constant temperature and vapor flow within the stripper. As
demonstrated in Figures 2b and 3a for a monoethanolamine
(MEA) case, the maximum temperature difference within the
stripper is greater than 20 °C. The vapor flow rate also varies
significantly along the stripper column. Such discrepancies
between assumed idealities and practical situations have limited
the dependability of the Qregen prediction.
On the basis of the considerations mentioned above, the
purpose of this research is to propose a novel shortcut method
to estimate Qregen for an absorption-based CO2 capture process
using a stripper. An examination of stripper characteristics
revealed that the stripper operation can be separated into two
regions. With the introduction of suitable energy balance
equations for each region and some simplified but reasonable
1479
Article
assumptions, a reliable estimation of Qregen was enabled using
only VLE and caloric data. Calculated values of Qregen were
compared to those from rigorous simulations for two well-
studied solvents, MEA and piperazine (PZ), at two different
stripper operating pressures to verify the pertinence of the
proposed method.
In the remainder of the paper, section 2 describes the
standard CO2 absorption process and stripper behaviors,
section 3 describes the derivation of the proposed shortcut
method, and section 4 demonstrates the performance of the
shortcut method by applying it to four different cases.
2. ABSORPTION PROCESS AND STRIPPER BEHAVIORS
Before introduction of the proposed shortcut method, stripper
behavior is investigated in this section. For the base case study,
an absorption process with a typical absorber−stripper
configuration is assumed for 30 wt % MEA solvent, and
stripper behavior of the process is studied by rigorous
simulation using Aspen Plus.23 Because Qregen is provided at
the reboiler of the stripper, understanding the stripper behavior
is crucial, and only the stripper is studied. Thermal energy
balance of the stripper discussed in section 2.3 shows that
knowing the top-stage temperature of the stripper is the key to
estimating Qregen, and stripper behavior investigated in section
2.4 reveals that the top-stage temperature can be easily
obtained.
2.1. Standard Carbon Capture Process. Figure 1 shows a
standard configuration of the absorption-based carbon capture
Figure 1. Typical configuration of the absorption-based carbon
capture process.
process, which is most widely employed in industrial processes.
The main equipment used in Figure 1 includes the absorber,
the stripper, and the heat exchanger. The cool CO2-rich solvent
stream (RICHOUT) exits from the bottom of the absorber,
gaining energy by exchanging heat at the heat exchanger with
the hot CO2-lean solvent stream (LEANOUT) exiting from the
bottom of the stripper. As a result of the heat exchange, CO2
and water in the RICHIN stream, which enter the stripper at
the top stage, are partially vaporized. The minimum temper-
ature approach (ΔTMTA) is formed at the RICHOUT side of
the heat exchanger because of a larger mass flow rate of the
RICHOUT stream than that of the LEANOUT stream. The
liquid portion in the RICHIN stream flows downward,
transferring CO2 to and receiving water from the upward
vapor flow inside the stripper. The CO2-stripped LEANOUT
stream is withdrawn from the reboiler.
2.2. Simulation Conditions for a MEA-Based Process.
Some basic assumptions and simulation conditions for the
rigorous simulation of the MEA-based process are described in
DOI: 10.1021/es504684x
Environ. Sci. Technol. 2015, 49, 1478−1485
Environmental Science & Technology Article

this subsection. Numbers are assigned to process streams If the heat of reaction, Δhrxn (kJ/mol of CO2), is a function of
around the stripper in Figure 1, in addition to names used to CO2 loading and the reference states associated with the four
simplify the designation of the associated heat and mass terms. streams in eq 4 are unloaded liquid solvent, gaseous CO2, and
Some basic assumptions of the process for simulation include liquid water at TR and 1 bar, the enthalpy terms would be
the following: (i) The flue gas contains 15% CO2, saturated reasonably expressed as follows:
water vapor at 40 °C, and N2 for balance. It enters the process
at a flow rate of 510 kg/h or equivalently 17.1 kmol/h. (ii) The H1 = (cam + rwc w + αrichcCO2)(T1 − TR )
solvent is an aqueous solution of 30 wt % MEA. (iii) Rate-based rich
simulation is used for the absorber, and VLE-based simulation + ∫0 Δhrxn(α) dα
with 20 equilibrium stages is applied to the stripper. The
operating pressures for the absorber and stripper are chosen as H2 = (cam + rwc w + αleancCO2)(T2 − TR )
1 and 2 bar, respectively. (iv) The temperature of the flue gas, lean
the LEANIN stream, and the condensate recycle stream of the + ∫0 Δhrxn(α) dα
stripper is 40 °C. (v) The CO2 recovery rate (percentage of
CO2 removed from the flue gas stream) is 90%, which H3 = (McCO2(Ttop − TR ) + m w c w(Ttop − TR ) + m w λ)
corresponds to a CO2 capture rate of 100 kg/h. (vi) ΔTMTA for
/(M + m w )
the main heat exchanger is 10 °C.
The assumptions above are typical, and the resulting stripper H4 = c w(T4 − TR )
behaviors would be generally applied to amine-based carbon (5)
capture processes. Rate and equilibrium models and data
provided in Aspen Plus were used without modifications. where λ (kJ/mol) denotes the latent heat of water and Ttop =
The amount of CO2 absorbed in the RICHOUT stream T3. Note that the heat capacity, c, is molar-based, having the
(rich loading) and the LEANIN stream (lean loading) can have unit of kJ mol−1 K−1. It is assumed that c for a species has the
various values depending upon equipment design, operating same value for both gas and liquid states and c for a mixture has
parameters, and solvent properties. In this study, rich loading a molar-weighted average value of pure species, regardless of
was fixed at 0.54 (mol of CO2/mol of amine), and lean loading the existence of reaction products inside the mixture.
was varied over a range. The chosen value of rich loading Substitution of eq 5 into eq 4 yields the following:
corresponds to CO2 vapor pressure of 5 kPa at 40 °C. Because Q regen = Q sen + Q rxn + Q latent
the CO2 partial pressure in the flue gas is 15 kPa (15% CO2 in
the 101 kPa flue gas), setting the CO2 vapor pressure of the
Q sen = mam(cam + rwc w + αleancCO2)(T2 − T1)
solvent at 5 kPa can offer a reasonable driving force for mass
transfer from the flue gas to the MEA solvent.18,19 The rich + McCO2(Ttop − T1) + m w c w(Ttop − T4)
loading value of 0.54 was maintained during simulation by rich
adjusting the absorber height and the amount of interstage
cooling. The CO2 recovery was maintained at 90% by adjusting
Q rxn = −mam ∫lean Δhrxn(α) dα
the solvent circulation rate. Q latent = m w λ (6)
2.3. Thermal Energy Balance around the Stripper.
Equations for Qregen computation can be derived from the It is interesting to note that Qlatent is determined by the amount
energy balance for the control surface around the stripper of water content at the top of the stripper, mw, instead of the
shown in Figure 1. It is convenient to write the energy terms amount of water boil-up at the reboiler.
based on molar amount of unloaded solvent wherever In eq 6, T2 − T1 is set to have ΔTMTA because it minimizes
applicable. For this, let us define mam (mol/tCO2) as the Qsen and all the other terms, except Ttop and mw, are known or
molar amount of amines in the circulating solvent streams per can be pre-specified. The value of Δhrxn can be obtained
tonne of CO2 product. In addition, let us define rw as the molar experimentally using an instrument, such as the reaction
ratio of water to amines in the unloaded solvent. Also, let us calorimeter, or using VLE data and the following Gibbs−
define M and mw as the molar amount of CO2 and the molar Helmholtz equation:
amount of water vapor in stream 3 per tonne of CO2 product,
respectively. Obviously, M = 2.2727 × 104 mol of CO2 (1 tonne Δhrxn ⎡ ∂ ln P* ⎤
=⎢ ⎥
CO2
of CO2). Finally, let α be the CO2 loading defined as moles of −
CO2 per mole of amines. Then, the following holds:
R ⎣⎢ ∂(1/T ) ⎥⎦α (7)

m1 = mam(1 + rw + αrich), m2 = mam(1 + rw + αlean) where P*CO2(T, α) is the CO2 vapor pressure.
m3 = M + m w , m4 ≈ m w The value of mw can be estimated using the pressure
relationship. The column pressure at the top is the sum of the
(3) * 2(Ttop, αtop), and the partial pressure of
CO2 vapor pressure, PCO
Let us denote Hi (kJ/mol) as the enthalpy of the ith stream per water.
mole of amines for i = 1 and 2 and per mole of the stream itself
for i = 3 and 4. According to the energy balance around the * (Ttop , αtop) + Pw(Ttop)
Ptotal = PCO (8)
2
control surface, Qregen can be represented as follows:
When P*CO2(Ttop, αtop) and Pw(Ttop) are known, mw can be
Q regen = mamH2 + (M + m w )H3 − mamH1 − m w H4 computed as follows:

(GJ/tCO2 ) (4) * (Ttop , αtop)

m w = MPw(Ttop)/PCO (9)
2

1480 DOI: 10.1021/es504684x

Environ. Sci. Technol. 2015, 49, 1478−1485
Environmental Science & Technology
Pw(Ttop) can be approximated by Raoult’s law, xw,topPvap w (Ttop),
where xw is the mole fraction of water, because xw is high (>0.8)
for most aqueous amine solvents. It is observed from simulation
studies that xw inside the stripper remains nearly constant
around the mole fraction of water in the unloaded fresh solvent,
xw,fresh, irrespective of the stage number, especially when the
bicarbonate formation is not excessive. On the basis of this
observation, eq 8 can be rewritten as follows:
* (Ttop , αtop) + x w,freshPwvap(Ttop)
Ptotal = PCO2 (10)
which has two unknowns, Ttop and αtop. Because Ptotal is given,
αtop can be obtained from eq 10 if Ttop is known and VLE data
for P*CO2(T, α) is available. This enables the computation of mw
in eq 9 and then Qregen from eq 6.
Additionally, when Δhrxn is given as a function of α only,
* 2(Ttop, αtop) can be expressed, as in eq 11, by integrating the
PCO
Gibbs−Helmholtz equation using VLE data at only 313 K.
* (Ttop , αtop) = PCO
PCO * (313, αtop)
2 2
⎛ ⎞
Δh ⎛ 1 1 ⎞⎟⎟
exp⎜⎜ − rxn ⎜⎜ − ⎟
⎝ R ⎝ Ttop 313 ⎠⎟⎠ (11)
In short, knowing one unknown, Ttop, is sufficient for
calculating Qlatent and then Qregen. Examining stripper behaviors
can provide a clue to estimate the unknown variable Ttop.
2.4. Stripper Behaviors. Stripper behaviors were inves-
tigated for different values of αlean, from 0.15 to 0.375, while T1
and αrich from the absorber were fixed at 40 °C and 0.54,
respectively. Three energy terms and Qregen are shown in Figure
2a as αlean varies. Qrxn remains nearly constant over the
Figure 2. (a) Individual energy terms contributing to Qregen and (b)
comparison of Ttop with TRICHIN from rigorous simulation for different
values of αlean when T1 = 40 °C and αrich = 0.5383.
considered αlean range. Qsens increases with αlean as the solvent
circulation rate is increased to achieve 90% CO2 recovery. Qlatent
increases sharply as αlean is lowered below 0.2 because of the
increased boiling in the reboiler. Qregen is strongly affected by
Qlatent and shown to have a minimum at αlean = 0.2.
In Figure 2b, Ttop is compared to TRICHIN or equivalently T5.
Ttop and TRICHIN agree quite closely in the region of αlean > 0.2
1481
Article
(region A), while they begin to deviate significantly as αlean
becomes smaller than 0.2 (region B). In region A, the flow rate
and enthalpy of the RICHIN stream dominate those of the
other incoming streams to the top stage (condensed water and
upward vapor from the lower stages) and Ttop inevitably follows
TRICHIN. In contrast, in region B, a larger amount of thermal
energy is provided to the reboiler to discharge CO2 by
increasing the reboiler temperature and the upward vapor
stream has a stronger effect on the top stage than in region A.
Consequently, Ttop of region B is determined to be higher than
TRICHIN, and the difference becomes more severe as αlean is
reduced further. The stripper behavior demonstrates that Ttop,
the important variable for estimation of Qlatent, can be simply
approximated by TRICHIN for region A.
Figure 3 illustrates the temperature, CO2 loading, and vapor
mole fraction profiles inside the stripper to better comprehend
Figure 3. Profiles of (a) temperature, (b) CO2 loading in the liquid
phase, and (c) mole fractions of CO2 and water in the vapor phase
inside the stripper for selected values of αlean.
that region A is governed by the RICHIN stream while region
B is governed by the vapor flow from the reboiler. Centering
around αlean = 0.2, the temperature, CO2 loading in the liquid
phase, and vapor mole fractions of CO2 and water at the
bottom stage (reboiler) continue to a near-top stage when αlean
< 0.2, and the reverse holds when αlean > 0.2. The column
profiles are best balanced, and minimum Qregen is achieved,
when αlean = 0.2.
3. SHORTCUT ESTIMATION METHOD FOR
REGENERATION ENERGY
In the previous section, it was revealed that the stripper behaves
differently in high and low lean loading regions. On the basis of
this observation, the shortcut estimation method for Qregen is
developed separately for each region.
3.1. Shortcut Estimation Method for Region A. For
region A, Ttop ≅ TRICHIN = T5 and accurate prediction of T5 is
the key to the estimation of Qregen. T5 can be easily obtained
from the energy balance around the main heat exchanger
shown in Figure 4a. The RICHIN stream is in a partially
vaporized state and can be expressed into vapor and liquid
streams.
The energy balance equation can be written as
mam(H1 − H2 − H5,liq − H5,vap + H6) = 0 (12)
where H1 and H2 are as given in eq 5. Assuming that the vapor
portion of the RICHIN stream is composed of only CO2 and
water vapor, the remaining three enthalpy terms are expressed
as follows:
DOI: 10.1021/es504684x
Environ. Sci. Technol. 2015, 49, 1478−1485
Environmental Science & Technology Article

Figure 5. (a) Temperature estimates and (b) estimates of the energy

terms by the rigorous simulation and the shortcut method for region A
(RIG, rigorous simulator; SC, shortcut method).
Figure 4. (a) Streams around the main heat exchanger and (b) energy
balance boundary for region B.

H5,liq = (cam + rw,5lc w + α5lcCO2)(T5 − TR ) from the proposed shortcut method for region A. Three energy
α5l terms that comprise Qregen calculated by the shortcut method
+ ∫0 Δhrxn(α) dα are also displayed in Figure 5b together with Qregen from the
rigorous simulation. Quite satisfactory agreement of the
H5,vap = ((rw − rw,5l)c w + (αrich − α5l)cCO2)(T5 − TR ) reboiler and RICHIN temperatures and the regeneration
+ (rw − rw,5l)λ energy from the rigorous simulation and the shortcut method
manifests for region A.
H6 = (cam + rwc w + αleancCO2)(T6 − TR ) 3.2. Shortcut Estimation Method for Region B.
lean Accurate estimation of Qregen for region B is not important
+ ∫0 Δhrxn(α) dα because it is not a recommended operating region as a result of
high regeneration energy. Nevertheless, Qregen for region B,
(13) together with Qregen for region A, enables us to figure out the
Rearranging eq 12 using T2 − T1 = ΔTMTA and m5,vap = mam((rw overall variation of Qregen with respect to αlean and, especially, to
− rw,5) + (αrich − α5)) yields the following relationship: locate the region boundary, where Qregen is likely to have the
minimum value.
0 = (cam + rwc w )(ΔTMTA + T6 − T5) To estimate Qregen for region B, energy balance around the
reboiler as shown in Figure 4b is used with an additional
+ cCO2(αlean(T6 − T2) − αrich(T5 − T1)) assumption that the temperature difference between the
rich reboiler (stage 20) and the upper next stage (stage 19) is
− (rw − rw,5l)λ + ∫α Δhrxn(α) dα
(14) small, which can be observed from Figure 3a for αlean = 0.15.
This assumption is valid, because upward vapor flow with a
5l

Because the column pressure varies only slightly from top to high enthalpy content from the reboiler renders the temper-
bottom, the same pressure relationship as in eq 10 holds at the atures at stages above the reboiler similar.
reboiler with respect to αlean and T6. The control surface and streams around the reboiler are
defined as shown in Figure 4b. Then, Qregen can be represented
* (T6 , αlean) + x w,freshPwvap(T6)
Ptotal = PCO (15)
2 as follows:
T6 can be determined from eq 15. Consequently, eq 14 has Q regen = −mamH6 − m8H8 + mamH7 (18)
three unknowns, T5, rw,5l, and α5l. They can be uniquely
determined using the following two more relationships: where H6 is in eq 13 and
* (T5 , α5l) + x w,freshPwvap(T5)
Ptotal = PCO (16)
H7 = (cam + rwc w + α7cCO2)(T7 − TR )
2 α7

* (T5 , α5l)
PCO
+ ∫0 Δhrxn(α) dα
αrich − α5l 2
=
rw − rw,5l x w,freshPwvap(T5) (17) H8 = ((m w,R c w + mCO2,R cCO2)(T6 − TR ) + m w,R λ)/m8

Figure 5a compares temperatures at the reboiler, the top stage, m8 = m w,R + mCO2,R
and the RICHIN stream from the rigorous simulation to those (19)

1482 DOI: 10.1021/es504684x

Environ. Sci. Technol. 2015, 49, 1478−1485
Environmental Science & Technology Article

where mw,R and mCO2,R represent molar flow rates of water Figure 7 compares the estimates of regeneration energy from
vapor and CO2 gas from the reboiler. They can be estimated by the shortcut method and rigorous simulation under various
solving the following:
mCO2,R = mam(α7 − αlean)

mCO2,R * (T6 , αlean)

PCO2
=
m w,R x w,freshPwvap(T6) (20)
Finally, α7 can be computed from the VLE relationship if T7 is
known.
* (T7 , α7) + x w,freshPwvap(T7)
Ptotal = PCO (21)
2

In Figure 3a, we can see that T7 (at stage 19) is slightly lower
than T6 (at stage 20) for region B. The difference is
approximately a few degrees Celsius at best and becomes
smaller as αlean becomes smaller. If T7 can be reasonably
assumed, Qregen for region B can be estimated using eqs 18−21.
Figure 6 compares Qregen estimates for both regions. In the
shortcut estimation for region B, four different T6 − T7 values
Figure 6. Comparison of the estimate of regeneration energy from the
shortcut method with that from the rigorous simulation.
Figure 7. Estimates of regeneration energy of MEA and PZ systems
from the shortcut method and rigorous simulation under various
operating conditions.
operating conditions. Estimates of the regeneration energy by
the shortcut method agree well with those from rigorous
simulation, especially in region A. Qregen in region B was
calculated for various values of T6 − T7, between 0 and 5 °C,
and the highest value at each αlean was selected.
For PZ, rigorous simulation was prone to fail in region B, and
the results could not be provided in Figure 7. VLE data for PZ
available in the literature are limited for αlean < 0.2, and the
associated VLE model can be unreliable in region B. This might
be the cause for the failure of simulation.
Three energy terms comprising the regeneration energy
calculated by the shortcut method and rigorous simulation are
compared in Figure 8. Because caloric data such as the heat of

were assumed. The results for 0.3, 1.0, and 3.0 °C show
consistency in that αlean at the region boundary becomes
smaller, while the Qregen curve becomes steeper. The result for
5.0 °C of T6 − T7 is out of the consistency mentioned above.
This may indicate that a 5.0 °C temperature difference is
unrealistic for this system. On the basis of this observation, we
suggest a method to estimate Qregen such that Qregen is
computed for various values for T6 − T7 (between 0 and 5
°C, for example) simultaneously and select the highest value at
each αlean.

4. APPLICATIONS OF THE SHORTCUT METHOD TO

OTHER CASES
Reliability of the proposed shortcut method was confirmed by
applying the method to additional cases and comparing the
results to those from rigorous simulations. As additional cases,
7 mol of MEA at 1 bar of stripper pressure and also 8 mol of
piperazine (PZ) at 2 and 5 bar of stripper pressure were
considered. The proposed method is applicable to other
aqueous amine solvent systems as long as VLE and caloric data
are available and volatility of amine is much lower than water.
Rate and equilibrium models for PZ necessary for rigorous
simulation are provided in Aspen Plus and were used without
modifications.24 The VLE information from Aspen Plus was
used for shortcut simulation. The rich loading corresponding to
CO2 vapor pressure of 5 kPa was assumed for all cases, while
lean loading was varied.
1483
Figure 8. Estimates of three energy terms comprising regeneration
energy from the shortcut method and rigorous simulation for (a) MEA
at 2 bar, (b) MEA at 1 bar, (c) PZ at 5 bar, and (d) PZ at 2 bar.
reaction and heat capacity are available or can be predicted
easily from VLE data, precise estimates of the sensible heat and
the heat of reaction can be performed without much difficulty.
Evaluation of the latent heat, the most troublesome part, could
also be reasonably performed using the proposed method, as
shown in Figure 8. Some deviation exists in the estimation of
the latent heat between the two methods. Underlying
assumptions, such as m4 ≈ mw in eq 3, xw ≈ xw,fresh in eq 10,
DOI: 10.1021/es504684x
Environ. Sci. Technol. 2015, 49, 1478−1485
Environmental Science & Technology
and non-volatility of amines, may have led to the uncertainty of
estimation.
Reliable estimation of the latent heat by the shortcut method
in region A can be achieved when top and bottom temperatures
of the stripper are correctly predicted and top and RICHIN
temperatures agree well with each other, which is one of the
key prerequisites of the shortcut method. Figure 9 exhibits the
estimates of top, bottom, and RICHIN temperatures from the
two calculation methods and shows that the required
performances are satisfactorily fulfilled.
Figure 9. Prediction of top and bottom temperatures of the stripper
and RICHIN temperature from the shortcut method and rigorous
simulation for (a) MEA at 2 bar, (b) MEA at 1 bar, (c) PZ at 5 bar,
and (d) PZ at 2 bar.
Performance evaluation of a solvent is perhaps the most
important but a quite complex and time-consuming step in the
development of an economically feasible CO2 capture process.
Through this study, a novel but simple method to reliably
estimate the regeneration energy, Qregen, for an aqueous amine
solvent in a typical absorption-based CO2 capture process with
a stripper is proposed. The method requires only VLE and
caloric data at various CO2 loadings and temperatures and can
provide estimates of Qregen at various conditions of lean loading,
rich loading, and stripper pressure. The method was derived
from energy balance equations around the stripper under some
ideal assumptions plus some crucial approximations drawn
from careful examination of stripper characteristics. The
assumptions and approximations include non-volatility of
amines, two distinctive stripper behaviors depending upon
the value of lean loading, coincidence of feed and top-stage
temperatures, invariance of water content in the liquid phase,
Raoult’s law for water, heat capacity of a mixture as a molar
average heat capacity of pure components, etc. Reliability of the
proposed shortcut method was verified by comparing it to the
results for MEA and PZ systems from rigorous simulation using
Aspen Plus.
It is believed that the proposed method enables more reliable
solvent screening with minimum experimental data, much faster
“shortcut” calculation compared to rigorous process simu-
lations, easier optimization of operating conditions, and
eventually acceleration of the development of economically
feasible absorption-based CO2 capture processes.
1484
Article
■ AUTHOR INFORMATION
Corresponding Author
*Telephone: +82-2-705-8477. Fax: +82-2-3272-0319. E-mail:
kslee@sogang.ac.kr.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the Korea Carbon Cpature and
Sequestration Research and Development Center (KCRC)
Grant funded by the Korean Government (Ministry of
Education, Science and Technology, 2012-0008886) and the
Sogang University Research Grant (201214007).
■ REFERENCES
(1) Wang, M.; Lawal, A.; Stephenson, P.; Sidders, J.; Ramshaw, C.;
Yeung, H. Post-combustion CO2 capture with chemical absorption: A
state-of-the-art review. Chem. Eng. Res. Des. 2011, 89 (9), 1609−1624.
(2) Richadson, K.; Steffen, W.; Schellnhuber, H. J.; Alcamo, J.;
Barker, T.; Kammen, D. M.; Leemans, R.; Liverman, D.; Munasinghe,
M.; Osman-Elasha, B.; Stern, L. N.; Wæver, O. Synthesis Report:
Climate Change, Global Risks, Challenges & Decisions; IARU Group:
Copenhagen, Denmark, 2009.
(3) International Energy Agency (IEA). Energy Technology
PerspectivesScenarios & Strategies to 2050; IEA: Paris, France, 2010.
(4) Tobiesen, F. A.; Svendsen, H. F. Study of a modified amine-based
regeneration unit. Ind. Eng. Chem. Res. 2006, 45 (8), 2489−2496.
(5) Rochelle, G. T. Amine scrubbing for CO2 capture. Science 2009,
325 (5948), 1652−1654.
(6) Feron, P. H. M. The potential for improvement of the energy
performance of pulverized coal fired power stations with post-
combustion capture of carbon dioxide. Energy Procedia 2009, 1 (1),
1067−1074.
(7) Markewitz, P.; Kuckshinrichs, W.; Leitner, W.; Linssen, J.; Zapp,
P.; Bongartz, R.; Schreiber, A.; Muller, T. E. Worldwide innovations in
the development of carbon capture technologies and the utilization of
CO2. Energy Environ. Sci. 2012, 5 (6), 7281−7305.
(8) Neveux, T.; Moullec, Y. L.; Corriou, J. P.; Farve, E. Modeling of
CO2 capture in amine solvents: Prediction of performance and insights
on limiting phenomena. Ind. Eng. Chem. Res. 2013, 52 (11), 4266−
4279.
(9) Yang, H.; Xu, Z.; Fan, M.; Gupta, R.; Slimane, R. B.; Bland, A. E.;
Wright, I. Progress in carbon dioxide separation and capture: A review.
J. Environ. Sci. 2008, 20 (1), 14−27.
(10) MacDowell, N.; Florin, N.; Buchard, A.; Hallett, J.; Galindo, A.;
Jackson, G.; Adjiman, C. S.; Williams, C. K.; Shah, N.; Fennell, P. An
overview of CO2 capture technologies. Energy Environ. Sci. 2010, 3
(11), 1645−1669.
(11) Cousins, A.; Wardhaugh, L. T.; Feron, P. H. M. A survey of
process flow sheet modifications for energy efficient CO2 capture from
flue gases using chemical absorption. Int. J. Greenhouse Gas Control
2011, 5 (4), 605−619.
(12) Puxty, G.; Rowland, R.; Allport, A.; Yang, Q.; Bown, M.; Burns,
R.; Maeder, M.; Attalla, M. Carbon dioxide postcombustion capture: A
novel screening study of the carbon dioxide absorption performances
of 76 amines. Environ. Sci. Technol. 2009, 43 (16), 6427−6433.
(13) Freguia, S.; Rochelle, G. T. Modeling of CO2 capture by
aqueous monoethanolamine. AIChE J. 2003, 49 (7), 1676−1686.
(14) Rubin, E. S.; Chen, C.; Rao, A. B. Cost and performance of fossil
fuel power plants with CO2 capture and storage. Energy Policy 2007, 35
(9), 4444−4454.
(15) Moullec, Y. L.; Kanniche, M. Screening of flowsheet
modifications for an efficient monoethanolamine (MEA) based post-
combustion CO2 capture. Int. J. Greenhouse Gas Control 2011, 5 (4),
727−740.
DOI: 10.1021/es504684x
Environ. Sci. Technol. 2015, 49, 1478−1485
Environmental Science & Technology Article

(16) Davidson, R. M. Post-combustion Carbon Capture from Coal Fired

PlantsSolvent Scrubbing; International Energy Agency Clean Coal
Centre: London, U.K., 2007.
(17) Ma’mum, S.; Svendsen, H. F.; Hoff, K. A.; Juliussen, O.
Selection of new absorbents for carbon dioxide capture. Energy
Convers. Manage. 2007, 48 (1), 251−258.
(18) Oyenekan, B. A.; Rochelle, G. T. Energy performance of stripper
configurations for CO2 capture by aqueous amines. Ind. Eng. Chem.
Res. 2006, 45 (8), 2457−2464.
(19) Oexmann, J.; Kather, A. Minimising the regeneration heat duty
of post-combustion CO2 capture by wet chemical absorption: The
misguided focus on low heat of absorption solvents. Int. J. Greenhouse
Gas Control 2010, 4 (1), 36−43.
(20) Mathias, P. M.; O’Connell, J. P. The Gibbs−Helmholtz
equation and the thermodynamic consistency of chemical absorption
data. Ind. Eng. Chem. Res. 2012, 51 (13), 5090−5097.
(21) Rochelle, G. T.; Chen, E.; Freeman, S.; Wagener, D. V.; Xu, Q.;
Voice, A. Aqueous piperazine as the new standard for CO2 capture
technology. Chem. Eng. J. 2011, 171 (3), 725−733.
(22) Notz, R.; Tonnies, I.; Mangalapally, H. P.; Hoch, S.; Hasse, H. A
short-cut method for assessing absorbents for post-combustion carbon
dioxide capture. Int. J. Greenhouse Gas Control 2011, 5 (3), 413−421.
(23) Aspen Technology. Rate-Based Model of the CO2 Capture Process
by MEA Using Aspen Plus; Aspen Technology: Burlington, MA, 2008.
(24) Aspen Technology. Rate-Based Model of the CO2 Capture Process
by PZ Using Aspen Plus; Aspen Technology: Burlington, MA, 2008.

1485 DOI: 10.1021/es504684x

Environ. Sci. Technol. 2015, 49, 1478−1485