Design and Operation Optimisation of a MEA-based CO2

Capture Unit
Artur Andrade
artur.andrade@ist.utl.pt

Instituto Superior Técnico, Lisbon, Portugal

Supervisors: Prof. Dr. Carla Pinheiro; Dr. Javier Rodriguez

November 2014

Abstract

The present thesis has the objective of analysing the cost reduction obtained through a rigorous
model-based optimisation of a post-combustion CO2 capture plant for carbon capture and storage
applications. Presently, capture technology is mainly based on chemical absorption with alkanolamines.
Even though this is a well-known technology, its application in power plants presents high costs, thus limiting
its implementation.
This way, a full scale capture plant model was developed considering MEA as the solvent. This model
is based on a conventional flowsheet and was implemented in gPROMS ®, using the gCCS® libraries. It
comprises an absorption section, in which CO2 is dissolved by reacting with the amine, and a regeneration
section where it is stripped from the solvent. After its validation, the model was optimised by modifying the
design and operation parameters.
A cost estimation model was applied to the plant model, in order to determine capital and operational
expenditures. From the total cost obtained, 69% is due to the steam required in the regeneration section. As
for the equipment cost, the absorber packing is the most relevant fraction.
Considering typical values for the capture rate, CO2 purity and MEA concentration in the solvent as
constraints, the plant’s model optimisation led to a reduction of 15% in the specific total cost. Without
imposing these typical values, the total cost was further reduced. These results clearly show the potential of
model-based optimisation in the reduction of the cost associated with CO 2 capture, thus contributing to its
effective implementation in power plants.

Keywords: Carbon capture and storage, post-combustion capture, chemical absorption, MEA, cost
optimisation, gPROMS
CO2 obtained in power plants, in the preparation
1. Introduction of natural gas, or in other chemical industries [2].
CO2 is a naturally-occurring gas with a For a power plant, the capture cost is the
major influence on Earth’s surface temperature. main component of the overall CCS costs, mainly
However, due to human invention and due to the process energy requirements. This
industrialisation, its concentration in the implies an extra consumption of steam and
atmosphere has greatly increased. According to electricity, leading to a reduction in net efficiency
the 2013 IEA report [1], between the years of and consequently an increase in the electricity
2001 and 2011, the worldwide CO2 emissions costs [2].
from fossil fuel combustion increased by 31%, The technology employed in the capture
reaching a value of 31 billion tonnes per year. process applied in power plants depends on the
From this value, approximately 42% are due to characteristics of the gas mixture being treated.
the electricity and heat production sector. These are related to the kind of fuel and
According to the Global CCS Institute, technology used in the production of electricity.
carbon capture and storage (CCS) has the This way, the capture processes can be divided
potential to significantly reduce the CO2 in: post-combustion capture (PCC), pre-
emissions. The CCS process chain comprises combustion capture and oxy combustion.
several technologies involved in removal of From the available technologies for CO2
carbon dioxide from a gaseous stream, its capture, absorption is at the present the only one
transportation and final sequestration in site away with commercially available processes.
from the atmosphere. This can be applied to the Nevertheless, adsorption, membranes and
cryogenic separation are currently being tested

1
for application in the CCS chain [3]. Even though
the absorption technology has been applied in
several other industries, due to the considerable
costs associated with the application of the
capture process to such high flow rates, its
application to the flue gas obtained in a large-
scale power plant fuelled by coal or natural gas is
currently on a demonstration phase [4]. The only
full scale capture unit already operating is located
on the Boundary Dam Power Station (Canada)
and was designed for the capture of 1 MtCO2/year.
Besides this operating capture unit, there are
several others planned to start operating in the
near future, all of them based on CO2 capture by
absorption [5]. The improvement of the currently
available processes should allow a reduction of
its costs by 20 to 30%, being the option with more
potential for the reduction of CO2 emissions in the
near future [2].
A literature review was conducted in order
to understand how the absorption is applied to
CO2 capture from a power plant, which
technologies are commercially available, and
which are the current trends to reduce the capture
cost.
With the reduction of costs associated with
the CO2 capture as the main objective, a
conventional capture plant model was built in the
gPROMS® ModelBuilder 3.7.1 environment using
the recently developed gCCS® libraries. After the
model validation, the optimisation features of
gPROMS® were used in order to minimise the
costs associated with the unit’s design and
operation.
2. Post-combustion Capture
Technology
Post-combustion capture is applied in
power plants based on the combustion of a fossil
fuel (coal, natural gas or oil), where a capture unit
is used to remove the CO2 present in the flue gas.
This flue gas is mainly composed of N2, CO2, H2O
and O2, and also of reduced amounts of SOx, NOx
and ash [6]. The flue gas being treated have a
considerably low CO2 content and is at
atmospheric pressure, leading to a reduced CO2
partial pressure. Therefore, the chosen solvent
has to be able to ensure acceptable loadings and
Table 1 – Commonly used chemical solvents and processes in which they are applied.
Solvent Type Processes
 ABB Lummus Cress
MEA Primary amine
 Fluor’s Econamine FG PlusSM
KS1TM Hindered amine  MHI’s KM-CDR
 Praxair’s Amine
MDEA Tertiary amine
 Shell’s Cansolv CO2 Capture System
NH3 Ammonia  Alstom’s Chilled Ammonia
Hot Potassium  UOP’s Benfield
K2CO3
Carbonate  Giammarco-Vetrocoke’s Low Energy
kinetics these conditions. Due to this, chemical
absorption poses a better option in PCC
processes, when compared with physical
solvents [2].
The processes by chemical absorption are
based on the CO2 chemical dissolution in an
alkaline solvent, through its selective reaction
with one or several of the solvent components.
Examples of these solvents, and the available
processes in which there are applied are shown
in Table 1. As can be observed, amines, more
precisely alkanolamines, are the chemical
solvents most used for CO2 capture, due its
reactivity and adequate basicity. From these,
monoethanolamine (MEA) is the one typically
considered. This compound have a primary
amine group, which confers a high reactivity to
the molecule, allowing a strong reaction with CO2
at elevated rates.
Due to this reactivity, MEA is highly prone
to oxidative and thermal degradation, which limits
the solvent concentration. The application of
oxidation inhibitors allows the increase of MEA
concentration to the typical value of 30 wt%, and
even 40 wt% [7]. In order to cope with this high
reactivity this amines can also be blended with
sterically hindered or tertiary amines which are
less reactive [8].
Concerning the thermal degradation, for
MEA it is negligible if the regeneration
temperature is kept below 110 to 120 °C [9].
The capture process is based on the CO2
dissolution, conducted in a packed column
(absorber). The solvent loaded with CO2 (usually
called rich solvent) is pumped to the regeneration
section. Before entering the regenerator, the rich
solvent is heated through an integrated heat
exchange with the regenerated solvent (also
called lean solvent). The regeneration process
typically occurs through stripping above
atmospheric pressure. The heat demanded by
this process is provided by a reboiler, which
constitutes the main energy requirement of the
capture unit. The lean solvent is pumped back to
the absorber after being regenerated. Since the
solvent is subject to losses during the process, a
make-up is required before re-entering the
absorber [2].
Typical composition
Up to 30 wt% with corrosion
inhibitors
Blend of sterically hindered
amines
Up to 40 wt%, blended with a
primary amine
Up to 28 wt%
Blend of potassium carbonate and
amine promoters
 In these processes, it is typical to achieve
capture rates between 80 and 90%, and a purity
as high as 99.9% (in volume) for the recovered
CO2 [2]. The inclusion of a PCC unit in a coal
fuelled power plant leads to an increase of 29%
in the energy input to achieve the same output,
while for a natural gas fuelled power plant this
increase is of 16% [4].
3. Materials and Methods
In the present work, gPROMS®
ModelBuilder 3.7.1 is the simulation platform
used for flowsheet model simulation and
optimisation. Starting from the existing gCCS®
model library, it is possible to assemble a
flowsheet, in which are also included any other
auxiliary equations and custom sub models
required.
Another feature of gPROMS®
ModelBuilder is the optimisation tool, which can
4. Models Validation
The validation of the models used in the
simulation of a capture unit was achieved through
the comparison of the simulation results with the
experimental data publically available. For that
purpose, were considered the papers by
Tobiesen et al., [12], and by Notz et al., [13],
whose flowsheets were implemented in
gPROMS®.
Tobiensen et al. article [12] presents the
experimental data for 20 non-equal runs in pilot
scale absorber. From the presented data, it was
possible to conclude that between Onda and
Billet & Schultes correlations for the calculation of
mass transfer coefficients, the first one is more
accurate. Using this correlation were obtained
deviations from -13% to 26%, comparing the
simulated and experimental flow of captured CO2,
as can be observed in Figure 1.

Simulated Absorbed
10
be used to optimise the steady state behaviour of
8
CO2 (kg/h)
a continuous flowsheet, considering both design
and operation properties. Since the models 6
considered in this thesis are non-linear, the 4
optimisation problem constitutes a nonlinear
2
programming problem (NLP). gPROMS®
ModelBuilder 3.7.1 uses the SRQPD solver in the 0
0 2 4 6 8 10
solution of NLP problems, with an “Improved
Experimental Absorbed CO2 (kg/h)
Estimation Based” convergence criterion [10].
Figure 1 – Parity diagram of the absorbed amount of CO2
The models included in the gCCS® library (using Billet & Schultes correlation).
use gSAFT as physical properties package. This These deviations are deemed acceptable
package is based on the Statistical Associating when considering that predictive models that do
Fluid Theory (SAFT) equation of state, an not consider any fitting to the experimental data
advanced molecular thermodynamic method, were applied. It was also verified that this
based in physically-realistic models of molecules deviation tends to increase with the decrease of
and their interactions with other molecules. For the solvent lean loading (Figure 2).
carbon capture, gSAFT presents a modelling
26
alternative to phase and chemical equilibrium in
Deviation in Absorbed

the CO2-MEA-H2O system, since the chemical 16

bound between CO2 and MEA can be
CO2 (%)

incorporated as a short-range association, being 6

included in the molecular model. This way, the
involved reactions are treated implicitly, thus -4 0.15 0.25 0.35 0.45
greatly reducing the complexity of the model, thus
increasing its robustness [11]. -14
Lean Loading (molCO2/molMEA)
Figure 2 – Deviation between experimental and simulated
absorbed CO2 with the considered lean solvent loading.

Table 2 – Experimental and simulation results for the process key parameters and respective variation
Example 1 Example 2
Deviation Deviation
Key parameter Experimental Simulated Experimental Simulated
(%) (%)
CO2 capture rate
75.91 70.14 -8 51.32 38.71 -25
(%)
Specific heat
requirement 5.01 5.43 8 3.98 5.27 32
(GJ/tCO2)

3
 In the Notz et al. article [13], two sets of order to meet a capture rate of 90% and a MEA
experimental data for a complete capture pilot mass fraction in the CO2 free lean solvent of 30%.
plant are presented. The key parameters used for This way, the base case is characterised by the
comparison and the respective deviations are parameters shown in Table 3.
shown in Table 2. From these parameters, it was Table 3 – Design parameters and operating conditions
considered in the original capture plant model.
observed that for a complete capture plant model
Parameter Value
with a specified heat input, the CO2 capture rate Diameter (m) 20
tends to be under estimated, with deviations that Height (m) 11.89
Absorber
can reach -25%, leading to an over prediction of Packing
Sulzer Mellapak
the specific heat requirement of 32%. 250YTM
Diameter (m) 8.5
Height (m) 10
Stripper
5. MEA Full Scale Capture Plant Packing
Sulzer Mellapak
250YTM
Model Lean-rich heat Cold stream outlet
89.65
exchanger temperature (°C)
5.1. Base Case Process stream
Lean solvent
outlet temperature 70.75
Assuming that the validation conclusions cooler
(°C)
presented above are still valid for a full scale Reboiler Temperature (°C) 117.84
plant, a MEA-based capture plant model was Reboiler pump Pressure (bar) 1.79
developed. The flowsheet considered was based Condenser Temperature (°C) 40
Flow rate (kg/s) 1450.14
on a case study developed by PSE. The flue gas Lean solvent MEA mass fraction
considered is characteristic of a natural gas 0.285
(g/g)
fuelled power plant emitting approximately 2 The referred conditions were applied in a
million tonnes of CO2 per year. The lean solvent conventional PCC flowsheet model, which
flow rate and MEA concentration were adjusted in topology is shown in Figure 3.

Figure 3 – MEA capture plant flowsheet as seen in gPROMS® ModelBuilder.

4
 In these model, the absorption section is
composed by an absorber model (A-301) in which
the Billet & Schultes correlation is used the
prediction of mass transfer coefficients and
pressure drop. The heat exchange section is
composed by the lean-rich heat exchanger (HX-
301) and the lean solvent cooler (HXU-301),
which are used for the rich solvent cooling and the
lean solvent cooling. In both these models, it was
assumed a constant overall heat transfer
coefficient of 5 kW/(m2.K) [14] and pressure drop
of 0.62 bar [15]. The regeneration section is
composed by a stripper model (ST-301),
associated with the reboiler (R-301) and
condenser (C-301) models, in which were
assumed heat transfer coefficients of 1.14 and
0.85 kW/(m2.K) [15], respectively. The model
P-304 is used to deliver the pressure required by
the stripper model, while the model P-305 is used
to specify the reboiler pressure. The lean solvent
flow rate and MEA concentration are set in the
model RB-303, which allows the calculation of the
required solvent make-up. Besides these
conventional components, the flowsheet model
also comprises a saturation section (flash model
(F-301), PID controller model (PID-301) and
pump model (P-301)). In order to keep the
absorber pressure above atmospheric, the pump
model P-302 acts as a gas blower, in order to
increase the flue gas pressure to 1.1 bar. In the
columns’ models the Billet & Schultes correlation
was used for the calculation of mass transfer
coefficients and pressure drop. At last, were also
added several flow multiplier models (FM-301 to
FM-310) at the inlets and outlets of the absorber,
regeneration section and reboiler to simulate the
existence of several equipment working in
parallel.
Based on these model, the key
parameters shown in Table 4 were obtained.
Table 4 – Results obtained from the simulation of the base
case.
Parameter Value
Capture rate (%)
CO2 purity (vol%)
MEA mass fraction in the CO2 free lean
30.0
solvent (wt%)
Number of absorption trains
Number of striping trains
Number of reboilers per stripping train
Specific heat consumption (GJ/tCO2)
Lean loading (molCO2/molMEA) 0.249
Rich loading (molCO2/molMEA) 0.463
5.2. Cost Estimation Model
To determine the costs associated with
the design and operation of a capture plant a cost
estimation model was implemented. For that
purpose, it was considered the procedure
described in [14]. Considering that the objective
of the present economic model is the optimisation
5
of the total cost associated to a carbon capture
plant, only the cost fractions that depend on the
plant design parameters and operation conditions
were considered, in order to simplify the
optimisation process.
Using this costing model, it is possible to
obtain the capture plant annualized investment,
or CAPEX, and the annual operating cost, or
OPEX, both in a euro bases referred to year
2013. In the case of the investment annualization,
it was considered a linear amortization over a
period of 10 year (equation (1)).
𝐼𝑛𝑣𝑒𝑠𝑡𝑚𝑒𝑛𝑡
𝐶𝐴𝑃𝐸𝑋 = (1)
10 𝑦𝑒𝑎𝑟𝑠
Both CAPEX and OPEX were also
expressed as functions of the captured amount of
CO2, designated specific CAPEX (sCAPEX) and
specific OPEX (sOPEX), respectively (equations
(2) and (3)).
𝑠𝐶𝐴𝑃𝐸𝑋(€⁄𝑡𝑜𝑛𝐶𝑂2 ) =
𝐶𝐴𝑃𝐸𝑋 (€⁄𝑦𝑒𝑎𝑟) (2)
=
𝐴𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝐶𝑂2 (𝑡𝑜𝑛𝐶𝑂2 ⁄𝑦𝑒𝑎𝑟)
𝑠𝑂𝑃𝐸𝑋(€⁄𝑡𝑜𝑛𝐶𝑂2 ) =
𝑂𝑃𝐸𝑋 (€⁄𝑦𝑒𝑎𝑟 ) (3)
=
𝐴𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝐶𝑂2 (𝑡𝑜𝑛𝐶𝑂2 ⁄𝑦𝑒𝑎𝑟)
For an approximate calculation of the
investment required, it was used the factorial
method, which is based on the cost of the main
process equipment [14]. For that, were
considered the columns (shell and packing), heat
exchangers, condenser, reboiler and pumps
(including drivers). Considering that amine
solvents are corrosive, stainless steel 304 (SS-
304) is required in all the equipment that contacts
directly with the capture solvent. The cost of the
referred equipment is calculated through cost
correlations [14], which upper bounds were used
to determine the number of equipment working in
parallel. Besides this, were also considered
installation factors, and other expenses, which
can be estimated as percentages of the main
equipment costs [14].
89.9 For the calculation of the operational
95.8 expenses, were considered fixed and variable
production costs. The fixed production also can
be approximated to a percentage of the main
2
2 equipment cost. For the variable production costs
4 were considered the annual consumption of
5.66 utilities (steam, cooling water and electricity) and
solvent, which unitary costs were retrieved from
[16].
Concerning the steam consumption, it was
considered low pressure steam (saturated at 3
bar). The cooling water requirements are given by
the utility consumption, considering that the used
water presents inlet and outlet temperatures of 29
and 49 °C, respectively [15]. For the estimation of
the electricity consumption, it was considered the
power required in both lean solvent and rich
8% 5%
solvent pump drivers.
The solvent (MEA) consumption is Total Utilities Cost
estimated based on the required make-up and
amine degradation. According to [17], the Solvent Cost
washing sections in a capture plant are able to 87% Fixed Production Costs
reduce the MEA concentration to 1 ppm.
Therefore it was considered that the MEA
concentration in the treated flue gas is reduced to
Figure 6 – Distribution of the OPEX
this value, and the washed MEA used to reduce (Total = 64.56 €/tonCO2).
the required make-up. Also in reference [17], it is This way, it is expected that the
referred that MEA has a degradation rate of 1.5 optimisation of the capture plant flowsheet will
kgMEA/tCO2. mainly rely on changing the absorbers’ size and
the steam consumption.
5.3. Cost Estimation Results for the Base
Case 6. Optimisation Problem
By applying the cost estimation model in
Formulation
the capture pant model, it was possible to obtain
a CAPEX of 15.99 M€/year and an OPEX of
6.1. Objective Function
64.56 M€/year, which correspond to a total cost
For the optimisation of the capture plant,
of 80.55 M€ per year, equivalent to 43.15 € per
both the specific CAPEX and specific OPEX
tonne of captured CO2. As can be observed in
should be minimised. Therefore, Equation (4) was
Figure 4, the CAPEX only represents 20% of the
total cost. defined as objective function.
𝑂𝐹 = 𝑠𝐶𝐴𝑃𝐸𝑋 + 𝑠𝑂𝑃𝐸𝑋 (4)

6.2. Decision Variables

20%
The decision variables define which of the
CAPEX capture flowsheet variables are used to minimise
80% OPEX the objective function. In this case, the variables
which define the equipment design and the
process operating conditions have been chosen
Figure 4 – Total cost distribution in the base case (Total = (Table 5).
43.15 €/tCO2). According to Zahra [17], given the lean
Considering the distribution of equipment solvent flow rate, capture rate and lean loading,
costs shown in Figure 5, it is observable that the the optimal steam consumption is obtained for the
columns’ packing represents the major fraction of combination of stripping pressure and reboiler
the equipment costs, from which 87% are due to temperature with higher values. Therefore, before
the absorber’s packing. proceeding to the process optimisation, the base
flowsheet was modified in order to start from the
5% 9% Columns Shell
maximum temperature (120 °C [9]). This way, this
2% variable was not directly included in the
Heat Transfer
Equipment optimisation problem.
Table 5 – Decision variables.
Pumps and Drivers
Model Variable
84% Diameter (m)
Packing A-301
Height (m)
C-301 Temperature (K)
HX-301 Cold outlet temperature (K)
Figure 5 – Distribution of main equipment costs for the HXU-301 Process outlet temperature (K)
base case. Source flow rate (kg/s)
RB-303
From the distribution show in Figure 6, it is Source MEA mass fraction (g/g)
observable that utilities represent the main P-305 Pressure (bar)
Diameter (m)
fraction of the OPEX, from which the steam ST-301
Height (m)
consumption corresponds to 98%. In fact the
annual steam consumption is 69% of the plant 6.3. Constraints
annual cost. The process constraints are used to keep
the standard conditions initially imposed, such as
the capture rate, the MEA mass fraction in the
CO2 free solvent and the minimum CO2 purity in
6
the product stream, and to keep technical 0.009

CO2 molar flux (kmol.m-2.s-1)

specifications, such as preventing the columns
flooding. These constraints are divided in equality 0.006
and inequality constraints, which are listed in
Table 6 and Table 7, respectively.
0.003
Table 6 – Equality constrained variables, with respective
constrained value.
Constrained variable Imposed value 0
Capture rate (g/g) 0.90 0 1000 2000 3000 4000
CO2 molar fraction in the CO2 Volume of packing from the absorber top
0.95
stream (mol/mol)
(m3)
MEA mass fraction in the CO2 Base Optimal
0.30
free lean solvent (g/g)
Figure 7 – CO2 molar flux to the liquid phase across the
absorber (top of the absorber equivalent to 0), before and
after the specific total cost minimisation with standard
Table 7 – Inequality constrained variables, with respective constraints.
upper and lower bounds.
An increase by 5% in the outlet
Lower Upper
Constrained variable temperature of the rich solvent in the lean-rich
bound Bound
Vapour velocity/vapour heat exchanger and by 1% in reboiler
flooding velocity in the top 10-10 0.7 temperature led to an increase of the overall
of the absorber
temperature in the stripping column, as can be
Vapour velocity/vapour
flooding velocity in the 10-10 0.7 observed in Figure 8.
bottom of the stripper 400
Process stream ΔT in the
10-10 1010
lean solvent cooler (°C)
Temperature (K)

The process stream temperature

difference (ΔT) in the lean solvent cooler is
required, since in some of the optimisation cases
it tended to achieve un-realistic values below 0.
Therefore, this variable was included in the
flowsheet model, where a very small positive
number was defined as a lower bound (10-10),
while the upper bound was considered an
excessively large number (1010). The ratio
between the vapour operating velocity and the
vapour flooding velocity should be kept below
70% to 80% in order keep the column’s efficiency
[18].
7. Optimisation Results
7.1. Specific Total Cost Minimisation
with Standard Constraints
The results obtained from this optimisation
380
360
0 0.5 1
Relative position from the stripper top
Optimal Base
Figure 8 – Axial temperature profiles in the stripping
columns for the liquid phase, before and after the specific
total cost minimisation with standard constraints.
The increase in the temperature profile
and in the columns’ height caused an increase of
its stripping efficiency. This can be observed in
Figure 9, where the CO2 flux from the gas phase
to the liquid phase across the stripper is always
negative.
0.01
CO2 molar flux (kmol.m-2.s-1)

process show that the main variations occur in the 0.005

absorber size (height and diameter are reduced
in 29% and 12%, respectively), in the stripper size 0
(diameter is reduced 15% and height is increased 0 200 400 600
-0.005
69%) and in the lean solvent flow rate (reduced
18%). -0.01
The reduction in the absorber size leads to
a reduction of the packing volume, as well as the -0.015 Volume of packing from the stripper top
shell’s mass. This reduction is possible due to the (m3)
Base Optimal
reduction in the lean loading (reduced to 0.200
Figure 9 – CO2 molar flux to the liquid phase across the
molCO2/molMEA) and the approach to the flooding striper (top of the stripepr equivalent to 0), before and
velocity in the absorber, which now reaches 70% after the specific total cost minimisation with standard
in the top of the column. Both these factors constraints.
improve the column’s efficiency, as can be Considering the improved efficiency and
observed in Figure 7. the increase in the lean loading, the heat required
in the reboiler is decreased. This way, the specific

7
heat requirement shows an optimal value of 4.87
GJ/tCO2 (less 14%).
Considering this main factors, it is
observed a reduction in the CAPEX of 21% and
in the OPEX of 13%, which lead to a specific total
cost of 36.69 €/tCO2 (-15%).
7.2. Effect of the Initial Guesses
Considering that in the formulated
optimisation problem exist ten decision variables
(Table 5) and only three equality constraints
(Table 6), it is expectable that multiple solutions
can lead to the same optimal solution. The initial
guesses of a non-linear optimisation problem may
influence the results obtained, and even
determine the convergence or not of the problem.
Since the lean solvent CO2 loading as a main
influence in the capture model, all the
optimizations performed started from a lean
loading of 0.2 molCO2/molMEA. In order to evaluate
the influence of this parameter in the process
convergence, the optimisation described in the
previous section was conducted starting from a
lean loading of 0.1 and 0.3 molCO2/molMEA, by
adjusting the lean solvent flow rate and MEA
mass fraction and the reboiler pressure. Through
the optimal results obtained it was observed a
variation of less than 1% in the total cost. It was
also possible to conclude that the lean solvent
temperature after the cooler isn’t a relevant
parameter in the considered conditions, and the
lean solvent cooler wouldn’t be required.
7.3. Effect of the Number of Absorption
Trains
The number of absorption trains was
chosen considering the construction limitations
regarding the column’s diameter and the vapour
flooding velocity. This variable was changed in
the base case and optimised for each value.
From the obtained results, it was possible
to conclude that the decision variable mainly
affected is the absorber diameter. Considering
only one absorber would be technically un-
feasible due to the elevated optimal absorber
diameter. The use of two absorption trains
conditioned by the possibility of constructing
absorbers with a diameter above 15 m.
Nevertheless, it was observed that increasing the
number from 1 to 4 only increased the specific
total cost in 0.4%, since the total volume of
packing tends to be the same.
7.4. Specific Heat Requirement
Minimisation
The steam consumption is directly
proportional to the heat required in the
regeneration reboilers, and represents 69% of the
8
capture plant annual cost. The minimisation of the
specific total cost allowed a reduction in specific
heat requirement in 14%. In order to evaluate if a
greater reduction in this parameter is possible,
and its effect in the capture total cost, the
described optimisation procedure was conducted
using the specific heat consumption as objective
function.
A further reduction of the specific heat
requirement to 4.46 GJ/tCO2 was obtained.
Nevertheless, this was achieved by greatly
increasing the columns’ height and therefore the
required packing volume. This led to an increase
in specific CAPEX by 674% and in the specific
OPEX by 23%, when compared to the initial
optimisation, which is equivalent to a specific total
cost is increased to 88.98 €/tCO2.
7.5. Effect of the Imposed Capture Rate
This variable was initially imposed as
90%. Its effect on the plant’s specific total cost
was evaluated by changing the imposed values
to 70%, 80% and 99% (Figure 11).
50
Specific total cost
40
(€/tCO2)
30
20
70 80 90 99
Capture rate (%)
Figure 10 – Variation of the optimal specific total cost
with the imposed capture rate.
Between 70% and 90%, the variation is
achieved through an increase in the lean solvent
flow rate and in the absorber and stripper height,
associated with a slight decrease in the lean
loading. This leads to an increase of 2% in the
optimal total cost. On the other hand, between the
capture rates of 90% and 99%, there is 28%
increase in the specific total cost, due to a major
decrease in the optimal lean solvent flow rate and
lean loading, accompanied by a further increase
in the columns’ height. In the case of a 99%
capture it was also concluded that due to the heat
released in the absorption process and the
reduced solvent flow rate, the lean solvent cooler
has higher relevance. In the same case, the rich
solvent temperature entering the stripper is
decreased, since the vapour flow rate is
increased and the solvent flow rate is decreased,
being the temperature across the columns kept at
higher values.
7.6. Effect of the Imposed CO2 Purity
This variable was initially imposed as
95%. Its effect on the plant’s specific total cost
was evaluated by changing the imposed values
to 75%, 85% and 99% (Figure 10).
39
Specific total cost
38
38
(€/tCO2)
37
37
36
36
75 85
CO2 Purity (%)
Figure 11 – Variation of the optimal specific total cost with
the imposed CO2 purity.
Between the purities of 75% and 95%, it
was observed an increase of only 0.2% in the
specific total cost. The condenser temperature is
related to this variation, since it defines the
amount of water condensed, and therefore the
purity of the final stream. On the other hand, for
lower purities the amount of lost solvent in the
regeneration process tends to increase, thus
leading to a minimum in the sOPEX. When the
purity is increased to 99%, the specific cost
increases in 4%, associated with a major variation
in the OPEX. This was due to the further
reduction in the condenser temperature that
required the use of chilled water, which was
considered eight times more expensive [16],
leading to an increase of 435% in the
cooling/refrigerating water annual costs.
Nevertheless, that it was verified that this
parameter did not have a considerable influence
in the specific heat consumption, thus the
reduced effect on the total cost.
7.7. Effect of the Imposed
Concentration
The MEA concentration was initially
defined by the imposition of a MEA mass fraction
in the CO2 free lean solvent of 30%. In order to
evaluate its effect on the process total cost, the
imposed value was modified to 20% and 40%
(Figure 12).
40
Specific total cost
(€/tCO2)
38
36
34
20 30
MEA mass fraction in the CO2 free lean solvent (%)
Figure 12– Variation of the optimal specific total cost with
the MEA mass fraction in the CO2 free lean solvent.
The obtained optimal results showed a
more significant variation in the specific total cost
was than in the previous cases, showing a
reduction in 5%, when changing this constraint
9
from 20% to 30%, and in 4%, when changing it
from 30% to 40%. These variations are mainly
due to the possibility of reducing the solvent flow
rate, with the increasing concentration,
associated whit an increase in the optimal lean
loading. Both these factors contribute to the
reduction of the specific heat requirement,
allowing the total cost reduction. Nevertheless, it
should be considered that there are implications
of using a more concentrate solvent, such as, the
95 99 size of the water washing sections or the costs
associated with the required oxidation inhibitors,
which were not considered.
7.8. Specific Total Cost Minimisation
with Inequality Constraints
Since it was observed that both the
capture rate and the CO2 purity tended to show a
minimum specific total cost, the optimisation
problem was conducted without any equality
constraints. This led to the optimal capture rate of
75%, CO2 purity of 88% and MEA mass fraction
in the CO2 free lean solvent of 40%, being the last
one the variable upper bound. This allowed a
specific total cost reduction to 34.70 €/t CO2 (5%
less when compared with the initial optimal
results), associated with the specific heat
requirement of 4.60 GJ/tCO2.
8. Conclusions
The gCCS® capture library allowed the
development of a capture plant model in the
gPROMS® ModelBuilder environment.
The full scale capture plant optimisation
was conducted using as base case a PSE’s case
MEA study, which was modified in order to meet a 90%
capture rate and a MEA fraction in the CO2 free
lean solvent of 30%. The application of a cost
estimation model to the base case, allowed the
calculation of a specific total cost of 43.15 €/tCO2,
from which the OPEX represents 80% and is
associated to a specific heat requirement of 5.66
GJ/tCO2. The cost estimation allowed to conclude
that the equipment with more influence in the
CAPEX is the absorber’s packing (73% of the
equipment total cost). For the OPEX, the main
fraction is steam consumption, which in fact
represents 69% of the total annual cost.
The base case specific total cost
minimisation, considering a capture rate of 90%,
a CO2 purity of 95 vol% and a MEA fraction in the
40
CO2 free lean solvent of 30%, led to its reduction
in 15%, associated to a specific heat requirement
of 4.87 GJ/tCO2.
Considering the specific heat requirement
as the objective function to be minimised, this
variables was further reduced to 4.46 GJ/tCO2.
Nevertheless, this led to an increase in the total
cost (143% when compared with the initial
optimal results).
The optimisation without any equality
constraints led to the optimal capture rate of 75%,
CO2 purity of 88% and MEA mass fraction in the
CO2 free lean solvent of 40%, being the last one
the variable upper bound. This allowed a specific
total cost reduction to 34.70 €/tCO2 (less 5% when
compared with the initial optimal results),
associated with the specific heat requirement of
4.60 GJ/tCO2.
The analysis presented shows that the
total cost is greatly affected by the trade-off
between the solvent’s flow rate, the absorber
height and the lean solvent’s loading. Increasing
the MEA concentration in the solvent has a
positive effect in all this variables. This is also
verified for the capture rate in a limited range of
values. It was also observed that at moderate
capture rates, increasing both the stripper’s
height and the rich solvent temperature at its inlet
also tend to reduce the steam consumption, and
therefore the total cost. The interconnection
between these variables shows the relevance of
a model-based full plant optimisation for the
reduction of the capture cost, which is an
important step for the effective CCS
implementation in real power plants.
9. Main Bibliography
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