Eera Ca Looping Simulation Guidelines
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mohsen ranjbarEera Ca Looping Simulation Guidelines
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mohsen ranjbar
Matteo C. Romanoa, Isabel Martínezb, Ramón Murillob, Bjørnar ArstadcRichard
Blomc, Dursun Can Ozcand, Hyungwoong Ahnd, Stefano Brandanid
a
Politecnico di Milano, Energy Department, via Lambruschini 4, 20156 Milano, Italy
b
Instituto de Carboquímica (ICB-CSIC), C/ Miguel Luesma Castán 4, 50018,
Zaragoza, Spain
c
SINTEF Material and Chemistry, P.O. Box 124 Blindern, N-0314 Oslo, Norway
d
IMP-SEE, The University of Edinburgh, Mayfield Road, Edinburgh, EH9 3JL, UK
1 Calcium looping for post-combustion CO2 capture applications .......................................... 2
1.1 Large-scale carbonator reactor modelling ..................................................................... 3
1.1.1 Guidelines for future works................................................................................... 4
1.2 Power plant simulations including CaL for CO2 capture ............................................ 10
1.2.1 Guidelines for future works................................................................................. 12
1.3 References ................................................................................................................... 20
2 Calcium looping for pre-combustion capture applications ................................................. 23
2.1 Modeling of SE-SMR reactors .................................................................................... 23
2.2 Process modeling......................................................................................................... 29
2.2.1 Guidelines for future works................................................................................. 39
2.3 References ................................................................................................................... 41
3 Calcium looping applications on cement production plants................................................ 44
3.1 Guidelines for future works......................................................................................... 50
3.2 References ................................................................................................................... 50
1
This part of the document is based on the carbonation-calcination loop (referred as Ca-looping,
CaL, in the text) to separate CO2 at high temperature of a flue gas stream coming from an
existing coal-fired power plant or any other large CO2 source. This process was first proposed
by Shimizu et al. (1999), and proposes using CaO as a regenerable sorbent to remove CO2 from
the flue gas according to the following chemical reaction:
Although different process configurations have been proposed to implement this concept
(Abanades et al., 2005), the general scheme of the CaL process is that depicted on Figure 1. Due
to the huge flue gas flow to be put into contact with a solid stream, two interconnected
circulating fluidized bed (CFB) reactors have been widely proposed to be used in this scheme
due to the high gas throughput per unit area of these reactors.
Flue gas coming from an existing power plant is forced to enter into a carbonator reactor
operating at 600-700ºC and atmospheric pressure, where CO2 reacts with CaO to be converted
into CaCO3. Solids from carbonator (mainly CaO and CaCO3) are separated in a cyclone from
the clean flue gas that is emitted to the atmosphere, and sent to a second reactor (calciner in
Figure 1) where CaCO3 is again decomposed into CaO that will be recirculated again to the
carbonator reactor. Calciner needs to operate at a very high CO2 partial pressure so that the gas
produced can be easily purified and compressed to be sent to geological storage. According to
the CaO-CaCO3 equilibrium reaction and considering calciner working under atmospheric
pressure, high CO2 partial pressures in the calciner impose a temperature around 900ºC to be
under calcining conditions. Since CaCO3 calcination is highly endothermic and solids from
carbonator need to be heated up to calcination temperature, a large heat input need to be
supplied to the calciner and therefore additional fuel has to be burnt in this reactor. Heat
required in the CaL system depends mainly on process assumptions, like the type of fuel chosen
to be burnt in the calciner or the fresh make-up flow and solid circulation considered to get a
desired capture efficiency.
Combustion in the calciner is usually proposed to be carried out under oxy-combustion mode to
avoid diluting the CO2 gas stream arising from calciner with N2 from air. The O2 introduced in
the calciner, coming from an Air Separation Unit, ASU, should be diluted by recycling part of
the rich-CO2 gas to avoid reaching excessive high local temperatures inside this reactor. In this
way, CO2 at the exit would be diluted mainly with steam coming from the hydrogen of the fuel
burnt, which contributes to facilitate and make cheaper the purification process.
2
0
Figure 1 - Scheme of the CaL process focused on removing CO2 from the flue gas of an existing
power plant
Despite the fact that the calciner employs a great fraction of the total heat introduced in the CaL
system (between 35-50 %) (Rodriguez et al., 2008), one of the main advantages of this capture
technique is that this energy is recovered as gas streams at high temperature and as carbonation
reaction heat from carbonator at 600-700ºC. This high-quality heat recovered from the capture
process is usually considered to be integrated into a power cycle to generate electricity, and
therefore contributing to improve the efficiency of the plant with CO2 capture. Furthermore,
CaL system proposes using natural limestone as regenerable sorbent because of its low price
and availability. The use of this CaO-based sorbent allows operating with flue gases with SO2
content as it can be removed as CaSO4, which would make unnecessary a desulphurisation unit
in the power plant. As mentioned before, CaL relies on CFB technology and is proposed to
operate under conditions similar to commercial CFB combustors, which allows CaL to take
advantages from the knowledge and experience acquired about hydrodynamics and performance
of these reactors (Diego et al., 2012). All these factors have made the CaL process being a
rapidly developing technology with a great potential of reducing capture cost with lower
efficiency penalties than other post-combustion technologies.
Different carbonator models have been proposed in the literature during years either to explain
the experimental results obtained from experimental rigs, or to design higher scale plants and
carry out predictions about their performance. A summary of the different carbonator models
proposed in the literature is reported in Table 1. Different level of detail and complexity arise
3
from each of these carbonator models, but all of them have resulted to be useful tools in making
preliminary calculations about carbonator performance under different operating conditions.
The first approach to the simulation of the carbonator in the CaL process came from Shimizu et
al. (1999) that proposed a bubbling fluidized bed model to evaluate the required bed height of
the carbonator to get an overall CO2 removal efficiency of 90 %. The model proposed was
based on that of Kunii and Levenspiel (1991) considering a two-region reactor: bubble and
emulsion. This simple model was later adapted by Abanades et al. (2004) to the conditions of
the experiments carried out in a fluidised bed carbonator, but including a full kinetic model for
the carbonation reaction in two stages proposed by Bhatia and Perlmutter (1983). According to
this kinetic model, carbonation reaction takes places in two stages at different reaction rate: a
first regime of chemical reaction control where reaction occurs at the highest velocity, and a
second period of product layer diffusion control due to the fact that the CaCO3 layer thickness
increases. The model of Abanades et al. (2004) showed that the most influencing parameter in
the carbonator model was the fraction of particles reacting in the fast regime, especially in the
later stages of the experiments, but remarked the need of a more detailed particle reaction model
for these operating conditions, typical of the CaL process.
From that model onwards, carbonator models proposed in the literature considered the reactor as
a circulating fluidised bed where two zones were distinguished: a bottom dense zone and a lean
one located above. Except for the model of Alonso et al. (2009), which modelled the dense bed
as an instantaneous and perfect mix of the solids with plug flow for the gas phase, the rest of the
models proposed (Hawthorne et al., 2008; Lasheras et al., 2011; Romano, 2012) have been
based on the core-annulus model of Kunii and Levenspiel (1997). Almost every of these models
concluded that the most influencing parameter on the carbonator efficiency is the fraction of
particles reacting in the fast regime, determined mainly by the fresh sorbent make-up flow
introduced in the system and the solid circulation between reactors. Further level of detail in the
fluid-dynamics has been considered in the reactor model developed by Romano (2012) that
evaluated the CO2 concentration profiles in the core and wall zone of the dense part, and the
CO2 profile in the lean zone. Moreover, this work included the effect of coal ashes and the
deactivation of Ca-sorbent due to the presence of sulphur compounds.
On the basis of the different carbonator reactor models reviewed, the following needs of
research and consideration are highlighted in this field:
• Accurate models on the CO2 carrying capacity of the sorbent should be included to
improve the reliability of the models and to better understand experimental results from
pilot scale plants.
4
As a consequence of the sorbent recycling and make-up flow ratios used in a real CaL
system, the CO2 carrying capacity of the Ca-sorbent entering the carbonator will be
different from that predicted because it depends on carbonation conditions (Arias et al.,
2011; Lysikov et al., 2007; Sun et al., 2008), on the partial conversion achieved in the
carbonator and calciner (Rodríguez et al., 2010) and on the possible reactivation
mechanism carried out in the process (Arias et al., 2012; Martínez et al., 2011a). It is
necessary an accurate model that considers the real age of the Ca particles in the system
(Nage) according to their CO2 carrying capacity, irrespective of their previous history of
partial or complete cycles experimented in the CaL system. This Nage represents the
number of equivalent carbonation/calcination cycles that the particles require to achieve
a conversion equal to their carrying capacity, and depends on carbonation conditions,
residence times in the reactors and also on certain regeneration techniques carried out.
Carbonator models proposed should include accurate models on capture capacity that
include this aspect.
• Ca-based sorbent reactivity influence reactors design and, therefore, performance of the
CaL process. Sorbent reactivity has been widely demonstrated to be influenced by the
type of limestone chosen and its deactivation curve against carbonation-calcination
cycles, and also by the sulphur content of the fuel used in the calciner.
Sulphur reacts not only with the CaO active for the carbonation reaction, but also can
form CaSO4 with the non-active CaO (Sun et al., 2005). Furthermore, the amount of Ca
in the system with respect to the sulphur is of one order of magnitude higher than in
conventional desulphurisation systems, and CaO conversion to CaSO4 would be low
enough for not considering a pore blocking mechanism. In this way, CaSO4 formation
would not entirely contribute to reduce the CaO prone to form CaCO3. It is important to
quantify this effect and determine the fraction of non-active CaO that reacts with
sulphur to form CaSO4 for not being excessively conservative when considering
sulphur.
Furthermore, the use of a natural limestone with a large deactivation constant force to
operate with a high CaCO3 make-up flow or a high solid circulation rate to maintain a
proper CO2 capture capacity in the CaL system. In this way, it is important that the
carbonator model proposed includes both deactivation mechanisms mentioned before to
help and contribute to a more realistic design of the CaL system, and contribute to the
scale-up of the technology.
• Ashes from coal burnt in the calciner affect the amount of inerts circulating in the
system and therefore, influence the heat required in the calciner to heat the solids up to
calcination temperature. Moreover, the type of the fuel burnt in the calciner, determines
the nature of the ashes and its facility to cause operating problems under certain
5
operating conditions. In this way, it is important to consider ashes in the simulation of
CaL systems as thermal balances and operational issues are going to be affected.
6
Table 1 - Summary of the carbonator models published in the literature
PART (1/2) Shimizu et al. (1999) Abanades et al. (2004) Hawthorne et al. (2008) Alonso et al. (2009)
Particle conversion Particle conversion model based on that proposed Particle conversion model based on that Average reaction rate of the active
model/ equation by Bhatia and Perlmutter (1983), including Xb,N: suggested by Bhatia and Perlmutter (1983), material, rave, based on that proposed by
Where: but modified including the maximum carrying Abanades et al. (2004) removing the term
capacity of the sorbent, Xmax: (1-X)2/3:
(kmol/m3)
D: maximum conversion
(dX/dt=0), decreases with Where: Where:
increasing N ks=5.95·10-10 m4/mol·s Where:
k=25 m3/kmol·s S0=40·106 m2/m3 ks=4·10-10 m4/mol·s
ks=5.95·10-10 m4/mol·s
ε0=0.5 (particle porosity)
S0=40·106 m2/m3 CCO2, Ceq: CO2 concentration in the bulk phase
ε0=0.5 (particle porosity) and in the equilibrium, respectively Being emax the maximum thickness of the
Xb,N: maximum carbonation conversion at the end CaCO3 layer formed on the pore wall (50
of the fast reaction stage for a cycle N nm)
CCO2, Ceq: CO2 concentration in the bulk phase and CCO2, Ceq: CO2 concentration in the bulk
in the equilibrium, respectively phase and in the equilibrium, respectively
t*: time that marks the end of the fast
reaction period
Sorbent capacity Although it is observed a sorbent Decay sorbent capacity law base on that Maximum conversion in each cycle, XN:
decay law capacity decay, it is not considered proposed by Abanades (2002) but depending
(Abanades and Alvarez, 2003)
and it is taken D<0.3 With fm and fw depending on the limestone tested on the CaCO3 content Xcarb achieved:
(Grasa and Abanades, 2006)
Being XN,pc the maximum conversion
achievable in cycle N due to partial
carbonation up to having a content Xcarb
Hydrodynamic BFB BFB (Intermediate regime between fast and slow CFB CFB
regime of the bubbles)
reactor
Hydrodynamic Two-regions: bubble and emulsion Two-regions: bubble and emulsion model of Kunii Three regions each with its hydrodynamic and Instantaneous and perfect mixing of the
model model of Kunii and Levenspiel and Levenspiel (1991) reaction model: solids (CSTR) and plug flow (PF) for the
(1991) Lower region of the CFB gas phase
Region I. Dense bed: bubble and emulsion
model of Kunii and Levenspiel (1991)
Upper region of the CFB (riser): core-annulus
flow structure modeled by Pugsley and Berruti
(1996), that divide the riser into two regions:
Region II. Acceleration region (developing
upward velocity and voidage)
Region III. Fully-developed flow region
(flow characteristics invariant with height)
7
Particle distribution Uniform (0.42-0.59 mm) Average particle sizes around 1 mm Uniform (500 µm) Kinetic parameters chosen correspond to
highly cycled particles (maintain a nearly
constant size)
Criteria for reactor Cross-sectional area of the Reactor dimensions (height and cross-sectional Reactor dimensions (height and cross- Results have been evaluated per m2 of
dimensioning carbonator is an input variable to area) are input variables to the model, as well as sectional area) are input variables to the cross-sectional area of carbonator and
the model (973 m2, determined by the superficial gas velocity and the solid inventory. model, as well as the gas inlet velocity and the using a dimensionless variable for height.
flow rate of gas and superficial gas Moreover, the fraction of active CaO reacting in solid inventory. Reactor dimensions are 12 m Solid inventory is given in kg/MW and to
velocity, 1.35 m/s) whereas rector the fast reaction regime (fa) has to be provided to of height and 0.07 m of diameter. give the results per m2 of cross-sectional
height is an objective of the reactor the model. The fraction of free active CaO, fa, have to be area, it is considered that typical heat duty
model (2.4 m, determined by heat also introduced to the model and will result in CFB combustors is 5 MW/m2
transfer). into a carbonation rate constant to be Flue gas entering the carbonator contains
introduced into the model. 0.1 kg CO2/s with 0.15 of volumetric
fraction of CO2.
Effect of coal ash No No No directly, but an average solid density of No
included 1800 kg/m3 has been considered
Effect of sulfur No (considered total removal of S No (since Ca/S ratios in this system will be >20, No No directly, although it has been
included in the CFB combustor prior to effective capture of SO2 might be achieved without considered the need of a solid purge to
carbonator) affecting carbonation) remove ashes and CaSO4.
Governing Heat removal from the carbonator fa has a great influence in the sensitivity of the The most important parameter affecting The fraction of active particles in the bed
parameters is the limiting factor as it model, concretely when having low values of fa (or carbonator performance is the active fraction fa (fa) is the most important variable in the
determines the reactor height what it is the same, to the later stages in the (model input), especially for values below 0.3. CO2 concentration profile in the
needed, and therefore, the CO2 carbonation cycles during experiments). In these Other parameters having significant influence carbonator, and therefore in the CO2
captured. cases, the sensitivity of the model to the reactivity are the carbonator temperature (especially in capture efficiency. The variables
of the sorbent is even more pronounced. the riser region) and the solid inventory. determining fa are: solid inventory,
FR/FCO2 and F0/FCO2.
Results Bed height determined by heat CO2 concentration profiles in the reactor are More than 70 % of CO2 capture is achieved for CO2 capture efficiencies > 80 % are
removal was found to be enough insensitive to values of fa higher than 0.1. a range of reasonable conditions: 600-650ºC, feasible with solid inventories higher than
for achieving more than 83 % of For low values of fa (typical of continuous fa>0.075, 4-5 kg/s of solid inventory) 200 kg/MW and solid circulation rates
CO2 capture, that is 90 % of overall operation of the CaL), general bed characteristics Most of the CO2 capture is observed to be higher than 3 kg/m2·s (FCa/FCO2~5)
CO2 recovery. (such as superficial gas velocity, bed temperature, occurring in the first 2 m (1.2 m of dense To increase capture efficiency up to 90 %,
bed height, bubble behavior,...) strongly affects the region) with a significant fraction occurring in maintaining solid inventory, solid
CO2 capture efficiency. the acceleration region due to the better gas- circulation rate should be increased up 6
solid contact than in the dense region. kg/m2·s
PART (2/2) Lasheras et al. (2011) Romano (2012)
Particle conversion Particle conversion model is that suggested by Particle conversion model based on the carbonation rate
model/ equation Abanades et al. (2004): suggested by Grasa et al. (2008), similar to that proposed by
Bhatia and Perlmutter (1983):
ks=5.95·10-10 m4/mol·s This reaction rate is valid for t<tlim, which corresponds to
S0=40·106 m2/m3 the time required by the sorbent particle to reach complete
Xb,N: active fraction of CaO entering the carbonator conversion. For t>tlim, reaction rate becomes zero.
given by Abanades et al. (2005) as:
8
ρCaO and MCaO are the CaO density and CaO molar ks=6.05·10-10 (m4/mol·s)
weight CCO2, Ceq: CO2 concentration in the bulk phase and in the
equilibrium, respectively
SN: specific surface area available in a particle having been
cycled N times (VMCaCO3=36.9·10-6 m3/mol)
Sorbent capacity
decay law
(Abanades and Alvarez, 2003)
With k=0.52 and Xr=0.075 (without sulfur deactivation)
(Grasa and Abanades, 2006)
Hydrodynamic CFB CFB
regime of the reactor
Hydrodynamic Core-annulus model with an upper lean and a Core-annulus model with an upper lean and a lower dense
model lower dense region based on an approach for CFB region proposed by (Kunii and Levenspiel, 1997, 2000)
of Kunii and Levenspiel (1997)
Particle distribution Constant particle diameter of dp (value not Uniform particle diameter (justified since dp does not affect
specified) kinetics and absorption capacity, Grasa and Abanades
(2006))
Criteria for reactor Flue gas coming from a 1052 MWe reference plant Ht (overall height of the riser) is an input variable to the
dimensioning has to be divided by half and therefore, assuming model, as well as u0 (mean superficial velocity in the riser)
an 80% of capture efficiency and a superficial and solid inventory.
velocity of 6 m/s, 194 m2 of cross-sectional area of A (riser cross-section) will be calculated from the mean
the carbonator is needed. It has been set a reactor volumetric flow between reactor inlet and outlet (result
height of 30 m. from solving the model) and u0.
Effect of coal ash Yes, to account for the solid density in the bed and Yes, ashes are considered in solid inventory and molar mass
included the total solid inventory of solids in the system (that will affect to the solid residence
time), and in the volume ratio between active solids and
total solids.
Effect of sulfur Not considered in the sorbent decay law (high ratio Yes, considered in the sorbent decay law through the
included Ca/S), but a 99% of conversion of the SO2 in the parameters k and Xr for different sulfation levels.
flue gas is achieved
Governing Performance strongly depends on the ratio FR/FCO2 Carbonator capture efficiency is strongly linked to the
parameters and the solid inventory (through the pressure drop), following input variables: ratios F0/FCO2 and FR/FCO2, solid
and to a lesser extent of the ratio F0/FCO2 inventory and sulfur and ash content of the coal burnt.
Furthermore, model parameters related to sorbent
performance (k and Xr) have also a strong influence on
capture efficiency.
Results 80 % of CO2 captured (an objective fixed in the The model is used for evaluating the effect of different
model), 14 kPa of pressure drop and 55 tonnes/h of parameters in the carbonator performance, and it is
make-up flow, maximize net plant efficiency. expected that the model will be used to optimize the
operating parameters of the CaL system that minimizes the
cost of CO2 avoided
9
Integration between a power plant and the CaL system relies on introducing the flue gas from
the boiler (after cooling) into the carbonator of the capture system. In case of retrofitting
applications, usually considered in the literature, no modifications in the existing power plant
are expected in this way, but power production (and then electric efficiency) would decrease
because of the additional fuel consumed in the calciner and the energy consumption of the ASU
and the CO2 compression train required in the CaL system. However, one of the main
advantages of the CaL system as a post-combustion CO2 capture mechanism is that the chemical
energy introduced in the system for sorbent regeneration with the fuel burned in the calciner is
recovered as gas streams at high temperature, and as carbonation heat at 600-700ºC. This energy
is usually proposed to be integrated in a power cycle to generate extra electricity which
improves the efficiency of the whole plant.
There are two ways proposed to use the energy recovered from the CaL system. The first one
makes use of this energy in the existing power plant to produce extra steam and to reduce coal
consumption in the boiler (Romeo et al., 2010; Yongping et al., 2010). In this option, a tight
thermal integration between the existing power plant and the capture process is required, which
limits its operational flexibility, and makes necessary new designs for the steam cycle. This
integration is more appropriate for new construction power plants with CO2 capture, and
therefore, represents an option in a longer term. The second integration deals with the
integration of the energy released from the CaL system into a new steam cycle decoupled to the
existing power plant, without involving modifications on its performance (Figure 2). In this
option, the CaL system is thermally integrated with a new efficient steam cycle and both
systems would act as an oxy-fired plant, with no integration between the existing power plant
and the CO2 capture plant but for the flue gas exiting the boiler that enters into the carbonator.
This retrofit option is the most-ready-to-use option in the short to medium term as it can take
advantage of existing power plants to fulfil CO2 constraints without major modifications.
Flue gas CO2 for transport
no CO2
CO2
HEAT
Carbonator
T>600ºC
Calciner oxyfuel
T>900ºC
coal
Power Plant
Flue gas
Oxygen
Air
Coal Air New oxyfuel CFB power plant
10
Figure 2 - General layout for the existing power plant integrated with the CaL system
A summary of the different research works and results published on the literature are gathered
in Table 2. Most of the works reviewed consider the integration of the CaL system into a coal-
fired power plant coupled with a high-efficiency supercritical steam cycle (Abanades et al.,
2005; Epple and Ströhle, 2008; Hawthorne et al., 2009; Martínez et al., 2011b; Romano, 2009;
Romeo et al., 2008; Romeo et al., 2009; Shimizu et al., 1999; Ströhle et al., 2009a; Ströhle et
al., 2009b), according to the thermal integration depicted in Figure 2. Yongping et al. (2010)
analyses several methods for the utilisation of the heat recovered from the CaL system, and
proposes modifications and some developments in the boiler and steam turbine of the existing
plant. Low electric efficiencies have been reported in this work for all the schemes proposed
because heat recovered from the CaL system has not been fully integrated into the plant.
However, it concludes that the only option likely to be developed in a near future is to use the
heat recovered from the CaL system to drive a new steam cycle, as it does not affect the
operation of the existing plant.
A common feature of the works reviewed is estimating an electric efficiency of the whole
process that results from coupling a CaL system into an existing coal-fired power plant, and
considering usually a supercritical steam cycle that takes advantage of the heat fluxes available
in the capture plant. Conventionally, the capture system has been assumed to be working under
a fixed and reasonable operating conditions in both reactors: carbonator at 600-650ºC with CO2
capture efficiency of 90 %, and calciner at 900-950ºC considering full calcination of the CaCO3
coming from carbonator, usually without CO2 recycle in the calciner. Romeo et al. (2009) and
Martínez et al. (2011b) carried out a sensitivity analysis to asses system performance under
different operating conditions of the CaL system, and determine the optimum fresh sorbent
make-up flow and solid circulation for the CaL from an economical (Romeo et al., 2009) or an
efficiency point of view (Martínez et al., 2011b). Both works conclude that working with low
purge percentages and high solid circulation between reactors lead to the highest electric
efficiencies and the lowest costs per tCO2 captured. Romeo et al. (2009) even quantify that the
maximum solid purge should be 5 % to avoid capture costs above 20 €/tCO2 captured.
Quantitatively, when comparing with a reference plant without capture, a broad range of electric
efficiencies have been reported. Lower efficiency penalties of the order of 3 percentage points
have been assessed by Epple and Ströhle (2008), Ströhle et al. (2009a) and Ströhle et al. (2009b)
that do not include CO2 compression or fan consumption in the calciner. Abanades et al. (2005)
analysed the efficiency obtained for different configuration schemes of the CaL, and assessed a
penalty of 5.75 percentage points with respect to a reference plant of 46 % of electric generation
efficiency, being 2.85 and 3.17 percentage points attributed to the CO2 compressor and the
ASU, respectively. In the rest of the reviewed works, efficiency penalties are typically between
11
6.5 and 8.5 percentage points with respect to the reference plant. Reasons for these differences
are the electric efficiency for the reference plant assumed, the different qualities of the thermal
integration proposed, the fact that in some cases no thermal integration has been carried out and
a reasonable electric efficiency has been applied to the total heat recovered from the CaL, or the
different power consumptions assumed for the auxiliaries, compressors and fans with respect to
other works.
From the papers reviewed here, it has been noticed that there is a lack of benchmark guidelines
for comparison among the different published works. Main parameters affecting not only the
CaL system (like the ASU, CO2 compressor, fans, ...) but also those of the reference power plant
should be collected and reported as a basis for comparison of the different works. The main
objective of these guidelines would be to make results more consistent and reliable, and also
easy to be compared with other technologies. For instance, reference to the European
Benchmarking Task Force (EBTF) (Franco et al., 2011) can be made, at least for the
fundamental techno-economic assumptions.
In addition, the following suggestions can be made for future modelling and simulation works:
• The power consumption of auxiliary units should be properly taken into account. In
particular, the consumption of the fan needed to offset the flue gas pressure losses in the
carbonator should be included, since it may provide a relevant contribution to the
auxiliary electric consumption. For a reliable estimation of this consumption, it is
important to consider the presence of inactive solids (inactive sorbent, ash from coal
and CaSO4) as part of the carbonator inventory and to use a carbonator model to
estimate the link between the fundamental CaL process parameters (carbonator
inventory, sorbent make-up and sorbent recycle rate) and CO2 capture efficiency.
• Improvements on the calculation methodology of the oxy-fuel combustion side should
be made with respect to the existing literature, where it is often treated in a simplified
way. For example, flue gas recycle and CO2 compression and purification unit should
be considered in future works.
• Assessments on the effects of different kinetics and stability of the sorbent on the
overall plant performance are lacking in the current literature. As cited in the former
section, considering the CO2 absorption capacity of the sorbent through the actual age
of the particles cycled in the system allows a better assessment of the whole
performance, and makes the results obtained more reliable. Longer carbonation times
(Arias et al., 2011; Lysikov et al., 2007; Sun et al., 2008) or certain reactivation
processes with steam (Martínez et al., 2011) or CO2 (Arias et al., 2012) impact sorbent
12
reactivity, and have been gaining further attention. Performance of the whole plant
including some of these reactivation methods should be assessed.
13
Table 2 - Summary of the assumptions and results obtained from process simulation on CaL process integrated with coal-fired power plants
PART (1/2) Ref1: Authors (year) Shimizu et al. (1999) Abanades et al. (2005) Romeo et al. (2008) Romeo et al. (2009)
Fuel (existing Composition and LHV- Coal burnt in the existing plant Coal burnt in the combustor In the existing plant, a low-rank In the existing plant, a high-rank
plant and HHV is the same burnt in the and in the calciner is the high-sulphur lignite is used: coal is burnt with air (66 %(wt.)
calciner) calciner: same: LHV=15.854 MJ/kg of C; 8 %(wt.)of H2O; 13 %(wt.)
Bituminous coal, LHV=25 MJ/kg C: 42.2 %(wt) of ashes, and LHV=25.3 MJ/kg).
HHV=33.2 MJ/kg-daf C: 65.0 %(wt) H: 2.7 % (wt)
(LHV=23.61 MJ/kg) H: 3.0 % (wt) O: 7.0 %(wt) Concerning the coal burnt in the
C: 69.2 %(wt) O: 8.0 %(wt) N: 0.7 %(wt) calciner, the influence of the coal
H: 4 %(wt) S: 0.0 %(wt) S: 4.8 %(wt) burnt in the calciner is analysed.
O: 9.3 %(wt) Ash: 16.0 %(wt) Ash: 23.5 %(wt) Coals with different ash and
Ash: 17.5 %(wt) Moisture: 8.0 %(wt) Moisture: 19.1 %(wt) sulphur contents are considered.
Moisture: 9.8 %(wt) In the calciner, a low-sulphur
high rank coal is used:
LHV= 25.2 MJ/kg
C: 66.9 %(wt)
H: 3.7 %(wt)
O: 6.5 %(wt)
N: 1.6 %(wt)
S: 0.7 %(wt)
Ash: 13.9 %(wt)
Moisture: 6.8 %(wt)
Type of plant Greenfield/retrofit Retrofit of an existing air- Retrofit of an existing Retrofit an existing Retrofit of an existing power plant
blown coal-fired supercritical reference power plant with supercritical power plant with a with a CaL system coupled with a
power plant coupled with a new CaL system coupled with a new supercritical steam cycle new supercritical steam cycle
supercritical steam cycle which new steam cycle coupled with a CaL system
energy is provided by CaL
system
Carbonator Operating temperature, °C 600ºC 650ºC 650ºC 650ºC
F0/FCO2 No make-up flow F0/FCO2=0.10 F0/FCO2=0.25 (F0/FCa=0.05) F0/FR=0.02 F0/FR=0.015
FCaO/FCO2 FCaO/FCO2 of 8.3 FCaO/FCO2=3 FCaO/FCO2 = 5 FCaO/FCO2=4 FCaO/FCO2=5
Ws, kg/MW or kg/m2 ~ 685 kg/m2 - - - -
Ca conversion*, % CaO conversion: 10 % 25.1 % (=maximum average 17 % of CaO conversion 22.1 % (=Xave) 22.4 % (=Xave)
conversion, Xave)
CO2 capture efficiency, % ~ 83 % (it is fixed by the 75.3 % of CO2 captured 85 % of CO2 captured 96 % of CO2
author) captured
Gas pressure drop, kPa Not mentioned - - Not specified
Model used BFB for intermediate size There is no a reactor model There is no a reactor model There is no a reactor model
Others? particle of Kunii and implemented (CaO implemented implemented
Levenspiel conversions are considered to CaSO4 is considered
CaSO4 formed
Ca(OH)2 is not formed be equal to Xave)
CaSO4 is not formed
Calciner Operating temperature, °C 950ºC 950ºC 875ºC 930ºC
Calcination efficiency, % 100 % of CaCO3 calcined 100 % of CaCO3 calcined - 100 % of CaCO3 calcined
14
O2 content in oxidant - 100 % O2 fed into the 100 % O2 (there is no CO2 30 % O2
stream, % - calciner recirculation)
CO2 recycle, % - 0 % of rich-CO2 recirculated 0 % of rich-CO2 recirculated 17-21 % of rich-CO2 recirculated
O2 content in calciner flue - - Not mentioned Not mentioned
gas, %
Steam cycle SH/RH pressure, bar 172.21 bar/30.39 bar 280 bar/40 bar 290 bar/48.5 bar
SH/RH temperature, °C 566ºC/538ºC 600ºC/600ºC 600ºC/620ºC
BFW temperature, °C ~ 250-300ºC 285ºC -
Condensing pressure, bar - 0.045 bar 0.045 bar
Turbine isentropic - - 89 % for HP turbine and 91 % for
efficiency HP/IP/LP, % IP and LP turbines
Electric-mechanical 100 % -
efficiency, %
Air separation Consumption for O2 25.9 MJe/kmol (~225 kWeh/t O2) 220 kWh/ton O2 (Metz et al., 220 kWh/ton O2 (Metz et al.,
unit production, kWh/tO2 2005) 2005)
O2 purity, % vol. 97.5 % O2 purity 95 % O2
95 % O2
CO2 Final CO2 pressure, bar - 100 bar 110 bar 120 bar (80ºC)
compression Final CO2 purity, % > 95% (dry basis) Not specified Not specified
and purification Number of IC compressors - - 4 turbo compressors
Compressors isentropic - - 80 % isentropic efficiency
efficiency, %
Electric-mechanical - - -
efficiency, % -
Overall specific 24.5 MJe/kmol-CO2 (~ 155 -
consumption, kJe/kgCO2 kWhe/t CO2)
Other Fans Isentropic efficiency, -
auxiliaries %
Fans electric-mechanical -
efficiency, %
Coal handling and milling, -
kJ/kg coal
Limestone handling and -
milling, kJ/kg
Others?
Results Gross power, MWe 1000 MWe (465 MWe CaL) 46 MWe 736 MWe (308.5 MWe CaL) 875.3 MWe 856.8 MWe
ASU consumption, MWe 69 MWe 3.2 MWe 46.6 MWe 61.9 MWe 59.6 MWe
CO2 compression 114 MWe 2.6 MWe 52.8 MWe (fans, solid and gas CO2 compression turbine is driven
consumption, MWe circulation and CO2 compr.) by steam extraction from the IP
turbine
Fans consumptions, MWe - - 15.4 MWe (power plant auxil.) 24.7 MWe 24.7 MWe
Net power, MWe 817 MWe 40.3 MWe 621.2 MWe (193.7 MWe CaL) 788.7 MWe 772.6 MWe
Net efficiency, % (Net 33.4 % (HHV)// 34.9 % (LHV) 40.25 %(LHV) 37.04 % (1677.24 MWth coal, 35.62 % 35.50 % (LHV)
output/heat of coal) LHV) (LHV) coal of coal of exist. plant
exist. plant
15
CO2 capture ratio, % 90.4 % 90 % 88.7 %
Credits for integration with No credits as solid purge has 1.10 points of increase (41.3 2.92 points of increase (39.96 0.67 points 0.70 points
cement industry** not been considered %(LHV) net effic.) % of net efficiency) (36.30 %) (36.20 %)
Specific CO2 emission, 77.6 g CO2/kWh gross //95.0 g 141.1 g CO2/kWh net 122 g CO2/kWh net 21.9 g Not specified
g/kWh CO2/kWh net CO2/kWh net
Comparison Efficiency penalty, % 7.22 points (40.7 %(HHV) 5.75 points of energy 7.89 points of energy penalty 6.76 points of 6.83 points of
with reference points reference plant)// 7.54 points penalty (46 %(LHV) without integration with cement penalty (42.4 penalty (42.3 %
plant w/o CO2 (42.4 % (LHV) reference) reference plant) industry (44.9 % reference % reference) reference)
plant)
capture***
Reduced specific emission, 89.1 % (872.3 g CO2/kWh net 81.1 % (746.1 g CO2/kWh 83.6 % (781 g CO2/kWh net 97.6 % (905.1 Not information
% existing plant) net existing plant) existing plant) g CO2/kWh available
net existing
plant)
Notes Base case of 100 MWth The net efficiency of the existing Ratios F0/FR and FCaO/FCO2 are those
*Ca conversion referred to the unsulfated introduced as coal in the plant and the new steam cycle are the that minimize the avoided CO2 cost
(sum of calciner and boiler) same and equal to 44.4 % under two scenarios: solid purge at
sorbent and defined as: Electricity generation efficiency carbonator (column left) and purge at
**Credits for cement industry have been is 46 % for reference plant and calciner (column right).
evaluated as: heat from CaL Apart from the heat recovered from the
CaL system, heat from the CO2
compression train has been also
integrated into the new supercritical
steam cycle, while a steam extraction
of the turbine is used for driving the
CO2 turbo compressor
Hcalc,F0: Heat required to calcine the Ca 45 % of efficiency of an SC steam
contained in F0 (Hcalc=182.9 MW/kmol) cycle is considered
***Reference plant has been considered as the
existing one and a new one with the same fuel
input as the calciner
Epple and Ströhle
(2008), Ströhle et al.
PART (2/2) Ref1: Authors (year) Romano (2009) (2009a), Ströhle et al. Hawthorne et al. (2009) Yongping et al. (2010) Martínez et al. (2011b)
(2009b), Lasheras et al.
(2011)
Fuel (existing Composition and LHV-HHV Low sulphur South African Bituminous coal which ultimate Not specified neither its Coals used have been taken In the existing plant, a low-rank
plant and coal is used in the plant: or proximate analysis is not analysis nor its heating value from Romeo et al. (2008) high-sulphur lignite is used:
calciner) LHV= 24.62 MJ/kg specified although LHV=17.02 MJ/kg
C: 64.4 %(wt) C: 45.2 %(wt)
H: 4.0 % (wt) H: 3.0 % (wt)
O: 7.4 %(wt) O: 7.2 %(wt)
N: 1.5 %(wt) N: 0.8 %(wt)
S: 0.9 %(wt) S: 4.1 %(wt)
16
Ash: 12.7 %(wt) Ash: 22.4 %(wt)
Moisture: 9.4 %(wt) Moisture: 17.3 %(wt)
In the calciner, a low-sulphur
high rank coal is used:
LHV= 25.3 MJ/kg
C: 66.3 %(wt)
H: 3.6 %(wt)
O: 7.0 %(wt)
N: 1.6 %(wt)
S: 0.6 %(wt)
Ash: 14.2 %(wt)
Moisture: 6.7 %(wt)
Type of plant Greenfield/retrofit A plant of new construction Retrofit of an existing coal-fired Retrofit of an existing coal- Introducing a CaL system Retrofit of an existing subcritical
where a fraction of coal is power plant with a CaL system fired power plant with a CaL into an existing supercritical power plant with a CaL system
burnt with air in a boiler and coupled with a new supercritical system coupled with a new power plant and using the coupled with a new supercritical
the remaining fraction is burnt steam cycle supercritical steam cycle heat recovered from CaL to steam cycle
in oxy-fuel mode in the produce additional steam that
calciner. The energy recovered will drive a new steam
from both boilers generates an turbine (there is no a detailed
ultra-supercritical steam that heat integration)
feeds a steam turbine
Carbonator Operating temperature, °C 650ºC 650ºC 650ºC 650ºC 650ºC
F0/FCO2 F0/FR=0.01 F0/FCO2=0.03 (55 t/h of F0) 45.7 kg/s of F0 F0/FCO2=0.34 F0/FCO2=0.1 (See Notes below)
FCaO/FCO2 8.74 kg solids/kg of CO2 F0/FR=0.01 F0/FR=0.004 FCaO/FCO2=7 FCaO/FCO2=6.82 FCaO/FCO2=4-7 (for 70 to 90 % of
captured FCaO/FCO2=3 FCaO/FCO2=7.8 CO2 capture, respectively)
Ws, kg/MW or kg/m2 Around 1000 kg/m2 - 1000 kg/m2 - - 1500-2000 kg/m2
Ca conversion*, % 11.6 % of CaO conversion 20 % of CaO 11.4 % 20 % of CaO conversion 13-18 % of CaO conversion
conversion depending on the case
CO2 capture efficiency, % ~ 90 % 80 % of CO2 captured 80 % of CO2 captured 85 % of CO2 captured 70-90 % of CO2 captured
Gas pressure drop, kPa 10 kPa - 10 kPa Not specified - -
Model used Kunii and Levenspiel 1D There is no 1D fluidized bed CFB model developed by There is no a reactor model Model developed by Alonso et
model used by Abanades et al. model model developed Hawthorne et al. (2008) implemented al. (2009), but using the kinetic
Others? implemented, it by Lasheras et al.
(2004) is assumed that (2011)
Although in this paper it has model of Grasa et al. (2009) and
XN is achieved been included the assumption considering a sorbent capacity
CaSO4 formation considered that CaO available for decay law for partially converted
(99% of conversion) carbonation can be sulfated up particles developed by Rodríguez
to Xsulf et al. (2010).
100 % of SO2 reacts with CaO
Calciner Operating temperature, °C 900ºC 900ºC 900ºC 900ºC 950ºC
Calcination efficiency, % 100 % of CaCO3 calcined 100 % of CaCO3 calcined 100 % of CaCO3 calcined 100 % of CaCO3 calcined 100 % of CaCO3 calcined
O2 content in oxidant stream, 50 %(vol.) 100 %(vol.) 100 %(vol.) 100 %(vol.) Around 25 %(vol.)
%
CO2 recycle, % Not given 0% 0 % of rich-CO2 recirculated 0 % of rich-CO2 recirculated 60-63 % of rich-CO2 recirculated
O2 content in calciner flue 2.5 %(vol.) Not specified 3 %(vol.) < 0.5 %(vol.) (calculated 2.5-3.0 %(vol.)
gas, % from the results published)
17
Gas pressure drop, kPa 20 kPa (0.2 bar) Not specified Not specified - -
Others? - A 99.5 % of coal conversion is A 99.8 % of coal conversion is Thermal efficiency of the A 99.6 % of coal conversion is
considered, while 100% of SO2 considered calciner is considered to be considered while 100 % of SO2
formed is captured due to the 89.1 %(vol.) of CO2 in the flue 93 % formed is captured due to an
high Ca/S ratio gas exiting the calciner extra CaCO3 make-up flow (with
a Ca/S=3)
Steam cycle SH/RH pressure, bar 300 bar/ 54 bar 285 bar/59 bar 300 bar/not given 242 bar/42.5 bar 280 bar/40 bar
SH/RH temperature, °C 600ºC/ 610ºC 600ºC/620ºC 600ºC/not given 566ºC/566ºC 600ºC/600ºC
BFW temperature, °C 315ºC 307ºC Not specified 278.6ºC 285ºC
Condensing pressure, bar Not given Not given Not specified 0.118 bar 0.045 bar
Turbine isentropic efficiency Not given Not given Not specified Not specified -
HP/IP/LP, %
Electric-mechanical 98.5 % Not given Not specified Not specified 100 %
efficiency, %
Air separation Consumption for O2 - 184.8 kWh/ton O2 - 220 kWh/ton O2 (Metz et al., 160 kWh/ton O2 (Darde et al.,
unit production, kWh/tO2 2005) 2009)
O2 purity, % vol. 97 %(vol) of O2 95 %(vol.) of O2 95.2 %(vol.) of O2 (N2 and Ar) 95 % O2 Not specified
Number of compression Four steps (1.013 bar/2.5
steps bar/3.9 bar/6 bar) with IC
CO2 Final CO2 pressure, bar Not information specified of Not included in the analysis 110 bar 110 bar 150 bar
compression Final CO2 purity, % this stage 95.3 %(vol.) (The remaining - Not specified
and purification gas is Ar, N2 and O2)
Number of IC compressors 5 compressors with IC (3.15, - 5 stages with IC
10.4, 31, 75 and 110 bar)
Compressors isentropic Not specified - Not specified
efficiency, %
Electric-mechanical Not specified - Not specified
efficiency, %
Overall specific Not specified 0.4 GJ/tCO2 (111 kWhe/tCO2) 100 kWhe/tCO2 (Darde et al.,
consumption, kJe/kgCO2 (Metz et al., 2005) 2009)
Other Fans polytropic efficiency, 80 % 88 % (isentropic efficiency) Not specified Not specified Not specified
auxiliaries %
Fans electric-mechanical 94 % 98 % Not specified Not specified Not specified
efficiency, %
Coal handling and milling, 30 kJe/kg coal Not considered Not specified Not specified Not specified
kJ/kgcoal
Limestone handling and 90 kJe/kg CaCO3 Not considered Not specified Not specified Not specified
milling, kJ/kg
Ash handling, kJ/kg 100 kJe/kg ash Not considered Not specified Not specified Not specified
Results Gross power, MWe 579.4 MWe 1737.8 MWe 2100.0 MWe 1875 MWe (775 MWe CaL) 1000 MWe (400 MWe CaL) 811.0 MWe 898.6 MWe 1048 MWe
ASU consumption, MWe 48.1 MWe 80.9 MWe 126.5 MWe 115 MWe 62 MWe 63.1 MWe 73.9 MWe 93.2 MWe
CO2 compression 48.6 MWe Not included Not included 128 MWe 92 MWe 66 MWe 75.6 MWe 90.1 MWe
consumption, MWe
Fans consumptions, MWe 10.4 MWe 20.95 MWe 20.95 MWe - - 15.4 MWe 16.3 MWe 17.9 MWe
(carbonator) (carbonator)
18
Auxiliaries (MWe) 19.9 MWe 51.6 MWe 53.9 MWe 99 MWe from auxiliaries - 9.9 MWe 11.8 MWe 15.0 MWe
Net power, MWe 452.4 MWe 1584.3 MWe 1898.6 MWe 1533 MWe 846 MWe 656.6 MWe 721.0 MWe 831.8 MWe
Net efficiency, % (Net 37.35 % (LHV) 42.85 % 42.44 % 39.24 % 36.8 % (LHV) 32.4 % 32.6 % 32.9 %
output/heat of coal) (LHV) (LHV) (LHV)
CO2 capture ratio, % 97.04 % of CO2 captured 87.3 % 89.6 % 88 % of total CO2 captured 93 % of total CO2 captured 86.2 % 91.5 % 96.3 %
Credits for integration with Not enough information to be 0.33 points 0.27 points 0.86 points of increase (40.10 2.8 points of increase (39.6 0.7 points 0.6 points 0.5 points
cement industry** evaluated (43.18 %) (42.71 %) % of net efficiency) % of net efficiency) (33.1 %) (33.2 %) (33.4 %)
Specific CO2 emission, 27.4 g/kWh 103 g CO2 86 g CO2 Not information available 74 g CO2 emitted/kWh net 156.3 g 94.8 g 41.0 g
g/kWh emitted/kWh emitted/kWh CO2/kWh CO2/kWh CO2/kWh
net net net net net
Comparison Efficiency penalty, % points 7.65 points of penalty 2.75 points of 3.16 points of 6.36 points of penalty (45.6 % 8.3 points of penalty (45.1 % 8.2 points 8.3 points 8.5 points
penalty penalty in the reference plant) in the reference plant (40.6 %) (40.9 %) (41.4 %)
with reference
plant w/o CO2 Reduced specific emission, Not information available 86.7 % 88.9 % Not information available 89.4 % reduction (696 g CO2 81.8 % 88.8 % 95.1 %
% reduction (774 reduction (774 emitted /kWh net existing (857.3 g (849.5 g (838.7 g
capture*** CO2/kWh CO2/kWh CO2/kWh
g CO2/kWh net g CO2/kWh net plant)
net) net) net)
existing plant) existing plant)
Notes Considering a 45 % of efficiency of Two different modeling approaches In this work, heat recovered from Several methods for the utilization In this work, the efficiency is
*Ca conversion referred to the unsulfated an USC steam cycle from Cziesla et to the carbonator are used. First CO2 compression stage has been of the heat recovered from the analyzed when capturing 70 (left
al. (2009) approach assumes that CaO achieves integrated into the new steam cycle, CaL system are analyzed. It is column), 80 (middle) and 90 % (right
sorbent and defined as: its maximum conversion (Xb,N) increasing net power output and concluded that the only option column) of CO2 in the carbonator for
**Credits for cement industry have been (column left), and the second one therefore net efficiency of the likely to be realized in a near different F0/FCO2 ratios between 0.1
evaluated as: evaluates CaO conversion according system future, as it does not affect the and 0.35. The highest efficiencies
to the 1D model explained by operation of the existing power were obtained for the lowest make-up
Lasheras et al. (2011) (column right). plant, is to use the heat recovered flows, that is F0/FCO2=0.1, and
45.6 % of net efficiency in the from the CaL system to produce therefore these are the cases analyzed
reference plant steam to drive a new steam cycle. here.
Fan consumption of calciner and Therefore, this is the option
CO2 compression have not been describe in this report.
Hcalc,F0: Heat required to calcine the Ca included in the efficiency provided.
contained in F0 (Hcalc=182.9 MW/kmol)
***Reference plant has been considered as the
existing one and a new one with the same fuel
input as the calciner
19
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Yongping, Y., Rongrong, Z., Liqiang, D., Kavosh, M., Patchigolla, K., Oakey, J., 2010. Integration and
evaluation of a power plant with a CaO-based CO2 capture system. International Journal of Greenhouse
Gas Control 4, 603-612.
22
Sorbent enhanced steam methane reforming (SE-SMR) is a process where a CO2 sorbent is used in
combination with a reforming catalyst to remove CO2 within the reactor, thus shifting the equilibrium of the
reforming reactions towards higher hydrogen yield. A number of papers have been reported where more or
less sophisticated modeling of SE-SMR reactors have been performed. The details of some selected papers
involving the use of CO2 sorbents have been given in Table 3.
Different reactor concepts (packed bed (Chen et al, 2011, Martavaltzi et al, 2011, Li et al, 2007, Zagoruiko et
al, 2007) and fluid bed (Wang et al, 2011-I, Wang et al, 2011-II, Wang et al, 2011-III, Di Carlo et al, 2010,
Jakobsen et al, 2009, Lee et al, 2006)) as well as hybrid concepts including membranes (Chen et al, 2008,
Fayyas et al, 2005) for in situ hydrogen removal and a special concept based on the combination of a fixed
catalytic monolith together with a circulating particular sorbent (Koumpouras et al, 2007) have been studied.
Mostly natural CaO sorbents such as limestone and dolomite are used, but also novel synthetic Ca, Li and
hydrotalcite (HTC) based sorbents have been included to see the effect of sorbent properties on the process
performance (Chen et al, 2011, Li et al, 2007, Jakobsen et al, 2009). Generally, for kinetics of the elementary
reactions of steam reforming, the parameters derived by Xu & Froment have been used.(Xu et al, 1989) For
the CaO carbonation reaction, some works rely on their own (apparent) kinetic constants derived from
thermo gravimetric analyses, while others have used kinetic expressions and parameters from earlier work by
Sun (Sun et al, 2008), Lee (Lee et al, 2004) or Bhatia. (Bhatia et al, 1983).
Fixed bed SE-SMR is typically modeled for temperatures from 500 to 650ºC, pressures from 1 to 15 atm and
for steam to methane ratios (S/M) from 2.0 to 5.5. In Chen et al. (2011) and Martavaltzi (2011), simple
modeling of breakthrough curves have been carried out where the parameters needed for the particle
conversion expressions have been derived from their own or literature thermo gravimetric measurements or
isotherm data of the various sorbents. The temperature and pressure dependencies on the enhancement in
hydrogen production are analyzed and hydrogen and CO2 concentrations in the reactor effluent with time are
modeled showing different behavior of the various sorbents. Only result from one (the first) cycle is
presented.
Li et al also considered sorbent capacity decay with cycle number (Li et al, 2007). The dependency of the
CaO conversion on cycle number derived by Grasa et al was used to model multi-cycle breakthrough curves
as well as CO2 evolution curves during regeneration from a packed bed reactor during cyclic SE-SMR
operation (Grasa et al, 2006). CaO sorbents such as limestone, dolomite and impregnated CaO systems were
compared. They conclude (obviously) that a synthesized sorbent with high performance and low cost would
be highly beneficial for the process.
23
Zagoruiko et al focused on modeling the thermal effects by using a "moving heat wave" generated by in situ
catalytic combustion of methane for regeneration of the sorbent (Zagoruiko et al, 2007). Both temperature
and CO2 concentration profiles throughout the fixed bed with time are modeled.
Fluid bed SE-SMR reactor modeling has been developed through a series of papers Wang et al using a 3D
two fluid Eulerian hydrodynamic model together with kinetic parameters of the reactions taking place (Wang
et al, 2011-I, Wang et al, 2011-II, Wang et al, 2011-III). No details on catalyst nor sorbent particle structure
were included assuming only that the reactions takes place on the particle surface without diffusion
limitations. Different gas flow rates show that higher rates give slightly lower methane conversions, lower
hydrogen yield and lower CO2 capture rate. The gas-particle flow within the reactor is simulated as well as
the gas composition throughout the reactor. CO2 sorption is fast compared with the rate of the reforming
reactions while the CO2 desorption rate is slow due to the increased CO2 concentration in the gas phase
making higher temperature needed to achieve the necessary kinetics of sorbents regeneration.
Di Carlo et al include both intra- and extra-particle mass transfer effects in their study of SE-SMR using a
similar two fluid Eulerian model as Wang (Di Carlo et al, 2010, Wang et al, 2011-III). A modified shrinking
core model (SCM) by Johnsen (Johnsen et al, 2006) was assumed. A Ni-catalyst/dolomite powder mixture
was used. At sorbent/catalyst mass ratios larger than 2, autothermal conditions in the reactor were simulated
where the heat produced upon sorption compensated the endothermicity of the reforming reaction. Particle
segregation due to differences in particle fluidization properties of catalyst and sorbent particles was partly
studied by assuming large difference in average particle size of the two. In this case no segregation was
observed for gas velocities above a critical minimum.
Jakobsen (Jakobsen et al, 2009) studied the SE-SMR process by using a linear plug flow model for fluid bed
reactor using different flow regimes and sorbents. Their results indicate that the contact time in a riser is too
short to reach high methane conversion and CO2 capture rates, while high hydrogen yield and capture rates
can be obtained in a bubbling bed. In the riser simulations, best performance was obtained with Na2ZrO3
sorbent (92.6% H2 and 3.0% CO2 in gas effluent) while CaO gave a poorer performance due to slower
kinetics (79.3 % H2 and 11.5% CO2 in effluent).
In none of the works dealing with modeling of SE-SMR in fluid bed reactors were degradation of the sorbent
considered. In addition, modeling of the total cyclic process including both the reforming and calcination
steps has to our knowledge not been done, not even in a simplistic way.
24
Table 3 - Summary of the assumptions and results of studies on reformer modeling
Source Chen et al., Sci. China Martavaltzi et al., Ind. Eng. Li et al., Energy Fuel, 21 Zagoruiko et al., React. Wang et al., Clean Techn. Wang et al., Ind. Eng.
Tech. Sci., 54 (2011) 2999. Chem. Res., 50 (2011) 539. (2007) 2909. Kinet. Catal. Lett., 91 Environ. Policy, 13 (2011) Chem. Res., 50 (2010)
(2007) 315. 559. 8430.
Particle conversion dX(CaO)/dt=kc(1-(t/(b+t))2 R= dX/dt= ks S(X)(1- dX/dt= kc(1-X/Xu)2/3 (CCO2- Wads= 0.58(pCO2- Ra = dX/dt = 56ks(1- Ra = dX/dt = 56ks(1-
X)2/3(CCO2-Ce, CO2)n X)(Pco2-Pco2,eq)nS X)(Pco2-Pco2,eq)nS
0.083
model/equation Ce,CO2)(p/po) pe,CO2)(gCO2/gCaO)(1/atm
sec)
dX/dt =ks (Pco2-Pco2,eq)n(1-
X)2 ks= ks0 exp(-Ea/RT)
Sorbent capacity decay law Not considered in the work Not considered in the work Xu,N= (1/(1/1-Xr)+kN) + Xr Not considered in the work Not considered in the work Not considered in the work
Hydrodynamic regime of Packed bed Packed bed Packed bed Packed bed (?). Sorbent Bubbling fluidized bed Bubbling fluidized bed
the reactor regeneration in a moving
heat wave of a catalytic
combustion reaction; 1D,
homogeneous model with
no diffusion restriction.
Hydrodynamic model 2D transient model Plug flow, 1D Plug flow 3D Eulerian two-fluid Eulerian two-fluid model
model
Particle distribution Uniform, 6 mm Uniform, 100-180 micron 200-425 µm 1-2 mm spheres Uniform, 500 micron, Uniform, 500 micron,
1500kg/m3 2400kg/m3
Criteria for reactor
dimensioning
Superficial velocity, m/s 0.3 m/s 0.3-0.89m/s 0.32-0.89 m/s
Not reported, unclear Lab scale Lab scale
Reactor height, m article 1 m height Height 0.4m Height 0.34m
Others? Diameter=0.2m Diameter=0.14m
Governing parameters
Temperature, °C 500,550,600 °C T= 773-923K (500-650°C), T= 923K (650°C) T= 500°C T=848K(575°C) T=848K(575°C)
Pressure, bar 1-4 bar P= 1 atm 15 atm 5 atm P=1bar P=1bar
S/C S/C=2, 3.5, 4.5, 5.5 S/C= 3.4 S/C= 4 S/C= 3 S/C=3-5 S/C=5
F0/FCO2
FR/FCO2
Ws
Results
CO2 capture efficiency, Reaction run until Reflect experimental Modeling of multi-cycle CO2 considered completely CO2 considered completely
% breakthrough findings; breakthrough curves and absorbed absorbed
CO2 evolution curves when
Dry H2 mole fraction >97% regenerating. Verification
25
H2 yield, molH2/molNG at lowest p and lowest S/C 93% H2 purity of model by experiments
H2 purity, %vol dry Best temp was 550°C Carbonation rates at 0.96-0.98 dry H2 yield 0.96-0.98 dry H2 yield
various temperatures depending on S/C
Pressure drop, kPa predicted from model.
Others?
Other notes Various Li based sorbents Commercial Ni-based Limestone, dolomite and Only interest in S/C=4 assumed to be
are also evaluated catalyst. impregnated CaO temperature profile through optimum for SE-SMR
compared. the bed during reforming
Impregnated CaO sorbent. and during (counter-
current) regeneration
Best temp 650°C due to
sorption kinetics.
26
Source Wang et al., Int. J. Di Carlo et al., Ind. Eng. Jakobsen et al., Energy Lee et al., Int. J. Hydr. Koumpouras et al., Chem. Chen et al., Chem. Eng. Fayyas et al., Ind. Eng.
Greenhouse Gas Contr., 5 Chem. Res., 49 (2010) Proc., 1 (2009) 725. Energ., 31 (2006) 649. Eng. Sci., 62 (2007) 2833. Sci., 63 (2008) 170. Chem. Res., 44 (2005)
(2011) 489. 1561. 9398.
Particle conversion Ra = dX/dt = 56ks(1- Scarb= εdρdMCO2 (6/dd(1- dX/dt= MCaOks(1- rcbn=dX/xt= (kc/MCaO)(1- rads= kLDF (q*CO2 – qCO2) r= k11 (1-XCaO)0.67 (CCO2- rads=dCs/dt= ka (Cseq – Cs)
model/equation X)(Pco2-Pco2,eq)nS X)1/3(1/RT)(pCO2- X/Xu)m(pCO2-pe,CO2)n S X/Xu)2 Ce,CO2)
pe,CO2)0.66)/(1/k3+(dd(2((1- Langmuir Langmuir
X)1/3-(1-X)2/3)/De + (1-
X)2/3/(hCO2(gd) )
ks= ks0 exp(-Ea/RT)
k3= ks0 exp(-Ea/RT)
Sorbent capacity decay law Not considered in the work Not considered in the work Not considered in the work Not considered in the work Not considered in the work Not considered in the work Not considered in the work
Hydrodynamic regime of Bubbling fluidized bed Bubbling fluidized bed Bubbling fluidized bed Moving bed reactor where Riser where sorbent Fluidized bed & Fluidized Hybrid adsorbent-
the reactor sorbent and catalyst move particles are transported bed membrane reactor (Pd) membrane reactor,
co-current with gas through a static catalytic
monolith Packed bed, Porous ceramic
membrane
Hydrodynamic model 3D non-axisymmetric two- 2D Eulerian-eulerian two- Plug flow. 1D reactor Riser Plug flow
fluid model fluid model kinetic model
Particle distribution Uniform, 500 micron, 200-500 µm Uniform, 150 µm Uniform, 3 mm pellets Uniform, 55 µm Uniform, 100 µm ?
1500kg/m3
Criteria for reactor
dimensioning
Superficial velocity, m/s
0.3 m/s 0.3 m/s 0.05-1 m/s 0.014 m/s 0.46 m/s 1.7 m/s 0.04 m/s
Reactor height, m
Height 4m 0.6 m 0.679 m height 1 m height 4 m height
Others?
Diameter=0.2m
Governing parameters
Temperature, °C T=848K(575°C) T= 873-993K (600-720°C), T= 873K (600°C) T= 700°C T= 723-823K (450-550°C) T= 823 and 873K (550 and T= 400 & 480°C
600°C)
Pressure, bar P=1, and 10bar P= 1 atm
S/C S/C=5 S/C= 3.4 P= 1 atm 3 atm 5 atm 3 atm
10 and 20 atm
F0/FCO2 Dolomite/catalyst= 0-5 S/C= 4 S/C= 3 S/C= 6 S/C= 3
S/C= 3
FR/FCO2
Ws
Results 94% H2 Up to 98.5% CO2 recovery
27
CO2 capture efficiency, >99% (at 1bar) 2.5% CO Up to 79% methane conv. Up to 90% CO2 capture
%
>93% H2 purity 98.7-99.9 % H2 purity 1.3% CO2 Membrane increases H2
H2 yield, molH2/molNG yield and CO2 capture rate
>99% (at 1bar) 2.2% CH4
H2 purity, %vol dry
Pressure drop, kPa
Others?
Other notes Dolomite used as sorbent Dolomite used as sorbent Sorbent + membrane "Adsorption system"… no
assisted reforming Effect of details on kind of sorbent…
Particle segregation studied Riser (2 m/s) give 75-79% membrane
using different cat/sorb H2 purity and low CO2
mixtures capture.
Temperature of outlet gas
28
The process most widely assessed for pre-combustion CO2 capture by CaO sorption is sorption-
enhanced steam methane reforming (SE-SMR). According to this concept, methane is converted
in a single reactor where CO2 is adsorbed over a solid sorbent while SMR and WGS reactions
occur. Therefore, progression of the SMR and WGS gaseous phase reactions is not limited to
equilibrium set by CO2 formation and can proceed almost to a complete depletion of reactants.
CH4 + 2H2O + CaO 4H2 + CaCO3 H°r = -14.5 kJ/mol
The enthalpy balance of the overall reaction is only 14.5 kJ/mol, meaning that it is well
thermally balanced, and therefore not only the carbonation reaction facilitates hydrogen
production by removing CO2 from the gaseous phase, but also provides the heat required for the
steam reforming reaction, allowing for the use of adiabatic reformers.
In Figure 1, some results from equilibrium calculations of a SE-SMR reactor with abundance of
solid sorbent are shown. The result of the contemporaneity of SMR, WGS and carbonation
reactions is a temperature range (roughly 500-650°C, at atmospheric pressure) with stable H2
yield and CO2 capture ratio. Higher temperatures lead to a reduced progression of carbonation
reaction, while lower temperatures lead to Ca(OH)2 formation, with negative effects related to
the removal of H2O from the gaseous phase and a reduction of the effective S/C. Apart from
temperature, steam to carbon ratio and pressure are the parameters which mostly affect the
process. In particular, high pressures require higher temperatures (650-750°C, at 25 bar) and
higher S/C to obtain H2 yields and CO2 capture ratios similar to atmospheric pressure values.
29
Figure 3 - Influence of temperature, pressure and steam to carbon ratio on hydrogen yield and CO2 capture ratio in a
SE-SMR process. The dot dashed curves in the upper diagram refer to a conventional SMR process carried out at 3.5
steam to carbon ratio.
An important issue of SE-SMR processes is sorbent regeneration, to be carried out via
calcination reaction. Decomposition of CaCO3 into CaO and CO2 can be obtained either by
increasing temperature (temperature swing) or by reducing the CO2 partial pressure (pressure
swing) by an actual depressurization or by means of steam purging. In any case, thermal power
is required in the calcination step to provide the heat for the endothermic calcination reaction.
Heat can be provided either by means of heat exchangers or by direct combustion in the
calciner. In the second case, calcination has to be carried out by means of oxy-fuel combustion
to avoid dilution of the CO2 released from calcination with nitrogen.
Different options can be considered for design of the reactors. The most feasible option is to
consider low pressure interconnected fluidized bed reactors. The feasibility of this option has
been demonstrated for other processes (post-combustion Ca-looping, CLC, sorption enhanced
gasification of biomass) in a number of pilot installations. Therefore, technology breakthrough
is not expected to be relevant for the application of the SE-SMR process. The limit of this
layout is related to the low pressure of the H2 delivered, which would require relevant energy
penalty associated to cooling and compression in case of a high pressure final utilization (e.g.
combustion in a gas turbine, utilization in high pressure refinery processes).
The use of pressurized interconnected fluidized bed is an alternative investigated in some works.
However, two kind of problems arise with such a configuration: (i) stable operations of
interconnected pressurized fluidized beds has not been demonstrated yet and requires
30
technology breakthrough and (ii) regeneration temperatures rise with pressure up to values
(roughly 1100-1200°C, at 20-30 bar) at which the activity of the catalyst and the capacity of the
sorbent are compromised.
A further alternative are packed beds, which allow operating reforming and calcination at
different pressures by keeping the solid material always in the same reactor, periodically
exposed to atmospheres favorable to carbonation and to calcination. The intrinsic dynamic
behavior of the system, the difficult control of peak temperatures and the complexity and cost of
high temperature valve system represent the limits of the packed bed-based process.
A summary of the process simulation studies on SE-SMR from the open literature is reported in
Table 1. Two studies (Chen et al, 2011; Fernandez et al., 2012) assessed only the SE-SMR
reactors system. Chen et al. (2011) focused on interconnected fluidized beds. Fernandez et al.
(2012) considered the innovative Cu-Ca looping process based on fixed beds, where calcination
is sustained by oxidation of fuel by means of a CLC loop using Cu/CuO as oxygen carrier.
Ochoa- Fernández et al. (2007) assessed a complete plant for hydrogen production based on
high pressure (10 bar) reforming and low pressure (1 bar) regeneration. Solieman et al. (2009)
and Romano et al. (2011) considered the integration of SE-SMR process into a combined cycle
based power plant. In the first case, a packed bed system was considered, while pressurized
interconnected fluidized beds were adopted in the second case. Finally, Meyer et al. (2011)
assessed the process based on the ZEG concept, where the H2-rich gas is converted in a high
temperature SOFC and the waste heat from the fuel cell is used to regenerate the Ca-based
sorbent.
In all the cases, reactors have been calculated at equilibrium, which is a reasonable assumption
according to experimental data and outputs from reactor modeling studies. Reforming was
assumed to be carried out at 550-600°C and S/C=2.5-3.5 for low pressure (1-2 bar) reformers
cases and at 600-700°C and S/C=4.2-4.8 for high pressure (17-35 bar) cases. In none of these
plants sorbent purging and makeup have been considered. This appears to be a reasonable
assumption when feeding a clean gaseous fuel as natural gas, with no ash and negligible sulfur,
considering that no impurity is expected to accumulate in the Ca-loop or to affect the capacity
and the activity of the Ca-sorbent (in case of CaO, sorbent capacity loss is a consequence of
calcination conditions, there is no need of using a fuel with sulfur or ashes). For this reason the
Ca conversion in the reformer cannot overcome the residual capacity of the sorbent after many
carbonation-calcination cycles. Conversion between 10 and 53% has been adopted in these
studies, significantly higher than the residual capacity of natural sorbents, but acceptable
considering the possible advancements in the development of synthetic sorbents and
reactivation techniques.
31
Overall H2 yields of 2.4-2.7 molH2/molCH4-eq (or 0.60-0.68 molH2/molH2-eq)1 and cold gas
efficiencies of 81-83% have been obtained in all the cases. In cases for power production, net
efficiencies of 50-51% have been obtained when using state of the art combined cycles, while
and efficiency of 76.9% is claimed for the SOFC-based ZEG concept.
1
Equivalent CH4 and H2 concentrations in a gas stream are referred to the capacity of H2 generation by
SMR and WGS reactions and are defined as follows:
xCH4-eq = xCH4 + 7/4xC2H6 + … + (1/2m+1/8n)xCmHn
xH2-eq = 4xCH4 + 7xC2H6 + … + (2m+1/2n)xCmHn + xCO + xH2 + 2xC
32
Table 4 – Main assumptions and results from process simulation studies on SE-SMR technology
33
34
35
The application of SE-SMR process has been proposed also for coal-fed power plants. In this
case, coal is gasified with a H2-rich recycled stream in a hydrogasifier, where carbon is
converted into a CH4-rich syngas to be sent to two stages of reforming/carbonation, where H2 is
produced and CO2 captured. The H2-based syngas is then converted into electric power by a
high temperature SOFC (ZECA concept), by a semi-closed internal combustion steam cycle,
based on H2 oxycombustion (Zecomix concept), or by a combined cycle (Zecomag layout).
Such a process has a much higher complexity than the NG-fed one and large uncertainties exist
on the feasibility of the process. In particular, (i) the use of a fuel rich of ash, sulfur and other
impurities which will affect the performance of the sorbent and probably prevent the use of
synthetic sorbents, (ii) the need of 4 interconnected gas-solid reactors (hydrogasifier + two
carbonators + calciner) operating at high pressure (at least the hydrogasifier and one
carbonator), (iii) the need of exotic components for gas cleaning, solids handling and power
generation, make this process extremely complex even in a long term view.
A few studies assessed this process with sufficient details, whose assumptions and results are
reported in Table 2. Optimistic assumptions, typical of a long term view, have been necessarily
made in these studies, mainly related to the sorbent performance, for which very high activities
have been assumed despite the harsh operating conditions.
36
37
Table 5 – Main assumptions and results from process simulation studies on coal hydrogasification and SE-SMR technology (ZECA – Zecomix/Zecomag)
38
The last application considered in the literature for pre-combustion CO2 capture with Ca-based
sorbents is sorption enhanced gasification. In this process, a solid fuel is gasified at high
pressure in the presence of a Ca-based sorbent, which removes the CO2 from the gaseous phase
favoring hydrogen production and provides the heat for the endothermic gasification reaction. A
relevant fraction of the coke (50-80%) is not converted in the gasifier but is sent into the
regenerator reactor together with CaCO3. By blowing pure O2 in the regenerator, coke is
oxidized providing the heat for calcination and producing a CO2-rich exhaust gas.
Table 6 - Main assumptions and results from process simulation studies on sorption enhanced coal gasification.
On the basis of the modeling and experimental findings, the following modeling guidelines and
needs of experimental investigation can be highlighted:
• Ca utilization can have an important influence on the performance of all the processes
considered, affecting the final efficiency by several % points (Romano and Lozza
39
2010a). In applications where sorbent must be purged to avoid ash buildup and sorbent
contamination by formation of stable sulfur species, it is highly probable that natural
sorbents will be preferred from an economic point of view. Therefore, deactivation
curves considering the average number of carbonation calcination cycles experienced
by the sorbent can be used to estimate the sorbent capacity, as implemented by Weimer
et al. (2008). However, most of the experimental activity on sorbent cyclic stability has
been carried out focusing on post-combustion applications. Therefore, experimental
activity on the capacity and reactivity of natural sorbents at conditions closer to pre-
combustion applications is required.
On the contrary, in NG-fed SE-SMR plants, no sorbent contamination is expected and
synthetic materials can be used. For this reason, higher capacities can be reasonably
assumed, also considering the expected progresses in the synthesis of artificial sorbents.
It can however be highlighted that, due to the relatively high uncertainty of the
performance of natural and synthetic sorbents at the actual process conditions,
sensitivity analyses on sorbent capacity represent an important added value for every
process simulation study.
• In plants for H2 production, it is important to include the PSA process for H2
purification within the process model as done by Ochoa-Fernandez et al. (2007). As a
matter of facts, PSA process can have a relevant effect on the mass and energy balance
since PSA off-gas, rich of CO, CO2, CH4 and a part of the H2 (10-20%, according to the
hydrogen recovery factors of commercial PSA) can be recycled to the calciner. These
gases, burned with O2, provide part of the heat for regeneration in case of
oxycombustion-based regeneration, reducing the required primary fuel input.
Modeling needs for PSA can also be highlighted. It is important to understand the
hydrogen recovery factor obtainable when a syngas with a very low content of carbon
species from SE-SMR is processed in a PSA. Since the N2/H2 ratio (associated to N2
content in natural gas) is not improved by SE-SMR process and N2 is often the limiting
species in commercial PSA applications, it is possible that hydrogen recovery factor
cannot be significantly improved despite the higher initial purity. For this reason, SE-
SMR process can take advantage from the development of new PSA sorbents more
active towards N2 than towards carbon species.
• When comparing SE-SMR with conventional processes for H2 production, it is
important to consider the pressure at which H2 is needed by the final user. As a matter
of facts, homogeneous H2 delivery pressures should be assumed when comparing
different technologies. Penalties for SE-SMR-based layouts using low pressure reactors
will arise when high pressure H2 is needed.
40
• Ca/catalyst ratio can be important for the mass and energy balance. Ni-based catalysts
are thermal ballast and can behave as oxygen carrier between calciner and reformer.
This phenomenon should be minimized since O2 produced at high cost with ASU may
react with Ni in the calciner to form NiO and eventually oxidize part H2-rich syngas in
the reformer. Therefore, low catalyst/Ca ratios are desirable.
A lack of modeling and experimental activity to find the minimum catalyst/sorbent ratio
can be highlighted.
• In case of regeneration by heat exchange, it is important to provide sufficient details on
the heat and mass balances (a good example on this issue is the work by Perdikaris et
al., 2009). As a matter of facts, heat transfer of high thermal power at high temperature
under relatively low Ts is a critical process which can lead to large heat transfer
surface operating at high temperature and relatively low fuel utilizations, voltages and
efficiency of the fuel cell of the ZEC/ZECA concepts.
• When calculating power plants based on gas turbines, it is important to use a reliable
model for the gas turbine. As reported by Romano and Lozza (2010a), considering
blades cooling flows can have a really important effect on the estimated overall plant
efficiency when adopting advanced high TIT gas turbines (of the order of 4-5% points).
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Koumpouras, G. C., Alpay, E., Stepanek, F., 2007. Mathematical modeling of low-temperature
hydrogen production with in situ CO2 capture. Chem. Eng. Sci. 62, 2833-2841.
Lee, D. K., 2004. An apparent kinetic model for the carbonation of calcium oxide by carbon
dioxide. Chem. Eng. J. 100, 71-77.
Lee, D. K., Baek, I. H., Yoon, W. L., 2006. A simulation study for the hybrid reaction of
methane steam reforming and in situ CO2 removal in a moving bed reactor of a catalyst
admixed with a CaO-based CO2 acceptor for H2 production. Hydr. Energ. 31, 649-657.
Li, Z-s., Cai, N-s., 2007. Modeling of multiple cycles for sorption-enhanced steam methane
reforming and sorbent regeneration in fixed bed reactor. Energy Fuel 21, 2909-2918.
Lin, S., Harada, M., Suzuki, Y., Hatano, H., 2005. Process analysis for hydrogen production by
reaction integrated novel gasification (HyPr-RING). Energy Conversion and Management,
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43
Cement is a key construction material, and global demand of cement is expected to
grow at around six percent in 2012, amounting to 3.8 billion tons (CW Group, 2012). Cement
industry, one of major CO2 emission source in industry, accounts for 8% out of global CO2
emission in 2011 (Olivier et al., 2012). Carbon emission reduction by more efficient use of fuel
is possible but highly limited to an extent of half of its CO2 emission since significant CO2 is
generated by calcination reaction as well as fuel combustion. Therefore, it is essential to retrofit
a carbon capture process into cement plant if more than 90% reduction of carbon emission at
cement plants would be targeted.
The most conventional capture technologies for cement plants are thought to be amine
process and oxy-combustion since they are considered mature technology or at least ready to be
implemented shortly. But it is likely that an amine process applied to cement plant would have
higher energy penalty than those with power plant since a separate steam boiler is needed for
steam supply to solvent regeneration stripper. If the separate steam cycle could be built in a way
of having such a high complexity as one found in coal-fired power plants, similar energy
penalty can be expected but no one would build a steam cycle with such a high complexity for
the purpose of carbon capture. In case of oxy-combustion, there has been a concern that clinker
quality may be affected by a kiln condition under oxy-combustion. Therefore, up to now, it is
generally accepted that oxy-combustion cannot be applied to kiln but only pre-calciner, which
significantly limits carbon capture rate in overall (IEA, 2008).
It has been argued that Ca-looping processes would have lower net energy consumption
than amine processes since heat of reaction can be recovered by generating steam and running a
steam cycle due to their relatively higher operating temperature. Ca-looping processes may be
even more advantageous when integrated with cement plants than those combined with any
other industrial plants in that their by-products, purge flow from calciner which is needed to
maintain sorbent activity, can be potentially used as kiln feed while they must be dumped as
waste or transferred to other sites in a distance for reuse when combined with power plants.
Since ECRA (2007) listed Ca-looping technologies as one of the promising capture
technologies for cement plants, there have been conceptual studies which proposed various
integration models, such as utilization of purge flow for the cement clinker and synergy between
cement and power plants (Bosoaga et al., 2009; Naranjo et al., 2011). Rodriguez et al. (2011)
proposed a way of producing CO2 from calciner by indirect heating using hot CaO circulating
between calciner and external combustor instead of oxy-combustion. The proposed design
tackles CO2 emission resulting from limestone calcinations only, which accounts for around
60% CO2 emission, and is not effective for CO2 emission relating to fuel combustion. To
44
enhance the performance, it was also suggested that the hot streams leaving the capture system
could be utilized as heat source for electricity generation. It should be noted that there is no
carbonator in this design as distinct from the regular Ca-looping configuration so the CO2 that
both external combustor and kiln generate cannot be recovered in the process, which means that
this process would be worth considering only if a moderate level of CO2 capture is adequate.
The key operating parameters and performances in this process are presented in Table 7.
Even though it was conceivable in earlier studies that the purge CaO could be sent to
kiln to make a clinker, there has been an issue that the deactivated CaO may deteriorate clinker
quality and the factors which can potentially limit or affect the re-use of purge CaO have been
discussed (Dean et al., 2011a). The study raised issues that sulphur conveyed by a purge stream
can lead to expansion and cracking of the cement paste upon hydration and also affects
formation of cement phases. Moreover, the trace elements released from fuel combustion in the
calciner as well as attrition and agglomeration have been identified to be another potential issue
in using purge materials. In the latter work of this group, it has been shown experimentally that
the cement can be successfully produced from the purge by utilizing CaO experienced many
cycles of calcination and carbonation (Dean et al., 2011b).
Given the postulate that the calciner purge can be used as kiln feed, a symbiosis model
of a power plant, a Ca-looping process and a cement plant has been proposed with its mass and
energy balances (Romeo et al., 2011). The flue gases from both plants are sent to the Ca-looping
process, and the CaO purge of this capture unit is returned to cement plant, mixed with CaO
from fresh raw material, and used as kiln feed. In this way, the CO2 emission and energy
consumption of the cement plant can be drastically reduced due to reduced calcinations load.
The surplus energy from the capture unit can be utilized to generate electricity by running a
separate steam cycle. A pinch analysis has been conducted in order to recover maximum energy
from carbonator, solid purge, clean flue gases and CO2 stream before compression. Part of this
electricity has been used for CO2 compression and air separation units. The total thermal energy
consumption increases by about 6.7% for the integrated system due to addition of capture unit.
CO2 emission avoided was estimated to be 94% on a basis of total CO2 emission at both
industries by this integration system, which would add about 12.4 €/ton of avoided CO2.
A similar assessment has been performed by Romano et al. (2012), who considered the
effect of the actual composition of the purge on the maximum “substitution rate” of the cement
plant raw meal. As a matter of fact, large amount of CaSO4 and ashes from coal combustion in
the calciner can limit the maximum amount of CaL purge that can be used in the cement plant.
Such a maximum “substitution rate” strongly depends on the fuel used in the calciner and on the
parameters of the CaL process.
45
As a direct integration of Ca-looping with a cement plant, Rodriguez et al. (2012)
investigated two alternative processes with economic study of both. One is a retrofit replacing
the existing pre-calciner with an oxy-calciner which can achieve 89% CO2 capture and the other
is capturing CO2 from the kiln gas using a carbonator in addition to capturing CO2 by oxy-
calciner to improve capture rate up to 99%. As similar with other Ca-looping processes, the
surplus energies from high temperature streams are recovered by integrated steam cycle. It is
reported that the total energy consumption of cement plant increases from 2.93 GJ/ton of
cement covering the electricity demand to 5.45 GJ/ton of cement by retrofit for carbon capture.
Ca-looping process can also be applied to a gas stream downstream of pre-calciner for
over 90% capture. Flue gas stream leaving the 3rd preheater stage has been identified to be an
optimum feed for a carbonator rather than the end-of-pipe flue gas, since it does not require
preheating, has higher CO2 partial pressure and lower volumetric flow rate (Ozcan et al., in
preparation). The CO2-depleted gas is routed back to 2nd preheater for raw material heating. The
effects of sulfidation and ash have been taken into account in the carbonator model. It has been
represented that this process is capable of achieving more than 90% CO2 capture with additional
energy consumption of 2.3 to 3.0 GJ/ton CO2 avoided by considering heat recovery.
46
Table 7 - Summary of process configuration models on integration of Ca-looping process with cement plants.
Authors Rodriguez et al. (2011) Rodriguez et al. (2012) Ozcan et al. (in preparation) Romeo et al. (2011)
The industrial symbiosis of cement and
Kiln gas is sent to carbonator for carbon Flue gases from the 3rd preheater stage are
Hot CaO circulates between calciner and power plants through Ca-looping process has
capture. All CaCO3 from carbonator and diverted to Ca-looping process. The CO2-
Type of integration CFB combustor. There is no carbonator in been proposed. The flue gases from both
fresh limestone are calcined in one common depleted gas from the carbonator is routed
the scheme. power and cement plants are fed to the Ca-
calciner. back to the 2nd preheater.
looping process.
Capacity of 3000 ton cement/day
3000 ton cement/day 3000 ton cement/day 3000 ton cement/day
reference plant 500 MWe power plant
Petroleum coke was used in kiln and calciner
[wt%]:
C: 85.5
H: 3.5
O: 1.8
S: 5.3
N: 1.8
Petroleum coke used in CFB combustor Petroleum coke used in cement kiln and Ash: 0.3 In the power plant, the coal composition
[wt%]: calciner [wt%]: Moisture: 1.8 [wt%]:
C: 82.2 C: 82.2 But, sulphur content in petcoke for calciner C: 61.6
H: 3.1 H: 3.1 was changed so as to have up to 1% H: 4.9
Fuel (existing plant
O: 0.5 O: 0.5 sulfidation rate in the Ca-looping process. O: 15.5
and calciner) S: 5.5 S: 5.5 N: 1.2
N: 1.9 N: 1.9 Coal is used in the pre-calciner. Ash: 6.7
Composition Ash: 0.3 Ash: 0.3 In the pre-calciner [wt%]: Moisture: 10.1
Moisture: 6.5 Moisture: 6.5 C: 64.5
H: 4.5 No information was given for fuel
18% excess oxygen is used. O: 7.2 compositions used in the kiln and calciner.
S: 0.9
N: 1.4
Ash: 12.0
Moisture: 9.5
10% excess oxygen is used.
Carbonator No carbonator in this system
-
Operating temperature - 650ºC 650ºC 650ºC
Pressure - 1.0 atm 1.0 atm 1.0 atm
F0/FCO2 4.5 0.2 – 5.8 A purge of 3.2% of the total solid inventory
-
47
- is assumed.
FCaO/FCO2 - 1.9 – 5.5 4 (fixed)
Ws - - Ws was set so as to have 0.1 bar ∆P along -
- the carbonator.
u0 - - 6.0 m/s -
Reactor height - - 10.0 m -
Ca conversion CaO conversion: 30 % Approx. 30 % CaO conversion -
Capture efficiency in 33%, it becomes 38% if CO2 emission by - 90% 90%
the carbonator extra electricity is excluded.
Net CO2 avoided - 99% 92- 99% 95.3%
efficiency -
Gas pressure drop - 0.1 bar -
Model used There is no a reactor model implemented. Carbonator modelling (Romano, 2012) There is no a reactor model implemented.
Calciner
Operating temperature 937 °C 950 °C 930 °C 950 °C
Calcination efficiency 100 % calcination 100 % calcination 100 % calcination 100 % calcination
O2 content in oxidant Air used 25 vol% O2 95 % O2 without CO2 dilution -
stream (75 vol% CO2 and H2O)
Assumed that the lower temperature limit for 180 bar/50 bar
A sub-critical steam cycle was chosen. Estimated as an enthalpy generated when
energy recovery is 150 °C. The net thermal 600 °C/600 °C
Steam cycle (120 bar/520 °C/520 °C) cooled down to 150 ºC. The gross steam
efficiency of 33% is estimated for steam A pinch analysis has been conducted to
No steam bleeds are performed. turbine efficiency of 46% was assumed.
cycle. recover maximum amount of surplus energy.
Air separation unit
Electricity
- 160 kWh/tonO2 200 kWh/tonO2 220 kWh/tonO2
consumption
- - 95 vol % O2 -
O2 purity
CO2 compression and
purification
Final CO2 pressure -
100 bar
- 150 bar -
Final CO2 purity > 95 vol % CO2
Compression train - > 95 vol % CO2 -
5 turbo compressors + pump
(Compressor efficiency) - 4 turbo compressors + pump
(75 % isentropic efficiency)
- (75 % isentropic efficiency) -
Overall specific -
consumption 100 kWhe/ton CO2 120 kWhe/ton CO2
-
Results
48
Total power demand - 37.0 MWe 36.0 – 42.0 MWe
(Cement plant + CO2 The total thermal energy consumption of
compressor + Air reference case (power + cement plants)
separation unit + increases 6.7% for the integrated system
Auxiliaries) (power + cement + Ca-looping plants)
Power production by 31.6 MWe 41.0 MWe 33.0 – 71.0 MWe The thermal energy requirement in the
steam cycle cement plant decreases by 39.5% since purge
CaO can be fed to kiln without calcination.
Energy demand of the 3.0 GJ/ton cement 2.9 GJ/ton cement 3.2 GJ/ton clinker
base cement plant
Energy demand of the 6.1 GJ/ton cement 5.5 GJ/ton cement 5.3 – 5.7 GJ/ton clinker
base cement plant +
Ca-looping process
CO2 avoided cost 11.6 $/t CO2 23.0 $/t CO2 30.0 €/t CO2 12.4 €/t CO2
49
Modelling of CaL process for CO2 capture in cement plants has many similarities with the post-
combustion capture from power plant flue gases case. Therefore, the suggestions described in
section 1.2.1 can be extended to this case for both CaL reactors modeling and process
simulation. An additional issue should however be considered for cement plants, related to the
limited variability of the composition of the final clinker, which may limit the maximum
amount of CaL purge to be used in the plant if too rich of CaSO4 and ash.
Bosoaga, A., Masek, O., Oakey, J.E., 2009. CO2 Capture technologies for cement industry.
Energy Procedia 1, 133–140.
CW Group, 2012. Global Cement Volume Forecast Report.
Dean, C.C., Blamey, J., Florin, N.H., Al-Jeboori, M.J., Fennell, P.S., 2011a. The calcium
looping cycle for CO2 capture from power generation, cement manufacture and hydrogen
production. Chem. Eng. Res. Des. 89(6), 836-855.
Dean, C.C., Dugwell, D., Fennell, P.S., 2011b. Investigation into potential synergy between
power generation, cement manufacture and CO2 abatement using the calcium looping cycle.
Energ. Environ. Sci. 4, 2050-2053.
ECRA, 2007. Technical Report: Carbon Capture Technology – Options and Potentials for the
Cement Industry.
IEA, 2008. CO2 Capture in the Cement Industry, July 2008/3.
Naranjo, M., Brownlow, D.T., Garza, A., 2011. CO2 Capture and Sequestration in the Cement
Industry. Energy Procedia 4, 2716-2723.
Olivier, J.G.J., Janssens-Maenhout, G., Peter, J.A.H.W., 2012. Trends in global CO2 emissions;
2012 Report, PBL Netherlands Environmental Assessment Agency.
Ozcan, D. C., Ahn, H., Brandani S., in preparation. Process Integration of a Ca-looping Process
with a Cement Plant for Carbon Capture.
Rodríguez, N., Murillo, R., Alonso, M., Martinez, I., Grasa, G., Abanades, J.C., 2011. Analysis
of a process for capturing the CO2 resulting for pre-calcination of limestone in a cement plant.
Ind. Eng. Chem. Res. 50 (4), 2126–2132.
Rodriguez, N., Murillo, R., Abanades, J.C., 2012. CO2 Capture from Cement Plants Using
Oxyfired Precalcination and/or Calcium Looping. Environ.Sci. Technol. 46 (4), 2460-2466.
Romano, M.C., 2012. Modeling the carbonator of a Ca-looping process for CO2 capture from
power plant flue gas. Chem. Eng. Sci. 69 (1), 257-269.
50
Romano, M.C., Spinelli, M., Campanari, S., Consonni, S., Cinti, G., Marchi, M., Pimpinelli, N.,
2012. The Calcium looping process for low CO2 emission cement and power. GHG-11
conference, November 2012, Kyoto, Japan.
Romeo, L.M., Cataline, D., Lisbona, P., Lara, Y., Martinez, A., 2011. Reduction of greenhouse
gas emissions by integration of cement plants, power plants, and CO2 capture systems.
Greenhouse Gas Sci. Technol. 1, 72-82.
51
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