Energy 117 (2016) 604e611

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Energy
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A comparison of CO2 mineral sequestration processes involving a dry

or wet carbonation step
Ron Zevenhoven a, *, Martin Slotte a, Jacob Åbacka a, 1, James Highfield b
a
Åbo Akademi University, Thermal and Flow Engineering, Turku, Finland
b
Institute of Chemical and Engineering Sciences, ICES/A*Star, Singapore

a r t i c l e i n f o a b s t r a c t

Article history: CO2 mineral sequestration is one method of the CCUS (carbon capture, utilisation and storage) portfolio,
Received 30 October 2015 and work on stepwise carbonation of serpentinites (serpentine-rich rock, 3MgO$2SiO2$2H2O) in Finland
Received in revised form has resulted in what is known as “the ÅA (Åbo Akademi) route”. This involves extraction of magnesium
11 May 2016
from rock using ammonium sulphate salt, precipitation of magnesium hydroxide and finally carbonation
Accepted 14 May 2016
Available online 3 June 2016
in a high temperature pressurised fluidised bed. Besides magnesium carbonate (MgCO3) significant
amounts of iron (hydr)oxides are produced. Disadvantages are the complexity and exergy consumption
associated with alternating (hot/cold/hot) treatment conditions. Therefore, an alternative ÅA route has
Keywords:
CO2 sequestration
been developed that, like the conventional route, can operate directly on flue gas. Here, the final
Gas/solid vs. aqueous solution carbonation carbonation step is accomplished in an aqueous solution. Products are magnesium (hydrocarbonates),
Serpentinite hydromagnesite (4MgCO3$Mg(OH)2), besides iron (hydr)oxides. Early results obtained with this route
Energy penalty method are reported, along with a comparison (using process simulation) of the both routes, operating
on flue gas from: 1) a lime kiln and 2) a natural gas fired power, addressing the external heat and power
input requirements. It was found that conversion levels and rates are similar for the two routes, although
excess NH3 may be needed to establish the working pH for hydromagnesite precipitation.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction and scope
1.1. CO2 mineral sequestration: the “Åbo Akademi route”
The very slow deployment of carbon capture and storage, CCS
(or more generally, carbon capture, utilisation and storage, CCUS)
based on underground storage of pre-separated CO2 and the
absence of suitable underground storage capacity at many locations
are some of the drivers of CO2 mineral sequestration, or mineral
carbonation technology development [1,2]. One important advan-
tage of the technology is its amenability to process flue gas (or other
CO2-containing gas) directly without an expensive CO2 pre-
separation (“enrichment”) step. Besides avoiding a significant en-
ergy input penalty, mineralization is chemically irreversible on a
geological time-scale, and the problem of O2-containing gas
degrading the amine solvent at typical wash temperatures is also
side-stepped [3].
* Corresponding author. Tel.: þ358 2 2153223.
E-mail address: ron.zevenhoven@abo.fi (R. Zevenhoven).
1
Currently with W€ artsil€
a Moss AS, Norway.
For more than a decade, work on stepwise carbonation of ser-
pentinites (rock rich in serpentine, 3MgO$2SiO2$2H2O) in Finland
has resulted in what has become known as “the ÅA (Åbo Akademi)
route” e see e.g. Refs. [4,5]. This involves extraction of magnesium
ion, Mg2þ, from the rock using a solid/solid reaction with AS
(ammonium sulphate) salt, producing water-soluble magnesium
sulphate. This aqueous extract is converted into magnesium hy-
droxide precipitate using ammonia vapour released from the solid/
solid reaction. Finally, the isolated magnesium hydroxide is
carbonated in a pressurised fluidised bed reactor. Besides magne-
sium carbonate, MgCO3, significant amounts of iron (hydr)oxides
are also produced. Fig. 1 gives a schematic of the procedure. Note
that more recently the focus has moved to processing on flue gases
directly [4,6], avoiding a CO2 pre-separation step.
The three reaction steps can be summarised (and simplified) as
follows:
Mg3Si2O5(OH)4 (s) þ 3(NH4)2SO4 (s) / 3MgSO4 (s) þ 2 SiO2 (s)
þ 2H2O(g) þ 2NH3(g) (R1)
at 400e440  C; DH298 ¼ þ245 kJ/mol Mg,

http://dx.doi.org/10.1016/j.energy.2016.05.066
0360-5442/© 2016 Elsevier Ltd. All rights reserved.
 R. Zevenhoven et al. / Energy 117 (2016) 604e611 605

Fig. 1. The “conventional” Åbo Akademi route for magnesium silicate rock carbonation. (dark arrows: solid material, light: aqueous, white: gas, AS ¼ ammonium sulphate) [5].

MgSO4 (s) þ 2H2O (l) þ 2NH3 (g) / Mg(OH)2 (s) þ (NH4)2SO4 (aq)(R2) complicated sequence involving a hot solid/solid reactor (Mg2þ
extraction) followed by aqueous precipitation reactors (Mg and Fe
at near ambient conditions; DH298 ¼ 153 kJ/mol Mg hydr(oxide) production), and finally a pressurised fluidised bed gas/
solid reactor (carbonation). For this reason an “alternative” ÅA
Mg(OH)2 (s) þ CO2 (g) / MgCO3 (s) þ H2O (g) (R3) route is being explored that can also operate directly on flue gas e
see Fig. 2. Here, the precipitation and carbonation steps are coupled
at ~ 500  C, 20 bar CO2; DH298 ¼ 64 kJ/mol Mg. in a low temperature aqueous solution process in which the pri-
mary reaction intermediate (a solution of Mg2þ and SO4 2 ions) is
The magnesium source rock used for the work reported here is a
carbonated directly by addition of NH4OH (recycled NH3 as before)
serpentinite that is available as overburden from a nickel mine at
while sparging with flue gas. Depending on temperature, the
Hitura, Finland. It is composed of ~83%-wt serpentine
products are magnesium (hydrocarbonates), primarily nesque-
Mg3Si2O5(OH)4, ~14%-wt iron oxides (FeO/Fe2O3/Fe3O4) and ~3%-wt
honite (MgCO3$3H2O) and hydromagnesite (4MgCO3$Mg(OH)2),
other compounds (CaSiO3, MnO, etc.). This corresponds to 21.8%-wt
besides iron(hydr)oxides.
Mg, 10.1%-wt Fe, 0,34%-wt Ca and 11.6%-wt Si.
The chemistry for this process scheme involves reaction (R1) as
The heat generated by the carbonation is ~1/3 of the heat that is
mentioned above, followed by
needed for the magnesium extraction, making it necessary to use
(waste) heat from, preferably, the process that generates the CO2. In
5MgSO4 (s) þ 10H2O (l) þ 10NH3 (g) þ 4CO2 (g)
addition, compressing the entire flue gas requires a significant
/ Mg5(OH)2(CO3)4$4H2O (s) þ 5(NH4)2SO4 (aq) (R4)
power input that in large measure can be recovered by expanding
the “CO2-free” vent gas. For the carbonation process it has been
at near ambient conditions; DH298 ¼ 217 kJ/mol Mg.
shown experimentally that a simulated flue gas and pure CO2 give
Note that the “alternative” ÅA route involves a simpler CO2
similar carbonation results for a given CO2 partial pressure [4,6].
contacting stage (to a low temperature aqueous solution)
Previous work describes the production of Mg(OH)2 from
compared to a route (still being?) developed in the U.K. by Maroto-
magnesium silicate rock [7e10], the subsequent carbonation of the
Valer and co-workers [19,20], as shown in Fig. 3.
Mg(OH)2 [11e14] and the energy efficiency when aiming at a useful
In the ÅA route, no chilled ammonia needs to be injected into
iron-containing by-product [15]. Below, some details on process
the flue gas channel. In the latter (U.K.) route (which has similarities
parameters are summarised.
with that described and patented earlier by Hunwick [21,22]), ABS
In a recent case study for an industrial lime kiln it was found
(ammonium bisulphate) is used to extract magnesium ion from
that the heat input requirements were completely satisfied by
silicate rock in a hot (~90  C) aqueous solution during 1e3 h. The
waste heat from the lime kiln, while a power input of 0.9 MJ/kg
(dissolved) magnesium ion is then carbonated at a similar tem-
CO2 fixed was determined primarily by the flue gas (kiln product
perature with AC/ABC (ammonium (bi-) carbonate), which is pro-
gas) compression stage [16,17]. The same case study was earlier
duced by reacting NH3 with a humid CO2-containing (flue) gas at
reported for an application to CO2 pre-separated from flue
10  C. Regeneration of the ABS for reuse requires a heat-driven
gas [18].
conversion of the dissolved AS (ammonium sulphate) to NH3 (for
Clearly, the energy input requirements of this CCS/CCUS method
CO2 capture reuse) and ABS at 330  C. This latter step puts an en-
depend very much on the CO2-producing process it is applied to
ergy penalty on the process of the order of 1.3 kWh/kg CO2 (4.7 MJ/
and should be integrated with. Just as for any other CCS/CCUS
kg CO2) at 330  C, i.e., an exergy requirement of 2.4 MJ/kg CO2 (at
process, the question “how much energy does this mineral
Tsurroundings ~ 15  C) due to the additional energy-demanding
carbonation process require” is difficult to answer when the CO2
dewatering of the dissolved AS salt prior to NH3
producer is not defined.
evolution (Exergy calculation is addressed in Section 3.1 below.).
In this paper, the above-summarized “conventional” ÅA route is
The extraction, capture, and carbonation stages of the UK route
compared to an “alternative” route (summarized below) as applied
produce 1.5 kWh/kg CO2 (5.4 MJ/kg CO2) at 80e90  C (i.e., an exergy
to two industrial applications.
generation of 1.0e1.1 MJ/kg CO2). A heat pump may be used to raise
the temperature of the generated heat to the level needed for the
1.2. CO2 mineral sequestration: the “alternative” Åbo Akademi ABS salt regeneration. Under favourable conditions, 95.9% of the
route magnesium in serpentine is converted to hydromagnesite
(Mg5(CO3)4(OH)2$4H2O). Assessing the performance of the ÅA
One disadvantage of the conventional ÅA route is the somewhat routes vis-a-vis the U.K. route was a side-goal of the work reported
606 R. Zevenhoven et al. / Energy 117 (2016) 604e611

Fig. 2. The “alternative” Åbo Akademi route for magnesium silicate rock carbonation. (dark arrows: solid material, light: aqueous, white: gas, AS ¼ ammonium sulphate).

Fig. 3. The Nottingham/Heriot-Watt route for magnesium silicate rock carbonation. (dark arrows: solid material, light: aqueous, white: gas, AS ¼ ammonium sulphate,
ABS ¼ ammonium bisulphate, AC ¼ ammonium carbonate, ABC ¼ ammonium bicarbonate) [5].

below. stable at reaction temperatures of ~500  C where chemical kinetics

1.3. Aim of this paper
In this paper some results on producing (hydro-)magnesites by
the alternative (“wet”) ÅA route are reported, followed by a com-
parison of the two ÅA process routes operating on flue gas from two
CO2 producers: 1) the process gas from a lime kiln in Finland and 2)
a natural gas fired power plant in Singapore. The energy penalty
assessment focuses on a comparison of the external heat and power
input requirements for these 2  2 test cases, while the implica-
tions of direct carbonation by contacting the untreated flue gas
with an aqueous solution are also considered. Table 1 gives the flue
gas compositions (limited to CO2, O2 and N2) for the processes as
used in the calculations reported here. Additional complications
arising from possible contaminants like SOx, NOx and CO are not
considered.
In the lime kiln gas the total pressure in the carbonator is 80 bar
while for the natural gasefired PP (power plant) it will be 400 bar
(see also Khoo et al. [23]), in both cases giving a CO2 partial
entrance pressure of 20 bar. Under these conditions, MgCO3 is
Table 1
Simplified flue gas compositions used for the calculations (mol-% ¼ vol-%).
Natural gas turbine
CO2 (dry) 5.20
O2 (dry) 11.47
N2 (dry) 83.33
H2O Not considered
can be considered acceptably fast. However, calculations for
carbonation at 80 bar total pressure for the natural gasefired PP
(for ease of comparison with the lime kiln) will also be presented.
For comparison with earlier work [17,18] the amount of rock
processed is 550 kg/h (optimised for the waste heat available at the
lime kiln), enabling the sequestration of ~190 kg CO2/h. Aspen Plus
(v. 7.2) was used for the process simulations.
2. Two ÅA carbonation routes: experimental work
In view of the scale of CO2 sequestration anticipated, the main
feasibility criterion for the plant is avoidance of unwieldy (large)
reactors. This translates into a key process goal of attaining as high a
conversion level as possible (ideally >80%) within 1 h.
2.1. The “conventional” ÅA route: dry carbonation of Mg(OH)2
A key benefit of this path is that the heat generated during the
(exothermic) carbonation stage can be fed back into the (endo-
thermic) Mg extraction stage. Experimental findings so far show
that our “in-house” serpentinite-derived Mg(OH)2 samples
perform better during carbonation, mainly as a result of a much
higher specific surface area (>40 m2/g) as compared to commercial
Mg(OH)2 samples (<10 m2/g) [13,24]. The origin (quality) of the
Lime kiln serpentinite determines (via its iron content) the optimal condi-
23.32 tions for Mg extraction, but the properties of the Mg(OH)2 pro-
7.60 duced are otherwise practically identical. Iron-based impurities
70.39 (visible as yellow discolouring) result in a lower specific surface
6.00
area and hence a lower carbonation reactivity.
 R. Zevenhoven et al. / Energy 117 (2016) 604e611
An Mg(OH)2 produced from a Lithuanian serpentinite was
carbonated up to 65% in 15 min in 51 bar pure CO2, while 70.3%
conversion in 30 min was obtained with Mg(OH)2 produced from
Portuguese rock at 510  C, 20 bar pure CO2, size fraction < 74 mm.
Typical reaction temperatures for the serpentinite/AS salt reaction
are somewhat lower, at 400e440  C as to avoid decomposition and
sublimation “losses” of the AS salt, as recently reported [25].
A drawback of using a fluidized bed is that it puts restrictions on
the particles size: the serpentinite-derived samples typically have
large amounts of particle size fractions <20 mm while most PFB
(Pressurised fluidised bed) tests were done with size fraction
74e125 or 125e212 mm.
With process times for Mg(OH)2 production from serpentinite of
the order of 30 min it can be concluded that total process times
from rock to carbonate can be accomplished in less than 1 h.
However, chemical conversion levels obtained are limited, The best
recovery of Mg (as carbonate) from serpentinite, expressed as “Mg
extracted (as Mg(OH)2)  Mg(OH)2 carbonated” so far is 80%  70%,
giving 56% overall. Our goal is to reach 90%  90% conversion levels.
Note, however, that for the wet process, e.g., via hydromagnesite
4MgCO3$Mg(OH)2, the maximum possible carbonation conversion
of Mg is only 80%.
As regards the salt used for the Mg extraction, recent work by
Rom~ ao et al. [26] has shown that ammonium bisulphate (ABS) gives
a 40% lower energy input requirement for Mg extraction than AS
(ammonium sulphate) as used in the work reported here. However,
this benefit is more than offset by an energy penalty that results
from thermally converting AS into ABS for re-use.
2.2. The “alternative” ÅA route: wet carbonation of aqueous MgSO4
As an alternative to the “conventional” ÅA route, as described
above, a modified process route has been analysed [27,28] e see
Fig. 2. This route combines the precipitation and carbonation of
magnesium ion into one step, thus simplifying the process. When
all unreacted rock, SiO2 and Fe(hydr)oxides have been removed
from the stream, the MgSO4 solution is exposed to a constant
stream of CO2 containing flue gas. The reaction between MgSO4 and
CO2 cannot proceed at the acidic pH typical of the extract. However,
addition of NH3 (a product of reaction R1) raises the pH sufficiently
to initiate precipitation of magnesium (hydro)carbonates. The AS
produced is recovered and recycled back to the extraction step (as
in the “conventional” ÅA route). Direct formation of MgCO3, the
ideal product, is kinetically inhibited at low temperatures, Instead,
hydrocarbonates such as hydromagnesite (Mg5(CO3)4(OH)2$4H2O),
nesquehonite (MgCO3$3H2O) and lansfordite (MgCO3$5H2O) are
typically formed. The last two are favoured at temperatures (CO2
pressures) in the range 30  C (0.01 bar CO2) to 50  C (1 bar CO2).
Above 50  C hydromagnesite starts to form [29]. Fig. 4 illustrates
the experimental procedure using aqueous solutions at room
temperature, starting with a solution of dissolved sulphate after the
thermal extraction using AS salt and filtration to remove unreacted
rock and quartz. Both TGA (thermogravimetric analysis) and XRD
(X-ray diffraction) confirmed that the carbonate product from a
series of 10 experiments starting with a commercial MgSO4 was
hydromagnesite [27,28].
On the path towards a functional and more continuous process,
work has been performed with (Mg,Fe)SO4 solutions extracted
from the AS/serpentinite reaction at 440  C while the released NH3
was used as base in the pH swing stage, raising the pH to promote
magnesium salt reaction with CO2. The main challenges to over-
come are achieving a sufficiently high carbonation degree of the Mg
present in the rock while simultaneously minimising losses of
ammonium sulphate throughout the process.
The full experimental set-up with a lab-scale rotary kiln
607
(Carbolite HTR11/75) and typical solution pH values is shown in
Fig. 5. Also shown on the right are product samples from processing
with or without iron (hydr)oxides separation, giving either one
skin-coloured product, or separated dark brown (iron) and white
(carbonate) products.
Preliminary tests showed that pH ¼ 10 is suitable for hydro-
magnesite precipitation. However, a pH level of just 9.62 was
reached with the set-up shown in Fig. 5, and some make-up NH4OH
(aqueous ammonia) was needed to attain a starting pH ¼ 10. Four
experiments were done: three without separation of iron before
carbonation, and one where the iron was removed before sparging
the solution with CO2. The products obtained were iron carbonate
(siderite) mixed with hydromagnesite, and iron oxyhydoxide
(goethite) separate from hydromagnesite, respectively e see the
product samples Fig. 5. At the end of the experiments the pH had
decreased to 8.0e8.2. For the first three tests the combined (Fe and
Mg) carbonation efficiency varied from 53 to 88%, while for the
carbonation of the iron-free solution the magnesium carbonation
efficiency was 72% [28]. For future work, the ammonia balance and
the need of a certain level of make-up (buffer) solution must be
carefully addressed and minimized since it defines the stoichio-
metric excess of AS (and associated cost factor) in the upstream
extraction.
3. Two ÅA carbonation routes: process simulations
3.1. The “conventional” route ÅA-dry carbonation of Mg(OH)2
While results obtained with the route given in Fig. 1 involving
pre-separated CO2 have been reported extensively elsewhere (see
theses [10,14] and recent paper [25]), direct operations on flue gas
at ÅA have been reported only more recently (since 2012 [6]).
Compression of the complete flue gas (followed by expansion of
the gas from the carbonator) is one of the requirements, as
addressed by Slotte [16,17], applying the Aspen Plus model given in
Fig. 6 to lime kiln flue gas (see Table 1). The Figure (taken from Ref.
[17]) shows the process units grouped into five sections: A ¼ solid/
solid extraction of Mg from rock, B ¼ dissolution and precipitation
of Mg(OH)2, C ¼ AS salt recovery by crystallisation, D ¼ carbonation
of Mg(OH)2 with pre-heating and power production through
expansion and E ¼ the flue gas compression.
More detail on (E) is given in Ref. [17], while the effect of
increasing compression stages is summarized in Ref. [16]. Here,
five-stage compression with intercooling is used.
Process calculation results for this route, applied to both a lime
kiln flue gas (operated at 80 bar total pressure for the carbonator)
and a natural gas-fired PP (power plant) (400 bar total pressure for
the carbonator) are given in Table 2.
Table 2 gives overall energy input requirements as exergy, Ex,
further distinguishing between the exergy of heat Q, and power P,
based on overall values that follow from the Aspen Plus process
simulations. For a certain amount of heat, Q, at temperature T(K), at
temperature of the surroundings T, the exergy follows from:

 X

T T
ExðQ Þ ¼ Q $ 1  or ExðQ Þtotal ¼ Qi $ 1  (1)
T T
i
for i streams with temperature Ti. This quantifies for how much
useful work may be obtained by converting this heat into power,
taking into account the quality of the heat as given by its temper-
ature with respect to the surrounding environment. For power, P,
the exergy is equal to the energy:
608 R. Zevenhoven et al. / Energy 117 (2016) 604e611

Fig. 4. Illustration of separate precipitation of FeOOH and carbonation of Mg using (Mg,Fe)SO4 from AS/S reaction. (the slight yellow tinge at lower left suggests that the separation
of iron compounds was incomplete.).

Fig. 5. (Left)- Experimental setup for separate FeOOH precipitation and Mg carbonation using ammonia from AS/S reaction; (right)- solid products from Fe and Mg precipitated/
carbonated together (one sample) versus separately precipitated FeOOH and carbonated Mg (two samples).

X before each compression step.

ExðPÞ ¼ P or ExðPÞtotal ¼ Pj (2) For processing lime kiln gas, heat available from the kiln flue gas
j is sufficient for covering process heat requirements. While for the
dry carbonation process at the natural gas-fired PP a full recycling
for j power input streams Pj. In Table 2 the overall values are given, of ammonium salt can be achieved, a make-up of 4 kg/h of the salt
adding up all inputs and subtracting all outputs. The exergy of is necessary for both the dry and wet process at the lime kiln. For
enthalpy streams are calculated from enthalpy, H(p,T), and entropy, the recovery of the salt the natural gas-fired PP, heat obtained from
S(p,T) values (as function of temperature T and pressure p) from the the heat exchanger indicated with * in Fig. 2 was used, integrated
Aspen Plus output using: with section C of the simulation model. (This heat was not used for
the lime kiln case.)
ExðHðT; pÞÞ ¼ DHðp ; T  /p; TÞ  T  $DSðp ; T  /p; TÞ
¼ ðH  H Þ  T  $ðS  S Þ (3) 3.2. The “alternative” ÅA route: wet carbonation of aqueous MgSO4

with surroundings conditions T ¼ 288 K, p ¼ 1.01325 bar [29].
The following assumptions were made for the Aspen Plus
modelling of this process route: the simulations use the “process
type” as “common” and the “base method” “electrolyte”. The
dissolution of sulphates after the serpentinite/AS solid/solid reactor
takes place at 80  C and pH 7.36, the iron and calcium hydroxides
are precipitated in the next step at 30  C and pH 5.5. (The latter
value is surprising since the streams entering this precipitator have
pH values 7.36 and 10.4, respectively.) The compressors operate at
the same pressure ratio of 2.4 when operating at 80 bar and 3.31
when operating at 400 bar. In both cases the gas is cooled to 40  C
The Aspen Plus model shown in Fig. 7 was used for simulation of
the “alternative” route. This doesn't require high pressure operation
of the carbonator, but at the penalty of not generating heat from the
carbonation reaction at a useful temperature.
The following additional assumptions were made for the Aspen
Plus modelling of this process route: an important assumption/
change was implemented for the modelling of the wet process
carbonator: since the equilibrium reactor (RGibbs) model calculates
oxidation of flue gas nitrogen, the N2 content of the flue gas is
replaced by a 60% vol./40% vol. mixture of neon and argon, giving an
inert gas with molar mass 28 g/mol. The carbonation reaction takes
 R. Zevenhoven et al. / Energy 117 (2016) 604e611 609

Fig. 6. Aspen Plus model of the dry/wet/dry carbonation process: the “alternative” ÅA route (Process sections A,B, …E defined in the text; Heat exchanger *: see text).

Table 2
Process simulation results for two ÅA carbonation routes and two flue gas types.

Serpentinite Flue gas Mg-product out,a kg/ Flue CO2 Exergy input Exergy input Exergy input Exergy input
rock in, in, h gas bound, heat power heat, power,
kg/h kg/h (T  C) Out, kg/h kW kW MJ/kg CO2 bound MJ/kg CO2 bound
(T  C) (T  C) kg/h
(T  C)

Dry carbonation, 550 620 386 489 187 135c 46 2.6b 0.89
lime kiln (15) (500) (150) (92)
Dry carbonation, 550 2427.4 385.8 2240.6 187 691d 439 11.44d 8.27
natural gas PP (15) 500 (150) (18)
(400 bar)
Wet carbonation, 550 620 353 400 190 814c 0 15.4c 0
lime kiln (15) (500) (30) (30)
d d
Wet carbonation, 550 2425.5 353.2 2294.2 189 635 0 12.1 0
natural gas PP (15) (500) (30) (30)
a
MgCO3 for dry carbonation, Mg5(CO3)4(OH)2$4H2O for wet carbonation.
b
This heat can be obtained from 28,620 kg/h lime kiln flue gas, lowering the temperature from 500  C to 380  C.
c
This heat can be obtained from 39,400 kg/h lime kiln flue gas, lowering the temperature from 500  C to 362  C.
d
This heat can be obtained from 28,500 kg/h flue gas, lowering the temperature of the gas from 500  C to 380  C. (It is assumed that while 2427.4 kg/h flue gas is processed in
the carbonation process, a larger flue gas of at least 28500 kg/h is produced by the power plant.)

place at 30  C and pH 8.9. Magnesium is extracted from serpentinite
rock using ammonium sulphate in a heated solid/solid reactor
(operated at 440  C), just as in the “conventional” ÅA route. The
water-soluble products from the reactor are dissolved in water and
the rest is removed from the process (“unreacted solids”) by
filtration. Gradually raising the pH of the solution using ammonia
released during the extraction, the other components (primarily
iron (hydr)oxides) are precipitated first (“precipitate 1”) leaving
only magnesium sulphate in solution.
The carbonation reaction takes place at 30  C in order to pro-
duce hydromagnesite and other hydrated magnesites like nesque-
honite and lansfordite (see the phase diagram in Ref. [30]). The
magnesium sulphate solution (containing also the ammonia
released from the extraction reactor) is fed into the carbonation
reactor together with flue gas. Carbon dioxide in the flue gas
equilibrates in water where it reacts rapidly with magnesium ion to
610 R. Zevenhoven et al. / Energy 117 (2016) 604e611
Fig. 7. Aspen Plus model of the dry/wet-wet carbonation process: the “alternative” ÅA route.
Fig. 8. Magnesium carbonate phase equilibrium at 30  C, 1 bar (gas phase 0.2 kmol
CO2 þ 0.2 kmol NH3).
precipitate magnesium hydrocarbonates at the alkaline pH (¼ 10)
established by the dissolved ammonia. The chemical equilibrium
for the magnesium carbonate phases was calculated using HSC 5.1
[31]: see Fig. 8 for the results. (The initial concentrations were set at
0.083 kmol MgSO4 (dissolved in water), 0.2 kmol NH3 gas and
0.2 kmol CO2 gas at 30  C.)
The magnesium extraction process requires heat at
T ¼ 400e480  C (here taken ¼ 440  C), for the heating of the re-
actants and to cover the reaction heat of 1.70 MJ/kg CO2 and
1.88 MJ/kg CO2, respectively. By using the high temperature heat of
the incoming flue gas, the external heat needed to heat the re-
actants can be lowered to 1.47 MJ/kg CO2. The carbonation process
releases 1.15 MJ/kg CO2 at 30  C, i.e. zero exergy if 30  C is also the
ambient temperature (see Table 2). The recovery of ammonium
sulphate for the material needed here requires 1.283 MJ heat/
kg CO2 at 140  C. This can be reduced to 0.059 MJ heat/kg CO2 by
using heat from the flue gas and from the hot steam coming from
the recovery process. According to the simulations it is possible to
recover 820 kg (99.5%) of the ammonium sulphate used to extract
the magnesium. This is comparable with reporting by Nduagu et al.
([9], Table 1).
When evaluating the “alternative” route with flue gas from a
natural gas fired turbine some difficulties arose. The flue gas from a
natural gas fired turbine is significantly different in the
concentrations to that of flue gas from a lime kiln (See Table 1). Note
that the conditions in the carbonator should prevent the decom-
position or oxidation of the ammonia. However, (similar to the
chilled ammonia process for CO2 capture from flue gas) there is a
risk of some NH3 leaving the carbonator reactor with the vent gas.
This was calculated to be 0.124 kmol NH3/kmol CO2 (0.048 kg/kg)
which would have to be compensated with “make-up” NH3 in order
to keep the process running. However, since such ammonia emis-
sions are unacceptable a technical solution is needed that prevents
these losses.
4. Conclusions
In this paper, two mineral carbonation routes producing either
magnesite or (hydro)magnesites are described and experimental
results reported. This is followed by a comparison of the two Åbo
Akademi process routes, operating directly on flue gas (i.e. no CO2
capture step) from two CO2 producers: 1) a lime kiln in Finland and
2) a natural gas fired power plant in Singapore. It was found
experimentally that conversion levels achievable and rates are
similar for the two routes, though perhaps slightly better for the
“alternative” (wet) route producing hydromagnesite. The dry
carbonation route with lime kiln gas has the lowest exergy demand
of the processes considered (2.6 GJ heat and 0.9 GJ electricity per
ton CO2), and significantly better than the wet process route
(15.4 GJ heat per ton CO2). However, the wet route has a zero exergy
input as power, requiring only (waste) heat. For both lime kiln cases
the heat required can be obtained from the kiln gas while the wet
process route does not require flue gas compression. When flue gas
from a natural gas fired power plant is to be treated the exergy
demand on the CCUS plant is significantly larger than the lime kiln
(11.4 GJ heat and 8 GJ electricity per ton CO2 for a dry process, or
12.4 GJ heat for the wet process) due to the much larger amounts of
gas being treated. For the wet carbonation process route a potential
risk of excessive NH3 losses with processed flue gas must be
prevented.
Acknowledgements
This work was partly supported by the Tekes Finland/A*Star
Singapore project “Novel Low Energy Routes to Activate Minerals
for Large-scale Carbonation for Useful Product” NEACAP (2010-
2014), project numbers Tekes 40300/10, ICES 1-413A01. M.S. ac-
knowledges the Academy of Finland's Graduate School of Energy
Efficiency and Systems (2012-2015) for financial support.
 R. Zevenhoven et al. / Energy 117 (2016) 604e611 611

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