Fuel Processing Technology 166 (2017) 209–216

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Fuel Processing Technology

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Research article

Aqueous mineral carbonation for CO2 sequestration: From laboratory to

pilot scale
Nassima Kemache, Louis-César Pasquier ⁎, Emmanuelle Cecchi, Ikbel Mouedhen,
Jean-François Blais, Guy Mercier
Institut National de la Recherche Scientifique, Centre Eau Terre et Environnement, 490 rue de la Couronne, Québec, QC G1K 9A9, Canada

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

Article history: In the actual context of the greenhouse gases (GHGs) control, the industrial sector must find efficient and prac-
Received 29 November 2016 tical solutions to reduce their emissions. The feasibility of an aqueous mineral carbonation (MC) process was
Received in revised form 17 May 2017 demonstrated at the laboratory scale under original mild conditions. In the continuity of this research, the process
Accepted 5 June 2017
was tested at a pilot scale using a cement plant flue gas comprising of 12% to 20% CO2. Experiments were per-
Available online 16 June 2017
formed in an 18.7 L Parr reactor. Two different magnesium (Mg) rich tailings were used during the MC reactions
Keywords:
with a solid/liquid ratio of 150 g/L, gas/liquid ratio of 3, room temperature (22 ± 3 °C) and a stirring speed of
Aqueous mineral carbonation 600 rpm. The total pressure ranged between 2 and 10 atm. Each experiment comprised of six batches of gas
CO2 sequestration with a residence time of 15 min to 30 min each for the liquid and 90 min for the solid. The results demonstrated
Pilot scale that at low pressure (2 and 4 atm), between 90% and 96% of the CO2 in the flue gas can be removed under dis-
Cement plant flue gas solved form. The rate decreased to 64–74% at 10 atm. The cumulative quantity of dissolved CO2 after six batches
of treated gas increased with CO2 partial pressure and from 0.08 to 0.25 g CO2/g of residue. The magnesium (Mg)
leaching followed the same trend as the captured CO2 quantity. The higher cumulative leaching rate for the mag-
nesium was 19%. These results were lower than those expected compared to the laboratory scale. The results
showed that 25% to 33% of the total dissolved CO2 was captured as nesquehonite (MgCO3·3H2O) of a high purity.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
Emissions of greenhouse gases (GHGs) are constantly increasing
with ever-growing energy needs. According to the International Energy
Agency, rising worldwide energy demand could reach 50% by 2030. This
increase implies a consequent increase in CO2 emissions, since 80% of
current total energy is provided by fossil fuels [1]. Despite the different
conferences and protocols agreements to force GHG emitters to reduce
their emissions, technical solutions remain limited against complexity
and the urgency of the situation. Among the alternatives currently avail-
able, mineral carbonation (MC) is a promising avenue, as it offers long
term CO2 sequestration. MC is a chemical reaction between CO2 and di-
valent cations such as Mg2+/Ca2+, which can be found in natural rocks
such as serpentinite, olivine (magnesium silicates) and wollastonite
(calcium silicate) [2–4]. They can also be found in alkaline industrial res-
idues such as steelmaking slags [5,6]. The reaction is part of the natural
phenomena known as the weathering process [7]. The formation of a
very stable carbonate during MC is an exothermic reaction. However,
the slow kinetic reaction remains a major barrier for its industrial appli-
cation. Several studies have been conducted at the laboratory scale to
⁎ Corresponding author.
E-mail address: louis-cesar.pasquier@ete.inrs.ca (L.-C. Pasquier).
improve this aspect. Before the formation of carbonates, several ele-
mentary steps occur. In the case of aqueous mineral carbonation, the
dissolution of CO2 in water is the first one. It is mostly controlled by
the partial pressure and the solution pH [8]. The second one is alkaline
solid dissolution and the release of the divalent cations [9]. Finally, the
precipitation of the thermodynamically stable carbonate occurs. Gener-
ally, the dissolution of silicates is considered as the rate-limiting step
[10] and, therefore, most efforts were concentrated on improving this
step. One of the most common methods used to improve the dissolution
rate of Mg silicates is comprised of several physical treatments, such as
grinding and particle size reduction in order to increase the specific sur-
face area [11] and, in the specific case of serpentine minerals, heat-treat-
ment at 600–650 °C to remove the hydroxyl groups surrounding Mg
atoms. Both treatments result in a partial amorphization of the struc-
ture, thereby increasing the magnesium leaching. The pH-swing route
proposes using inorganic/organic acids, such as NH4HSO4 to improve
the dissolution of serpentine. During this first step, the leached magne-
sium is separated from the other elements by precipitation of the iron
and the silicone after adding the aqueous ammonia. This step is follow-
ed by a carbonate precipitation at a high pH by adding NH4HCO3 and
NH3 [12,13]. The ammonium salts were also used by Nduagu et al.
[28] to produce the more reactive Mg(OH)2 at 400–450 °C from
serpentinite. The advantage of using the pH-swing route lies in the

http://dx.doi.org/10.1016/j.fuproc.2017.06.005
0378-3820/© 2017 Elsevier B.V. All rights reserved.
210 N. Kemache et al. / Fuel Processing Technology 166 (2017) 209–216
possibility of optimizing the two steps (leaching and precipitation) sep-
arately but its feasibility relies on the acids' regeneration and their asso-
ciated energy requirements [14]. Another way to improve the leaching
rate is to operate under high pressure and high temperature. However,
this process could be too energy intensive, and thus limit its implemen-
tation at an industrial scale [15]. In addition, the methodologies previ-
ously discussed mostly focused on reacting a pure CO2 stream.
Nowadays, operations on diluted flue gas have gained in interest. In
fact, it would prevent/avoid the capture step, and thus reduce the ener-
gy penalty, increasing the applicability potential [16–18]. Pasquier et al.
[4] performed experiments at the laboratory scale using mining resi-
dues and a cement plant like synthetic flue gas with 18.2% CO2 at
10 atm and room temperature. The advantage of this process, in addi-
tion to the mild conditions, is that carbonate precipitation occurs out-
side of the carbonation reactor. This allows the obtainment of
carbonates with high purity and added value that can be valorized. Be-
fore this pilot project, the operating conditions were optimized at labo-
ratory scale. To increase the process performance, the same solid was
reacted with the equivalent of six batches of gas with a residence time
of 15 min each; and the retention times for the liquid and solid phases
were 30 min and 90 min, respectively. Next, the solid feedstock was re-
generated by a second series of grinding, before being reacted with a
further six batches of gas. The laboratory scale results showed that
after 12 batches, approximately 63% of the total CO2 uptake and 50%
of the total Mg leaching rates. The assays of carbonates precipitation
carried out at 40 °C showed that 90% of leached Mg was precipitated
under hydrated carbonates form (nesquehonite) [4]. A technical and
economic study of this process using laboratory results showed a se-
questration efficiency of 235 kg CO2/t of serpentine [19].
In the continuity of this project, and to prepare an implementation of
an industrial full scale plant, the process was tested at a pilot scale. Tests
at this scale allowed for parameter adjustments when needed, genera-
tion of new data for a better understanding of the problematic and to
better design the required equipment.
To achieve this objective, the pilot plant was installed for one year in
a cement plant with the gas capacity treatment of 56.4 10− 3 m3/h.
Under the same optimum conditions obtained at laboratory, the seques-
tration capacity corresponds to 273 kg CO2/t of serpentine per hour. Dif-
ferent parameters were studied during this project. The effect of liquid
recirculation on the CO2 uptake and carbonate precipitation was pre-
sented in our previous publication [20]. The present paper provides
the results and interpretation for the impact of the global pressure
under real flue gas conditions using two serpentinite mining residues is-
sued from chromite and chrysotile exploitation, sampled from two dif-
ferent closed mines sites.
2. Materials and methods
2.1. Raw material preparation
Two different serpentinite-based tailings (magnesium silicates)
were used for this study. These residues were sampled from two closed
mines in the south of the province of Quebec, Canada, and labeled MJef
and MCol. The latter residue was sampled as coarse rocks with a piece
size N 2 cm, while the MJef residue was sampled as powder with a me-
dium particle size of 279 μm. Both residues had undergone a series of
physical treatments prior to reaction. First, the MCol residue underwent
a crushing step using a jaw crusher (C-RC-335), and a first grinding with
an oscillating mill discs (Tetsch-RS200) in order to obtain a powder
with a medium particle size of 168 μm. Preliminary analyses indicated
that the MCol and MJef residues contained 12% and 7.8% of iron oxide
(magnetite), respectively. During mineral carbonation, this iron oxide
is susceptible to form a hematite passive layer that could inhibit the re-
action. To prevent this step, the magnetite is recovered after magnetic
separation and the concentrated iron could be used in the iron and
steel making industries, thus reducing the process costs [21]. Therefore,
the first step was the recovery of this magnetite-rich fraction. The differ-
ence between the magnetite density (4.2–5.1 g/cm3) and the silicates
fraction density (2.9–3.1 g/cm3) allowed the use of gravimetric methods
to separate the two fractions. Both samples underwent a first separation
on a spiral (model 5LL400). The dense fraction recovered in this step
underwent a second separation using a Wilfley table (Outokumpu Tech-
nology, model SA-13A) as already described in detail in our previous
work [20]. The silicates fraction recovered at the end of the physical sep-
aration step was ground several times (3–4 times), until an average par-
ticle size of 67 μm for the MCol residue and 47 μm for the MJef residue
was obtained. The grinding step was then followed by a heat treatment,
at 650 °C with a 30 min residence time, using an electric rotary kiln
(Pyromaître Pyro 106 HE). The residence time was ensured by a solid
input rate of 200 g/min and a kiln inclination of 9°.
2.2. Material characterization
The chemical composition of each solid sample was determined by
inductively coupled plasma optical emission spectroscopy (ICP-OES,
Varian). This analysis was preceded by an alkaline fusion using lithium
metaborate, following the Claisse method [22]. Loss on ignition (LOI)
analyses of the raw material and the precipitated carbonate were con-
ducted at 1025 °C for 6 h. The particle size measurements were carried
out with a particle size analyzer (Model Horiba LA-950V2). The inorgan-
ic carbon content of the solids was obtained from a CHNS Leco analyzer
(LECO Instruments ULC, Ontario, Canada), and the dissolved inorganic
carbon was measured in the liquid phase with a total organic carbon an-
alyzer (Shimadzu TOC-VCSH). The solid's density was determined by
using a Micromeritics Accupyc 1330 Pycnometer. The X-ray diffraction
(XRD) patterns of the solids were obtained with a Siemens D5000
Monochromatic Diffractometer using CuKα radiation (λ = 1.54 Å).
The patterns were acquired between 5 and 90° with a step size of 0.02°.
2.3. Mineral carbonation and carbonates precipitation assays
The MC reactions were carried out in an 18.7 L Parr Reactor Model
4555 (Parr Instrument Co., Moline, Illinois) equipped with a tempera-
ture and pressure control unit. The chimney gas was pumped into the
experimental unit; it passed through a heat exchanger and was cooled;
and the water vapor condensed. The gas was then compressed to ap-
proximately 12 atm using a double stage compressor (Ingersoll Rand
2340L5-V, Ingersoll Company). Prior to reaction the gas composition
was measured using an IR cell analyzer (NOVA plus, MRU Instrument).
The desired quantity of gas was then introduced and reacted with the
already prepared pulp with a solid/liquid ratio of 150 g/L and a gas/liq-
uid ratio of 3. After 15 min of reaction under stirring at 600 rpm, the gas
was purged and analyzed to determine the quantity and the rate of CO2
removal. The operation was then repeated for a total of six batches of
treated gas. After every two batches, the liquid charged with inorganic
dissolved carbon and leached Mg cations were recovered by vacuum fil-
tration. A fresh liquid fraction was introduced into the reactor with the
recovered solids for the next batches (Fig. 1). The pulp pH was mea-
sured before and after the reaction using a pH meter (Orion Star
A1111). In summary, the residence time for the gas is 15 min per
batch, 30 min for the liquid and 90 min for the solid.
At the end of the six batches, the liquid recovered between every
two batches was transferred into an 18 L container and heated between
32 and 40 °C using a water bath, and stirred at 300 rpm for 6 h to precip-
itate the magnesium carbonate. The latter was recovered by filtration
and dried at room temperature, and its chemical and mineralogical
composition was determined by ICP-OES and XRD, respectively. Liquid
and solid fraction inorganic carbon concentration were measured
using a total organic carbon analyzer (Shimadzu TOC-VCSH) and car-
bon, hydrogen, nitrogen and sulfur analyzer (Leco-CHNS).
 N. Kemache et al. / Fuel Processing Technology 166 (2017) 209–216 211

Fig. 1. Aqueous mineral carbonation process.

The different results were obtained using the following equations: (magnetite) is higher in the MJef residue with 12% compared to 7.6%
in the MCol sample. After the physical separation, the analysis showed
CO2 ðcapturedÞ ðgÞ ¼ CO2 ðinletÞ ðgÞ–CO2 output ðgÞ ð1Þ that 45% of the iron oxide concentration initially present in MJef residue
was removed, while for the MCol residue, the amount was roughly the
CO2 ðcapturedÞ ð%Þ ¼ CO2 ðcapturedÞ ðgÞ=CO2inlet ðgÞ  100 ð2Þ same. The variation of iron oxide content in the two samples can be ex-
Leached Mgð%Þ ¼ ðLeached MgðgÞ=Total MgðgÞ in initial solidÞ plained by the variation in the mineral composition. Indeed, it was
 100 ð3Þ found that the MCol residue contain a spinel group (magnetite and
chromite), and the release study of the chromite, conducted by an exter-
. nal laboratory (COREM, Québec, QC, Canada), indicated that a little
Precipitated MgðgÞ : mMg ðpreÞ ¼ ðMMg mc Þ ð4Þ more than half of the chromite/magnetite grains presented a good de-
Mc
gree of liberation.
.
Precipitated Mgð%Þ : %MgðpreÞ ¼ mMg ðpreÞ ð5Þ The mineralogical compositions of the two raw residues were ob-
Mg leached tained by XRD analysis and their patterns are provided in Fig. 2. The
. MJef sample diffractogram is characterized by two major peaks at ap-
Precipitated CO2 : mCO2 ðpreÞ ¼ ðMCO2 mc Þ ð6Þ proximately 13° and 25° that correspond to lizardite, which is the pri-
Mc
mary phase present in this serpentinite. Magnetite with some
. impurities was also detected. For the MCol residue, three phases were
Precipitated CO2 ð%Þ : %CO2 ðpreÞ ¼ mCO2 ðpreÞ ð7Þ observed: the major phase lizardite, and chlorite and magnetite. Back-
dissolved CO2
ground noise was more present in the MJef sample, indicating a more
where MMg,MCO2 and Mc are, respectively, the molar mass of Mg, CO2 abundant amorphous phase in this serpentinite. The comparison be-
and carbonates (g/mol) and mMg,mCO2 and mc, are their corresponding tween the XRD patterns, before and after the physical pre-treatments
masses (g), respectively. The mass of CO2 in the flue gas (inlet and out- for both residues, showed more background noise interpreted as an
let) was obtained by using the ideal gas law. amorphous phase, indicating a change in the crystalline structure. The
results of the heat treatment showed a loss of mass of only 7% and ap-
3. Results proximately 9% for MCol and MJef residues, respectively. These values
are less than expected from the LOI, which are, respectively, 13 and 14%.
3.1. Solids characterization

The chemical composition, provided in Table 1, for the two residues

showed that both of them are mainly composed of magnesium silicates
with 44% to 46% MgO and 39 to 43% SiO2. The amount of iron oxide

Table 1
Chemical composition (%) of MCol and MJef residues before and after physical treatment.

Proportion (%) Al2O3 CaO Cr2O3 Fe2O3 K2O MgO MnO SiO2 LOI⁎

MCol raw material 1.4 0.1 0.7 7.6 – 46.3 0.1 43.0 13.0
MCol treated 2.0 0.9 2.1 7.9 0.0 43.4 0.1 42.5 7.1
material
MJef raw material 1.0 0.4 0.3 12.1 0.1 44.3 0.1 39.0 14.0
MJef treated 1.3 0.7 0.3 7.1 0.2 47.6 0.1 47.1 9.0
material
⁎ Loss on ignition. Fig. 2. XRD patterns of the raw materials.
212 N. Kemache et al. / Fuel Processing Technology 166 (2017) 209–216
Fig. 3. Effect of CO2 partial pressure on CO2 dissolution.
3.2. Effect of CO2 partial pressure on the CO2 removal from the gas
The effect of CO2 partial pressure on the amount of dissolved CO2
during the first two batches of gas is presented in Fig. 3. For comparison,
the theory line for pure water at 20 °C was added. The dissolved amount
of CO2, correspond to the mass of CO2 captured obtained with the Eq. (1)
brought to liquid volume and CO2 molar mass. Curves for both residues
show that the amount of CO2 dissolved in solution is proportional to its
partial pressure. This result is in perfect agreement with Henry's law,
given by the following equation: (PCO2 = H∗ ⌈CO2 ⌉ ); where PCO2 is the
CO2 partial pressure (atm), H is the Henry constant (L·atm/mol), and
⌈CO2 ⌉ is the dissolved CO2 concentration (mol/L). According to Henry's
law, the curves' slopes in Fig. 3 correspond to 1/ H. The H values obtain-
ed from the slopes were approximately 9 and 8.8 L·atm/mol for the
MCol and MJef residues, respectively. These values are approximately
three times lower than the HCO2constant in pure water, which is 29.4
L·atm/mol at 20 °C and neutral pH. These results indicate the promoting
effect of the serpentinite residue on CO2 dissolution. Indeed, the residue
addition instantly increases the pulp pH to 10.6–10.8 because of solids
dissolution and Mg leaching. The dissolved CO2 increases with the pH
due to the increase in bicarbonate (HCO− 2−
3 ) and carbonate (CO3 ) ion
concentrations. Such observations are in accordance with the results
previously reported in similar condition at the laboratory scale [4].
3.3. Effect of total pressure on CO2 capture
The rate of captured CO2 and the corresponding amounts per gram
of residue are shown in Fig. 4. The data obtained after six successive
batches of gas showed that the removal rate decreased with the
Fig. 4. Evolution of CO2 uptake rate and quantity with total pressure for MJef and MCol
residues.
increasing total pressure for both residues. At 2 atm, approximately
95% of the CO2 present in the flue gas passed into the solution. This
rate decreased to 89% and 77% at 4 atm in the presence of MJef and
MCol solids, respectively. The rate continued to decline when increasing
the pressure for both residues, to reach 83% and 77% at 8 atm and 74%
and 64% at 10 atm for MJef and MCol solids, respectively. This trend
can be explained by the fact that, at low pressure, a small amount of
CO2 initially enters the reactor and then the totality could be dissolved,
as the maximum CO2 solubility is not reached. Even if the removal rate is
higher at low pressure, the quantity of the dissolved CO2 is greater at
high pressure (Fig. 4). The carbonation results with MCol serpentinite,
for six batches of gas, showed that the CO2 uptake increased from
0.08 g CO2/g of MCol residue at 2 atm to 0.22 g CO2/g of MCol residue
at 10 atm. In the case of MJef residue, the CO2 uptake at 8 atm was
higher compared to 10 atm. This could be explained in part by the CO2
partial pressure, which was higher at 8 atm. Indeed, as has been
shown above, the dissolution of CO2 is proportional to its partial pres-
sure, and thus dependent from the CO2 proportion in cement plant
flue gas (pCO2 ¼ %CO2  P T ). As seen in Table 2, the CO2 content varied
from test to test, and this parameter was difficult to predict.
When comparing the two residues, the results obtained with MJef, in
terms of CO2 uptake, were better, but the variability of the CO2 partial
pressure is not sufficient to explain these results. At a total pressure of
8 atm, pCO2 was on average 2.8 and 2.5 atm per 2 batches of gas during
the essays with MJef and MCol residues, respectively, and despite the
small difference in pCO2, the amount of captured CO2 was much higher
with 0.25 g CO2/g of MJef residue compared to 0.20 g CO2/g of MCol
solid. Also at 10 atm, pCO2 was higher during the experiments with
MCol while the CO2 uptake was quasi-similar for both residues. The
CO2 dissolution is also dependent of the pulp pH. In this case, this param-
eter is directly linked to the solids dissolution [4,16,23]. Thus the CO2 up-
take is promoted by a smaller particle size due to the higher surface
exchange. Therefore, with an average particle size of 47 μm (compared
to 67 μm for MCol) and an important amorphous phase, the MJef residue
showed better performances during the mineral carbonation.
3.4. Evolution of CO2 uptake with batches of gas
The amounts of CO2 captured (g CO2/g residue) after each two
batches of gas are shown in Fig. 5 for the two residues. The theoretical
amounts corresponding to 100% CO2 uptake were also provided for
each pressure.
At low total pressure (2 and 4 atm), the mass of the treated CO2 is al-
most constant for the three pairs of batches. At 2 atm, the average per
two batches is 0.028 g CO2/g of MCol residue and 0.025 g CO2/g of
MJef residue. During batches 1 and 2 at 4 atm, the amount of treated
CO2 is approximately 0.05 g CO2/g of residue, for both solids. This
amount decreases by approximately 22% and 11% to reach, respectively,
0.038 g CO2/g of MCol residue and 0.046 g CO2/g of MJef residue at the
end of the 6th batch. As could be seen on Fig. 5, in the case of MJef,
the experimental results at low pressure were almost identical to the
theoretical ones. On the other hand, a slight deviation was observed
with MCol residue. This deviation increased with increasing the total
pressure, especially when the MCol solid was used. As explained in
Table 2
Example of CO2 content in the cement plant flue gas during the batches 1 & 2.
Total pressure/batch (atm) % CO2 in cement plant flue gas
MCol residue MJef residue
2 20.4 ± 2.2 18.7 ± 0.6
4 17.4 ± 2.5 18.6 ± 0.8
8 15.1 ± 2.0 17.6 ± 2.5
10 16.4 ± 2.7 13.8 ± 0.9
 N. Kemache et al. / Fuel Processing Technology 166 (2017) 209–216
Fig. 5. Quantity of captured CO2 from flue gas during the different batches and the theoretical values.
the Section 3.3, the difference between the two solids granulometry and
the higher CO2 partial pressure during the assays with MJef residue. This
may also explain the fact that the amount of CO2 treated with MJef res-
idue, is higher at 8 atm than at 10 atm. The high pressure curve profile is
different from the low pressure one. As it can be observed in Fig. 5, at 8
and 10 atm, the amount of captured CO2 is high during the first two
batches (0.082 to 0.112 g CO2/g of MCol residue and 0.095 to
0.100 g CO2/g of MJef residue). For the following batches, the amount
of treated CO2 decreased by 40 to 60% (w/w). When the CO2 is dissolved
in the solution, the HCO− 3 ions react with the Mg
2+
cations, accessible
on solid surfaces, to form the complex (MgHCO3)+, promoting Mg
leaching [4,23]. A greater amount of dissolved CO2 means a solid surface
saturation, and the reduction of Mg cation availability for the next
batches of gas. Without Mg leaching, the solid alkaline potential is re-
duced, which allows for maintaining the pH up to 7, and thus promoting
CO2 dissolution. For example, at 2 atm for the MCol residue, the initial
pH was 10.76 and at the end of the second batch, the pH had decreased
to 9.20. Once the liquid charged with the dissolved ions was replaced by
the fresh liquid, the pH rose again to 10.3 at the beginning of the 3rd
batch before going down again to 9.17 at the end of the 4th batch. For
batches 5 and 6, the pH passed from 10.08 to 9.08. Thus at low pressure,
the final pH after six batches of gas was still high. On the other hand, at
10 atm, the initial pH of 10.6 decreased to 8.55 at the end of the second
batch, and despite the replacement of the liquid after every two batches,
the pH did not exceed 9.63 and 9.09 at the beginning of the batches 3
and 5, respectively. Contrary to the results for 2 atm, the pH after six
batches of gas at 10 atm was as low as 7.33. So, at low pressure (2 to
Fig. 6. Mg leaching rate evolution with the number of batches and comparison between the MCol and MJef residues.
213
4 atm), it is possible to add more than six batches of gas due to the
final alkaline pH.
3.5. Residues dissolution and magnesium leaching
The rates of Mg leached (%), obtained at different total pressures, for
both MCol and MJef serpentinite are shown in Fig. 6.
During the first two batches, the Mg leaching increased with the
pressure from 4.2 to approximately 8.0% and from 2.6 to 7.9% in the
presence of MCol and MJef residues, respectively. This trend was main-
tained for the second round of batches (3 and 4) except for 10 atm, es-
pecially when the MJef sample was used. With this residue, the leached
Mg was 8.6% at 8 atm, compared to 6.5% at 10 atm. During batches 5 and
6, the rate of leached Mg obtained at 2 atm, for both solids, was compa-
rable to the results of batches (1 & 2) and (3 & 4) while when the pres-
sure increased, the Mg leaching decreased with the two last batches of
treated gas. These results were consistent with the trend observed in
the CO2 dissolution, indicating a relationship between the dissolved
CO2 and the leached Mg. As explained above (Section 3.4), the forma-
tion of HCO− 3 during the dissolution of CO2 increased the release of Mg
thanks to the complex (MgHCO3)+ formation and, consequently, to
the Mg\\O bond weakening. The decrease in rate of Mg leached during
batches 5 and 6 is attributed to solid deactivation, caused by a passive
layer of silica formed on the solid surface [24]. This layer is formed be-
cause only a small quantity of silica is leached with Mg. The Mg/Si
ratio in the raw serpentinite was 1.3, while this ratio could be as high
as 30 in the reacted residue, indicating an incongruent dissolution of
214 N. Kemache et al. / Fuel Processing Technology 166 (2017) 209–216

the serpentinite [25]. To prevent this problem, a second grinding and Table 3
second heat treatment after six batches of gas was considered. Results of carbonates precipitation obtained with MCol residue (32–40 °C, 6 h, 300 rpm).

The cumulative leached Mg for the six successive batches was ap- Total Leached Dissolved Formed Precipitation Precipitation
proximately 19% and 15% with MJef and MCol residues, respectively. pressure Mg (%) CO2 (g) carbonate rate for Mg (%) rate for CO2 (%)
The higher rate was obtained with MJef residue because of the smaller (atm) (g)

particle size and the amorphous phase. On the other hand, the less effi- 2 19.6 56.3 13.0 11.6 7.3
cient chromite/magnetite fraction removal for the MCol sample, and the 4 24.9 70.7 74.0 52.2 33.3
8 30.6 112.4 88.2 50.6 25.0
subsequent formation of an iron oxide layer during the heat-treatment,
10 25.2 100.6 55.0 38.3 17.4
can explain the less effective leaching with this sample. In addition, the
variation in the mineralogical composition is also known to affect the
solids reactivity [26]. The leaching efficiency obtained during the assays, concentrations of HCO− 2–
3 /CO3 and Mg
2+
ions in the precipitation liquid
at a pilot scale, was lower than the laboratory results reported by increases, oversaturation is rapidly achieved, allowing for a faster
Pasquier, Mercier [4]. Many aspects can explain this difference. First, precipitation.
as mentioned, the instability of the gas composition can affect the over- With the conditions used in this work, the expected carbonate is
all reaction efficiency. Furthermore, the low efficiency of the heat treat- nesquehonite (MgCO3·3H2O) [27]. The XRD pattern shown in Fig. 8
ment and the particle size could play a major role. Optimization of the confirms this result, as nesquehonite was the only crystalline phase.
heat transfer is easier during the calcination of a small quantity of resi- The chemical analysis of the sample subjected to loss on ignition (LOI)
due at a laboratory scale compared to the preparation of 200 to 400 kg of showed that the carbonate was composed of 97% MgO, with small
residue for the pilot scale project. This is also true for the grinding quantities of CaO and SiO2 (CaO/SiO2 ratio of 0.65) and b1% of
efficiency. impurities.

3.6. Carbonates precipitation

The quantities of the precipitated carbonates obtained for each pres-
sure are shown in Fig. 7. At 2 atm, the amount of carbonates is very low,
especially during the experiments with MJef residue. This is because of
the low concentration of both dissolved CO2 and leached Mg (Tables 3
and 4). By increasing the total pressure during the experiments with
MCol residue, the amount of carbonates increased by N 5 and 6 orders
of magnitude for 4 and 8 atm, respectively. At 10 atm, the amount of
precipitated carbonates was less than at 8 atm, following the results of
leached Mg (Fig. 5). For experiments with the MJef residue, the amounts
of carbonate increased when increasing the total pressure. At 2 atm, the
quantity was negligible (0.003 g carbonate/g of residue) and increased
up to 0.160 g/g of residue at 10 atm. According to the higher quantities
of leached Mg and dissolved CO2 at 8 atm compared to 10 atm with MJef
residues (Table 4), one would expect to obtain more carbonates at
8 atm, which was not the case, since at 10 atm, the carbonates were
slightly higher. It should be reiterated that the precipitation assays
were performed using a water bath and consequently, the temperature
may vary slightly from test to test. This variation could explain the re-
sults obtained at 8 and 10 atm using MJef samples. By comparing be-
tween the two solids, more carbonates were obtained with MJef
residue, except at 2 atm. The maximum yield of precipitated Mg was ob-
tained after experiments performed at 10 atm and was as high as 60%.
The carbonate precipitation depends, essentially, on the temperature
and the different ion concentrations. As shown in our previous work
[20], the Mg concentration is the limiting factor. Indeed, when the
3.7. Overall process efficiency
The main objective of the MC is the CO2 sequestration under carbon-
ate form. For this reason, the overall efficiency of the process was deter-
mined with respect to the yield of precipitated CO2. As showed above,
the amount of carbonates increased with increasing gas pressure. Con-
sequently, the amount of precipitated CO2 followed a similar trend, ex-
cept for some particular cases for the reasons previously discussed. For
the experiments with the MCol sample, the quantity of the precipitated
CO2 increased from 0.006 g CO2/g at 2 atm to 0.033 g CO2/g of residue at
4 atm. The best result was obtained at 8 atm with 0.040 g CO2/g of res-
idue. Knowing that the maximum amount of CO2 that could be captured
by the serpentinite (based on stoichiometric calculation) is 0.47 g CO2/g
of residue, the overall efficiency corresponding to this best result was
approximately 8.5%. This represents 25% of the total dissolved CO2 and
50% of leached Mg. During the experiments with the MJef sample, the
overall efficiency increased to 9.3% and 10.8% at 8 and 10 atm, respec-
tively. This latter result corresponds to the precipitation of 33% of total
dissolved CO2 and 60% of leached Mg. Considering these results, the pre-
cipitation step is critical for improving the CO2 sequestration process. It
is therefore important to optimize the solid leaching and precipitation
conditions. The laboratory results proved that it's possible to increase
both leached Mg and dissolved CO2 rates by reacting the same solid
with six other batches of gas, after a second pre-treatment (grinding
and heat treatment) to remove the passive silica layer [4]. On another
hand, the operation, in batch mode, is limiting the amount of CO2 enter-
ing the reactor. Thus, to counteract this effect, the global pressure
should be raised to have a sufficient amount of CO2. In addition, batch
wise operation was not the most appropriate for the treatment of indus-
trial gas flow with a high velocity. Operating with a continuous flow of
gas might help to reduce total operating pressure while keeping the
amount of CO2 sufficient to maintain the overall reaction efficiency.

Table 4
Results of carbonates precipitation obtained with MJef residue (32–40 °C, 6 h, 300 rpm).

Total Leached Dissolved Formed Precipitation Precipitation

pressure Mg (%) CO2 (g) carbonate rate for Mg (%) rate for CO2 (%)
(atm) (g)

2 15.3 49.9 2.0 2.3 1.3

4 30.4 83.7 57.5 33.2 21.9
8 36.7 150.9 97.0 46.4 20.5
10 32.7 106.7 112.5 60.5 33.5
Fig. 7. Carbonates formation at different pressures.
 N. Kemache et al. / Fuel Processing Technology 166 (2017) 209–216
Fig. 8. Nesquehonite XRD pattern.
4. Conclusions
MC pilot tests were performed in an 18.7 L Parr reactor. The same
operating conditions optimized at a laboratory scale were used. The
project was installed on the site of a cement plant for a year and allowed
us to test the process under real industrial flue gas conditions. The chim-
ney flue gas had a variable CO2 content ranging between 12 and 20%.
The assays were performed for different total pressures (2, 4, 8 and
10 atm) and for each pressure, six successive batches of gas were treat-
ed without replacing the solid, but with changing the liquid between
every, two batches of gas treated. Two serpentinites sampled from
two different mines (MCol and MJef), were used in this project. The re-
sults obtained during the two first batches, at different CO2 partial pres-
sures, showed an improvement in its dissolution in the presence of both
solids. Indeed, the Henry's constant values obtained from the experi-
mental results were much lower than the constant for the H2O-CO2 sys-
tem. The results also showed that approximately 95% of the CO2 in the
flue gas was dissolved at 2 atm for both residues while this rate de-
creased to 74% and 64% at 10 atm with MJef and MCol solids, respective-
ly. On the other hand, the quantity of CO2 captured/g of residue
increased with an increase of the gas pressure. The highest efficiency
for the cumulative six batches was obtained at 10 atm for the MCol res-
idue, with 0.22 g CO2/g of residue (220 kg CO2/t of residue), and at 8 atm
for MJef solid with 0.25 g CO2/g of residue (250 kg CO2/t of residue). In
the latter case, pCO2was higher at 8 atm than at 10 atm because of the
punctual higher CO2 content in the flue gas. The Mg leaching showed
slightly better results when using the MJef solid, with approximately
19% compared to 15% when MCol was used. This difference was linked,
in part, to the smaller particle size for the MJef residue, highlighting the
importance of fine grinding. Compared to the laboratory results, the
leaching rates at a pilot scale were relatively lower because, essentially,
of the less effective heat treatment. Hydrated carbonates
(nesquehonite) were obtained after 6 h of precipitation at 32–40 °C.
The chemical analysis showed a high purity carbonate, which contained
primarily Mg, with some impurities (like Si, Ca and Fe) at a rate of b3%.
Compared to the maximum capacity of capture of the serpentinite, the
global efficiency, considering the extent of precipitated CO2, was
found to be 8.5% and 10.8% in presence of MCol and MJef materials, re-
spectively. This efficiency could be improved by reacting the solid, re-
grounded and re-heat-treated at the end of the 6th batch, with six
other batches of gas.
Results of this pilot proved that the MC for CO2 sequestration is tech-
nically feasible at a large scale, and can be seriously considered as a
215
solution for reducing GHGs. However, the transition from a laboratory
to a pilot scale requires some adjustments. To improve the process effi-
ciency, it is essential to optimize two key parameters: the heat-treat-
ment and the carbonate precipitation. The first would allow a larger
Mg leaching, and the second, the total precipitation of both leached
Mg and the dissolved CO2. In this context, two research projects, well-
advanced, are currently under way in our laboratory. On the other
hand, the operation utilizing a continuous flow of gas must be addressed
to offer a process more adapted to the reality of industrial flue gas
treatment.
Acknowledgments
The authors gratefully acknowledge Carbon Management Canada
(CMC) (Project ID: C0319), which provided funds for this research.
The authors also acknowledge the cement plant partner who provided
gas and help.
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