The Journal of Supercritical Fluids 171 (2021) 105191

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The Journal of Supercritical Fluids

journal homepage: www.elsevier.com/locate/supflu

Pressurized in situ X-ray diffraction insights into super/subcritical

carbonation reaction pathways of steelmaking slags and constituent silicate ]]
]]]]]]
]]

minerals
Ye Eun Chaia,1, Quin R.S. Millerb,2, H. Todd Schaefb,3, Dushyant Barpagac,4,
Reza Bakhshoodehd,5, Marius Bodore,6, Tom Van Gervenf,7, Rafael M. Santosa, ,8
⁎

a
School of Engineering, University of Guelph, Guelph, Ontario N1G 2W1, Canada
b
Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, WA 99352, USA
c
Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA 99352, USA
d
Department of Civil, Environmental and Mining Engineering, The University of Western Australia, Perth, Western Australia 6009, Australia
e
Department of Materials and Environmental Engineering, "Dunarea de Jos" University of Galati, Galaţi 800201, Romania
f
Department of Chemical Engineering, KU Leuven, Leuven 3001, Belgium

H IGHL IGH TS GRA PHICA L A B ST RAC T

• Slags (AOD, CC) and six synthetic si-

licates are carbonated in wet CO2(g)
and scCO2.
• In situ high-pressure XRD analysis al-
lows tracking the carbonation path
and rate.
• Ca- and Mg-carbonates that form are
time- and silicate-dependent.
• Real-time monitoring of mineralogy
enables detecting transient and un-
stable phases.
• Varying carbonation behavior of sili-
cates motivates better slag chemistry
control.

A R T I C L E I N F O A B S T R A C T

Keywords: This study explores mineral carbonation of industrial stainless steelmaking slags and relevant synthetic con-
Accelerated mineral carbonation stituent minerals via in situ pressurized X-ray diffraction, to clarify carbonation reaction pathways and efficiency
Time-resolved XRD for carbon storage and waste valorization. The primary mineral phases of Argon Oxygen Decarburization (AOD)
Silicate and carbonate mineralogy and Continuous Casting (CC) slags, namely, åkermanite, bredigite, cuspidine, merwinite, and β- and γ-C2S, were
Carbon sequestration
reacted in a custom-built beryllium-capped XRD reactor filled with either water-saturated (wet) subcritical

⁎
Corresponding author.
E-mail address: santosr@uoguelph.ca (RM. Santos).
1
0000-0001-6923-7979
2
0000-0003-3009-9702
3
0000-0002-4546-3979
4
0000-0003-2271-6213
5
0000-0001-5921-3957
6
0000-0002-8056-4556
7
0000-0003-2051-5696
8
0000-0002-8368-8618

https://doi.org/10.1016/j.supflu.2021.105191
Received 22 September 2020; Received in revised form 10 January 2021; Accepted 4 February 2021
Available online 10 February 2021
0896-8446/© 2021 Elsevier B.V. All rights reserved.
Y.E. Chai, Q.R.S. Miller, H.T. Schaef et al.
Supercritical CO2 CO2(g), or wet supercritical CO2(SC), in a series of carbonation experiments. Formation of calcite and aragonite
Slag valorization was observed for most Ca-bearing minerals, transient precipitation of metastable vaterite was observed, while
carbonation of AOD and CC slags in CO2(SC) resulted in hydrated crystalline calcium carbonates and indirect
evidence of amorphous carbonate. Results obtained suggest that low-pressure subcritical carbonation routes are
attractive for standalone slag carbonation processes, while high-pressure supercritical carbonation routes are
amiable to symbiotic integration with CO2(SC)-generating green technologies.
1. Introduction
Global warming has stimulated renewed interest in issues relating to
carbon capture and storage to reduce CO2 emissions from fossil-fuel
power stations and other industrial facilities. Since carbon dioxide
(CO2) is the most significant anthropogenic greenhouse gas [1], its re-
duction is crucial for climate change mitigation. Mineral carbonation is
a CO2 sequestration method that can safely store CO2 as a solid com-
pound with very low risk for leakage. In mineral carbonation, CO2 is
fixed by promoting calcium or magnesium oxides in silicate-based
materials to react with CO2 and form stable solid carbonates [2]. This
approach has a larger capacity for CO2 storage than any of the other
CO2 storage method because suitable silicate mineral resources, con-
taining calcium or magnesium oxides, are abundant [3]. In addition,
mineral carbonation allows carbon utilization, in addition to capture
and sequestration, when the carbonated products are used in large-scale
applications, such as in construction materials [4–6].
While there have been commercial implementations of mineral
carbonation in recent years, it remains challenging to implement mi-
neral carbonation at a large scale. Bourgeois et al. [7] argue that suc-
cessful mineral carbonation processes must become part of a viable
economic framework that uses resources available in a given region to
produce commercializable materials that meet identified market needs.
This also entails consideration of economic, societal, and environmental
factors, beyond the technical feasibility of mineral carbonation pro-
cesses. Notably, mineral carbonation applied to alkaline waste mate-
rials has the potential to address these additional factors. Waste va-
lorization aims to generate added value, by commercialization of
upcycled products or avoidance of waste disposal, storage or treatment
costs, while also reducing the environmental impact or risk of industrial
operations, and addressing societal concerns on the sustainability of the
energy- and resource-intensive industries that generate these wastes.
Renforth [8] has recently estimated that 7 billion tonnes of alkaline
waste materials are annually produced globally, possessing a CO2 sto-
rage potential of 2.9–8.5 billion tonnes per year by 2100. Renforth [8]
identified the top five industrial waste materials in terms of carbonation
potential, from highest to lowest, as follows (in kg CO2 per tonne units):
blast furnace (BF) slag (413 ± 13); basic oxygen furnace (BOF) slag
(402 ± 17); electric arc furnace (EAF) slag (368 ± 10); ultrabasic mine
tailings (40-250); and red mud (47 ± 8). Steelmaking slags thus have
substantial potential for CO2 emissions reduction via mineral carbo-
nation of waste materials, and much research on this topic has been
done in recent years [9,10].
The annual steel production exceeds 1.8 billion tonnes worldwide
[11]. For every tonne of steel produced, 1.9 tonnes of CO2 is generated,
and as a result, the steel industry is one of the biggest sources of in-
dustrial CO2, accounting for about 7% of the total anthropogenic
emissions to the atmosphere [12]. The reduction of these emissions for
climate change mitigation is difficult because the industry is heavily
dependent on either coke or coal for power generation. Since modern
integrated LD/converter steel plants produce about 90–100 kg of slag
per tonne of steel, vast amounts of steelmaking slag are being co-pro-
duced [11]. Estimations of the world’s annual steelmaking slag pro-
duction vary between 190 and 290 Mt [13]. High calcium oxide content
of steelmaking slags makes them suitable for use as raw material in
mineral carbonation. With a calcium oxide content of 40–52% [14],
ideally, this amount could store up to 170 Mt of CO2 per year by
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The Journal of Supercritical Fluids 171 (2021) 105191
mineral carbonation [15]. While low compared to global CO2 emis-
sions, such reduction potential of steelmaking slag will be significant
for an individual steel mill.
Due to its suitable chemistry and mineralogy, BF slag, once ex-
tensively stockpiled, has found utilization in the construction domain,
as an additive in lightweight mortars, as a component of concrete
mixtures, as aggregates in road building, or as a raw material for the
preparation of ceramic glass, silica gel, ceramic tiles and bricks
[16–18]. Similar aims are intended for steelmaking slags, including BOF
(also known as converter slag), EAF, Argon Oxygen Decarburization
(AOD) (also known as Linz-Donawitz slag), and Continuous Casting
(CC) slags. Yet, various reasons, such as high basicity and the pro-
pensity for heavy metal leaching and pulverization [17,19–23], have
made the reutilization of these materials challenging. In order to im-
prove the negative properties of steelmaking slags and enable greater
opportunities for recycling, steelmaking slags have been the subject of
mineral carbonation research in recent years, with the purpose of CO2
sequestration, due to the geochemical stability of alkaline earth metal
carbonates, and for waste valorization [17,24–27].
Process limitations, including high energy intensity, low reaction
conversion, and slow reaction kinetics, have prevented mineral carbo-
nation of waste materials from being widely applied. These barriers are
caused by inefficient or nonoptimal processing and reactor technolo-
gies, morphological limitations (e.g. shrinking core model), and mi-
neralogical aspects inherent to the materials. While the first two mo-
tives have been well reported in literature [17], limited attention has
been paid to mineralogical susceptibility of individual minerals
[28–30]. Alkaline waste materials are typically composed of several
mineral phases that may or may not be susceptible to mineral carbo-
nation, and which, if reactive to CO2, may exhibit varying degrees of
carbonation kinetics and influence the material’s basicity. The forma-
tion and character of passivating layers (e.g., thickness, porosity) can
also be affected by the relative solubility of the minerals [31,32].
We have previously studied the carbonation of AOD and CC slags,
which have powdery morphology that provides sufficient surface area
for the active reaction during direct aqueous carbonation [33]. By
utilizing two carbonation methodologies, unpressurized thin-film car-
bonation and pressurized slurry carbonation, carbonation of CC slag
resulted in a greater CO2 uptake and carbonate conversion compared to
those of AOD slag, at essentially all processing conditions [33]. In our
subsequent work, seven high-purity minerals (åkermanite, bredigite,
cuspidine, merwinite, srebrodolskite (Ca2Fe2O5), β- and γ-dicalcium
silicate (C2S)) that are commonly found in ironmaking and steelmaking
slags were synthesized and underwent carbonation experiments to un-
derstand the affinity of the individual mineral phases of the slags to-
wards mineral carbonation [34]. The synthetic minerals were produced
at high purity (>70 wt% target mineral) with small composition of
residual free oxides (<10 wt%). Even though we demonstrated that
bredigite is the most favorable mineral phase for mineral carbonation,
not all results of the synthetic minerals corresponded to those of the
slags. For example, the carbonation conversion of the two C2S poly-
morphs was higher in CC slag than that of these synthetic minerals
when both samples were carbonated via thin-film carbonation [34].
The inconsistency of the results indicates that it is not only the mi-
neralogical susceptibility towards mineral carbonation that affects the
carbonation reactivity of the slags, but also the particle morphology
including the intra-particle location of the mineral phase components
Y.E. Chai, Q.R.S. Miller, H.T. Schaef et al.
[34]; solid solutions, degree of crystallinity and crystal defects, and
cooling hystory may be other important factors. For both studies, ex situ
X-ray powder diffraction (XRD) was performed on the carbonated
samples to analyze their mineral phases. As the analysis was conducted
solely on the final products, it was not possible to determine reaction
pathways, including identification of intermediate metastable phases or
quantifying the rate of carbonation conversion of individual silicate
phases.
Herein, we report in situ XRD results for a series of carbonation
experiments conducted in a custom-built beryllium-capped reactor
filled with either water-saturated (wet) subcritical (70 °C, 6 bar) CO2
(CO2(g)), or wet supercritical (50 °C, 82 bar) CO2 (scCO2), and con-
taining AOD slag, CC slag, or one of their six constituent synthetic
minerals: åkermanite, bredigite, cuspidine, merwinite, β-C2S, and
γ-C2S. The carbonation products, which include various forms of cal-
cium and magnesium carbonates, were characterized both with respect
to their amounts and rate of formation and to the process conditions
that promote their formation. The in situ XRD approach allowed to
determine reaction pathways of individual mineral phases and their
transformation during carbonation, which subsequently led to identi-
fication of the phases most susceptible to carbonation reaction. The link
between mineral composition, mineral structure and carbonation extent
is also discussed to clarify the mineralogical influence on carbonation.
By knowing which mineral phases in stainless steel slags are susceptible
to reacting under certain conditions during mineral carbonation,
steelmakers can use this information to tune the chemical composition
of the slag and control the slag cooling path so that the cooled material
has a more desirable mineralogy for mineral carbonation. Also, by
conducting in situ XRD analysis, the behaviour of each mineral during
carbonation and the mineral phases that appear and disappear can be
been identified, which contributes to increasing confidence in the
predictability of carbonation effects and encourages future research for
a more feasible CO2 sequestration process at industrial scale.
2. Materials and methods
2.1. Synthetic minerals
The six target minerals were synthesized based on solid-state sin-
tering methodology and conditions (sintering temperatures, duration,
cooling path) found in published literature [34], with the goal of
achieving >70 wt% purity of the target mineral and <10 wt% free
oxides. Table S1 shows the complete mineralogical composition of the
synthesized minerals.
2.2. Stainless steelmaking slags
The AOD and CC stainless steelmaking slags were obtained from the
production process of a Belgian steelworks, and had <500 µm particle
size. The slags were composed of high concentrations of calcium and
moderate to low concentrations of magnesium. These concentrations
contribute the alkaline properties of the slags and the reactivity towards
mineral carbonation [33,34]. The mineralogical compositions of the
slags were previously determined by quantitative X-ray diffraction
(QXRD). The main mineral phase of both AOD and CC slags is γ-C2S, with
compositions of 24.1 and 38.6 wt%, respectively. Other mineral phases
identified include bredigite, cuspidine, β-C2S, merwinite, and periclase.
Table S1 summarizes complete mineralogical composition of AOD and CC
slags. Given their small but significant free lime content, prior to experi-
ments, the synthetic C2S samples were refreshed in an oven at 900 °C to
remove initial trace carbonates that can form upon atmospheric exposure.
2.3. Pressurized in situ X-ray diffraction carbonation experiments
Time-resolved XRD experiments were conducted in a pressure-
compatible static reactor with a beryllium cap and stainless-steel base.
3
The Journal of Supercritical Fluids 171 (2021) 105191
The in situ XRD experimental apparatus and procedures are described
in detail elsewhere [35,36]. Briefly, the in situ XRD reactor was housed
in a Bruker D8 Discover X-ray powder diffractometer equipped with a
HI-STAR GADDS detector, an experimental configuration capable of
analysing mineral assemblages at elevated pressure and temperature
under a 45 kV and 200 mA Cu Kα-sourced microfocus X-ray beam. The
diffractometer automatically scanned the sample for 200 s with an
approximate nine second delay in between each 10–46°2θ pattern.
The experiments were performed independently using two different
water-saturated (wet) CO2 phases: subcritical and supercritical. The
equilibrium concentrations of H2O were 5.36 and 0.33 mol% for gas-
eous and supercritical conditions, respectively [37]. For experiments in
which wet CO2(g) was supplied, temperature of 70 °C, CO2 pressure of
6 bar, and 40 μl of water was used, while 10 μl of water was placed in
the reactor prior to pressurization at 50 °C with scCO2 at pressure of
82 bar. Table S2 presents the reaction conditions used for carbonation
of each material, and nomenclature used to refer to each set of condi-
tions (EXP #1 to EXP #11). The nominal amount of mineral used in
each experiment was ~ 10 mg. A predetermined amount of water (40 or
10 μl) was deposited in the base of the reactor to ensure that the CO2
was always fully saturated with H2O [37]. A Model 100D ISCO syringe
pump was used to adjust the pressure in the reactor and the tempera-
ture of the reactor was maintained within ±1 °C for all experiments.
The XRD patterns were analyzed using both GADDS XRD software
(Bruker-AXS) and JADE XRD software (MDI). Each mineral phase was
identified based on the database provided by Mineralogy Database
(webmineral.com). Analysis of GADDS detector images provided in-
formation on crystallite microstructure [38] of single crystal or pow-
dered solid samples, such as phase identification, grain size, poly-
crystallinity, and texture [39].
To provide quantitative insight into carbonate abundance and com-
position, reacted subsamples recovered from in situ experiments were
subjected to thermogravimetric analysis coupled with mass spectrometry
(TGA-MS). As described previously [40], sample weight changes during
thermal decomposition in an N2 atmosphere were measured with a
precision microbalance, while associated CO2 and H2O releases were
monitored by observing ion currents (m/z) 44 and 18, respectively. TGA-
MS analyses were performed with a Netzsch Instruments TG-209F1
thermogravimetric analyzer connected to a QMS 403 C Aëolos quadru-
pole mass spectrometer. Each sample was heated in an alumina crucible
at 2 °C/min to 900 °C under 20 ml/min N2 flow. Eq. (1) was used to
calculate the maximal CO2 uptake of each material, which uses Ca and
Mg contents of the materials. In Eq. (1), QCO2 is the CO2 uptake de-
termined by TGA, expressed as grams CO2 captured per gram of initial
material mass; MW are elemental molar masses, and w are elemental
mass fractions in the original material. Table 1 summarizes the Ca and
Mg mass fractions in the original materials and maximal CO2 uptake
calculated.
QCO 2
MWCO2
CO2 uptake (% maximal) = wCa wMg
+ MW
MWCa Mg (1)
3. Results
The main research questions that have been investigated herein
include: (i) do different silicates minerals that make up steelmaking
slags have different rates of conversion under super/subcritical condi-
tions; (ii) how do different silicates govern the type of carbonates that
form; (iii) do carbonates crystallize throughout the reaction or only
upon depressurization (i.e. pressure swing), and does this depend on
whether super/subcritical CO2 is used; and (iv) do individual silicate
phases that make-up steelmaking slags behave differently when they
carbonate as pure mineral phases. To investigate the latter, the six
silicate minerals synthesized were compared against the two types of
Y.E. Chai, Q.R.S. Miller, H.T. Schaef et al.
Table 1
Ca and Mg mass fractions and maximal CO2.
Material CO2 Ca (wt%) Mg (wt%) Carbonate content, maximum (wt%)
β-C2S sc 46.55 0 51.1
γ-C2S sc 46.55 0 51.1
Cuspidine g 43.75 0 48.0
Bredigite g 41.67 3.60 52.3
Bredigite sc 41.67 3.60 52.3
AOD slag g 40.62 4.52 52.8
CC slag g 37.19 5.96 51.6
slags (AOD and CC). The carbonation reaction pathways involving Ca-
rich minerals, Ca- and Mg-rich minerals, and stainless steelmaking slags
are presented in Sections 3.1, 3.2, and 3.3, respectively.
3.1. Ca-rich minerals
The C2S minerals and cuspidine contain Ca as their alkaline earth
metal. According to the XRD diffractogram of β-C2S carbonation under
wet CO2(g) conditions (EXP #1), β-C2S intensities (32.17 and 32.61°2θ)
immediately decreased within 1 h of reaction, and no further change in
intensity was observed (Fig. S1). At the same time, spurrite
(Ca5(SiO4)2CO3) intensities (33.14, 33.57, and 33.85°2θ) dropped and
did not change until the end of the reaction time. In terms of carbonates
formation, calcite (29.4 and 39.4°2θ) and aragonite (26.22°2θ) intensities
increased in the middle of the reaction time. When β-C2S was carbonated
under wet scCO2 condition (EXP #2), the intensities of β-C2S and spurrite
decreased in the same manner as seen in EXP #1 (Fig. S2). However,
formation of aragonite was not detected, and sole formation of calcite
indicates that carbonation in wet scCO2 was more thermodynamically
stable than that in wet CO2(g). The TGA-MS results indicate its thermal
behavior regarding calcination was most consistent with that of calcite
(Fig. S3) [41]. The GADDS images generated for EXP #2 showed a dis-
tinct indication of calcite formation and absence of aragonite, being in
line with the other analysis results (Fig. S4).
When γ-C2S was carbonated with wet CO2(g) (EXP #3) the in-
tensities of the main peaks of γ-C2S, observed at 29.7 and 32.5°2θ in the
QXRD, started to decrease immediately and quickly within 1 h of re-
action, as well as the peaks of β-C2S (Fig. S5). In contrast, the intensities
of the calcite peaks (29.4 and 39.4°2θ) increased gradually throughout
the reaction time. Interestingly, formation of aragonite, which was
formed during β-C2S carbonation in wet CO2(g) (EXP #1), was not de-
tected. The carbonation of γ-C2S in wet scCO2 (EXP #4) showed similar
decrease in γ-C2S and β-C2S intensities, however, carbonate formation
was not seen (Fig. S6). According to [34], slower carbonation kinetics is
suggested for C2S polymorphs as they benefit more from extended
carbonation time, and the small CO2 uptakes of these materials under
thin-film carbonation are caused by their free oxides contents. Con-
tradicting the results of XRD, TGA-MS result of γ-C2S carbonated under
wet scCO2 condition (EXP #4) suggests decomposition of calcite
(Fig. S7) [41], and GADDS images generated for EXP #4, at the end of
the experiment after depressurization, showed the increased presence
of calcite (Fig. S8); thus both results imply formation of calcite. It is
justifiable to believe that calcite formation did occur during carbona-
tion of γ-C2S in scCO2, but the increased intensities of the calcite peaks
were too minimal to be detected in the XRD diffractograms, or the
calcite precipitated/crystallized only upon depressurization.
Cuspidine carbonation in wet CO2(g) (EXP #5) showed simulta-
neously occurring transformations throughout the reaction time, as
seen in Fig. 1. Fig. 1a presents the 3D XRD diffractogram and Fig. 1b is
the 2D waterfall plot of Fig. 1a. The intensities of the cuspidine peaks
(27.24 and 29.14°2θ) immediately decreased in the beginning of the
reaction time and continued to gradually drop, while calcite (29.4 and
39.4°2θ) and aragonite (26.22°2θ) gradually formed throughout the
reaction time, and the sample became enriched in fluorite (28.28°2θ).
4
The Journal of Supercritical Fluids 171 (2021) 105191
Carbonate content, TGA-MS (wt%) % maximal
14.6 30
24.8 48
27.4 51
18.9 37
24.5 48
9.8 19
21.8 42
Also, vaterite intensities (24.85, 27, and 32.78°2θ) began to increase in
the beginning of the reaction time. However, intensities at 24.85 and
27°2θ started to decrease in the middle of the reaction time. This de-
crease may have resulted from intensities of the wollastonite peaks
(25.28 and 26.88°2θ) decreasing in the middle of carbonation, hin-
dering the continuous increase in vaterite formation (24.85, 27, and
32.78°2θ), which then converted to more stable calcite. When cuspidine
was carbonated using thin-film and slurry carbonation methods, for-
mation of vaterite or aragonite carbonates was not identified by XRD
[34]. The observed formation of vaterite and aragonite during cuspi-
dine carbonation may have been promoted by the in situ XRD method
used in this study, allowing detection of transient phases. The thermal
behavior according to the TGS-MS results was consistent with crystal-
line carbonates (Fig. S9) [41]. According to the calculated values
summarized in Table 1, cuspidine achieved comparable CO2 uptake in
wet CO2(g) as γ-C2S in wet scCO2 carbonation, while β-C2S performed
poorer, indicating that the synthetic cuspidine is most susceptible to
carbonation among the Ca-rich minerals tested. The GADDS images of
carbonated cuspidine indicated distinct calcite and aragonite forma-
tion, as seen in Fig. 2. Fig. 2a is the GADDS image of unreacted syn-
thetic cuspidine. The uniform Debye powder rings at the cuspidine
peaks (27.2 and 29.1°2θ) indicate that cuspidine is a fine-grained
polycrystalline phase with a random orientation [39]. If the GADDS
image exhibited “graininess,” consisting of discontinuous Debye
powder rings, then it is consistent with the presence of relatively few
crystallites [39]. Fig. 2b is GADDS image after carbonation still under
pressure, and Fig. 2c is after carbonation, depressurized. When pressure
was removed, the bright diffraction rings became more noticeable.
Fig. 2c reveals that calcite and aragonite formed by carbonation, which
is consistent with the XRD results. Also, the vaterite peaks are absent in
these figures as explained by their disappearance observed in Fig. 1c in
the middle of the carbonation reaction.
3.2. Ca- and Mg-rich minerals
Bredigite, merwinte, and åkermanite contain both Ca and Mg in
their elemental composition. During bredigite carbonation in wet
CO2(g) (EXP #6), intensities of bredigite (32.78 and 33.63°2θ) and
merwinite (33.32, 33.52, and 33.76°2θ) peaks decreased immediately
in the beginning and continued to gradually drop throughout the re-
action time (Fig. S10). Huntite (31.55°2θ) and åkermanite (31.24°2θ)
intensities decreased moderately throughout the reaction time. Arago-
nite intensities (26.22 and 27.22°2θ) increased gradually throughout
the reaction time and that of hydromagnesite (30.82°2θ) rose at a
slower rate compared to aragonite. The dominant formation of arago-
nite was expected as similar results were obtained by bredigite carbo-
nation using thin-film and slurry carbonation methods, confirmed by
Bodor et al. [34]. As seen in TGA-MS results, the early decomposition
(~320–420 °C) may have resulted from thermal behaviour of amor-
phous hydromagnesite (Fig. S11). During carbonation of bredigite in
wet scCO2 (EXP #7), similar disappearance in bredigite and merwinite
and growth in aragonite and hydromagnesite intensities were seen
(Fig. S12). The TGA-MS results are very similar to those of EXP #6
(Fig. S13). The GADDS images for bredigite carbonated in wet CO2(g)
Y.E. Chai, Q.R.S. Miller, H.T. Schaef et al.
Fig. 1. 3D (a) and 2D waterfall (b) plots for time-resolved diffractograms of synthetic cuspidine carbonation in water-saturated CO2(g) at 70 °C and 6 bar.
(EXP #6) exhibited uniform Debye lines at aragonite peak (26.2°2θ) but
not hydromagnesite (Fig. S14). Similar GADDS images were produced
for bredigite carbonated in wet scCO2 (EXP #7) as seen in Figs. 2d to 2f.
When Figs. 2d and 2e are compared, distinct rings for aragonite ap-
peared. In Fig. 2f, after depressurization, the aragonite rings became
more visible. The absence of hydromagnesite peaks in these figures
could have resulted because its growth during carbonation was minimal
compared to other phases with greater intensities.
During merwinite carbonation in wet CO2(g) (EXP #8) (Fig. S15),
similar XRD results to bredigite carbonation were seen (EXP #6)
(Fig. S10). The intensities of merwinite (33.32, 33.52, and 33.76°2θ)
immediately decreased as the reaction started and continued to drop
gradually. The åkermanite intensities (31.24°2θ), a secondary phase in
the synthetic merwinite, sharply decreased in the beginning of the re-
action. Aragonite (26.22 and 27.22°2θ) formed gradually throughout
the reaction time and hydromagnesite (30.82°2θ) started to appear in
the middle of the reaction time. The formation of aragonite and hy-
dromagnesite in bredigite and merwinite carbonation was encouraged
by the presence of Mg in their original composition. The presence of Mg
is known to inhibit precipitation of calcium carbonate as the more
stable calcite and to promote aragonite formation [42]. According to
our earlier study on merwinite carbonation through thin-film and slurry
carbonation, merwinite had the slowest carbonation conversion out of
5
The Journal of Supercritical Fluids 171 (2021) 105191
the synthetic minerals tested in this study, while bredigite was found to
be the most reactive mineral [34].
During carbonation of synthetic åkermanite in wet CO2(g) (EXP #9),
the intensities of åkermanite (28.87 and 31.14°2θ) and diopside (30.88
and 35.48°2θ) decreased in the beginning of the reaction, however,
formation of carbonates was not observed. This observation is reflected
on the XRD diffractograms of åkermanite carbonation, provided as
Fig. S16. This result is in contrast with åkermanite carbonation using
thin-film and slurry carbonation methods by Bodor et al. [34].
3.3. Stainless steelmaking slags
During carbonation of AOD slag in wet CO2(g) (EXP #10), the in-
tensities of γ-C2S (29.7 and 32.5°2θ), cuspidine (27.34 and 29.14°2θ),
bredigite (32.78 and 33.63°2θ), and merwinite (33.32, 33.52, and
33.76°2θ) responded immediately (Fig. S17). Such mineral phases were
the main component of fresh AOD slags according to the QXRD results.
The dominant conversions of bredigite and γ-C2S during AOD carbo-
nation were also seen in thin-film carbonation by Santos et al. [33].
Near the end of the reaction time, monohydrocalcite (20.49°2θ) formed
and formation of calcite or aragonite was not exhibited by the XRD
diffractograms. Monohydrocalcite is an intermediate product in the
transition of amorphous calcium carbonate (ACC) to stable calcite or
Y.E. Chai, Q.R.S. Miller, H.T. Schaef et al.
Fig. 2. GADDS images of: (a) unreacted cuspidine; (b) carbonated cuspidine in wet CO2(g) at 70 °C and 6 bar with 40 μl of H2O before depressurization and (c) after
depressurization; (d) unreacted bredigite, (e) carbonated bredigite in wet scCO2 at 50 °C and 82 bar with 10 μl of H2O before depressurization and (f) after de-
pressurization.
aragonite. The TGA-MS results showed that mass drop of 8.8% between
300 and 620 °C (Fig. 3a). Calcination began at 300 °C and continued
gradually until 426 °C. Early decomposition (~330–420 °C) depicts
calcination of ACC [43,44]. In coincidence, between such temperature
range, significant release of H2O was detected. The early calcination
and simultaneous release of H2O is consistent with the behavior of
hydrated ACC. Then, the mass drop ceased until 560 °C and then ap-
peared a second peak, which was much steeper, at 622 °C with a sharp
decrease. This behavior is consistent with monohydrocalcite [45],
which was also proven to emerge in thin-film carbonation of AOD slag
by Santos et al. [33].
Carbonation of CC slag in wet CO2(g) (EXP #11) showed decrease in
β-C2S (32.17 and 32. 61°2θ), γ-C2S (29.7 and 32.5°2θ), bredigite (32.78
and 33.63°2θ), and merwinite (33.32, 33.52, and 33.76°2θ) intensities
(Fig. S18). The dominance of C2S polymorphs in carbonation conver-
sion is in parallel with the results found by Santos et al. [33], in which
CC slag was carbonated by thin-film carbonation method. Near the end
of the reaction, calcite intensities (29.4°2θ) increased. However, neither
Ca-Mg-carbonates nor Mg-carbonates formation were detected despite
the decrease in bredigite and merwinite peaks. The reacted Mg could
have been incorporated in the calcite lattice, widening the calcite peak
[46]. Similar to the AOD slags, CC slag experienced two peaks of CO2
release according to the TGA-MS results shown in Fig. 3b. The first and
minor one occurred at 445 °C and the second one was at 620 °C.
However, distinct H2O release was not observed. This phenomenon may
imply that the AOD slag was more hydrated than CC slag, but both slags
contained ACC and crystalline carbonates formed after carbonation in
wet CO2(g).
The GADDS images of the slags (AOD and CC) presented the
“graininess” in the diffraction rings with random bright diffraction
6
The Journal of Supercritical Fluids 171 (2021) 105191
spots, which was not observed in the synthetic materials, in both un-
reacted and carbonated slags (Figs. S19 and S20). These features in-
dicate the presence of relatively few crystallites and coarse-grained
crystallites (>40 µm) [39]. The GADDS images generated for EXP #10
and EXP #11 did not show distinct indication of carbonate formation,
however, the peaks of carbonates may have been obscured by nearby
peaks. When the results from TGA-MS are compared, CC slag resulted in
a greater CO2 uptake compared to AOD slag (Table 1), in agreement
with thin-film and slurry carbonation experiments done previously
[33]. Cuspidine and bredigite exist in higher amounts in fresh AOD slag
than fresh CC slag, while CC slag contains more C2S polymorphs in its
composition, as the values can be found in Table S1. Despite compar-
able CO2 uptake of individual minerals (Table 1), it appears that cus-
pidine and bredigite are poorly reactive in AOD slag carbonation, while
C2S largely contribute to the higher CO2 uptake achieved by CC slag.
4. Discussion
In Section 4.1, supercritical and subcritical CO2 carbonation are
contrasted, and in Section 4.2, links between the crystal structure of
silicate minerals and their behavior during mineral carbonation are
discussed.
4.1. Subcritical vs. supercritical CO2
Reacting minerals with scCO2 has been gaining attention to evaluate
the potential impacts it has to reservoir and caprock systems [47–50].
Studying carbonation of forsterite in wet scCO2 determined that thin
liquid water film formation on the mineral surface resulting from water-
bearing scCO2 is crucial to the carbonation rate and extent [51]. The
Y.E. Chai, Q.R.S. Miller, H.T. Schaef et al.
Fig. 3. TGA-MS curves of: (a) carbonated AOD slag; (b) carbonated CC slag in wet CO2(g) at 70 °C and 6 bar with 40 μl of H2O.
investigations discovered the impact of dissolved water concentration
in scCO2 on carbonation performance and that increased water content
increases reactivity. In the present study, carbonation in wet scCO2 with
constant concentration of water was conducted for β-C2S, γ-C2S, and
bredigite carbonation to investigate the reaction of such materials in
scCO2 and study how it affects the reaction compared to carbonation in
wet CO2(g).
Overall, contradicting effects were seen in C2S minerals. During β-
C2S carbonation in wet CO2(g) (EXP #1), calcite formed as well as
aragonite (Fig. S1). When it was exposed to wet scCO2 (EXP #2), for-
mation of only calcite was detected, indicating that carbonation was
more thermodynamically stable than that in wet CO2(g) (Fig. S2).
During carbonation of γ-C2S in both wet CO2(g) and wet scCO2 (EXP
#4), it was verified that calcite formed (Fig. S6). In bredigite carbo-
nation, significant difference between using wet CO2(g) and using wet
scCO2 during for carbonation was not seen as formation of aragonite
and hydromagnesite was exhibited in both conditions (Figs. S10 and
S12). According to Table 1, bredigite carbonation in wet scCO2
achieved greater CO2 uptake than in wet CO2(g). This result was
7
The Journal of Supercritical Fluids 171 (2021) 105191
produced due to difference in reaction conditions, which could have
increased passivation by silica layers, limiting carbonation reaction in
wet CO2(g), as commented by Daval et al. [52]. It is too early to make a
conclusion on the effect of using scCO2 as opposed to CO2(g) as only a
few experimental results were produced from scCO2 carbonation, but it
is confirmed that steel slag mineral phases carbonate in scCO2, thus
there is potential for the integration of mineral carbonation processes
with processes that generate scCO2 as a byproduct, such as supercritical
water oxidation and gasification [62].
4.2. Crystal structure and mineral carbonation
Crystal structure of minerals affects the carbonation kinetics and
extent of carbonation. The crystal structure of the unreacted minerals is
responsible for their dissolution in H2O [53], and it influences the
breaking of ionic bonds to release the alkaline earth metal ions. The
minerals that were subject to this study are classified as two silicate
types: nesosilicate and sorosilicate. The C2S minerals, bredigite, and
merwinite belong to nesosilicate group, and cuspidine and åkermanite
Y.E. Chai, Q.R.S. Miller, H.T. Schaef et al.
are in the sorosilicate group. Nesosilicates constitute an isolated silicon
tetrahedra, in the form of orthosilicate ion (SiO44-), which is connected
only by interstitial cations [54]. The dissolution of such silicates occurs
in multiple steps where Ca‒O and Mg‒O bonds break followed by the
release of SiO4 tetrahedra or double tetrahedra, without the need to
break Si‒O bonds [55]. Sorosilicates contain a bridging oxygen
(Si‒O‒Si) resulting in double tetrahedra, in the form of isolated pyr-
osilicate anion (Si2O76-). The strong Si‒O‒Si bonds make these minerals
less susceptible to dissolution and chemical reaction [56].
In terms of the minerals synthesized in this study, the C2S minerals
were expected to have the simplest dissolution step as the only bond
required to be broken is the Ca‒O bond to liberate the SiO4 tetrahedra
[55]. In C2S, all Si atoms are part of a silicate group and all Ca atoms are
ionic in character [57]. The weaker Ca‒O ionic bond of β-C2S compared
to γ-C2S contributes to its elevated reactivity and leads to higher car-
bonation extent. β-C2S has two classes of Ca atom in which one class is
six-coordinated and the second is eight-coordinated [58]. The Ca atoms
in γ-C2S are six-coordinated and the Ca‒O bond of the Ca in the poly-
hedral coordination sites is less stable and breaks down before that in
the octahedra sites, in which the presence of distortions that disturb the
structure of a regular octahedron increases its stability [58]. The simple
extraction of the Ca present in C2S contributes to quick conversion of
C2S, as seen during XRD carbonation (Figs. S1, S2, S5 and S6).
Bredigite and merwinite are also nesosilicates but they contain both
Ca and Mg, meaning Mg‒O bond exists in their crystal structure as
well [63,64]. In contrast to C2S carbonation behavior, both bredigite
and merwinite showed continuous conversion throughout the reaction.
For example, in the XRD results during bredigite carbonation in wet
CO2(g) (EXP #6) both bredigite and merwinite intensities decreased
immediately in the beginning of the reaction and the gradual drop
continued until the end of the reaction time (Figs. S10 and S15). It may
be predicted that the Mg, which has smaller ion size compared to Ca,
dissolved slower in water leading to gradual carbonation rate [59].
Cuspidine and åkermanite are sorosilicates and have double Si tet-
rahedra that share an oxygen atom (i.e. pyrosilicate anion), but cuspi-
dine also contains F ions in its structure, forming ionic bond with
Ca [64,65]. During XRD carbonation, cuspidine intensity immediately
decreased and continued to gradually drop until the end of the reaction
(Fig. 1). It can be suggested that Ca loosely bound to O led to immediate
carbonation, while the breaking of Ca–O‒Si bonds and release of Ca
bonded to F occurred subsequently, thus contributing to a more gradual
rate of carbonation and fluorite enrichment.
The structure of åkermanite consists of (MgSi2O7)4- layer of inter-
connected tetrahedra and the Ca atoms lie between these layers [60].
Mg has a 4-fold tetrahedral coordination and Ca an 8-fold polyhedral
coordination [61]. During XRD carbonation, åkermanite did not show
any transformation except for the decrease in åkermanite and diopside
peaks in the very beginning of the reaction time nor any formation of
carbonation was observed (Fig. S16). As carbonation of åkermanite was
seen in previous studies [34], it was the reaction conditions that did not
favor carbonation of this specific mineral rather than its crystal struc-
ture. In our previous work, in which the same synthetic minerals were
carbonated through thin-film and slurry carbonation, åkermanite
showed moderate carbonation conversion and CO2 uptake compared to
others.
5. Conclusions
Through identifying the behavior of individual minerals in the
steelmaking slags during carbonation, new insights into utilizing
steelmaking slags as a mean for mineral carbonation were observed.
The motivation of this work was to use slags as carbon sink, which can
benefit steelmakers by reducing their emissions and also by stabilizing
their slags. In addition, by knowing which silicate minerals that make-
up slags are most reactive to carbonation, this work informs steel-
makers of what slag composition to aim for when tuning the slag
8
The Journal of Supercritical Fluids 171 (2021) 105191
chemistry with fluxes and by control of slag cooling path.
The set of experimental conditions and approaches used in this work
is unique in relation to the present literature, and the findings help this
research field progress towards better understanding of the geochem-
istry and mineralogy that govern the carbonation of complex calcium-
and magnesium-silicates mixtures. The in situ XRD technique clearly
demonstrated the minerals that are susceptible to mineral carbonation
in steelmaking slags, the transient phases that form and reactions that
cease early or commence late, and the relative conversion rates and
degrees of reaction conversion, which is an information that cannot be
obtained in the conventional ex situ XRD approach. It also demon-
strated how supercritical and subcritical CO2, in absence of liquid
aqueous phase, promote conversion of silicates into carbonates. Mineral
carbonation without liquid aqueous phase is attractive since it facil-
itates recovery of the exothermic heat of carbonation reaction, which
can be interrupted by the large heat capacity of the water phase in
aqueous systems. Developing better mechanistic understanding of in-
dividual mineral phases on the reaction kinetics will help make a better
use of the steelmaking slags as the feedstock for mineral carbonation
and make predictive models for utilization of the steelmaking slags for
CO2 sequestration.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
RMS would like to acknowledge the Discovery Grant research
funding provided by the Natural Sciences and Engineering Research
Council of Canada, Canada (NSERC), and the travel funding provided
by the Fonds Wetenschappelijk Onderzoek, Belgium (FWO). QM and
HTS acknowledge support from the U.S. Department of Energy, USA
(US DOE), Office of Science, Office of Basic Energy Sciences (BES),
Chemical Sciences, Geosciences, and Biosciences Division through its
Geosciences program at Pacific Northwest National Laboratory (PNNL),
Richland, Washington, and the US DOE Office of Fossil Energy at PNNL
through the National Energy Technology Laboratory, Morgantown,
West Virginia.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.supflu.2021.105191.
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