pubs.acs.

org/journal/ascecg Research Article

Direct Air Capture and Sequestration of CO2 by Accelerated Indirect

Aqueous Mineral Carbonation under Ambient Conditions
Raghavendra Ragipani, Keerthana Sreenivasan, Robert P. Anex, Hang Zhai, and Bu Wang*
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ABSTRACT: Mineralization of gaseous carbon dioxide into solid carbonates

using alkaline industrial residues such as coal fly ash has a dual advantage of
Downloaded via AMERICAN UNIV IN CAIRO on February 27, 2023 at 21:18:50 (UTC).

reducing the carbon dioxide footprint of coal power plants and improving ash
utilization. However, the slow mineral carbonation rate under atmospheric
conditions is a major challenge, especially when using natural minerals or
industrial residues for direct air capture (DAC) of CO2. In this study, using
coal fly ash samples and concentrated alkali carbonate aqueous solutions as a
recyclable solvent, we show the feasibility of coupling mineral carbonation
with DAC under atmospheric conditions. Findings show that carbonation
efficiency is best under alkaline conditions, achieving as high as ∼80% conversion to calcium carbonates within 1 h in a 1.9 M
sodium carbonate solution. Based on the experimental results, a process coupling DAC and mineral carbonation that operates
entirely under ambient conditions is proposed. The techno-economic and life cycle assessments for the proposed process project a
levelized cost of $116−133/t-CO2-sequestered (US $2019) and process carbon emissions (GWP) in the range of 0.03−0.25 t-
CO2e/t-CO2-sequestered. Considering the low cost, simplicity, and gigaton-scale sequestration potential, we believe that DAC based
on alkaline industrial residue carbonation can be considered a “low-hanging fruit” in the pursuit of negative emissions to combat
climate change.
KEYWORDS: CO2 mineralization, coal fly ash, industrial alkaline waste, calcium carbonate, techno-economics, life cycle assessment

■ INTRODUCTION
Mineral carbonation is one of the safest and most
thermodynamically favorable carbon dioxide capture and
storage (CCS) methods with CO2 disposal potential believed
to exceed emissions from fossil fuels.1 The method is
analogous to natural weathering and fixes carbon dioxide as
sparingly soluble carbonates [see reaction (1), e.g.] at an
accelerated rate using naturally occurring alkaline minerals
such as olivine and wollastonite or industrial mineral wastes
such as ferrous slags and coal combustion residues. Mineral
carbonation is an important CCS strategy, especially
considering the added benefit of simultaneous solid waste
utilization and sequestration of hazardous materials.2 A recent
study3 projected that alkaline industrial wastes alone could
sequester about 8.5 GtCO2/year by the end of this century.
Ca 2SiO4 + 2CO2 (g) → 2CaCO3 + SiO2
ΔGr0 = −108.5 kJ; ΔHr0 = −207.4 kJ
The most significant challenge for mineral carbonation
processes is to overcome slow carbonation kinetics under
atmospheric conditions. Previously proposed direct (slurry4
and thin-film5) and indirect aqueous mineral carbonation
routes (pH swing6−9 and pressure swing10,11) were mainly
focused on acidic media,12 including pressurized carbon
dioxide,13,14 to enhance the mineral dissolution rate and
overall carbonation efficiency. These methods require energy-
intensive process steps such as pressurization and, more
importantly, concentrated CO2 streams, making them largely
suitable for point-source emissions only. On the other hand,
mineral feedstocks, especially industrial wastes, are geo-
graphically dispersed. The logistical challenges, cost, and
emissions associated with siting of the facilities and trans-
portation of the feedstocks often render implementing mineral
carbonation-based CO2 capture processes impractical.
In this article, we propose to couple mineral carbonation
with the direct air capture (DAC) process. Compared with
CO2 capture from point sources, DAC offers flexibility in
locations and the ability to address historical emissions and
emissions that are hard to mitigate. DAC using alkaline
chemical solvents such as sodium hydroxide [NaOH; see
reaction (2)] or potassium hydroxide (KOH) is promising,
owing to these solvents’ high alkalinity and CO2 scrubbing
(1) efficiency.15,16 However, one of the main challenges to this
Received: November 19, 2021
Revised: May 25, 2022
Published: June 9, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acssuschemeng.1c07867

7852 ACS Sustainable Chem. Eng. 2022, 10, 7852−7861
ACS Sustainable Chemistry & Engineering
approach is the cost-effective regeneration of hydroxide
solution.
CO2 (g) + 2NaOH(aq) → Na 2CO3(aq) + H 2O
ΔGr0 = −58.7 kJ; ΔHr0 = −110.1 kJ (2)
Regeneration of sodium hydroxide is typically carried out
based on the soda ash/Kraft process chemistry. However, lime
regeneration in this process by calcination is endothermic,
requires high temperature, and hence is energy-intensive.
Moreover, it produces a concentrated CO2 stream that must be
compressed and transported for geological storage or chemical
synthesis.
We overcome critical issues of both mineral carbonation and
strong hydroxide DAC simultaneously by an indirect route
described using reaction set (3)
2CaO·SiO2 (s) + 2Na 2CO3(aq) + 2H 2O
→ 2CaCO3(s) + SiO2 (s) + 4NaOH(aq) (3)
CaO·Al 2O3 ·2SiO2 (s) + Na 2CO3(aq) + 4H 2O
→ CaCO3(s) + 2Al(OH)3 + 2SiO2 (s) + 2NaOH(aq)
This reaction generates NaOH solution by carbonating Ca-
rich silicate or aluminosilicate minerals or industrial residues
using Na2CO3. Then, Na2CO3 is regenerated in a subsequent
DAC step as described in reaction (2), thereby coupling
mineral carbonation with DAC. The success of this coupling is
dependent on the ability to achieve high carbonation efficiency
in alkaline carbonate-bearing solutions, which has received
little attention in the literature. In our opinion, the absence of
studies under alkaline conditions may be due to emphasis on
enhancing dissolution rates to overcome the suspected
passivation effects of leached layers or secondary precipitates
such as amorphous silica and calcium carbonate.12,17−19 A few
important studies considered using bicarbonate and pressur-
ized carbon dioxide to accelerate the carbonation of
olivine.20,21 However, the pH in these experiments was
below 7, and an increase in carbonation efficiency was largely
attributed to changes in dissolution mechanisms and
passivating layers.22 In this study, we report the possibility of
achieving high carbonation efficiency (as high as ∼95% of total
Ca) at alkaline pH under atmospheric conditions for two coal
fly ash samples with distinct chemical composition and
mineralogy.
To our knowledge, there are no previous studies that used
silicate or aluminosilicate-based minerals or industrial residues
for the proposed process. Although more research is needed to
elucidate the acceleration mechanisms under alkaline con-
ditions and to identify the most suitable parameters for
different mineral feedstocks because of the simplicity and low
cost, we believe that the presented process has the potential to
provide substantial negative emission capacity in the near term.
In this article, we determine the carbonation potential of
coal fly ash samples in carbonate-bearing solution. We
conducted batch carbonation of fly ash samples to study the
parametric effects of pH and carbonate-ion concentration. The
benefits of coupling mineral carbonation and DAC are
discussed based on the techno-economic and life cycle
assessment.
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■
pubs.acs.org/journal/ascecg Research Article
MATERIALS AND METHODS
Coal Ash Sample. Two coal fly ash samples, FA-1 and FA-2, were
used in this study. Ash sample FA-1 is a commercial class C fly ash,
whereas FA-2 is a mixed residue of fly ash with spray dryer absorber
products from the Weston Power Plant, WI, USA. Both these fly ash
samples were used as obtained without any pretreatment. The
chemical composition of ashes (FA-1 and FA-2), as determined by X-
ray fluorescence (XRF) in mass % of oxides, is CaO (28.01 and
25.90), SiO2 (32.09 and 31.8), MgO (7.23 and 3.95), Al2O3 (18.48
and 15.60), Fe2O3 (5.27 and 4.94), and SO3 (2.96 and 10.44),
respectively. Crystalline mineral phases determined from X-ray
diffractograms of FA-1 are tricalcium aluminate (3CaO·Al2O3),
anhydrite (CaSO4), α-quartz (SiO2), gehlenite (Ca2Al2SiO7),
periclase (MgO), lime (CaO), and anatase (TiO2). On the other
hand, crystalline phases in FA-2 are calcium sulfite hemihydrate
(CaSO3.0.5H2O), tricalcium aluminate (3CaO·Al2O3), periclase
(MgO), α-quartz (SiO2), magnetite (Fe3O4) with traces of portlandite
(Ca(OH)2) and calcite (CaCO3). Calcite in the raw sample was
determined using a thermogravimetric analyzer and found to be <0.5
wt % in both cases.
Ash Carbonation Experiments. Slurry carbonation experiments
were conducted in a 100 mL glass reactor under atmospheric
conditions for coal ash samples. The experiments involved studying
the effect of sodium carbonate loading [carbonate-to-ash (C/S):
0.125−5.0 g/g of ash] at a liquid-to-solid ratio (L/S) of 25 mL/g on
carbonation efficiency. Similarly, the effect of L/S was studied in the
range of 5−100 mL/g at a C/S ratio of 1 g/g; the corresponding
carbonate-ion concentration was 0.1−1.9 M. To study the effect of
pH (7.8−11.7) on ash carbonation characteristics, experiments were
conducted using sodium carbonate and bicarbonate solution of
strength 0.375 and 0.75 M, respectively. Use of pressurized CO2 up to
5 atm in 0.75 M sodium bicarbonate solution allowed us to reduce the
solution pH down to 7.45. For experiments involving CO2 pressure, a
50 mL Parr reactor was used. For these experiments, CO2 at desired
pressure was first introduced into sodium bicarbonate solution by
stirring at 800 rpm. After 10 min, the reactor was opened to add ash
without any stirring. Subsequently, the reactor was pressurized and
depressurized cyclically three times to remove air from the reactor.
After pressurizing the reactor to the desired pressure, stirring at 800
rpm was started, and the reaction was ended after 60 min. Slurry pH
was measured during atmospheric experiments using a pH meter with
a glass electrode that was calibrated using pH buffers 4.01, 10.01, and
13.0 on a daily basis.
We carried out direct carbonation of coal ash samples in 1 atm CO2
in deionized water in the same experimental setup as above and
compared the direct carbonation efficiency with that of the proposed
method.
Analytical Methods. The supernatant from the batch reaction
slurry was filtered using a 0.2 μ syringe filter, and the obtained
aqueous solution was acidified and diluted up to 10 times using a
combination of 0.5 M HNO3 and 0.03% H2O2 solutions. The addition
of peroxide was required to avoid the formation of dissolved sulfur
dioxide upon acidification, which was previously found to elevate
overall sulfur concentration when measured using inductively coupled
plasma (ICP) spectrometry.23 The dissolved elemental concentrations
in the aqueous solution were measured using inductively coupled
plasma optical emission spectroscopy (ICP-OES; Varian Vista-MPX,
Varian, Palo Alto, CA, USA). Reported concentrations are averages
from three measurements. The remaining batch reaction slurry was
vacuum-filtered on a filter paper with 1 μm retention to separate
carbonated residue, which was dried overnight at 100 °C. A
thermogravimetric analyzer (TA Instruments) in a N2 environment
was used to determine the extent of carbonation by measuring the
weight loss between 580 and 850 °C. A custom dynamic segment
temperature ramp program was used to reduce the ramp rate from the
usual 20 to 5 °C/min, whenever the recorded weight loss was
>0.25%/min, and toggle back to 20 °C/min when the recorded
weight loss was <0.075%/min. Powder X-ray diffraction (XRD;
Bruker D8 Discover) with a Cu-Kα source was performed on the
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ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Figure 1. Temporal changes in (A) CaO carbonation (%) and (B) slurry pH evolution in a batch reactor for the FA-1 sample at a C/S ratio of 1 g/
g (pHi = 11.53) and 3 g/g (pHi = 11.7) Na2CO3 solutions, 1.585 g of NaHCO3/g of ash (initial pH of 7.77), 0.79 g of NaHCO3 + 0.5 g of
Na2CO3/g of ash (initial pH of 9.3), and 1.585 g of NaHCO3 + 1 atm CO2/g of ash (initial pH of 7.45) at L/S of 25 mL/g.

carbonated residues using a 2.0 mm collimator and 2D VANTEC

detector at a scan rate of 120 s/step and a step size of 17° to
determine the changes in crystalline mineral phases. Reference XRD
patterns from the Inorganic Crystal Structure Database (ICSD) were
used for mineral phase identification.

■ RESULTS
Carbonation Characteristics under Alkaline Condi-
tions. To explore carbonation of industrial alkaline wastes
under basic conditions, we evaluated reaction (3) in a batch
reactor using two calcium-rich coal fly ash samples (FA-1 and
FA-2; see §5 for sample details). Different combinations of
sodium carbonate/bicarbonate solutions and CO2 atmosphere
were used to vary the initial carbonating solution pH while
keeping the total carbonate-ion alkalinity (defined as 2[CO3−2]
+ [HCO3−]) constant. Molar fractions of sodium bicarbonate
and sodium carbonate salt mixtures were varied in the range of
0−1; besides, carbon dioxide pressure (1−5 atm.) and sodium
hydroxide (0.04−0.1 M) were used to increase the span of
initial pH to 6.7−12.8. For this study, total carbonate-ion
alkalinity was fixed at 0.75 M such that bicarbonate-rich
solution was undersaturated with respect to nahcolite
(NaHCO3) (see Section A.1 of Supporting Information for
observations on nahcolite precipitation at [HCO3−] > 0.75
M); equivalent concentration for pure anhydrous Na2CO3
carbonating solution was 0.38 M [or 1.0 g of Na2CO3/g of C/
S loading at a L/S of 25 mL/g].
Figure 1A shows the temporal changes in CaO conversion
(%) to calcium carbonate (henceforth, we refer to this
parameter as carbonation efficiency; see A.2 of Supporting
Information for the determination method) for sample FA-1
with initial pH in the range of 7.4−12.0 and [CO3−2] up to 1.0
M. Data for FA-2 are included in the A.2 of Supporting
Information, which show a similar behavior. Corresponding
elemental concentration data sets for FA-1 and FA-2 are
included in A.3 of Supporting Information. In most of the
carbonating solutions, carbonate precipitation approaches a
steady state after 30 min. As expected from reaction (3),
carbonation of aluminosilicates in fly ash led to generation of
sodium hydroxide and an increase in slurry pH (Figure 1B).
Figure 2 summarizes the carbonation efficiency after on hour at
a L/S ratio of 25 mL/g as a function of the initial pH. The
7854
Figure 2. Influence of solution pH at a carbonate alkalinity of 0.75 M
and a ratio L/S of 25 mL/g on carbonation efficiency of FA-1 and FA-
2 coal fly ash samples in 1 h batch experiments. Initial pH values are
simulated using the Pitzer activity coefficient model in PHREEQC24
as measurements were not possible with the existing setup under CO2
pressure. A.4 of SI shows that, wherever measurements were possible,
simulated pH values were in good agreement with measured pH
values.
influence of pH on carbonation efficiency shows surprising
trends for both ashes, wherein lowering of pH by introducing
carbon dioxide was found to be detrimental.
As illustrated in Figure 2, the complex influence of solution
chemistry on carbonation characteristics and can be segregated
into three regimes−low-pH (<7.8), intermediate-pH (7.8−
11.5), and high-pH (>11.5) regimes. Within the investigated
pH range, the best carbonation efficiencies were recorded for
both FA-1 (43.2%) and FA-2 (48.9%) in the high-pH regime
with an initial pH of 11.5 and a carbonate-ion concentration of
0.38 M. A further increase in the initial pH of carbonating
solution, up to 12.8, by addition of NaOH did not affect the
carbonation efficiency.
In the low-pH regime, where the solution was saturated with
CO2 (pressure up to 5 atm) and contained 0.75 M bicarbonate
ions, carbonation efficiency was as low as 19.3 and 9.1% for
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ACS Sustainable Chemistry & Engineering
FA-1 and FA-2, respectively. Characterization of carbonated
ash samples using XRD (see A.5 of Supporting Information)
suggests that otherwise reactive Ca-rich primary phases in the
ash under alkaline conditions, such as free lime (CaO) and
tricalcium aluminate (C3A) in FA-1, remained noticeable in
the carbonated residue.
In the intermediate pH range, low-sulfur FA-1 and high-
sulfur FA-2 ash samples demonstrated starkly different
carbonation characteristics. In the case of FA-2, the
carbonation efficiency (43.5−48.5%) showed a marginal
influence of pH and carbonation was comparable to that of
the high-pH regime (48.9%). On the other hand, the FA-1 ash
sample showed a complex behavior, exhibiting a minimum
carbonation efficiency in the pH range of 7.8−11.5. The
carbonation efficiency in a solution made up of a 1:1 M ratio of
sodium carbonate and bicarbonate (initial pH of 9.3) was only
22.2% compared to 43.2% in pure sodium carbonate solution
(initial pH of 11.5) of the same carbonate-ion alkalinity.
Enhancing Carbonation Efficiency with Carbonate-
Ion and Slurry Concentrations. We studied the effect of
carbonate-ion concentration to understand(a) its role in
enhancing the carbonation efficiency of FA-1 in the high-pH
regime compared to the intermediate-pH regime and (b) the
influence of concentration on 1 h carbonation efficiency of FA-
1 and FA-2 in the high-pH regime. Toward these objectives,
parametric studies were conducted by varying the C/S ratio
from 0.25 to 5.0 g/g at a water-to-ash ratio (L/S; also referred
to as the liquid-to-solid ratio) of 25 mL/g, and L/S was
independently varied from 5 to 100 mL/g at a C/S ratio of 1.0
g/g. The resulting sodium carbonate solution concentrations
were in the range of 0.95−1.89 M, and the slurry concentration
was in the range of 1.0−20.0 wt %. As shown in Figure 3, when
Figure 3. Influence of sodium carbonate concentration [L/S (solid
symbols) and C/S (open symbols) were varied independently] on
carbonation efficiency from 1 h batch carbonation experiments. The
chart also shows data points in the intermediate pH range from Figure
2 on the carbonate-ion concentration scale.
C/S was independently varied at an L/S ratio of 25 mL/g, the
influence of carbonate-ion concentration differed significantly
for FA-1 and FA-2 carbonation characteristics. In the case of
FA-1, CaO carbonation (%) increased sharply to 78.8%, with
an increase in sodium carbonate concentration to 1.89 M. At
the same time, FA-2 did not show significant sensitivity in the
range of 0.094−1.5 M. A further increase in concentration to
1.89 M increased the FA-2 carbonation efficiency to 69.1%. As
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pubs.acs.org/journal/ascecg Research Article
shown in Figure 3, we also compared the carbonation
efficiencies achieved in the intermediate pH range (shown in
Figure 2) at available carbonate-ion ([CO3−2]) concentration
in the initial solution. FA-1 ash showed much lower
carbonation in the intermediate-pH regime at similar
carbonate-ion concentrations compared to the high-pH
regime, which suggests that [CO3−2] alone cannot explain
the poor carbonation efficiency in the intermediate-pH regime.
On the other hand, FA-2 ash showed comparable efficiencies
in the intermediate-pH regime and the high-pH regime, which
agreed with its invariant characteristics in the high-pH regime
at a concentration below 1.5 M.
The L/S ratio at constant sodium carbonate loading per
gram of ash showed a marginal increase with an increase in
carbonate-ion concentration for both ashes up to 1.5 M. A
further increase in [CO3−2] to 1.89 M improved the CaO
carbonation efficiency (%) to 69.3 and 66.4% for FA-1 and FA-
2, respectively. At a chosen carbonate-ion concentration
(Figure 3), the influence of slurry concentration was not
significant for the FA-2 ash sample. However, in the case of
FA-1, dilution of slurry enhanced the overall carbonation
efficiency.
In these 1 h batch experiments, carbonation efficiency of FA-
1 and FA-2 ash samples reached as high as 78.8 and 69.1%,
respectively, under atmospheric conditions in solution with a
[CO3−2] of 1.89 M. Extending the carbonation time to 24 h
showed that 95.2% (∼210 g of CO2/kg of FA-1 ash)
carbonation efficiency was achievable at a C/S of 3 g/g
(1.13 M). To substantiate the extent of enhancement observed
in carbonate-bearing solutions, we compared it with results
from direct aqueous carbonation experiments in deionized
water saturated with CO2. Direct aqueous carbonation of FA-1
in deionized water under 1 atm CO2 pressure resulted in only a
CaO carbonation efficiency of 4.25%. Under similar con-
ditions, FA-2 did not show any appreciable carbonation. These
results from two fly ash samples firmly establish that sodium
carbonate solution is promising for ash carbonation.
Differences in carbonation efficiencies in low- and high-pH
regimes is understood based on the carbonation and hydration
kinetics, shown in Figure 4. As shown in Figure 4A,
carbonation kinetics in the high-pH regime demonstrated a
distinct peak in rate between 5 and 10 min, which was absent
in the low-pH regime. Figure 4B shows the corresponding
negative hydration rate, which suggests carbonation of
intermediate hydration products. A corresponding increase in
solution pH between 5 and 10 min, shown in Figure 1B,
corroborates the above data. A hypothesis that the hydration
products are amenable to further carbonation in carbonate-
bearing solutions is significant in view of speculations about
the passivating behavior of secondary precipitates.
Although drawing mechanistic insights was not within the
scope of this article, based on multi-phase kinetic data
collected for this study, we suggest that in addition to
dissolution and carbonation precipitation, the carbonation
mechanism should include formation and carbonation of
intermediate hydration products. Multi-phase kinetic data for
fly ash dissolution, hydration, and carbonation reactions in
carbonate-bearing solutions and the proposed mechanism are
provided in the Supporting Information (Section A.9) along
with this article for interested readers.
Design of The DAC and Sequestration Process. Based
on the carbonation experiment results, a DAC and
sequestration process is designed. The proposed process
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Figure 4. (A) Influence of solution chemistry on the FA-1 carbonation rate at an L/S of 25 mL/g obtained using piecewise cubic Hermite
interpolating polynomial (PCHIP) spline interpolation in MATLAB. The carbonation rate could not be estimated at 5 atm pressure (pHi = 7.45)
as it was not possible to collect solid samples in short duration from the high-pressure setup used in this study; solid samples were collected at 20
and 60 min, where a steady-state behavior was noticed (see Figure 1A). In the legend, pHi is the initial pH and [DIC]i is the initial dissolved
inorganic carbon (which is the sum of [CO3−2] and [HCO3−] in the solution). (B) Rate of formation of hydration products in the FA-1 residue
estimated by PCHIP interpolation of weight loss (gH2O/g of residue) observed in the temperature range of 105−440 °C using a
thermogravimetric analyzer in a N2 environment [thermogravimetric analysis (TGA) measurements are shown in A.7 of Supporting Information].

Figure 5. Process scheme for coupled mineral carbonation with DAC.

scheme, illustrated in Figure 5, has two major steps: (a) ash
carbonation in carbonate-bearing solution and (b) CO2
absorption from air or flue gas. As shown in Figure 1B, ash
carbonation in sodium carbonate solution (0.38−1.13 M)
raised the solution pH significantly from 11.5 to 11.7 to a final
pH in the range of 12.8, which is comparable to the pH of 0.1
M NaOH solution. Presence of carbonate ions in the
absorbent is known to enhance the CO2 absorption rate as
compared to that in pure NaOH solution. Such a behavior is
expected due to the reaction of CO2 with carbonate ions to
form bicarbonate ions.25 A mixture of sodium carbonate and
sodium hydroxide solution may be used to achieve 1 M NaOH
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(considered a benchmark for DAC 26 ) from the ash
carbonation step without affecting the carbonation efficiency.
Higher sodium hydroxide concentrations up to 7.2 M may be
desirable to accelerate the DAC step and minimize water
evaporation losses.27
Carbonate residue from the mineralization step is separated
by filtering the slurry. The filter cake is washed with water to
recover sodium carbonate either adsorbed on the residue or
formed as gaylussite (CaCO3·Na2CO3·6H2O) during the
carbonation step. Gaylussite precipitation was not noticed in
the current study, while some previous studies on fly ash
activation in concentrated carbonate solutions suggested its
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formation.28,29 The carbonated ash cake from filtration was carbonation parametric studies, a L/S ratio of 5 mL/g and a
dried and sent for storage. [Na2CO3] of 1.9 M with a carbonation efficiency of ∼70%
Previously, carbon engineering (CE) proposed significantly were chosen for process simulation and plant design. Figure 5
inexpensive DAC technology compared to others using a shows internal stream flow rates for the 1 tCO2/h output plant
K2CO3−KOH absorbent pair.30 The CE-proposed process with a solvent recycle-to-purge ratio of 99. Design basis for unit
captures CO2 from air in an air contactor, where air and KOH- operation sizing for each equipment is provided in Table 2. A
rich solutions are contacted in a cross-flow fashion over typical design margin of 25% was considered for all auxiliary
structured packing. The obtained carbonate-rich aqueous equipment such as pumps, conveyers, filters, and dryers.
solution converts CaO to CaCO3, which is subsequently
calcined at high temperature to generate gaseous CO2 and Table 2. Operating Cost for FA-1 Mineral Carbonation at
solid CaO. A concentrated CO2 stream is compressed and L/S of 5 mL/g, 20 and CaO Carbonation Efficiency of
transported for sequestration. 70.4%
When compared with the CE process, the process proposed
in this study avoids the calcination, CO2 compression, and energy
(kW h/t of costa ($/t
transportation steps, which is expected to further reduce the unit operation design basis CO2) of CO2)
cost of CO2 capture. Furthermore, the proposed process uses FA Mineral Carbonation
industrial wastes instead of calcium carbonate (or oxide) reactor/agitator stirring rate: 200 rpm 19.5 1.4
feedstock. Since the design of “air contactor” was not within operating volume: 70%
the scope of this article, we consider CE design as a benchmark residence time: 20 min;
for techno-economics and life cycle analysis. motor efficiency: 0.9
Techno-Economics and Life Cycle Carbon Emissions filtration vacuum: 500 mmHg 63.8 4.5
of the Process. Capital costs were estimated using previous air flow required:
0.24 m3/kg
equipment cost estimates (2014 reference year when the CE
cake moisture content:
annual plant cost index was 576.1) from Matches web 30 wt %
program31 with inflation being adjusted to the year 2019 solids transport motor efficiency: 0.9 3.8 0.26
(CEPCI; 607.5). Installation factors were used to determine pumping ΔP: 120 kPa; pumping 5.3 0.37
the overall direct field costs. Indirect field costs and other costs efficiency: 0.82
were estimated using the factors considered for CE DAC plant motor efficiency: 0.9
design.30 Contingency cost of 20% of overall plant capital cost Direct Air capture of CO2
was included. A plant life of 25 years, capital recovery factor of air contactor CE design; ΔP/L: 61 4.3
7.5%, and plant factor of 90% were assumed in calculating the 9.7 Pa/m
pumping CE design; pumping 21.0 1.5
capital cost per metric ton of carbon dioxide captured. Table 1 efficiency: 0.82
shows estimates for operating and capital expenditures for the make-up costb
coupled process shown in Figure 5. The design basis for the materials design basis (t/t-CO2) ($/t-CO2)
plant is to sequester 1 tCO2/h from air. Based on the FA Na2CO3 eecycle/purge: 0.0065−0.065 1.36−13.6
99−999
Table 1. CAPEX Estimate for Plant with a Capture Capacity process water eecycle/purge: 0.0027−0.272 8.3−13.2
99−999
of 1 tCO2/h
cake wash: 30 wt % of 3.2
carbonated solid
purchased Eq. cost installed cost moisture loss with air 5−10
unit ($M) ($M) stream
Mineral Carbonation total energy cost 12.2
pumps 0.15 0.20 ($/t of CO2)
conveyer 0.02 0.03 total material cost 9.7−26.9
($/t of CO2)
filtration 0.71 1.20
a
carbonation Reactor 0.66 1.04 Cost of heat. bCost of Na2CO3 and process water were taken to be
storage tanks &; silos 0.40 0.76 $250/ton and $1/m3, respectively.
total mineral carbonation cost 2.17 3.60
DAC of CO2 Operating cost for the capture of 1 metric ton of carbon
contactor (pro rata from CE data30) 1.9 dioxide is estimated to be $21.9−39.1 (US $2019). Major
total DAC cost 1.9 energy costs are due to air contactor operation and slurry
total direct field costs 5.1 filtration. Material replacement costs include make-up sodium
indirect field costs (12.5% of TDFC) 0.64 carbonate ($250/t) and process water ($1/m3) to compensate
total field costs (TFC) 5.8 for solvent purge and moisture loss due to evaporation in the
engineering (12.0% of TPC) 0.99 air contactor, respectively. Recovery of sodium carbonate from
other project costs (4.27% of TPC) 0.35 the purge stream and cheaper water source could further
contingency (20% of TFC) 1.2 reduce the overall operating costs. Capital cost for the process
total non-field costs 2.5 is estimated to be $94 per metric ton of CO2 captured.
total project costs (TPC) 8.3 Estimated plant cost is cheaper than that of CE30 process by
annualized Cost (25 years, 0.7 about 22%. The calciner−slaker, air separation unit, CO2
7.5% CRF) $M/y compressor, power plant in the CE design, which are not
CO2 captured (t/y) PF: 90% 7884 part of the proposed process, contribute about 27.8−31.0% of
CAPEX ($/t-CO2-captured) 94 the total capital cost estimated by CE. Thus, we anticipate
7857 https://doi.org/10.1021/acssuschemeng.1c07867
ACS Sustainable Chem. Eng. 2022, 10, 7852−7861
ACS Sustainable Chemistry & Engineering
further reduction in the plant cost for the proposed process
with optimization of the carbonation reactor and slurry filter
designs. Additional operating and capital costs for the
proposed process could arise from feedstock pulverization
needed to process coarse waste materials, which will be
considered in future studies. The levelized cost of CO2 capture
from air and its sequestration as stable carbonates by the
proposed process, which includes capital and operating costs, is
$116−133/t-CO2-captured (US $2019).
The carbon emissions of the process were calculated as the
GWP of the greenhouse gases (GHGs) released through the
operation of the mineral carbonation−DAC process per ton of
carbon dioxide captured in the process, measured in units of
CO2 equivalents (CO2e). Figure 6 shows a breakdown of the
Figure 6. Breakdown of the carbon footprint of the process.
sources of the GHG emissions associated with the process. It
can be seen that the most significant emission is from the
make-up Na2CO3 used to compensate the solution loss from
the filtration process. The rest of the GHG emissions of the
process are associated with the process energy and to a much
smaller extent the provision of water. The direct energy
requirement of the process is estimated to be 174 kW h per ton
of CO2 captured (Table 2). Air contactor and filtration
operations are the two most energy-intensive steps in the
process and therefore responsible for significant portions (43
and 34%, respectively) of the direct emissions by the process
(i.e., emissions excluding those embodied in the Na2CO3
make-up and water). Solid material handling and the
carbonation reactor operation account for a small percentage
of the overall GHG emissions. As such, accommodating
variability in the feedstocks via moderate variations in material
quantities and carbonation duration will not have a significant
impact on life cycle emissions.
We assume that the process uses electric power obtained in a
particular subregion of the United States transmission system
with associated GHG emissions as reported in the Emissions
and Generation Resource Integrated Database (eGRID)
inventory.32 Because the fuel mixtures used to generate
electricity in the grid subregions differ, the GWP associated
with producing the electrical energy required to capture a ton
of CO2 varies with the region where that carbon is captured.
7858
pubs.acs.org/journal/ascecg Research Article
For example, in the eastern portion of the Midwest Reliability
Organization (MROE) subregion, where relative to the
national average more coal is used, the carbon emission ratio
would be 0.13 t-CO2e/t-CO2-captureda. In the California and
Mexico subregion of the Western Electricity Coordinating
Council (CAMX), where more solar, wind, and natural gas are
used than the national average, the carbon emission ratio
would be 0.04 t-CO2e/t-CO2-captured, while in the Upstate
New York subregion of the Northeast Power Coordinating
Council (NYUP), where significantly more hydropower and
nuclear power are used, the carbon emission ratio would be
0.02 t-CO2e/t-CO2-captured.
The amount of replacement process water that must be
provided due to evaporative water loss during DAC is
determined from ambient temperature, relative humidity, and
molarity of the capture solution.30 With a 2M capture solution,
expected water evaporative water loss ranges from approx-
imately 4 t-H2O/t-CO2 to 35 t-H2O/t-CO2, depending on the
ambient temperature and relative humidity (i.e., as temper-
ature ranges from 10 to 30 °C and RH ranges from 35 to
75%). Energy used for treatment, source extraction, and
distribution of this water in a large capacity (>0.3 MGD)
municipal groundwater supply system is taken as 0.64 kW h/
m3.33 The carbon emission ratio associated with energy used to
provide make-up process water in the range of 4−35 t-H2O/t-
CO2 is 0.002−0.005 t-CO2e/t-CO2-captured.
The cradle-to-gate GWP of Na2CO3 production is 1.84 t-
CO2e/t-Na2CO3 (modified Solvay process, Hou’s process,
Ecoinvent V3.3). For the range of make-up Na2CO3 estimated
(see Table 1), the resulting carbon emission ratio is 0.01−0.1
t-CO2e/t-CO2-captured. The total process carbon emissions
associated with process energy and material replacement
depend on the fuel mixture used in the regional electric power
grid, the local weather, and the amount of replacement
material required. The estimated total process carbon
emissions (GWP) are estimated to be in the range 0.03−
0.25 t-CO2e/t-CO2-captured. Note that this net carbon
analysis result is uncertain and dependent on local variables
like the carbon intensity of electricity on the local grid.
Nonetheless, it compares favorably with analysis of other
proposed DAC technologies.30
■ DISCUSSION
Process Economics and Emissions. The acceleration of
mineral carbonation under alkaline conditions offers a route for
directly coupling direct air capture with mineral carbonation.
With the process proposed in §3.4, it is possible to complete
capture and sequestration in a two-step loop, all under ambient
conditions. Prominently, the process avoids calcinating the
carbonated residue for pure CO2. We estimate that the total
cost of capturing 1 ton of CO2 by the proposed process is
about $116−133, based on realistic data on strong hydroxide
DAC costs in the literature. On the other hand, the cost
estimated for capturing CO2 via DAC from several previous
studies varied in the range of 43−780 $/tCO2.34 Capturing
CO2 via traditional DAC and subsequent conversion to
synthetic chemicals or CO2 disposal in geological storage is
expected to be 25−30% more expensive than the process
proposed here due to costs associated with calcination and
CO2 compression, storage, transport, and sequestration. The
proposed process operates at ambient temperature and
pressure, thus requiring relatively low energy input, and the
resulting “carbon cost” of capture is less than 0.25 t-CO2e/t-
https://doi.org/10.1021/acssuschemeng.1c07867
ACS Sustainable Chem. Eng. 2022, 10, 7852−7861
ACS Sustainable Chemistry & Engineering
CO2-captured. It is also worth noting that carbonated
industrially derived minerals are being actively studied as
supplementary cementitious material (SCM).35,36 Beneficial
use of the carbonated residues from the proposed process will
provide additional economic benefits and carbon emission
reduction (e.g., reducing cement usage).
Industrial alkaline wastes such as coal fly ash and steel slags
typically contain pollutants such as Co, Cr, Ni, V, Zn, and so
on. Pollutants released into the aqueous phase during our
process would be largely contained within the process loop
because the aqueous solution is cycled between the
carbonation and capture steps. Nonetheless, landfilling
carbonated residues can be a source for contamination of
ground and surface waters in the long term. Carbonation of
alkaline residues was previously shown to stabilize some
pollutants such as Cr.4,37 On the other hand, mobility of V was
found to increase in carbonated residues at alkaline pH.4 Both
stabilization and high mobility can potentially benefit the use
of carbonated residues in structural applications and recovery
of “strategic elements”, respectively.38,39 Understanding the
leaching characteristics of pollutants and their implications on
the proposed process, which was beyond the scope of this
study, would be addressed in future investigations.
Feedstock Availability and Gigaton-Scale Capture
Potential. Although the acceleration mechanisms of the
alkaline carbonates require further investigation, the exper-
imental evidence from coal fly ash suggests that dissolution is
not the rate-limiting step. It is, therefore, reasonable to
postulate that those mineral feedstocks with higher or similar
hydration kinetics to coal fly ash would show a similar
behavior. Such feedstocks include calcium-bearing alkaline
wastes with similar physiochemistry, such as ground slag,
cement kiln dust, and municipal solid waste incinerator ash.
Preliminary carbonation experimental results on cement kiln
dust and wollastonite in carbonate-bearing solutions (see
Section A.8 of Supporting Information) showed high
carbonation efficiency, confirming their suitability as a
feedstock for the proposed process.
Despite the uncertainties in the future production volume of
waste materials, there exist extraordinary amounts of these
materials in reservoirs such as landfills and ash ponds from
decades of intensive industrial operations around the world.
Recent estimates3,40 project a CO2 capture potential of 2.9−
8.5 GtCO2/y for these mineral wastes. Utilizing all these
feedstocks has the potential to capture and remove gigaton-
scale CO2 from the atmosphere.
Opinion on the feasibility of achieving industrial-scale direct
air capture (DAC) for CCS in the near term is equivocal.41,42
Due to the nascent stage of technology, some researchers
consider DAC to be inappropriate or only transient with
limited benefits vis-à-vis renewable energy options. However,
we feel that it is pertinent to seek technology readiness with a
portfolio of solutions to tackle scenarios that could potentially
threaten the biosphere. Because of the simplicity and low cost
of the process presented, this could be considered a “low-
hanging fruit” in pursuit of the negative emissions required to
achieve climate change goals.
■ CONCLUSIONS
The study demonstrates the feasibility of rapid mineral
carbonation under alkaline conditions (pH > 11.5), contrary
to the common perception that low pH is favorable for
achieving high carbonation efficiency. Enhanced carbonation
7859
pubs.acs.org/journal/ascecg Research Article
rates under alkaline conditions in the presence of high
carbonate-ion concentration could be due to carbonation of
intermediate hydration products occurring as a parallel step in
addition to solution-mediated carbonation. The implication of
the intermediate hydration products amenable to carbonation
is significant and warrants further investigations.
The availability of alkaline industrial wastes and high
carbonation efficiency (up to 95%) demonstrated in this
study substantiates that the proposed route can achieve
gigaton-scale CO2 capture and sequestration from ambient
air. Techno-economic analysis and life cycle assessment
suggest that the CO2 capture and mineralization cost and
corresponding carbon emissions (GWP) are in the range of
$116−133/t-CO2-captured (US $2019) and 0.03−0.25 t-
CO2e/t-CO2-captured, respectively. We estimate the cost of
CO2 capture by the proposed process to be about 30% cheaper
than that by the previously proposed DAC process with
calcination (e.g., CE). Given the simplicity of the process
scheme and negative CO2 emissions over the life cycle, direct
air capture utilizing alkaline industrial wastes through the
proposed method can be considered a “low-hanging fruit” in
the pursuit of negative emissions. Furthermore, finding
beneficial use of carbonated residues is expected to provide
additional carbon emission reduction and improve the
economic viability of the process.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssuschemeng.1c07867.
Precipitation of nahcolite; estimation of carbonation
yield and efficiency; ICP data for FA-1 and FA-2
carbonation experiments; simulated saturation data;
XRD studies on carbonated residues; solubility of calcite
and magnesite in Na+-rich aqueous solution; formation
of hydration products in FA-1; and additional results and
discussion on carbonation mechanisms (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Bu Wang − Department of Civil and Environmental
Engineering, University of Wisconsin-Madison, Madison,
Wisconsin 53706, United States; orcid.org/0000-0002-
9294-0918; Email: bu.wang@wisc.edu
Authors
Raghavendra Ragipani − Department of Chemical
Engineering, Indian Institute of Technology Kanpur, Kanpur
208016, India; orcid.org/0000-0003-0519-7570
Keerthana Sreenivasan − Department of Civil and
Environmental Engineering, University of Wisconsin-Madison,
Madison, Wisconsin 53706, United States
Robert P. Anex − Department of Biological Systems
Engineering, University of Wisconsin Madison, Madison,
Wisconsin 53726, United States
Hang Zhai − Department of Civil and Environmental
Engineering, University of Wisconsin-Madison, Madison,
Wisconsin 53706, United States
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.1c07867
https://doi.org/10.1021/acssuschemeng.1c07867
ACS Sustainable Chem. Eng. 2022, 10, 7852−7861
ACS Sustainable Chemistry & Engineering
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We thank the WEC Energy Group and Holcim (US) Inc. for
providing ash samples used in this study. This material is based
upon work partially supported by the Department of Energy
under award number DE-FE0031705.
■
ADDITIONAL NOTE
a Linking Nm-Scale Measurements of the Anisotropy of Silicate Surface
The eGRID inventory uses 100-year global warming
potentials from the Fourth IPCC Assessment Report (AR4)
to align with other EPA sources reporting CO2 equivalent
emissions.
■
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