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Sustainable and Negative Carbon Footprint Solid-Based NaOH Technology for

CO2 Capture

Article  in  ACS Sustainable Chemistry & Engineering · December 2020

DOI: 10.1021/acssuschemeng.0c07093

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 pubs.acs.org/journal/ascecg Research Article

Sustainable and Negative Carbon Footprint Solid-Based NaOH

Technology for CO2 Capture
Claudia Ruiz, Luis Rincoń , Ricardo R. Contreras, Claudio Sidney, and Jorge Almarza*

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ABSTRACT: We report a highly efficient system for CO2 capture and conversion
to a “green” solid carbonate that utilizes solid NaOH. This novel technology has
Downloaded via UNIV OF GOTHENBURG on December 18, 2020 at 01:18:38 (UTC).

important advantages over the currently available technologies regarding percent of

CO2 capture, heat production, and carbonate yields. The study uses a techno-
economic analysis as a quantitative tool in the valuation of CO2 capture for an
environmental and economic gains objective. We highlight two important
advantages of this technology that go hand in hand with a sustainable development:
low economic cost and negative energy and carbon footprint.

KEYWORDS: NaOH technology, Carbon dioxide capture, Energy efficient, Negative footprint technology, Green carbonate,
Circular economy, Green chemical

■ INTRODUCTION
CO2 emissions are currently a major global issue 1−3
that has
prompted scientists to develop processes for capturing CO2
from point and diffuse sources.4 Now, in the beginning of the
21st century, a sustainable technology is required.5−9 Even
though there are many technological proposals, the results of
recent techno-economic studies are not very encouraging.10,11
Some of the processes for CO2 capture from industries
involve hot-carbonate (alkali salt) systems,12 using potassium
carbonate (K2CO3) or sodium carbonate (NaCO3), adsorb-
ents,13−15 or more recently, molecular-sieve (zeolite), activated
bauxite, activated alumina, silica-gel processes,16 and tradi-
tional chemical looping.17 Chemical absorption using aqueous
amine18,19 and ammonia solutions is currently the only mature
technology regarding CO2 capture, which has been widely
deployed on industrial applications since the late 1970s.20
These processes, under high pressure and low temperature
conditions, use primary, secondary, or tertiary amines.
Conventionally, monoethanolamine (MEA),21 piperazine
(PZ),22 diethanolamine (DEA),23 and, in particular, methyl-
diethanolamine (MDEA)24 have increasingly been studied and
used during the last years.25 More recently, a process has been
proposed for CO2 capture founded in metal−organic frame-
works (MOF). Using this technology that requires far less
energy though large-scale production has not been perfected,
and questions over its long-term stability for sustained CO2
capture projects mean that its high cost is not yet merited.26
Solid sorbents have the potential to reduce the overall costs
related to CO2 capture by reducing the energy required to
release CO2 during material regeneration due to less
evaporation of water and lower specific heat capacity. Sjostrom
and Krutka27 evaluated 27 different sorbent materials on a
laboratory scale in a cyclic temperature swing adsorption/
regeneration CO 2 capture process in simulated coal
combustion flue gas. The supported amines exhibited the
highest working CO2 capacities, although they can become
poisoned by the presence of SO2. On the other hands, solid
sorbents are technologies based on organic sorbents or
inorganic mix compounds with the capacity for mmol
capture/g of sorbent.28 Furthermore, the synthesis process of
any compound and the union to a polymeric matrix
significantly increases both the cost of the sorbent and its
carbon footprint involving economic and environmental
viability.
Metal hydroxides and particularly sodium materials have
long been known to capture CO2 and have been extensively
studied with different capture methods.29−32 Nikulshina et al.33
reported three Na-based thermochemical cycles for capturing
Received: September 24, 2020
Revised: November 30, 2020

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CO2 from synthetic air (500 ppm). The energetic and kinetic heated from room temperature to 1050 °C, with a ramp of 10 °C/min
parameters obtained impede the application of Na-based in synthetic air (21% v/v oxygen in argon) employed as the carrier
gas.

■
sorbents (NaOH, Na2CO3, NaHCO3, Na2O) for capturing
CO2. Although Tavan et al.34 reported that in a 4% CO2 gas
stream, which passes through a spray dryer at 100 °C to RESULTS AND DISCUSSION
achieve drying of NaOH, the capture capacity doubles if the Carbon Dioxide Capture Process Using Solid-Based
same conditions are compared but at temperatures below 50 NaOH Technology. We used a small-scale model converter
°C. Alternatively, the captured CO2 can be converted into to test the amount of CO2 captured using a solid-based NaOH
value-added products.35 Furthermore, the separation of the technology. Sodium hydroxide was chosen as the sorbent due
carbonate and bicarbonates generated require high energy to its ability to adsorb CO2 at ambient temperature with fast
during the drying process. At this moment, among the kinetics and an affordable price. Figure 1a shows a schematic
challenges in CO2 capture, we can highlight that the
regeneration step is energy consuming (>750 °C). On the
other hand, current technologies for CO2 capture would also
require appropriate disposal that “delays” its reentry into the
atmosphere.
The purpose of this research is to present an efficient patent
technology based on solid NaOH for CO2 capture by
estimating the energy requirements per unit of CO2 captured.
Accordingly, we present a novel solid-based NaOH technology
for CO2 capture from air. A small-scale test result shows a
nonconventional capture capacity, even if only sodium
carbonate is formed.
Furthermore, we present results on prototypes (indoor and
semi-industrial systems) to measure CO2 absorption and
provide an engineering−economic analysis and its feasible
technology to reduce atmospheric CO2 concentrations. Finally,
we present a preliminary energetic and eco-economic assess-
ment and the possible integration of this technology into a
sustainability model. Consequently, the final objective is for
our technology to be a full circle carbon capture and utilization
(CCU), where we minimize CO2 capture costs by selling the
green high-purity value-added green carbonates to industry.
Additionally, we compared the present technology with the
best amine processing technology (methyldiethanolamine,
MDEA) and indirect calcium looping with alkali (KOH/
NaOH). In all cases, substantial gains in terms of energy and
carbon footprint are observed.

■ MATERIALS AND METHODS

Sodium hydroxide was purchased from Gie-Tec GmbH (Eiterfeld,
Germany). Sodium carbonate was obtained from PanReac Appli-
Chem (Darmstadt, Germany). CO2 gas was purchased from Air
Liquid (Madrid, Spain). The gas concentration was determined using
an analyzer type HORIBA Multi-Component Gas Analyzer/VA-
5112G, consisting of a nondispersive infrared method of double
beams (NDIR-Non dispersive infrared). The instrumentation bench
also has a mixer Environics Gas Dilution System/Series 4040, a
sample changer M&C Gas Conditioning Unit with Temperature
controller/CSS series, two flow controller systems Precision Gas Mass
Flow Controller/MCS-Series, M-Series, a differential pressure trans-
ducer OMEGA Differential Pressure Transmitter/Model PX2300 and
a trace detector of humidity in gases based on a P2O5 sensor DKS
Aquatrace IV/Typ-R. These instruments were operated using CO2
REMO software from TCA Spain. Determination of the NaOH
concentration used the ASTM E15.01 method and was additionally
measured through a pH-meter pH60 DHS, with a 0.1/0.01 unit of pH
resolution. For the characterization of X-ray powder diffraction, a
XRD Panalytical Empyrean diffractometer (Cu Kα) was employed.
CO2 capture by the prototype (8.500 ppm v/v in atmospheric air)
was evaluated with three Aranet internal sensors (Araranet Pro 12
station with four sensors in line/Sofware Aranet Pro v2.3.5) placed in
different positions inside the metal box. Solid product obtained after
capture of CO2 in the prototype was analyzed by TG-DSC-MS (Delta
Engineering & Chemsitry GmbH). Here, 100 mg of sample was
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Figure 1. (a) General scheme of the gas analyzing system Horiba-
Environics. The overall circuit is operated via the software CO2-
REMO. (b) Commercial NaOH captured CO2 after three rounds at
ambient temperature. In each round, the entire sample is massed. One
part is analyzed through potentiometric studies, and the other is used
for the CO2 capture study. (c) Stages of the study process in each
round of capture. Stabilization of the gas source in 5% CO2 and
capture phase until saturation of chemical converter.
drawing of the apparatus. The pressure of the inlet stream is
considered to be 1 bar; a pressure drop of 0.50 bar is observed
inside the tube. Under the capture conditions, 3.00 g of
commercial NaOH in layers of 1.00 g inside a Falcon canonical
tube captured CO2 after three rounds (Figure 1b) at ambient
temperature (20 °C). The solid is crushed and dried after each
step. A 5% CO2 stream was used throughout the experiment.
The amount of CO2 captured was obtained through two
methods: I (direct) and II (indirect). Method I consisted of
following the concentration of CO2 at the end of the reactor
until the system was saturated and no more CO2 was adsorbed.
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Figure 2. (a) XRD patterns of Na2CO3 obtained by CO2 capture (red line) and Na2CO3 standard (blue line). (b) Thermal curves recorded as well
as the spectra of selected mass detected during the heating of the sample sodium carbonate from RT to 1050 with a rate of 10 °C/min.

The general instrumentation system used to evaluate the
capture capacity of the converters included gas sensors (see
Materials and Methods). A typical profile of the CO 2
concentration percentage is shown in Figure 1c. From the
gas flow (1.3 L/min), we obtained the volume of CO2
captured. From this volume, we calculated the moles of CO2
using the ideal gas equation. Similar values were obtained by
employing the virial equation. The typical error in moles of
CO2 from this method is about 1%. This error was calculated
assuming a 1% random error in the CO2 profile per second.
Method II was based on the ASTM E291-18 standard
procedure36 for NaOH determination. Carbon dioxide capture
was obtained from the amount of NaOH remaining as a
function of the pH value in a solution of 1% (p/v) NaOH. We
assumed that the pH values come from a solution of NaOH
and a hydrated form of NaOH or Na2CO3. The typical error in
moles of CO2 from this method is about 1.5%.
Method I showed a mean value of 0.0443 + 0.0012 mol of
CO2 per 3.0 g of NaOH (0.650 kg of CO2 per kg of NaOH).
In the case of 100% pure NaOH, this value means a
relationship of 0.57 mol of CO2 per mole of NaOH. A similar
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analysis for method II showed a relationship of 0.642 + 0.022
mol of Na2CO3 per mole of NaOH. The fact that in both cases
the ratio between the moles of CO2 (or Na2CO3) and moles of
NaOH was larger than 0.50, without any evidence of NaHCO3
formation, is indicative of a departure from classic reaction
stoichiometry.37
Alternatively, it is possible to consider the NaOH purity to
obtain an accurate ratio between CO2 moles (method I) or
Na2CO3 moles (method II) per mol of NaOH. To estimate the
purity of NaOH, it is assumed that a solution of 1.00 g of fresh
NaOH in 100 mL of water must have a pH of 13.40. In all
cases, the pH was lower, typically between 13.11 and 13.23;
therefore, purity between 68% and 72% is assumed. The
powder X-ray diffraction of the fresh NaOH only detected
NaOH and NaOH·H2O; thus, it is assumed that fresh NaOH
is nearly 30% water. After considering the NaOH purity,
method I indicated a ratio of 0.89 CO2 moles per moles of
NaOH and 0.96 Na2CO3 moles per moles of NaOH.
Surprisingly, even with these high yields of CO2 adsorption,
the different experimental techniques, including powder X-ray
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Figure 3. (a) Capacity of the indoor prototype at a concentration of 0.85% CO2 (8500 ppm). Sensors 1−3 are located inside the experimental box.
Sensor 4 is located outside the experimental box with ambient conditions. (b) Capacity of the laboratory prototype with an industry source at a
concentration of 16% CO2.
diffraction, indicate that pure Na2CO3 is a unique result
(Figure 2a).
Additionally, classic volumetric techniques and TG-DSC-MS
analysis were used. A titration with HCl solution and analysis
using Metrohm automatic equipment in line was used. In the
last technique, the titration curve of the sample is highly similar
to that of Na2CO3. In the TG-DSC-MS analysis (Figure 2b),
four peaks were selected to be monitored: 18 m/z (H2O), 17
m/z (OH), 28 m/z (CO), and 44 m/z (CO2). The melting
point of sodium carbonate is reported to be 851 °C37 and was
found experimentally to be 869 °C, a shift that may evidence
the presence of different phases of sodium carbonate.38−40
Two additional experiments were carried out under real
conditions. The first experiment consisted of carbon dioxide
capture using a prototype for indoor spaces. The prototype
included laminar plates of 7 cm × 12 cm with solid NaOH (3−
4 mm thick) that were introduced in a hermetic metal box
(dimensions 101.5 cm × 80.5 cm × 61.5 cm; volume 0.503
m3). An interior fan blowed air through the plates at a flow of
20 m3/h. Before turning on the prototype, the average
concentration of the air in the metal box, measured with an
Aranet sensor (see Materials and Methods), was 8.500 ppm of
CO2. The experiment was stopped when the internal sensors
reached the value of zero. Figure 3a shows the capacity of the
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prototype in ambient conditions at a concentration of 0.85%
CO2 (8500 ppm). It should be noted that 5 min after the
equipment was switched on the CO2 concentration of the
system changed from very contaminated (or toxic) to an
acceptable concentration of 1200 ppm (ASHRAE recommen-
dations for indoor air quality).41 Also, just 11 min after this
result, the CO2 values inside the box dropped to 0 ppm.
The second real-condition experiment was evaluated under
real conditions of a gas stream from the furnace of a Spanish
cement plant (Figure 3b). The emissions at the end of the
furnace were measured with the gas analyzer (in onward) at a
controlled flow rate of 0.4−0.5 L/min, and the gases treated by
the system with the NaOH technology were measured in the
gas analyzer (out onward). During the test, 12 L of gases were
processed with an observed CO2 uptake of 99.9% that
corresponds to uptake of 3.7 g of CO2.
In summary, these two last evaluations undoubtedly
demonstrate that the solid-based NaOH technology for carbon
dioxide capture in laboratory experimental conditions and real
conditions exhibits excellent performance.
On one hand, based on the experimental results (methods I
and II), the presence of sodium bicarbonate was not observed,
and less than 1% water was detected in the final product.
However, water was present in the initial gas fed into the
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Figure 4. Input−output balance of NaOH-based technology for (a) flue gas and (b) atmospheric air per kg of CO2 at the point of capture.
stream or finally bound to carbonate as a sodium carbonate
hydrate. It is interesting to notice the relation of approximately
1 mol of CO2 absorbed per mole of solid NaOH to produce
one mole of high purity sodium carbonate (“green carbonate”).
This observation prompts us to think in alternative ways for
CO2 absorption under solid NaOH that contains sodium
carbonate. On the other hand, the use of solid sodium
hydroxide under our study conditions allows for a favorable
stoichiometric balance both during the capture of CO2 and in
the generation of nearly two times the expected mass of
sodium carbonate.
Moreover, the high percent of CO2 adsorption per NaOH
can be explained due to the additional energetic stabilization of
nearly 35 kJ per bond of Na+ for CO32− (based on preliminary
DFT PBE/cc-pvDZ calculations on laminar sheets of planar
sodium carbonate using the pyscf sorftware).42 It is worth
mentioning that one of the phases of sodium carbonate shows
planar graphite-like structure, where an interaction between
sodium and the carbon of the carbonate ion Na-CO3 is plated,
and that would become the anhydrous form of NaCO3.43 This
stabilization would explain the increased thermal stabilization
in the TGA-DSC-MS studies. These planar configurations
partially compensate for a deficit of the Na+ atoms. It should
not be forgotten that the TGA/DSC seems to indicate
hydration water. Thus, other forms of octahedral carbonates,
like α-Na 2 CO 3 , β-Na 2 CO 3 , γ-Na 2 CO 3 , and δ-Na 2 CO 3
phases,39 can be found. Further experiments can clarify if the
exact nature is planar or octahedral.
Sustainability Model for Carbon Capture. A sustain-
ability assessment of new technologies focuses on three main
areas. In the following sections, we briefly discuss environ-
mental assessment, economic assessment, social impact
assessment.
Environmental Assessment. Life cycle assessment
(LCA) is a standardized methodology widely used to evaluate
the potential environmental impacts of a product system. For
carbon capture, storage, and/or utilization, LCA is a key
methodology for the evaluation of the environmental credit of
CO2 removal from air or from flue gas. The goal of this LCA
study is to evaluate and compare the life cycle environmental
performance of various different systems aimed to capture
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carbon dioxide from air or a flue gas stream (coming from a
nearby production plant) per kg of avoided emission of CO2.
For comparison, as reference technologies, we include the best
amine processing technology (methyldiethanolamine, MDEA)
and an indirect Ca-looping process with NaOH and
causticization but modified in order to use NaOH instead of
KOH.29 In this last technology, there are two connected
chemical cycles. In the first CO2 cycle capture, carbon dioxide
(flue gas or air) reacts with NaOH (aqueous) to form Na2CO3.
In the second cycle, this sodium carbonate precipitate reacts
with Ca(OH)2 to form CaCO3. The calcium carbonate is
calcined to liberate CO2 producing CaO, which is hydrated to
produce Ca(OH)2 and close the cycle.29 More recently, a new
study on the absorption of CO2 using KOH and causticization
was published.44 The process consists of a first CO2 cycle
capture from atmospheric air using a 1 M aqueous solution of
KOH. In the second cycle, Na2CO3 reacts with Ca(OH)2 to
regenerate KOH and produce CaCO3, which is reacted in a
calciner to release captured CO2, while the calcium oxide is
reacted with steam water to produce again Ca(OH)2 which is
recycled back into the process. The process is self-sustained
from an energy point of view; it uses methane to generate heat,
steam, and electricity. In order to determine the life cycle
profile of the systems under analysis, inventory data for the
supply of chemicals and energy were taken from the ecoinvent
3.5 database (average European data), and the analysis was
implemented in specific LCA software (SimaPro 8.5). The
final mass balances of the NaOH system with flue gas and
atmospheric air (approximate content of 0.04% of CO2) are
represented in Figure 4.
The production of sodium hydroxide is likely the main
contributor to the carbon footprint of the present technology.
Three sources of sodium hydroxide can be considered:
commercial NaOH, low-energy NaOH, and low-impact or
green NaOH. Low-energy NaOH is produced through an
experimental process called ABLE (alkalinity based on low
energy), which reduces the energy consumption from the
conventional electrolytic process by 80% due to the
coproduction of HCl instead of H2 and Cl2. For the green
(or low-impact) NaOH, the ABLE process was assumed to
employ wind power instead of electricity from the grid. The
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ACS Sustainable Chemistry & Engineering
Figure 5. (a) Operating cost of CO2 capture, (b) energy footprint, (c) carbon footprint, and (d) LCA index between MDEA technologies,
carbonate-looping technology, and solid-based NaOH technology.
scale of analysis is 1 Mt/year of CO2 (fed from flue gas) or 1
ton per day (fed from atmospheric air). The utilization of CO2-
based products, in particular, sodium carbonate, reduces the
carbon footprint of our technology, as it replaces the carbon
footprint of current mining and chemical manufacturing
processes of high-purity carbonates. The results of the
assessment are summarized in Figure 5. The lowest carbon
and energy footprints have been found for the present solid-
based NaOH technology when using flue gas from power
stations as a source of CO2, substituting a commercial sodium
carbonate technology.
Carbon footprint (CF) is the total emissions caused by the
process, expressed as kg CO2 equivalents. Just like a carbon
footprint, energy footprints (EF) are environmental footprints
focusing on a single environmental issue, the balance of
primary nonrenewable energy consumption. Hence, an energy
footprint is the assessment of the energy consumption related
to a defined product. From the analyst point of view, this
indicator represents the environmental efficiency of the overall
scenario of the application of the technology; higher cost
means lower environmental efficiency of carbon capture and
lower cost means higher efficiency. It is often convenient to
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combine carbon and energy footprints into a single score, in
particular, if you need a simple way to evaluate several CO2
capture technologies. Here, we integrated both values in a
single index. Figure 5 shows the integrated value of the carbon
and energy footprints for each system in relative values to
facilitate a comparative study for the identification of the most
suitable CO2 capture solutions. For the carbon footprint, a
reference value of 0.50 kg CO2eq per kg of NaOH and 8.58 MJ
per kg of NaOH was used (ABLE process) and a production of
“green” Na2CO3 with an impact of −1.01 kg of CO2 per kg of
Na2CO3 produced. Since EF is an order of magnitude larger
than CF, the index is calculated as EF + 10 CF. The NaOH-
based technology footprints were calculated using the scheme
of Figure 4 using reference footprints. For flue gas, the energy
balance is negligible, while it is of high relevance for
atmospheric air due to the high consumption of electricity
for compression. Two options are evaluated: atmospheric CO2
and flue gas from power plants. The energy footprint and
primary energy demand of the selected scenarios have been
assessed using LCA methodology. Negative values indicate net
greenhouse gas (GHG) emission savings, and they are
therefore considered to have the most favorable life cycle
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performance regarding global warming. Overall, the solid-
based NaOH technology might have a great potential as a CO2
capture solution for the treatment of flue gas streams when
guaranteeing the use of environmentally friendly sodium
hydroxide and the displacement of conventional sodium
carbonate production. A causticization cycle is not mandatory
in the NaOH solid base technology. The causticization step, an
endothermic process, is energetically and carbon footprint
demanding, particularly in liquid solutions. Therefore, totally
or partially avoiding the causticization step represents a
considerable savings in energy. Additionally, the energy
released is significantly higher than in aqueous solution
methods; as a consequence, there is a greater potential to be
recycled than in the liquid phase where the energy tends to
disperse.45
The following findings are highlighted: (i) It is highly
advisible to use either low-energy or green low-energy NaOH
with this technology. (ii) Better energy footprint results appear
when capturing CO2 from flue gas instead of capturing it from
the air. (iii) It is also advisible to use the sodium carbonate
product from the present technology to avoid the conventional
production of sodium carbonate, rather than using it for
NaOH generation or the production of construction materials.
In comparison with the other models built for comparison
with alternative carbon capture and storage systems, the solid-
based NaOH technology has the lowest associated costs and
the lowest life cycle impact provided that (i) low impact
sodium hydroxide is sourced and (ii) full substitution of
sodium carbonate production is achievable. The results of the
life cycle assessment, using flue gas from power stations as a
source of CO2 for the energy footprint (−16.72 MJ/kg CO2)
and the carbon footprint (−2.45 kg CO2eq/kg CO2abs)
suggest that the use of solid hydroxides is an interesting
technology to consider as a CO2 capture tool.
Economic Assessment. The economic performance is
evaluated through the calculation of three main indicators: raw
material transformation costs during the CO2 capture process,
energy assessment, and GHG avoidance cost/benefits.
Raw Material Transformation Costs of Carbon
Dioxide Capture. The economic performance is evaluated
through the calculation of raw material consumption costs,
which are reported in cost per ton of CO2 adsorbed at the
point of capture. This indicator represents the operational cost
of the process, without considering the life cycle emissions of
CO2. The revenues from secondary products or byproducts,
which can be directly marketed, are subtracted. For reference
cases, it includes the cost of CO2 compression and transport.
Figure 5 shows the operating cost per ton of CO2 captured.
Since this is a simplified assessment, this work only produced
gross estimates of the operating cost rather than a precise
estimation. A more detailed evaluation is probably not required
at this stage of technology development. We considered several
scenarios for the present carbon capture technology, and the
best reference technology scenarios are reported. The
minimum calculated cost for the solid-based NaOH technol-
ogy per ton of avoided CO2eq is around 16.5 EUR2018
(calculated from an operating cost perspective) when conven-
tional stoichiometry is used. This value is negative, −52.6
EUR2018, when we consider the yield of sodium carbonates
reported in this work. These costs are estimated when the
solid-based NaOH technology uses CO2 from flue gas, uses
low carbon footprint sodium hydroxide, and substitutes the
current production methods of sodium carbonate. Our findings
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show that solid-based NaOH technology is the only CO2
capture strategy with negative overall operating costs. Using
COMTRADE data for 2019, in the mass balance of the
NaOH(solid)-based technology, 1 ton of NaOH is equivalent
to 2.6 tons Na2CO3. Then, 1 ton of NaOH per €540/ton is
equal to €540; minus 2.6 tons Na2CO3 per €270/ton is equal
to €702, resulting in negative €162, with a gross margin of €62/
ton Na2CO3. The operating cost is extremely sensitive to the
cost of sodium hydroxide and the selling price of sodium
carbonate. The blast parameter produces a negative cost; i.e., a
benefit is obtained from the avoidance of CO2.
We understand there may be demand for pure CO2 to be
used in other CCU applications, in which case, our technology
allows for the causticization to take place at the most
convenient location using the lowest-cost transport and
logistics. In this case, we would regenerate the hydroxides
that can be reused with a neutral energy footprint by
compensating the energy harnessed from our CO2 capture
reaction
On the other hand, stoichiometric simulations show
potentially higher gross margins when producing alternatives
such as potassium and calcium carbonates. Although other
factors may also have a role (e.g., electricity price), their
influence and the system’s sensitivity are of a much lower
magnitude.
Energy Assessment. New technologies like solid-based
NaOH have a chance if they are economically and
thermodynamically feasible. A theoretical value of 127.6 kJ
per mol of CO2 is predicted for the heat of reaction between
solid NaOH and CO2 based on classic stoichiometry (1 mol of
CO2 reacts with 2 mol of NaOH). This value corresponds to
0.872 kWh per kg of CO2 captured and is considered a low
limit value. A theoretical value of 1.319 kWh per kg of CO2 is
predicted for a 1:1 relation between NaOH and CO2 assuming
a heat of formation for the reaction product of −1062.0 kJ per
mol of CO2. Unfortunately, the increment of temperature in
the reactor in the small-scale model converter used in this work
did not allow an indirect quantification of the reaction heat. To
illustrate how heat could be recovered in an industrial process,
the reactor exit gas temperature is estimated at 175 °C and
used to generate 12-bar steam, with a minimum temperature
drop of 18 °C. Using this approach, the heat exchanger can
recover 0.66 kWh per kg of captured CO2 (approximately 50%
efficiency). If the steam obtained is then used for electricity
generation in a steam cycle microturbine, the recovered
electricity is approximately 8% efficiency of the thermal energy
released during the capture and transformation reaction. These
numbers, however, are not indicative of the potential energy
recovery but are an example of dependencies between the flow
of gas and the amount of available heat and work. To study the
heat and electricity recovery potential would require a much
deeper research, which is outside the scope of this work.
The GHG avoidance cost/benefits are reported per ton of
CO2eq actually removed from industrial emissions or air in a
life cycle perspective. The solid-based NaOH technology can
therefore be of particular interest to industrial emitters located
in jurisdictions where allowance emissions are required, often
at a cost to emitters, as it creates an additional opportunity to
reduce operating costs.
Social Impact Assessment of Sodium Hydroxide
Technology. Looking beyond the current “take−make−
waste” extractive industrial model, a circular economy aims
to redefine growth, focusing on positive society-wide benefits.
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ACS Sustainable Chemistry & Engineering
Figure 6. Sustainability model (CCS−CCU) of solid hydroxide technology.
This entails gradually decoupling economic activity from the
consumption of finite resources and designing waste out of the
system. Underpinned by a transition to renewable energy
sources, the circular model builds economic, natural, and social
capital (Figure 6). The high-purity carbonates produced with
our technology stimulate a circular economy by providing an
economically viable operation with a negative carbon footprint
and producing value-added raw materials for various other
industrial applications. This technology provides economic and
environmental sustainability to a carbonate industry facing
ever-increasing resistance to new mining concessions, while
creating convenient availability of carbonates wherever CO2
emissions can be captured. On the other hand, market surplus
carbonates can be processed to regenerate chemical converters
by separating pure CO2 at convenient locations for both the
existing CCS applications as well as the growing CCU uses like
enhanced oil recovery and synthetic fuels. The advantage of
sodium hydroxide technology when regenerating the chemical
converters is that both the solid carbonate and solid hydroxide
are stable and innocuous, which allows using the existing land
and sea freight infrastructure for a lower CO2 transport cost.
Current European legislation and the costs associated with
CO2 emission allowances increasing in value, pose a threat to
the global market competitiveness of the European industry
and therefore to employment levels within the European
Union (EU). Infrastructure investments, both by private
enterprise and governments, are built around the current
urban and industrial complexes developed based on a CO2-
emitting energy sources. We propose that developing the “solid
hydroxide technology” to the industrial level will not only
address GHG reduction targets generating a circular economy
through the production of “green carbonates” but will also
protect and enhance the current labor force in the EU.
■
CONCLUSIONS
The use of solid sodium hydroxide under our study conditions
allows a favorable stoichiometric balance both in CO2 capture
and in the generation of nearly twice the mass of sodium
carbonate. This mass gain allows an interesting and sustainable
economic balance in relation to both the CO2 capture and the
investment cost of the NaOH used. From a life cycle
perspective, the lowest carbon and energy footprints were
found for the present technology using flue gas from power
H https://dx.doi.org/10.1021/acssuschemeng.0c07093
pubs.acs.org/journal/ascecg Research Article
stations as a source of CO2, using sodium hydroxide with the
lowest carbon footprint, and substituting commercial sodium
carbonate. The absolute value of the lowest carbon footprint is
actually much higher than the actual mass of carbon dioxide in
the final carbonate. This means that the system is able to avoid
larger emissions than the amount chemically adsorbed by the
solid, assuming there is no barrier for the commercialization of
the produced sodium carbonate. Economically, the minimum
calculated cost for the solid-based NaOH technology per ton
of avoided CO2eq is negative €52.6. These costs are estimated
when using CO2 from flue gas, using green sodium hydroxide,
and producing sodium carbonate. No process using
commercial sodium hydroxide has been found to have an
actual negative carbon footprint, except for those regenerating
sodium hydroxides with CaO looping and producing com-
pressed CO2 for storage. Finally, the solid-based NaOH
technology for the capture of CO2 proposed in this article has
the advantage that sodium hydroxide is widely available and
that it is energy efficient since all the steps of the process are
exothermic. Furthermore, the total regeneration of the
hydroxides is not rigorously necessary. This implies that
additional causticization steps could be required. Consistently,
this technology has a negative carbon footprint and valuable
products. Direct commercialization of the produced carbonates
results in a net reduction of carbon emissions, thereby
increasing the sustainability index of the present technology.
■
AUTHOR INFORMATION
Corresponding Author
Jorge Almarza − Ecological World of Life, Laboratorio de
Transformación Química de Gases Efecto Invernadero
(LTQGEI), Fundación Gómez Pardo, 28003 Madrid,
España; Ecological World for Life GmbH, Berlin-Köpenick
12557, Deuschland; Email: jalmarza@ewltech.eu
Authors
Claudia Ruiz − Ecological World of Life, Laboratorio de
Transformación Química de Gases Efecto Invernadero
(LTQGEI), Fundación Gómez Pardo, 28003 Madrid,
España
Luis Rincón − Ecological World of Life, Laboratorio de
Transformación Química de Gases Efecto Invernadero
(LTQGEI), Fundación Gómez Pardo, 28003 Madrid,
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering
España; Grupo de Química Compuntacional y Teórica
(QCT-USFQ), Departamento de Ingeniería Química,
Universidad San Francisco de Quito (USFQ), Quito 17-
1200-841, Ecuador; orcid.org/0000-0003-4273-1787
Ricardo R. Contreras − Laboratorio de Organometálicos,
Departamento de Química, Facultad de Ciencias,
Universidad de Los Andes, Mérida 5101, Venezuela
Claudio Sidney − Ecological World of Life, Laboratorio de
Transformación Química de Gases Efecto Invernadero
(LTQGEI), Fundación Gómez Pardo, 28003 Madrid,
España
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.0c07093
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare the filing of Patent WO/2017/163135.
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors thank José Luis Gálvez (Instituto Madrileño de
Estudios Avanzados, IMDEA) for reading the manuscript and
for his helpful comments.
■
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