Carbonation Curing In-situ Filler Approach

Calcium Aluminate Carbonate P. 01

Calcium Aluminate Carbonate

P. 02
CO2 Capture Sodium Aluminate
In this work, sodium aluminate alkaline solution was used to capture CO 2 in a continuous bubble column scrubber
and aluminum tri-hydrate (ATH) precipitates were produced.
To carry out this process, the mechanism of CO 2 absorption of the aqueous solution is described below:

When the pH is 7–10, as α1 in the figure, the

main component of the solution is bicarbonate
radicals. When the pH is larger than 12, as α2 in
the figure, the main component of the solution is
carbonate. When the pH is smaller than 6, the
main component of the solution is carbonic acid
(H2 CO 3 * ), so the pH has an important effect on
the carbonate distribution.

Carbonation Mixture
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CO2 Capture Bicarbonate MIT Approach
Cementing CO 2 into C-S-H: A step toward concrete carbon neutrality
Using bicarbonate-substituted alite as a model system (NaHCO 3 )
In these reactions, the carbonation of transient disordered calcium hydroxide particles at the hydration site leads to the
formation of a series of calcium carbonate polymorphs including disordered calcium carbonate, ikaite, vaterite, and calcite,
which serve as nucleation sites for the formation of a calcium carbonate/calcium-silicate-hydrate (C-S-H) composite, and the
subsequent acceleration of the curing process. The results from these studies reveal that in contrast to late-stage cement
carbonation processes, these early stage (precure) out-of-equilibrium carbonation reactions do not compromise the material’s
structural integrity, while allowing significant quantities of CO 2 (up to 15 w%) to be incorporated into the cementing matrix. The
out-of-equilibrium carbonation of hydrating clinker thus provides an avenue for reducing the environmental footprint of
cementitious materials via the uptake and long-term storage of anthropogenic CO 2 .
Early stages of the precure carbonation process
During the early stages of hydration (first 10 hours), all bicarbonate-substituted samples exhibit significantly higher M* and H*
compared with the bicarbonate-free control (with a 2-fold increase in mechanical performance in the case of sample with 5% of
bicarbonate substitution), evidencing a clear nucleating effect of the carbonates (which are derived via bicarbonate
deprotonation) and subsequent strengthening of the hydrating clinker. While after 7 days, the control sample slightly
mechanically outperforms its carbonated equivalents, no statistically significant difference in terms of hardness can be
observed for samples with up to 15% bicarbonate substitution. Statistical analysis was performed using the T-test at a signifi-
cance level of 5%.
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Effects of bicarbonate substitution MIT Approach
Previously unreported ikaite was observed during the earliest stages of hydration (in the first 5 h) for all bicarbonate-substituted
samples, whereas calcite and vaterite dominated the carbonate-related species after 5 h of hydration, and only calcite was
observed after 7 days. Furthermore, CRM revealed the presence of a CaCO 3 /C-S-H composite phase, where the coexistence of
calcite and DCC suggests their potential role in the nucleation of C-S-H and the co- precipitation of the CaCO 3 /C-S-H composite.

Effects of forced carbonation on C-S-H formation

If we assume that the amount of mineralizable CO 2 is strictly related to the amount of DCH available for carbonation, we are able
to estimate the theoretical CO 2 uptake capacity from the forced carbonation process. If the hydration of clinker leads to a high Ca/Si
ratio C-S-H (Ca/Si = 1.7), then the theoretical offset of CO 2 amounts to at least 40% of carbon emissions from cement production,
not including emissions associated with fossil fuels used in the process
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A schematic representation of early stage hydration reactions (precure I-III
and postcure IV) for samples with and without bicarbonate substitution
MIT Approach
By combining these results, we can begin to explain the processes of
early stage (pre- and postcure) clinker carbonation. In the bicarbonate-
free controls, C 3 S slowly hydrates to produce C-S-H and DCH, and
nanoparticles of DCH migrate into the pore spaces and crystallize.
In the bicarbonate-substituted samples, the presence of carbonate
ions at the hydration sites (the regions of direct water-clinker contact)
leads to an out-of-equilibrium conversion of the amorphous DCH
particles into amorphous DCC, which in turn, serves as a nucleation
site for the formation of C-S-H, leading to a series of subsequent
changes: (i) the formation of a CaCO 3 /C-S-H composite phase; (ii) the
acceleration of clinker hydration, and its subsequent (iii) increased
early stage mechanical performance. Since this out-of-equilibrium
carbonation takes place in the freshly mixed stage before solid
percolation, the min- eralized carbonates effectively serve as sites for
permanent CO 2 storage in the CaCO 3 /C-S-H composite, allowing a
partial offset (up to 15%) through mineralization of the carbon
emissions associated with clinker production and leading to a material
with improved early stage mechanical performance
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Carbonation Curing
CO2 + OPC+ GGBS + Slaked Lime / Gamma C2S

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Carbonation Curing (OPC+GGBS+Slaked Lime / Gamma C2S)
Carbonation curing, which will be described later, calcium hydroxide is carbonated to become calcium carbonate, thereby
absorbing carbon dioxide and contributing to immobilization of carbon dioxide.
Although the temperature during carbonation curing is not particularly limited, it is preferably 15° C. or higher, more preferably
50° C. or higher.
Also, the temperature during the carbonation curing is preferably 70° C. or less, for example.
GGBS Fineness

BFS
There are four types of ground granulated blast furnace slag depending on the specific
surface area (cm2/g),
a) ground blast furnace slag 3000: specific surface area 2750 or more and less than 3500
b) ground blast furnace slag 4000: specific surface area 3500 or more and less than 5000
c) ground blast furnace slag 6000: specific surface area 5000 or more and less than 7000
d) blast furnace slag ground Powder 8000: specific surface area of 7000 or more and less than
10000

CH
Calcium hydroxide has the advantage of being inexpensive and readily available.

Calcium hydroxide may be, for example, by-produced lime discharged from the
acetylene gas production process. This enables effective utilization of waste.
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Carbonation Curing (OPC+GGBS+Slaked Lime / Gamma C2S)

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Carbonation Curing (OPC+GGBS+Slaked Lime / Gamma C2S)
The amount of carbon dioxide absorbed is the result of measuring the difference
between before and after carbonation by an inorganic carbon analysis method
(unit: kg-CO2/m3).
CH-C is the measurement result of the
carbonated portion, and CH-NC is the
measurement result of the
uncarbonated portion.
Porosity

γC2S-C is the measurement result of the

carbonated portion, and γC2S-NC is the
measurement result of the uncarbonated
portion.
Replacement Rate

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Organic Carbonate + Amine Dendrimer
Carbon Dioxide carrier
Selective Dissolving Hydrolysis Mineralization
Glycerol/ Thixotropic Agent Carbide Slag
Propylene
Carbonate

Propylene Glycol + Carbonate

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Propylene Carbonate -CO2 capturing

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Propylene Carbonate –Thixotropic
Influence of Thixotropy on Stability Characteristics of Cement Grout
Common viscosity-enhancing admixtures function by imparting structure to the liquid
phase, whereas thixotropy admixtures function by imparting structure to the solid
phase. Grout and concrete mixtures made with the thixotropic admixture exhibited
a greater demand for high-range water-reducing admixtures and losses in
fluidity than those made with a viscosity-enhancing admixture.
The use of PPC led to considerable improvement in time-dependent
stability characteristics, including static bleeding and surface settlement.
On the other hand, the increase in thixotropy was not effective in improving
stability characteristics determined shortly after mixing and prior to the
development of thixotropy. This included resistance to pressure filtration
and washout. The combined additions of PPC and low concentrations of a
cellulose- based viscosity-enhancing admixture were very efficient, however,
in enhancing stability compared with similar mixtures made with either
admixture. No adverse effects on setting or strength development were
Flow curve showing thixotropic behavior. observed with these combinations.
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Propylene Carbonate –Thixotropic
Thixotropic admixtures (such as propylene carbonate [PPC]) function by inducing a network structure in the fluid phase through increased
interactions of the solid particles. PPC, used in this study as a thixotropic admixture, is a liquid cyclic organic carbonate with a water
solubility of approximately 8%. PPC undergoes a chemical reaction in the aqueous alkaline environment of cement-based materials and rapidly
reacts to form propylene glycol and carbonate anion. At typical application temperatures, the half-life for alkaline hydrolysis of PPC is less
than one minute.
As shown in the structure of the PPC as follows, the PPC hydrolyzes rapidly to propylene glycol and carbonate.
It is unlikely that the PPC itself is responsible for the gel formation. The
hydrogens on the propylene glycol hydroxyls can develop hydrogen bond.
Since propylene glycol does exhibit the same effect as PPC, it is not
responsible alone for the observed effects. While hydrogen bonding is
one possible source of the increase in viscosity of cement-based systems,
the actual mechanism is probably a combination of effects, including the
interaction of the carbonate with the cement particles.
The thixotropic and set-accelerating properties of cyclic organic
carbonates such as PPC have been shown in prior research. The use of
PPC at relatively high dosages (greater than 0.5% by mass of water) can
lead to the formation of a gel structure within 10 min following the first
contact of the cement with water.
A grout mixture containing 0.8% PPC made without any high-range
water-reducing admixture (HRWR) and a mixture with 1% PPC made
Bond between molecules and gel formation with HRWR were found to lead to the formation of a gel structure shortly
after the end of mixing. The fluidity of the resulting thixo-tropic grout
could, however, be reestablished following rigorous mixing. P. 14
Propylene Carbonate –Thixotropic
Grout and concrete mixtures incorporating a PPC thixotropic admixture were shown to have a greater HRWR demand and a lower degree of
fluidity retention than similar mixtures containing VEA such as welan gum and cellulose-based admixture. The use of PPC was shown to
significantly increase the thixotropic properties of cement grout. Grout made with welan gum had very a limited degrees of static and forced
bleeding.
Composition and results of underwater concrete mixtures
0.5 PPC + 0.5 PPC + The use of a low dosage of liquid-based cellulosic
Mixture No VEA 0.5 PPA 0.15 HPMC 0.3 HPMC 0.15 HPMC 0.3 HPMC
Cement, kg/m3 421 418 420 425 415 413 admixture was not efficient in eliminating static and
w/c 0.41 0.41 0.41 0.41 0.41 0.41 forced bleeding. Such VEA admixture incorporated
Sand, kg/m 3 742 736 744 754 736 732
5- to 14-mm aggregate,
with a low PPC content, however, proved efficient in
1095 1086 1100 1114 1086 1082
kg/m3 reducing time-dependent static bleeding, but not
HRWR, L/m 3
%C
2.0 5.5 3.4 4.3 6.0 6.7 pressure filtration. Combinations of 0.5% PPC with
0.23 0.63 0.4 0.5 0.70 0.78
PPC, % water 0 0.5 0 0 0.5 0.5 powdered HPMC at low and medium contents of 0.15
HPMC, % water — — 0.3 0.15 0.15 0.3 and 0.3%, respectively, can result in highly flowable
De-air, mL/m 3 0 0 80 40 80 80
10 min 225 230 230 220 210 210
concrete with proper washout resistance and high
30 min 200 150 175 205 130 150 resistance to bleeding and settlement without hindering
Slump, mm 45 min — — 145 195 85 90
60 min 150 100 100 130 60 70
setting time and strength development.
Air volume, % 1.5 1.7 1.6 1.8 2.0 2.4
Washout loss, % 8.5 6.9 10.1 9.0 6.6 3.3
Bleeding, 10–3 mL/cm2 32 46 0 0 0 0
Surface settlement, % 0.90 0.33 0.72 0.62 0.11 0.12
Initial set, h 6.17 8.67 5.58 5.08 6.00 6.33
Final set, h 8.07 11.33 6.67 6.25 7.16 7.75
3 days 36.8 40.6 35.3 38.1 37.6 36.8
Compressive 28 days 47.6 43.1 47.6 49.3 51.5 54.2
strength, MPa
56 days 50.3 44.9 49.5 51.3 56.2 56.9
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Reducing the carbon footprint of concrete

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CO2 capturing
 In order to reduce the CO2 of the atmosphere and mitigate global warming, Geosilex® has been used in the formulation of our pavings.
 Geosilex® is an innovative product consisting of calcium hydroxide (Ca(OH)2) which captures CO2.

Obtaining process of
From an industrial waste amortized energetically and environmentally

Production process
Purifying and
optimizing process

Nano calcium hydroxide (Ca(OH)2) From Carbide Slag

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KLIMCO flagstone’s decontaminating action
 From a natural compound (calcium hydroxide), obtained in an industrial process as a non-valorizable byproduct.

 When the CO2 gets in touch with the tile, which has calcium hydroxide in its composition, a chemical reaction is produced, and water and calcium
carbonate are the resulting products:

Ca (OH ) 2  CO2  CaCO3  H 2O

Calcium hydroxide Carbone dioxide Calcium carbonate Water

 This reaction takes place gradually during the lifespan of the material, until all the Ca(OH)2 is converted into CaCO3.

 Calcium carbonate is an inert compound which forms limestone, so that it gives excellent mechanic properties to the tile for its use in paving.

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CO2 capturing results
 The result of CO2 capturing using Geosilex in our pavings are:

 2550 kg CO2 is captured per 1000 m2 of material with a 4 cm thick tile.

 3530 kg CO2 is captured per 1000 m2 of material with a 6 cm thick tile.

These results mean that 1400 and 1930 m3 of CO2 are eliminated by a 4 and 6 cm thick flagstone, respectively.

Therefore, KLIMCO flagstone is able to decontaminate 12.730.000 m3 and 17.550.000 m3 of polluted air depending on the thickness of
the tile (4 or 6 cm) for each 1000 m2 of material (110 ppm CO2 excess in the air).

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Using KLIMCO we help to stop climate change, eliminating up to 3530 kg of CO2 from
the atmosphere per 1000m2 of paving. The decontaminating action of KLIMCO is
equivalent to the purification more than 17.000.000 m3 of air contaminated with CO2
excess.

KLIMCO has Geosilex as the active principle, an additive obtained from a reaction by
product in an industrial process. Thus, the process of getting Geosilex has a null
energetic and environmental cost.

At the same time, we recover a compound that, if not used for this alternative
purpose, would be considered a residue, and it would need to be sent to the
dumpsite.

The mechanic properties of calcium carbonate are excellent for their use in paving,
since this is the compound which forms limestone.
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 Obra Significativa en España
Ejemplo de aplicación

Ciudad: Bilbao, España.

Localización: Parque de la Campa de los Ingleses
Fabricante del Pavimento: UGP United Global Pavings
Producto: Losetas Prefabricadas Captadoras de CO2 Ambiental.

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 Experiencia en CHILE

Ciudad: Santiago.
Localización: Universidad Finis Terrae. Facultad de Arquitectura y Diseño
Proyecto y Fabricante : AEGEON / LA CANTERA S.A.
Producto: Pavimento y Mobiliario Urbano Sustentable Captador de CO2 Ambiental

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 Experiencia en CHILE

Ciudad: Santiago.
Localización: Planta San Bernardo.
Proyecto y Fabricante : AEGEON / Prefabricados de Hormigón Grau.
Producto: Pavimento Sustentable Captador de CO2 Ambiental.

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