Waste and Biomass Valorization (2021) 12:1591–1597

https://doi.org/10.1007/s12649-020-01121-2

SHORT COMMUNICATION

Surface‑Assisted Crystallization of Highly Pure ­CaCO3 Films Using

Bagasse Ash as a Raw Material
A. Esquivias‑Fierro1 · J. R. González‑López2 · L. Chávez‑Guerrero1

Received: 28 February 2020 / Accepted: 8 June 2020 / Published online: 13 June 2020
© Springer Nature B.V. 2020

Abstract
The Tequila industry produces agave bagasse, which in most cases is transformed into ash to reduce its volume. Here we
present the synthesis of floated calcium carbonate ­(CaCO3) films using ash as raw material. A nylon mesh serves as a
growing platform to facilitate the uptake of calcium from the ash, allowing a recovery up to 64% during the synthesis at
the interface water/air. The interaction of carbon dioxide ­(CO2) with water gets carbonic acid ­(H2CO3) which reacts with
calcium ions (­ Ca2+) to generate a film of ­CaCO3 on the nylon mesh surface. The C ­ aCO3 films were studied by scanning
electron microscopy, and its microstructure and composition were analyzed by Raman spectroscopy, X-ray diffraction and
X-ray Fluorescence. Our findings show this technique has a potential for large scale production of highly pure ­CaCO3 powder.
Graphic Abstract

Keywords Limestone · Calcite · Xerophyte · Agave · Floated calcium carbonate

Statement of Novelty
* L. Chávez‑Guerrero
leonardo.chavezgr@uanl.edu.mx
The manuscript presents an alternative use of processed
ash obtained from agave bagasse to produce pure calcite.
1
Facultad de Ingeniería Mecánica y Eléctrica, Universidad Besides, the manuscript includes the wide structural char-
Autónoma de Nuevo León, Pedro de Alba s/n, acterization of calcium carbonate (XRD, RAMAN, SEM,
San Nicolás de Los Garza, N.L. CP 66451, Mexico
XRF), obtained through an innovative technique called
2
Facultad de Ingeniería Civil, Universidad Autónoma de “floated calcium carbonate”. Our findings provide important
Nuevo León, Pedro de Alba s/n, San Nicolás de Los Garza,
N.L. CP 66451, Mexico

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information about the synthesis of a renewable source of
­CaCO3 with high impact applications.
Introduction
The tequila industry generates around 37,000 tons of solid
waste per year [1], generally known as agave bagasse. Com-
monly, agave bagasse is used as animal feed and compost;
while in the harvest fields, the residual biomass remains in
the place, serving as compost or fertilizer. The tequila indus-
try commonly manages the bagasse generated by drying it
under the sunlight, followed by its incineration inside boil-
ers, producing steam; which is used in the production pro-
cess of tequila or used to produce electrical energy. It is esti-
mated that around 14% of the energy is generated through
the direct burning of biomass [2]. However, this process
produces large amounts of ash. At present, some applica-
tions using biomass ash have been studied as a pH regula-
tor, adsorbent for desulfurization [3], an additive in cement,
production of concrete blocks or biogas purification [4–7].
These applications are mainly due to the minerals contained
within the ash. Some researchers agree that agave bagasse
is a source of calcium, mainly in the form of limestone or
calcium oxalate [8–11], and recently, it has been found that
the use of calcined biomass (ash) is a source of calcium
carbonate ­(CaCO3) microcrystals [9, 10].
CaCO3 is extracted from limestone, a carbonate sedimen-
tary rock. Its mining has several negative environmental
impacts, such as the introduction of fine particles into the
environment, it is non-renewable, most of the natural sources
are in remote areas, which require the intensive use of fossil
fuels to extract, grind and transport the rocks [5, 9]. Then,
it is mandatory to find a sustainable way to obtain calcium
carbonate, especially if waste such as biomass sub-products,
is used for such purpose. The world demand for C ­ aCO3 has
been rising steadily; exceeding 110 million tons in 2018
[12]. The demand for amorphous calcium carbonates (ACC)
and precipitated calcium carbonates (PCC) continue increas-
ing, where the usual synthesis procedures are precipitation
with different additives [13, 14] or the milling route [15].
As the demand grows, it is necessary to look for alterna-
tives in the generation of these materials. In this investiga-
tion, we propose a new method called floated calcium car-
bonate (FCC) to recover ­Ca2+ ions. Calcium oxide (CaO)
contained in the ash tends to form ­CaCO3 films around a
nucleation surface that facilitates its crystallization. The
resultant ­CaCO3 crystals were observed by scanning elec-
tron microscopy, while the structure was studied by Raman
spectroscopy, X-ray fluorescence and X-ray diffraction. A
preliminary calculation to determine the performance of the
process is also reported.
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Waste and Biomass Valorization (2021) 12:1591–1597
Materials and Methods
Materials
Agave tequilana bagasse was used as a raw material; it
was obtained from a tequila company located in the state
of Tamaulipas (Mexico) and used as received. The nylon
mesh (125 μm × 125 μm) was bought into a local store,
­ m2. Distilled
which was cut to have square pieces of 10 m
water was used during all procedures.
Experimental
The ash was obtained by calcining the Agave tequilana
bagasse (Fig. 1a) inside a Felisa FE-340 muffle with a
temperature ramp as follows. Step 1: ramp from 25 °C to
950 °C at 10 °C/min. Step 2: steady at 950 °C for 300 min.
Step 3: cooling down from 950 °C to 25 °C at 5 °C/min.
This sample will be named A950 (Fig. 1b) from now
on. Subsequently, 0.15 g of A950 was slowly added to
50 ml of distilled water (pH 5.5), while the flask (contain-
ing the water) was inside an ultrasonic bath. Then, the
obtained suspension was deposited on a plastic petri dish,
with an increase in the pH to 12.2 due to the formation of
Ca(OH)2. Finally, a nylon mesh without previous treatment
was placed on the petri dish surface (Fig. 1c).
The nylon meshes were removed from the Petri dish
after 24 h; then it was dried in an oven at 40 °C for 2 h
(Fig. 1d). Later, the meshes were characterized to evaluate
the morphology and the composition of the film formed
among the scaffold.
The percent yield is the ratio of the actual yield (A) to
the theoretical yield (T) as shown in Eq. 1. To calculate
the percent yield, the measurements of 23 experiments
were utilized.
Percent Yield = A∕T × 100 (1)
Characterization
X-ray diffraction (XRD) measurements were conducted
using a D8 Advance Bruker powder diffractometer. The
tests were done at room temperature in the range 2θ = 20°
to 50°, using Cu Kα radiation (λ = 1.54184 Å).
Scanning electron microscopy (SEM) analysis was car-
ried out using a SEM FEI NOVA NANOSEM 200 with
an energy dispersive X-ray (EDX) microanalysis system,
with acceleration energy of 5–15 kV, a spot size of 3 and a
working distance of 5 mm. The samples were prepared by
placing the nylon mesh (previously dried) on an aluminum
Waste and Biomass Valorization (2021) 12:1591–1597 1593

Fig. 1  Digital pictures of the

materials obtained after each
stage of the process for ­CaCO3
films formation, a raw material
(bagasse from the tequila indus-
try), b calcined ash at 950 °C
(A950), c A950 hydration and d
nylon mesh

pin covered with graphite adhesive tape and finally dried
for 24 h at 40 °C.
Micro Raman spectra were collected at room temperature
using a Thermo Scientific XDR Raman microscope with
532 nm laser excitation. The samples were deposited on pre-
viously dried glass slide. The spectral data was accumulated
up to 30 times with a laser exposure time of 30 s.
The chemical composition of the homogenized samples
was obtained by X-Ray Fluorescence (XRF), on a PANalyti-
cal Epsilon 3XL spectrometer with a Rh tube. The results are
reported as oxides in Table 1.
Results and Discussion
The bagasse ash is composed of several minerals such as Ca,
Mg, Al, Si, Fe, Sr, Ti and K [9]; for that, it is attractive to
recover some of these minerals. The agave plant absorbs the
calcium cations from the soil using the roots since it is required
for structural roles in the cell wall and membranes [16]. After
the bagasse calcination at 950 °C, all the organic matter was
consumed, for that reason, the calcium was found as calcium
oxide into the ash.
Carbon dioxide (­ CO2) is dissolved in water until it reaches
an equilibrium with the atmosphere, forming carbonic acid
­(H2CO3) [17], then, through a series of equilibrium reactions
bicarbonate ­(HCO3) will be obtained. Due to the interaction
between anions of H ­ CO3− and C ­ a2+ cations, they give rise
to a film of C
­ aCO3 suspended (floated) on the surface of the
water (Eq. 2).
Ca2+ + 2HCO3 + H2 O ↔ H2 CO3 + H2 O + CaCO3 (2)
The pH increases in the solution, given by the increase of the
(OH)−1 concentration (Eq. 3), due to the formation Ca(OH)2,
an intermediate compound which generates an alkaline pH.
The nylon mesh is suspended due to the surface tension of
the water; then the mesh surface will facilitate the organiza-
tion of the ions in order to start the nucleation. From this
interaction, a ­CaCO3 film under atmospheric conditions can
easily be synthesized. In previous experiments, the film was
mechanically recovered employing a plastic plate, so that
the film has adhered to it [18]. It is worth mentioning that if
the film is not properly adhered to, it will precipitate mak-
ing impossible to recover it. On the contrary, with the use

Table 1  Compound percentage Al2O3 SiO2 K2O Fe2O3 SrO CaO MgO TiO2
present in the ash and film
A950 0.115 2.064 3.242 2.855 0.344 90.628 0.211 0.197
Film 0.0285 0.247 0.353 0.0518 0.181 99.025 0.0105 0.0353

Values expressed in wt%

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of the mesh, it is possible to recover it in its entirety without
losing material.
Figure 2 shows the SEM images of the original nylon
mesh (Fig. 2a), and later at 3 h after starting the process
(Fig. 2b), where the crystals begin to wrap the mesh by self-
organization between ions of calcium and carbon dioxide
­(CO2) dissolved in water (Eq. 2). After 24 h, the holes in the
mesh are covered by a film (Fig. 2d). Figure 2d suggests that
the crystals will be larger if they are farther from the edge
of the mesh, possibly because their space is not limited to
continue nucleation. According to Kyu Lee et al. [19], the
structure of microcrystals is created using aligned nanopar-
ticles giving way to a structure on a larger scale, as seen in
Fig. 2b. The results suggest that in the first instance, small
particles of amorphous ­CaCO3 will be individually nucle-
ated on the nylon/water interface, then, in a second stage,
the structures will continue to grow and merge with other
particles, this process will continue as long as there are free
­Ca2+ ions and C ­ O2 molecules. After the mesh is filled with
­CaCO3 (Fig. 1c, d), the film will remain floating on the water
surface, then FCC will be obtained, while the other elements
present in the ash will be precipitated, which was previously
demonstrated by Chavez-Guerrero et al. [18].
It has been shown that the ­Ca+2, and ­CO2 sources have
a big effect on the microstructure of the films [20]. In
comparison with other processes, it was possible to obtain
Fig. 2  Images of reference and growing with time; a t = 0 control, b after 3 h of ­CaCO3 growing on the surface, c mesh totally cover after 24 h, d
zoom of a small section after 24 h of growing, e zoom of recovered particles and f EDX results of the film
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Waste and Biomass Valorization (2021) 12:1591–1597
­CaCO3 films without the use of additives [21]. Moreover,
this process becomes simpler because it does not need an
external ­CO 2 source, like pressurized ­CO 2, thus reduc-
ing the cost. Figure 2d shows a totally formed film with
­CaCO3, where the mesh needs to be bent to recover the
powder, then the film can be converted into powder by
simply grinding (Fig. 2e). The EDX spectrum obtained
from the calcium carbonate film (Fig. 2f) revealed that
only the presence of carbon, oxygen, and calcium is
detected; showing the purity of the synthesized film, leav-
ing out other elements initially present in the ash.
Micro-Raman spectra (Fig. 3) of the C ­ aCO3 and the
mesh sample show the characteristic bands of calcite
according to the literature [22]. The strongest Raman
signal was found at 1089 cm −1 (v 1). A secondary peak
appeared at 716 cm−1 (v4) and it is known as an in-plane
band, the lattice mode vibration region at 284 cm−1 was
also present. The region of the nylon mesh also was
analyzed; as expected, in the nylon fiber the peaks cor-
responding to the NH functional groups were obtained
at 3085 cm−1, C=O at 1760 cm−1 plus C–N and N–H at
1617 cm−1. In the same way, the nylon/film interface was
analyzed too, the same vibrations were found as in the
nylon mesh, although with less intensity, in addition to
the vibrations corresponding to ­CaCO3. These results also
corroborate the purity of the calcium carbonate film.
Waste and Biomass Valorization (2021) 12:1591–1597 1595

features of the α phase of the nylon mesh that is designated

α1 and α2, respectively [23].
The synthesized film on the Petri dish surface was recov-
ered and weighed, obtaining an average of 0.096 g of C­ aCO3
in each container. This indicates we were able to recover
64.03% of calcite (Fig. 5 a), based on the ash used initially
(0.15 g). In theory, if we use 0.15 g of pure CaO to perform
the same experiment, the final weight of ­CaCO3 will be
0.267 g (Eqs. 3 and 4), which is not obtained experimentally.
Instead, the obtained yield (percent yield, Eq. 1) of calcite
is about 35.89% (Fig. 5b), which can be explained by the
fact that the ash is not composed entirely of calcium oxide,
and there is a residue at the bottom of the container with
low calcium concentration and a higher concentration of
the other elements originally present in the ash [18]. Previ-
ous reports indicate that burning agave bagasse can produce
Fig. 3  Raman spectra of the film, the nylon mesh and the interface
mesh/fim

Fig. 4  X-ray diffractogram of the sample and interface between the

film and the mesh

The XRD results show the maximum intensity peak at

2θ = 29°, which was found in ­CaCO3 films (Fig. 4), cor-
responding to the (104) plane according to the RRUFF
database. Then, XRD results indicate that the produced
powder corresponds with the polymorph of calcium car-
bonate (calcite), corroborating the results obtained by EDX
(Fig. 2f), regardless of the appearance of the crystals on the
film (Fig. 2d). Nylon 6.6 was also studied before the experi-
ments; the nylon mesh has two crystalline phases that can
Fig. 5  Graphic representation of the actual yield of calcium carbonate
be present in the XRD, the α phase, and the γ phase. The in relation to the ash in (a) and percent yield considering the entire
two peaks exhibited at 2θ = 20.4° and 24.1° are distinctive reaction (Eq. 1) in (b)

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up to 16% of ash, which represents an important source of
calcium oxide if this waste is properly utilized [9]. Then,
based on the results we can suggest that for every kilogram
of ash utilized, about 640 g of pure ­CaCO3 will be obtained
(64.03%), with the proportional C ­ O2 uptake (281 g) by the
calcium carbonate (Eq. 4).
CaO + H2 O → Ca(OH)2 + Heat (3)
Ca(OH)2 + CO2 → CaCO3 + H2 O (4)
XRF results corroborate the purity of the material, showing
the composition of the raw material (A950) and the puri-
fied film ­(CaCO3) in Table 1. These results show that the
obtained product has a purity of 99 wt%. It can be seen from
the results, that the reduction of other oxides in the film
is notorious, and the subsequent increasing of CaO in the
formed crystals, as seen in Fig. 2e. Another advantage of the
present procedure is the small crystals that can be obtained
(≈ 10 µm), which can be even more than 10 times smaller,
compared with other calcium carbonate particles obtained
by milling [24], with similar purity (≈ 99 wt%). In conse-
quence, these particles can be used in applications where the
particle size matters, such as in cement mortars, where the
reactivity is proportional to the size [5]. Also, these small
particles are used as fillers in paper, where controlled mor-
phology is required to obtain specific properties, such as
brightness, opacity, and porosity [25].
Using this innovative procedure, we were able to recover
­CaCO3 using ash as a starting material, demonstrating that
using a nylon mesh will help the calcite nucleation on the
fiber surface. Also, ­CO2 from the environment was removed
and integrated permanently into the calcite structure, helping
to keep neutral the emissions during the burning process of
the biomass ­(CO2 cycle) and the floated calcite synthesis.
Conclusions
It has been shown that it is possible to obtain C
­ aCO3 crys-
tals from agave bagasse ash, and thus be able to introduce
an alternative to limestone since thousands of tons of agave
bagasse are discarded annually. Also, it was found that it
is possible to form a thin film without the use of additives
under atmospheric conditions, using an innovative proce-
dure. In addition, we introduce the use of a defined surface,
such as a nylon mesh, to help the growth of C­ aCO3 crystals,
facilitating their self-assembly. The nucleation starts with
small particles formed by the interaction of the C ­ a2+ ion
(from the liquid) and ­CO2 from the environment (air). The
process manages to build bigger crystals by aligning/adding
small particles with each other. In addition, we were able to
recover the calcium carbonate film in a simple way avoiding
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Waste and Biomass Valorization (2021) 12:1591–1597
great losses, reporting a process with a reaction recovery
around 64% and purity of 99 wt%.
Author Contributions Not applicable.
Funding The authors want to thank the program PAICYT-UANL for
the funding provided to develop the present project.
Availability of Data and Material The data used to support the findings
of this study are included within the article.
Compliance with Ethical Standards
Conflict of interest All authors declare that they have no conflict of
interest.
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