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Synergizing Carbon Capture Storage and Utilization in a Biogas
Upgrading Lab-scale Plant Based on Calcium Chloride:
influence of precipitation parameters.
Francisco M. Baena-Moreno a,b *, Mónica Rodríguez-Galán a, Fernando Vega a, T. R.
Reina b, Luis F. Vilches a, Benito Navarrete a.
a Chemical and Environmental Engineering Department, Technical School of
Engineering, University of Seville, C/ Camino de los Descubrimientos s/n, Sevilla
41092, Spain
b Department of Chemical and Process Engineering, University of Surrey, GU2 7XH
Guildford, United Kingdom
*Corresponding author.
E-mail address: [email protected] (Francisco M. Baena-Moreno)
Abstract
Herein a strategy for biogas upgrading in a continuous flow absorption unit using CaCl2
as capturing agent is reported. This process is presented as an alternative to the
standard physical regeneration processes to capture carbon dioxide (CO2) from biogas
effluents with inherent high energy penalties. This work showcases a systematic study
of the main parameters (reaction time, reaction temperature, and molar ratio
reactant/precipitator) affecting calcium carbonate (CaCO3) precipitation efficiency in a
reaction between sodium carbonate (Na2CO3) and CaCl2. In addition, the purity and
main characteristics of the obtained product were carefully analysed via in a combined
characterisation study using Raman, XRD, and SEM. Our results indicate that
acceptable precipitation efficiencies between 62-93% can be reached by fine tuning the
studied parameters. The characterization techniques evidence pure CaCO3 in a calcite
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structure. These results confirmed the technical feasibility of this alternative biogas
upgrading process through CaCO3 production.
Keywords
Carbon Capture and Utilization; Biogas Upgrading; Calcium Carbonate Precipitation;
Chemical Absorption;
1. Introduction
Biogas from landfills, agricultural or industrial wastes, and wastewater treatment is a
valuable material for the production of bioenergy, biofuels and chemical products, such
as hydrogen and methanol (Bacenetti et al., 2013; Styles et al., 2016; Wheeler et al.,
1999). For practical applications, biogas quality must be improved, being required to
eliminate all the harmful components that biogas mixtures contain, which are reflected
in Table 1.
Table 1. Mainly biogas compounds (Francisco M. Baena-Moreno et al., 2019;
Schneider et al., 2019; Toledo-Cervantes et al., 2018; Ullah Khan et al., 2017).
COMPONENT BIOGAS COMPOSITIONMethane 60-70 (% vol)
Carbon dioxide 30-40 (% vol)
Nitrogen 0-0,2 (% vol)
Hydrogen sulfide 0-4.000 (ppm)
Ammonia 0-100 (ppm)
Table 2. Biogas preliminary techno-economic analysis (Bright et al., 2011; Hoo et al.,
2018; Jørgensen, 2009; Patrizio et al., 2015; Pipatmanomai et al., 2009).
COMPONENT VALUEBiogas combustion price (p/kWh) 0.89-2.97
Biomethane injection price (p/kWh) 1.49-3.30
Biogas calorific value (MJ/ m3) 20.7-27.8
Biomethane calorific value (MJ/ m3) 37.7-39.8
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As manifested in Table 1, biogas is typically rich on carbon dioxide (CO2) which
remarkably limits its direct application for power and heat generation. Table 2 presents
the biogas combustion price in comparison to bio-methane injection price, as well as
both calorific values, being bio-methane values comprehensively higher. For this very
reason, many research groups focus their efforts on finding novel techniques that
remove CO2 from biogas resulting in a clean bio-methane stream (Bacenetti et al.,
2014; Castellani et al., 2018; Dou et al., 2018; Qin et al., 2018). Furthermore CO2
clearly represents an environmental problem for the society. The ongoing increasing of
carbon dioxide levels in the atmosphere is causing problems such as ocean
acidification (Connell et al., 2013; Doney et al., 2009) soil acidity (Longdoz et al., 2000;
Six et al., 2001) and global warming. Moreover, CO2 is considered to have a
considerable impact in human’s health as demonstrated by some authors (Karl et al.,
2011; Veltman et al., 2010). Among the CO2 capture techniques for bio-methane
production, chemical absorption through monoethanolamine (MEA), piperazine (PZ),
sodium hydroxide (NaOH) or potassium hydroxide (KOH), have been proved as an
efficient method to obtain high quality bio-methane (Baciocchi et al., 2013b, 2011a; Li
and Zhang, 2018; Vega et al., 2017a, 2017b; Zhang, 2016; Zhang et al., 2018).
However, these processes involve a remarkable energy penalty mainly given the
necessary thermal regeneration of the solvents (Leonzio, 2016; Steel et al., 2018;
Zhang et al., 2015, 2014; Zhang, 2016). Considering these restrictions the
development of cost efficient and less energy intensive approaches for biogas
upgrading is an appealing research topic within the engineering community..
Alternative method describe in literature (Baciocchi et al., 2013b, 2012, 2011b, 2010;
Librandi et al., 2017; Said et al., 2013) have proposed more economically attractive
routes via chemical regeneration with a precipitant agent such as calcium hydroxide
(Ca(OH)2) (Baena-Moreno et al., 2018) or high calcium content industrial residues, as
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for example steel slags (Librandi et al., 2017; Wang et al., 2017) or Air Pollution Control
(APC) (Baciocchi et al., 2013a, 2013b, 2011a), in order to obtain a calcium carbonate
precipitated. This process is illustrated in Figure 1.
Figure 1. Process for biogas upgrading and CO2 mineralization.
Briefly this process implies first the CO2 capture from biogas in a packed tower by
NaOH or KOH solution to form sodium carbonate (Na2CO3) or potassium carbonate
(K2CO3) respectively, according to reaction (1). This step was studied previously by
several research teams, observing capture yields over 90% (Baciocchi et al., 2013b;
Kismurtono, 2011; Läntelä et al., 2012; Mahmoudkhani et al., 2009). To mineralize the
captured CO2 and avoid it returns to the atmosphere, the resulting solution of Na2CO3
or K2CO3 is fed into a precipitation reactor, where it is chemically reacted with the
precipitant agents mentioned above (reaction (2)).
2NaOH /KOH (aq )+CO2(s )→Na2CO3/K2CO3 (aq )+H 2O (1)
Na2CO3/K2CO3 (aq )+Ca (OH )2(s)→2NaOH /KOH (aq )+CaCO3(s) (2)
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The bottleneck of this process is the low regeneration efficiency mainly ascribed to the
utilization of industrial residues in the regeneration step (50-60%) (Baciocchi et al.,
2012, 2011b). Despite its potential for high regeneration efficiencies, the use of raw
Ca(OH)2 presents some disadvantages from the CO2 emissions mitigation perspective
(Baena-moreno et al., 2018a; Baena-Moreno et al., 2018; Francisco Manuel Baena-
Moreno et al., 2019). For instance, Ca(OH)2 is manufactured by calcination of
limestone a process that releases CO2 into the atmosphere and therefore increases the
carbon fingerprint of the overall process. In order to overcome these limitations, our
work suggests an innovative method for CO2 capture for biogas upgrading units (Figure
2).
Figure 2. Proposed method for biogas upgrading and CO2 utilization.
Figure 2 presents a biogas cleaning process with precipitate calcium carbonate (PCC)
production from a source of calcium chloride (CaCl2). The first step is exactly as
explained previously in Figure 1 (CO2 absorption in a packed column using caustic
solutions). For NaOH or KOH regeneration, the resulting carbonate solution from the
packed tower is fed in a precipitation reactor, where a CaCl2 solution is added to
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produce the mineralization reaction (reaction (3)). This CaCl2 solution could come from
brines (Arti et al., 2017; Galvez-Martos et al., 2018) or residual streams, such as
residual CaCl2 solutions from potassium chlorate (KClO3) production (Erdogan and
Eken, 2017), or from waste liquids which mainly come from the distiller waste in
ammonia-soda process (Dong et al., 2018), making the process even more interesting
from an industrial waste valorization point of view. In the overall process, CO2 would be
mineralized in the form of PCC.
Na2CO3/K2CO3 ( aq )+CaCl2(s)→2NaCl /KCl ( aq )+CaCO3(s) (3)
Finally, it would be necessary a step of NaOH regeneration from sodium chloride
(NaCl), formed in the previous stage. For this, bipolar membrane electrodialysis
(BMED) has been intensively studied offering very promising results. Indeed BMED
can be fully powered using renewable/low carbon energy sources, leading to
hydrochloric acid as a valuable by-product (Ghyselbrecht et al., 2014; Paleologou et
al., 1997; Wei et al., 2013; Ye et al., 2015).
In this scenario it seems clear that the first and third step of the proposed strategy are
validated for the overall performance of the process. Nevertheless, the studies for the
precipitation reaction taking place in the second step are scarce from a reaction yield
point of view despite they are vital to corroborate the technical feasibility of the process.
Therefore, the purpose of this work was to study the parameters affecting the PCC
formation using aqueous solutions of Na2CO3 and CaCl2 targeting CaCO3 as main solid
marketable product along with NaCl as valuable side product which could be further
upgraded via BMDE.
2. Materials and Methods.
2.1 Materials
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CaCl2, Na2CO3 and CaCO3 employed in this work were provided by PanReac-
AppliChem (pure-grade or pharma-grade, 99% purity).
2.2 Experimental Study
The experiments have been carried out in two differentiated phases: first, the reaction
between CaCl2 and Na2CO3 to produce PCC was carried out. Afterwards, the
precipitated particles are duly extracted from the precipitation reactor for their analysis
using different techniques.
- Precipitation experiments
Generally, the precipitation experiments were done according to the methodology
exposed below, which will be further explained later. First, both the solutions of the
reactants and the instruments needed for the precipitation reaction were prepared.
After this step, the reaction was carried out and once finished, the solution was filtered
and separated quickly for analysis. The main result was set on the PCC precipitation
efficiency, which was defined as follow.
PCC precipitation efficiency (% )= PCC obtainedMaximum PCC ¿
obtain ¿ x100
PCC precipitated was determined as the solid result of each experiment. For sake of
calculations, the maximum PCC obtainable corresponds to that stochiometrically
reachable in a complete reaction. The key variables studied were the reaction time, the
reaction temperature, and the CaCl2 / Na2CO3molar ratio (R), since these variables
were proved to have an effect on the reaction rate (Ahn et al., 2005; Baciocchi et al.,
2013b, 2012, 2011b; Baena-moreno et al., 2018b; Lombardi et al., 2011). In order to
study the effect of each parameter, a standard value was set for each of them based
on findings proposed in similar studies (Baciocchi et al., 2012, 2011b). The standard
value for the reaction temperature was set at 50°C, molar ratio at 1.2 mol Ca/Na2CO3,
and reaction time at 30 minutes. Then each parameter was individually modified one at
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a time to corroborate their genuine impact in the overall process and hence establish
the optimum limits. In the case of Na2CO3, the aqueous solution was set at 20 g/100 ml
according to the basis typical values expected after the absorption step (Baciocchi et
al., 2013a, 2013b), while the concentration of CaCl2 solution were stochiometrically
calculated for each test, as varying the molar ratio. Table 3 represents the experiments
carried out to analyze the effect of the variation of each parameter.
Table 3. Matrix of experiments carried out.
TEST TIME (MIN) TEMPERATURE (ºC) MOLAR RATIO (R)Standar
d30 50 1.2
1 5 50 1.22 15 50 1.23 45 50 1.24 60 50 1.25 90 50 1.26 120 50 1.27 30 30 1.28 30 35 1.29 30 40 1.210 30 45 1.211 30 50 1.212 30 55 1.213 30 60 1.214 30 65 1.215 30 70 1.216 30 50 0.717 30 50 0.818 30 50 0.919 30 50 120 30 50 1.121 30 50 1.222 30 50 1.323 30 50 1.424 30 50 1.5
As showcased in Table 3, the reaction time, temperature and molar ratio were tested
from 5 to 120 minutes, from 30°C to 70°C, and from 0.7 to 1.5 mol Ca/Na2CO3,
respectively. Lab scale batch precipitation experiments were conducted in a 600 mL
beaker whose temperature is controlled using an isothermal water bath. During the
experiment the solution was stirred by an electromagnetic magnet at a constant speed
of 1,000 rpm. A Trison instrument was used and data was logged for temperature and,
in order to agree with the carbonates pH range (8-11), it was measured by the same
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instrument. Both CaCl2 and Na2CO3 solutions were previously prepared and then 100
mL of each were poured into the reaction vessel.
- PCC Physicochemical Characterization
The solid obtained by filtration was dried at 105°C.The solid was then characterized by
means of SEM, XRD and Raman spectroscopy to corroborate the formation of the PCC
and get some insights on its main features
Raman measurements of the powders samples were recorded using a Thermo DXR2
spectrometer equipped with a Leica DMLM microscope. The wavelength of applied
excitation line was 532nm ion laser and 50x objective of 8-mm optical was used to
focus the depolarized laser beam on a spot of about 3 µm in diameter.
A JEOL JSM6400 operated at 20 KV equipped with energy dispersive X-ray
spectroscopy (EDX) and a wavelength dispersive X-ray spectroscopy (WDS) systems
was used for the microstructural/chemical characterization (SEM with EDS and WDS).
X-ray diffraction (XRD) analysis was completed by an X’Pert Pro PAN analytical
instrument. The 2θ angle was increased by 0.05o, with a 450 time per step over a
range of 10-90o. Diffraction patterns were then recorded at 40 mA and 45 kV, using Cu
Kα radiation (λ=0.154 nm).
3. Results
First of all, chemical characterization of PCC particles obtained is presented aiming to
verify the formation of a carbonate phase for all the different tests. Then, precipitation
efficiencies are shown and the influence of the reaction parameters in the precipitation
experiments is discussed.
3.1 PCC Physicochemical Characterization Results
A combined Raman, XRD and SEM was carried on the obtained precipitated samples
in order to check their purity. Commercial standards samples of CaCO3 were also
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studied for sake of comparison. Figure 3 represents the Raman spectrum of the PCC
obtained for the test corresponding to 30 minutes, 50oC and R=1.2, in comparison with
the spectrum of a standard CaCO3 sample. The strongest band of CaCO3 appears at
1100 cm-1 (Ahn et al., 2005; Dandeu et al., 2006). As can be seen in Figure 3, both
PCC and standard CaCO3 show this peak, as well as another characteristic band at
700 cm-1, confirming that the precipitated sample is completely CaCO3. This is an
interesting observation since previous works in literature reported an uncompleted
precipitation and the presence of impurities such as hydroxides when different
precipitating agents are used (Baena-moreno et al., 2018b). It seems that calcium
chloride is a suitable option as precipitator to favor full and neat CaCO3 formation.
Indeed this is reinforced in the following sections described in this work.
400 600 800 1000 1200 1400 1600
PCC
Ram
an In
tens
ity (a
.u.)
Raman shift (cm-1)
Standard CaCO3
Figure 3. Raman spectra of the PCC obtained (time=30min, T=50°C, R=1.2) and
standard CaCO3.
Once confirmed that the solid samples obtained are CaCO3, it is important to
investigate the crystal polymorphs in which the precipitation has resulted. PCC can be
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obtained in three main crystal polymorphs form: calcite, aragonite, and vaterite (Altiner
and Yildirim, 2017; Dandeu et al., 2006). The type of CaCO3 polymorphs are difficult to
distinguish by routine Raman spectroscopy. For this reason, a XRD analysis was
conducted. Figure 4 shows X-Ray diffraction patterns of the PCC obtained precipitated
(same sample used for the Raman study). According to previous studies, the type of
PCC obtained correspond to calcite, the most stable form of CaCO3 (Altiner and
Yildirim, 2017; Said et al., 2013). Calcite present an intense and narrow diffraction peak
at around 28 2Өdegrees, as well as less strong reflections at 23, 36, 39, 43, 47 and 48
2Ө degrees.
Also, as can be seen in Figure 4 the XRD diffraction pattern of the obtained PCC
matches perfectly that of the reference CaCO3 indicating that both samples present the
crystalline structure of calcite and they are both free of impurities.
20 25 30 35 40 45 50 55 60
PCC
Inte
nsity
(a.u
.)
2q (degree)
Calcite
Figure 4. Comparison of XRD diffractogram of the PCC obtained (time=30min,
T=50°C, R=1.2) and standard calcite.
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Further physicochemical information about the nature of the precipitated carbonates
was obtained via scanning electron microscopy. Selected SEM images were taken
showcasing the morphology of the solid samples. Previous reports in literature pointed
out the tetrahedral morphology of calcite. Indeed, as it can be observed in Figure 5,
PCC samples obtained in our experiments show this typical shape, what in general
terms confirms the previous XRD and Raman results validating the purity of the
precipitated samples. Under these premises, we can assess the precipitation
efficiencies of our process in the next section since it is save to point out that the
obtained solid was pure.
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Figure 5. SEM images of the PCC obtained (time=30min, T=50°C, R=1.2).
Given the purity of our PCC market opportunities are worth to be explored. The
characteristics market options for PCC in its calcite form are depicted in Figure 6.
Generally speaking, there are many potential applications for PCC calcite and its
market price depends on the purity obtained, being around 100€/ton for less refined
PCC (Eloneva et al., 2012), and ca. 350 €/ton for the finest PCC batches (Katsuyama
et al., 2005). As a matter of practical example, calcium carbonate is employed as a
paper filler and coating in the paper industry to its natural brightness (Domingo et al.,
2006; McGonigle and Ciullo, 1996). In the paints sector, its lower price compared to
titanium oxide favors the utilization of calcite as coating for paints manufacturing
(McGonigle and Ciullo, 1996). Also its economic viability makes PCC a very versatile
chemical with multiple applications including adhesive and sealant production or as
filler plastics in polymers industry (Gorna et al., 2008; Osman et al., 2004).
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Figure 6. PCC calcite morph potential applications.
3.2 Precipitation results
As explained above, the aim of this study was to ascertain the influence of the reaction
parameters in the formation of PCC during the precipitation reaction, as well as to
establish trends of the precipitation efficiencies upon variation of the key reaction
parameters. Figures 7, 8 and 9, display the influence of the reaction temperature, molar
ratio (R) variation and reaction time in the precipitation efficiency.
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25 30 35 40 45 50 55 60 65 70 7579.2
79.4
79.6
79.8
80.0
80.2
80.4
80.6
80.8
81.0
PCC precipitation efficiency (%) PCC precipitated / °C
Temperature (°C)
PC
C p
reci
pita
tion
effic
ienc
y (%
)
0.00004
0.00005
0.00006
0.00007
0.00008
0.00009
0.00010
PC
C m
ol p
reci
pita
ted
/ °C
Figure 7. Influence of a temperature on CaCO3 efficiency. Tests carried out at t=30min
and R=1.2.
As shown in Figure 7, there is not much difference between regeneration efficiency at
30°C and 70°C (less than 2%). It means that good results could be obtained at room
temperature making the process much less energy intensive than traditional
alternatives such as CO2 absorption with MEA or AMP (Vega et al., 2017a; Zhang et
al., 2018, 2014). This result matches well with previous investigations dealing with
carbonate driven CO2 capture alternatives (Arti et al., 2017; Chen et al., 2016).
Regarding CaCO3 moles precipitated per degree of temperature increase, it is
observed that generally the trend is positive in the studied range, which indicates
positive effect of the temperature in the precipitation. However, the increase is
considerably small – even inappreciable in some points - an aspect that agrees with
the results obtained for PCC efficiency.
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0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.660
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70
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Molar ratio
PC
C p
reci
pita
tion
effic
ienc
y (%
)
PCC precipitation efficiency (%) PCC precipitated / mol CaCl2
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
0.20
0.22
0.24
PC
C m
ol p
reci
pita
ted
/ CaC
l 2 m
ol in
trodu
ced
Figure 8. Effect caused on PCC efficiency by molar ratio variation. Tests carried out at
t=30 min and T=50oC.
Interestingly, the molar ratio between the reactants seems to play a major role in the
process. Figure 8 clearly demonstrates that the best point to operate the reactor is an
R value of 1.2. Indeed, a reasonable value of precipitation efficiency is obtained at this
point and further improvement beyond this threshold may not compensate the cost of
the reagents. Also, the amount of free calcium remaining in the NaCl solution formed
could be easily removed in a previous BMED stage by altering pH with the addition of
small quantities of aqueous NaOH. Further relevant information concerning the process
yield can be inferred from Figure 8. Following the squared symbols curve it seems
clear that a better utilization of each CaCl2 mol is obtained at R=1 since in this point the
curve reaches the maximum. However at this ratio the net precipitation yield, is not as
good as it is at R=1.2, which represent a good balance in terms of precipitation
efficiency and reactant utilization and seems to be an ideal starting point for further
studies seeking an industrial implementation.
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0 20 40 60 80 100 12074
76
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90
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94
Time (min)
PC
C p
reci
pita
tion
effic
ienc
y (%
) PCC precipitation efficiency (%) PCC precipitation rate (mol/min)
0.0000
0.0001
0.0002
0.0003
0.0004
0.0005
0.0006
PC
C p
reci
pita
tion
rate
(mol
/min
)
Figure 9. Evolution of CaCO3 precipitation efficiency in time. Test carried out at R=1.2
and T=50oC.
Finally, the evolution of CaCO3 precipitation efficiency during the reaction time was
studied. As shown in Figure 9 a remarkable improvement can be obtained from 15
minutes (75.93%) to 60 minutes (87.22%), but doubling the reaction time to 120
minutes only produces a minor impact (5% enhancement) on the overall efficiency.
Such a reaction time increment would result in doubling the size of a potential industrial
reactor in a realistic application and therefore it is not recommended given the subtle
efficiency improvement. From the squared symbols plot we can infer that the maximum
precipitation rate is achieved at 45 minutes (84.19% yield), with a remarkable decrease
beyond this point suggesting that 45 mins is a suitable operation point from a general
process efficiency perspective.
4. Conclusions and future remarks
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The results obtained from this lab scale work have confirmed the technical feasibility of
this biogas upgrading process through PCC production from CaCl2 brines or residues.
This process allows to obtain a high purity CaCO3 from CO2 and CaCl2 waste opening
a new route for the simultaneous valorization of gas and solid residues. As an
additional advantage, this process may lead to substantial savings in terms of CaCO3
extraction from natural sources while opening an economically viable route for carbon
capture utilization and storage (CCUS) alleviating the CO2 penalty in heavy carbon
industries. In general, most of the tests showed acceptable precipitation efficiencies
(62-93%). Raman spectra confirmed that the obtained solid sample contains principally
a carbonate phase, while XRD and SEM affirmed that the PCC samples were calcite
type materials which are the most stable form of carbonates with broad market
opportunities in the chemical industry.
The reaction performance can be controlled by fine tuning key reaction parameters
such as temperature, reactants ratio and reaction time. For instance, it was asset that
for temperature reaction there is no remarkable difference between working at room
temperature or at 70°C, for t=30 minutes and R=1.2. This is really meaningful from an
energy savings point of view, since it would not be necessary to heat up the reactor
(leading to extra CO2 emissions) to conduct the reaction. As for the molar ratio CaCl2/
Na2CO3, the ideal working point would be around 1.2, for t=30 minutes and T=50°C.
This result has been chosen based on the best balance PCC precipitation efficiency
and PCC mol precipitated per CaCl2 mol introduced. The impact of the reaction time is
also interesting, it was identified that the ideal reaction time would be around 60
minutes for T=50°C and R=1.2, leading to compact reactor units and saving capital
cost investment. Furthermore, the optimal temperature conditions are achievable by
means of renewable energy sources indicating minor environmental impact of the
proposed biogas upgrading route.
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Overall, this paper suggests an innovative alternative to synergize CO2 capture and
utilization since our absorption unit permits the upgrading of biogas flue gases resulting
in a CO2-free methane stream with multiple potential applications such as sustainable
heat and power production. Environmentally our process has proved to be friendly in
terms of potential damages and optimization of resources. Moreover, the high purity of
the produced carbonates allow their potential commercialization as by-products of the
upgrading process.
Acknowledgments and Funding
This work was supported by University of Seville through V PPIT-US. Financial support
for this work was also provided by the EPSRC grant EP/R512904/1 as well as the
Royal Society Research Grant RSGR1180353. This work was also partially sponsored
by the CO2Chem UK through the EPSRC grant EP/P026435/1. Furthermore this work
was supported by EMASESA through NURECCO2 project and Corporación
Tecnológica de Andalucía (CTA).
References
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