Article

pubs.acs.org/EF

Demineralization of Brazilian Coals for Use in Gasication and Oxy-

Fuel Combustion Processes, Aiming to Reduce CO2 Emissions
Keila Guerra Pacheco Nunes,*, Kirstin Milbradt Engel, Eduardo Osorio, and Nilson Romeu Marclio

Department of Chemical Engineering, Federal University of Rio Grande do Sul (UFRGS) Rua Engenheiro Luiz Englert, s/n Campus
Central, CEP 90040-040, Porto Alegre, RS, Brazil

Iron and Steelmaking Laboratory (LASID), University of Rio Grande do Sul Avenida Bento Goncalves, 9500. Porto Alegre, RS Brazil

ABSTRACT: Mineral matter in coal has an environmentally negative eect, as it is responsible for the generation of soot and
slag. Technically, the mineral matter causes corrosion of equipment and reduces the combustion rate of coal, as well as
inuencing the sizing of equipment. Therefore, removal of this unwanted portion of the carbon matrix would reduce the need for
importing high-quality coals and minimize transportation costs. This work aims to study the eects of the removal of mineral
matter on the structure of southern Brazilian coal at the temperature of gasication and considering the kinetic parameters of the
oxy-fuel combustion reaction. The demineralization process was conducted using solutions of HF, HCl, and HNO3 with
concentrations of 20% (v/v). The samples were characterized by elemental analysis, proximate analysis, SEM, FT-IR
spectroscopy, petrographic analysis, XRD, and XRF. The removal of the mineral portion introduced major changes in the
structure of coal, reecting an increase in the start temperature of the Boudouard reaction to 160 K. The oxy-fuel reaction was
performed at temperatures of 873, 973, 1073, and 1173 K with O2/CO2 concentration ratios ranging from 10% to 30% (v/v).
Before the demineralization process, the activation energy for the oxy-fuel reaction was 10.8 kJmol1. The value obtained with
demineralized char was 56.46 kJmol1.

1. INTRODUCTION soot as byproducts, causes corrosion of equipment, and reduces

Approximately 50% of the electricity produced worldwide
comes from nonrenewable resources. The use of this type of
fuel generates large amounts of environmental pollution and
causes considerable damage to human health. The burning of
coal alone is responsible for 35% of the emissions of
greenhouse gases.1 Environmental issues associated with the
accumulation of CO2 in the atmosphere constitute one of the
main reasons for focusing attention on renewable energy
sources and cleaner fuels.
Because of the global energy situation, coupled with the fact
that high-quality coal reserves are declining, the production of
an ultraclean coal has gained more prominence. Ultraclean
coal is a byproduct of coal whose main feature is a low ash level,
approximately 0.1%.2 Thus, this new raw material has the
potential to be used directly in gasication combined cycles, gas
turbines, and advanced technologies such as pressurized
uidized beds, where the eciency can reach 48%. In this
way, high-ash, high-sulfur coals, which are unsuitable for
combustion, gasication, or liquefaction, become environ-
mentally acceptable after the demineralization process, because
the CO2 emissions are reduced by 2535%.3
The mineral matter in coal is composed of clays, sultes,
carbonates, sulfates, pyrites, halogenides, chlorates, silicates,
oxides, hydroxides, and phosphates. These components
represent all of the elements present in coal except for those
in organic components, such as C, H, N, S, and O. There are
some macroconstituents whose concentrations usually exceed
1% of the weight of the ash. The principal elements are Al, Ca,
Fe, S, and Si, followed by K, Mg, Na, P, and Ti.4
The mineral matter in coal has negative eects on the
environment and on equipment because it generates slag and
the overall rate of combustion. On the other hand, the catalytic
actions of alkali metals, alkaline earth metals, and transition
metals can have positive eects. These elements inuence not
only the combustion process, gasication, and liquefaction but
also equipment design. The goal of treatment for the removal
of mineral matter is to produce a high-quality coal with a high
caloric value, reduce the amounts of y ash and air pollutant
precursors emitted, reduce the costs of operation and
maintenance of burners in thermal generation plants, minimize
transportation and storage costs, and reduce the need for
imports of high-quality coals. In addition, the reagents used can
be recycled, thus increasing the economics of the gasication
and pyrolysis process.5
It is known that, during the process of thermal decom-
position of coal, its properties are altered, and the formation of
free radicals provides information about the chemical structure
of the product generated. Although the mechanisms of the
reactions are still unknown because of the complex structures of
the macromolecules involved, studies have shown catalytic
eects of some metals present in the carbon network.
The metals K, Na, Mg, and Ca qualitatively and
quantitatively inuence the products of pyrolysis and gas-
ication. According Samaras et al.,6 impurities such as Fe, K,
Mg, and Ca catalyze the gasication reaction.
The heating of coal during gasication produces carboxylate
salts in the ash and generates CO2, leaving other inorganic
species highly dispersed.7
Received: April 10, 2017
Revised: June 17, 2017
Published: July 5, 2017

XXXX American Chemical Society A DOI: 10.1021/acs.energyfuels.7b01025

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Table 1. Reagents Used for the Removal of Mineral Matter, as Reported by Various Authors, in Chronological Order
authors year reagent(s) raw material
Hengel and Walker7 1984 HF, HCl coal
Calahorro et al.10 1987 HF, HCl, HNO3 coal
Kister et al.11 1987 HF, HCl coal
Kusakabe et al.12 1989 KOH, NaOH, HCl coal
Samaras et al.6 1994 HF, HCl, HNO3, CH3COOH coal
Sentorun et al.13 1996 HCl, HF coal and biomass
Wu and Ohtsuka14 1997 HCl coal
Bolat et al.4 1998 HF, HCl, HNO3, H2SO4, NaOH coal
Haykiri-Acma et al.8 2000 HCl, HF coal
Linares-Solano et al.15 2000 HF, HCl coal
Davidsson et al.16 2002 CH3COOH biomass
Wu et al.17 2002 ethanol, HCl coal
Wu et al.9 2003 HCl coal
Mukherjee18 2003 NaOH, KOH, HCl coal
Mukherjee and Borthakur19 2003 HCl, HNO3, H2SO4 coal
Zhao et al.20 2003 HF, HCl coal
Das et al.21 2004 HF biomass
Yagmur et al.22 2005 HF, HCl coal
Vamvuka et al.23 2006 HCl, CH3COOH biomass
Vamvuka et al.23 2006 HCl, HF coal
Fierro et al.24 2007 H2SO4 biomass
Wu and Steel25 2007 HF coal
Keown et al.26 2008 H2SO4 biomass
Ahmad et al.27 2009 HCl coal
Sun et al.28 2009 HF, HCl coal
Eom et al.29 2011 HCl, HF biomass
Liu and Bi30 2011 CH3COOH biomass
Mourant et al.31 2011 HNO3 biomass
Suzuki and Nakajima32 2011 HCl biomass
Manoj33 2012 C6H12O7, C6H8O7, EDTA, CH3COOH, HO2CCO2H coal
Mandapati et al.34 2012 HCl, HF coal
Mayer et al.35 2012 HCl biomass
Wijaya et al.2 2012 acid pyroligneous, C6H8O7, EDTA-Na coal
Wang et al.36 2012 HCl, HF coal
Jiang et al.37 2013 CH3COOH, HCl, H2SO4, HNO3, H3PO4 biomass
Liu et al.38 2013 HCl coal and biomass
Reichel et al.39 2013 HCl, HF biomass and coal
Asadieraghi and Daud40 2014 H2SO4, HClO4, HF, HNO3, HCl biomass
Liu et al.41 2014 HCl, HF coal
Li et al.42 2014 H2SO4, NaOH biomass
Kong et al.43 2014 1-methylnaphthalene biomass
Bai et al.44 2014 HF, HCl coal
Prationo et al.45 2014 HF, HCl coal

Samaras et al.6 investigated the eects of treatments with
dierent acid solutions on the reactivity and development of
lignite pores. Specically, they observed the eects of dierent
acids (i.e., HNO3, HF, HCl) on the coal. They found that nitric
acid promotes a greater removal of pyrite and sulfur,
hydrouoric acid removes silicate, and hydrochloric acid
removes suldes and carbonates. The catalytic behavior of the
ash could also be observed. After 45 min of heating at 1173 K, a
sample containing 22% ash reached 100% conversion. At the
same temperature, for a sample containing only 0.14% of
mineral matter, 7 h was required to reach 98% conversion. With
the aid of surface area and porosity analyses by the Brunauer
EmmettTeller (BET) method and thermogravimetry, it was
concluded that demineralization contributed to increased
porosity and reduced reactivity of the treated coal samples.
B DOI: 10.1021/acs.energyfuels.7b01025
Bolat et al.4 performed the chemical demineralization of
Turkish coal with a high ash content using acid solutions (HF,
HCl, HNO3, and H2SO4) with concentrations of 10%, 20%,
and 30%, as well as acidic solutions combined with 0.5 N
NaOH. The authors observed that the degree of demineraliza-
tion decreased with an increase in the concentration of the acid.
This was due to the possible formation of stable compounds. It
was also noted that 10% HCl removed more mineral matter
that 10% H2SO4 or 10% HNO3, suggesting that smaller
molecules more easily diuse within the coal particles. In
addition, calcareous minerals are abundant in coal, and they
found that the reaction of CaO/CaCO3 with sulfuric acid
created insoluble gypsum.
Using hydrouoric acid and hydrochloric acid, Haykiri-Acma
et al.8 studied the eects of demineralization on the reactivity of
lignites. They observed an increase in the activation energy as a
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consequence of a reduced reactivity to combustion. An increase
in porosity in the particle structure was also observed, but this
did not aect the pore structure.
Wu et al.9 studied the eects of demineralization and the
addition of a catalyst on the formation of nitrogen compounds
during the pyrolysis of coal and the gasication of char. Coal
was demineralized by acid washing, and a catalyst was added. A
large eect on N2 emissions was observed during the pyrolysis
of the treated coal, specically reducing the emissions of that
gas. The back-addition of 0.5% Fe promoted the formation of
N2, although the catalytic eect of the metal varied with the
rank of the coal. According to the results for gasication,
demineralization reduced the reactivities of coals of both high
and low rank.
Chemical processes for removing ash are the most
commonly used and include washing with acids, bases, and
other reagents. Table 1 provides a chronology of the reagents
used for the removal of mineral matter, listed by author and
including the raw material studied in each case.
According to the information contained in Table 1, several
authors performed the removal of the mineral matter contained
in coal using strong acids such as HCl and HNO3 for the
removal of alkaline-, alkaline-earth-, and iron-containing
compounds. For the removal of silica, HF has generally been
used, and for the demineralization of biomass, weaker acids
such as organic acids have been used. In the case of biomass,
the use of strong acids could aect the structures of
carbonaceous materials such as cellulose, hemicellulose, and
lignin.
The study of the demineralization of coal has already covered
various areas, such as the formation of N2 during the pyrolysis
of demineralized coals,14 the change in the chemical structure
of coals after demineralization,11 and the eects on the
formation of free radicals and phenols.44,41 Recent research
has focused on the eects of demineralization on the structure
of biomass,37,39,40,43 but little is known about the inuence of
ash under oxy-fuel combustion conditions.
The inuence of metals and alkali metals on the coal
gasication reaction is well-known in the steel industry.
Steelmaking begins with the production of pig iron in a blast
furnace, where the CO generated by the coke gasication
reaction (the pyrolysis product of coal) is responsible for the
reduction of Fe2O3 to FeO. To reduce reagent consumption
and promote the reduction of CO2 emissions during the
production of steel, researchers have studied the impregnation
of metals in coal samples and/or coke. Nevertheless, the
inuence of metals on the gasication, combustion, and oxy-
fuel combustion reactions of southern Brazilian coal for energy
purposes is unknown.
Southern Brazilian coal is mainly used in powdered form for
power generation in thermal power plants. Because of the high
contents of mineral matter in this coal, the grinding process is
very costly. Therefore, demineralization can give this low-rank
coal a high quality for energy purposes, thus increasing the
eciency of power generation plants. This coal represents the
largest energy reserves in Brazil, and thus, there is a constant
search for processes that are more ecient from the technical
and economic points of view to improve the use of this energy
resource.
This work aimed to study the eects of the removal of
mineral matter on the structure of southern Brazilian coal and
on the gasication temperature and to perform a kinetic
analysis of the atmosphere during oxy-fuel combustion of this
C DOI: 10.1021/acs.energyfuels.7b01025
Article
coal. The eects of the main metals present in the
carbonaceous matrix on CO 2 reactivity were assessed
separately.
2. MATERIALS AND METHODS
2.1. Preparation of the Samples. The coal used in this work was
from the Candiota mine located in Rio Grande do Sul, Brazil. The
Candiota mine has an estimated reserve of 1 billion tons of coal
amenable to open-pit mining and is the largest coal mine in Brazil.
The demineralization process was adapted from the procedures of
Calahorro et al.,10 Samaras et al.,6 Bolat et al.,4 and Asadieraghi and
Daud,40 who suggested the use of HF, HCl, and HNO3 for the
removal of mineral matter.
During the process of removing the mineral matter of coal, the
eects of the concentration of the acid solution, the particle size of the
coal, and the reaction temperature were evaluated. Acid solutions with
concentration of 10%, 20%, and 30% by volume were prepared. Two
granulometry fractions were selected to assess the eects of particle
size during the removal of ash: fraction A contained particles with sizes
of 0.2120.250 mm, and fraction B contained particles with sizes of
0.4250.850 mm. The temperatures used were 293 and 333 K. The
tests were conducted as shown in Table 2.
Table 2. Experiments Carried out for the Removal of
Mineral Matter from Candiota Coal
test solution concentration (%) granulometrya temperature (K)
1 10 B 298
2 10 B 323
3 10 A 298
4 20 B 298
5 30 B 298
a
A = 0.2120.250 mm, B = 0.4250.850 mm.
A coal sample of 50 g was weighed into a beaker to which was
added 200 mL of HF solution. This solution was in contact with the
coal for 1 h under agitation. After the specied time, the reaction
solution was ltered and washed with hot distilled water. The coal
sample was returned to the beaker, and HCl was added to the solution.
The coal was ltered and washed with hot distilled water after reaction
for 1 h with stirring. Finally, if HNO3 was used, the same experimental
procedure was repeated. Finally, the coal was washed with hot distilled
water and held in an oven for 24 h at 373 K for drying.
After the acid treatment, the sample was characterized by proximate
analysis, elemental analysis, scanning electron microscopy (SEM),
petrographic analysis, Fourier transform infrared (FT-IR) spectrosco-
py, X-ray diraction (XRD), and X-ray uorescence (XRF).
2.2. Inuence of Mineral Matter on the Gasication
Temperature. The demineralization process aects the petrographic
composition of a coal sample, a parameter that directly inuences its
reactivity.5 With the removal of mineral matter, the carbon content
increases. In carbonaceous materials such as char from coal, the
reactivity decreases with increasing carbon content.46
To investigate the catalytic eect of ash on the Boudouard reaction
(CO2 + C CO2), char gasication tests were conducted with CO2
in a thermobalance. During the experiments, an alumina crucible-type
plate with a diameter of 17 mm was used. The reagent CO2 gas
entered the top of the balance, and exhaust gases exited from the
bottom. This arrangement was used in an eort to minimize the
diusive eects that can occur during the char gasication reaction.
The heating rate used was 20 Kmin1 from room temperature to 1273
K with a CO2 ow of 100 mLmin1.
2.3. Oxy-Fuel Reactions. For the kinetic study of demineralized
coals, a sample of char was rst produced. The char (pyrolyzed coal)
was prepared in an atmosphere of N2 at a heating rate of 20 Kmin1
from room temperature to 1173 K. The sample remained at this nal
temperature for 1 h.
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During the experiments, kinetic studies under the conditions of the the carbon matrix. As expected, there was an increase in the
the oxy-fuel combustion reaction were performed on a NETZSCH carbon content after the removal of the mineral matter.2,37
409 thermobalance model using an alumina crucible-type plate. The An increase in the nitrogen content was also observed in this
reactant gases entered the top of the thermobalance and had direct study. Wijaya and Zhang2 also observed an increase in the N
contact with the sample of char. The inuent ow of inert gas (N2) in
the thermobalance was 100 mLmin1 during the pyrolysis step, and
and O contents in the chemical composition of coal after
the inuent ow of reactant gases (O2/CO2) was 100 mLmin1. The treatment with HNO3. HNO3 is generally used in coal
O2 concentrations used were 10, 20, and 30 vol %. The temperatures treatment after HF to remove possible insoluble compounds
used in the oxy-fuel combustion reaction were 873, 973, 1073, and that have remained in the sample, mostly pyrite. The possible
1173 K. reactions that occur during treatment involving pyrite and
HNO3 are as follows
3. RESULTS AND DISCUSSION
FeS2 + 2HNO3 Fe(NO3)2 + H 2S + S (1)
3.1. Characterization of the Samples. The character-
ization of samples before and after the demineralization process
2FeS2 + 6HNO3 2Fe(NO3)3 + 3H 2S + S (2)
is of great importance to the understanding of the physical and
chemical changes that occur in the structure of coal after acid
treatment. 2FeS2 + 10HNO3
The coal samples produced in tests 15 were characterized
Fe2(SO4 )3 + H 2SO4 + 10NO + 4H 2O (3)
using proximate and elemental analyses; the results are reported
in Table 3. Thus, the H2SO4 formed during reaction 3 reacts with HNO3,
producing NO2+ and causing the oxidation of carbon and
Table 3. Composition of Coal Produced after the Acid Wash nitrogen species forming a new structure, as shown in the
levels (%)
reaction
analysisa ROMb test 1 test 2 test 3 test 4 test 5 HNO3 + 2H 2SO4 NO2+ + H3O+ + 2HSO4 (4)
c
granulometry B B B A B B
proximate The reduction in the sulfur content, present in the form of
volatile matter 21.1 34.8 38.3 42.4 41.4 45.7 pyrite, can be conrmed by tests with XRD.
ash 52.9 17.8 9.3 8.2 5.7 5.1 The coal samples produced were also subjected to
xed carbon 26.1 47.4 52.4 49.4 52.9 49.2 morphological analysis by scanning electron microscope, as
elemental shown in Figure 1. With this test, the surface structure and
C 35.3 66.3 65.2 57.6 65.5 64.0 particle porosity were evaluated.
N 0.7 3.3 4.2 3.8 4.2 4.8
S 1.6 1.5 1.3 0.9 1.1 0.9
H 3.9 4.6 4.7 4.0 4.6 4.3
O 58.5 24.3 24.6 33.7 24.6 26.0
caloric value (calg1) 3186 5292
a
Dry basis. bROM = run of mine cA = 0.2120.250 mm, B = 0.425
0.850 mm.

Because of the high mineral matter content in Brazilian coal

formations, as can be seen in Table 3, the grinding process is
very costly. Caloric value analysis provides an indication that
the process of removing the mineral matter contributes to an
increase in the fuel coal power, as suggested by Speight.47
However, an economic analysis must be conducted to compare
the costs of milling and of coal demineralization.
From the results presented in Table 3, it is possible to note
the greater removal of mineral matter in test 4, with a reduction
in ash content of 90% after the acid wash. The fact that the
degree of demineralization was not complete in either of the
coal samples can be explained by the formation of stable and
insoluble compounds, such as carbonates and suldes, that
remained in the sample, as mentioned by Bolat et al.4 As the
results of tests 4 and 5 were similar, it was decided to treat the
coal with less concentrated solutions.
The reduction in the amount of ash generated a signicant
increase in the contents of volatile matter and xed carbon.
Such an eect was also observed by Kizgut et al.48 and Jiang et
al.37 upon the removal of the mineral matter from coal and
biomass samples, respectively. In addition to an increase in
volatile matter content, Kizgut et al.48 observed an increase in Figure 1. SEM images of demineralized samples of coal from the
nitrogen and oxygen as a result of the oxidation and nitration of Candiota mine.

D DOI: 10.1021/acs.energyfuels.7b01025
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Figure 2. Results of the XRD analysis of a sample of Candiota coal before and after demineralization.

Analysis of the SEM images shown in Figure 1 indicates that Table 4. XRF Analysis of ROM and Demineralized Samples
the acid washing carried out as described in test 5 (30% of Candiota Coal
concentration of acid solutions) left a less porous structure in
levels (%)
the carbon sample. In test 4 (20% concentration of acid
solutions), the attack on the carbon surface was less vigorous, component ROM demineralized
giving particles with good porosity and greater removal of the SiO2 28.93 5.34
mineral content. Al2O3 7.91 0.47
To characterize the composition of the ash remaining in the Fe2O3 2.91 0.07
samples of test 4, XRD and XRF analyses were conducted. SO3 3.36 1.91
Figure 2 presents the X-ray diractograms of samples from TiO2 0.79 0.12
the Candiota coal mine before and after the process of K2O 0.90 0.07
demineralization. From the incidence of peaks after acid CaO 0.79 0.02
washing, a signicant reduction in the levels of Si (in the form MgO 0.30
of quartz) can be observed. After the demineralization step, the ZrO2 0.05
peaks relating to caolinita and pyrite could no longer be Y2O3 0.03
observed, conrming the results obtained in the elemental Cl 0.17
analysis, that the level of S2 had been reduced. CO2a 54.12 91.81
a
From our results, it can be seen that the use of HNO3 to Organic matter.
remove compounds such as pyrite was ecient for samples of
the mineral coals used. The removal of the contents of Al, Mg,
K, Ca, and Al using HCl also showed good results, as observed the largest acid constituent of mineral matter, use of HF also
in the XRD analysis. According Mukherjee and Borthakur,19 promotes the dissolution of some organic species in coal. After
HCl is an eective acid for demineralization because its small the process of demineralization, the mass loss observed in the
molecules can readily diuse into the carbonaceous matrix. total samples was approximately 50%. About 1 g was lost during
The results obtained in the XRD analysis were conrmed by ltration and washing with distilled water. After demineraliza-
determining the chemical composition of the mineral matter tion, only 55% of the original mass remained (granulometry B).
remaining in the samples by XRF. The results are reported in Table 5 reports the maceral compositions of the coal samples
Table 4. before and after the removal of their mineral matter.
The XRF analysis conrmed the results observed in the XRD According to the results shown in Table 5, a large reduction
diractograms in Figure 2. From an examination of the results of the vitrinite content was observed, indicating an increase in
in Table 4, it can be seen that a reduction in the levels of all the inertinite fraction. According to Bengtsson,49 inertinite is
compounds was observed, as well as the appearance of Cl in the
demineralized samples because of the use of HCl in the process Table 5. Maceral Compositions (%) of Coal Samples before
of removing the mineral matter. and after the Process of Removing Mineral Matter
Several authors have observed large mass losses as a result of
maceral group ROM coal demineralized coal
the use of acidic solutions for the removal of mineral
matter.2,4,6,10,37 They reported reductions in the organic matter vitrinite 72 66
content when HF was used in the demineralization process. liptinite 15 11
According to Bolat et al.,4 in addition to this attack on silicon, inertinite 13 23

E DOI: 10.1021/acs.energyfuels.7b01025
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Figure 3. FT-IR spectra of ROM and demineralized Candiota coal.

the maceral component responsible for a higher combustion

temperature, followed by vitrinite and liptinite. The inuence of
the reduction on the content of this maceral can be observed in
the CO2 reactivity tests.
As part of the organic matter was removed along with the
mineral matter, it is believed that some chemical bonds were
broken and/or rearranged.
To evaluate the formation of chemical bonds in the organic
matter of the coals studied, Fourier transform infrared (FT-IR)
tests were performed on the coals from the Candiota mine
before and after the process of demineralization. FT-IR spectra
are presented in Figure 3.
Analysis of the FT-IR spectra of Candiota coal shown in
Figure 3 indicates that, after the demineralization process,
functional groups containing oxygen disappeared, suggesting
the formation of a polycyclic structure.11 This phenomenon
was conrmed by an increase in the intensities of the bands at
approximately 1400 and 1650 cm1, characteristic of aromatic
CC bonds.40 The band observed between 3000 and 3600
cm1 can be attributed to the OH stretch of phenolic,
alcoholic, or carboxylic groups or possibly humidity present in
the sample. Intense bands in the same region were also
observed by the Asadieraghi and Daud40 after the demineraliza-
tion of biomass samples.
3.2. Inuence of Mineral Matter on the Gasication
Temperature. Figure 4 shows the mass loss and dierential Figure 4. Mass loss and dierential mass loss curves as functions of
mass loss with time for the demineralized coal. time for the demineralized Candiota coal.
It can be observed in both cases that the pyrolysis step
occurred between the temperatures of 373 and 1173 K. It is
noted that such temperatures are high enough for the complete In Figure 4, the mass loss curve in a CO2 atmosphere for
removal of the mineral matter. Seo et al.,50 Wu and Ohtsuka,14 demineralized Candiota coal starts after 1173 K. In a study of
and Salatino et al.51 used pyrolysis temperatures in the range of Candiota run of mine (ROM) coal, Nunes et al.53 found that
11731223 K in studies on pyrolysis, gasication, and reactivity coal gasication occurred at approximately 1013 K.
with CO2. Radovic et al.52 observed that, in pyrolysis at a high An increase in the gasication start temperature of
heating rate, the amount of volatile matter released was approximately 160 K was therefore observed for demineralized
independent of temperature. The temperatures used in that Candiota coal. This increase in temperature might indicate that
study were 9731473 K. the mineral matter could be acting as a Boudouard reaction
F DOI: 10.1021/acs.energyfuels.7b01025
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catalyst, as suggested by Alonso et al.,54 Wigley et al.,55 combustion reaction, a change in reaction control to diusion
Backreedy et al.,56 Liu et al.57 Su et al.,58 and Vamvuka et al.23 kinetics could be expected. Once the surface is not as available
3.3. Production of Char from Demineralized Coal for the reaction and there is a widening in the pore diameters,
Samples. Table 6 presents the characterization of char one would expect a diusion-controlled reaction in the gaseous
produced from the demineralized Candiota coal (test 4). layer.
3.4. Thermogravimetric Analysis of Demineralized
Table 6. Characterization of Char Produced from Samples. 3.4.1. Eect of Temperature. The temperatures
Demineralized Candiota Coal used for the oxy-fuel combustion reaction in this work were
873, 973, 1073, and 1173 K. These temperatures were
analysis level (%) previously selected based on thermogravimetric testing with
ROM samples, according to Nunes and Marcilio59 and Nunes
a
proximate
volatile matter 3.1 et al.,53 so that we could compare the results obtained with
ash 9.4 demineralized and ROM samples using the same temperatures
xed carbon 87.5 and O2 concentrations in CO2.
elementala Figure 6 shows the conversions as functions of time of
C 86.2 demineralized Candiota chars at temperatures of 873, 973,
H 0.8 1073, and 1173 K for O2/CO2 concentration ratios of 10%,
N 2.3 20%, and 30% (v/v).
S 0.6 From Figure 6, it can be observed that increasing the
others 10.1 temperature also increased the speed of consumption of char
BET surface area (m2 g1) 6.05 (i.e., increased the reaction rate) for the concentrations of 10
BJH average pore diameter (nm) 3.47
a
Dry basis

Considering the data presented in Table 6 in light of the

results published by Nunes et al.,53 a reduction in surface area
and an increased average pore diameter were observed
compared for the Candiota char.
With the results obtained by the BET and BarrettJoyner
Halenda (BJH) methods, the eects of the acid solution on the
structure of the carbonaceous matrix were observed, increasing
the pore diameter and decreasing the surface area. The same
eects were also observed by Jiang et al.37 Calahorro et al.10
attributed the changes in the surface area of the char to the
removal of inorganic matter from the pores and the
displacement of insoluble inorganic matter in the carbonaceous
matrix to the pores. HCl was found to favor an increase in the
micro- and mesoporous structure. The HNO3 and HF used in
this work were already known to contribute to a reduction in
the surface area.10 In addition, the release of volatile matter
from the coal during heating in N2 might result in a widening of
the pores, thereby decreasing the specic surface area.
The SEM images shown in Figure 5 reinforce the results
obtained by the BET method. Comparison of the surfaces of
samples of ROM and demineralized char shows that there was a
reduction in the exposed surface of the demineralized samples
as a result of the acid treatment process employed for the
removal of mineral matter. As a result, during the oxy-fuel

Figure 6. Conversion rates of chars from demineralized Candiota coal

Figure 5. SEM images of Candiota char samples: (a) ROM and (b) at temperatures of 873, 973, 1073, and 1173 K for O2 concentrations
demineralized. in CO2 of 10, 20, and 30 vol %.

G DOI: 10.1021/acs.energyfuels.7b01025
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Figure 7. Conversion rates of chars from demineralized Candiota coal at O2/CO2 concentration ratios of 10%, 20%, and 30% (v/v) for temperatures
of 873, 973, 1073, and 1173 K.
and 20 vol % O2 in CO2. This behavior shows that the kinetic
regime controlled the reaction process under these conditions.
For the concentration of 30 vol % O2 in CO2, the eects of
temperature were less evident, as can be observed by the
overlapping of the conversion rate curves obtained at dierent
temperatures.
3.4.2. Eect of O2 Content in the Gas Mixture. Figure 7
shows the conversions as functions of of Candiota char at
dierent concentrations of O2 for temperatures of 873, 973,
1073, and 1173 K.
For the four temperatures studied, it was observed that
increasing the concentration of O2 in the reagent gas increased
the oxy-fuel combustion reaction rate of the demineralized char
samples. No overlap of the curves was observed with increasing
temperature, as was seen for the ROM samples and as reported
by Nunes et al.53 Despite the increase in O2 concentration, the
similar behaviors of the curves indicate a strong resistance to
mass transfer.
3.4.3. Kinetic Model. The experimental data obtained for the
demineralized samples were modeled according to the
unreacted-core model. According to Szekely and Evans,60 the
unreacted-core model has some deciencies as to the limits of
reaction control and does not consider solid characteristics,
such as porosity and pore distribution, in the modeling. Because
structural parameters are incorporated into the calculations,
working with the pore model or the grain model is
recommended.
Figure 8 presents the ts of the unreacted-core model to the
experimental data, at temperatures of 873, 973, 1073, and 1173
K for Candiota char in three situations: (1) when the diusion
in the outer gaseous layer of the particle controls the process,
(2) when the diusion of the reagent in the ash layer controls
the process, and (3) when the chemical reaction controls the
process.
As can be seen in the leftmost column of Figure 8, there is
not a good t of the model with the equation conversion = 1
3(1 X)2/3 + 2(1 X) to the experimental data because this
H DOI: 10.1021/acs.energyfuels.7b01025
Article
model does not adequately reproduce the experimental
measurements. In the center and rightmost columns of Figure
8, the ts to the experimental data of the models with the
equations conversion = X and conversion = 1 (1 X)1/3,
respectively, are similar, especially at higher temperatures. In
this case, there is a change from chemical reaction control to
diusion kinetics. The limiting step of the chemical reaction
was used to calculate the kinetic parameters of the reaction.
Figure 9 shows a sample of Candiota char before the oxy-fuel
combustion reaction and a sample of Candiota char after the
oxy-fuel combustion reaction in the thermobalance. As these
samples had much of the mineral matter removed, there was a
small reduction in the size of the particles.
Using the unreacted-core model, the reaction time () for the
complete conversion of the particle can be expressed, according
to Levenspiel,61 as
RCf
=
12( rA ) (5)
where is the particle-specic mass of char determined by
measurement with a pycnometer ( = 2.50 gcm3 to Candiota
char), R is the radius of the particle (R = 0.03375 cm), Cf is the
fraction of xed carbon (Cf = 0.84 for Candiota char), rA is
the reaction rate (g2min1), and is an experimental value
obtained from the char conversion versus time curves, as shown
in Figure 7 for Candiota coal.
Thus, the reaction rate can be calculated using the equation
RCf
( rA ) =
12 (6)
Assuming that the reaction rate (rA) for the reaction C + O2
CO2 obeys the equation
( rA ) = kPO2 n (7)
where PO2 is the partial pressure of O2, the values of the specic
reaction rate k and the reaction order n can be determined.
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Energy & Fuels Article

Figure 8. Unreacted-core model for demineralized Candiota char.

temperature used, it will not be considered in the calculations

of the occurrence of gasication.
Using the linearized Arrhenius equation, the pre-exponential
factor k0 and activation energy Ea were then calculated for the
oxidation reaction using the equation

E
ln k = ln k 0 exp a
RT (8)

Figure 10 shows a plot of the linearized Arrhenius equation.

The results show a satisfactory t to the model. This indicates
Figure 9. Demineralized Candiota char before and after the oxy-fuel that the temperatures at which the tests were performed
combustion reaction at a temperature of 973 K. worked within the chemical scheme.
The linear regression coecient in Figure 10 indicates that a
Given that the Boudouard reaction occurs only at temper- good t exists between the Arrhenius equation and the data
atures of 1173 K and above and that 1173 K was the maximum obtained for the reaction C + O2 CO2 for the Candiota char.
I DOI: 10.1021/acs.energyfuels.7b01025
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Energy & Fuels Article

Table 9. Levels of Metals in Demineralized and Impregnated

Samples
levels (%)
metal demineralized impregnated
Al 0.5 1.0
Fe 0.07 0.7
Ca 0.02 0.7

After the impregnation step, the samples were subjected to

Figure 10. Fit of the Arrhenius equation to the data obtained by
unreacted-core model under chemical reaction control for the oxy-fuel
combustion reaction.
The values of the kinetic parameters of the oxy-fuel combustion
reaction are reported in Table 7.
gasication tests to evaluate the eect of each metal on the CO2
reactivity. For comparative purposes, the same tests were
performed for ROM and demineralized samples. Figure 11
shows the conversion rate curves obtained at a temperature of
1273 K for ROM and demineralized samples, as well as samples
impregnated with the metals Al, Fe, and Ca.

Table 7. Kinetic Parameters for the C + O2 CO2 Reaction

in Demineralized Candiota Char
Ea = 56.46 kJmol1
k0 = 5.37 103 gmolmin1cm2
T (K) n
873 0.7
973 0.8
1073 0.8
1173 0.9
Figure 11. Conversion rates for ROM, demineralized, and
Thus, the reaction C + O2 CO2 can be written as impregnated Candiota coal samples at a temperature of 1273 K.
56.46 n
( rA )O2 = 5.37 103 exp P
From the results shown in Figure 11, it can be observed that
RT O2 (9)
the demineralization process reduced the coal conversion rate
The values for the order of the reaction, n, showed little with respect to that of the ROM coal, thus decreasing its
variation and had an average of 0.8. reactivity. This eect was also observed in the comparison
No data were found in the literature for the kinetic curves in Figure 5. For the impregnated samples, it was
parameters of demineralized coal. Table 8 presents the results observed that calcium is a metal that promotes faster coal
obtained for the activation energy, Ea, and the pre-exponential conversion in a CO2 atmosphere, followed by iron and
factor, k0, for the oxy-fuel combustion reaction of the ROM and aluminum. Some inhibiting elements and other gasication
demineralized chars. reaction catalysts could have been present in the ROM sample.
This combination might explain why the reactivity of the ROM
Table 8. Kinetics Parameters for the Oxy-Fuel Combustion sample was less than that of the sample impregnated with only
Reaction of ROM and Demineralized Samples of Candiota one element, namely, calcium.
Char
4. CONCLUSIONS
parameter ROMa demineralized
Based on the results presented herein for the demineralization
Ea (kJmol1) 10.8 56.46
process of southern Brazilian coal, it can be concluded that the
k0 (gmolmin1cm2atmn) 13.8 5.37 103
a
procedure employed for the removal of mineral matter was
Nunes et al.60 bNunes and Marcilio.59 satisfactory. A 90% removal of ash content was obtained using a
20% solution by volume of HF, HCl, and HNO3. These
removals were conrmed by measurements obtained by XRD
As reported in Table 8, an increase in the values of the and XRF.
activation energy and pre-exponential factor was observed after Along with the removal of the mineral portion contained in
the removal of the mineral matter. According to these results, it the sample, a loss of chemical groups was observed in the FT-
can be inferred that the ash previously present in the mined IR spectrum, as well as an increase in carbon content, according
coal could act as an oxidation-reaction catalyst. to the proximate and elemental analyses. This increase in
3.5. Candiota Coal Impregnating Demineralized with carbon content was responsible for the reduction in CO2
Metals. Table 9 reports the impregnated metal contents in the reactivity, demonstrated by an increase in temperature for the
original (ROM) and demineralized samples. Boudouard reaction.
The levels of metals in the demineralized and impregnated An increase in the activation energy values was observed for
samples were measured by atomic absorption. the demineralized samples when subjected to the oxy-fuel
J DOI: 10.1021/acs.energyfuels.7b01025
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Energy & Fuels
combustion reaction under the same conditions as for the
ROM samples. Before the demineralization process, the values
for the activation energy and pre-exponential factor were 10.8
kJmol1 and 13.817 gmolmin1cm2, respectively. The new
values for the activation energy and pre-exponential factor after
demineralization were 56.46 kJmol1 and 5.37 103 gmol
min1cm2, respectively.
Starting from demineralized Candiota coal, dierent samples
were impregnated with an alkaline-earth metal, Ca; a transition
metal, Fe; and a semimetal, Al. These samples were used to
assess the reactivities of the impregnated carbons in a CO2
atmosphere, where it was observed that calcium had a catalytic
eect superior to those of the other metals used. The reaction
rate of the ROM sample was higher than the reaction rate of
the samples impregnated with iron and aluminum but lower
than the reaction rate of the sample impregnated with calcium.
It is possible that there might be inhibitors and elements that
act as catalysts for the Boudouard reaction in the composition
of the coal. This combination could explain the dierence in
reactivity.
AUTHOR INFORMATION
Corresponding Author
*E-mail: keila@enq.ufrgs.br.
ORCID
Keila Guerra Pacheco Nunes: 0000-0001-7332-096X
Notes
The authors declare no competing nancial interest.
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L DOI: 10.1021/acs.energyfuels.7b01025
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