Article

pubs.acs.org/EF

Improvement of Activated Carbon from Jixi Bituminous Coal by Air

Preoxidation
Dongdong Liu, Jihui Gao,* Qingxi Cao, Shaohua Wu, and Yukun Qin
School of Energy Science and Engineering, Harbin Institute of Technology, 92 West Dazhi Street, Harbin, Heilongjiang 150001,
People’s Republic of China

ABSTRACT: Air preoxidation has been demonstrated as a good method to change the structure of Jixi bituminous char for
controlling development of porosity at low burnoff under physical activation. In this work, the influences of different oxidation
times in air at 200 °C (0, 3, 15, 48, and 96 h) were studied. The removal of aliphatic chains and the increase of the type and
quantity of oxygen functional groups occur at the preoxidation stage, resulting in an open structure for oxidized coals; however,
slight improvement is made on the porosity and surface morphology. In the pyrolysis stage, the evolution of different oxygen-
containing structures plays a more important role than the loss of plastic behavior on disordered conversion of oxidized chars,
leading to production of more active sites and development of the meso- and macropores. In the activation stage, serious carbon
losses at the surfaces of particles is observed in JX-800-59.1 with the low values of SBET (589.41 m2/g) because of the unfavorable
diffusion of activated gas. Alternatively, the well-developed pore structure of JXO15-800 and JXO48-800 chars promotes the
favorable diffusion of activated gas, thereby hindering the severe carbon losses at the particle surface, but JXO48-800 char with
more disordered structure and active sites has a high value of SBET (818.98 m2/g) at a low value of burnoff of 30.5% compared to
the values of SBET (705.69 m2/g) of JXO15-800 char at a value of burnoff of 42.6%.

1. INTRODUCTION approximately 50−80% during activation.16−18 However, at this

The main gas pollutants (e.g., SO2, NOx, and CO2) from a large
coal-fired power plant constitute the major cause of pollution in
the atmosphere, which not only threatens human health but also
prevents economic development. In the case of the current
technologies in gas desulfurization, they must all be based on
economic sustainability and environmental sustainability to
satisfy requirements of environmental protection.1−4 For the
removal of sulfur dioxide, the traditional wet flue gas
desulfurization technology using calcium-based absorbents now
faces the issues of its high cost, large water consumption, and
release of CO2. Alternatively, carbon-based porous solid
adsorbents, such as activated carbon (AC), are a promising
choice to achieve the adsorption and catalytic conversion of SO2
because of their low price, low water use, and ability to generate
byproducts (such as sulfuric acid).5−9 In the case of AC, the
hierarchical structure (micro- and mesopores) is critical to the
SO2 removal process. Sun et al.10 and Shu et al.11 reported that
the adsorption and catalysis processes of SO2 are performed
within the micropores, and the developed mesopores promote
the migration and storage of produced sulfuric acid. In addition, a
high specific surface area (SBET), which is related to the degree of
well-developed pores, promotes desulfurization.12,13
In the special case of coal-fired power plant desulfurization,
coal is the most suitable raw material for AC rather than
biomasses and some wastes. In addition, the traditional physical
activation with steam or CO2 resulting from high-temperature
flue gas of coal-fired boilers is preferred for the production of
coal-based AC over chemical activation because of its low cost
and environmental friendliness.14,15 In previous significant
studies of traditional physical activation, most of the works
reported that an obvious hierarchical structure and specific
surface area (SBET) values between 500 and 800 m2/g of
bituminous coal-based AC are formed for high burnoff values of
burnoff value, the surface of the particles has been damaged
severely and the external loss of quality only promotes the total
amount of carbon loss but does not produce the pores that
increase the specific surface area. Zhu et al.19,20 adjusted the
activation temperature from 800 to 950 °C and the type and
dosage of activating gases (steam and CO2). They concluded that
the change of the activation condition is unable to effectively
control an excessive loss of the particle surface. A specific analysis
is as follows: the diffusion of the activated gas (such as steam or
CO2) and activated product (such as H2 and CO) is hindered by
the coal char structure produced by pyrolysis that has a large
amount of ordered microcrystalline structure and fewer pores
and active sites, which are related to the presence of plastic
properties of bituminous coal during pyrolysis.16,17,21−24 He et
al.25 found that the higher amount of transferable hydrogen from
the decomposition of aliphatic hydrocarbons stabilizes other
radical groups (such as •CnH2n + 1, •OCnH2n + 1, and substituted
benzene) at 400−600 °C to produce the metaplast material,
which plugs the pores and acts as a lubricant between aromatic
layers to promote the ordered conversion of the microcrystalline
structure. Therefore, an ideal char structure, which includes a
well-developed pore structure, a large amount of disordered
crystalline structure, and active sites obtained by pyrolysis, has
been one of the most important factors in controlling the pore
development at a low burnoff value during activation.
In comparison to other pretreatment methods for preparation
of AC, such as the template method and solvent extraction,26−29
air preoxidation provides an efficient method to change the coal
Received: November 1, 2016
Revised: January 12, 2017
Published: January 18, 2017

© XXXX American Chemical Society A DOI: 10.1021/acs.energyfuels.6b02875

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Table 1. Proximate and Ultimate Analyses of the Acid-Treated Sample
proximate analysis (wt %)
sample Vdaf FCdaf Ad Mad
JX 39.66 60.34 0.125 3.62
a
By difference.
Figure 1. Schematic figure of the tube furnace reactor system.
char structure because of the low expense and simplicity.30−32
Because of the high reactivity of air (oxygen), it is relatively easy
to effectively control the chemical reaction between air and coal
at a moderate temperature during the preoxidation stage, which
promotes pore development and microcrystalline adjustment at
the subsequent pyrolysis and activation stage. Previously, de la
Puente et al.33 used thermogravimetric analysis (TGA) to study
the pyrolysis behavior of bituminous coal and its oxidized coal.
They concluded that the plastic behavior of oxidized coal could
be effectively suppressed by air preoxidation via removal of the
aliphatic CH groups. Teng et al.16,17 showed that the
preoxidation method is favorable to the loss of the plastic
properties of bituminous coal and the growth of char
microporosity. The air preoxidation process presented in this
paper is relatively similar to the oxidation step of the cyclic
oxygen chemisorption−desorption method, which has been
studied deeply by Francisco et al.34−38 They concluded that
evolution of oxygen functional groups promotes pore develop-
ment, thereby enabling AC with a high SBET/burnoff ratio even
after several cycles, and that the mesopores are first produced and
then micropores are formed with the increase of the cycle
number. Although the effect of air preoxidation in the
preparation process of coal-based AC on the structure of coal
chars plays an important role in controlling the final AC product,
this effect has rarely been studied in detail.
The goal of this paper to prepare AC with high SBET at a
relatively low burnoff via an air preoxidation treatment. The
effects of different oxidation times at 200 °C in air on physical
and chemical structures of samples at the preoxidation and
pyrolysis stages are studied, respectively. In comparison of the
development of the pore structure at different burnoffs for
different chars with typical characteristics in the activation stage,
the relationship between structural properties of chars and pore
structure of the final AC product at different external loss of
quality was determined in more detail. The feature parameters of
all samples were obtained by nitrogen adsorption, scanning
B DOI: 10.1021/acs.energyfuels.6b02875
Article
ultimate analysis (wt %, daf)
Cdaf Hdaf Odafa Ndaf Sdaf
74.81 19.49 4.01 1.31 0.38
electron microscopy (SEM), X-ray diffraction (XRD), and
Raman spectroscopy.
2. EXPERIMENTAL SECTION
2.1. Sample Preparation. Jixi bituminous coal from China was
used in this experiment and was crushed and sieved to a particle size of
250−380 μm. To eliminate the interference of ash in coal, the sample
coal was processed using 6 mol/L HCl and 40 wt % HF sequentially in
accordance with the demineralization procedure.39 First, the mixture
including 4 g of raw coal and 200 mL of 6 mol/L HCl was stirred for 15
h, which was then filtered and added to 150 mL of 40 wt % HF, followed
by stirring again for 15 h. After filtration, the chloride ions in the mixture
were washed repeatedly using deionized water and then the hot-air
treatment at 80 °C was applied for 12 h to remove the water in
demineralized coal before use.40 After the demineralization procedure,
the proximate and ultimate analysis data of acid-treated samples were
obtained, as shown in Table 1. The content of the ash in the acid-treated
sample was below 1%, and this sample was denoted as JX. In addition, JX
was oxidized in air at 200 °C for 3, 15, 48, and 96 h, and these samples are
denoted as JXO3, JXO15, JXO48, and JXO96, respectively.
2.2. Experimental Process. (1) Pyrolysis experiment: 3 g of the
sample coals (JX, JXO3, JXO15, JXO48, and JXO96) were placed in a
three-stage fixed-bed reactor, heated at 8 °C/min to 800 °C, and then
maintained for 60 min in a N2 flow of 450 mL/min, as illustrated in
Figure 1. Next, the sample coals JX, JXO3, JXO15, JXO48, and JXO96
were rapidly cooled under a N2 atmosphere and denoted as JX-800,
JXO3-800, JXO15-800, JXO48-800, and JXO96-800, respectively. (2)
Activation experiment: these char samples were continuously heated to
900 °C under a N2 atmosphere, then were held for the appropriate time
under CO2 to obtain AC with different porous structures at different
burnoffs, and were denoted as (JX-800, JXO3-800, JXO15-800, JXO48-
800, and JXO96-800)- burnoff values.
2.3. Measurement Analysis. The structural parameters of the
crystalline structure were obtained by a D/max-rb X-ray diffractometer,
with the measurement performed in the 2θ range from 5° to 85° at a
scan rate of 3°/min. Next, the char powder was investigated by Raman
spectroscopy using a 532 nm wavelength laser and observing the scatter
in the range of 1000−1800 cm−1. SEM (Quanta 200) was performed
using an instrument operated at 200 kV to visualize the surface
topography of samples. These samples were analyzed by Fourier
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transform infrared spectroscopy (FTIR) in the 500−4000 cm−1 range,
employing standard pellets of the KBr matrix, and 200 scans were
performed at a resolution of 4 cm−1. The pore structure characteristics of
prepared samples were obtained by nitrogen adsorption at an analysis
temperature of 77 K using a Micromeritics adsorption apparatus
(ASAP2020), with the measurement performed for the adsorption data
in the relative pressure (P/P0) range from 10−7 to 1.41 The prepared
samples were degassed under vacuum at 473 K for 12 h before N2
adsorption analysis. The specific surface area (SBET), the micropore area
(Smic), the micropore volume (Vmic), and pore size distribution were
calculated using the Brunauer−Emmett−Teller (BET) equation, t-plot
method, Horvath−Kawazoe (HK) method, and non-local density
functional theory (NLDFT), respectively.42−44 In addition, the total
pore volume (Vt) was determined at 0.98 relative pressure.
3. RESULTS AND DISCUSSION
3.1. Chemical Structure Analysis by FTIR. The FTIR
spectra of unoxidized and oxidized coals are shown in Figure 2.
Figure 2. FTIR spectra of unoxidized and oxidized coals.
First, the gradual disappearance of three bands at approximately
1460, 2830, and 2953 cm−1 with the increase of the oxidation
Figure 3. Curve-fitted FTIR spectrum of the 1800−1000 cm−1 zone for (a) JX and (b) JXO15.
C DOI: 10.1021/acs.energyfuels.6b02875
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time was attributed to asymmetric CH3− and CH2−, symmetric
CH2−, and asymmetric CH3−, respectively.45 The intensity of
the three bands are obvious for JX, but the disappearance of 2830
and 2953 cm−1 can be observed in air at 200 °C for 3 h (JXO3);
however, the aliphatic bands (1460, 2830, and 2953 cm−1) have
completely disappeared above 15 h (JXO15/48/96). These
changes indicate that the aliphatic structure is removed gradually
with the increase of the oxidation time. Most of the works found
that the loss of plastic behavior for bituminous coal during
pyrolysis is derived from the removal of the aliphatic
structure.16,17,21−24 In addition, the aliphatic structure in coal is
in the form of cross-linking bonds (methylene groups)
connecting aromatic rings and as side chains (methylene and
methyl groups) attached to aromatic rings.46 Thus, the cleavage
of aliphatic chains at the air preoxidation stage will likely lead to
the change of the microcrystalline structure for oxidized coals
and corresponding oxidized chars.
Then, the changes in oxygen-containing structures in the
1800−1000 cm−1 zone in FTIR spectra are investigated further
by curve-fitted bands according to the previous literature,45,47
and an example of curve-fitted FTIR spectra of the 1800−1000
cm−1 zone for JX and JXO15 is shown in Figure 3. According to
the result of curve-fitted bands, some ratios of integrated
absorbance areas are used to quantify the change of oxygen
functional groups of unoxidized and oxidized coals during air
preoxidation. The specific relationships of these parameters are
the following:
CO/Car = 1780−1650 cm−1 zone/1605 cm−1 band
(1)
COOH/Car = 1700 cm−1 zone/1605 cm−1 band (2)
C−O/Car = 1260−1030 cm−1 zone/1605 cm−1 band
(3)
Equations 1−3 give a quantitative assessment of the changes of
CO (including carboxylic acids, carbonyl acids, aryl esters,
etc.), COOH, and other C−O−R (including aryl ethers, etc.)
structures against the aromatic structure network of samples. The
results of structural parameters from this curve-fitting analysis
(1800−1000 cm−1 zone) for unoxidized and oxidized coals
during air preoxidation are given in Table 2.
As shown in Table 2, small quantities of oxygen functional
groups (CO mainly as carboxylic acids and C−O) can be
found in JX but JXO3 has an increase in CO (mainly as
carboxylic acids) and C−O structures, indicating the selective
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Table 2. Curve Fitting for the 1800−1000 cm−1 Region of
Unoxidized and Oxidized Coals
JX JXO3 JXO15 JXO48 JXO96
CO/Car 0.26 0.60 1.27 1.86 1.90
COOH/Car 0.26 0.56 0.76 0.91 1.02
C−O/Car 0.72 1.05 1.39 1.92 2.01
oxidation of aliphatic structures at the beginning of air
preoxidation to produce the specific oxygen functional groups.
The presence of new bands near 1650 cm−1 (carbonyl acids) and
1770 cm−1 (aryl esters) can be observed in JXO15, resulting in an
obvious increase in CO, COOH, and C−O groups. The
quantity of CO, COOH, and C−O groups continues to
increase for JXO48 and JXO96, but the percentage of COOH in
CO groups has an obvious decrease (namely, a rapid increase
in carbonyl acids and aryl esters with high stability), indicating a
progressive conversion of oxidized coals into a relatively stable
structure with the increase of the oxidation time during the air
preoxidation stage. In addition, there is a slow increase in
parameters of oxygen functional groups from JXO48 to JXO96,
indicating that longer oxidation time (96 h) may have a limited
role on the further development of oxygen functional groups.
Thus, the predominance of oxidation reactions, which promotes
the production of more oxygen type and quantity of oxygen
functional groups with the increase of the oxidation time, is
ensured during the air preoxidation stage. Francisco et al.35−37,48
reported that the increase of the type and quantity of oxygen
functional groups for oxidized coals can be important for pore
development at a subsequent pyrolysis stage.
3.2. Surface Morphology Analysis by SEM. The SEM
images of unoxidized and oxidized coals and carbonized chars are
given in Figure 4. From panels a−e of Figure 4, there are no
obvious differences in the surface morphology of unoxidized and
oxidized coals, although a slight rough surface in oxidized coals
depends upon the oxidation reaction between oxygen and
carbon, suggesting the generation of more oxygen functional
groups with an increasing oxidation time at the preoxidation
stage, as inferred from the result of FTIR spectra analysis in Table
2.
From panels f−j of Figure 4, an extremely smooth surface with
almost no porosity is observed in the JX-800 char, resulting from
the development of plastic behavior in the pyrolysis stage.
Moreover, the surface morphology of JXO3-800 is similar to that
of JX-800, indicating that the plastic behavior still exists during
Figure 4. SEM images from unoxidized and oxidized coals and carbonized chars.
D DOI: 10.1021/acs.energyfuels.6b02875
Article
pyrolysis, although a part of the aliphatic structure is removed
and a few oxygen functional groups are produced for JXO3-800.
Such surface morphology of JX and JXO3 will become a barrier
for the subsequent diffusion of gas molecules during activation.
Significant changes in surface morphology of oxidized chars
prepared with the gradual increase of oxidation time from 15 to
96 h can be seen observed as a result of the loss of plastic
properties and the evolution of oxygen functional groups by
almost complete oxidation. There is no metasplast material
available to block the pores because of the complete removal of
the aliphatic structure; however, the generation of more new
pores may be closely related to the change of different types of
oxygen functional groups during pyrolysis. According to the
literature,36,49,50 oxygen functional groups with different stability
may decompose and combine with the carbon structure at
different pyrolysis temperatures to release a large amount of
volatile matter (such as CO2 and CO) and generate active sites,
resulting in the development of a wider porosity.
3.3. Pore Structure Analysis by N2 Adsorption. The N2
adsorption−desorption isotherms and the SBET and Smic values of
unoxidized and oxidized coals and carbonized chars are given in
Figure 5 and Table 3. The N2 isotherms of unoxidized and
oxidized coals exhibit a typical type I characteristic, according to
the International Union of Pure and Applied Chemistry
(IUPAC) classification, without the appearance of a hysteresis
loop, showing all materials possess microporous features. Next,
the N2 adsorption capacities and the values of SBET and Smic of
unoxidized and oxidized coals are still small, although those of
oxidized coals increase gradually with the increase of the
oxidation time, indicating the generation of fewer pores.
However, the knee becomes broader and rounder for JXO48
and JXO96 at a relative pressure of less than 0.2, implying the
presence of wider micropores under a longer oxidation time. The
above results represent that there is only a slight improvement on
the pore structure with the increase of the oxidation time during
the air preoxidation stage.
With regard to the unoxidized and oxidized chars produced by
pyrolysis at 800 °C for 60 min, first, the N2 adsorption capacities
and SBET and Smic values of JX-800 and JXO3-800 are also very
low, indicating the generation of fewer pores. These results are
related to the formation of metaplast material, which blocks the
pores during the plastic stage. Then, the N2 adsorption isotherms
of JXO15-800, JXO48-800, and JXO96-800 exhibit type I at low
pressures and type IV at high pressures. These isotherms become
steep. N2 adsorption capacities at low pressures increase
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Figure 5. N2 adsorption/desorption isotherms of (a) unoxidized and oxidized coals and (b) carbonized chars.

Table 3. Specific Surface Area (SBET) and Micropore Area (Smic) Values of Unoxidized and Oxidized Coals and Carbonized Chars
JX JXO3 JXO15 JXO48 JXO96 JX-800 JXO3-800 JXO15-800 JXO48-800 JXO96-800
SBET 21 27 40 54 78 10 15 123 156 180
Smic 18 22 35 48 71 4 10 100 111 123

Figure 6. XRD of (a) unoxidized and oxidized coals and (b) carbonized chars.

Table 4. XRD Data of Unoxidized and Oxidized Coals and Carbonized Chars
JX JXO3 JXO15 JXO48 JXO96 JX-800 JXO3-800 JXO15-800 JXO48-800 JXO96-800
La (Å) 23.759 23.419 21.824 20.441 20.112 24.912 25.165 26.081 27.145 27.312
Lc (Å) 14.534 14.813 15.285 15.951 16.089 13.721 13.514 13.002 12.758 12.701
d002 3.545 3.534 3.470 3.401 3.391 3.501 3.581 3.653 3.792 3.814
N 4.10 4.19 4.4 4.69 4.74 3.92 3.77 3.56 3.36 3.33

evidently, and a clear hysteresis loop appears gradually as the
oxidization time continues to increase, leading to an obvious
increase in SBET and Smic values. The development of porous
structures in JXO15-800, JXO48-800, and JXO96-800 are related
to the disappearance of the plastic properties and the evolution of
different oxygen functional groups during pyrolysis. However,
the changes in the adsorption isotherms and hysteresis loop of
JXO48-800 and JXO96-800 become more obvious at a relative
pressure of more than 0.1; moreover, the SBET value of JXO48-
800 and JXO96-800 also exhibits a distinct growth, whereas the
Smic value increased slowly. This result indicates that the
evolution of more oxygen functional groups obtained by a long
oxidization time (48 and 96 h) rather than the loss of plastic
E DOI: 10.1021/acs.energyfuels.6b02875
behavior has advantages for developing mesopores during
pyrolysis.
3.4. Crystal Structure Analysis by XRD. The XRD profiles
of the unoxidized and oxidized coals and the chars prepared by
pyrolysis at 800 °C for 60 min are given in Figure 6. There are
two obvious broad diffraction peaks at 2θ = 24−27° and 41−44°
in all samples, which are related to an interplanar spacing
between the two aromatic layers and the degree of condensation
of aromatic layers.51 According to the peak fitting treatment used
by Liu et al.,52 XRD profiles of all samples are processed using the
software Origin 9.1 to obtain some important parameters
regarding the microcrystalline structure (such as the aromatic
structure layer distance d002, stacking height Lc, width La, and
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Figure 7. Raman spectra of (a) unoxidized and oxidized coals and (b) carbonized chars.

Table 5. Summary of Raman Band Assignment

band band position
name (cm−1) description bond type
D2 1620 graphite E22g; carbonyl group CO sp2
G 1590 graphite E22g; aromatic ring quadrant breathing; alkene CC sp2
D3 1530 aromatics with 3−5 rings; semi-circle breathing of aromatic rings; methylene or methyl; amorphous carbon structures sp2 and sp3
D1 1350 C−C between aromatic rings and aromatics with no less than 6 rings; introduced disorder carbon sp2
D4 1200 Caromatic−Calkyl; aromatic (aliphatic) ethers; C−C on hydroaromatic rings; hexagonal diamond carbon sp3; C−H on sp2 and sp3
aromatic rings

number of aromatic layers N = Lc/d002), which are given in Table oxygen functional groups (such as ether and carbonyl acids) with
4. high stability.55−57 These results show that the evolution of a
As shown in Table 4, in comparison to the parameters of JX, large amount of oxygen-containing structures plays a more
the values of La and d002 of oxidized coals decrease and their important role than the loss of plastic behavior on the change of
values of Lc and N increase gradually with the increase of the microcrystalline size during pyrolysis.
oxidation time. The aliphatic structure exists in coal as aliphatic 3.5. Carbon Structure Analysis by Raman. The Raman
chains to connect aromatic nuclei and as small molecule spectra of unoxidized and oxidized coals and the carbonized
substances between the aromatic layers.46 The breaking of chars prepared by pyrolysis at 800 °C for 60 min are given in
aliphatic chains and removal of small molecule substances during Figure 7. According to the peak fitting treatment using five bands
air preoxidation leads to the depolymerization of aromatic nuclei, by Li et al.,58 Table 5 shows the assignment of the five bands. The
the decrease of layer distance, and the increase of the stacking Raman spectra of all samples are processed with a smoothing
height and number of aromatic layers. However, the longer function, baseline correction, and normalization using Origin 9.1
oxidization time (96 h) cannot continue to obviously improve software to obtain the parameters of different hybrid carbon
the size of microcrystalline structures, showing that the removal structures, as shown in Figure 8 and Table 6. Importantly, the
of the aliphatic structure rather than the introduction of oxygen different band area ratios represent the relative structure;59−61
functional groups has a major impact on the parameters of
microcrystalline structures during the air preoxidation stage.
Alternatively, the change in parameters of JX-800 indicates
that its microcrystalline structure has been changed into a
graphite-like structure because of the presence of plastic behavior
during pyrolysis. In comparison to the parameters of JX-800, the
values of Lc and N decrease and the values of La and d002 increase
for oxidized chars, indicating that the microcrystalline structure
has been transformed into a type of disordered structure during
pyrolysis because of the evolution of oxygen functional groups
and the loss of plastic behavior during pyrolysis. The cross-
linking reaction of oxygen functional groups at a low temperature
(such as carboxyl groups) produces more cross-linking bonds,
and no metaplast material acts as a lubricant between aromatic
layers, which hinder the movement of aromatic layers toward
order during pyrolysis.53 Moreover, the increase of La is related to
the connecting role of cross-linking bonds between aromatic
layers rather than condensation of aromatic layers.54 The vertical
stacking and condensation of aromatic layers can be hindered by
the existence of heterocyclic compounds containing oxygen and Figure 8. Deconvolution of the Raman spectrum using five bands for JX.

F DOI: 10.1021/acs.energyfuels.6b02875
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Table 6. Raman Data of Unoxidized and Oxidized Coals and Carbonized Chars
JX JXO3 JXO15 JXO48 JXO96 JX-800 JXO3-800 JXO15-800 JXO48-800 JXO96-800
ID1/IG 2.436 2.477 2.664 2.877 2.890 3.197 3.224 3.600 4.147 4.151
ID3/IG 0.712 0.708 0.512 0.494 0.485 1.922 2.013 2.513 3.165 3.171
ID4/IG 0.425 0.411 0.364 0.325 0.320 0.611 0.675 0.809 0.961 0.972
Iall 320.56 316.12 294.65 281.64 278.19 310.62 321.51 349.60 376.04 382.98

Figure 9. N2 adsorption isotherms and pore size distribution of JX, JXO15, and JXO48 chars during activation.

this is ascribed to the following: (1) ID1/IG can be related to the can be also related to active sites in samples. In addition, the total
defect degree of the microcrystalline structure; (2) ID3/IG is spectral area (Iall) can be expressed to sample reactivity under
considered as the amorphous carbon; and (3) ID4/IG can be spectral normalization treatment.
described as the relative quantity of cross-linking bonds. In As shown in Table 6, in comparison to the parameters of JX,
particular, the defect (ID1/IG) and cross-linking bonds (ID4/IG) the values of ID1/IG of oxidized coals increase, whereas ID3/IG, ID4/
G DOI: 10.1021/acs.energyfuels.6b02875
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Table 7. Pore Structure Parameters of JX, JXO15, and JXO48 Chars during Activation
sample SBET (m2/g) Vt (m3/g)
JX-800-15.5 109.41 0.065
JX-800-25.9 297.74 0.142
JX-800-59.1 589.41 0.298
JXO15-800-26.8 345.51 0.184
JXO15-800-42.6 705.69 0.324
JXO48-800-15.9 380.54 0.337
JXO48-800-30.5 818.98 0.417
IG, and Iall decrease gradually with the increase of the oxidation
time. The aromatic nuclei in coal have been depolymerized by
the removal of aliphatic side chains, cross-linking bonds, and
small molecule substances with high reactivity during the air
preoxidation stage, leading to a decrease in the amorphous sp2
bonding carbon atoms and sp2−sp3 bonding carbon atoms.
However, the introduction of a large amount of oxygen
functional groups attached to aromatic rings results in the
increase of isolated and defective sp2 bonding carbon atoms. The
above changes in hybrid carbon structures lead to the decrease of
sample reactivity during air preoxidation. Alternatively, in
comparison to the parameters of JX-800, all four parameters of
oxidized chars increase as the oxidation time increases. The
constant generation of active sites caused by evolution of some
oxygen-containing structures, which includes the breaking of
oxygen functional groups with low stability and the existence of
heterocyclic compounds containing oxygen and oxygen func-
tional groups with high stability, facilitates the formation of the
isolated and defective sp2 and amorphous sp2 bonding carbon
atoms, finally leading to the high reactivity of oxidized chars.
These results show that the evolution of a large amount of
oxygen-containing structures plays an important role on the
evolution of different types of hybrid carbon atoms during
pyrolysis.
3.6. Pore Structure Development of Typical Chars
during Activation. To study the pore development under
different burnoff values during activation, three typical precursor
chars (JX-800, JXO15-800, and JXO48-800) were compared
under the same activation conditions. The results of the pore
structure analysis of the three porous materials by N2 adsorption
are given in Figure 9 and Table 7.
The N2 adsorption−desorption isotherm of JX-800-15.5 in
panels a and b of Figure 9 can be classified as type I, showing the
obvious micropore characteristics. With the increase of burnoffs
from 25.9 to 59.1%, the N2 isotherms have exhibited the
characteristics of type I at low pressures as well as those of type IV
at high pressures and the N2 adsorption capacities also increase
constantly at a low pressure, indicating the increase of
micropores. The clear hysteresis loop is observed gradually,
indicating that the production of some mesopores (2−5 nm) was
derived from widening micropores. However, the severe carbon
loss at the surface of the particles for JX-800-59.1 can be seen in
Figure 10a, although JX-800-59.1 with SBET values of 589.41 m2/
g has formed a hierarchical structure. The changes in the pore
structure and surface morphology for JX-800 char under different
burnoffs during activation indicate that the pore formation
follows the hierarchical development. The diffusion of the
activated gas is hindered and follows from the surface to the core
for JX-800 char with the limited pores and active sites as well as
more ordered crystallites, leading to the occurrence of more
reactions at the surface of the particles rather than the interior.
H DOI: 10.1021/acs.energyfuels.6b02875
Article
Vmic (m3/g) non-Vmic (%) Dap (nm)
0.062 4.6 2.38
0.127 12.1 1.91
0.217 27.2 2.0
0.117 36.41 2.13
0.261 19.44 1.83
0.201 40.36 3.54
0.363 12.95 2.00
Figure 10. SEM images of JX, JXO15, and JXO48 chars under final
burnoff values.
The N2 adsorption isotherms of JXO15-800 and JXO48-800
chars with different burnoff values all have displayed the typical
hierarchical characteristics of type I at low pressures and type IV
at high pressures in panels c and e of Figure 9. The adsorption
capacity of JXO48-800 char increases rapidly at low pressures but
has almost no change at high pressures with the increase of
burnoffs from 17.1 to 30.5%, which contributes to the
development of micropores during the activation stage. A high
value of SBET (818.98 m2/g) at a low value of burnoff (30.5%) for
JXO48-800 char is observed in Table 7. However, the adsorption
capacity of JXO15-800 char exhibits a relatively slow growth
trend at low pressures and an obvious growth trend at high
pressures with the increase of burnoffs from 26.8 to 42.6%,
indicating the obvious development of mesopores during the
activation stage. JXO15-800-42.6 with a relatively low value in
SBET (705.69 m2/g) is also observed in Table 7. In particular, no
severe carbon losses that occur at the particle surface for JXO48-
800-30.5 and JXO15-800-42.6 are shown in panels b and c of
Figure 10. The surface morphology of JXO15-800-42.6 and
JXO48-800-30.5 indicates that the developed porous structure of
oxidized chars acts as channels to help with the diffusion of
activated gas, thereby hindering the severe carbon losses at the
particle surface. However, the differences in the microstructure of
oxidized chars can affect the pore development during activation.
JXO48-800 char produced by a longer oxidization time has
formed a large amount of disordered microcrystalline structure
and active sites compared to that of JXO15-800 char, which are
favorable for rapid production of micropores; however, a rapid
development of mesopores in JXO15-800 char mainly results
from the widening of the pores.
4. CONCLUSION
Physical activation of Jixi bituminous coal upon air preoxidation
followed by different oxidation times has demonstrated its
potential interest for the preparation of AC with high SBET at low
burnoff values. This method provides good control of the
structure of Jixi bituminous char to obtain the ideal AC. The air
preoxidation stage exhibits an obvious increase of the type and
quantity of oxygen functional groups for oxidized coals with the
increase of the oxidization time and the depolymerization of the
aromatic structure caused by the removal of aliphatic chains;
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels
however, a slight change in the pore structure and surface
morphology for oxidized coals is found. In the pyrolysis stage,
oxidized chars are transferred into a disordered structure with the
increase of the oxidation time compared to ordered conversion
for unoxidized char (JX-800); moreover, more active sites and
porosity structure (corresponding mainly to meso- and macro-
pores) of oxidized chars are created by the evolution of oxygen-
containing structures with different stabilities. The longer
oxidation time (96 h) may have a limited role on the further
improvement of the oxidized char structure. In the activation
stage, the low SBET value (589.41 m2/g) of JX-800-59.1
corresponds to its more ordered structure, which hinders the
diffusion of the activated gas, leading to the appearance of serious
carbon losses at the surfaces of the particles. Alternatively, the
developed porous structures of JXO15-800 and JXO48-800 chars
act as channels to promote the favorable diffusion of activated
gas, leading to no severe carbon losses at the particle surface. The
SBET/burnoff ratios of JXO48-800 char (818.98 m2/g versus
30.5%) obtained are higher than those of JXO15-800 char
(705.69 m2/g versus 42.6%) because of more disordered
structures and active sites of JXO48-800 char that promote the
rapid increase of micropores during activation.
■ AUTHOR INFORMATION
Corresponding Author
*Telephone: +86-451-86412618. E-mail: gaojh@hit.edu.cn.
ORCID
Dongdong Liu: 0000-0003-4789-7663
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors greatly thank the financial support from the research
project supported by the National Natural Science Foundation of
China (51276052).
■
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