Fuel 231 (2018) 134–144

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Full Length Article

Transformation of sulfur and nitrogen during Shenmu coal pyrolysis T

⁎
Jili Hou, Yue Ma, Shuyuan Li , Jian Shi, Lu He, Jia Li
State Key Laboratory of Heavy Oil Processing, China University of Petroleum-Beijing, Beijing 102249, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: Transformation of sulfur and nitrogen and properties of pyrolysates (semicoke, retorting gas, coal tar) during
Coal Shenmu coal pyrolysis were investigated using XPS, TG-FTIR-MS, GC–MS and GC-PFPD. The results showed that
Pyrolysis total sulfur content in the semicoke decreased gradually and turned to sulfate sulfur and thiophenic sulfur with
S/N transformation increasing pyrolysis temperature. In Shenmu coal, predominant nitrogen species consisted of pyrrolic and
XPS
pyridinic compounds. Total nitrogen content was decreased, resulting from mutual conversion of different ni-
TG/GC-FTIR-MS
trogen compounds. The composition of retorting gas from TG-FTIR indicated that H2S began to release at 400 °C
and reached maximum at about 600 °C. This trend was consistent with the release of carbonyl sulfide
(500–650 °C) and SO2. GC-PFPD analysis revealed that detected sulfur compounds in coal tar were benzothio-
phene, dibenzothiophene and thiophene with the contents of 0.141%, 0.110% and 0.0004%, respectively. In
coal tar, 57 kinds of nitrogen-containing compounds were identified using GC–MS, in which basic nitrogen was
0.90% and non-basic nitrogen was 0.23%.

1. Introduction rank, atmosphere, etc. Gryglewicz [10] studied the characteristics of

Coal is the second largest source of energy in the world and accounts
for more than 60% of energy consumption in China. As China's lack of
oil resources, coal is impossible to be replaced by oil in the near future.
However, the utilization of coal is facing with a number of strict en-
vironmental challenges.
As a main environmental pollution element, sulfur compounds are
present in coal in organic and inorganic forms. There are four classes of
organic sulfurs, including thiophene, organic sulfide, sulfoxide and
sulfone. Inorganic sulfurs primarily include sulfate and ferric sulfide
[1]. Nitrogen compounds were produced as volatile-N (tar-N, HCN, NH3
and N2) and the char-N (pyridinic nitrogen, pyrollic nitrogen, qua-
ternary nitrogen and oxidized nitrogen) during coal pyrolysis [2–4]. As
the precursors of nitrogen oxides, tar-N, HCN, NH3 and char-N were
partly released in the form of N2O and NOx after coal combustion [5].
During traditional transformation and utilization, the sulfur in coal
usually turns into SO2 or H2S, resulting in air pollution, acid rain, etc
[6,7]. The emission of NOx from coal combustion can also cause acid
rain and N2O was known to have impact on the greenhouse effect as
well as on the destruction of the ozone layer [5]. Therefore, the in-
vestigation on sulfur and nitrogen transformation becomes very im-
portant for clean coal utilization.
Majority of research work on coal was carried out in the past and
recently. Experiments [8,9] showed that sulfur transformation in coal
was complicated and influenced significantly by temperature, coal
sulfur species during the pyrolysis of low rank coal, and found that the
organic sulfur was enriched between 330 °C and 600 °C and the de-
composition temperature of ferrous sulfide was over 1000 °C. Besides,
further results [11] showed that removal ratio of sulfur was decreased
with increasing coal rank. 32 kinds of bituminous coals were in-
vestigated by Khan [12] and results showed that the yields of sulfur in
liquid, solid and gaseous state were related to the contents of total
sulfur, pyritic and organic sulfur in coal. Li [13,14] compared the sulfur
release from coal pyrolysis with coal partial oxidation. The results
showed that little oxygen in inert atmosphere was advantageous to
enhance sulfur removal efficiency without a lot of char reduction. There
were also many researches [15–17] about nitrogen transformation of
bituminous coals in the past. Nelson [18–20] surveyed the effect of coal
rank and temperature on HCN and NH3 emissions and on the occurring
forms of nitrogen in tar. Bassilakis [21] pointed out that the heating
rate conducted an important influence on the generating rate and yield
of HCN and NH3. The releasing trends of NH3 and HCN during fast
pyrolysis were studied [2,3,22] using a new type of fixed/fluidized bed
reactor. The results showed that pyrolysis of different ranking coals or
different mine coals had different characteristics of nitrogen transfor-
mation and distribution. Leppalahti [4] concluded that changing
heating rate led to the occurrence of varying degree secondary reactions
which affected the transformation of nitrogen.
Despite a considerable amount of publications, in which the ma-
jority was mostly carried out in studies of the pyrolysates of coal

⁎
Corresponding author.
E-mail address: syli@cup.edu.cn (S. Li).

https://doi.org/10.1016/j.fuel.2018.05.046
Received 6 July 2017; Received in revised form 8 May 2018; Accepted 9 May 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
J. Hou et al. Fuel 231 (2018) 134–144

Table 1
Analysis of proximate, ultimate and sulfur speciation of different samples.
Sample Proximate analysis (%) Ultimate analysis, wad/% Sulfur speciation analysis

M, ad V, ad A, ad FC, ad C H O S N St,d% Ss,d% Sp,d% So,d%

SM coal 9.65 30.44 4.99 54.92 71.50 5.02 7.39 0.34 1.11 0.34 0.04 0.19 0.11
Semicoke 4.48 8.70 8.38 78.44 80.73 2.45 2.84 0.30 0.82 0.30 0.10 0.07 0.13

Note: M, moisture; V, volatile; A, ash; FC, fixed carbon; ad, air-dried basis. O determined by difference.

Table 2 was put into small scale retorting reactor. After programmed heating
Yields of pyrolysates of SM coal at different pyrolysis temperatures (wt, %). process, the reactor reached to different temperatures (300, 400, 500,
T, °C Gas Semi-coke Tar Water 600, 700 °C). 20 min at each temperature was necessary to ensure that
decomposable volatiles can be maximum. After coal pyrolysis, solid
300 2.64 92.54 0.01 4.81 product obtained in the retort was semi-coke. Other pyrolysates (tar,
400 4.20 84.12 6.26 5.42
water, and retorting gas) would pass through the outlet tube into a
500 9.17 72.58 9.01 9.24
600 9.61 70.23 10.07 10.09
conical flask that was cooled using an ice-water bath. Tar and water
700 9.75 70.14 10.03 10.08 were remained in the conical flask. Retorting gas was collected using a
vacuum gas bag for further testing. The yields of pyrolysates (gas, semi-
coke and tar) at different pyrolysis temperature are listed in Table 2.
Table 3 The retorting gas was analyzed using Agilent-6890 gas chromato-
XPS results of SM coal and semicokes at different temperatures. grapher. The chromatographic conditions are as follows. Initial column
Sample Content, w% temperature was 50 °C. 3 min was needed at this temperature. And then
temperature was increased to 100 °C within 10 min using a heating rate
C N O S of 5 °C/min and to 180 °C using a heating rate of 10 °C/min. Finally
3 min was needed at 180 °C. Carrier gas flow rates in flame ionization
SM coal 59.20 4.87 35.70 0.23
Semicoke-300 °C 69.45 2.58 27.78 0.19 detector (FID) were 40, 650, and 20 mL/min for H2, air, and N2, re-
Semicoke-400 °C 69.74 1.94 28.18 0.14 spectively. The front inlet pressure was 0.05 MPa and back inlet pres-
Semicoke-500 °C 70.33 1.36 28.22 0.09 sure was 0.10 MPa. Temperatures of injection port and detector for FID
Semicoke-600 °C 70.04 1.69 28.15 0.12 and thermal conductivity detector (TCD) were 50 and 250 °C, respec-
Semicoke-700 °C 70.76 2.01 27.03 0.20
tively.
Note: as XPS cannot detect H, so put C, N, O and S normalized to 1: C + N The basic and non-basic nitrogen compounds were analyzed using
+O + S = 100%. Agilent 6890/5975 GC–MS. The chromatographic conditions are as
follows. HP-5MS quartz capillary chromatographic column
separately, there were less studies about the comprehensive analysis of (60 m × 0.25 mm × 0.25 μm) was used. Gasification chamber tem-
coal pyrolysis. In the present work, several analytical methods (XPS, perature is 300 °C. The flow rate of He, as a carrier gas, was 1 mL/min.
TG-FTIR-MS, GC–MS and GC-PFPD) were used to analyze transforma- Temperature was increased from initial 50 °C to 120 °C using a heating
tion characteristics and distribution of sulfur and nitrogen in the solid, rate of 20 °C/min, to 250 °C using a heating rate of 4 °C/min and to
liquid and gas phases at different temperatures during SM coal pyr- 310 °C using a heating rate of 3 °C/min. The mass spectrum conditions
olysis. The information obtained could help to understand removal are as follows: ion source of electron impact (EI), ionizing voltage of
mechanism of sulfur and nitrogen for clean coal utilization and design 70 eV, interface temperature of 260 °C, ion source temperature of
of commercial coal retorting plants. 200 °C.
The distribution of sulfur compounds in coal tar was determined
using SP3420 capillary gas phase configuration 5380 with pulse flame
2. Materials and methods
photometric detector (PFPD). Chromatographic analysis conditions are
as follows: column HP-5, 30 m × 0.25 mm i.d. × 0.25 μm, injection
2.1. Materials
port temperature of 300 °C, and detector temperature of 250 °C. Column
temperature was maintained at 50 °C for 3 min, and then rose to 300 °C
The raw coal was from Shenmu (SM coal), Shanxi province of China.
using a heating rate of 5 °C/min. The shunt ratio is 50:1. The flow rates
Crushed samples with a size fraction of 0–0.2 mm were selected.
of nitrogen, air 1, air 2 and H2, as carrier gases are 1 mL/min, 10 mL/
Proximate and ultimate analyses were conducted following ASTM
min, 14 mL/min and 11.5 mL/min, respectively. The injection volume
Standards D3173-03, D3175-02, D3174-04 and D3176-15. Total sulfur
is 0.4 μL.
content and sulfur forms were determined following ASTM Standards
X-ray photoelectron spectroscopy ESCALab 250Xi (XPS) was used in
D3177-02 and D2492-02 (2012), respectively. The data in table 1
this study. According to binding energy of sulfur and nitrogen com-
clearly shows that SM coal is a typical bituminous coal with high vo-
pounds [23–25], sulfur (2p) spectra were resolved using components at
latile of 30.44% and high carbon content of 71.50%. After 550 °C, vo-
the peaks of 2p1/2 and 2p3/2 with separated energy of 1.18 eV, fixed
latile decreased to ∼22%, and semicoke with low S/N content was
energy positions and full width at half maximum (fwhm) value. Ni-
obtained. Some harmful elements have been removed to some extent
trogen (1s) spectra were resolved using four peaks at fixed energy po-
followed by the release of volatiles during coal pyrolysis. Besides, re-
sition and fwhm of 1.4 ± 0.1 eV. Experiments on the generation of
sults of sulfur speciation analysis show that semicoke contains about
sulfurous and nitrogenous gaseous products were carried out using TG-
40% organic sulfur and 60% inorganic sulfur. Sulfate sulfur content
FTIR-MS (TG: NETZSCH TG209F1 Libra, FTIR: Bruker ALPHA FTIR,
increased after coal pyrolysis.
MS: MSD Agilent). In each experiment, the sample (25 ± 0.01 mg) was
put into alumina crucible of TG. The sample was heated from room
2.2. Apparatus and procedure temperature to 650 °C with a heating rate 10 °C/min for pyrolysis in
argon atmosphere. The flow rates of protection gas and purge gas were
The coal sample (50 ± 0.5 g) with a particle size of less than 3 mm 60 mL/min and 20 mL/min, respectively. In order to get a better

135
J. Hou et al.
Fig. 1. Curve-fitting of XPS-S2p spectra for SM coal and semicoke at different temperatures.
analytical result, the resolution of FTIR was set as 2 cm−1. Time re-
solution was 8 s and number of scans of infrared instrument was 16.
3. Results and discussion
3.1. The species of sulfur and nitrogen compounds in semicoke at different
pyrolysis temperatures
The species of sulfur and nitrogen compounds in SM coal and
semicokes were investigated using XPS. According to binding energy
signal, different sulfur compounds were identified using the following
values of pyritic sulfur (162.5 ± 0.3 eV), organic sulfide
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Fuel 231 (2018) 134–144
(163.3 ± 0.4 eV), thiophenic sulfur (164.1 ± 0.2 eV), sulfoxide sulfur
(166.0 ± 0.5 eV), sulfone sulfur (168.0 ± 0.5 eV) and sulfate sulfur
(169.5 ± 0.5 eV). The lower and higher fwhm values are approxi-
mately 1.1 ± 0.1 eV and 1.5 eV [26–28]. Nitrogen (1s) spectra were
resolved using four peaks at fixed energy positions of 398.8 ± 0.4,
400.2 ± 0.3, 401.4 ± 0.3 eV and 402.9 ± 0.5 eV, corresponding to
the forms of pyridinic nitrogen (N-6), pyrrolic nitrogen (N-5), qua-
ternary nitrogen (N-Q) and oxidized nitrogen (N-X), respectively
[29,30].
Table 3 listed the contents of surface elements of SM coal and semi-
cokes at different temperature through XPS analysis. From Table 3 it
was shown that concentrations of nitrogen and sulfur on semicoke
J. Hou et al.
Fig. 2. The contents of sulfur species of SM coal and semicoke at different temperatures.
surface were decreased with increasing temperature when temperature
was below 500 °C, due to the reaction of free sulfur radical and free
hydrogen radical produced from organic matter pyrolysis. After 500 °C,
the generation rate of free sulfur radical in coal exceeds the rate of
hydrogen supplied, resulting in increasing sulfur content.
137
Fuel 231 (2018) 134–144
3.1.1. The species of sulfur compounds in semicoke at different pyrolysis
temperatures
Fig. 1 shows a curve-fitting of XPS-S2p spectra of sulfur species on
the surface of SM coal and semicoke at different temperature. Ac-
cording to the peak numbers in Fig. 1, XPS spectra fitting results of six
samples are basically consistent with each other. The sulfur species of
different samples were changed with rising pyrolysis temperature,
which is mainly caused by the mutual transformation and
J. Hou et al.
Fig. 3. XRD spectra of pyrite evolution in the pyrolysis of SM coal.
decomposition between different sulfur forms. In addition, sulfur exists
mainly in coal in the forms of organic sulfur. Specifically the highest
content is thiophenic sulfur (54.54%), followed by sulfoxide sulfur
(13.51%) and pyritic sulfur (10.90%). The contents of sulfate sulfur,
organic sulfide sulfur and sulfone sulfur are 8.57%, 6.23% and 6.25%,
respectively.
Fig. 2 shows the contents of sulfur species of SM coal and semicokes
at different pyrolysis temperatures through XPS spectrographic fitting
analysis.
From Fig. 2 (1), with the increasing temperature, the sulfur com-
pounds in coal was decomposed into ferrous sulfide and active sulfur.
The active sulfur could be combined with the hydrogen radical to
generate H2S or combined with the organic matter in semicoke to be
converted into new organic sulfur. Small amount of ferric sulfide would
be oxidated to sulfates. Pyrites would be broken down almost com-
pletely at 700 °C [31–33]. Besides, XRD results in Fig. 3 shows that FeS2
gradually decomposed into Fe(1-x)S with increasing temperature at early
stage, and then to generate FeS [34] after 500 °C. It cannot be detected
after 700 °C, which was consistent with results of XPS.
Fig. 2 (2) shows that content of organic sulfide in pyrolysis process
decreases with increasing temperature. The aliphatic sulfide was de-
composed between 300 °C and 400 °C. Cyclic sulfide and aromatic sul-
fide were cracked between 500 °C and 600 °C. After 500 °C, the sulfide
sulfur was basically completely decomposed.
As is shown in Fig. 2 (3), the content of thiophenic sulfur increased
with increasing temperature. There was a slight reduction at about
500 °C, due to a small amount of thiophene formed during coal tar
production [35]. Coal tar generation was almost complete after 600 °C.
After 600 °C, the increase of thiophene content was mainly caused by
condensation reaction of organic sulfide sulfur in coal.
Fig. 2 (4) shows that content of sulfoxide sulfur decreases with in-
creasing temperature and basically disappears at 700 °C. The decreasing
sulfoxide sulfur contents before and after 550 °C were resulted mainly
from the removal of aliphatic sulfoxide and aromatic sulfoxide, re-
spectively. Sulfoxide could be oxidized to sulfone by oxygen-containing
functional groups on the surface of coal.
From Fig. 2 (5), it was shown that sulfone sulfur content increased
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Fuel 231 (2018) 134–144
with rising temperature, which was mainly from the oxidation of sulf-
oxide sulfur. And then sulfone sulfur began to be decomposed. Its
content decreased to 8.86% at 700 °C as the continued increasing
temperature.
Fig. 2 (6) shows that content of sulfate sulfur increased rapidly with
rising temperature. This was mainly caused by the oxidizing reaction of
ferric sulfide in coal with some oxygen-containing functional groups
and oxidized state sulfur. Probably, there is another reason that sulfates
were gradually transferred from center to surface of the sample as
temperature increased.
3.1.2. The species of nitrogen compounds in semicoke at different pyrolysis
temperatures
Previous work showed that four types of nitrogen compounds exist
in coal, including N-6, N-5, N-Q and N-X. Nitrogen exists predominately
in the forms of pyrrolic and pyridinic compounds, in which content of
pyrrolic nitrogen is greater than pyridinic nitrogen [26]. Fig. 4 gives the
results of curve-fitting of XPS-N1s spectra for SM coal and semi-coke at
different temperatures. Four types of nitrogen species were identified
by the peaks at different position. And their relative contents have been
obtained, indicating that contents were N-6 (15.79%), N-5 (69.08%), N-
Q (9.21%) and N-X (5.92%). Pyrrole and pyridine become main species
of nitrogen compounds in SM coal.
Fig. 5 shows the contents of various nitrogen species in SM coal and
semicoke at different pyrolysis temperatures. From Fig. 5 (1), it was
found that N-6 has a trend of decreasing at first and then increasing
with rising temperature. Before 300 °C, the content of pyridine in raw
coal and semicoke changed slightly. From 300 °C to 500 °C, there was a
significant decrease due to combination of pyridine nitrogen with some
oxygen-containing functional groups in coal to form oxidative nitrogen.
After 500 °C, some unstable N-5 species were converted to N-6. Because
of high temperature, N-O bonds in the nitrogen species would be
broken to release a small amount of N-6, resulting in the increasing
content of total amount of N-6.
From Fig. 5 (2), N-5 increased with increasing temperature because
N-Q was converted to N-5 before 500 °C. Compared to pyridine, thermal
stability of pyrrole was slightly poor. With rising temperature, the
J. Hou et al. Fuel 231 (2018) 134–144

Fig. 4. Curve-fitting of XPS-N1s spectra for SM coal and semicoke at different temperatures.

content of N-5 reduced while N-6 increased in the semicoke, indicating slightly before 300 °C. After 300 °C, N-X content was gradually in-
that transformation reactions happened between N-5 and N-6. This creased because of the combination of N-6 with oxygen-containing
conclusion was consistent with the results of Nelson [36] and other functional groups to generate N-X species. N-O bond was broken to
studies [37–39]. produce N-6 after 600 °C. N-X compound was gradually decreased. It
Results from Fig. 5 (3) shows that N-Q decreased with increasing will be completely decomposed after 900 °C [40].
temperature. At 700 °C, the content of N-Q in semicoke was decreased
to 2.41%. N-Q compounds would be converted to pyrrole at low tem-
perature and decomposed after 600 °C.
From Fig. 5 (4), N-X compounds were found to be increased first,
and then to be decreased with rising temperature. N-X content changed

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J. Hou et al. Fuel 231 (2018) 134–144

Fig. 5. The contents of nitrogen species of SM coal and semicoke at different temperatures.

Table 4
Composition of retorting gas at different pyrolysis temperatures (%).
T, °C H2 CO CO2 CH4 C2H6 C2H4 C3H8 C3H6 C4H10 C4H8 C5H12 C5H10

400 1.71 16.61 49.87 18.82 5.28 1.45 2.22 1.59 0.7 0.97 0.32 0.46
500 8.64 16.06 27.98 34.00 6.25 1.37 2.01 1.33 0.73 0.79 0.42 0.42
550 15.94 16.83 21.75 35.64 4.97 1.06 1.44 1.00 0.44 0.30 0.20 0.43
600 19.50 16.93 19.65 35.47 4.07 0.87 1.23 0.81 0.47 0.47 0.29 0.25
650 26.29 15.86 15.51 35.54 3.39 0.77 0.94 0.71 0.28 0.39 0.13 0.19

3.2. Analysis of the components of retorting gas at different temperatures
3.2.1. Analysis of main components of retorting gas at different
temperatures
The retorting gas produced during coal pyrolysis mainly contains
CH4, C2H6, C2H4, C3H8, C3H6, C4H10, C4H8, CO2, CO and H2. Among
them, CH4、CO2、CO and H2 have the larger contents. The main gas
components and their formation behavior were obtained at different
pyrolysis temperature using gas chromatography. Results are shown in
Table 4.
Literatures [41–43] indicated that retorting gas was mainly derived
from organic matter decomposition. CO2 was mainly generated from
decarboxylation reaction of carboxylic acid compounds. CO was mainly
produced from decomposition of non-carboxylic acid compounds, such
as, ethers, phenols, ketones, etc. H2, CH4 and C2+ were derived from
decomposition of aliphatic compounds and aromatic side chains.
Because different compound has different energy needed to be de-
composed, formation of retorting gas will show certain regularity with
the changes of pyrolysis temperature. Using formation characteristics of
gaseous products, the pyrolysis mechanism of coal can be reasonably
understood.
One small amounts of retorting gas were generated before 400 °C.
Gas production was found to be increased quickly after 400 °C. Fig. 6
shows H2 production at different temperature. When pyrolysis tem-
perature reached 500 °C, the formation rate of H2 was obviously ac-
celerated. CO2 content decreased as the temperature increased, in-
dicating that CO2 was mainly generated at low temperature.
The changes of CO content were not obvious with rising tempera-
ture, indicating that temperature has a little effect on CO generation
during whole pyrolysis process. The content of CH4 increased with in-
creasing temperature. The yield of C2+ components was smaller than
that of H2 and CH4. It can be seen from the formation mechanism of

140
J. Hou et al.
Fig. 6. Retorting gas composition at different pyrolysis temperatures.
retorting gas that the decomposition of carboxylic acid compounds
occurred mainly at low temperature to release a lot of CO2 and CO.
With increasing pyrolysis temperature, large molecular compounds in
coal, like aliphatics and aromatic compounds, were decomposed to
produce large amount of CH4, C2+ and H2. The reactions during this
process mainly involved the aromatization of aliphatic hydrocarbon,
the cracking of alkyl side chain of aromatic compounds and con-
densation of oxygen-containing compounds.
3.2.2. The analysis of gaseous S/N compounds at different pyrolysis
temperatures
TG-FTIR-MS was used to detect sulfur/nitrogen gases (H2S, COS,
SO2, NO2, NO, HCN, NH3) produced during the pyrolysis of SM coal.
These gases are important intermediate or final product. According to
common gas standard infrared spectrum [44], the contents of specific
gases in the coal pyrolysis can be obtained. Fig. 7 shows 3D TG-FTIR
spectra of retorting gas production during SM coal pyrolysis with the
heating rate of 10 °C/min.
Fig. 7. TG-FTIR spectra of gas production during SM coal pyrolysis.
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Fuel 231 (2018) 134–144
From Fig. 7, it is apparent that with increasing temperature, typical
CH4 peak was found at 3016 cm−1 and reached maximum at 600 °C.
CH4 was mainly generated by chain scission of aliphatic side chains and
aromatic side chains. The release of water shows a double peak at
3500–4000 cm−1. In the early stage, water was released from adsorbed
moisture in coal. At high temperature, water was formed mainly from
chain broking of oxygen-containing functional groups in coal. Carboxyl
and oxygen-containing heterocyclic groups in coal are more sensitive to
temperature. When the temperature increased to higher than 250 °C,
these two groups began to be broken to produce CO2. Compared with
carboxyl and oxygen-containing heterocyclic groups, thermal stability
of carbonyl and hydroxyl groups was stronger and they began to be
broken to produce CO after 300 °C.
Generally, the formation of H2S was from different sulfur species in
coal. Free sulfur radicals or elemental sulfur reacted with H2 or gen-
erated hydrogen radicals to form H2S during coal pyrolysis [45]. COS
was mainly produced from reduction of CO with pyrite, or from reac-
tions of CO/CO2 with elemental sulfur, H2S, sulfur radicals and or from
the decomposition of oxygen-containing organic sulfur compounds
[46]. SO2 was mainly derived from the decomposition of sulfonic
compounds in coal and the combination of sulfur and active free oxygen
radicals formed by the fracture of sulfur ether bond, thiol and oxygen
bridge bond [47,48]. Several weak peaks were detected at 1289 cm−1,
2042 cm−1 and 1350 cm−1, showing that preliminary inferences were
H2S, COS and SO2, respectively. The releasing trend of these com-
pounds was consistent with each other. They began to be released at
about 400 °C and reached a maximum at about 600 °C then decreased.
However, these peaks were probably from disturbed peaks, because
these characteristic bands have too low intensity and are easily dis-
turbed by water or CO2.
As is seen in Figs. 7 and 8, few amounts of NH3 were released before
400 °C. From 400 °C to 650 °C, NH3 peaks at 966 and 948 cm−1 were
found. Before 200 °C, the peak was caused by interference of moisture
in coal. A suspected peak of HCN was detected at 650 cm−1, but its
intensity was too weak to be accurately identified. In addition, in the
range of 1547–1668 cm−1, as well as 1800 cm−1 and 1900 cm−1, the
suspected peaks of NO2 and NO were detected, respectively. These
compounds began to be released at early temperature and were easily
interfered by water.
J. Hou et al. Fuel 231 (2018) 134–144

shown in Fig. 8.
From Fig. 9 it was shown that main sulfur compounds in coal tar are
thiophenes (Ts), benzothiophenes (BTs) and dibenzothiophenes (DBTs)
while mercaptan, thoiether and other chain sulfide compounds were
not detected. Low content of thiophenes was found. XPS results in
Fig. 2(3) indicated that content of thiophenes in semicoke increased
with increasing pyrolysis temperature. Small amount of thiophenes was
formed in coal tar at around 500 °C, which was consistent with the
result of GC-PFPD detection.
Table 6 shows the content of sulfur compounds in SM coal tar.
Sulfur compounds in coal tar mainly include thiophene, benzothio-
phene and dibenzothiophene with the corresponding contents of
0.141%, 0.110% and 0.0004%, respectively.

3.3.2. Analysis of nitrogen compounds of SM coal tar

The composition of SM coal tar was relatively complex and many
kinds of compounds with large molecular weight were identified. SM
coal tar has a high nitrogen content of 1.27%, which is shown in table 5.
Fig. 8. Ion current intensity of nitrogen gases versus temperature during SM
The main nitrogen compounds in coal tar are basic nitrogen compounds
coal pyrolysis.
(pyridines, anilines, quinolines, acridines) with the content of 0.58%
and non-basic nitrogen (indoles, carbazoles) with the content of 0.69%.
Table 5 Table 7 listed 57 kinds of nitrogenous compounds in SM coal tar
Results of ultimate analysis of SM coal tar. determined by GC–MS. The total nitrogen content is about 1.13%,
Sample C% H% O% N% S% slightly lower than that from corresponding ultimate analysis. The basic
nitrogen accounted for 0.90%, and non-basic or weakly basic nitrogen
SM coal tar 82.96 8.32 7.18 1.27 0.27 accounted for 0.23%.

3.4. Sulfur and nitrogen transfer during SM coal pyrolysis

The pyrolysates (tar, semicoke and gas) were obtained after SM coal
pyrolysis at 550 °C. Calculated results of sulfur and nitrogen transfor-
mation in Fig. 10 showed that about 62% sulfur was remained in the
semicoke, in which thiophenic sulfur and sulfate sulfur were main
products. Around 38% sulfur was removed from raw coal during the
pyrolysis. 43.7% sulfur was transferred into coal tar with main forms of
benzothiophene (52%), dibenzothiophene (41%), thiophene (0.15%)
and the other (6.85%). 56.2% sulfur was transferred into retorting gas
with main forms of H2S, carbonyl sulfur and a small amount of SO2. The
remaining 0.1% sulfur was possibly in pyrolysis water or lost during
pyrolysis process. For nitrogen transformation, 74% nitrogen was en-
riched in semicoke with the forms of pyridinic nitrogen (26%) and
pyrrolic nitrogen (74%). The removed nitrogen was mainly transferred
into coal tar, including basic nitrogen and non-basic nitrogen com-
pounds. The remaining nitrogen was released as the gaseous products
(NO, NO2 and NH3).

Fig. 9. GC-PFPD analysis of sulfur compounds in SM coal tar. 4. Conclusions

S/N transformation rule and pyrolysate properties were investigated

Table 6
Content of sulfur compounds in SM coal tar. during SM coal pyrolysis using XPS, TG-FTIR-MS, GC-PFPD and GC–MS.
The following conclusions were obtained.
Sulfur compounds Content, % Sulfur compounds Content, %

Thiophenes 0.0004 C4-benzothiophene 0.038 (1) In the semicoke, as a solid product, contents of sulfate and thio-
Benzothiophene 0.005 C5-benzothiophene 0.033 phenic sulfur increased while contents of pyrite, sulfoxide and or-
C1-benzothiophene 0.014 dibenzothiophene 0.012 ganic sulfide decreased with increasing pyrolysis temperature.
C2-benzothiophene 0.015 C1, C2-benzothiophene 0.098 Sulfone content increased before 600 °C and then decreased after
C3-benzothiophene 0.036
600 °C.
(2) In the semicoke, N-6 content increased first and then decreased
3.3. Analysis of sulfur and nitrogen compounds in SM coal tar with rising temperature. The contents of N-5, N-Q and N-X de-
creased as the temperature increased during coal pyrolysis.
3.3.1. GC-PFPD detection analysis of sulfur compounds in SM coal tar (3) In gaseous products, H2S, COS and SO2 were mainly produced by
Results from table 5 show that SM coal tar produced at 600 °C has the reactions of different forms of sulfur and free sulfur radicals
low sulfur content of 0.27%. Gas chromatography-pulsed flame pho- with hydrogen radicals, carbon monoxide or free oxygen radicals.
tometric detector (GC-PFPD) was used for the qualitative and quanti- Nitrogenous compounds (NO, NO2 and NH3) were hardly detected
tative analysis of sulfur compounds in coal tar, and the results were in pyrolysis gases due to water interference.
(4) 37% sulfur and 26% nitrogen were transferred into coal tar and

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J. Hou et al. Fuel 231 (2018) 134–144

Table 7
GC–MS results of nitrogen compounds in SM coal tar.
Relative content/% Molecular formula Possible compound Relative content/% Molecular formula Possible compound

0.006 C6H7N methylpyridine 0.065 C11H11N dimethylquinoline

0.019 C7H9N dimethylpyridine 0.053 C11H11N ethylquinoline
0.009 C7H9N ethylpyridine 0.024 C11H11N methylisoquinoline
0.020 C8H11N C3—pyridine 0.030 C11H11N ethylisoquinoline
0.017 C8H11N C3—pyridine 0.029 C12H13N trimethylisoquinoline
0.023 C8H11N C3—pyridine 0.012 C12H13N trimethylisoquinoline
0.019 C9H13N C4—pyridine 0.013 C12H13N methylethylquinoline
0.020 C9H13N C4—pyridine 0.008 C12H13N methylethylisoquinoline
0.011 C9H13N butyl pyridine 0.013 C12H13N propylquinoline
0.004 C9H13N methylpropylpyridine 0.009 C12H13N propylisoquinoline
0.008 C9H13N ethyldimethylpyridine 0.037 C13H15N tetromethylquinoline
0.002 C9H13N trimethy aniline 0.033 C15H13N acridine
0.002 C9H13N ethylmethylaniline 0.013 C15H13N acridine isomer
0.005 C12H11N benzidine 0.017 C15H13N acridine isomer
0.001 C13H13N methylbenzidine 0.050 C16H15N Methyl acridine
0.008 C9H11N methylindole 0.020 C17H17N dimethylacridine
0.009 C10H13N dimethylindole 0.016 C17H17N ethylacridine
0.053 C10H13N ethylindole 0.017 C18H19N trimethylacridine
0.060 C11H15N trimethyindole 0.011 C18H19N methylethylacridine
0.025 C11H15N methylethylindole 0.005 C18H19N propylacridine
0.017 C11H15N propylindole 0.009 C19H21N C4—acridine
0.007 C12H17N tetramethylindole 0.013 C13H9N carbazole
0.002 C12H17N C4—indole 0.035 C14H11N methylcarbazole
0.031 C9H7N quinoline 0.092 C11H15N dimethylcarbazole
0.080 C10H9N methylquinoline 0.069 C11H15N propylcarbazole
0.027 C10H9N methylisoquinoline 0.070 C10H13N

0.019 C8H7NO 0.052 C9H11N

0.079 C10H13N

Fig. 10. Transformation of sulfur and nitrogen during SM coal pyrolysis.

retorting gas during coal pyrolysis. Most of sulfur (63%) and ni-
trogen (74%) were remained in the semi-coke after coal pyrolysis.
Acknowledgements
The authors are grateful for the financial support from the National
Basic Research Program of China (973 programs, No. 2014CB744302).
References
[1] Calkins WH. The chemical forms of sulfur in coal: a review. Fuel 1994;73:475–84.
[2] Tan LL, Li CZ. Formation of NOx and SOx precursors during the pyrolysis of coal and
biomass. Part I–III. Fuel 2000;79(15):1883–906.
[3] Xie ZL, Feng J, Zhao W, Xie KC, Pratt KC, Li CZ. Formation of NOx and SOx pre-
cursors during the pyrolysis of coal and biomass. Part IV. Pyrolysis of a set of
Australian and Chinese coals. Fuel 2001;80:2131–8.
[4] Leppalahti J. Formation of NH3 and HCN in slow-heating-rate inert pyrolysis of

143
J. Hou et al.
peat, coal and bark. Fuel 1995;74:1363–8.
[5] Glarborg P, Jensen AD, Johnsson JE. Fuel nitrogen conversion in solid fuel fired
systems. Prog Energy Combust 2003;29:89–113.
[6] Saikia J, Saikia P, Boruah R, Saikia BK. Ambient air quality and emission char-
acteristics in and around a non-recovery type coke oven using high sulphur coal. Sci
Total Environ 2015;530–531:304–13.
[7] Baruah BP, Saikia BK, Kotoky P, Rao PG. Aqueous leaching on high sulfur sub-
bituminous coals, in Assam, India. Energy Fuel 2006;20:1550–5.
[8] Liu F, Li W, Chen H, Li B. Uneven distribution of sulfurs and their transformation
during coal pyrolysis. Fuel 2007;86:360–6.
[9] Gonsalvesh L, Marinov SP, Stefanova M, Carleer R, Yperman J. Organic sulphur
alterations in biodesulphurized low rank coals. Fuel 2012;97:489–503.
[10] Gryglewicz G, Jasienko S. The behaviour of sulphur forms during pyrolysis of low-
rank coal. Fuel 1992;71:1225–9.
[11] Gryglewicz G. Effectiveness of high temperature pyrolysis in sulfur removal from
coal. Fuel Process Technol 1996;46:217–26.
[12] Khan MR. Prediction of sulphur distribution products during low temperature coal
pyrolysis and gasification. Fuel 1989;68:1439–49.
[13] Qi Y, Li W, Chen H, Li B. Sulfur release from coal in fluidized-bed reactor through
pyrolysis and partial oxidation with low concentration of oxygen. Fuel
2004;83:2189–94.
[14] Qi Y, Li W, Chen H, Li B. Desulfurization of coal through pyrolysis in a fluidized bed
reactor under nitrogen and 0.6% O2–N2 atmosphere. Fuel 2004;83:705–12.
[15] Friebel J, Kopsel RFW. The fate of nitrogen during pyrolysis of German low rank
coals-A parameter study. Fuel 1999;78:923–32.
[16] Cai HY, Guell AJ, Dugwell DR, Kandiyoti R. Heteroatom distribution in pyrolysis
products as a function of heating rate and pressure. Fuel 1993;72:321–7.
[17] Xu WC, Kumagai M. Nitrogen evolution during rapid hydropyrolysis of coal. Fuel
2002;81:2325–34.
[18] Nelson PF, Kelly MD, Wornet MJ. Conversion of fuel nitrogen in coal volatiles to
NOx precursors under rapid heating conditions. Fuel 1991;70:403–7.
[19] Nelson PF, Buckley AN, Kelly MD. Functional forms of nitrogen in coals and the
release of coal nitrogen as NOx precursors (HCN and NH3). Symp Combust
1992;24:1259–67.
[20] Li CZ, Buckley AN, Nelson PF. Effects of temperature and molecular mass on the
nitrogen functionality of tars produced under high heating rate conditions. Fuel
1998;77:157–64.
[21] Bassilakis R, Zhao Y, Solomon PR, Serio MA. Sulfur and nitrogen evolution in the
Argonne coals. Experiment and modeling. Energy Fuel 1993;7:710–20.
[22] Chang LP, Xie ZL, Xie KC, Pratt KC, Hayashid JI, Chiba T, et al. Formation of NOx
precursors during the pyrolysis of coal and biomass. Part VI. Effects of gas atmo-
sphere on the formation of NH3 and HCN. Fuel 2003;82:1159–66.
[23] Olivella MA, Palacios JM, Vairavamurthy A, et al. A study of sulfur functionalities
in fossil fuels using destructive-(ASTM and Py-GC-MS) and non-destructive-(SEM-
EDX, XANES and (XPS) techniques. Fuel 2002;81:405–11.
[24] Zhang YC, Zhang J, Sheng CD, et al. X-ray photoelectron spectroscopy (XPS) in-
vestigation of nitrogen functionalities during coal char combustion in O2/CO2 and
O2/Ar atmosphere. Energy Fuels 2011;25:240–5.
[25] Wang L, Zhang PZ, Zheng M. Study on structural characterization of three Chinese
coals of high organic sulphur content using XPS and solid-state NMR spectroscopy. J
Fuel Chem Technol 1996;24:539–43.
[26] Kelemen S, George G, Gorbaty M. Direct determination and quantification of sul-
phur forms in heavy petroleum and coals: 1. The X-ray photoelectron spectroscopy
144
Fuel 231 (2018) 134–144
(XPS) approach. Fuel 1990;69:939–44.
[27] Kelemen SR, Afeworki M, Gorbaty ML, Sansone M, Kwiatek PJ, Walters CC, et al.
Direct characterization of kerogen by X-ray and solid-state. Energy Fuel
2007;21:1548–61.
[28] Urban NR, Ernst K, Bernasconi S. Addition of sulfur to organic matter during early
diagenesis of lake sediments. Geochim Cosmochim Ac 1999;63:837–53.
[29] Kelemen SR, Gorbaty ML, Kwiatek PJ. Quantification of nitrogen forms in Argonne
premium coals. Energy Fuel 1994;8:896–906.
[30] Boudou JP, Schimmelmann A, Ader M, Mastalerz M, Sebilo M, Gengembre L.
Organic nitrogen chemistry during low-grade metamorphism. Geochim Cosmochim
Ac 2008;72:1199–221.
[31] Li M, Yang JH, Zhang QF, et al. Structure change and organic sulfur forms trans-
formation during pyrolysis of high-sulfur vitrinite. J Fuel Chem Technol
2014;42:138–45. (in Chinese).
[32] Semra K. Desulfurization of a Turkish lignite at various gas atmospheres by pyr-
olysis. Effect of mineral matter. Fuel 2003;82:1509–16.
[33] Liu FR, Li W, Guo HQ, Li BQ. XPS study on the change of carbon-containing groups
and sulfur transformation on coal surface. J Fuel Chem Technol 2011;39:81–4.
[34] Gryglewicz G, Wilk P, Yperman J, Franco DV, Maes II, Mullens J. Interaction of the
organic matrix with pyrite during pyrolysis of a high-sulfur bituminous coal. Fuel
1996;75:1499–504.
[35] Lin SY, Suzuki Y, Hatano H, Tsuchiya K. Pressure effect on char combustion in
different rate-control zones: initial rate expression. Chem Eng Sci 2000;55:43–50.
[36] Nelson PF, Kelly MD, Wornat MJ. Conversion of fuel nitrogen in coal volatiles to
NOx precursors under rapid heating conditions. Fuel 1991;70:403–7.
[37] Tseng HP, Edgar TF. The change of the physical properties of coal char during
reaction. Fuel 1989;68:114–9.
[38] Remenyi K, Kertesz V, Voros L, Horvath F. Dynamic behavior of coal char particle
combustion. Combust Flame 1989;76:311–23.
[39] Ninomiya Y, Dong ZB, Suzuki Y, Koketsu J. Theoretical study on the thermal de-
composition of pyridine. Fuel 2000;79:449–57.
[40] Li M, Yang JH, Zhang QF, Chang HZ, Sun H. XPS study on transformation of N-and
S-functional groups during pyrolysis of high sulfur New Zealand coal. J Fuel Chem
Technol 2013;41:1287–93.
[41] Wang P, Wen F, Bu XP, Liu YH, Bian W, Deng YY. Study on the pyrolysis char-
acteristics of coal. Coal Convers 2005;28:8–13.
[42] Cui YP, Qin LL, Du J, Chang LP. Products distribution and its influencing factors for
coal pyrolysis. Coal Chem Ind 2007;35:10–5.
[43] Zhu TY, Xiao YH, Wang Y. Effect of gas residence time on coal pyrolysis. J Combust
Sci Technol 2001;7:307–10.
[44] Speitel LC. Fourier transform infrared analysis of combustion gases. J Fire Sci
2002;20:349–71.
[45] Tian LN, Yang W, Chen ZH, Wang XH, Yang HP, Chen HP. Sulfur behavior during
coal combustion in oxy-fuel circulating fluidized bed condition by using TG-FTIR. J
Energy Inst 2016;89:264–70.
[46] Zhang YC, Zhang J, Sheng CD, Chen J, Liu YX, Zhao L, et al. X-ray photoelectron
spectroscopy (XPS) investigation of nitrogen functionalities during coal char com-
bustion in O2/CO2 and O2/Ar atmosphere. Energy Fuel 2011;25:240–5.
[47] Wan KJ, Xing YW, Liu XJ, Feng L, Miao ZY. Migration study of sulfur in coal pyr-
olysis process based on TG-GC-MS system. Coal Technol 2015;34:304–6.
[48] Liu F, Li B, Li W, Bai Z. Py-MS study of sulfur behavior during pyrolysis of high-
sulfur coals under different atmospheres. Fuel Process Technol 2010;91:1486–90.