Fuel 85 (2006) 114–120

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Short communication
Reductive pyrolysis study of sulfur compounds
in different Tabas coal samples (Iran)
E. Jorjania, J. Ypermanb,*, R. Carleerb, B. Rezaic
a
Mining Engineering Department, Research and Science campus, Azad University, Poonak, Hesarak, Tehran, Iran
b
Laboratory of Applied Chemistry, Hasselt University, CMK, Agoralaan - Gebouw D, B-3590 Diepenbeek, Belgium
c
Mining, Metallurgical and Petroleum Engineering Department, Amirkabir University of Technology, Tehran, Iran
Received 7 July 2004; received in revised form 11 May 2005; accepted 12 May 2005
Available online 9 June 2005

Abstract
A comparative study of the effects of mineral and pyrite removal on the determination of organic sulfur functionalities in representative, as
well as its low and high sulfur analogue samples of Tabas coal (C1 seam) were studied by atmospheric pressure–temperature-programmed
reduction (AP-TPR) method. The AP-TPR investigation showed the presence of di-aryl sulfides, aryl–alkyl sulfides, simple and complex
thiophenic structure in all representative, low and high sulfur samples. There is no indication of the presence of pure di-alkyl sulfides,
disulfides or thiols, nor oxidised sulfur forms in the samples. Only minor differences in sulfur functionalities were detected qualitatively
between the three analogue samples. Quantitatively differences in sulfur forms were found to be more pronounced. The presence of CH
fragments on gases emitted during AP-TPR investigation of demineralised and demineralised pyrite-free samples, shows evidence for the
formation of shorter CH chains and of polyaromatic compounds, and lower molecular weight material in the demineralization and pyritic
sulfur removal stages.
q 2005 Elsevier Ltd. All rights reserved.

Keywords: Coal; Sulfur; Mass spectrometry; Reductive pyrolysis

1. Introduction
Sulfur in coal occurs in organic and inorganic forms. The
inorganic sulfur is present mainly in two forms, as disulfides
(pyrite and marcasite) and sulfate (mainly calcium, iron and
barium). The organic form, which is bound directly to the
organic coal matrix, generally occurs in the forms of thiols,
sulfides, disulfides, thiophenes and cyclic sulfides [1].
Recently the presence of iron in coal bound with organic
sulfur functionalities in aromatic and aliphatic systems has
been reported [2].
In recent decades, one of the disadvantages associated
with the use of coal as energy for combustion systems is the
emission of sulfur oxides and hydrogen sulfide in the
environment. In the steel industry, the coke process cannot
remove all sulfur forms from coal. Further, sulfur combines
* Corresponding author. Tel.: C32 11 268320; fax: C32 11 268301.
E-mail address: jan.yperman@uhasselt.be (J. Yperman).
0016-2361/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2005.05.007
with molten iron in the blast furnace. The sulfur sediments
on the iron crystal surface make steel more brittle and
decrease its plasticity properties. It is known that alkyl and
aryl thiols, sulfides and disulfides are readily hydrogenated
or decompose during the coke process, whereas thiophene
compounds remain in large parts in the residue [3,4].
To determine the suitability of any particular coal
desulfurization method, knowledge of the distribution of
different forms of sulfur within the coal is required. The
total sulfur content determined with an ASTM standard
method will not provide sufficient information to assess the
suitability of a specific method; quantitative determination
of sulfur speciation is imperative. Several techniques are
available for this task. Some of them rely on thermal
degradation of the sample [5], whilst others include X-ray
techniques such as X-ray photoelectron spectroscopy [6]
and X-ray absorption near-edge structure spectroscopy [7].
A relatively new technique used for determining organic
and inorganic sulfur functionalities in different solid
materials is Atmospheric Pressure–Temperature Pro-
grammed Reduction (AP-TPR). In this method, the sample
is heated in a reducing atmosphere and specific sulfur
 E. Jorjani et al. / Fuel 85 (2006) 114–120 115

functionalities are hydrogenated/reduced at discrete tem-
peratures to form H2S. An average reduction order of the
different sulfur compounds is found: thiols!elemental
sulfur!disulfides!dialkyl sulfides!aryl alkyl sulfides!
pyrite!diaryl sulfides!thiophens!troilite (FeS)!
sulfates [8].
There are four limitative factors in the study of organic
sulfur functionalities by the AP-TPR method:
(1) Overlapping of H2S evolution related to the hydro-
genation/reduction of organic sulfur groups with the
H2S signal attributed to inorganic compounds, more
specific pyrite or organic oxidized sulfur forms;
(2) Released H2S captured by coal mineral matter (as
siderite) and prevented from reaching the detection
system;
(3) Sulfur functional groups that are not easily hydrogen-
ated within the temperature range of the AP-TPR
experiment (1025 8C), leading to a poor sulfur recovery;
(4) Secondary reaction due to the thermal treatment.
The aim of this work has been to study sulfur compounds
in representative and analogue samples with a low and high
sulfur contents from the Tabas coal mine in Iran.
Demineralised and demineralised pyrite-free samples were
prepared from representative, low and high sulfur samples
and examined by the AP-TPR method to determine any
difference in sulfur compounds in comparison to the
untreated samples. In order to check the sulfur recovery of
an AP-TPR experiment, besides Mass Spectrometry (MS)
also potentiometry was used as detection system, the last
one allows only H2S monitoring [8,9].
samples. Each group has one untreated sample, one
demineralised and one demineralised and pyrite-free
sample. The mineral free samples were obtained by
dispersing the sub 200 mesh coal in HCl (5%) at 60 8C for
1 h. The slurry was then separated by filtration. The
filtration residue was then redispersed with HF (concen-
trated) at 60 8C for 1 h to dissolve any remaining unliberated
mineral matter. The filtration residue was washed for the
third time with HCl (35%) at 60 8C for 1 h and then washed
3 times with hot distilled water and was dried at room
temperature for 48 h [10]. The pyrite was removed by dilute
nitric acid (17%) in the presence of a small amount of
bromine water at room temperature for 48 h to avoid the
degradation of the organic coal matrix and the organic sulfur
compounds [11]. Characterisation of these coal samples are
presented in Table 1.
The representative sample was collected from all
active stopes in C1 seam of Tabas coal mine. The
sampling techniques similar to those of Jones rifles and
conning, and quartering methods were adopted and
representative samples were prepared for further studies.
The high and low sulfur samples were picked at specific
locations from the mine (C1 seam). Proximate analysis
of the samples has been carried out according to
standard methods. Total, pyritic and sulfate forms of
sulfur in all samples were determined by ISO methods
334 [12] and 157 [13] in duplication. For pyritic sulfur,
the iron concentration in a nitric acid solution has been
determined by colorimetry. Organic sulfur was deter-
mined by difference.

2.2. Sample preparation for AP-TPR experiments

2. Area description, methods and material studied
2.1. Coal samples
Nine coal samples from the C1 seam of the Tabas coal
mine with different amount of sulfur contents are studied:
three Representative, three High Sulfur and three Low Sulfur
For each experiment, an amount of 40 mg of sample
(!88 mm) was weighed and mixed with 40 mg of fused
silica and put into a quartz reactor and stirred to achieve
homogenisation. The reactor was placed inside the oven and
connections made (cooling system and H2 gas). The emitted
gases were transferred to the potentiometry or mass
spectrometry detection system.

Table 1
Characteristics of the different coal samples

Coal sample S content (%) Proximate analysis (%)

Total Pyritic Sulfate Organic Ash Volatile matter Moisture Fixed carbon
Representative 1.44 0.77 0 0.67 32.3 20.12 0.75 46.83
Representative, demineralised 1.84 0.99 0 0.85 1.42 51.11 2.14 45.33
Representative, demineralised, pyrite free 1.12 0 0 1.12 0 57.43 2.89 39.68
High sulfur 3.69 2.38 0.01 1.3 33.68 32.25 0.37 33.7
High sulfur, demineralised 4.89 2.88 0 2.01 5.07 55.12 3.67 36.14
High sulfur, demineralised, pyrite free 1.75 0 0 1.75 0 57.11 5.21 37.68
Low sulfur 0.83 0.405 0 0.425 46.24 20.89 1.54 31.33
Low sulfur, demineralised 1.51 0.885 0 0.625 5.12 51.37 2.82 40.69
Low sulfur, demineralised, pyrite free 0.71 0 0 0.71 0 53.13 3.05 43.82
116 E. Jorjani et al. / Fuel 85 (2006) 114–120

2.3. AP-TPR procedure Table 2

AP-TPR sulfur recovery of raw and treated samples
The sample was subjected to a linear heating program of Coal sample Total sulfur Pyritic sulfur AP-TPR
5 8C minK1 from room temperature up to 1025 8C in a content (%) fraction (%) recovery (%)
continuous flow of pure hydrogen gas at 100 ml minK1. In Representative 1.44 53.5 85
this reducing atmosphere, most sulfur functionalities will be Representative, 1.84 53.8 97
hydrogenated/reduced in H2S and swept out of the reactor demineralised
Representative, 1.12 0 95
by the H2-gas acting as a carrier. The released H2S can then
demineralised, pyrite free
be measured by potentiometric detection or additionally, High sulfur 3.69 64.5 85
analyzed using a mass spectrometer. High sulfur, 4.89 58.9 86
demineralised
High sulfur, 1.75 0 90
2.4. Potentiometric detection
demineralised, pyrite free
Low sulfur 0.83 48.8 94
The H2S was collected in an aqueous solution of sulfide Low sulfur, demineralised 1.51 58.6 100
antioxidant buffer (SAOB) and converted into HSK and Low sulfur, deminera- 0.71 0 100
S2K. One liter of this SAOB aqueous solution was made lised, pyrite free
with 80 g of sodium hydroxide (pastilles) (Merck), 36 g of
ascorbic acid (ACROS) and 85 g of di-sodium EDTA
(ACROS). The SAOB solution flask must be kept in a dark the reaction of H2S with mineral compounds in the coal
box at 20 8C and discarded as soon as the colored solution (mainly calcium compounds) [16].
becomes dark. Potentiometric calibration is performed
every 2 months using Na2S standard solutions with 3.2. AP-TPR–MS measurements
concentrations ranging from 10K3 to 10K7 M [14,15].
Sulfur recovery detected by the potentiometric system can The AP-TPR reactor is also coupled to the mass
be calculated using the following equation spectrometer enabling the monitoring of the H2S release
and also of all other volatiles (up to m/z of 300), resulting in
Sulfur recovery Z f½ðms =mcoal Þ !100=Stotal g !100 (1)
a more detailed information on the pyrolysis pathways
where ms, mcoal and Stotal are, respectively, the mass of sulfur involved. Typical H2S evolution temperature regions of
hydrogenated/reduced during the AP-TPR experiment, the sulfur functionalities in the coals are summarised in Table 3.
mass of the coal used (40 mg) and the total amount of sulfur
in the analysed sample.
3.2.1. Representative samples
Fig. 1 shows the evolution of H2S using the m/z values of
2.5. MS detection 34 and 33 for all representative samples. For the
demineralised pyrite-free sample the main result (profile
The samples were heated in the same way as described c) besides the results of the two independent AP-TPR
for the potentiometric detection system. The MS signals, experiments (profiles quoted as c1 and c2) are shown on the
from mass 10 to 160, were monitored on-line. H2S emission same figure as an example demonstrating the reproducibility
is the sum of the intensity of m/zZ34 (H2SC) and m/zZ33 of the set-up within its limitation of the small sample size
(HSC) because they exhibit the same evolution. Moreover
the presence of SO2 can be studied through the signal output Table 3
AP-TPR temperature regions for the different sulfur functionalities [18]
for m=zZ 64ðSOC 2 Þ and m/zZ48 (SO ), if both profiles have
C

the same shape. Sulfur functional group Temperature (8C)

Thiols 180–400
Sulphonic acids (as SO2 and SO) 180–400
Elemental sulfur 250
3. Results, analyses and discussion
Disulfides 400–450
Di–alkyl sulfides 380–475
3.1. Potentiometric results Aryl–alkyl sulfides 440–550
Aryl–alkyl sulphoxides (as SO2 and SO) 510
Pyrite 470–600
The sulfur recovery obtained by these AP-TPR measure-
Di-aryl sulfides 500–630
ments is shown in the Table 2. For the analysed coals the Aryl–alkyl sulphones (as S02 and SO) 540
sulfur recovery is quite high, for the untreated representative Di-aryl sulphoxides (as S02 and SO) 580
and untreated high sulfur samples around 85%, and for the Di-aryl sulphones (as S02 and SO) 650
untreated low sulfur sample it is around 94%. These Thiophenic structures 600 and higher
Troilite (FeS) 740 and higher
recoveries are lower than for the treated samples. The low
Sulfates 800 and higher
sulfur recovery for the native samples can be explained by

1.2x10–11
1.0x10–12
Intensity (mbar)
8.0x10–12
c1
–12
c 2.0x10–11
6.0x10 c2
430 750
480
4.0x10–12
a
2.0x10–12 b
100 200 300 400 500 600 700
Temperature (˚C)
Fig. 1. Evolution of H2S (m/zZ33Cm/zZ34) emission during the AP-
TPR–MS for the representatives samples: (a) native; (b) demineralised; (c)
demineralised pyrite free.
and the possible inhomogeneity of the coal matrix (absolute
intensity cannot be compared, since MS detection system is
only a qualitative method). Other profiles always show the
main result. For the native coal [profile (a) in Fig. 1], the
peak at 430 8C and for the demineralised coal [profile (b)],
the peak at 480 8C reflect pyrite hydrogenation/reduction.
Some shift in peak temperature may be possible due to
matrix and particle size effects [17]. For both samples
(native and demineralised), the area under the first peak is
G33% of the total amount of sulfur as found from the
potentiometric results. This confirms the assignment of this
first peak to the reaction of pyrite to form troilite. Indeed, the
pyrite content is very high in these samples, almost 54% of
the total sulfur and thus dominating the AP-TPR profile. The
shift of the peak temperature towards higher values for the
demineralised sample can also be attributed to the higher
AP-TPR recovery (Table 2). Due to this demineralisation
treatment other sulfur functionalities become visible in the
lower as well as in the higher temperature zone, revealing
also the altering of the coal matrix structures. The broad
second peak signal for the native coal at higher temperatures
must be attributed to di-aryl sulfides and thiophenic
structures, as well to the hydrogenation of troilite to form
Fe and H2S. For the demineralised sample this is observed
by a more pronounced maximum at around 750 8C, due to
the fact that H2S is not longer trapped by the minerals at the
higher temperature range.
The pyrite free coal sample (profile c) contains large
amounts of thiophenic sulfur compounds as shown by the
one large peak found in the higher temperature region (max.
around 790 8C). Only small amounts of di-aryl sulfides and
minor amounts of mixed aryl–alkyl sulfides are probably
originally present in this coal. There is no real indication
that di-alkyl sulfides are present (perhaps some traces),
certainly no thiols or disulfides.
For the native and pyrite-free representative samples no
significant SOC 2 and SO
C
signals were found to show the
presence of oxidised sulfur groups. Only for the
E. Jorjani et al. / Fuel 85 (2006) 114–120 117
3.5x10–11
805
790
3.0x10–11
Intensity (mbar)
800
2.5x10–11
530-560
b
795
530
1.5x10–11
a
1.0x10–11 c
5.0x10–12
800 900 1000 100 200 300 400 500 600 700 800 900 1000
Temperature (˚C)
Fig. 2. Evolution of H2 S (m/zZ33Cm/zZ34) emission during the AP-
TPR–MS for the high sulfur samples: (a) native; (b) demineralised; (c)
demineralised pyrite free.
demineralised coal sample some experimental evidence
was found for the presence of minor amounts of organic
sulphonic acid groups [19].
3.2.2. High sulfur samples
The pyrite concentrations for the native high sulfur coal
(64.5%) and for the demineralised one (58.9%) are also very
high, thus dominating the H2S profiles. The samples with
high sulfur content are characterized by two peaks in the
H2S evolution profile, as seen in both samples (Fig. 2). The
first peak, below 600 8C, must be attributed to pyrite
hydrogenation/reduction in the case of the native and
demineralised samples. For both samples (native and
demineralised), again the area under the first peak is
G33% of the total amount of sulfur as found from the
potentiometric results. This confirms again the assignment
of this first peak to the reaction of pyrite to form troilite. In
the case of the demineralised coal sample (Fig. 2b), the
larger first peak, at the higher temperature range, must also
be attributed to mixed alkyl–aryl sulfides and di-aryl
sulfides. The second peak in both profiles, around 800 8C,
suggests the presence of complex thiophenes. The shoulder
on the second peak in the native sample profile (Fig. 2a) at
the lower temperature range must be related to hydrogen-
ation of troilite formed in situ and originally present simple
thiophenic structures. In general, the H2S formed during the
AP-TPR experiment in the demineralised sample is less
trapped by its matrix compared with the native sample, and
thus results in a larger peak.
The H2S profiles of the pyrite-free high sulfur coal
(Fig. 2c) can be mainly assigned to the presence of mixed
alkyl–aryl sulfides and di-aryl sulfides (400–600 8C). Their
presence is much more pronounced than in the case of
representative or low sulfur coal samples (see also further).
There is no indication of the presence of pure di-alkyl
sulfides (perhaps traces), nor for disulfides or thiols. The
peak at 795 8C indicates the presence of complex thiophenic
118 E. Jorjani et al. / Fuel 85 (2006) 114–120

structures. The lower temperature of these peaks suggests qualitative conclusions can be formulated. Only some
less complex thiophenic structures. quantitative differences in the amount of the different sulfur
The intensities of the m/z 48 and 64 profiles of all coal functionalities can be noticed to some extend.
samples are much lower compared to the H2S/HS profiles.
Therefore, there are only very weak indications for the
3.2.4. Profiles of CH-fragments
presence of sulphonic groups, but they are really not
Only the CH-fragment profiles of the high sulfur samples
convincing.
are discussed as an example since the representative and low
sulfur samples give almost identical figures. Due to the
3.2.3. Low sulfur samples demineralization and pyrite removing process, the organic
Generally quite similar AP-TPR profiles for H2S are coal matrix is destroyed, resulting in shorter CH-chains and
found as for the representative samples and thus the same the formation of poly-aromatic compounds. This gives

9.00E-012 9.00E-012
I I
8.00E-012 8.00E-012

7.00E-012 7.00E-012

ion intensity (mbar)

ion intensity (mbar)

6.00E-012 6.00E-012 b

5.00E-012 5.00E-012
a c
4.00E-012 4.00E-012

3.00E-012 3.00E-012
a
2.00E-012 2.00E-012
b d
1.00E-012 d 1.00E-012 e
c f
e e g
0.00E+000 0.00E+000
100 200 300 400 500 600 700 800 900 1000 100 200 300 400 500 600 700 800 900 1000

Temperature (˚C) Temperature (˚C)

1.20E-011 1.20E-011
II II
1.00E-011 1.00E-011
ion intensity (mbar)

ion intensity (mbar)

8.00E-012 b
8.00E-012

6.00E-012 6.00E-012
c
a 4.00E-012
4.00E-012 a
c c
b 2.00E-012 d
2.00E-012 d e
f g
e
0.00E+000 0.00E+000
100 200 300 400 500 600 700 800 900 1000 100 200 300 400 500 600 700 800 900 1000

Temperature (˚C) Temperature (˚C)

6.0x10–12
III III
1.0x10–11
5.0x10–12

8.0x10–12
Intensity (mbar)

Intensity (mbar)

4.0x10–12
b
–12
a 6.0x10–12
3.0x10

4.0x10–12
2.0x10–12
a
c c
–12
1.0x10–12 d 2.0x10
d
e
e f
f g
0.0 0.0
100 200 300 400 500 600 700 800 900 1000 100 200 300 400 500 600 700 800 900 1000

Temperature (˚C) Temperature (˚C)

Fig. 3. The effect of the demineralization and pyrite removal for the high sulfur sample: (I) saturated and unsaturated CH-chains; (II) aromatic compounds. (I)
Saturated and unsaturated CH-chains (alkenes and alkanes): (a) m=zZ 55K ðC4 HC 7 Þ; (b) m=zZ 57K ðC4 H9 Þ; (c) m=zZ 69K ðC5 H9 Þ; (d) m=zZ 71K ðC5 H11 Þ;
C C C

(e) m=zZ 83K ðC6 H11 Þ (II) Aromatic compounds: Benzene: (a) m=zZ 77ðC6 H6 Þ; (b) m=zZ 78ðC6 H5 Þ Toluene: (c) m=zZ 92ðC7 H8 Þ; (d) m=zZ 91ðC7 HC
C C C C
7Þ
Xylene: (f) m=zZ 106ðC8 HC 10 Þ Alkyl-benzene: (e) m=zZ 105ðC8 H9 Þ Naphthalene: (g) m=zZ 128ðC10 H10 Þ.
C C
 E. Jorjani et al. / Fuel 85 (2006) 114–120 119

(a) 2.00E-012 results in a decrease in intensity of the lower temperature

signals within 500–600 8C for the m/z fragments 77, 91, 92,
105, 106 and in the disappearance of the distinct shoulder at
1.50E-012 555
the lower temperature range of the signal m/z 78 (Fig. 3II)
Intensity (mbar)

710
A1
going from the native to the demineralised pyrite-free
1.00E-012
sample.
A2
622 There is a small shift of the peak maximum of all
aromatic fragments towards higher temperature due to poly-
5.00E-013 aromatic ring formation as a result of the demineralization
and pyrite removal treatments. The reagents used to remove
minerals and pyrite not only result in the oxidation of the
0.00E+000
100 200 300 400 500 600 700 800 900 1000
coal matrix, but also cause a simultaneous degradation of
Temperature (˚C)
the organic matrix. As a result lower molecular weight
material can be formed. This will induce a decrease of the
(b) 3.0x10–12 higher molecular weight material. This is clearly demon-
725 strated in Fig. 3I where the second peak arises from the high
2.5x10–12
molecular fragments for m/z 55 and even for m/z 69 decrease
as a function of treatment. The first peak (temperature range
Intensity (mbar)

555
2.0x10–12
300–400 8C) arises from low molecular fragments for m/z
1.5x10–12 A1
55 and also, but less visible, for m/z 69, increases as a
A2 function of the temperature. The same trends are found for
–12 632
1.0x10 m/z 57 and m/z 71.
The oxidation of the coal matrix can also result in the
5.0x10–13
formation of reactive species, which can further react to
0.0 form aromatic structures by cyclisation (carbonization).
100 200 300 400 500 600 700 800 900 1000 These structures have a higher stability. On the other hand,
Temperature (˚C) the low molecular weight aromatic fraction can also
(c) 3.0x10–12
undergo degradation, and will thus induce a decrease in
intensity of this fraction in the AP-TPR–MS profile. This is
confirmed by the m/z 78 profile where the lower temperature
735 shoulder disappears as a function of the treatment. For the
Intensity (mbar)

2.0x10–12 m/z 91 profile the peak at 550 8C decreases and the shoulder
at 650 8C increases or becomes more dominant compared
with the lower temperature signals as a function of the
treatments. The same trend is observed for m/z 92 profile,
1.0x10–12 A2
560 the asymmetric peak decreases at the low temperature side
A1
610 while at the higher temperature side an increase occurs as a
function of the treatments. Signals for m/z 105 and 106 show
0.0 analogous changes as a function of treatment.
100 200 300 400 500 600 700 800 900 1000
For the m/z 77, the first peak at around 550–560 8C
Temperature (˚C) decreases, and the second peak around 720–730 8C
Fig. 4. The area profiles for m/z 77 for high sulfur sample: (a) native; (b) increases. At the same time, the peak maxima for all
demineralised; (c) demineralised pyrite free. fragments shift systematically towards somewhat higher
temperatures as a function of treatment, provides additional
higher intensity signals at lower temperatures for the m/z evidence for the above described changes in the coal matrix.
fragments 55, 57, 69, 71, 83 indicating unsaturated and Since the total intensity is different for each experiment
saturated CH-chains and cyclic compounds (Fig. 3I going in an AP-TPR–MS analysis, it is necessary to normalize the
from the raw (I) to the pyrite-free sample (III)). This also profiles for comparison of selected fragments within

Table 4
Normalizing of peak areas for m/z 77

Coal samples SIntensities Atotal A1 A2 A1/ATotal A2/ATotal

High sulfur 1.876!10K8 1.999!10K2 9.318!10K3 1.068!10K2 4.660!10K1 5.340!10K1
High sulfur demineral 2.003!10K8 3.047!10K2 1.225!10K2 1.872!10K2 4.019!10K1 6.145!10K1
High sulfur demineral, pyrite free 1.703!10K8 2.626!10K2 6.159!10K3 1.952!10K2 2.345!10K1 7.431!10K1
120 E. Jorjani et al. / Fuel 85 (2006) 114–120

different samples. The total area under the curve for m/z 77 Acknowledgements
is divided by the total area (or total intensity of all measured
fragments from m/z 10 until m/z 160). The same calculation The Flemish authors like to thank P. A. M. Martins for
is repeated for the first and second peak areas (see Fig. 4). performing the AP-TPR experiments. The Iranian authors
Table 4 shows clearly that the ratio A1/Atotal decreases while like to thank the Iranian Steel Company in helping the
the A2/Atotal increases slightly. This emphasizes the above sampling and like to thank the Azad University for financial
hypotheses, that the low molecular fraction undergoes support for some parts of this research project.
degradation and must decrease. The high molecular fraction
becomes more important due to the formation of more stable
aromatic structures, and thus the corresponding signal must References
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