Fuel Processing Technology 92 (2011) 547555

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Fuel Processing Technology

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / f u p r o c

Analysis of polycyclic aromatic sulfur heterocycles in Egyptian petroleum condensate

and volatile oils by gas chromatography with atomic emission detection
Nagy E. Moustafa , Jan T. Andersson
Institute of Inorganic and Analytical Chemistry, University of Mnster, Corrensstrasse 30, 48149 Mnster, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Eight Egyptian petroleum condensates and two volatile oils were analyzed by gas chromatography. The
Received 30 July 2010 condensate oils range in color from colorless to yellow and brown. The samples are composed mainly of
Received in revised form 30 October 2010 saturates hydrocarbons (C3 to C35). The polycyclic aromatic sulfur heterocycles (PASH) were isolated through
Accepted 2 November 2010
use of a silica bonded palladium(II)-complex and their distribution investigated by gas chromatography (GC)
Available online 3 December 2010
with atomic emission detection (AED) in the sulfur-selective mode. The condensate oils show distinctly
Keywords:
different distributions of the PASHs, some containing mainly benzothiophenes, and others both benzo- and
Polycyclic aromatic sulfur heterocycles dibenzothiophenes and a third group in which the dibenzothiophenes strongly dominate. The alkyl
AED substituted sulfur compounds are quantied. The distribution patterns of the PASHs are correlated to the type
Gas chromatography of reservoir source rocks.
Condensates 2010 Elsevier B.V. All rights reserved.
Petroleum

1. Introduction be analyzed to give an indication about the relative amounts of the

There are ve types of petroleum materials: dry gas, wet gas,
condensate oil, volatile oil and crude oil. The volatile oil is similar to
crude oil in its appearance and color, whereas its bulk composition is
similar to condensate oil. Petroleum condensate is single phase gas in
the subsurface but produces both liquid and gaseous phases when it is
brought to the surface and the pressure and temperature are reduced
to near ambient conditions. The liquid phase is known as condensate
or natural gas liquid (NGL) and is a commercially important raw
material for reneries in Egypt and other countries. The condensate
oil is a fraction of petroleum comprising hundreds of hydrocarbon
compounds, with a distillation range usually from 30 to 330 C, and
has been used to substitute naphtha in the petrochemical industry for
producing a wide range of chemical products [1]. The most important
parameter describing gas condensate phase behavior is the dew point
(or saturation) pressure. At a given temperature, this is the pressure at
which a gas condensate will turn into a two-phase system in response
to a reduction in pressure. Gas and liquid samples are taken at the
head of the condensate reservoir by a test separator using a Welker
cylinder for PVT studies and to determine how much condensate is
produced from a given volume of subsurface gas. Compared to crude
oil, the condensate oil shows an abnormal behavior in PVT studies
since the one gaseous phase turns into two phases on pressure
release, and forms the so-called retrograde condensate oil [2]. This can
Corresponding author. Permanent address: Egyptian Petroleum Research Institute,
11727 Nasr City, Cairo, Egypt.
E-mail address: nemoustaf@yahoo.com (N.E. Moustafa).
constituents in the condensate oil matrix.
Sulfur compounds in petroleum products are often associated with
adverse effects such as catalyst poisoning, corrosion or pollution
through acid rain on combustion and thus hydrodesulfurization
(HDS) has become a major industrial process. The current specica-
tion in Europe calls for a maximum sulfur content of 10 ppm in
transportation fuels. The polycyclic aromatic sulfur heterocycles
(PASH) constitute a major class of sulfur compounds in petroleum
and can be particularly difcult to desulfurize catalytically. The two-
and four-ring PASHs, benzothiophenes (BT) and benzonaphthothio-
phenes (BNT), occur in considerable amounts in petroleum but are
somewhat easier to desulfurize than the three-ring PASH diben-
zothiophene (DBT). The recalcitrance of DBTs to HDS is strongly
inuenced by the position of the alkyl substituents. Alkyl-DBTs can be
divided into three groups with respect to their HDS reactivity: those
without 4- and 6-substituents have the highest activity, followed by
DBTs with one substituent in the 4- or 6-positions, and DBTs with both
4- and 6-positions substituted. The latter are generally recognized as
the least reactive sulfur species [35] although at least one
tetramethyl-DBT with one free 4-position has been found to be
recalcitrant [6]. The speciation of alkyl-PASHs in material that is
intended to be hydrodesulfurized can therefore give information on
the ease of the reaction [7,8].
Condensates seem to be a fossil material that has not received
much attention by analytical chemists yet and we know of no studies
of the sulfur compounds in them. The discovery of condensate
reservoirs in Egypt occurs at a faster pace than that of crude oils and
will thus contribute importantly to the supply of fossil-fuel based
energy in that country as well as in many others that have access to

0378-3820/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2010.11.010
548 N.E. Moustafa, J.T. Andersson / Fuel Processing Technology 92 (2011) 547555
condensate oils. If the condensates are going to be industrially
desulfurized, analytical information on the sulfur species is necessary.
Condensates associated oil fall largely in the gasoline and diesel
boiling range and the aliphatics range from C2 to C36+. Gas
chromatography is therefore suitable as a convenient and high-
resolution technique for the analysis of sulfur compounds. The
predominance of hydrocarbons requires selective detectors but
analytical problems such as shifts in retention times, interference in
MS detection [9] and maybe changes in peak heights may be traceable
to the presence of a large excess of hydrocarbons. Therefore it is
preferable to separate the sulfur compounds from the hydrocarbons
as a rst step in the analysis.
PASHs have long been investigated as conveyors of geochemical
information in fossil materials. Abundant BTs and DBTs in petroleum
are regarded as indicators of a carbonate-evaporate source environ-
ment. The types and the concentrations of BTs and DBTs and the ratio
of DBT to phenanthrene have been related to the type of reservoir
source rocks [10,11]. DBTs were found to be more abundant in oils
derived from marine carbonates than in those from freshwater
environments [12]. The relative abundance of dimethyl- and
trimethyl-DBTs in total PASHs of oils from freshwater environments
were lower than those of saline and hypersaline oils.
The atomic emission detector (AED) exhibits a sulfur response
being compound independent [13] and is an established technique for
PASH analysis in petroleum uids [1419]. The present study is the
rst one to investigate PASHs in condensates as possible industrial
raw materials for the production of transportation fuel and uses GC-
AED to obtain a distribution analysis of BTs and DBTs of six petroleum
condensates and two volatile oils and GC-MS to obtain further
information on unknown PASHs. An identication of the aromatic
parent systems and the degree of alkylation is thus possible for many
of the compounds present.
2. Experimental
2.1. Samples and standard compounds
The petroleum condensate samples were collected directly from
the separator at the head of the well. The condensate oil samples were
kindly provided by different Egyptian companies: Khalada, Centurion,
Petrobel, Wapeco, El-Hamara and Bedr Eldien. The volatile oil samples
are from VE-gas and Phobis petroleum companies. The physical
appearance of different samples is illustrated in Fig. 1. All the
condensate samples are from Egyptian Western Desert reservoirs.
The reference compounds used for the identication were all
synthesized in our laboratory [20]. The following abbreviations are
used to denote the alkyl substituents of the BTs and DBTs: M, methyl,
E, ethyl, DM, dimethyl, and TM, trimethyl. The alkylated BT reference
Fig. 1. Variation in color of condensate oils. Left to right: Waxy (BDR Co.); light yellow
(Wapco-Ast-2); yellow (Khalada); colorless (Centurion-Azher); light brown (Petrobel-
Fayroyz) and brown (Centurion-El-bassant-2).
compounds used are as follows: BT, 2-MBT, 2,6-DMBT, 3,5-DMBT,
2,3,4-TMBT, 2,3,6-TMBT, 2,5,7-TMBT and the DBTs are: DBT, 1,4-
DMDBT, 1,2,4-TMDBT, 2,3,4-TMDBT, 2,6-DMDBT, 2,8-DMDBT, 3,6-
DMDBT, and 4,6-DMDBT. The internal standard used for the
quantications was 2-uorodibenzothiophene (2-FDBT) (99.9 wt.%
purity) and was synthesized in our laboratory [21]. The solvent did
not contain any traces of sulfur compounds. Chemicals for synthesis
and HPLC grade solvents were from SigmaAldrich (Taufkirchen,
Germany).
2.2. Instrumentation
Gas chromatographic analyses for sulfur compounds were per-
formed on an HP 5890 II chromatograph with a split/splitless injector
at 300 C with the Agilent atomic emission detector (AED) [6,13]
operated at the sulfur wavelength of 181 nm. The column was a
Varian VF-5 ms (30 m 250 m 0.25 m). The oven temperature
was held at 80 C for 3 min and then programmed at 3 C min1 to
220 C, then at 8 C min1 to 270 C and nally at 20 C min1 to
300 C and held there for 20 min. The injection volume was 2 L.
Gas chromatographic analyses of the fractions separated on silica
were performed on an HP 5890 II chromatograph with a split/splitless
injector (260 C), a ame ionization detector (300 C) and a similar
column as above. The oven temperature was held at 60 C for 2 min
and then programmed at 5 C min1 to 300 C, held for 5 min. The
injection volume was 1 L.
2.3. GC-MS
The GC-MS analyses were carried out on a GCQ-Finnigan MAT
chromatograph with an ion trap mass analyzer. The conditions were:
initial temperature 60 for 1 min, ramp at 5 C min1 to 300 C, held for
20 min. The capillary column was a DB-5 from J&W (30 m
250 m 0.25 m).
2.4. Synthesis of Pd(II)-mercaptopropano silica gel [22]
Silica gel (60 mesh) was dried at 130 C for 24 h. 3 g of dried silica
gel was reuxed with 5 mL 3-mercaptopropanotrimethoxysilane (3-
trimethoxysilyl-1-propanethiol) in 20 mL dry toluene for 5 h. The
resulting bonded silica gel was ltered off and washed with toluene
and methanol successively. The obtained mercaptopropano silica gel
(MPS) was dried at 50 C in an oven. 2.5 g of MPS was further treated
with 250 mL aqueous palladium chloride solution (0.01 M) for 12 h.
The palladium bonded silica phase was ltered off, washed succes-
sively with water, iso-propanol and cyclohexane, and dried in vacuo at
room temperature.
2.5. Column chromatography
Separation of the higher molecular-weight compounds and
ltration: 0.51 mL of the sample was separated by column
chromatography. A glass column 20 cm 0.8 cm was lled to about
3 cm with 2 g silica gel. The bulk of the oil was eluted with 40 mL
cyclohexane and then with cyclohexane:dichloromethane (3:1). The
cyclohexane fraction was used for the next step.
Separation of PAHs and PASHs: 1.5 g Pd(II)-mercaptopropano silica
gel was packed into a glass column of 20 cm 0.8 cm. A sulfur-free
fraction eluted with 40 mL cyclohexane:dichloromethane (9:1). The
PASHs were eluted with 40 mL cyclohexane:dichloromethane (2:1)
containing 1% iso-propanol. The suldes were eluted with 40 mL of
cyclohexane:dichloromethane (2:1) containing 1.5% iso-propanol satu-
rated with NH3. Finally the column was washed with 50 mL of
cyclohexane:dichloromethane (9:1) for regeneration. The solvent vol-
ume was reduced to 1 mL by rotary evaporation before GC-AED analysis.
The quantitative analysis was based on 2-uorodibenzothiophene as
 N.E. Moustafa, J.T. Andersson / Fuel Processing Technology 92 (2011) 547555 549

Condensate / volatile oil 3. Results and discussions

silica column chromatography

3.1. Separation of the PASHs

The PASHs were analyzed after the sample was ltered through a
1st fraction short silica gel column to remove polar compounds possibly present.
They were then separated from the hydrocarbons on a column
Pd(II)-mercaptopropano silica gel
containing a Pd(II) complex that is a powerful phase for the
separation of hydrocarbons, that are not retained, from the PASHs
that are retained on the phase and can be eluted using a more polar
solvent [23]. Fig. 3 illustrates the efciency of the Pd(II) stationary
2nd fraction 3rd fraction
+ Sulfides phase in this separation. The two chromatograms are for the same oil
PASHs
and detected once by the sulfur-selective AED and once by the
universal MS. This result is also conrmed by GC-AED if the carbon-
GC -AED analysis selective and the sulfur-selective traces are compared with each
other. As a further test of the separation, the transparent condensate
Fig. 2. Analysis scheme for PASHs in condensate and volatile oils. samples were separated directly on the Pd(II) column (without the
initial ltration on silica) to conrm that there is no carry-over of
hydrocarbons into the PASH fraction and that there is no loss of PASHs
in the cyclohexane/dichloromethane silica fraction. In both cases the
chromatograms of the fractions taken were identical.
internal standard. Fig. 2 illustrates the procedure for the PASHs separation
from the condensate and volatile oils. 3.2. Qualitative analysis of the PASHs

The gas chromatogram of the PASHs in the volatile oil sample of

2.6. Quantitative analysis VE-gas Co. Assil-13x is depicted in Fig. 4 with the identications
suggested through comparison with standard compounds and GC-MS.
The quantitative analysis was performed by adding an aliquot of a The chromatogram is characterized by homologues of alkylated BTs,
100150 mole/mL 2-uorodibenzothiophene standard in cyclohex- DBTs and BNTs. Fig. 5 represents chromatograms of the different types
ane to the separated second fraction of sulfur compounds from Pd(II)- of condensates that were found. Compared to most crude oil samples,
mercaptopropano silica column. An Excel spread sheet was used to the chromatograms show relatively few peaks.
calculate the sulfur concentrations based on the area of the internal Fig. 6 illustrates exemplied mass spectra taken at various
standard. The total sulfur amount was calculated by summing all the retention times. The major signals can be assigned to alkylated
peaks while excluding that of the internal standard. PASHs. The number of isomers increases with an increasing number of

RT: 0.00 - 66.25

100 NL:
2.67E5
95 TIC MS
90 2ndPd-4
85
80
75
Relative Abundance

70
65 C1 -DBT
60
55 DBT
50
45 C2 -DBT
40
35
30 C3 -DBT
25
20 C1 -BT C2 -BT
15 BT C3 -BT
10
5
0 0 5 10 15 20 25 30 35 40 45 50 55 60 65
Counts AED2 B, Sulfur 181 (NAGY\2NDPD-4.D) Time (min)

60
C1 -DBT

50
DBT
C2 -DBT
40

30 C3 -DBT

C1 -BT
20
C2 -BT

10
BT C3 -BT

0 10 20 30 40 50 60 70 min

Fig. 3. Comparison between the gas chromatograms for the PASH fraction of the condensate oil from the El-Hamra company with different detectors: MS (top) in the total ion mode
shows all components of the sample, and AED (bottom) in the sulfur-selective mode that detects only sulfur-containing compounds.
550 N.E. Moustafa, J.T. Andersson / Fuel Processing Technology 92 (2011) 547555
AED2 A, Sulfur 181 (NAGY\09091602.D)
Counts C1 -DBT
60
50
4
40
2,3
DBT
30
C2 -BT I.S.
20
2,6
C1 -BT 1
3,4 3,5
10 C3 -BT
2 2,5,7
2,3,6
BT 2,3
7 5,6
0
10 20 30
Fig. 4. Gas chromatogram with AED detection and identications of the PASHs in the VE-gas volatile oil sample. I.S. = internal standard 2-uoro-DBT. For mass spectra of the rst
three boxes, see Fig. 6.
alkyl substituent carbon atoms and the retention ranges of the isomer
groups start overlapping so that coelution becomes severe at higher
alkylation. Thus, in the MS in the C1-BNT region, not only is this
compound discernable at m/z 248 (Fig. 6, lower MS) but also C13-
(266) and C14-thiophenes (280) as well as C8-(296) and C9-DBTs
(310). The signal at 294 can be either a C19-thiophene or a C4-
substituted cyclohexenodibenzothiophene. If the alkyl carbons are
present in one chain, then the corresponding benzylic (or, after
rearrangement, tropylium type) fragment would be expected to be
clearly noticeable, in this case at m/z 97 (from the C19-thiophene) or
at 251 (from the C4-cyclohexenodibenzothiophene). In fact, a clear
signal at 251 is present, indicating that the naphthenodibenzothio-
phene may be the compound here. This is in agreement with the C13-
and C14-alkylthiophenes that appear in this retention region; C19-
thiophenes would be expected to elute at longer retention times. Also
the other odd number fragments probably represent benzylic ions
after loss of all but one of the carbon atoms in a side chain. Therefore
the m/z 265 may represent a methylbutylcyclohexenodibenzothio-
phene (after loss of C4H9). The series 221, 235, and 249, all present in
the mass spectrum, may represent the benzyl ions of mono-, di- and
trimethylphenanthro[4,5-bcd]thiophenes. Similar inspection of the
other mass spectra in Fig. 6 leads to a tentative assignment of a large
number of alkylated PASHs.
PASHs have no obvious biological precursors. Reacting with S,
many types of compounds, including n-alkanes, might ultimately turn
into sulfur aromatic components of the crude. The relatively high
content of BNTs and the higher molecular weight PASHs in petroleum
oil indicate that the oil has undergone an intense sulfurization in the
source rock or reservoir.
The isomer distribution in a volatile oil is similar as shown in Fig. 7.
This chromatogram should be compared with the similar one from a
condensate in Fig. 5 (middle). Both chromatograms display a more or
less pronounced "hump" derived from a large number of higher
molecular weight sulfur compounds, the unresolved complex mixture
(UCM). The hump in the GC of the volatile oil is more developed than
that of the condensate oil. As is evident in Figs. 4 and 6, alkylbenzo-
C2 -DBT
1,3
2,4
C3 -DBT
2,4,6
1,6
C4 -DBT
C3-BNT M.Wt. = 276.4
C2-BNT M.Wt. = 262.2
1,8
C1-BNT M.Wt. = 248
1,4
2,4,8
M.Wt. = 240.1
2,4,7
C5 -DBT
1,7
M.Wt. = 254.1
M.Wt. = 268.13
M.Wt. = 282.14
M.Wt. = 296.16
1,4,8
2,3 1,3,7
4ET
1,2
40 50 min
naphthothiophene isomers are present in the volatile oil, going up to at
least C3-BNT. This is expected since larger aromatic systems are
preferentially found in materials that have been subjected to more
severe conditions such as those that are found in the volatile oil reservoir
[24]. These UCM sulfur compounds should be taken into consideration
in catalytic studies.
The oils investigated can be divided into three types based on the
distribution of PASHs: Type 1 only contains alkyl-BTs, Type 2 both BTs
and alkyl-DBTs, and Type 3 only (or nearly only) DBTs (Fig. 5, from top
to bottom). In the PASH fraction, DBT and MDBT are abundant
compared to BT. The investigated oils can thus be classied according
to their patterns. The condensate oils from the reservoirs of El-Hamra,
Centurion-Ezher and El-basent-2 have similar distribution patterns
with respect to BTs and DBTs. Oils derived from carbonate source
rocks are rich in alkylated BTs and DBTs. Hypersaline sedimentary
environments might contribute to the alkylation reaction of DBTs [13].
This also gives an indication as to the source rock types of the volatile
oil reservoirs which are characterized by abundant BT and DBT
isomers.
Many published studies have investigated the relationships
between the sulfur compound distributions and the types of reservoir
rocks and also the ratio of these isomers, particularly C1-DBT isomer
ratios, as maturity indicators. The sulfur compounds were investigat-
ed alone or in ratios with other aromatic compounds [2527]. The
present materials present quite different PASH patterns. As it was not
our intention to do a detailed geochemical study, we just note the
different patterns observed.
The condensate oils from reservoirs of Wapeco-AST-2, Petrobel-
Fayroyz-ST1 and Wapeco companies have similar distribution patterns
containing alkyl-DBTs only. On the other hand, the condensate oils from
the reservoirs of Khalada and Bedr El-dien companies exhibit mainly
alkyl-BTs, and nally the Salama reservoir does not contain any
detectable amounts of PASHs. The relative concentration of PASHs in
petroleum is inuenced by the lithology of source rocks. Clay-poor
sources generate a PASH-rich petroleum whereas clay-rich sources
containing much iron produce petroleum with a very low concentration
 N.E. Moustafa, J.T. Andersson / Fuel Processing Technology 92 (2011) 547555 551

AED2 A, Sulfur 181 (NAGY\RSD33RD5.D)

Counts

120

100
C1-BT

80

C2-BT
60

BT
40 C3-BT

DBT C1-DBT
20
C2-BT

0
5 10 15 20 25 30 35 40 45 min
AED2 A, Sulfur 181 (NAGY\09091501.D)
Counts
70

60

I.S.
50

C1-DBT

40
DBT

30
C2-BT

20
C3-DBT
C1-BT
10 C2-BT

BT C3-BT

0
10 20 30 40 50 min
AED2 A, Sulfur 181 (NAGY\09091804.D)
Counts
80

70

DBT
60
C1-DBT
50

C2-BT
40
I.S.

30
C3-DBT

20

10

0
10 20 30 40 50 min

Fig. 5. Sulfur-selective chromatograms for condensate oils from three reservoirs. Top: Petrobel-Fayroyz (yellow colour), middle: El-Hamra Company (brown colour), and bottom:
Bedr El-dien Company (waxy yellow oil). I.S. = internal standard 2-uorodibenzothiophene.
552 N.E. Moustafa, J.T. Andersson / Fuel Processing Technology 92 (2011) 547555

6 #3728 RT: 41.14 AV: 1 NL: 1.26E2

T: + c Full ms [ 50.00-650.00]
240.0
100
95
90 C4-DBT
225.1
85
80
75
70
65
Relative Abundance

60
55
50
211.1
45
40
226.1
35
30
25 241.1
115.0 208.1
20 165.1
69.0 212.1
197.2 239.2
15 55.0 81.0
223.1

10 62.0
75.1 110.6 142.1 152.1 185.0
189.1 283.9
104.3 135.1 229.0
89.3
5 255.2 259.1 274.5 286.1
322.1 345.6
0
60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360
m/z
6 #3891 RT: 42.80 AV:1 NL: 8.30E1
T: + c Full ms [ 50.00-650.00]
225.1 254.1
100
95
90 C5-DBT
85
80 239.1
75
70
65
Relative Abundance

60
55
50
211.0
45 240.1
40
35
30 197.1
224.2 226.2
25 55.0
165.1 268.1
20 176.0
105.0 152.2 244.1
15 67.1 91.0 150.1 178.1 227.1
121.1 162.2
10 56.0 69.0 77.0 93.1 126.2 141.2 192.2 255.1
269.0
190.3 299.0 306.4 354.4
5
285.2 312.1
0
60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360
m/z
6 #4462 RT: 48.63 AV: 1 NL: 7.40E1
T: + c Full ms [ 50.00-650.00]
248.1
100
95
90 C1-BNT
85
80
75
70
Relative Abundance

65 280.1

60
55
50
45
247.1
40 265.1
55.0
225.2 235.2
35 266.2 294.1
30 251.1
57.0 189.1
211.1
25 81.1
95.1 199.2 267.1
20 67.0
176.2
109.2 115.0 263.1
221.1 281.1
15 96.1
124.8 296.0
85.1
164.0
10 73.4 131.1
135.0
187.1
298.1
314.2
107.1 282.1
5 62.9 349.1
323.2 340.9
352.3
0
60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360
m/z
 N.E. Moustafa, J.T. Andersson / Fuel Processing Technology 92 (2011) 547555 553

AED2 A, Sulfur 181 (NAGY\09091602.D)

Norm.
C1-DBT

60

C2-DBT
50

40

C3-DBT

30 DBT

I.S.

20 C2-BT

C1-BT
10
C3-BT

BT
UCM
0

10 20 30 40 50 60 70 min

Fig. 7. Sulfur-selective chromatogram for the volatile oil from VE-gas company.

AED2 A, Sulfur 181 (NAGY\RSD33RD5.D)

Counts

120
AED2 A, Sulfur 181 (JULIANE\RSD32D2V.D)
Counts

30

100
C1-BT
25
C1-BT
Thiophene

20
Alkylated-thiophenes

80
BT
15

10
C2-BT
5
60

0 2 4 6 8 10 12 14 min

BT
40 C3-BT

DBT C1-DBT
20
C2-BT

0
5 10 15 20 25 30 35 40 45 min

Fig. 8. GC-AED chromatogram showing sulfur aromatic compounds of lower boiling ranges than benzothiophenes in the condensate oil of Petrobel-Fayroyz.

of PASHs [13,2527]. Oils derived from siliceous sources are rich in
methylated BTs. However, DBT and its methyl homologues MDBT and
DMDBT are also abundant [13,2527].
The distribution pattern of the C1-DBT isomers indicates the
maturity degree of the given condensate oil [28]. The present oils all
show a stepwise pattern 4- N 2- + 3- N 1-MDBT, indicating mature
condensate oils.
As seen above, the identication of a large number of isomers is
hampered by the fact that coelution is very common due to the large
number of isomers. Even the six C1-BTs cannot be resolved and only
four peaks are observed due to the coelution of the 5-/6- and the 3-/4-
isomers on standard nonpolar stationary phases [29]. Higher
substituted compounds suffer an even greater degree of overlap.
Although there are 21 possible isomers of C2-BTs (15 dimethyl and six

Fig. 6. GC-MS spectra of the VE-gas volatile oil (see Fig. 4) taken at retention times 41.14, 42.80, and 48.63 min. The largest signals in the mass spectra correspond to C4-DBT (m/z
240), C5-DBT (m/z 254) and C1-BNT (m/z 248) but many other compounds coelute with them.
554 N.E. Moustafa, J.T. Andersson / Fuel Processing Technology 92 (2011) 547555

Table 1 Table 1 (continued)

Retention times and concentration of the sulfur (in ppm) for some volatile and Compound VE-gas volatile oil El-Hamra Phobis volatile oil
condensate oils reservoirs. All values are the mean of three determinations. condensate oil
Rt = retention time. ppm is the fraction (in parts per million) of the total sulfur that
is derived from the compound listed as determined by atomic emission detection. Rt ppm Rt ppm Rt ppm

Compound VE-gas volatile oil El-Hamra Phobis volatile oil C3-DBT

condensate oil 39.349 1090
C4-DBT
Rt ppm Rt ppm Rt ppm 39.852 1730 39.865 550
BT 10.005 450 9.990 590 40.123 5370
40.339 2430 40.339 2100
C1-BT 40.450 1170 40.45 1020
7 12.725 520 12.708 870 40.643 1690
2 13.226 1530 13.218 960 40.785 1880
5/6 13.519 400 13.505 800
3/4 13.939 3710 13.938 3430 C5-DBT
15.938 360 41.139 3520 41.145 980
41.795 5170
C2-BT 16.035 470
42.214 3870
16.193 580
16.421 420 16.407 580 43.913 700 43.897 2100
16.578 380 16.567 480 46.606 1260 46.579 2150
16.804 1220 16.808 1780
17.063 780 17.064 475 47.179 2100 47.164 4930
2,6 17.289 6350 17.293 3200 47.858 1250
3,5 17.921 3560 17.926 1890 49.340 1520
49.460 1670
2,3 18.303 570 18.302 600
49.769 1580
19.328 390 19.342 376
19.511 300 19.496 600 49.917 1380
19.658 460 19.660 510 50.078 1130
19.901 350 50.324 1170
50.592 720
C3-BT 51.281 570
20.142 1470 20.142 1610 51.355 720
51.630 1230
20.394 1280 20.390 915
20.872 470 52.020 1420
2,5,7 21.096 2410 21.103 1520 52.407 940
21.444 327
21.685 770 21.688 1250
22.327 1350 22.334 760 ethyl substituted isomers), they are resolved only into 15 peaks on
22.931 760 such phases, etc. Furthermore, standard compounds are not available
2,3,6 23.363 1580 23.307 1190 for all isomers. Although the retention indexes are known for all of the
23.893 980 23.945 1030
C1- and C2-substituted benzothiophenes [29], only three isomers
2,3,4 24.106 780
DBT 25.377 11700 25.394 18080 25.375 4510 could be identied unambiguously from the 21 possible isomers of C2-
BTs and eight isomers from the 20 possible isomers of C2-DBTs.
C1-DBT In Fig. 8 the chromatogram of the condensate oil from Petrobel-
4 28.706 30900 28.697 21470 28.668 10580 Fayroyz is shown as the only oil in this series containing lower boiling
2/3 29.385 18830 29.380 15670 29.363 5950
1 29.969 6740 29.973 3280
alkylated thiophenes as identied by GC-MS. These sulfur compounds
are probable precursors of the geochemically formed BTs and DBTs.
C2-DBT This alkylated thiophene distribution is similar to that of uid catalytic
4Et 31.605 3340 31.611 1820 31.602 700 cracked (FCC) gasoline. Such a material will be much easier to
4,6 31.844 21000 31.837 12200 31.813 5810
hydrodesulfurize than materials in which DBTs dominate. Generally,
32.364 10800 32.351 6690 32.330 3500
2,4 32.576 34200 32.545 16300 32.495 8690 the sulfur distributions of condensate oils are similar for those of
1,6/1,8/1,4 33.192 20000 33.177 10820 33.161 2810 diesel fuels [30].
1,3 33.648 7300 33.652 4000 33.656 1070
1,7 33.782 2870 33.788 1460
34.237 2030 34.234 1650 3.3. Quantitative analysis of the PASHs
34.372 1909 34.376 810
2,3 34.552 20780 34.547 990 Table 1 gives the concentrations for the BT and DBT isomers for one
1,2 34.905 3377 34.906 2030 condensate and two volatile oils. The concentrations were determined
by using the sulfur-selective atomic emission detector and are thus
C3-DBT
2,4,6 35.326 20780 35.310 9700 35.290 5360 the concentration of this element, given with an accuracy commen-
35.718 3380 35.772 1590 35.716 700 surate with the standard deviation. The remaining oils also contain
2,4,7/2,4,8 35.989 11750 35.981 5850 35.967 3220 considerable amounts of sulfur in PASHs. The condensate oil of the
1,3,7 36.244 2970 36.239 3920 36.241 850
Centurion Company from the Azher reservoir contains the lowest
1,4,8 36.630 8550 36.624 4650 36.611 1270
36.827 1220 36.833 1200 concentration whereas the Petrobel condensate oil shows the highest
37.215 3314 37.208 3080 37.208 1740 sulfur concentration with the C1-BT isomers predominating.
37.653 5130 37.658 590 37.891 1120
37.914 2450 37.937 1320
38.138 2290 38.137 1890
4. Conclusions
38.380 2100 38.377 1060
38.620 1090 38.617 1040 38.610 690 This is the rst analysis of condensates and volatile oils with respect
38.759 1630 38.762 780 to the sulfur-containing aromatic heterocycles. Since more stringent
39.048 5060 39.052 630
legislation regarding sulfur concentration in fuels will be introduced in
39.178 2290
many countries in the future, it will be important to understand the
 N.E. Moustafa, J.T. Andersson / Fuel Processing Technology 92 (2011) 547555
chemical forms of sulfur in fossil matter that is being increasingly used in
industry for facilitating the hydrodesulfurization process. Here we
analyze a range of natural gas liquids and nd that they contain sulfur
aromatic compounds in the form of alkylated benzothiophenes,
dibenzothiophenes, phenanthro[4,5-bcd]thiophenes and benzo-
naphthothiophenes with the smaller systems dominating. This is in
analogy to crude oils where these parent compounds are common.
Distinct differences were seen between different materials, so that the
ratio between the two-ring and the three-ring compounds goes from
practically 0 to very high values, e.g., BTs/DBTs ratio equals 1.8 (highest),
0.078 & 0.085 (middle) and 0.008 (lowest) for Petrobel-Fayroyz, El-
Hamra & Centurion-El-basant and waxy-Bedr Eldien condensates,
respectively. This seems more extreme than the differences that exist
among crude oils; the pattern also hints at a correlation with the
maturity of the materials and should be explored in coming work.
To the rening industry the large amounts of dibenzothiophenes
should be of particular concern since this group of compound is the
most recalcitrant one to hydrodesulfurization. Dibenzothiophenes
substituted in the 4- and 6-positions are traditionally regarded as the
most recalcitrant ones, but instances have been recorded where
1,3,6,7-tetramethylDBT was one of the most prominent isomers to
survive HDS [6]. Thus it would be valuable to perform a speciation of
condensates and their hydrodesulfurized products to identify the
particular isomers of DBT that are present. That is a work that goes
beyond the present survey.
Acknowledgment
The corresponding author thanks the Deutsche Forschungsge-
meinschaft for making his stay in Germany possible. The members of
the working group are thanked for supporting the laboratory work.
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