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Fuel
journal homepage: www.elsevier.com/locate/fuel
Centro Tecnolgico de Repsol, Carretera de Extremadura, NV, km 18, 28935 Mstoles, Madrid, Spain
Universidad Complutense de Madrid, Departamento de Qumica Analtica, Avda. Complutense s/n, 28040 Madrid, Spain
h i g h l i g h t s
! It was developed a PIONA analysis for kerosene samples by GC " GCTOFMS.
! Semiquantification was based on the area of characteristic fragments and molecular ions.
! Results were compared with reference methods and they closely resemble.
a r t i c l e
i n f o
Article history:
Received 7 August 2012
Received in revised form 11 July 2013
Accepted 18 July 2013
Available online 3 August 2013
Keywords:
Comprehensive two-dimensional gas
chromatography
GC " GC
Time of flight mass spectrometry
TOFMS
Kerosene
a b s t r a c t
A method to determine n-paraffins, iso-paraffins, olefinsnaphthenes and aromatics (PIO-NA) in kerosene
samples by comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry (GC " GCTOFMS) is reported. This method is based on a correct identification of kerosene compounds by Scripting (Visual Basic programming) which establishes rules for filtering spectral data to
locate compounds having defined spectral properties of a particular compound class. This tool implies
a significant reduction of analysis time for very complex samples. Semiquantification of compound families is performed by adding the areas of the characteristic mass fragments of each compound class and
their respective molecular ions. The kerosene samples for analysis were produced by different conversion
processes such as catalytic reforming, alkylation, catalytic cracking and hydroprocessing depending on
the kerosene distillation process. To assure the reliability of the method, samples were also analyzed
by reference methods and good concordances were found between the results obtained.
! 2013 Elsevier Ltd. All rights reserved.
1. Introduction
Detailed hydrocarbon analysis of petrochemical samples has
great importance in the petrochemical industry. It allows a correct
characterization of samples to predict their behavior in further
processing and applications. There are numerous methods able to
characterize petrochemical samples providing detailed information. In particular, the ASTM D2425 [1] provides the content (expressed in mass percentage) of eleven hydrocarbon families in
middle distillates. According to this method, mass fragments and
molecular ions of a hydrocarbon family are summed and used to
calculate concentrations from matrix coefficients which depend
on carbon number. However, samples must be previously separated into saturate and aromatic fractions by test method D2549
[2], and then each fraction is analyzed by mass spectrometry.
Corresponding author. Tel.: +34 91 753 76 33; fax: +34 91 753 86 13.
E-mail address: shuertasdlt@repsol.com (S. Huertas).
0016-2361/$ - see front matter ! 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2013.07.077
The so-called PIONA analyzers are based on the use of a standardized gas-chromatography technique to determine n-paraffins,
iso-paraffins, olefins, naphthenes and aromatics in gasoline and
petroleum naphtha containing hydrocarbons having boiling points
between #42 and 216 "C [3]; its operation principle is based on a
combination of traps for hydrocarbons with a similar functional
group, separating columns and a hydrogenator for olefins. However,
the main disadvantage is that this PIONA analysis technique is limited to hydrocarbons with boiling points below 200 "C, corresponding to compounds containing a carbon number around C11. More
recently, GC " GC has been applied to the analysis of heavier cuts
(middle distillates) [4,5], especially due to its high peak capacity,
resolution power and high sensitivity which are obtained by combining two chromatographic columns in contrast to
one-dimensional gas chromatography [6,7]. GC " GC analysis of
petrochemical products is normally performed using a flame ionization detector (FID) or a time of flight mass spectrometer (TOFMS)
[810]. As petrochemical products consist of thousands of
717
3. Results
2. Experimental
Table 1
Chromatographic and MS conditions.
GC " GC
1D Column
2D Column
Injection
Flow rate of He Carrier gas
First oven T program
Second oven T program
Modulator T
Modulation period
TOFMS
Source T
Transfer line T
EI ionization
Acquisition frequency
250 "C
225 "C
#70 eV
150 Hz
718
Table 2
Mass fragments and molecular ions used for semiquantitation.
Class compound
Ions
n-Paraffins
Iso-paraffins
Mononaphthenes/olefins
Dinaphthenes/olefins
Trinaphthenes/olefins
Alkylbenzenes
Benzonaphthenes
Dinaphthobenzenes
91 + 92 + 10 + 106 + 119 + 120 + 133 + 134 + 147 + 148 + 161 + 162 + 175 + 176
103 + 104 + 117 + 118 + 131 + 132 + 145 + 146 + 159 + 160 + 173 + 174 + 187 + 188
115 + 116 + 129 + 130 + 143 + 144 + 157 + 158 + 171 + 172 + 185 + 186
Naphthalenes
Acenaphthenes, biphenyls
Acenaphthenes, fluorenes
141 + 142 + 155 + 156 + 169 + 170 + 183 + 184 + 197 + 198 + 211 + 212 + 225 + 226 + 239 + 240
153 + 154 + 167 + 168 + 181 + 182 + 195 + 196 + 209 + 210 + 223 + 224 + 237 + 238 + 251 + 252
151 + 152 + 165 + 166 + 179 + 180 + 193 + 194 + 207 + 208 + 221 + 222 + 235 + 236
Phenanthrenes
177 + 178 + 191 + 192 + 205 + 206 + 219 + 220 + 233 + 234 + 247 + 248
Table 3
Column sets tested in GC " GCTOF-MS. 1D column DB-1 (30 m " 0.25 mm " 0.25 lm) was maintained in all tests.
Set
2D column
Characteristics
2
3
4
Fig. 1. Zoomed view of four 2D color plots of a kerosene sample obtained with the tested column sets: 1D column DB-1; 2D column: (a) ZB-50, (b) BPX-50, (c) IL-59 and (d)
ZB-1701.
temperature ramps, at 2 "C min#1. Furthermore, since a small difference between the temperatures improved compound separation in
2D, the temperature in the second oven was set 5 "C higher than in
the first oven. For this reason, in order to prevent wrap-round, it
was necessary to establish a high modulation time, 8 s.
As shown in Fig. 1, the separation between paraffins and naphthenes with ZB-1701 and IL-59 columns was very poor; for that reason,
they were discarded. Regarding the medium polar 2D columns, the
719
Fig. 2. 2D color plot of a kerosene sample. Elution zones of saturates (a) and aromatics (b) are plotted according to the carbon number and class compound. The number
inside each zone indicates the carbon atoms number of the alkyl chain or alkyl groups.
Table 4
Validation results of the in-laboratory method for determination of n-paraffins in
petroleum products. Determination coefficient has been obtained from a set of
standards covering the concentration range from 5% to 25% of n-paraffins. LOD and
LOQ were obtained considering 3 and 10 times, respectively, the intercept SD divided
by the slope.
Equation
R2
RSD (%)
LOD (%)
LOQ (%)
Recovery (%)
y = 37 557x # 69 023
0.999
1.3
1.6
4.9
90
720
0.00
100
100
100
100
0.00
0.00
100
100
100
100
0.00
0.00
100
100
100
100
0.00
0.00
100
23.56
22.86
15.16
7.70
0.00
0.70
0.67
0.03
0.00
0.00
100
Aromatics
Monoaromatics
Alkylbenzenes
Benzonaphthenes
Dinaphthobenzenes
Diaromatics
Naphthalenes
Biphenyls
Fluorenes
Triaromatics
Total
0.00
100
100
0.25
0.13
0.00
0.00
0.00
0.00
1.30
1.26
1.25
0.01
0.00
0.00
0.10
0.00
0.00
0.00
0.00
0.00
0.17
0.00
0.00
0.00
0.00
0.00
0.19
0.08
0.08
0.00
0.00
0.00
0.59
0.30
0.30
0.00
0.00
0.00
0.23
0.23
0.00
0.00
0.00
0.76
0.73
12.05
11.80
11.01
10.88
8.34
2.54
0.00
27.01
25.74
16.47
9.27
0.00
3.74
3.74
2.98
0.76
0.00
16.46
16.46
13.22
3.23
0.00
15.33
15.25
11.41
3.84
0.00
18.86
18.27
21.54
21.24
19.77
1.47
0.00
5.91
5.68
4.90
0.78
0.00
21.88
21.12
34.51
24.41
9.77
0.33
Naphthenes/olefins
Monoditri-
5.42
7.81
7.79
0.02
0.00
4.05
3.32
53.49
19.02
18.56
0.46
0.00
23.10
38.75
29.39
9.03
0.33
5.05
12.69
12.50
33.20
25.70
7.50
0.00
17.33
17.16
15.94
68.22
42.73
25.48
0.00
3.40
3.30
4.51
31.95
23.27
8.68
0.00
5.15
27.93
26.63
52.22
36.07
15.72
0.44
7.20
87.95
88.99
36.76
7.38
29.39
72.07
72.99
41.05
5.38
35.67
96.6
96.26
28.04
3.48
24.56
82.67
83.54
50.34
15.94
34.41
87.31
84.67
45.92
5.24
40.68
81.14
78.46
59.44
21.83
37.61
95.95
94.09
86.28
54.23
32.05
78.12
76.44
41.93
5.84
36.09
Saturates
Paraffins
n-Paraffins
iso-Paraffins
K8
K7
K6
K5
K4
Ref.
method
K3
GC " GC
TOFMS
Ref.
method
K2
GC " GC
TOFMS
Ref.
method
GC " GC
TOFMS
K1
Table 5
Results obtained by GC " GCTOFMS and reference methods of eight real kerosene samples; %, m/m.
GC " GC
TOFMS
Ref.
method
GC " GC
TOFMS
Ref.
method
GC " GC
TOFMS
Ref.
method
GC " GC
TOFMS
Ref.
method
GC " GC
TOFMS
Ref.
method
721
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
Total
Paraffins
n-Paraffin
iso-Paraffin
0.00
0.00
0.00
0.41
0.19
0.23
0.58
0.19
0.39
2.21
0.49
1.72
4.79
0.70
4.09
6.09
0.75
5.33
7.52
1.15
6.37
5.93
0.87
5.06
6.03
0.89
5.14
6.21
0.57
5.63
2.16
0.05
2.11
0.00
0.00
0.00
0.00
0.00
0.00
41.93
5.84
36.09
Naphthenes/olefins
monoditri-
0.00
0.00
0.17
0.17
0.63
0.63
0.00
2.38
1.96
0.41
5.83
4.66
1.17
0.00
6.93
3.77
3.16
0.00
7.40
4.07
3.33
0.00
4.49
3.09
1.40
0.00
3.78
3.61
0.18
0.00
1.67
1.55
0.12
0.00
0.74
0.74
0.00
0.00
0.48
0.15
0.00
0.33
0.00
0.00
0.00
0.00
34.52
24.41
9.77
0.33
Monoaromatics
Alkyllbenzene
Naphtobenzene
Dinaphtobenzene
0.00
0.00
0.00
0.00
0.09
0.09
0.00
0.00
0.61
0.61
0.00
0.00
1.78
1.56
0.22
0.00
3.78
2.72
1.06
0.00
4.00
2.19
1.81
0.00
6.47
3.00
3.48
0.00
3.81
2.91
0.90
0.00
1.98
1.74
0.24
0.00
0.35
0.35
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
22.86
15.16
7.70
0.00
0.09
0.09
0.25
0.25
0.30
0.29
0.01
0.06
0.04
0.02
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.70
0.67
0.03
0.00
0.00
0.00
0.00
0.00
0.00
0.00
14.49
17.26
21.69
14.29
11.79
8.22
2.90
0.48
0.00
100.00
Diaromatics
Naphthalene
Biphenyl
Fluorene
Triaromatics
Total
0.00
0.68
1.82
6.36
Fig. 4. n-Paraffin distribution given in % (m/m) obtained from middle distillate samples. Green bars correspond to GC " GCTOFMS while yellow ones correspond to GCFID.
(For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
722