International Journal of Petroleum and Petrochemical Engineering

Volume 6, Issue 3, 2020, PP 1-12

ISSN No.: 2454-7980
DOI: https://doi.org/10.20431/2454-7980.0603001
www.arcjournals.org

Detailed Characterization of Light Cycle Oil for BTX Production

Purposes
Georgina C. Laredo*, Patricia Pérez-Romo, Ricardo Águeda-Rangel, José Escobar and Pedro
Vega-Merino.
Instituto Mexicano del Petróleo, Lázaro Cárdenas, México

*Corresponding Author: Georgina C. Laredo, Instituto Mexicano del Petróleo, Lázaro Cárdenas, México

Abstract: Samples of Mexican light cycle oils were characterized by several techniques. Physical and chemical
characteristics are presented. Besides the usual American Standard Test Methods (ASTM) a gas
chromatography – mass spectrometry (GC-MS) technique was presented. Based on the GC-MS technique a
detailed chemical characterization method was proposed by considering the retention times and sorting out the
compounds as hydrocarbon-type derivatives such as benzene, naphthalene, phenanthrene and alkanes
derivatives. This procedure is a useful tool for assessing the feasibility and potential of LCO samples as
feedstocks for petrochemical or gasoline production. A sample was also distilled in fractions and characterized
for the ASTM and GC-MS methods to define the optimum final boiling point for attaining a certain upgrading
method.
Keywords: Light cycle oil; BTX, gasoline, chemical characterization, chromatography, mass spectrometry

1. INTRODUCTION
Light cycle oil (LCO) is a middle distillate from FCC (fluid catalytic cracking) units with high sulfur
(up to 4 wt.%), nitrogen (up to 400 mg/kg), and aromatic contents (up to nearly 90 wt.%) [1, 2], which
make the processing of this middle distillate very difficult and suitable to comply with the
environmental legislation [3, 4].
There have been several technological alternatives for producing diesel from LCO and SRGO/LCO
mixtures that includes:
 LCO fractionation into light fractions (final boiling point lower than 340 °C) to avoid the strong
inhibition of aromatics due to competing hydrogenation of those species with that of highly
refractory organo-sulfur compounds [5, 6].
 Utilization of more active catalysts [7-10]

 Newer and revamped technologies [11-13]

A remarkably interesting alternative for LCO upgrading is obtaining a benzene, toluene, and xylenes
(BTX) enriched fraction after hydrogenation/hydrotreating (HYD/HDT) and hydrocracking (HCK)
from LCO feedstock. Reaction pathways from LCO (naphthalene as model compound representing di-
aromatics present in that middle distillate) to a BTX enriched fraction is shown in Figure 1 [14]. After
HYD/HDT, the naphthalene derivatives produced 1,2,3,4-tetrahydronaphthalenes (tetralins). In the case
of real feedstocks, HDT is required to decrease the amount of sulfur- and nitrogen-bearing contaminants
that could act as poison for further processes. Then, the tetralin derivatives were subjected to HCK for
BTX production.

International Journal of Petroleum and Petrochemical Engineering Page | 1

Detailed Characterization of Light Cycle Oil for BTX Production Purposes

Benzene Toluene
Hydrogenation Hydrocracking

Tetralin
Naphthalene

Hydrogenation
m-Xylene p-Xylene o-Xylene Ethylbenzene

Hydrocracking
LPG, Naphtha

cis-Decalin trans-Decalin

Figure1. Reaction scheme for obtaining BTX and LPG (liquefied petroleum gas) and naphtha from LCO [15]
Physical and chemical characterization of the feedstocks and corresponding products of different
processes is crucial to face future refining challenges. Characterization by ASTM D-5186 method [15]
provides approximated values of mono-, di- and tri-aromatic compounds in the LCO. However, it was
designed for middle distillates with less than 50 wt.% of aromatic content and it does not describe the
chemical structures involved (i.e., benzene or tetralin derivatives in the case of mono-aromatics) or the
type of naphthalene derivatives which are present or remain after HYD/HDT and HCK processes. This
type of characterization is crucial because each type of species could provide different product slates.
Regarding the corresponding state of the art, detailed chromatograms of fractionated LCO were
presented by Choi et al. [16] although no detailed characterization of the crucial compounds was
attempted. LCO characterization by using two-dimensional high-resolution gas chromatography and
time-of-flight mass spectrometry (TD-GC-HRMS) followed by enhanced software processing has been
presented by Bisht and Petri [13] and Alonso et al. [17]. Vendeuvre et al. [18] revealed that by using a
comprehensive two–dimensional gas chromatography (GC x GC) combined with the boiling range
distribution of complex mixtures allowed them to obtain the group type separation of a gas oil. Ruiz-
Guerrero et al [19] studied straight run gas oils (SRGOs), and LCOs and demonstrated the effectiveness
of two-dimensional gas chromatography coupled to sulfur chemiluminescence detection (SCD) as a
powerful tool for improving characterization and identification of sulfur compounds. Adam et al [20]
reported the use of supercritical fluid chromatography (SFC) coupled to a twin comprehensive two-
dimensional gas chromatography allowed the detailed characterization of middle distillates avoiding
the risk of misidentifications. The extended PIONA analysis of middle distillates in one single injection
was for the first time reported. Jennerwein et al [21] established a two-dimensional GC x GC-time-of-
flight mass spectrometric (TOFMS) method the complete group-type quantification of petroleum
middle distillates. The combination of these two techniques offered the possibility to distinguish
between compounds groups based on their fragmentation patterns where exact retention time
information is missing. This method needed the application of Visual Basic Scripting as an analytical
tool for the analysis of mass spectral data. Alvarez-Majmutov et al. [22]. reported a technology based
on trends followed by the different hydrocarbon families against their boiling point, allowing the
chemical characterization of middle distillates. Although the technology is not always reliable due to
the presence of different hydrocarbons families of the LCO that does not always follow the predicted
normal configuration provided by that authors. The LCO is not a natural occurring mixture and its
composition depends highly in the FCC procedure i.e. crudes oils source, HDT or not HDT involvement
before FCC, FCC catalyst and configuration. Additionally, the hydrocarbon differentiation is not as
carefully as required for the purposes described in this paper.
The main purpose of this work is to provide an accessible method using a GC-MS technique to
characterize different LCOs to assess the suitability of each one either for production of valuable
petrochemicals or gasoline.

International Journal of Petroleum and Petrochemical Engineering Page | 2

Detailed Characterization of Light Cycle Oil for BTX Production Purposes

2. EXPERIMENTAL
2.1. Materials
LCO samples were kindly provided by PEMEX. The samples were named LCO 1 to 8.
Distillated fractions: The LCO sample No. 6 was fractionated into nine 20 °C-cuts by using an Older-
Shaw distillation equipment following the ASTM D86 [15].
2.2. ASTM Characterization of LCO Samples and Distillation Fractions
LCO samples were chemically characterized using the ASTM standards shown in Table 1 [15].
Table1. ASTM and UOP characterization methods used for middle distillates and their hydrotreated products [26]
Characteristic Method Description
Standard Test Method for Sulfur in Petroleum and Petroleum
Sulfur, wt% ASTM D4294 Products by Energy Dispersive X-ray Fluorescence
Spectrometry
Standard Test Method for Nitrogen in Petroleum and
Petroleum Products by Boat-Inlet Chemiluminescence
Nitrogen, mg/kg ASTM D4629 Standard Test Method for Trace Nitrogen in Liquid
Petroleum Hydrocarbons by Syringe/Inlet Oxidative
Combustion and Chemiluminescence Detection
Basic nitrogen, mg/kg UOP 269 Nitrogen Bases in Hydrocarbons by Potentiometric Titration
Standard Test Method for Bromine Numbers of Petroleum
Bromine number, gBr/100g ASTM D1159 Distillates and Commercial Aliphatic Olefins by
Electrometric Titration
Standard Test Method for Refractive Index and Refractive
Refraction index ASTM D1218
Dispersion of Hydrocarbon Liquids
Standard Test Method for Determination of the Aromatic
Chemical composition ASTM D5186 Content and Polynuclear Aromatic Content of Diesel Fuels
By Supercritical Fluid Chromatography
Standard Test Method for Calculated Cetane Index of
Cetane index ASTM D 976
Distillate Fuels
Standard Test Method for Density, Relative Density, or API
Specifity gravity ASTM D1298 Gravity of Crude Petroleum and Liquid Petroleum Products
by Hydrometer Method
Standard Test Method for API Gravity of Crude Petroleum
API gravity ASTM D287
and Petroleum Products (Hydrometer Method)
Standard Test Method for Distillation of Petroleum Products
Atmospheric distillation, °C ASTM D86
and Liquid Fuels at Atmospheric Pressure
2.3. Gas Chromatograph Coupled to Mass Spectrometry Detector (GC-MS)
LCO samples and distillated fractions were characterized with an Agilent Technologies 6890N gas
chromatograph coupled to a 5973N mass spectrophotometer (GC-MS) was used by following the EPA
method 8270D [23] through SIM mode (quantitative analysis) for naphthalene and phenanthrene
derivatives and SCAN mode (qualitative analysis) for the alkanes and iso-alkanes, 1,2,3,4-
tetrahydronaphthalene (tetralin, T) and decahydronaphthalene (decalin, D). Table 2 shows the retention
times of the several compounds found: benzene, naphthalene, phenanthrene, alkenes and (1,2,3,4-
tetrahydronaphthalenes/Tetralins) derivatives respectively.
Table2. Retention times (tR) obtained by the GC-MS method
Compound tR Compound tR
(min) (min)
Benzene derivatives [24] Naphthalene derivatives 100.9
Benzene 48.5 Naphthalene 100.9
Toluene 66.9 1-Methy-lnaphthalene 113.5
Ethylbenzene 80.2 2-Methyl-naphthalene 119.0
p-Xylene 80.4 2,6/2,7-Dimethyl-naphthalene 130.8
m-Xylene 81.5 1,3/1,7-Dimethyl-naphthalene 132.7

International Journal of Petroleum and Petrochemical Engineering Page | 3

Detailed Characterization of Light Cycle Oil for BTX Production Purposes

o-Xylene 83.9 1,6-Dimethyl-naphthalene 133.3

1,3-Dimethyl-benzene 86.7 1,4/2,3-Dimethyl-naphthalene 135.3
Mesitylene 92.5 1,5-Dimethyl-naphthalene 135.6
1-Ethyl-2-methyl-benzene 93.1 1,2-Dimethyl-naphthalene 137.0
1,2,3-Trimethyl-benzene 95.6 1,3,7-Trimethyl-naphthalene 145.1
1-Methyl-3-propy-lbenzene 97.0 1,3,6-Trimethyl-naphthalene 146.0
2-Ethyl-1,4-dimethyl-benzene 97.4 1,3,5/1,4,6-Trimethyl-naphthalene 147.6
1-Methyl-2-propyl-benzene 97.9 2,3,6-Trimethyl-naphthalene 148.2
1,2,7/1,6,7/1,2,6-Trimethyl-
1-Ethyl-2,4-dimethyl-benzene 98.4 naphthalene 149.6
2-Ethyl-1,4-dimethyl-benzene 98.8 1,2,4-Trimethyl-naphthalene 151.5
1,2,3,4-Tetramethyl-benzene 99.9 1,2,5-Trimethyl-naphthalene 152.5
1,2,4,5-Tetramethyl-benzene 100.5 1,3,5,7-Tetramethyl-naphthalene 161.2
1-Methyl-4-butyl-benzene 102.2 1,3,6,7-Tetramethyl-naphthalene 162.9
1,2,4,6/1,2,4,7/1,4,6,7-Tetramethyl-
1-Ethyl-2,4-dimethyl-benzene 102.3 naphthalene 163.4
(1-Methyl-2-cyclopropen-1-yl)-benzene 102.5 1,2,5,7-Tetramethyl-naphthalene 164.3
1-Methyl-4-(1-methylpropyl)-benzene 102.8 2,3,6,7-Tetramethyl-naphthalene 165.2
1-Methyl-4-(2-methylpropyl)-benzene 103.3 1,2,3,7-Tetramethyl-naphthalene 165.7
Pentamethyl-benzene 104.4 1,2,3,6-Tetramethyl-naphthalene 166.4
1,2,5,6/1,2,3,5-Tetramethyl-
(1,3-Dimethylbutyl)-benzene 104.9 naphthalene 168.0
2,4-Dimethyl-1-(1-methylpropyl)-benzene 105.7 Phenanthrene 174.1
1,4-Dimethyl-2-(2-methylpropyl)-benzene 106.5 1-Methyl-phenantrene 185.1
1,3,5-Trimethyl propyl-benzene 107.1 2-Methyl-phenantrene 185.7
3-Methyl-phenantrene 188.0
3. RESULTS AND DISCUSSION
3.1. LCO Characterization by the ASTM Standards [15]
Sulfur concentration of LCO samples varied from 2.07 to 3.34 wt.% (Table 3). Due to high content of
heterocyclic sulfur compounds LCO HDT requires moderate temperature and high hydrogen partial
pressures because sulfur removal reaction pathways via hydrogenated intermediaries are inhibited at
high temperature and low pressure due to low equilibrium concentrations of the latter species [9].
Distribution of various organo-sulfur compounds in LCO depends on the origin of the processed crude
blend, the catalyst type, feed quality and operating conditions used in the FCC units where that middle
distillates come from. Benzothiophenes with alkyl substituents containing 1-7 carbon atoms are
concentrated in fractions having boiling points below 300 °C whereas dibenzothiophenes with alkyl
substituents containing 1-5 carbon atoms belongs to fractions with boiling points above 300 °C. The
three-ring sulfur compounds are one order of magnitude less reactive than the two-ring sulfur species [9].
The total and basic nitrogen concentrations were from 132 to 545 mg/kg and from 27 to 71 mg/kg,
respectively (Table 3). Based on average values, the basic nitrogen represented 15.8 % of the total
nitrogen. Nitrogen-rich feedstocks are harmful for the LCO hydrocracking because they have to be
processed at higher hydrogen partial pressure and/or lower LHSV in the HDT reactors in order to
efficiently reduce the nitrogen content of the effluent to levels acceptable for hydrocracking. Besides,
ammonia poisons the acid sites of HCK catalysts resulting in weakened catalyst cracking function and,
consequently, in loss of the catalytic activity [10].
Table3. Chemical characterization of LCO samples 1 to 8 by ASTM D5186 method

LCO simple 1 2 3 4 5 6 7 8 Averaged

Sulfur, wt% 3.22 2.4 3.34 2.68 3.3 2.94 2.28 2.07 2.78
Nitrogen, mg/kg 337 269 544.8 253.6 346 132 224 319 303.2
Basic nitrogen, 47.7
71.3 40 57.3 48.2 38.1 54.3 45 27.3
mg/kg

International Journal of Petroleum and Petrochemical Engineering Page | 4

Detailed Characterization of Light Cycle Oil for BTX Production Purposes

Bromine number, 16.41

10.24 18.97 19.4 13.15 14.39 11.6 15.48 28.04
gBr/100g
Chemical
Composition
Mono-Aromatics 9.40 23.60 12.70 19.80 14.70 29.30 22.00 11.10 17.83
Di-Aromatics 70.70 51.40 56.30 52.50 54.60 44.10 45.10 55.00 53.71
Tri-Aromatics 7.10 8.60 14.40 6.10 6.70 2.00 5.40 5.60 6.99
Total Aromatics 87.20 83.60 83.40 78.40 76.00 75.40 72.50 71.70 78.53
Aliphatics 12.80 16.40 16.60 21.60 24.00 24.60 27.50 28.30 21.48
Cetane Index 17.9 20.7 21.08 23.62 24.8 23.7 28.7 28.3 23.60
Specific gravity 0.91 0.97 0.98 0.94 0.96 0.9 0.92 0.965 0.94
API gravity 23.99 14.38 12.89 19.03 15.90 25.72 22.30 15.13 18.67
Atmospheric
distillation, °C
IBP 236.9 173.5 225.2 214.8 200.3 173.4 151.5 178.8 194.3
5 vol.% 248.2 210.7 242.6 230.7 239.7 199.6 214.5 240.7 228.3
10 vol.% 250.5 221.1 246.5 236.2 249.7 207.2 221.9 257.5 236.3
30 vol.% 257.3 235.7 261.7 251.6 265.2 228.3 252.5 265 252.2
50 vol.% 264.2 259.2 279.1 264.5 275 248.5 268.2 277.8 267.1
70 vol.% 274.6 277.3 302.9 275.1 288.1 266.8 284.8 298.8 283.6
90 vol.% 285.5 316.3 349 288.3 310.7 288.9 310.5 329.5 309.8
95 vol.% 310.2 330.6 365.8 314.3 323.9 299.9 321.6 337.3 325.5
FBP 326.9 344.2 392.3 335.6 345.8 315.5 334.5 350.5 343.2
Aromatics concentrations in LCO samples were in the following intervals (Table 3): mono-aromatics:
9.4-29.3 wt.%; di-aromatics: 44.1-70.7 wt.%; tri-aromatics: 2.0-14.4 wt.%; total aromatics: 71.7-87.2
wt.%, respectively. According to the average values, the ratio of mono-/di-/tri- aromatics (i.e.
2.6/7.7/1.0), showed a predominant presence of di-aromatics (i.e., 68.4% of the total aromatics content),
which were followed by the mono-aromatic compounds (i.e. 22.7% of the total aromatics content). Due
to the greater stabilization by resonance of mono-aromatic species those compounds are generally an
order of magnitude less reactive than di-aromatics [9]. HYD of aromatics is sequential and cracking of
the saturated outer ring of tri-aromatics occurs above 427 °C [9]. HCK of aromatic feeds needs catalysts
with good saturation function and moderate-to-high acidity because those species could be cracked only
after HYD and show tendency to deposit coke on the catalyst surface [24]. HYD of aromatics are
exothermic and reversible reactions with lower equilibrium conversions under practical processing
conditions of industrial interest. Thus, increasing temperature to achieve higher saturation reaction rates
often results in lower equilibrium conversions, especially at lower pressures. In this line, during LCO
HDT at high hydrogen partial pressure (7.8 MPa) in batch reactor over a CoMo/Al2O3 sulfided catalyst
[25] the minimum concentration of di-aromatics was found when operating at 360 °C. At higher
temperatures (400 °C) thermodynamically favored dehydrogenation reactions resulted in mono-
aromatics transformation back to corresponding di-aromatics which they came from. Summing up,
operating at high hydrogen partial pressure, moderate temperature, low LHSV and using active dual-
function catalysts is recommended to hydrogenate aromatics to an appreciable extent.
High concentration of mono- and di-aromatics could be valuable for BTX production [26]. Following
that criterion, in Figure 2 various LCO samples are shown ordered from the most valuable to the least
one. Tri-aromatics and alkanes are considered as not suitable for that particular purpose. After
processing, poly-aromatics provided an array of hydrogenated hydrocarbons not particularly suitable to
produce BTX as shown in reaction pathways of Figure 1. For example, phenanthrene hydrogenation
demands for higher temperature and pressure, and enhanced hydrogen consumption as well, producing
among other compounds: octahydrophenanthrene (OHP), octahydroanthracene (OHA),
tetrahydrophenanthrene (THP) and dihydrophenanthrene (DHP) at 9.07%, 34.84%, 18.36% and 32.85%
[27]. During the hydrocracking procedure, aliphatic compounds are converted to LPG gases [24].
Alternatively, a low presence of all kinds of aromatics and a high presence of long chain alkanes and
iso-alkanes can be very suitable for diesel fuel production, as it is known that long linear hydrocarbons
increased the quality of the diesel produced [28].
International Journal of Petroleum and Petrochemical Engineering Page | 5
Detailed Characterization of Light Cycle Oil for BTX Production Purposes

90
More suitable compounds, wt%
80 Compounds less suitable, wt%

Chemical composition(SFC), wt%

70

60

50

40

30

20

10

0
1 6 2 4 5 7 3 8 Averaged
LCO Sample
Figure2. Chemical composition of various LCO samples by the ASTM D5183 method, from the most to the least
suitable hydrocarbon type distribution for BTX production
Cetane index varied from 17.9 to 28.7 (Table 3), accordingly to the aromatics content. That is, the
lowest value of the cetane index (i.e. 17.9) corresponded to the sample of the highest content of both
di-aromatics (i.e., 70.7 wt.%) and total aromatics (i.e., 87.2 wt.%).
API gravities varied from 12.9 to 25.7 °API. Boiling point ranged from IBP: 151.5-236.9 °C, to FBP:
315.5-392.3 °C. Higher FBP means higher amounts of heavy aromatics not suitable for BTX production [26].
3.2. Identification of the LCO Composition by Lumps Using the GC-MS Technique.
Using mass spectrometry, the samples were analyzed. The retention times (TR) obtained compared
successfully with the values presented by Alonso et. al. [17]. The identified compounds from Table 2
were grouped into lumps according to their chemical type as: alkanes and iso-alkanes, benzene and
tetralin derivatives, naphthalene, mono-, di-, tri- and tetra-methylnaphthalenes (MN, DMN, TMN,
TMN and TTMN respectively) and phenanthrene derivatives. This type of chemical characterization
based on GC-MS chromatography technique of the sample 6 is shown in Figure 3. This characterization
represents a fingerprint of a middle distillate and goes beyond the usual characterization of mono-, di-
and tri-aromatics by the ASTM D5186 method (supercritical fluid chromatography with flame
ionization detection, SFC-FID) and it could provide information on the potential of a sample to be used
as feedstock in a given process.
4.5
Dimethyl-naphthalenes
2-Methyl-naphthalenes

Tri-methyl-naphthalenes

4
Tetra-methyl-naphthalenes

3.5
i-C16
1-Methyl-naphthalene

3
Phenanthrenes
Area, %

2.5
C17

2
i-C15
Naphthalene

C18

1.5
Benzenes

i-C20

C21
C19
C16

C20
C14

i-C17
C15

1
i-C19

i-C21

C22
i-C18

C23
i-C14

0.5
C24

0
50 70 90 110 130 150 170 190 210 230
Retention time, min
Figure3. Detailed GC-MS analysis of the LCO sample 6
International Journal of Petroleum and Petrochemical Engineering Page | 6
Detailed Characterization of Light Cycle Oil for BTX Production Purposes

Table2. Retention times (tR) obtained by the GC-MS method (continuation)

Compound tR (min)
Alkanes
Tetradecane 126.0
Pentadecane 137.7
Hexadecane 148.9
Heptadecane 159.2
Octadecane 169.1
Nonadecane 178.6
Eicosane 187.6

1,2,3,4-Tetrahydronaphthalenes /Tetralins) derivatives (only the HDT sample)

Naphthalene, 1,2,3,4-tetrahydro Tetralin 97.2
Naphthalene, 1,2,3,4-tetrahydro-2-methyl- 2-Methyl-tetralin 104.9
Naphthalene, 1,2,3,4-tetrahydro-1-methyl- 1-Methyl-tetralin 106.0
Naphthalene, 1,2,3,4-tetrahydro-5-methyl- 5-Methyl-tetralin 111.7
Naphthalene, 1,2,3,4-tetrahydro-1,4-dimethyl- 1,4-Dimethyl-tetralin 113.0
Naphthalene, 1,2,3,4-tetrahydro-6-methyl- 6-Methyl-tetralin 115.1
Naphthalene, 1,2,3,4-tetrahydro-1,8-dimethyl- 1,8-Dimethyl-tetralin 119.6
Naphthalene, 2-ethyl-1,2,3,4-tetrahydro- 2-Ethyl-tetralin 120.2
Naphthalene, 1,2,3,4-tetrahydro-2,6-dimethyl- 2,6-Dimethyl-tetralin 121.3
Naphthalene, 1,2,3,4-tetrahydro-2,7-dimethyl- 2,7-Dimethyl-tetralin 121.9
Naphthalene, 1,2,3,4-tetrahydro-1,5-dimethyl- 1,5-Dimethyl-tetraline 123.0
Naphthalene, 5-ethyl-1,2,3,4-tetrahydro- 5-Ethyl-tetralin 123.6
Naphthalene, 1,2,3,4-tetrahydro-1,1,6-trimethyl- 1,1,6-Trimethyl-tetralin 124.6
Naphthalene, 1,2,3,4-tetrahydro-1,4,6-trimethyl- 1,4,6-Trimethyl-tetralin 125.2
Naphthalene, 1,2,3,4-tetrahydro-5,7-dimethyl- 5,7-Dimethyl-tetralin 127.8
Naphthalene, 1,2,3,4-tetrahydro-5,6-dimethyl- 5,6-Dimethyl-tetralin 128.3
Naphthalene, 1,2,3,4-tetrahydro-1,5,7-trimethyl- 1,5,7-Trimethyl-tetralin 129.4
Naphthalene, 1,2,3,4-tetrahydro- 2,5,8-trimethyl- 2,5,8-Trimethyl-tetralin 133.5
A comparison between LCO samples 1 and 7 in Figure 4, shows some differences between LCOs. SIM
in the GC-MS technique demonstrated the presence of naphthalene derivatives. However, when using
the SCAN mode, tetralin derivatives could be observed.
7
Sample 1
2-Methyl-naphthalene

naphthalenes

Sample 7
Di-methyl-

6
Tri-methyl-naphthtalenes
1-Methyl-naphthalene

Tetra-methyl-
naphthalenes

4
Area, %

Mono-aromátics

i-C16
Naphthalene

C18

3
C19

C20
i-C19
i-C20

C21
C17

2
i-C21

C22
C23

0
50 70 90 110 130 150 170 190 210 230
Retention time, min
Figure4. Comparison of GC-MS chromatograms of LCO samples 1 and 7.

International Journal of Petroleum and Petrochemical Engineering Page | 7

Detailed Characterization of Light Cycle Oil for BTX Production Purposes

Table 4 shows the characterization of the LCO samples according the lump separation depicted before.
The presence of methyl-naphthalene (MN), di-methyl-naphthalene (DMN), tri-methyl-naphthalene
(TMN) and tetra-methyl-naphthalene (TTMN) derivatives in the LCO samples were from 4.3 to 10.0,
12.1 to 28.5, 13.8 to 20.3 and 10.1 to 14.8 wt.%, respectively. It is quite clear that, DMN and TMN
derivatives were predominant in almost all studied samples, being the percentages of the average ratios
11.6, 31.4, 32.5, and 23.5.
Table4. GC-MS characterization by lumps of LCO samples 1 to 8
LCO sample 1 2 3 4 5 6 7 8 Averaged

n-Alkanes, wt% 6.23 6.70 8.01 8.75 9.55 8.53 9.74 8.96 8.31
I-Alkanes, wt% 6.09 10.24 8.94 12.31 13.32 14.30 15.38 17.69 12.28
Benzene der. , wt% 9.48 24.54 12.85 20.47 16.89 28.00 21.08 13.04 18.29
Naphthalene, wt% 0.48 0.32 0.45 0.79 0.42 1.14 0.54 0.20 0.54
MN, wt% 8.26 9.99 6.47 6.74 4.39 5.11 4.33 4.86 6.27
DMN, wt% 28.46 14.90 19.06 16.30 18.24 13.74 12.15 14.94 17.22
TMN, wt% 20.31 13.79 16.41 17.28 16.74 16.95 18.06 19.94 17.44
TTMN, wt% 13.70 10.91 13.40 11.37 13.54 10.14 13.33 14.80 12.65
Phenanthrene der. ,
wt% 7.00 8.60 14.41 6.00 6.90 2.10 5.40 5.56 7.00
It is noteworthy to remember that heavily alkylated naphthalenes, phenanthrene derivatives and
aliphatic hydrocarbons are not suitable as feedstock for BTX production, and the presence of the tetra-
methylated aromatics are going to face difficulties during HYD for any upgrading purpose due to the
steric hindrance exerted by these groups. Furthermore, it has been reported [16, 26] that as the number
of methyl moieties attached to aromatic rings in naphthalene derivatives increases so does the difficulty
for their hydrogenation to tetralin derivatives. Therefore, presence of large amounts of highly branched
naphthalenes could affect the yield towards BTX fraction from a given LCO sample.
For the BTX production a term was defined as most suitable compounds for BTX production or MSCB,
by summing up benzene, mono-, di- and tri-methylnaphthalene derivatives. In Figure 5 the LCO
samples were ordered from the most to the least suitable.
80
More suitable compounds, wt%
Compounds less suitable, wt%
Chemical composition(GC-MS), wt%

70

60

50

40

30

20

10

0
1 6 2 4 5 7 3 8 Averaged
LCO Sample
Figure5. Chemical composition of various LCO samples by the GC-MS method, from the most to the least suitable
hydrocarbon type distribution for BTX production.
3.3. Characterization of the Fractionated LCO Sample 6 by ASTM Methods.
The results of some ASTM standards of the fractionated LCO sample 6 is shown on Table 5. Sulfur
compounds presented the usual bimodal distribution where benzothiophenes appeared before 300 °C
International Journal of Petroleum and Petrochemical Engineering Page | 8
Detailed Characterization of Light Cycle Oil for BTX Production Purposes

boiling point whereas dibenzothiophenes were identified after that temperature, as already disclosed in
previous publications [1]. The nitrogen compounds increased as the boiling point of the fraction [1].
Carbazole type compounds are expected to be the main nitrogen compounds present [1].
Table5. Characterization of the 20 °C-boiling point fractions of LCO sample 6 according to used ASTM methods
Boiling point interval 175- 195- 215- 235- 255- 275- 295- 315- >33
(°C) 195 215 235 255 275 295 315 335 5
Distillated amount AST
(wt.%) M 1.82 1.87 8.53 15.98 19.88 19.98 11.87 10.54 9.52
D429
Sulfur (wt%) 4 0.90 1.42 2.95 4.41 4.39 3.20 2.58 3.45 3.82
D462 145
Nitrogen (mg/kg) 9 138 179 139 189 351 343 199 522 1
Chemical composition D518
(wt.%) 3
Mono-aromatics 63.9 60.7 48.9 17.8 8.9 6.2 4.8 4.2 4.4
Di-aromatics 15.3 22.3 35.8 69.1 78.2 76.8 60.4 36.8 19.9
Tri-aromatics 0.1 0.2 0.3 1.5 2.1 4.6 18.7 40.1 50.5
Total aromatics 79.3 83.2 85.0 88.4 89.2 87.6 83.9 81.1 74.8
Aliphatic 20.7 16.8 15.0 11.6 10.8 12.4 16.1 18.9 25.2
The chemical composition obtained by using the ASTM D5186 followed the tendency reported
previously [1, 2]. As it was already discussed, both aliphatic and tri-aromatic hydrocarbons are not
desirable when intending to use LCO as feedstock for BTX petrochemicals production [24, 27] although
aliphatic hydrocarbons would be suitable for diesel [28]. Aliphatic compounds appeared all along the
boiling point intervals from 10.8 to 25.2 wt%. Clearly, higher heavy aliphatic concentration was
registered at the upper end of the distillation curve and mostly of them were long n-alkane hydrocarbons.
Tri-aromatics showed up in the 295-315 °C boiling point interval their amount increasing in heavier
fractions. Evidently, final boiling point temperature should be lower than 295 °C to eliminate that type
of compounds in each LCO sample.
3.4. Chemical Characterization of the Fractionated LCO Sample 6 by the GC-MS Method.
The chemical characterization of 20 °C-boiling point fractions from LCO sample 6 according to the
detailed GC-MS method previously described, is shown in Table 6 Phenanthrene (tri-aromatic)
derivatives appeared in very low concentration in the 275-295 °C fraction notably increasing their
amount in the subsequent heavier cuts. TTMN which did not show good reactivity towards
hydrogenation aiming to tetralin formation [16, 26], were the main components exactly in the 295-315 °C
fraction, and it is convenient to avoid them.
Table6. Characterization of the 20 °C-boiling point fractions of LCO sample 6 according to the detailed GC-MS
technique.
Boiling point interval 175- 195- 215- 235- 255- 275- 295- 315-
(°C) 195 215 235 255 275 295 315 335 >335
Distillation (wt.%) 1.82 1.87 8.53 15.98 19.88 19.98 11.87 10.54 9.52
16.8
n-Alkanes 8.60 6.17 6.82 4.52 8.55 6.07 5.50 9.55 8
iso-Alkanes 12.31 11.03 9.07 6.22 9.21 8.43 10.72 7.63 9.43
Benzene der. 62.21 65.50 40.52 6.54 0.00 0.00 0.04 0.00 0.00
Naphthalene 6.61 6.93 2.42 0.07 0.00 0.00 0.00 0.00 0.00
MN 5.83 6.04 31.04 7.50 43.76 0.00 0.00 0.00 0.00
DMN 3.63 4.10 10.05 73.76 37.96 8.27 0.00 0.00 0.00
TMN 0.59 0.18 0.06 1.33 0.34 57.30 16.36 1.16 0.00
13.1
TTMN 0.05 0.06 0.04 0.06 0.18 19.33 58.50 37.87 5
60.5
Phenanthrene der. 0.16 0.00 0.00 0.00 0.00 0.60 8.88 43.79 3
3.5. Practical Relations to Apply for Selecting a Suitable LCO Feedstock for Upgrading.
A better LCO for upgradeability purposes to BTX must possess a low value of FBP, to avoid highly
methylated naphthalene and phenanthrenes derivatives as is shown in Figure 6. The lowest the value of
International Journal of Petroleum and Petrochemical Engineering Page | 9
Detailed Characterization of Light Cycle Oil for BTX Production Purposes

the 90 vol% distillation boiling point was, the higher the more suitable hydrocarbons presence was. It
is convenient that the LCO presented a high API value (Figure 7). A rapid suitability analysis may be
carried out graphically after summing the mono- and di-aromatic compounds values obtained from the
ASTM D5186 test versus the most suitable compounds for BTX (MSCB) and calculate according to
Figure 8.
80

Useful aromatic compounds (GC-MS), wt%

70

60

50

40

30

20

10

0
270 280 290 300 310 320 330 340 350 360
90 vol% - Boiling Point,°C

Figure6. Effect of the 90 vol% distillation boiling point on the amount of the more suitable compounds for BTX
production.
80
Useful aromatic compounds (GC-MS), wt%

70

60

50

40

30

20

10

0
10 12 14 16 18 20 22 24 26 28
API

Figure7. Effect of the API on the amount of the more suitable compounds for BTX production

75
Useful aromatic compounds (GC-MS), wt%

70

65
y = 1.219x - 27.108
R² = 0.9412

60

55

50

45
60 65 70 75 80 85
Mono- + Di-aromatic compounds (SFC), wt.%

Figure8. Effect of the mono- + di-aromatic content on the amount of the more suitable compounds for BTX
production
International Journal of Petroleum and Petrochemical Engineering Page | 10
Detailed Characterization of Light Cycle Oil for BTX Production Purposes

4. CONCLUSION
A detailed chemical characterization of samples of LCO was presented. The method could be useful for
decision-making regarding the suitability of certain distillate as feedstock for valuable petrochemicals
(like benzene, toluene and xylene) production or gasoline. Detailed characterization allowed not just
the usual separation as mono-, di- and tri-aromatic compounds, obtained by the ASTM D5186 method
(supercritical fluid chromatography with flame ionization detection) but also provided information
regarding the complexity of the naphthalene derivatives (mono-, di-, tri- o tetra-methyl-naphthalenes)
which could have different reactivities during the hydrogenation-hydrocracking processes required
when aiming to valuable petrochemicals or diesel production.
By using the provided data, the amount of the more suitable compounds for upgrading to BTX (MSCB)
production was defined by summing up benzene, mono-, di- and tri-methylnaphthalene derivatives.
This value presented an inverse relation with 90 vol% boiling point and a direct relation with API. An
equation relating the amount of mono- and di-aromatic compounds obtained by ASTM D55186 with
the most suitable compounds for BTX (MSCB) value, is also provided.
ACKNOWLEDGEMENT
The authors are grateful for the financial support provided by Instituto Mexicano del Petróleo (IMP)
through the research project D.61065.
REFERENCES
[1] Laredo G.C., Leyva S., Álvarez R., Mares M.T., Castillo J., Cano J.L. Nitrogen compounds characterization
in atmospheric gas oil and light cycle oil from a blend of Mexican crudes. Fuel 81(10) 1341 (2002);
[2] Laredo G.C., Figueroa Y., Cano J.L., Mares M.T., Castillo J. Chemical composition of LCO obtained from
Mexican crudes. Rev. Soc. Quím. Mex., 46(2), 115 (2002).
[3] Norma Oficial Mexicana de Emergencia NOM-EM-005-CRE-2015, Especificaciones de calidad de los
petrolíferos. Diario Oficial de la Federación. 30/10/2015.
[4] https://www.epa.gov/diesel-fuel-standards/diesel-fuel-standards-rulemakings.
[5] Choi K.-H., Sano Y., Korai Y., Mochida I. An approach of deep desulfurization of light cycle oil. Appl.
Catal. B. 53 (4), 275 (2004).
[6] Laredo G.C., Saint-Martin R., Martinez M.C., Castillo J., Cano J.L. High quality diesel by hydrotreating of
atmospheric gas oil/light cycle oil blends. Fuel;83(10), 1381 (2004).
[7] Turaga U.T., Song C. MCM-41 support Co-Mo catalyst for deep hydrodesulfurization of light cycle oil.
Catal. Today; 6 (1-4), 129 (2003).
[8] Yao S., Zheng Y., Ding L., Ng S., Yang H. Co-promotion of fluorine and boron on NiMo/Al2O3 for
hydrotreating light cycle oil. Catal. Sci. Technol. 2(9),1925 (2012).
[9] Azizi N., Ali S.A., Alhooshani K., Kim T., Lee Y., Park J-I., Miyawaki J., Yoon S-H., Mochida I.
Hydrotreating of light cycle oil over NiMo and CoMo catalysts with different supports. Fuel Process.
Technol. 109, 172 (2013).
[10] Yun G-N., Lee Y-K. Dispersion effects on Ni2P catalysts on hydrotreating of light cycle oil. Appl. Catal. B.
150-151 (May), 647 (2014).
[11] http://www.mustangeng.com/NewsandIndustryEvents/Publications/Publications/MUSTANGPTQ.pdf.
[12] Lee C.K., McGovern S. J., Zagorsk J. A. Refiners have many options to convert high-aromatic streams into
ULSD. Oil & Gas J. (05/15/2006).
[13] Bisht D., Petri J. Considerations regarding light cycle oil upgrading with hydroprocessing technologies. Ind.
Chem. Eng. 56 (4), 321 (2014).
[14] Laredo G.C.; Perez Romo P., Escobar J., Garcia-Gutierrez J.L. Vega-Merino P. Light Cycle Oil Upgrading
to Benzene, Toluene and Xylenes by Hydrocracking: Studies Using Model Mixtures. Ind. Eng. Chem. Res.
56 (39), 10939 (2017).
[15] https://www.astm.org/.
[16] Choi Y., Lee J., Shin J., Lee S., Kim D., Lee J.K. Selective hydroconversion of naphthalenes into light
aromatics. Appl. Catal. 492 (Feb),140 (2015);
[17] Alonso D.E., Klitzke C. Blinkey J. Light and Middle Petroleum Distillate Characterization Using Two-
Dimensional Gas Chromatography–High-Resolution Time-of-Flight Mass Spectrometry and Enhanced
Software Processing. Spectrometry. 14 (1), 21 (2016).

International Journal of Petroleum and Petrochemical Engineering Page | 11

Detailed Characterization of Light Cycle Oil for BTX Production Purposes

[18] Vendeuvre C., Ruiz-Guerrero R., Bertoncini F., Duval L., Thiébaut D., Hennion M-Cl. Characterization of
middle-distillates by comprehensive two-dimensional gas chromatography (GC x GC): A powerful
alternative for performing various standard analysis of middle-distillates. J. Chromatogr. A,; 10861-2), 21
(2005).
[19] Ruiz-Guerrero R., Vendeuvre C., Thiébaut D., Bertoncini F., Espinat D. Comparison of comprehensive
two-dimensional gas chromatography coupled with sulfur chemiluminescence detector to standard methods
for speciation of sulfur-containing compounds in middle distillates. J. Chromatogr. Sci. 44(9), 566 (2006).
[20] Adam F., Thiébaut D., Bertoncini F., Mourtiade M., Hennion M-Cl., Supercritical fluid chromatography
hyphenated with twin comprehensive two-dimensional gas chromatography for ultimate analysis of middle
distillates. J Chromatogr. A, 1217 (8), 1386 (2010).
[21] Jennerwein M.K., Eschner M., Gröger Th., Wilharm Th., Zimmermann R. Complete group-type
quantification of petroleum middle distillates based on comprehensive two-dimensional gas chromatography
time-of-flight mass spectrometry (GCxGC-TOFMS) and visual basic scripting. Energy Fuels. 28 (9), 5670
(2014),
[22] Alvarez-Majmutov A., Gieleciak R., Chen J. Deriving the Molecular Composition of Vacuum Distillates by
Integrating Statistical Modeling and Detailed Hydrocarbon Characterization. Energy Fuels 29(12). 7931
(2015).
[23] EPA. 1998. “Method 8270D (SW-846): Semivolatile Organic Compounds by Gas Chromatography/ Mass
Spectrometry (GC/MS), Revision 4.
[24] Sahu R., Song B.J., Jeon Y-P., Lee C.W. A review of recent advances in catalytic hydrocracking of heavy
residues. J. Ind. Eng. Chem. 27(July), 12 (2015).
[25] Palos R., Gutiérrez A., Arandes J.M., Bilbao J. Upgrading of High-Density Polyethylene and Light Cycle
Oil Mixtures to Fuels via Hydroprocessing. Catal. Today 305 (May), 212 (2018).
[26] Kim Y.S., Yun G.N., Lee Y.K. Novel NiP/zeolite catalyst for hydrocracking of naphthalene to BTX. Chem.
Commun. 45(Feb), 133 (2014);
[27] Zhang D., Zhao J., Zhang Y., Lu X. Catalytic hydrogenation of phenanthrene over NiMo/Al 2O3 catalysts as
hydrogen storage intermediate. Int. J. Hydrogen Energ. 41 (27), 11675 (2016);
[28] Stanislaus A., Marafi A., Rana MS. Recent advances in the science and technology of ultra low sulfur diesel
(ULSD) production. Catal. Today 153 (1-2), 1 (2010).

Citation: Georgina C. Laredo, et.al, “Detailed Characterization of Light Cycle Oil for BTX Production
Purposes”, International Journal of Forestry and Horticulture, 6(3), pp. 1-12. DOI: https://
doi.org/10.20431/2454-7980.0603001
Copyright: © 2020 Authors, this is an open-access article distributed under the terms of the Creative
Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium,
provided the original author and source are credited.

International Journal of Petroleum and Petrochemical Engineering Page | 12