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Characterization of Indian origin oil shale using advanced analytical

techniques
Ravindra Kumar

, Veena Bansal, R.M. Badhe, Indu Sekhara Sastry Madhira, Vatsala Sugumaran,
Saeed Ahmed, Jayaraj Christopher, Mitra Bhanu Patel, Biswajit Basu
Indian Oil Corporation Limited, Research & Development Centre, Sector-13, Faridabad 121 007, Haryana, India
h i g h l i g h t s
v The paper highlights the detailed characterization of Indian origin oil shale.
v There is no work reported on detail characterization of Indian origin shale oil.
v The ICAP and XRD identify the metals and minerals in oil shale.
v The IR, NMR and MS give the information regarding hydrocarbons and structural parameters.
v Indian origin shale oil is carbon rich in nature and contains a signicant component of aromatics.
a r t i c l e i n f o
Article history:
Received 5 January 2013
Received in revised form 4 May 2013
Accepted 17 May 2013
Available online 4 June 2013
Keywords:
Oil shale
Metal analysis
Hydrocarbon analysis
Analytical techniques
a b s t r a c t
The paper highlights the detailed characterization of Indian origin oil shale using various analytical tech-
niques viz., Elemental analysis, Induced Coupled Argon Plasma (ICAP), X-ray Diffraction (XRD), Gas Chro-
matography (GC), Infrared spectroscopy (IR), Nuclear Magnetic Resonance (NMR) spectroscopy and High
Resolution Mass Spectrometry (HRMS). The study also focused on the molecular characterization of two
shale oil samples obtained by retorting method from oil shales. A method based on NMR spectroscopy
has been developed for the estimation of total aromatics, types of aromatic substituents and average
alkyl chain length of saturates in shale oil samples. Detailed hydrocarbon type analysis in terms of 22
classes has been carried out by HRMS. The results of aromatics obtained by the
1
H NMR method, corre-
lated with HRMS data. The detailed analyses of Indian origin oil shale provide in depth structural infor-
mation regarding the metals, minerals and hydrocarbons.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
Oil shale is a natural, impermeable, ne-grained, laminated
black or brown combustible material, and it consists of complex
organic material of high molecular weight called kerogen which
is nely distributed in an inorganic matrix [1]. As a kind of fossil
fuel similar to coal, oil shale has a higher mineral content. It is be-
lieved that the minerals in oil shale will affect the reaction of or-
ganic matter physically and chemically [2,3]. In the western
United States, large oil shale deposits exist in Colorado, Utah, and
Wyoming [4] and have been considered for utilization during peri-
ods of high crude oil prices. Patterson [5] did substantial research
on Australian oil shale from different deposits. Their main focus
was on the mineralogy of Australian oil shale and its effect on oil
shale retorting. Jabber et al. [6] described about Jordan oil shale
from different deposits and compared with Colorado oil shale.
According to Jabber et al. Jordan organic matter (shale oil) contains
8.510.3% of sulfur. Oil shales have been divided into three catego-
ries based on mineral composition carbonate-rich shale, siliceous
shale and cannel shale. Carbonate-rich shales derive their name
from the large amount of carbonate minerals such as calcite and
dolomite. Siliceous oil shales are usually dark brown or black
shales. Siliceous oil shales are not rich in carbonates but rather in
siliceous minerals such as quartz, feldspar, clay, chert and opal.
Cannel shales are usually dark brown or black shales, which consist
of organic matter that completely encloses other mineral grains
[7]. Wang et al. [8] identify the mineral composition of oil shale
from different locations and relate it to their interval of occurrence.
The physical and chemical compositions of shale oil, a complex
mixture of hydrocarbons, depend on the source of the raw shale
and the type of processes used to obtain the oil. It is well-known
that liquid products from petroleum, oil shale and coal are difcult
to characterize in terms of chemical structure, as they consist of
large numbers of structurally diverse compounds. Basically, shale
oils differ from petroleum primarily in that they have higher
0016-2361/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2013.05.055

Corresponding author. Tel.: +91 1292294235.


E-mail address: kumarr88@indianoil.in (R. Kumar).
Fuel 113 (2013) 610616
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nitrogen content and as shale oils are produced by pyrolysis, they
also contain some concentrations of olens, which are generally
found in natural crude oils in low concentrations. Shale oil rich
in alkanes, cyclanes, arenes, as well as nitrogen-, sulfur-, and oxy-
gen-containing non-hydrocarbons; Hence, it is hard to analyze
oxygen compounds in question without pretreatment of oils. Ear-
lier traditional methods such as column chromatography and also
distillation were used for the component analysis of oils. With the
development of chromatographic separation methods, the molecu-
lar constitutions of shale oil and coal tar were gradually
established. Zhu [9] separated two kinds of shale oils from moun-
tainous area (land) and coastal shelf rock (sea), both China, into
four fractions using silica gel column chromatography. The compo-
nents of each fraction were identied by GCMS. The results show
that shale oil from land contains 269 compounds, with abundant
hydrocarbon compounds (79%), and some sulfur, oxygen and nitro-
gen compounds. Shale oil from sea rocks contains 284 compounds
with a high amount of hydrocarbon and oxygen compounds (60%
and 29%, respectively), and some sulfur and nitrogen compounds.
Guo and Ruan [10] analyzed by GCMS shale oils from Fushun
oil shale of Liaoning province and Maoming oil shale of Guangdong
province, both China. The main oxygen-containing compounds
identied are phenols, diphenols, 2-, 3- and 4-alkanones, furans
and benzofurans. Among the oxygen compounds, phenols consti-
tute 78 wt% of oil (<350 C), the next most abundant being ke-
tones. Bae et al. [11] compared the molecular compositions of
two shale oils of oil shales from US Western and Russian mines,
using 15 T FT-ICR MS coupled with ESI, and atmospheric pressure
photoionization (APPI). Geng et al. [12] was performed, a compre-
hensive compositional analysis of the oxygen containing com-
pounds present in shale oil and low temperature coal tar using
FT-ICR MS and GCMS. Due to the presence of these components,
shale oils are relatively thermally unstable [13], have poor long-
term storage stability and require modications of the analytical
methods used for petroleum characterization.
Estimation of oil shale reserves in India is greater than 15 billion
tons. North-East India is endowed with rich deposits of coal, found
in the Barail formation of tertiary age. Carbonaceous shale occurs
interblended with the coal. The presence of coal and shale has been
recorded in wells drilled for hydrocarbons by Indian companies.
These formations outcrop on the surface towards the south of
the oil elds in a region called the Belt of Schuppen. Studies have
indicated that this oil shale constitute the principal source rocks
that have generated the hydrocarbons produced from the region.
There is no work reported on detailed characterization of Indian
origin oil shale.
The present work discusses in-depth characterization of Indian
origin oil shale using analytical techniques such as CHNS analyzer,
Induced Coupled Argon Plasma (ICAP), Gas Chromatography (GC),
Infrared spectroscopy (IR), Nuclear Magnetic Resonance (NMR)
spectroscopy and High Resolution Mass Spectrometry (HRMS).
The study also focused on the molecular characterization of two
shale oil samples obtained by retorting method from Indian origin
oil shale.
2. Experimental
2.1. Samples
Oil shale samples S1S7 were obtained from Upper Assam Oil
shale deposits and S8S10 from neighboring area in Arunachal Pra-
desh shale deposits. Indian origin oil shales were dark brown or
black in color. Shale oil samples are obtained by retorting method
from oil shale S-7 and S-10. Retorting of oil shale has been carried
out at -500550 C in Retorter pilot plant using CO
2
as sweep gas.
Shale oil samples were obtained by condensing the oil vapors
downstream of the retorter.
2.2. CHNS Analysis
Oil shale and shale oil samples were analyzed by CHNS analyzer
Vario EL-III from M/s Elementar, Germany as per ASTM D 5291
method.
2.3. ICAP Analysis
The ICAP spectrometer used in this study was radial viewing
Optima 5300V from Perkin Elmer, USA. Deionized water of Milli-
pore quality and Suprapure grades of hydrochloric acid, hydrou-
oric acid, AR grade of perchloric acid and multi-element
standards in water matrix from E. Merck (Germany) were used
throughout this analytical work.
2.3.1. Sample and blank preparation
Sample (-0.5 g) was taken in platinum dish and ashed at 650 C
in mufe furnace to remove carbonaceous matter prior to the acid
digestion. To this, 10 ml each of hydrouoric acid and perchloric
acid were added and the contents were heated on hot plate till dry-
ness to remove silica. To the residue obtained, 20 ml of hydrochlo-
ric acid was used to get it dissolved. The solution was transferred
to 100 ml volumetric ask and made up to 100 ml with water.
Blank solution was also prepared by following exactly the same
procedure as for the sample.
In order to maintain the same acid concentration, stock solution
of multi-element standard (100 ppm) was diluted with blank to
prepare 1, 5 and 10 ppm standard solutions. The peaking of ICAP
spectrometer was performed with Mn line (257.61 nm) to cover
all the elements.
2.3.2. Calibration and analysis
After spectral lines alignment using 10 ppm standard to cover
all the elements, ICAP was calibrated using blank and 1, 5 and
10 ppm standard solutions. Blank subtraction mode was used for
the sample analysis for all analytes.
2.4. X-ray diffraction (XRD)
XRD studies were carried out in an 18 KW X-ray diffractometer
(Rigaku, Japan). XRD patterns were recorded at 50 kV and 250 mA,
at a scan rate of 1/min with a step size of 0.01 in the temperature
range of 275 2-Theta. XRD patterns were processed for smooth-
en, determination of inter-planner distance (d) of observed peaks
and search match was conducted by using search match softwares
to nd out different compounds present in the sample.
2.5. IR Analysis
IR spectra of the oil shale samples are recorded on PerkinElmer
BX-II FT-IR instrument. Known weight (-2 mg) of the sample is
mixed with 100 mg KBr and KBr pellet is prepared using the entire
sample under 58 kg pressure employing a Hydraulic Press. The IR
Spectrumof the KBr pellet is recorded at 4 cm
1
resolution and 100
scans were collected. The IR spectra were corrected for baseline
correction and smoothed to remove the noise and then analyzed
for the presence of organic and inorganic moieties.
2.6. Open-column chromatography
The shale oil samples were fractionated into saturate and aro-
matic fractions as per the ASTM-2549/91 (reapproved 1995)
method.
R. Kumar et al. / Fuel 113 (2013) 610616 611
2.7. NMR Spectroscopic analysis
The
1
H/
13
C NMR spectra were recorded on a Bruker ACP-
300 MHz NMR spectrometer.
1
H,
13
C, Distortion Enhancement
Polarization Transfer (DEPT-135) and Heteronuclear Single Quan-
tum Coherence (HSQC) experiments were carried out using the
pulse sequence of as per the experimental conditions described
in our previous work [14].
2.8. MS Analysis
Samples of shale oil were subjected to high resolution mass
spectrometry using Auto Spec Ultima HRGCMS instrument. Ioni-
zation was carried out at 70 eV electron ionization (EI). The mass
spectrometer was set at 6000 resolution for detailed analysis of
22 classes of hydrocarbon.
3. Results and discussion
3.1. Oil shale analysis
3.1.1. Elemental and metal analysis
The elemental and metal analysis data of all oil shale samples
studied are given in Tables 1 and 2 respectively. The elemental
analysis shows the presence of carbon (625%), hydrogen (0.6
2.5%), nitrogen (0.081.5% and sulfur (211%). The elemental com-
position of an oil shale can be correlated with oil yields [15].
The organic carbon content is a good indicator of the quality of
organic matter in the oil shale. Indian origin oil shale contains low
concentration of carbonates and bicarbonates which are conrmed
by ICAP, calcium (0.070.2%) and XRD. The comparison of XRD pat-
tern of oil shale samples with XRD pattern of standard CaCO
3
con-
rmed the low concentration of carbonate minerals in all the
samples. Indian origin oil shale is siliceous in nature and found
to contain siliceous minerals such as quartz and clay. Other major
deposits of world oil shale viz., Kukersite (Estonia), Jurf ed Dara-
wish and the Sultani deposits (Jordan) [6] and Colorado, Utah,
and Wyoming (United States of America) [4] are carbonaceous in
nature. Due to the presence of very low concentration of carbon-
ates, it is conrmed that carbon (625%) in Indian origin shale is
organic in nature. The samples are found to contain aluminum
(27% range), ferrous (1.89% range), calcium (0.070.2%), sodium
(0.11.05%) and potassium (0.41.23%) as major metals. A correla-
tion among the iron content of the samples with sulfur content is
observed, indicating the presence of iron sulde type component
in all the samples.
3.1.2. X-ray diffraction (XRD)
XRD is one of the techniques normally used for characteriza-
tion of shale [1618]. A labeled XRD pattern of representative
Indian origin oil shale sample is shown in Fig. 1. The XRD spec-
tra are recorded using high power 12.5 kW, because at high
power even though the crystalline compounds present at low
concentration level can give visible diffraction peaks in XRD pat-
tern and there will no doubt to distinguish between peak and
noise. From the XRD spectrum the most probable crystalline
compounds present in the samples are obtained by the search
match programme, which is based on inter-planner distances
(D) and intensity of peak (I) value. There are many compounds
having the same D value and search match programme will
not able to pin point the compound and give number com-
pounds with matching index. XRD analysis showed the presence
of both crystalline and amorphous phase in all the samples.
Based on the search match analysis, the crystalline components
were identied as quartz (SiO
2
) along with kaolin clay (Al
2
SiO
5
(-
OH)
4
), Illite and pyrite (FeS
2
). The XRD pattern shown in this pa-
per are smoothened one which clearly distinguishes noise from
peaks of kaolin and pyrite as evidenced from clear peaks of at
(2h) degree, 12.3, 20.3, 24.8 for kaolin and 33.1, 37.1, 40.8,
47.4 for pyrite. The intensity of these components was found
to be different in all these samples indicating that % weight of
these components varies from sample to sample. However, in
all these samples Quartz was found to be the major component.
XRD analysis also indicated presence of small amounts of oxides
of Iron in all these samples. XRD analysis indicated that SiO
2
was high in S-3 while low in sample S-9. Clay was high in sam-
ple S-2 and low in S-7. Hydrotalcite (magnesium aluminum hy-
droxy carbonate) was found in few of the samples (S-2, 4, 9 and
10) while this phase was absent in S-1, 3 and 8. XRD spectrum
showed a broad weak hump in the two theta range 2030,
which indicates the presence amorphous material in oil shale.
Generally, in XRD even for 100% material amorphous material
it gives broad weak diffraction peak, in two theta range 20
30. Therefore, the weak diffraction observed in the present
samples may be due to shale oil present in the oil shale, which
is amorphous in nature.
3.1.3. IR Spectral analysis
The IR spectrum of Indian origin shale is shown in Fig. 2, which
comprises aliphatic and aromatic stretching and bending vibra-
tions from kerogen overlapped with contributions from the miner-
als present, in particular silica and clay materials. IR spectra of all
the samples indicate the presence of various sharp hydroxyl bands
in 37003600 cm
1
region (3693, 3676.1, 3651.2, 3620,
3398 cm
1
) along with hydrocarbon bands in 30002700 cm
1
re-
gion. A sharp band at 3697 cm
1
has been attributed to OH of
kaolinite, the sharp band at 3625 cm
1
arises from illite in the oil
shale [19]. The broad OH band at 3380 cm
1
is also attributed
to kaolinite, with possible contribution from moisture in the oil
shale, absorbed during sample preparation. The broad OH band
obscures aromatic CH vibrations, expected around 3030 cm
1
.
Aliphatic hydrocarbon stretching bands are observed at
2930 cm
1
(m
as
CH
2
) and (m
s
CH
2
) [20]. A small peak observed at
1865 cm
1
is most likely an overtone or combination band of the
silicate mineral fundamental. A shoulder observed at 1710 cm
1
,
due to carboxylic acids in kerogen, is not completely resolved as
a strong band at 1640 cm
1
(aromatic and olenic carboncarbon
double bond) overlaps. The broad band at 1460 cm
1
arises from
methyl and methylene deformation modes, with overlap from car-
bonate minerals, if present. The three unresolved bands at 1190,
1160 and 1105 cm
1
are characteristic of pyrite. The bands in the
region 1000450 cm
1
are due to clay and minerals in the oil shale
and silica, with characteristic silicate vibrations occurring at 537
and 470 cm
1
. The band at 2930 cm
1
is associated with aliphatic
hydrocarbons present in the sample and is assumed to be corre-
lated with the samples kerogen content [21]. IR Spectral analysis
of the sample as such indicates the presence of inorganic materials
such as silica, and clay (Kaolin Clay Al
2
O
3
2SiO
2
2H
2
O) as major
constituents.
Table 1
CHNS data of oil shale samples (wt%).
Sample Carbon (%) Hydrogen (%) Nitrogen (%) Sulfur (%)
S-1 6.1 1.2 0.08 2.3
S-2 14.0 1.9 0.4 2.2
S-3 8.6 1.4 0.4 2.2
S-6 15.4 2.0 1.5 3.6
S-7 11.5 1.7 0.6 4.9
S-8 16.7 2.1 0.6 10.3
S-9 22.9 2.7 1.0 2.4
S-10 17.2 2.1 0.8 4.6
612 R. Kumar et al. / Fuel 113 (2013) 610616
3.2. Molecular characterization of shale oil
3.2.1. Elemental analysis of shale oil
Two shale oil samples were obtained by retorting method from
oil shale S-7 and S-10. The elemental composition of shale oil 7
and 10, given in Table 3 showing H/C ratio as 0.123 and 0.124
respectively, indicating that the Indian origin shale oil is carbon
rich in nature and contains a signicant amount of aromatics.
The main characteristics of the organic matter of oil shale are high
hydrogen and a low nitrogen percentage. Oil shale organic matter
contains on average 2.1% of organic sulfur (Table 3). The sulfur con-
tent of the Indian origin shale oil is low (1.92.3 wt%), whereas
deposits of Jordanian oil shale ranges from 0.3% to 4.3%. The sulfur
content of shale oil from the Jurf ed Darawish and the Sultani
deposits (Jordanian) is high (810%) [6] compared to Indian origin
shale oils. One of the combustible components of oil shale is pyrite
with the general chemical formula FeS
2
. The sum of organic and
pyretic sulfur is called combustible or volatile sulfur: The elemen-
tal composition and chemical nature (H/C ratio and hydrocarbon),
of Indian origin shale oil is similar to Estonian (Kukersite) shale oil
[22].
3.2.2. Estimation of total aromatic content by
1
H NMR method
Estimation of the total aromatic content in the Indian origin
shale oil sample using a
1
H NMR spectrum is based on the group
molecular weight method and the determination of the relative
number of carbon atoms. The philosophy of the group molecular
weight method is to rst assign the
1
H NMR spectrum in terms
of CH
n
groups (n = 1, 2, and 3) in order to calculate the relative
number of carbon atoms. The latter part requires estimation of
the quaternary carbons and the average chain length of the substit-
uents attached to aromatic rings.
1
H NMR spectrum of a represen-
tative Indian origin shale oil sample is shown in Fig. 3. Various
resonance signals assigned to different groups have been marked
in the spectrum. The complete assignment of the
1
H NMR spec-
trumin terms of various hydrocarbon groups is included in Table 4.
The assignments with regard to a-CH
n
(n = 13) have been
made by the application of 2D HSQC and 13C-DEPT-135 NMR
experiments.
Shale oil samples are rich in aromatics; especially, the di-ring
plus aromatics are present in an appreciable amount. The degree
of substituents (r) and the chain length of the alkyl substituents
on the aromatics depend on the boiling range of the sample. The
total aromatic content, therefore, will be the contribution of the
ring and the substituents. Knowledge about the average chain
length attached to aromatics (other than a-methyl groups) de-
noted as n is a must for estimation of the total aromatics using
Table 2
Metal analysis data of oil shale samples (in%).
Sample Al Ca Cr
a
Fe Mg Na Ni
a
V
a
K Zn
a
Ti
a
S-1 4.57 0.10 53 2.24 0.14 0.27 97 <50 0.81 112 55
S-2 3.67 0.14 57 3.19 0.48 0.14 81 56 0.91 60 154
S-3 3.68 0.04 53 2.85 0.14 0.18 <50 <50 0.69 <50 108
S-6 4.21 0.19 79 2.68 0.13 0.11 99 56 0.92 84 183
S-7 4.67 0.11 63 5.32 0.23 0.16 120 52 0.93 82 137
S-8 2.02 0.07 <50 9.06 0.27 0.18 115 72 0.47 83 109
S-9 5.07 0.10 103 1.76 0.25 0.13 186 106 0.67 82 283
S-10 3.78 0.10 74 4.35 0.12 0.13 86 75 0.63 64 155
a
Values in ppm.
Table 3
Hydrocarbon type analysis and CHNS data of Indian origin shale oils.
% w/w wt%
Sample Aromatics by NMR Saturates by NMR Aromatics by MS Saturates by MS C H N S O
Oil-1 85.1 14.9 77.8 22.0 82.0 10.1 0.54 1.9 5.46
Oil-2 72.0 28.0 73.0 27.0 81.4 10.1 0.42 2.33 5.75
Fig. 1. Representative XRD pattern of Indian origin oil shale sample.
4000 3500 3000 2500 2000 1500 1000 500
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3698
3620
2924
1638
1031
912
796
694
537
476
A
b
s
o
r
b
a
n
c
e

Wavenumber (cm
-1
)
Fig. 2. Representative IR Spectrum of oil shale sample.
R. Kumar et al. / Fuel 113 (2013) 610616 613
the present methodology. The nature and average length of the al-
kyl substituents greater than CH
3
groups cannot be estimated di-
rectly, as their signals are merged with the signals of parafns
(0.52.0 ppm) in
1
H NMR spectra. Besides this, knowledge about
the contribution of substituted aromatic ring (ARs) and bridge-
head aromatic carbons (ARb) is also required. However, these car-
bons cannot be estimated directly from a
1
H NMR spectrum be-
cause they are non-protonated and not appear in
1
H NMR
spectrum.
In the present method, an indirect approach has been adopted
to obtain information about the parameters: ARs, ARb, and n.
The relative ARs carbons have been realized from the signals in
the region 2.04.0 ppm assigned to a-CH
3
and a-CH
2
groups. ARb
carbons have been realized by the developed equations. An average
value of n has been estimated from the
1
H NMR spectral analysis
of the pure aromatic fractions collected from open-column chro-
matographic separation of a shale oil sample. After the complete
assignment of the
1
H NMR spectrum has been made and the rela-
tive contribution of ARs and ARb has been realized, the total aro-
matic content of a sample can be estimated by the following
equations.
Tc = A=1 B=2 C=3 D=1:25 E=2 F=3 ARs=1
ARb=1 (1)
Tw = 13(A B) 9C 13:25D=1:25 7E 5F 12 0:7Id (2)
Aw = 13A n 7B 5C 12ARs 12Arb (3)
where Tc, Tw, Aw, and n are the relative total carbons, total group
molecular weight of the sample, total group molecular weight of
aromatics, and average alkyl chain length of the alkyl substituents
(other than methyl groups) on the aromatic rings.
The total aromatic content (A) of the sample (weight %) can then
be estimated as
A = 100[Aw=Tw[ (4)
The total aromatic content for the shale oil samples have been
estimated from the developed equation and the data are given in
Table 3.
3.2.2.1. 2D HSQC. Protoncarbon chemical shift correlation exper-
iments (HSQC) provide both carbon and proton chemical shifts at
the same time and establish a one-to-one correspondence for each
pair of directly bonded carbon and hydrogen atoms. Fig. 4 shows
the HSQC contour spectrum of the shale oil sample. The 2D HSQC
heteronuclear correlation NMR spectra analysis has resolved the
complexity of the region 2.04.0 ppm of the
1
H NMR spectra and
provided useful and reliable information regarding the identity of
the a-CH
n
(n = 13) group. Thus, the regions of 2.052.65 and
2.654.0 ppm in the
1
H NMR spectra are used for the estimation
of a-CH
3
and a-CH
2
groups, respectively.
3.2.2.2. Estimation of substituted aromatic ring carbons (ARs). On the
basis of the above discussion, the substituted carbons can be esti-
mated by the following equation:
ARs = B=2 C=3 (5)
where B and C are integral areas as shown in Fig. 3.
Fig. 3. 300 MHz
1
H NMR spectrum of shale oil 1.
Table 4
Divisions of
1
H NMR spectrum of Indian origin shale oil (for measuring integral
intensity as per Fig. 1).
Region
(ppm)
Assignment Integral
intensity
9.06.5 CH of aromatics rings A
4.02.65 a-CH
2
to aromatic rings B
2.652.00 a-CH
3
to aromatic rings C
2.001.40 CH, CH
2
of naphthenes, and iso-parafns
(average CH
1.25
groups)
D
1.01.4 CH
2
E
0.51.0 CH
3
F
4.56.5 CH of olens
7.49.0 di-plus aromatic rings Id
614 R. Kumar et al. / Fuel 113 (2013) 610616
3.2.2.3. Contribution of bridge-head carbons (ARb). The contribution
of bridge-head carbons is required to be known, in samples where
polyaromatics are also present (7.49.0 ppm region). The following
equation will be applicable for feed samples also, where apprecia-
ble amounts of di-plus aromatics are present as discussed in our
earlier work [14].
ARb = 0:7Id (6)
where Id is the integral intensity of the signals in the region 7.4
9.0 ppm.
3.2.3. Determination of average alkyl chain length (n)
The value of n is required to be known in order to realize the
contribution of longer alkyl chains (b, c, and d carbons) attached to
aromatic rings whose signals overlap with those of parafn chains
in the region 0.52.0 ppm. The average alkyl chain length (n) of
aromatic ring substituents (other than a-CH
3
) has been estimated
from the
1
H NMR spectral analysis of pure aromatic fractions of
two samples separated by silica gel column chromatography. The
value of n has been calculated using the following equation:
n = [(I
4:02:65
=2) (I
2:01:0
=2) (I
1:00:5
=3)[=(I
4:02:65
=2) (7)
The a-CH
3
groups have been excluded as their contribution can
be directly realized from the integral intensity of the region 2.05
2.65 ppm. The average value of n has been estimated to be 3.0 in
both shale oil samples. The value of n has also been estimated
according Cantor [23], which is also found to be same.
3.2.4. Structural characterization of aromatics by NMR
The total aromatic carbon (Ca) has been estimated from
13
C
NMR spectral analysis as per the equation given below:
Ca = 100(I
120:0160:0
=I
T
) (8)
where I
120.0160.0
and I
T
correspond to the integral intensities of the
aromatic region and the total integral intensity in the region 5
160 ppm.
Cs = 100 Ca (9)
The Ca content has been found to be 42.1% w/w and 39.7% w/w
in shale oil S-7 and shale oil S-10 respectively; whereas in column-
separated aromatic fractions of shale oil S-7, Ca has been estimated
56.4% w/w. Other structural parameters estimated by NMR spec-
troscopy are given in Table 5.
3.2.5. MS Analysis of shale oil
Detailed hydrocarbon type analysis in terms of hydrocarbon
(HC 22) classes was carried out by HRMS, The details of HC 22 clas-
ses for both shale oils are given in Table 6. The results conrm the
high aromatic nature of Indian origin shale oils. The analysis
indicate that the nature of aromatics are naphthalenes (16.0
18.8% w/w) and acenaphthylenes (8.112.4% w/w) type in majorly
and sulfur compounds are found to be 13.4% w/w and 16.9% w/w in
shale oil S-7 and S-10 respectively. Saturates are found to contain
parafns and naphthenes approximately in equal amount in both
samples. There is a good correlation between the
1
H NMR and
MS methods (Table 3) for aromatics. The MS data show the differ-
ence in saturates due to presence of olens, which is conrmed by
1
H NMR spectroscopy. IR and
13
C NMR analysis conrmed the pres-
ence of small amounts of carboxylic acids, amides and carbonate
moieties also in both shale oil samples.
4. Conclusions
The detailed analyses of Indian origin oil shale provide in depth
structural information regarding the metals, minerals and hydro-
carbons. The ICAP and XRD identify the metals and minerals in
oil shale. Indian origin oil shale is siliceous in nature and found
Fig. 4. 2D-HSQC contour plot of the shale oil 1.
Table 5
Structural parameters by NMR spectroscopy.
Sample n Deg. of sub. ARs ARb Ca
Oil-1 2.8 63.1 9.3 3.2 42.1
Oil-2 3.2 52.2 9.3 3.6 39.7
n = Average alkyl chain length on aromatics, ARs = Substituted aromatic ring
carbons.
ARb = Contribution of bridge-head carbons, Ca = aromatic carbon.
Table 6
Mass spectrometry analysis HC 22 classes.
Hydrocarbon Classes (% w/w) Oil-1 Oil-2 Hydrocarbon classes (% w/w) Oil-1 Oil-2
Parafns 11.0 8.2 Naphthalenes 16.0 18.8
Monocycloparafns 4.8 4.5 Acenaphenes, biphenyls 8.2 5.0
Dicycloparafns 2.9 4.7 Acenaphthylenes, uorenes 12.4 8.1
Tricycloparafns 3.5 6.1 Phenanthrenes 5.6 4.4
Tetracycloparafns 0.0 2.3 Pyrenes 3.6 2.8
Pentacycloparafns 0.0 1.2 Chrysenes 0.3 0.8
Hexacycloparafns 0.0 0.0 Benzopyrenes 0.0 0.0
Heptacycloparafns 0.0 0.0 Aromatics 64.3 56.0
Saturates 22.2 27.0 Thiophenes 1.0 1.7
Alkylbenzenes 7.6 6.1 Benzothiophenes 9.2 10.5
Benzocycloparafns 4.6 3.0 Dibenzothiophenes 3.2 4.7
Benzodicycloparafns 5.8 7.0 Naphthobenzothiophenes 0.0 0.0
Sulfur compounds 13.4 16.9
R. Kumar et al. / Fuel 113 (2013) 610616 615
to contain siliceous minerals such as quartz and clay. The elemen-
tal composition and chemical nature of Indian origin shale oil is
similar to Estonian (Kukersite) shale oil which is potential shale
oil producers in the world. The main characteristics of the organic
matter of Indian origin oil shales are high hydrogen and a low
nitrogen percentage. Oil shale organic matter contains on average
2.1% of organic sulfur. There is no work reported on detailed
molecular characterization of Indian origin oil shale. The results
obtained in this study suggest that the Indian origin shale oil is car-
bon rich in nature and contains a signicant component of aromat-
ics. Even though the oil yields are lower comparative to other
known oil shales. The IR, NMR and MS spectroscopy give the infor-
mation regarding hydrocarbons and structural parameters. The
structural parameters can be used for the prediction of product
proles and their physico-chemical properties.
Acknowledgments
The authors wish to acknowledge the Management of IOC, R&D
Faridabad, for allowing them to publish the present work.
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