Fuel 126 (2014) 109115

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Fuel
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Production and characterization of pyrolytic oil by catalytic pyrolysis

of Niger seed
Krushna Prasad Shadangi, Kaustubha Mohanty
Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati 781039, India

h i g h l i g h t s
 Pyrolysis of Niger seed was investigated with and without the presence of catalyst.
 The yield of oil during thermal and catalytic pyrolysis was more or less similar.
 Kaolin at 8:1 ratio was more suitable to enhance caloric value of pyrolytic oil.
 CaO at 8:1 ratio was able to reduce the viscosity of pyrolytic oil.
 Pyrolytic oil contains both saturated and unsaturated hydrocarbon compounds.

a r t i c l e

i n f o

Article history:
Received 7 January 2014
Received in revised form 14 February 2014
Accepted 18 February 2014
Available online 3 March 2014
Keywords:
Bio-oil
Catalytic pyrolysis
Fuel characteristics
Niger seed
Thermal pyrolysis

a b s t r a c t
Conventional pyrolysis of Niger seed was investigated in a semi batch reactor with and without the presence of catalyst. Thermal pyrolysis yielded maximum 34.5% of oil (by weight basis) at 550 C temperature. The catalytic pyrolysis was carried out using catalysts Al2O3, CaO and Kaolin at 2:1, 4:1 and 8:1
feed to catalyst ratio at this temperature. The yield and fuel properties of thermal and catalytic pyrolytic
oils were compared. The results conrmed that the presence of catalysts decreased the oil yield marginally whereas enhanced the fuel properties compared with thermal pyrolysis. It was observed that the
three catalysts had different effect on the fuel properties of pyrolytic oils. Among the three different feed
to catalyst ratios used, 8:1 resulted in higher oil yield and thus the fuel properties were evaluated at this
ratio. Kaolin at 8:1 ratio was more suitable to enhance caloric value whereas CaO at 8:1 ratio was able to
reduce the viscosity of pyrolytic oil. The FTIR and DSC analysis conrmed that pyrolytic oil was a mixture
of saturated and unsaturated hydrocarbon compounds.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
The Niger seed (Hyoscyamus niger L.) is one of the non-edible oil
seed available in huge quantity in India and African Countries. Inga,
Ramtil, Black seed and Henban seed are the additional names of
Niger seed. In general, the seed is used as a feed for birds. The tree
grows in waste area, sandy area, road-sides, on rubbish heaps and
near old buildings, old herb gardens and particularly near the
coastal areas. These seeds bear high oil content and wealthy in
protein and other nutrition. The plant owers in July and the seed
are collected in the month of August [1]. Due to more oil content
(3540%) the seeds can be used as a source for the production of
alternative fuel by different biomass conversion methods. Pyrolysis

Corresponding author. Tel.: +91 361 2582267; fax: +91 361 2582291.
E-mail address: kmohanty@iitg.ernet.in (K. Mohanty).
http://dx.doi.org/10.1016/j.fuel.2014.02.035
0016-2361/ 2014 Elsevier Ltd. All rights reserved.

is one of the alternative thermo-chemical processes used to

convert biomass in to bio-fuels in the form of solid, liquid and gaseous products. Among the three forms of fuel, the pyrolytic liquid
is gaining a lot of attention due to its inherent advantages than
other fuels. The organic rich phase of the pyrolytic liquid is known
as pyrolytic oil or bio-oil. Literatures reveal that non-edible oil
seeds are suitable for the production of pyrolytic oil [25].
However due to several draw backs of the crude pyrolytic oil such
as high viscosity, acidic nature and high water content, the pyrolytic oil cannot be used as a fuel in diesel engine. It was reported
that during biomass pyrolysis the use of catalyst increased the fuel
quality of pyrolytic oil compared to the thermal process [6,7].
Catalytic pyrolysis increases the fuel properties by reducing the
oxygen content in the pyrolytic oil in presence of some selected
catalysts [68].
Various catalysts were used for seed pyrolysis such as zeolites,
aluminum oxide, Al-MCM-41, CaO and MgO [914]. Zeolite is

K.P. Shadangi, K. Mohanty / Fuel 126 (2014) 109115

2nd.

0.004

5th.

0.003

40

0.002

1st.
20

0.001

40

-0.001
0

100

200

300

400

500

600

700

Temp. ( C)
Fig. 1. TGA/DTG thermograph of Niger seed.

available in various compositions of silica and alumina. The pyrolytic liquid yield and its composition vary with the silica and
alumina ratio. The zeolite catalytic cracking reactions involve the
breaking of CAC bonds associated with dehydration, decarboxylation and decarbonylation of organic compounds to produce
several aromatic hydrocarbon compounds [9,10]. Putun et al.
[11] used aluminum oxide as catalyst and suggested that pyrolysis
with less amount of catalyst increased the yield as well as quality
of oil [11]. The comparison between catalytic (Al-MCM-41) and
non-catalytic pyrolysis of Beta seeds conrmed that catalytic pyrolysis increased the total liquid yield and total organic compounds
[12]. Literatures reveal that zeolite is one of the most suitable
catalysts whose catalytic effect enhances the quality of pyrolytic
oil. Kaolin is composed of silica and alumina which is quite similar
to zeolite and comparably cheap also. Hence it was decided to
study the effectiveness of Kaolin as a catalyst on the yield and quality of pyrolytic oil. It was reported that catalytic pyrolysis of cotton
seed with MgO resulted in lower oil yield however with better
quality of pyrolytic oil [13]. Catalytic pyrolysis of oil seeds with
Calcium oxide (CaO) increased the yield of oil as well as enhanced
the fuel properties. Moreover, it absorbs the emitted CO2 during
pyrolysis [7,14].

54
52
50
48
46
44
42
40
38
36
34
32
30
28
26
24
22
20
18
16

30
20
10

0.000

Pyrolytic yield (wt. %)

50

8:1

ld
Yie ield d
tal al Y Yiel eld
o
t
Yi
eld
n T o tal
oli aO T To Oil il Yi Yield ld
a
3
n
K C O oli
O
il
ld
Yie
Al2 Ka CaO O3 O ous s Yie ield
Y
e
Al2 Aqu ueou ous
q
e
n
i
u
A
l
q
o
Ka CaO O3 A
Al2

4:1

ly

ta

2:1

ed

to

Ca

Fe

Fig. 3. Effect of catalyst on Niger seed pyrolytic yield.

Table 1
Fuel properties of pyrolytic oil.
Niger seed pyrolytic
oil

pH

Caloric value
(MJ kg1)

Water
(%)

Viscosity
(cP)

8:1 CaO
8:1 Al2O3
8:1 Kaolin
Thermal
Diesel

9.08
8.24
8.01
7.34

35.87
35.49
38.72
34.95
45

14.18
13.92
18.14
11.34

9.007
19.17
13.135
35.37
4.57

4.0

Thermal -14.17
-10.71
8:1 CaO
-14.75
8:1Al2O3 T2

3.5

8.22
T1

14.16

T2

8:1 Kaolin
3.0

6.35

T1

T1

10.24

To

T1

2.5
-5.51

2.0

To

15.00

To

1.5
27.59

To

1.0

Aqueous phase yield

Char yield
Non-condensable gas yield
Oil phase yield
Total liquid yield

io

at

R
st

Exothermic

0.005
60

60

0.006

Heat Flow (mW)

% Weight loss (mg.)

0.007

Weight % Yiel

3rd.
80

0.008

-1

TGA
DTG

4th.

100

Rate of Weight loss (mg.s )

110

0.5

Region-2

Region-1

0.0
-30

-20

-10

10

20

30

Temp. o C
Fig. 4. DSC analysis of pyrolytic oil.

500

520

540

560

580

Temp. ( o C)
Fig. 2. Effect of temperature on Niger seed pyrolytic yield.

600

The present work was carried out to study the effect of various
catalysts on the yield and fuel properties of Niger seed pyrolytic oil.
Niger seed, being a non-edible oil seed is outside the food chain
and contains a good amount of oil. In-situ catalyzation was carried
out in a semi batch reactor using three different catalysts such as
CaO, Al2O3 and Kaolin (Al2Si2O5(OH)4). The yield of thermal and
catalytic pyrolytic oils is compared along with their fuel properties.

111

K.P. Shadangi, K. Mohanty / Fuel 126 (2014) 109115

60

Niger Thermal
8:1 CaO
8:1 Al2O3

55
50

8:1 Kaolin

45
40

%T

35
30
25
20
15
10
5
0
4500

4000

3500

3000

2500

2000

1500

1000

500

Wave no. cm-1

Fig. 5. FTIR spectra of pyrolytic oil.

2. Experimental methodology

25 C min1 facilitated by electrically heated cylindrical furnace.

Pyrolysis experiments were performed in between 500 and
600 C. The desired temperature was attained by a PID controller
attached to the furnace. The reactor was one way opening from
the top, made to collect the generated condensable volatiles in
the form of liquid. The volatiles were passed through a single pass
water cooled condenser and the condensed liquid was collected in
a measuring cylinder. The reactor was 21.5 cm long and made up of
stainless steel with an inside diameter of 6 cm. The opening portion of the reactor was attached to the condenser by means of a
ange whereas asbestos gasket was used in between the ange
to make it leak proof. At the end of the experiment the reactor
was cooled to room temperature and the left over biomass was collected as the char.
Catalytic pyrolysis experiments of Niger seed were performed
at various feed to catalytic ratios in the same reactor. The catalyst
was mixed with Niger seed powder at 2:1, 4:1 and 8:1 feed to catalyst ratio. The rate of heating for catalytic pyrolysis was identical
with thermal pyrolysis process. The product yield such as liquid
and char was calculated on the basis weight of feed used whereas
the yield of non-condensable gas was calculated by difference.

2.1. Biomass

2.5. Characterization of pyrolytic oil

The Niger seed (H. niger L.), used in this study was procured
from the forests of Brahmapur, Ganjam, Odisha, India. Prior to their
use as the feed for pyrolysis, the seeds were sundried and
grounded in a mixer grinder (Bajaj, India) to less than 1 mm size.
The proximate, ultimate and component analysis of Niger seed
are reported elsewhere [15].

The pyrolytic oils were characterized on the basis of viscosity,

caloric value, water content, pH, FTIR and GC-MS analysis. The
viscosity was determined by using HAKEE Rheostress 1 rheometer
at 25 0.05 C temperature, attached with cone (Meas. Cup Z 43
(Series 1) and plate (PP 35 Ti, D = 35 mm) type geometry and
HAAKE DC-50 temperature controller. A series of rheological data
were collected and the average was considered as the viscosity of
the oil. The caloric value of pyrolytic oil was calculated using a
bomb calorimeter using ASTM D 4809-95 standard methods. The
water content in the pyrolytic oil was determined using Metrohm
787 KF Titrino Karl Fischer water analyzer. Each experiment was
repeated three times and the average was taken into consideration.
The acidic and basic properties of the pyrolytic oil was found out
by using Eutech water proof (pH Spear) pH meter. DRS attached
with Excalibur Bio-Rad spectrophotometer (Model FTS 3500 GX)
was used for FTIR analysis. The IR spectra of the respective oil samples was collected within the range of 4004000 cm1 at scan rate
of 40 and step size of 4 cm1. GC-MS analyses were carried out to
identify the composition of the oils with the help of a Perkin Elmer
Clarus 600/680 GC-MS analyzer (Elite 5 MS column). Helium of
purity 99.99% was used as carrier gas at constant ow of
1.51 mL min1. The GC oven temperature was programmed from
25 to 70 C at heating rate of 10 C min1 and kept at the nal temperature for 2 min, and then again heated to 300 C at heating rate
of 10 C min1 and held for 32 min. Typical operating conditions
were: ionization energy 70 eV; ion source temperature 200 C;
scan per s over mass range electron (m/z) = 40600. The mass
spectra of the compounds were identied from the respective GC

2.2. Catalysts
The catalysts such as Al2O3, CaO (Loba Chemie Pvt. Ltd., India)
and Kaolin (Central Drug House (P) Ltd., India) were purchased
and used without any further treatment.
2.3. Thermogravimetric analysis (TGA)
TG analysis was carried out in a Mettler Toledo, Switzerland;
TGA 851e/LF/1100 analyzer using a platinum crucible. Approximately 10 mg of powdered seed sample was heated at a constant
preset heating rate of 5 C min1 from room temperature to
700 C under continuous N2 ow rate of 40 mL min1.
2.4. Pyrolysis experiment
Thermal pyrolysis experiments were performed on Niger seed
using a semi batch reactor. Prior to the experiment, the reactor
was partially lled with Niger seed powder (about 40 g) while
the rest was atmospheric air. The reactor was heated at a rate of

Table 2
FTIR analysis of pyrolytic oil.
Functional groups

Alkane (CAH)
Acetylenic CC
Ketone groups
CAH
Alkane (ACAH)
(C@O)
Unsaturated hydrocarbon > C@C or ACCA
Alkyl Halide (CACl)

Types of vibrations

Stretch
Stretch
Stretch
Deformation
Bending
Stretch
Stretch
Stretch

Characteristic vibrations (cm1)

28503000
2246
17001725
13451385
13501480
12101320
9001000
600800

Intensity

Strong
Strong
Strong
Strong
Variable
Strong
Strong
Strong

Pyrolytic oil
Thermal
p

8:1 Kaolin
p

8:1 Al2O3
p

p
p
p
p
p
p

p
p
p
p
p
p

p
p

8:1 CaO
p
p
p
p
p
p
p
p

112

K.P. Shadangi, K. Mohanty / Fuel 126 (2014) 109115

chromatograms using the NIST library. The cold ow properties of

thermal (obtained at 550 C) and catalytic (8:1 ratio) pyrolytic oils
were studied by DSC analysis using METTLER TOLEDO DSC 1 stare
system analyzer. About 10 0.05 mg of oil sample was lled in an
aluminum crucible covered by a single perforated lead. The
experiment was performed under N2 ow rate of 50 mL min1.
Prior to the experiment the analyzer was programmed from
30 C to 30 C temperatures at a cooling rate of 5 C min1. The
DSC thermograms were collected in the form of heat ow prole
with respect to temperature.
3. Results and discussion
3.1. TG analysis of Niger seed
The thermogravimetric and derivative thermogravimetric (TGA/
DTG) thermograph of Niger seed are shown in Fig. 1. Initially, moisture and more volatile compounds were removed within 160 C
(1st peak) and subsequently the thermal degradation of Niger seed
started with degradation of hemicelluloses, extractives and celluloses. At higher temperature lignin degraded within the range of
475700 C, denoted by the 5th peak. Since the DTG thermograph
notied a series of three degradation peaks such as 2nd, 3rd, and
4th within the range of 160475 C, the exact determination of
degradation of hemicelluloses, extractives and cellulose was not
possible. As per literature hemicelluloses degrade at lower temperature compared to cellulose [15,16]. It can be predicted that the
4th peak might be due the degradation of celluloses obtained in
between 360 and 475 C [15]. The 2nd and 3rd peak observed in
between 160 and 260 C and 260360 C might be due to the degradation of extractives and hemicelluloses. This analysis conrmed
that the active pyrolytic zone of Niger seed was within 260475 C.
3.2. Effect of temperature on pyrolytic yield
Fig. 2 demonstrates the effect of temperature of the yield of
pyrolytic liquid, char and non-condensable gas. It was observed
that the yield of total pyrolytic liquid was high at 550 C compared
to other temperatures. The increase in temperature above 550 C
amplied the formation of more non-condensable gases which
lowered down the total liquid yield and simultaneously decreased
the yield of pyrolytic char also. The decrease in the yield of
char conrmed that pyrolysis at high temperature enhanced the
conversion of biomass. High temperature pyrolysis beyond
550 C improved the formation of non-condensable gases (such
as H2 and CO) which may be due to the secondary cracking or
reforming reactions of the heavy-molecular-weight compounds
in the pyrolysis vapors. The condensable gases were collected as
the total pyrolytic liquid which got separated into oil phase and
aqueous phase [5,7,17,18]. The effect of temperature on the yield
of oil and aqueous phase is also depicted in Fig. 2. The result conrmed that at 550 C, pyrolysis of Niger seed produced maximum
yield of oil with lesser amount of aqueous phase in comparison
with other temperatures. Thus, the thermal pyrolysis study of
Niger seed conrmed that 550 C was the optimum temperature
to produce maximum 34.5 wt.% of pyrolytic oil.
3.3. Effect of catalyst on yield
Catalytic pyrolysis of Niger seed was carried out at 550 C for
2:1, 4:1 and 8:1 feed to catalyst ratios. During catalytic pyrolysis
the feed was constant (40 g) and the amount of catalyst was varied
accordingly. Fig. 3 displays the catalytic liquid yield of Niger seed
pyrolysis at various conditions. The yield of oil during catalytic
pyrolysis illustrated interesting results. The yield of oil was more

or less same for both 2:1 and 8:1 feed to catalyst ratios for all
the three catalysts used, however it can be considered that 8:1 feed
to catalyst ratio is the best since the amount of catalyst used was
less. Catalyst at 4:1 ratio produced more aqueous product with respect to other ratios. In general, the formation of aqueous product
is due to the dehydration reaction occurs during pyrolysis. Here in
this case catalytic pyrolysis at 4:1 ratio resulted in more aqueous
product. This might be due to the pyrolysis reaction of the acid
and aldehyde vapors that were generated during the degradation
of cellulose which again reacts with alcohol to produce more water
and oxygenated compounds. The catalytic effect at 4:1 ratio might
be more active to initiate the reaction between acids and aldehydes with alcohol which thus resulted in more aqueous product.
This conrmed that pyrolysis at lower feed to catalyst ratio resulted in higher yield of oil. However the comparison between
thermal and catalytic pyrolytic yield of oil showed that catalysts
had no such impact on the yield of pyrolytic oil. The yield of
pyrolytic oil was more or less equal in both thermal and catalytic
pyrolysis which can be observed from Figs. 2 and 3.

3.4. Fuel properties of Niger seed pyrolytic oil

The fuel properties of thermal and catalytic pyrolytic oil
obtained at the optimum condition is compared in Table 1. The
comparison clearly demonstrates the effect of catalyst on the fuel
properties of pyrolytic oil. It was observed that catalytic pyrolysis
increased the pH, caloric value, water content and reduced the
viscosity compared to thermal. However the thermal pyrolytic oil
was not acidic nature. According to literature, catalyst increases
the formation of water during pyrolysis [7,13,17]. Similar effect
was also observed in this case. All the catalysts increased the water
content in the pyrolytic oil. The increase in water content reduced
the viscosity signicantly. However, the composition of pyrolytic
oil has an effect on viscosity and that is the reason the viscosity
varied with water content and catalyst types. It was conrmed that

Table 3
GC-MS analysis of Niger seed thermal pyrolytic oil.
RT

Compound name

Area
%

Molecular
weight

14.97
15.91
17.64
17.75
18.08
18.92
19.05

Octadecanenitrile
Benzene, pentylChloroacetic acid, tetradecyl ester
Hentriacontane
Clofexamide
Indigo
Trans-2-methyl-4-n-pentylthiane, s,sdioxide
Sydnone, 3-(3,3-dimethylbutyl)Trans-2-methyl-4-n-pentylthiane, s,sdioxide
9-Octadecenamide, (z)9-Octadecenamide, (z)Octadecanamide
N-methyldodecanamide
N-methyldodecanamide
Hentriacontane
Trans-2,4-dimethylthiane, s,s-dioxide
Octadecanophenone
2-Pentacosanone
Hexadecanenitrile
Tetradecanoic acid, 5,9,13-trimethyl-,
methyl ester
Octadecanenitrile
Methyl 11,14-eicosadienoate
1-Undecene, 11-nitroOctadecanenitrile
Hexadecamethyl ester
Hexadecanamide

0.906
0.909
0.849
0.681
1.638
3.020
0.674

265
148
290
436
284
262
218

0.675
0.589

170
218

3.385
2.311
1.988
4.568
3.143
1.536
4.211
2.469
1.331
1.436
2.691

281
281
283
213
213
436
162
344
366
237
284

7.048
0.897
2.079
1.623
1.229
0.587

265
322
199
265
578
255

19.15
20.38
20.71
20.92
21.63
22.03
22.80
22.86
23.39
24.39
25.17
25.24
25.35
25.70
27.52
27.61
27.85
28.28
29.06

113

K.P. Shadangi, K. Mohanty / Fuel 126 (2014) 109115

the catalyst Kaolin at 8:1 ratio was more suitable to enhance

caloric value whereas CaO at 8:1 ratio was able to reduce the
viscosity of pyrolytic oil.
3.5. Effect of catalyst on clod ow properties: DSC analysis
The thermal properties of the thermal and catalytic pyrolytic oil
were examined by Differential scanning calorimetry (DSC) method.
DSC analysis requires the intake or release of thermal enthalpy to
characterize ow properties of the oil. Each of the thermal curves
were used to determine two DSC parameters, such as onset temperature (T0) and peak crystallization temperatures (T1 and T2),
where, T1 and T2 correspond to the higher (Region 1) and lower
temperature (Region 2) crystallization peaks respectively. The
exothermic peaks that signied the crystallization behavior of
the pyrolytic oils were shown in Fig. 4. The formation of crystals
in the oil is usually inuenced by the gradual reduction of temperature. At low temperatures, the crystals in the oil can easily form
impermeable lumps which block the lter and ultimately lead to
engine failure. Several additives such as pour point depressants
(PPD), cold ow improvers, parafn inhibitors, wax crystal modiers etc. is being used to decrease the crystal forming temperature.
In this study various catalysts were used during pyrolysis to
observe the effects in the cold ow properties. In Fig. 4, the

Table 4
GC-MS analysis of Niger seed catalytic (8:1 Kaolin) pyrolytic oil.
RT

Compound name

Area
%

Molecular
weight

13.94
14.22
14.27
15.60
15.91
16.07
17.64
17.74
19.00
19.15
20.38
20.46

Benzene, 1-ethoxy-4-methyl2-Propen-1-ol, 3-phenylPhenol, 3-methyl1-Docosanol, methyl ether

Benzene, pentylBenzenepropanal, .beta.-methyl
Benzenamine, 2,3,4,5,6-pentauoroDodecane, 1-uoro2,20 -Thiodisuccinic acid ester
Tetradecane
1,2-Benzenedicarboxylic acid, 3-nitroAcetic acid, 2,2,2-triuoro-, 4methoxyphenyl ester
8-Hydroxyquinoline-5-sulfonic acid
Benzene, 2-methyl-1,3,5-trinitroMalonic acid, hexadecyl isobutyl ester
Acetic acid, [o-(trimethylsiloxy)phenyl]-,
trimethylsilyl ester
Chloroacetic acid, tetradecyl ester
L-phenylalanine, N-(m-toluoyl)-, methyl
ester
Benzoic acid, 2-amino-, 2-phenylethyl ester
Benzene, (1-methyldecyl)Benzene, (1-methyldecyl)Octadecane
Benzene, 1-methyl-3-propylHexadecane, 2,6,10,14-tetramethyl
Acetamide, N-(4-bromophenyl)-2,2-dichloroHexadecanenitrile
Methyl 14-methyl-eicosanoate
Fumaric acid, ethyl 2,3,4,6-tetrachlorophenyl
ester
P-hexyloxybenzylidene p-aminophenol
Benzoic acid, 3,5-dibromo-2-hydroxy2-Nonadecanone
Octadecanenitrile
Methyl 16-methyl-heptadecanoate
4,5-Dihydro-4,4-hexamethylene-2-phenyl1,3-oxazin-6-one
3-Phenylpropanoic anhydride
Hexadecanamide
1-[6-(1,3-dimethyl-ureido)-6-oxo-hexanoyl]1,3-Dimethyl-urea

0.681
0.750
0.760
0.774
0.476
0.599
1.038
0.511
1.280
0.803
1.173
2.454

136
134
108
340
148
148
183
188
266
198
211
213

1.365
1.359
0.488
0.892

225
227
384
296

2.654
1.110

293
297

3.304
0.884
0.501
1.188
0.591
0.625
1.887
4.187
2.507
2.740

241
232
232
254
236
280
237
340
356

2.494
8.118
3.586
5.527
0.787
1.130

297
294
282
265
298
258

1.105
0.936
0.850

282
255
286

21.62
21.69
21.74
22.01
22.71
22.79
22.86
23.14
23.34
23.96
24.13
25.06
25.18
25.24
25.36
25.70
27.53
27.62
27.73
27.85
27.93
28.35
28.55
29.06
29.53

crystallization curves were displayed by two major exothermic regions. The higher temperature region was in between 0 and 30 C
and the lower temperature region in between 0 and 30 C. The result showed that when thermal and 8:1 kaolin catalytic pyrolytic
oil gave only single crystallization peak, 8:1 CaO and 8:1 Al2O3
catalytic pyrolytic oil resulted in two crystallization peaks. The
peak observed in the region 2 at temperatures under 0 to 30 C
may be attributed to the formation of low-temperature freezing
crystals usually associated with methyl esters of unsaturated fatty
acids. The peak obtained in the region 1, attributed to the formation of high temperature freezing crystals, between 0 and 30 C,
primarily consists of methyl esters of saturated fatty acids
[7,17,19]. Azis et al. [20] reported that the higher temperature peak
corresponded to the crystallization of the stearin fraction, whereas
the lower temperature peak was attributed to the crystallization of
the olein fractions [20]. Knothe [21] and Dunn [22] reported that
the presence of high concentration of saturated fatty acids in the
range of C16C18, and low concentrations of low-melting point
unsaturated mono-alkyl esters may show poor cold ow properties
[21,22]. The saturated compounds are responsible for the unfavorable cold ow properties whereas unsaturated esters are mainly
responsible for the reduced oxidation stability which reduces the
thermal stability [22]. This conrmed that pyrolytic oil obtained
by thermal and mainly by 8:1 kaolin and CaO catalytic process
resulted in a mixture of saturated and unsaturated esters whereas
8:1 Al2O3 catalytic pyrolytic oil contain only the esters of unsaturated fatty acids. It was observed that the onset crystallization
temperature gradually reduced for catalytic pyrolytic oils in comparison to thermal. The most signicant decrease was noticed for

Table 5
GC-MS analysis of Niger seed catalytic (8:1 CaO) pyrolytic oil.
RT

Compound name

Area
%

Molecular
weight

14.27
14.49
14.62
16.07
16.24
17.64
19.05
19.14
20.38
20.46
20.88

Phenol, 3-methylCyclopropane, 1-butyl-1-methyl-2-propylDodecane, 1-uoroBenzenepropanal, .beta.-methylDodecane

Chloroacetic acid, tetradecyl ester
Benzanilide
Tetrabromoethene
Methyle 3,4,5-trimethoxybenzoate
Benzene
1-Ethanone, 1-phenyl-2-(2-nitro-3cyclohexenyl)
Benzene, 1-bromo-3-iodoChloroacetic acid, tetradecyl ester
Heptadecane, 2,6,10,15-tetramethylMalonic acid, 2-butyl tetradecyl ester
Benzene, (1,1-diethylpropyl)8-Heptadecene
8-Heptadecene
Hentriacontane
Benzene, (1,1-diethylpropyl)Benzene, (1-methylbutyl)3-Phenylpropionic acid, 4-cyanophenyl
ester
Hexacosanol, acetate
Hentriacontane
Benzene, (1-methyldecyl)Hentriacontane
2-Pentacosanone
Hexadecanenitrile
Tetradecanoic acid, 10,13-dimethyl-, methyl
ester
Hentriacontane
Octadecan-4-one
Methyl 6,10-octadecadienoate
Methyl 11,14-eicosadienoate

0.598
0.496
0.856
0.543
0.576
1.007
1.111
0.795
1.110
1.764
0.819

108
155
188
148
171
290
197
342
226
213
245

0.710
2.540
1.525
0.811
0.721
2.766
1.797
3.189
0.743
0.542
0.458

281
290
254
354
173
238
238
436
176
148
251

0.814
1.226
0.566
0.531
3.544
3.532
0.708

421
436
232
436
366
236
270

0.637
1.084
4.286
4.228

436
268
294
322

21.47
21.62
21.69
21.74
22.02
22.71
22.79
22.86
23.14
23.24
23.38
23.90
23.96
24.12
25.05
25.18
25.24
25.36
26.23
26.31
27.34
27.52

114

K.P. Shadangi, K. Mohanty / Fuel 126 (2014) 109115

8:1 Al2O3 catalytic pyrolytic oil. It is conrmed that catalytic pyrolysis reduced the onset crystallization temperature which could be
due to the reduction in the concentration of saturated methyl
esters of saturated fatty acids present in the pyrolytic oils.
3.6. FTIR analysis of thermal and catalytic pyrolytic oil
The FTIR spectra of pyrolysis oils are shown in Fig. 5 which provided the information regarding the presence of various groups of
chemical compounds. The functional groups, type of vibrations and
intensity of the respective characteristics wave numbers of thermal and catalytic pyrolytic oils are provided in Table 2. It was observed that all the pyrolytic oil restrained more or less similar
functional groups with a variation in intensity. The presence of
Acetylenic (CC) group was only observed in 8:1 CaO catalytic
pyrolytic oil. This analysis conrmed that thermal pyrolytic oil
was free from stretching vibration of CC, (C@O) and the deformation of CAH group of compounds. Other than this all the pyrolytic
oils demonstrates similar functional groups. It has been observed
that both thermal and catalytic pyrolytic oil was a mixture of
saturated and unsaturated hydrocarbons.
3.7. Composition study by GC-MS analysis
The composition of biomass pyrolytic oil varies with respect to
their compositions. The main components such as hemicelluloses,

Table 6
GC-MS analysis of Niger seed catalytic (8:1 Al2O3) pyrolytic oil.
RT

Compound name

14.48

Trans-2-methyl-4-n-pentylthiane, s,sdioxide
Hentriacontane
Benzene, (1,2-dimethylpropyl)Trans-2-methyl-4-n-butylthiane, s,sdioxide
Chloroacetic acid, tridecyl ester
Hentriacontane
Trans-2-methyl-4-n-pentylthiane, s,sdioxide
Chloroacetic acid, tetradecyl ester
Hentriacontane
Trans-2-methyl-4-n-pentylthiane, s,sdioxide
8-Heptadecene
Hentriacontane
8-Heptadecene
Hentriacontane
8-Heptadecene
Trans-2-methyl-4-n-pentylthiane, s,sdioxide
Hentriacontane
Benzene, (1-methyl-1-propylpentyl)3-Phenylpropionic acid, 2-formyl-4,6dichlorophenylester
3-Phenylpropionic acid, 4-cyanophenyl
ester
Hentriacontane
Decane, 1-iodo2-Pentacosanone
Hexadecanenitrile
Tetradecanoic acid, 10,13-dimethyl-,
methyl ester
Octadecan-4-one
3-Methyl-2-(2-oxopropyl)furan
2-Pentacosanone
Octadecanenitrile
N-(2-cyano-1-methylvinyl)benzamide
Benzene, 1-methyl-2-(1-ethylpropyl)3-Eicosanone

14.60
16.06
16.11
17.50
17.63
17.74
19.06
19.15
20.40
20.48
21.59
21.67
21.74
22.79
22.87
22.94
23.21
23.32
23.46
24.10
25.28
25.38
25.44
25.60
26.62
27.98
28.15
28.25
28.67
28.89
29.74

Area %

Molecular
weight

0.503

218

0.503
0.680
0.655

436
148
204

0.946
0.946
0.518

276
436
218

1.045
0.737
0.937

290
436
218

1.821
0.621
1.766
1.436
2.938
1.229

238
436
238
436
238
218

3.292
0.699
0.647

436
204
322

0.526

251

0.695
0.755
2.822
4.766
0.831

436
436
366
237
270

0.700
12.958
4.660
6.108
1.036
1.115
0.746

268
138
366
265
186
162
296

cellulose, lignin and extractives (mainly long chain fatty acid ester
and free fatty acid) usually gets converted into various hydrocarbons, acids, esters, ketones, phenols, aldehydes and amides during
thermal degradation processes. The composition may also vary
with pyrolysis conditions (thermal and catalytic) [23]. The GCMS analyses of thermal and catalytic pyrolytic oils are presented
in Tables 36. This analysis conrmed that the pyrolytic oil was
a mixture of several compounds. The use of catalyst had signicant
effect on the composition of pyrolytic oils. Catalytic pyrolysis produced more ester compounds compared to thermal pyrolysis.
Among all catalysts, pyrolysis with kaolin (8:1 ratio) enhanced
the yield of ester compounds from 5.66% to 18.22%, whereas catalyst CaO and Al2O3 produced 15.95% and 3.97% of ester compounds.
The formation of benzene and it compounds in the catalytic pyrolytic oils was much higher than thermal pyrolytic oil. Among the
three catalysts studied, the presence of benzene and its compounds
was less (2.99%) for Al2O3 compared to CaO and kaolin catalytic
pyrolytic oil which resulted in 6.69% and 6.13% of benzene and
its compounds respectively. It was found that the amide group of
compounds was very high in thermal pyrolytic oil (about 17.62%)
compared to kaolin (2.823%) and Al2O3 (1.036%) catalytic pyrolytic
oil. CaO catalytic pyrolytic oil did not contain any such compounds.
The presence of nitrile compounds were found in both thermal and
catalytic pyrolytic oils. At about 11.01% and 10.87% of nitrile compounds were noticed in thermal and Al2O3 catalytic pyrolytic oil,
however CaO and kaolin catalytic pyrolytic oils contained 3.53%
and 5.52% of nitrile compounds respectively. Hentriacontane was
not identied in kaolin catalytic pyrolytic oil, however, Al2O3 catalytic pyrolytic oil contains higher Hentriacontane (about 8.23%)
compared to CaO (5.617%) and thermal (2.22%) pyrolytic oil. The
literature with respect to the formation of higher alkane such as
hentriacontane during biomass pyrolysis also supports this statement [7]. It was observed that both thermal and Al2O3 pyrolytic
oil consists of Trans-2-methyl-4-n-pentylthiane, s,s-dioxide compounds which was not identied from CaO and kaolin catalytic
pyrolytic oils. One of the important compounds that observed in
all pyrolytic oils was decane and its compounds. However their
presence was lower in thermal pyrolytic oil compared to other
three catalytic pyrolytic oils. The existence of furan was only observed in Al2O3 pyrolytic oil. Apart from these, a less percent of
several compounds were also present in both of thermal and catalytic pyrolytic oils as presented in Tables 36. As discussed, the
pyrolytic oil contains both aliphatic and aromatic compounds.
The presence of higher aromatic compounds in fuel oil increases
the carbon content and thus decreases the cetane number which
in turn results in more soot formation. However, aliphatic
compounds such as alkane in the fuel oil enhance the cold ow
properties. This analysis conrmed that pyrolysis the presence of
catalyst had a signicant effect on the composition which plays a
major role to alter the fuel properties of the pyrolytic oils.

4. Conclusion
Thermal and catalytic pyrolysis of Niger seed was carried out in
the present study. The effect of temperature on the yield of pyrolytic oil concluded that 550 C was the optimum temperature to
produce maximum yield of pyrolytic oil. The variation in the yield
of pyrolytic oil during thermal and catalytic pyrolysis was very
less. The yield of oil during catalytic pyrolysis was more or less
similar to thermal pyrolytic yield. The result conrmed that lower
feed to catalyst ratio (8:1) produced more liquid. Catalytic pyrolysis enhanced the fuel properties of pyrolytic oils by means of
reducing the viscosity and increasing the pH and caloric value
of pyrolytic oils. The FTIR and DSC analysis conrmed that pyrolytic oil was a mixture of saturated and unsaturated hydrocarbon

K.P. Shadangi, K. Mohanty / Fuel 126 (2014) 109115

compounds. The comparison between thermal and catalytic pyrolysis conrmed that low feed to catalyst ratio increased the yield of
oil. Catalytic pyrolysis also enhanced the quality of pyrolytic oil
compared to thermal. This experimental investigation conrmed
that catalytic pyrolytic oil and diesel seems to have similar fuel
properties which further indicate that it can be suitably blended
with diesel for use as transportation fuel.

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