Fuel 117 (2014) 372380

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Fuel
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Comparison of yield and fuel properties of thermal and catalytic Mahua

seed pyrolytic oil
Krushna Prasad Shadangi, Kaustubha Mohanty
Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati 781 039, India

h i g h l i g h t s
 Thermal and catalytic pyrolysis of one non-edible oil seed Mahua was carried out.
 525 C was the optimum temperature to produce maximum pyrolytic liquid.
 Yield of pyrolytic oil was higher for catalytic pyrolysis than thermal pyrolysis.
 CaO as catalyst increased the caloric value and decreased the viscosity.
 The catalytic pyrolytic oil has closer fuel properties with that of diesel.

a r t i c l e

i n f o

Article history:
Received 7 August 2013
Received in revised form 2 September 2013
Accepted 2 September 2013
Available online 13 September 2013
Keywords:
Mahua seed
Thermal pyrolysis
Catalytic pyrolysis
Fuel properties
Composition

a b s t r a c t
In this work, the production and evaluation of fuel properties of pyrolytic oil from one non-edible oil seed
Mahua was reported. Both thermal and catalytic pyrolysis using CaO was carried out. The aim of the
study was to detect the optimum temperature to produce maximum pyrolytic oil and to increase the
quality of oil using catalyst. It was observed that thermal pyrolysis of Mahua seed at 525 C produced
maximum yield of liquid. Hence the inuence of catalyst was examined at the optimum temperature
(525 C) on liquid yield and its properties.
The catalytic effect of CaO, on Mahua seed pyrolysis at a feed to catalyst ratio of 2:1, 4:1 and 8:1 was
studied. The pyrolytic liquid collected was separated into two phases. The top phase (organic) was considered as oil phase where as the bottom phase as aqueous. Maximum yield of 40.71 wt.% of oil with better fuel properties was obtained as Mahua seed pyrolyzed in the presence of CaO at the ratio of 2:1. The
result conrmed that catalyst (CaO) not only increased the heating value (4143.15 MJ kg1), viscosity
(0.0330.018 Pa s) and cold ow properties but also altered the pH (4.868.58) signicantly when compared with thermal pyrolysis.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
The fuel which does not originate from fossil fuel is termed as
alternative fuel. Alternative fuel is the advanced and future fuel derived from non-conventional sources of earth. Among various
alternative fuels, biofuel is gaining a lot of interest due to its various advantages over other alternative fuels. Biofuels can be solid,
liquid or gaseous fuel derived from biomass and hence it is CO2
neutral fuel. Owing to their renewability; biodegradability and
generating adequate quality exhaust gases, it is an approving option to be consumed as fuel [1]. The rapid growth of population
and industrialization decreases the forest level and as a result increases the percentage of CO2 level in the atmosphere. Deforestation and burning of fossil fuel causes more than 90% of global
warming [2]. Plantation is the only one approach which can be
Corresponding author. Tel.: +91 361 2582267; fax: +91 361 2582291.
E-mail address: kmohanty@iitg.ernet.in (K. Mohanty).
0016-2361/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2013.09.001

an obstacle for global warming. The production of fuel from biomass is accepted as an advance and future fuel.
Among various biofuels, pyrolytic oil derived from biomass
(commonly known as bio-oil) is also another alternative fuel of
interest. Verities of non-edible oils were traditionally used as lightening agents in various parts of the world since many decades. The
non-edible seeds are the main sources for this which contains
maximum quantity of oil and fats. Mahua (Madhuca indica) seed
is one of such oil containing seeds whose oil is being used for lightening as well as for the production of biodiesel [3]. Mahua trees are
vastly available in various parts of India as well as other countries.
It can grow in rainy area and all types of soils. Mahua seed holds
maximum 35% of oil and 16% of protein. During expelling at most
1520% of oil can be possible to extract whereas the rest remain in
the cake and used as cattle feed or to increase the fertility of soil.
Literatures reveal that pyrolysis is one of the suitable processes
to produce maximum 65% of oil from oil containing seeds [411].
The process pyrolysis means, heating materials at elevated

K.P. Shadangi, K. Mohanty / Fuel 117 (2014) 372380

temperature in presence of very less amount of air or oxygen. During pyrolysis the higher molecular weight compounds such as
hydrocarbon, breaks to form lower molecular weight, short chain
hydrocarbons. The condensable liquid hydrocarbon is known as
pyrolytic oil. Pyrolysis of biomass yields three form of fuel such
as solid fuel which remains at the end of the process, condensable
volatiles as liquid fuel and the non-condensable gases as gaseous
fuel [5]. The quality and quantity of the pyrolytic oil depends on
the oil content and the composition of the feed stock. One of the
advantage of pyrolytic oil that it is easier to handle, store and
transport and can be a source of production of several chemicals
[6]. Literature reveals, the pyrolytic liquid produced from castor
seed separated into two layer such as oil and aqueous [4]. The caloric value and density of oil layer were very close to diesel. Maximum 64.5% of production of oil could be possible by thermal
pyrolysis of castor seed [4]. Linseed pyrolysis produced 57.7 wt.%
of liquid yield at 550 C where, [7] 44% yield was possible at
550 C from safower seed at a heating rate of 5 C min1 and
sweep gas (N2) ow rate 100 mL min1 [8] and maximum liquid
yield observed at 500 C during slow pyrolysis of pomegranate
seeds [9]. Duman et al. found maximum pyrolytic oil yield of
44 wt% at pyrolysis temperature of 500 C for both CWS and CSS
[10]. Catalytic pyrolysis of Pistacia khinjuk seed was carried out
with BP3189 and Criterion-424 as catalyst and a liquid yield of
66.5% and 69.2% was found for the two catalysts respectively.
The thermal pyrolysis yield for the same seed was only 57.6%.
The results conrmed that the use of catalyst increased the pyrolytic liquid yield both qualitatively and quantitatively [11].
A lot of work has been done on thermal pyrolysis of different
seeds but a few works were reported on catalytic pyrolysis of
seeds. This paper reports the thermal and catalytic pyrolysis of Mahua seed. Thermal pyrolysis was carried out to study the maximum
yield of oil at minimum temperature. The effect of catalyst (CaO) in
three different feed to catalyst ratio (2:1, 4:1 and 8:1) were studied
to determine the optimum ratio for maximum liquid yield with
better fuel properties. The aim of selecting this particular catalyst
was that literature reveals catalytic cracking with CaO reduces
the tar yield as well as emission of CO2. CaO absorbs CO2 and form
CaCO3 and results in zero emission of CO2 during pyrolysis. The
reactions involved are provided below [1215]:
1

C H2 O CO H2 ; DH0298 131:3 kJ mol

CO H2 O CO2 H2 ; DH0298 41:5 kJ mol

1

1

CaO CO2 CaCO3 ; DH0298 178:1 kJ mol

373

analysis and the oxygen content was calculated by difference.

The % extractives present in the seeds were determined experimentally using NREL standard methods given elsewhere [19].
The thermal degradation temperature of Mahua seed was decided
with the help of thermogravimetric analyzer (TGA). TGA experiment was performed in a Mettler Toledo, Switzerland; TGA 851e/
LF/1100 analyzer using platinum crucible. Around 10 mg of powdered seed sample was heated at room temperature from 25 C
to 700 C at the rate of 15 C min1 in a platinum crucible under
a sweeping gas (N2) ow rate of 40 mL min1. The weight loss result from TGA was collected with respect to temperature and time.
Consequently % conversion of seed to volatiles was calculated by
the ratio of the difference between the initial and remaining
weight of the sample to the difference of the initial and nal
weight of the sample. The region of maximum conversion was accepted as the pyrolytic zone for Mahua seed.
2.3. Thermal pyrolysis
Thermal pyrolysis experiments were conducted in a stainless
steel batch reactor (ID: 6 cm and Length: 21 cm) with one end
opened to collect the volatiles. The reactor was heated electrically
by using a cylindrical furnace where PID controller maintained the
appropriate temperature with an error of 2 C. The reactor was
loaded with 40 g of powdered seed sample and inserted vertically
into the furnace and pyrolysis experiment was accomplished from
500 to 600 C at every 25 C augment of temperature. The generated volatiles were condensed by a water cooled condenser. The
condensed liquid was collected using measuring cylinder and measured by weight basis and accordingly the optimum temperature
for highest oil yield was determined. At the end of each experiment
the reactor was cooled and the solid residue remaining in the reactor was accumulated as char. The % yield of products such as pyrolytic liquid and char was calculated on the basis of their feed using
Eq. (4), whereas gas/non-condensable volatile was calculated by
difference.

% yield Product weight=Feed weight  100

It was observed that the liquid product was easily separated

into two layers as per their gravity. The top layer was considered
as oil and bottom as aqueous. Hence at each run the weight % yield
of oil and aqueous phase was also determined.

2.4. Catalytic pyrolysis

Catalytic pyrolysis experiments were conducted at the optimum temperature determined by thermal pyrolysis, at different
feed to catalyst ratio (2:1, 4:1 and 8:1) in the same stainless steel
batch reactor as mentioned in the earlier section. Calcium oxide
(CaO) was purchased from Loba Chemie, India, (P) Ltd. and used
as catalyst (BET surface area: 37 m2 gm1, MW: 56.0074 g mol1).
The catalyst was used directly without any treatment and the yield
was calculated as described in the above section. The product obtained from thermal and catalytic pyrolysis was compared on the
basis of yield, physical and chemical properties. Later on the process was optimized and the ratio of feed to catalyst for maximum
production of pyrolytic oil was determined.

2. Materials and methods

2.1. Raw material
Fresh Mahua (Madhuca indica) seeds were collected from local
market of Ganjam, Odisha, India. The seeds were sun dried for
1012 h and grinded to less than 1 mm sized particle and stored
in air tight plastic bottles for pyrolysis.
2.2. Characterization of Mahua seed

2.5. Characterization of pyrolytic oil

The seed was characterized for its proximate (moisture, volatile,
ash and xed carbon) and ultimate analysis (C, H, N, S, O), extractives content and thermal degradation prole. ASTM standard
methods such as ASTM D 3173-3187 for moisture analysis, ASTM
D 3175-89 for volatile analysis and NREL/TP-510-42622 for ash
analysis were followed [1618] whereas Variael CUBE C, H, N, S
elemental analyzer made in Germany was used for ultimate

The pyrolytic oil was characterized on the basis of their physical

properties, functional groups present and composition. The physical properties such as viscosity, density, caloric value, water content, distillation temperature, pH and cold ow properties (DSC
analysis) were calculated. The presences of functional groups were
determined by FTIR analysis and compositions by GCMS analysis.

K.P. Shadangi, K. Mohanty / Fuel 117 (2014) 372380

2.5.6. FTIR analysis

FTIR analysis is being considered as preliminary analysis of
pyrolytic oil which provides the information regarding the presence of different chemicals as per their functional groups. FTIR
analysis of pyrolytic oil was also performed by several earlier
researchers to support their results [2527]. The FTIR analyses of

3.1.1. TGA analysis

Thermogravimetric analysis (TGA) is a robust technique which
provides the thermal degradation prole, was employed to determine the weight loss prole of Mahua seed pertaining to temperature [27]. The % conversion of seed sample was determined
from the degradation prole obtained by the ratio of the difference
between the initial and remaining weight of the sample at certain
temperature to the difference between the initial and nal weight
of the sample. Fig. 1 illustrates the % weight loss vs. temperature. It
was observed that 92% of conversion took place within 600 C
where maximum conversion detected within 200400 C temperature. This temperature range was considered as the active pyrolytic zone for Mahua seed.
3.1.2. Proximate, ultimate analysis and extractives content
The proximate and ultimate analysis distinguished the raw
material as per their composition. The proximate and ultimate
analysis of Mahua seed is reported in Table 1 which explained that
sun dried Mahua seed is less in moisture, ash, xed carbon content
and rich in volatile matter content. The presence of higher volatile

100

92%
88%

80

74%

60
n

2.5.5. DSC analysis

Cold ow properties generally correspond to pour point which
is the lowest temperature at which it becomes semi solid and loses
its ow characteristics. DSC analysis is considered as a method to
determine the cold ow properties of oil which was compared with
ASTM standard methods by Manuel et al. and Robert [23,24]. In the
present study the cold ow properties of the pyrolytic oil were
determined by DSC analysis. The DSC analysis was performed
using METTLER TOLEDO DSC 1 stare system analyzer. To determine
the cold ow property, exactly 10 0.05 mg of the pyrolytic oil
sample was placed in an aluminum crucible covered by single perforated lid. Initially the sample was cooled from 30 C to 30 C
followed by heating from 30 C to 30 C under N2 ow rate of
50 mL min1. The heat ow (mW) to the oil samples with respect
to temperature was observed during cooling and heating of the
sample. During cooling period the parameters such as onset and
maximum heat ow temperature of the high-freezing peak (P2)
during heating period, minimum heat-ow temperature of the
high-melting peak (P1) was determined to observe their cold ow
properties.

3.1. Characterization of seed material

er
sio

2.5.4. Distillation temperature

Thermogravimetric analysis was also used to detect the distillation temperature of petroleum fuel [21,22]. Thermogravimetric
analyzer (Mettler Toledo, Switzerland; TGA 851e/LF/1100) was
used to determine the distillation temperature of pyrolytic oil.
Approximately 10 mg of pyrolytic oil was heated from 25 to
450 C in platinum crucible at a heating rate of 20 C min1. The
evaporation study of pyrolytic oil was observed under nitrogen
atmosphere at a ow rate of 40 mL min1. The weight loss data
was collected with respect to temperature. The % of evaporation
of oil with temperature was considered as % separation with respect to temperature (as distillation temperature).

3. Results and discussion

40

nv

2.5.3. Water and pH analysis

The water content of the pyrolytic oil was determined by Karl
Fischer water analyzer (Metrohm 787 KF Titrino) by using methanol as the solvent and pyridine free (single solution) Karl Fischer
solution. Each experiment was repeated three times and the average was taken into consideration. The acidic and basic properties of
the pyrolytic oil was calculated by using Eutech water proof (pH
Spear) pH meter.

2.5.7. GCMS analysis

Gas chromatography and Mass spectrometry (GC/MS) has been
an authoritative device to identify qualitative analysis of any unknown sample for many years. The compound class separation is
the major advantage where the compound groups are well separated as per their parent masses. GCMS analysis was applied to
pyrolytic oil to determine the composition and carried out in a Perkin Elmer Clarus 600/680 GCMS analyzer programmed at 40 C
for 0.5 min, then increased at 10 C/min to 300 C where total GC
run time was 30 min. Elite 5 MS column of diameter 0.250 lm,
length 30 m was used where 1 lL volume of sample was injected
where the ow rate of carrier gas was 0.6 mL min1. The chromatogram was collected with their retention time and respective mass
spectra of the compounds were identied by comparing the spectral data with the NIST Mass Spectral library.

Co

2.5.2. Caloric value

The caloric value of pyrolytic oil was determined by bomb calorimeter. Around 1 0.05 g of oil was lled in the sample holder
and burned in presence of oxygen inside the bomb and the increase
in temperature was noted down accurately (0.01 C) and was
used to determine the caloric value as given by ASTM standard
D 4809-95 [20].

the liquid samples were performed using Excalibur Bio-Rad spectrophotometer (Model FTS 3500 GX) attached with DRS without
using KBr. One drop of liquid sample was loaded in the sample
holder and the IR spectra were collected at scan rate of 40 with a
step size of 4 cm1 within the range of 4004000 cm1.

20

13%

M
ax
im
um

2.5.1. Viscosity
The viscosity of the pyrolytic oil was determined at 25 C and
50 rpm using rheometer (HAKEE Rheostress 1). Cone and plate
type (Meas. Cup Z 43 (Series 1) and Plate PP 35 Ti, D = 35 mm)
geometry was used to determine the viscosity where temperature
was controlled accurately 0.05 C by HAAKE DC-50 temperature
controller. A series of rheological data collected and the average
was accepted as viscosity of the oil.

Weight loss (%)

374

0
0

100

200

300

400
o

Temp. ( C)
Fig. 1. TG analysis of Mahua seed.

500

600

375

K.P. Shadangi, K. Mohanty / Fuel 117 (2014) 372380

60
55
50

Yield (wt.%)

matter indicated the formation of more volatiles during pyrolysis

where as lower moisture and xed carbon content make the raw
material more appropriate for pyrolysis. There is a direct relation
between the percentages of carbon with respect to heating value
as per Garcia et al. [28]. The ultimate analysis offered the presence
of more carbon and oxygen content with fewer quantities of
hydrogen, nitrogen and sulfur content in the seed. The observed result revealed the presence of maximum 57% extractives in the seed
by weight basis which will yield more amount of oil during
pyrolysis.

Table 1
Composition of Mahua seed: Proximate and ultimate analysis.
Proximate analysis

Wt. (%)

Ultimate analysis

Wt. (%)

Moisture content
Volatile matter
Ash content
Fixed carbon

5.65
91.76
1.49
1.1

Carbon (C)
Hydrogen (H)
Nitrogen (N)
Oxygen (O)
Sulfur (S)

55.87
7.94
2.74
33.201
0.249

Extractive Content
Hexane extractives (%)

56.75

Ethanol extractives (%)

0.41

40
35
30
25

3.2. Determination of optimum temperature from thermal pyrolysis of

Mahua seed

20
500

525

550

575

600

Temperature ( C)
Fig. 2. Thermal pyrolysis yield of Mahua seed with respect to temperature.

81

Conversion (%)

Pyrolysis of biomass normally shows the ways to the formation

of condensable volatiles in the form of liquid, non-condensable volatiles such as combustible gases and char [29]. The optimum temperature for maximum production of liquid product from Mahua
seed was determined by thermal pyrolysis experiments. Fig. 2
shows the weight % yield of liquid, char and non-condensable
gas/volatiles formed during thermal pyrolysis of Mahua seed from
500 to 600 C with 25 C escalating temperature. The result spelled
out that liquid yield increased with increase in temperature but up
to certain temperature (up to 525 C) which was also reported in
literatures [411,29,30]. The liquid yield was utmost 57.7% by
weight (78% of conversion) at 525 C and then dropped off with increase in temperature up to 600 C which may be due to formation
of more non-condensable gases. At 525 C the liquid yield was
more which resulted in less yield of gas compared to other temperature. This conrmed that more condensable vapor was produced
at 525 C in comparison with other temperature. The formation
of non-condensable gas/volatiles amplied beyond 525 C and char
yield reduced with increase in temperature. The decrease in yield
of char with temperature was the evidence for increase in conversion concerning temperature and depicted in Fig. 3. This result concluded that temperature had a positive afnity towards increasing
the conversion. The comparison between the % conversion observed from TGA analysis and pyrolysis experiment (Figs. 1 and
3) showed that there was an error of 10% in case of pyrolysis experiment. It was observed that pyrolysis of Mahua seed yield two varieties of liquid product. Generally, higher the % of extractives in
biomass, the higher is the liquid yield with two different layers
such as oil and aqueous phase [4,5]. Hence optimum temperature
was determined on the basis of higher weight % yield of oil. The
weight% yield of both oil and aqueous product is provided in
Fig. 2. Initially the oil yield was 30.51% at the temperature of
500 C and increased to 34.64% at 525 C (optimum) and later on
decreased with increase in temperature due to formation of more
non-condensable gases. Literature reveals that pyrolysis at high
temperature generates higher amount of H2 and CO gas which does
not condense and hence resulted in less liquid yield [26]. The formation of aqueous product was slightly decreased from 22.07 to
19.64% with increasing in temperature up to 550 C. A variation

45

Pyrolytic Liquid Yield

Oil Yield
Aqueous Yield
Char
Non-condensable Gas

80

79

78

77
500

520

540

560

580

600

Temp. ( C)
Fig. 3. Conversion of Mahua seed with respect to temperature.

in aqueous yield was observed after 550 C. The increase in aqueous yield was due to the formation of more water in pyrolytic liquid at higher temperature which gets separated as bottom layer.

3.3. Effect of catalyst on pyrolysis of Mahua seed and their products

Catalytic pyrolysis of Mahua seed was carried out at 525 C
using CaO as catalyst in three different feed to catalyst ratios
(2:1, 4:1 and 8:1). The effect of catalyst on liquid yield (weight %
basis) is discussed in this section. The weight % yield of oil and
aqueous product is depicted in Fig. 4. The weight % yields of pyrolytic liquid for various feed to catalyst ratios were more or less
same. However this gure also provides the information regarding
the yield of oil which was considered as the main product of pyrolysis. It was observed that the yield of oil and aqueous product was
40.71% and 12.89% respectively at 2:1 feed to catalyst ratio. This
conrmed that catalytic pyrolysis of Mahua seed with CaO at 2:1
ratio produced higher oil and less aqueous yield compared to thermal pyrolysis. Literature reveals the aqueous phase is mainly rich
in water and other water soluble chemicals whereas the top liquid
contains oil and can be used as fuel [4]. Hence pyrolytic oil was
considered as the main product of seed pyrolysis and on the basis
of yield of oil and by considering better fuel properties (described
latter on) the optimum feed to catalyst ratio was decided for maximum production.

376

K.P. Shadangi, K. Mohanty / Fuel 117 (2014) 372380

Table 2
pH analysis of thermal and catalytic pyrolytic liquid.

60

Pyrolytic Liquid Yield (wt.%)

55
Conditions

50

Pyrolytic Liquid Yield

Oil Yield
Aqueous Yield

45
40

Thermal
2:1 CaO
4:1 CaO
8:1 CaO

35

25

Aqueous phase

4.86
8.58
8.42
8.33

4.81
8.63
8.72
8.72

the application of catalyst and a synergetic effect of CaO catalyst

was noticed. The inuence of catalyst on pH at different feed to catalyst ratio was observed and reported in Table 2. Catalytic pyrolysis (with CaO) altered the nature of pyrolytic liquid from acidic to
basic. This effect was valid for both oil and aqueous pyrolytic yield.
The pH of thermal pyrolytic oil (4.86) changed to 8.58 when the
seed was pyrolyzed with CaO as catalyst in the ratio of 2:1. The increase in pH and water content is directly related to the catalyst
CaO which plays the important role at the time of pyrolysis. The related chemical reactions are provided below:

20

10
2:1

4:1

8:1

Feed to catalyst (CaO) ratio

Fig. 4. The effect of catalyst on pyrolytic liquid yield.

3.4. Characterization of pyrolytic liquid

3.4.1. Water analysis and pH study
The foremost drawback of pyrolytic oil is water content produced as a byproduct of pyrolysis. Literature reveals that 1530%
of water usually found in pyrolytic oil [31]. Water produced as a result of the dehydration of moisture in the biomass during initial
stage of thermal degradation as well as due to the catalytic effect
of CaO Eq. (5) [32]. The increase in water content may also be
due to the partial combustion reactions inside the reactor [33].
Most of the water and water soluble chemicals got separated by
normal gravity separation [4,5]. A very less amount remains inside
the pyrolytic oil in the form of bubble which is not easy to separate.
The presence of water decreases the heating value of oil. The water
content of both the phases was measured and reported in Fig. 5. It
can be seen from Fig. 5 that pyrolytic oil contains less than 1% of
water where as aqueous pyrolytic liquid contained maximum percentage of water (96.5%) and very less amount of water soluble
chemicals. This also conrmed the formation of more water during
catalytic pyrolysis than thermal pyrolysis. The conclusion observed
from the water analysis was that lower feed to catalyst ratio increased the water content of the pyrolytic liquid.
Biomass pyrolytic oil is usually acidic in nature and the pH lies
in between 2 and 4 [4,5,3134]. Accordingly it may causes corrosion to IC engine and hence cannot be used directly in diesel engine. The aim of the present investigation was to alter the pH by

97

0.70
Oil phase
Aqueous phase

96

0.60
95
0.55
94

0.50

93

0.45
0.40

92

0.35

91

0.30
90
Thermal

2:1 CaO

4:1 CaO

8:1 CaO

Pyrolytic liquid at different conditions

Fig. 5. Water content of pyrolytic liquid at different conditions.

Water content in aqueous phase (%)

Water content in oil phase (%)

Oil phase

30

15

0.65

pH

CaO 2R  COOH ! RCOO2 Ca H2 O

RCOO2 Ca ! CaCO3 R  COR

CaO

R  COOH ! CO2 RH

CaO R  COOH ! CaCO3 RH

The reaction pathway involves neutralization, thermal cracking

and catalytic cracking. The acid compounds converts to hydrocarbons by catalytic decarboxylation reaction with CaO. Eq. (5) conrmed that the acids convert to calcium carboxylate and H2O by
the neutralization reaction with CaO and calcium carboxylate
would decompose to ketones and CaCO3 (Eq. (6)). During thermal
cracking reaction the acids converts to hydrocarbons and CO2
(Eq. (7)). Consequently, the chemical equilibrium is shifted to the
direction that favors the removal of acids and the formation of
hydrocarbons, as observed from the reaction (Eq. (8)) [35].
3.4.2. Distillation temperature
Pyrolytic oil is a mixture of number of valuable chemicals and
can be separated with the knowledge of distillation temperature.
The inuence of catalyst on distillation temperature over thermal
pyrolysis is reported in Table 3. The result revealed that the use
of catalyst decreased the distillation temperature of pyrolytic oil
at each feed to catalytic ratio. It was found that for thermal pyrolysis, maximum 90% separation was possible at 386 C which
was reduced to 365 C in the presence of CaO at 2:1 ratio. For
the same catalyst, 10% and 50% of distillation was possible at
177 C and 306 C for thermal pyrolysis which were reduced to

Table 3
Inuence of catalyst on distillation temperature of pyrolytic oil.
Distillation temperature, C
Feed to catalyst ratio
% Distillation
10
20
30
40
50
60
70
80
90

Thermal
177
230
265
288
306
320
333
348
386

2:1 CaO
108
137
168
195
232
262
290
320
365

4:1 CaO
161
202
230
255
271
291
314
339
377

8:1 CaO
131
181
209
234
255
275
296
321
366

377

K.P. Shadangi, K. Mohanty / Fuel 117 (2014) 372380

Viscosity

0.035

Heat flow (mW)

Viscosity (Pa s)

0.030
0.025
0.020
0.015
0.010
Thermal

2:1 CaO

4:1 CaO

3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
-0.5
-1.0
-1.5
-2.0
-2.5
-3.0
-3.5

2.53

Diesel
Thermal
2:1 CaO
4:1 CaO
8:1 CaO

3.96

11.30 Cooling

2.97

2.53

17.21

13.89

6.73

26.63
6.85
10.86

-9.34
Heating

-30

8:1 CaO

-3.46

10.43

-1.88

-20

-10

24.86

10.09
8.97

10

20

30

Pyrolytic oil at various condition

Temp. C

Fig. 6. Comparison between viscosity of thermal and pyrolytic oils.

Fig. 7. DSC analysis of thermal and catalytic pyrolytic oil.

108 C and 232 C respectively. The results indicated that CaO is a

good catalyst for the production of lighter hydrocarbon pyrolytic liquid and has a positive upshot on pyrolytic product composition
[36].

revealed that lower the feed to catalytic ratio lower is the caloric
value. The highest caloric value (43.15 MJ kg1) was obtained
from the pyrolysis of Mahua seed with CaO in the ratio of 2:1
which was closer to the caloric value of diesel fuel (45 MJ kg1).
Catalytic pyrolysis increased the caloric value of pyrolytic oil than
that of the thermal pyrolytic oil (from 41 to 43.15 MJ kg1). The increase in caloric value may be due to the decrease in acid content
and oxygen content of the pyrolysis oil as well as formation of
more volatile compounds which is discussed in the above section.
CaO helps to decrease the oxygen content of pyrolytic oil by the
formation of water [1215,38]

3.4.3. Viscosity study

In general, pyrolysis of biomass produced high viscous oil which
is another disadvantage associated with these types of alternative
fuels. The effect of catalyst ratio on the viscosity of pyrolytic oil is
shown in Fig. 6. It was observed that catalytic pyrolysis of Mahua
seed with CaO reduced the viscosity of the oil compared to thermal
pyrolytic oil. The formation of lighter compounds during the catalytic pyrolysis (observed from distillation temperature) and the
catalytic effect of CaO may be the causes for reduction of viscosity
of the pyrolytic oil [37].
Literature also revealed that the formation of more water during catalytic pyrolysis results in less viscous pyrolytic oil. In the
present study, similar results were observed. However, due to
phase separation, most of the water and water soluble chemicals
were collected as aqueous phase and hence resulted in less than
1% of water content in the oil phase. The comparison between
the viscosity of thermal and catalytic pyrolytic oil conrmed that
catalytic pyrolysis with CaO helped to reduce the viscosity signicantly [38].
3.4.4. Caloric value
A number of advantages of catalytic pyrolysis over thermal
pyrolysis were reported in the literatures [38,39]. Catalytic pyrolysis is being used as one of the suitable and convenient up-gradation processes to increase the physical and chemical properties of
pyrolytic oil. In general, direct use of thermal pyrolytic oil in diesel
engine offers less performance as a consequence of lower heating
value. The heating value can be increased by catalytic pyrolysis
which was evident from the present analysis. The heating value
of both thermal and catalytic pyrolytic oil was determined and
compared with diesel and reported in Table 4. The analysis

Table 4
Caloric value of thermal and catalytic pyrolytic oil and diesel.
Pyrolytic oil

Caloric value (MJ kg1)

Thermal
2:1 CaO
4:1 CaO
8:1 CaO
Diesel

41
43.15
42.39
41.85
45

3.4.5. DSC analysis: determination of cold ow properties

The DSC analysis of thermal pyrolysis oil, catalytic pyrolysis oil
and diesel is illustrated in Fig. 7. The cold ow properties of pyrolytic oil were compared with diesel and observed the suitability of
pyrolytic oil to be used as a fuel in diesel engine. The detail about
cold ow properties of diesel, thermal and catalytic pyrolytic oil is
presented in Table 5. During heating scan of diesel and thermal
pyrolytic oil, only one region and for the catalytic pyrolytic oils
two regions were noticed. The rst region was observed within
5 to +5 C which corresponds to the melting region of low temperature freezing crystals, generally associated with methyl esters
of unsaturated fatty acids. The effect of feed to catalytic ratio on the
formation of conversion of unsaturated fatty acids to methyl esters
was noticed in this reason. It was observed that the DSC peak
height in the rst region increased with increase in feed to catalyst
ratio. A clear peak was observed for Mahua pyrolysis at 2:1 CaO.
This means the unsaturated fatty acids converted to its ester where
no peak was observed for thermal pyrolytic oil. The peak temperature of the respective peak is displayed in Fig. 7. The second melting region corresponds to higher temperature freeing crystals
observed within +5 to +30 C may be associated by methyl esters
of saturated fatty acids. The lower temperature melting peak was
Table 5
Lower temperature melting peak, minimum high melting peak, onset freeze and
maximum high freezing peak temperature of pyrolytic oil obtained from DSC analysis.
Oils

Lower
temperature
melting peak
(C)

Minimum high
melting peak
temp. (C)

Onset
freeze
temp. (C)
P2

Maximum high
freezing peak
temp. P1 (C)

Diesel
Thermal
2:1 CaO
4:1 CaO
8:1 CaO

3.46
1.88
9.33

8.97
24.86
10.09
10.43
10.86

6.73
26.63
12.89
11.30
6.85

3.96
17.21
2.97
2.53
2.53

378

K.P. Shadangi, K. Mohanty / Fuel 117 (2014) 372380

observed in this region. The observed result showed that increasing feed to catalyst ratio lowered the low temperature melting
peak. The comparison of DSC analysis of diesel with thermal and
catalytic pyrolytic oil conrmed that the lower temperature melting temperature decreased from 24.86 to 10.09 by catalytic pyrolysis with CaO in the ratio of 2:1 which was very closer to diesel
(8.97). Similarly, during cooling period all the pyrolytic oil and diesel endowed with a single peak. The onset temperature of each
peak was regarded as onset crystallization temperature where
the peak point denoted to the maximum high freezing peak temperature (P1) of the oils. At the onset temperature the oils started
to freeze and at the peak temperature (P2) it completely freezes
and was considered as pour point of that oil which lies in between
the peak temperature and onset temperature. The P1 and P2 was
lower for the catalytic pyrolytic oil obtained at lower feed to catalyst ratio than thermal. The use of CaO catalyst decreased the pour
point of pyrolytic oil which was conrmed from this analysis and
the detail about cold ow temperature of diesel, thermal and catalytic pyrolytic oil can be observed from Table 5. The catalytic
pyrolytic oil offered the lower onset crystallization temperature
(2.53 C) which is comparable with diesel (3.96 C).

the use of catalyst. The formation of carboxyl and carbonyl groups

may be due to the pyrolysis of cellulose whereas the phenolic and
methoxy groups were produced during pyrolysis of lignin [7]. The
presence of ester group was identied at 17251750 cm1 in thermal and catalytic pyrolytic oil [25]. A unique aromatic (C@CAC)
stretch bond at 15101450 cm1 was notied in both thermal
and catalytic pyrolytic oil. In case of thermal pyrolytic oil the peak
height was too small where catalytic pyrolytic oil showed a sharper
peak. This provides the evidence of increase in the concentration of
aromatic compounds by catalytic process. The occurrence of
(ACH3) trimethyl compounds was observed in all pyrolytic oil in
the range of 12501350 cm1. The peak identied within 3640
3530 cm1 explains the presence of phenol (AOH group) which
may be formed due to the secondary reaction inside the reactor
Table 6
Functional groups with respect to wave number present in pyrolytic oil and diesel.

90

90

85

85

80

80

75

75

70

70

65

65

60

60

55

55

50

50

45
4500 4000 3500 3000 2500 2000 1500 1000 500

45
4500 4000 3500 3000 2500 2000 1500 1000 500

cm-1

cm-1

100

100
4:1 CaO

95
90

90

85

85

80

80

75

75

70

70

65

65

60

60

55

55

50

50

45
4500 4000 3500 3000 2500 2000 1500 1000 500

8:1 CaO

95

%T

%T

2:1 CaO

95

%T

%T

CAI stretch, aliphatic organo halogen compounds, aliphatic

iodo compounds
CAH, aromatic CAH out of plane bend
ACH3 groups
CAH, aromatic CAH in plane bend
C@CAC, aromatic ring stretch, unique ring
Ester group
Carboxylic acid
Aromatic ring (aryl) group, aromatic combination bond
Methylene CAH asymmetric stretch
Alcohol and hydroxyl compound, normal AOH stretch
AOH stretch, phenol compounds

100

Thermal

95

Functional groups and its signicance

600500
900670
12501350
1225950
15101450
17251750
17001725
20001800
2922
35703200
36403530

3.4.6. FTIR analysis

FTIR analysis of catalytic pyrolytic oil is illustrated in Fig. 8. It
was observed that all pyrolytic oil has similar functional groups.
The presence of carboxylic acid group in thermal pyrolysis oil was
observed in the range of 17001725 cm1, but was not found in catalytic pyrolysis oil. This analysis also conrmed that thermal pyrolytic oil is acidic in nature which could be altered signicantly by

100

Wave No.

45
4500 4000 3500 3000 2500 2000 1500 1000 500

cm-1
Fig. 8. FTIR Comparison between thermal and catalytic pyrolytic oil.

cm-1

379

K.P. Shadangi, K. Mohanty / Fuel 117 (2014) 372380

Table 7
GCMS analysis of Mahua thermal and catalytic pyrolytic oil.
Mahua thermal pyrolytic oil
RT

Catalytic pyrolytic oil (2:1 CaO)

Peak area,
%

Name of Compound

Molecular
weight

RT

Peak area,
%

Name of Compound

Molecular
weight

8.63
8.80
8.96
8.21

1.653
0.820
0.412
0.544

116
193
281
355

12.80
12.96
14.70
14.85

0.462
0.306
0.490
0.289

Cyclopropane
Nonane
1-Decene
Decane

126
128
140
142

10.47
10.74
10.92
12.47
12.79
12.95
13.05
14.70
14.85
16.47
16.59
18.21

5.352
1.097
1.171
0.967
0.870
0.822
0.672
0.658
0.833
0.635
0.537
0.658

Fumaric acid
Pyrimidine, 4,6-dichloro-5-nitroAcetamide, N-(4-bromophenyl)-2,2-dichloroBenzamide, N-(2-iodo-4-methylphenyl)-3uoroNitric acid, ethyl ester
Pterin-6-carboxylic acid
Phenol, 2,4-dichloro-6-nitro3-Pyridinecarboxaldehyde
2,4-Dichloro-6-nitrophenol
1-Amino-2-ethylhexane
Benzamide, N,N-didecyl-3-methoxyHentriacontane
Pyridine, 3-(triuoromethyl)N-(4-triuoromethylbenzoyl)-, dodecyl ester
Acetic acid butoxyethanol ester
Benzamide, N,N-diundecyl-2-uoro-

91
207
207
107
207
129
431
436
147
429
320
447

16.47
16.64
16.60
18.10
18.22
19.71
19.611
21.022
21.117
22.34
22.43
22.93

0.656
0.349
0.349
0.676
0.446
0.965
0.840
2.073
1.208
1.739
3.072
0.524

168
168
212
168
184
184
186
210
212
228
166
132

19.71
21.02
21.10
22.33
22.42
23.58

0.745
1.028
1.001
0.938
2.055
1.281

Fumaric acid, decyl 2,3,5-trichlorophenyl ester

Benzamide, N,N-diundecyl-3-methylBenzene, (2-bromo-1-methylethyl)1H,1H,2H-Peruoro-1-decene
N-methyldodecanamide
Hentriacontane

434
443
198
446
213
436

23.51
23.58
23.66
24.75
24.81
24.82

0.625
2.031
1.424
2.212
6.783
7.343

1-Undecene
Cyclopropane, nonylDodecane, 2,6,11-trimethylCyclododecane
Decane, 2,6,8-trimethylTridecane
1-Dodecanol
1-Pentadecene
Pentadecane
N-heptadecanol-1
4-Cyclohexyl-1-butanol
Benzene, 4-ethenyl-1,2dimethyl4-Hexadecylester
Cyclohexadecane
Octadecane
N-tridecyl ester
Oxacyclohexadecan-2-one
Hexadecane, 2,6,10,14tetramethyl-

23.65

2.493

226

24.64

5.813

24.81

2.359

1,4-Benzenediamine, N-(1-methylethyl)-N0 phenyl1,2-Benzenedicarboxylic acid, 4-nitro-, dimethyl

ester
Oxacyclohexadecan-2-one

224
224
254
296
240
282

283
240

[26]. Peak noticed in the range between 3570 and 3200 cm1 may
be due to alcohol and other hydroxyl compounds (normally AOH
stretch). The presence of AOH group in the pyrolytic oil also may
be due to the presence of water content. It can be observed that
the peak of AOH group increased with decrease in feed to catalytic
ratio. Aromatic ring (aryl) group and aromatic combination bond
was obtained at 20001800 cm1. The presence of functional
groups and their respective wave number is listed in Table 6. The
comparison between thermal and catalytic pyrolytic oil clearly conrmed that the presence of CAH stretch of an aliphatic compound
of methyl and methylene group compounds in the range of 2850
3000 cm1 were increased in catalytic pyrolytic oil. This conrmed
that catalytic pyrolysis increased the concentration of methylene
group compounds than thermal pyrolytic oil.
3.4.7. GCMS analysis
The results of physical properties conrmed that catalytic pyrolysis of Mahua seed with CaO in the ratio of 2:1 offered good quality of oil compared to thermal pyrolytic oil. The composition was
determined by GCMS analysis and presented in Table 7. The comparison of GCMS results between thermal and catalytic pyrolytic
oil conrmed that catalytic pyrolysis generated lower molecular
hydrocarbons than thermal pyrolysis. No such acid, amide and pyridine compounds were detected in catalytic pyrolytic oil. The presence of acid compounds made the thermal pyrolytic oil acidic in
nature. Catalytic pyrolysis of Mahua seed with CaO catalyst produced short chain hydrocarbon compounds, where as thermal
pyrolytic oil resulted in long chain hydrocarbons. Several benzene
and its derivative compounds were noticed in thermal pyrolytic oil
whereas the catalytic pyrolytic oil contained very less amount of
benzene compounds. Thermal pyrolytic oil was a mixture of several compounds with higher area% of acid and ester compounds
whereas catalytic pyrolytic oil contained higher decane and its
derivatives.

4. Conclusions
In this work, Mahua seed was used to produce pyrolytic oil by
thermal and thermo-catalytic process and compared. The optimum
temperature for maximum production of total pyrolytic liquid was
525 C as observed from thermal pyrolysis of Mahua seed. The
pyrolytic liquid product was separated into oil and aqueous phase
where the oil phase holds good fuel properties. Catalytic pyrolysis
conrmed that CaO in the ratio of 2:1 (feed to catalyst) produced
34.64% of oil which was higher than thermal pyrolytic yield. The
water analysis concluded that pyrolytic oil contains less than 1%
of water. Use of CaO catalyst decreased the viscosity, distillation
temperature of the pyrolytic oil with increase in caloric value.
The pH was completely altered from acidic to basic with the use
of the catalyst CaO. Comparison of GCMS analysis of thermal
and catalytic pyrolytic oils conrmed that Mahua catalytic pyrolytic oil contains short chain hydrocarbon compounds such as decane and its derivatives where as thermal pyrolytic oil contains long
chain hydrocarbons.
From this study it was concluded that non-edible oil seed such
as Mahua can be used as a suitable feed stock for pyrolysis and the
pyrolytic oil can be used as fuel oil. The catalytic pyrolysis of Mahua seed conrmed that the presence of catalyst increased the fuel
quality, however, the amount of catalyst required to achieve this
was high. In this work only CaO was used as it has the ability to
capture CO2, however more study using different catalysts needs
to be done to nd out the best catalyst which will improve the fuel
quality with a much less amount of catalyst.

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