Energy Conversion and Management 108 (2016) 529–538

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Energy Conversion and Management

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Pyrolysis of Mahua seed (Madhuca indica) – Production of biofuel

and its characterization
Debalaxmi Pradhan a,⇑, R.K. Singh a, Harisankar Bendu b, Rachna Mund c
a
Department of Chemical Engineering, National Institute of Technology Rourkela, India
b
Department of Mechanical Engineering, National Institute of Technology Rourkela, India
c
Department of Biotechnology and Medical Engineering, National Institute of Technology Rourkela, India

a r t i c l e i n f o a b s t r a c t

Article history: The thermal pyrolysis of Mahua seed (Madhuca indica) has been carried out in the present study to verify
Received 30 July 2015 its potentiality for biofuel production. Pyrolysis was conducted in a semi-batch reactor at various temper-
Accepted 22 November 2015 atures from 450 to 600 °C under 30 mL/min nitrogen flow rate and at 20 °C/min constant heating rate. At
Available online 7 December 2015
an optimum temperature of 525 °C, the maximum bio-oil yield of 49% was obtained along with 18% of
bio-char. Both the products were further physically and chemically characterized, and their results
Keywords: demonstrated their efficiency and potentiality as beneficial energy resources. The chemical characteriza-
Mahua seed
tions through FTIR, 1H NMR, and GC–MS showed that the bio-oil consisted of significant number of ali-
Biomass
Thermal pyrolysis
phatic compounds than aromatics. The obtained calorific value of bio-oil was found to be 39.02 MJ/kg
Bio-oil which is closer to the calorific values of the conventional petroleum fuels. Moreover, the morphological
Bio-char characteristics of bio-char was carried out using SEM and BET analysis which revealed their macroporous
surface with a low surface area of 13.2 m2/g. Bio-char had calorific value of 26.053 MJ/kg which is more
than that of fossil fuel coal. Such favorable outcomes endorse the Mahua seed biofuel as a promising can-
didate to be used as hydrocarbon fuel and chemical feed stock.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction devoid of creating toxic effects. The annual production of Mahua

seed in India is around 0.50 million tons with seed yield ranging
The widespread availability of biomass has not only offered an from 20 to 200 kg per tree every year [3–5]. Such properties of
alternative to the declining oil reservoirs and fossil fuel sources but Mahua seed can favor the higher production of bio-oil.
has also earned the recognition of being an attractive biofuel The thermochemical biomass energy conversion process, in
source for clean energy production. Biomass doesn’t release CO2 comparison to other biochemical processes, is preferred presently
to the environment unlike the fossil fuels and is mainly composed because of the production of more fuel to feed ratio in the former
of carbohydrate compounds (cellulose, hemicellulose, lignin and case [6,7]. Thermochemical process like, pyrolysis is the thermal
minor amounts of other organics) containing very high energy decomposition of biomass in an inert atmosphere to produce var-
[1]. Biomass like non-edible seeds are very useful feedstock for bio- ious product such as liquid fuel, solid residue and gas. These prod-
fuel production. Approximately 23.7 million hectares of land in ucts have potential application in boiler and diesel engine for
India is occupied by the oilseed crops and a productivity of just power generation, and also it can be used as a source of pure chem-
about 1 ton/ha is reached. The rich forest resources and the favor- icals [8].
able climatic conditions of India have promoted the harvesting of Previously, numerous research work has been done by various
around 300 non-edible oil bearing plant species across the country, researches to produce different products from pyrolysis of seeds
among which Mahua (Madhuca Indica) tree is an important eco- that has been summarized in Table 1.
nomic plant yielding significantly high quantity of oil [2]. The plant Such results urged us to carry out the pyrolysis of Mahua seed
is extensively cultivated in central and southern India for its oil and characterize the bio-oil and bio-char obtained from it to deter-
bearing seed which have 35% oil content, 16% protein, and desir- mine if it can be a good candidate as it is widely available and
able levels of oleic and stearic acids which are comparatively cheaper source for renewable energy production. This work
presents the production of the bio-oil and bio-char obtained from
⇑ Corresponding author. conventional pyrolysis of Mahua seed in a semi-batch reactor at
E-mail address: debalaxmichemical@[Link] (D. Pradhan). 450–600 °C temperature range and 20 °C/min heating rate under

[Link]
0196-8904/Ó 2015 Elsevier Ltd. All rights reserved.
530 D. Pradhan et al. / Energy Conversion and Management 108 (2016) 529–538

Table 1
Comparision studies of pyrolytic product yield from different biomass resources.

Biomass Author Temperature (°C) Bio-oil (%) Bio-char (%) Gas (%) Aqueous fraction (%)
Tamarind seed Kader et al. [8] 400 45 39–40 10–15 n/a
Sal seed Kumar et al. [9] 600 52.8 23–25 20–25 n/a
Neem Seed Kumar et al. [10] 475 38 30–32 32–35 n/a
Mahua seed Shadangi and Mohanty [5] 525 34.64 20–30 20–21 19–20
Cotton seed Panda et al. [11] 550 58.6 25–30 12–15 n/a
Lin seed Kumar et al. [2] 550 68 20–23 10–12 n/a
Karanja seed Kumar et al. [12] 500 57 25–30 10–25 n/a
Castor seed Singh and Shadangi [13] 550 64.4 18–24 10–15 n/a
Pomegranate seeds Uçar and Karagöz [14] 500 21.98 29.83 16.13 32.06
Kanar seed Panda et al. [15] 600 79 10–11 9–10 2.2

n/a: Not available.

2.4. Characterization of feedstock

2.4.1. Thermogravimetric analysis

Thermogravimetric analysis (TGA) of Mahua seeds was done
using a SHIMADZU model DTG-60/60H. Approximately 12.30 mg
of powdered seeds of <100 lm size were taken in an Al2O3 crucible
and heated up to 600 °C at 20 °C/min heating rate. High purity
nitrogen gas at around 100 mL/min flow rate was used as an inert
purge gas to displace air in the pyrolysis zone for avoiding
unwanted oxidation of the sample.

2.4.2. Thermal pyrolysis of feedstock

The feedstock is fed into the stainless steel semi-batch reactor
of 17.5 cm length with the inside and outer diameter 4.7 and
Fig. 1a. TGA plot of Mahua seed. 5 cm respectively. Air was purged from reactor with a nitrogen
flow rate of 30 mL/min for 15 min to create an inert atmosphere
to perform all the experiments. The reactor was heated by electri-
inert atmosphere. The effect of temperature on product yield were cal furnace and the temperature of the pyrolysis reactor was mea-
studied. The bio-oil obtained was characterized for its various sured with Cr-Al (K type) thermocouple (error ±2 °C) and
physical and chemical properties. Further the obtained bio-char controlled by using high sensitive PID controller. The temperature
after pyrolysis of Mahua seed was also characterized for their was maintained from 450 to 600 °C in steps of 25 at constant heat-
physical and chemical properties. ing rate of 20 °C/min and the maximum yield of the liquid product
was obtained at 525 °C. The volatiles from the pyrolysis reactor
outlet pipe were condensed with a water-cooled condenser main-
2. Materials and methods
tained at 25 °C. After pyrolysis, the reactor was cooled down to
room temperature and weighed to estimate the weight percentage
2.1. Materials
of bio-char (solid residue). The weight percentage of gas (non-
condensable volatiles) was determined from the material balance.
Mahua seeds were obtained from National Institute of Technol-
The total liquid product consisted of two phases i.e., aqueous and
ogy Rourkela, India. The high grade chemicals used during the
oil phase. Separation of pyrolysis oil from the aqueous phase was
chemical analysis are KCl, chloroform-d and n-hexane which were
done by centrifuging at 5000 rpm and then both were weighed
obtained from Fisher scientific, Merck, and Sigma Aldrich.
individually. The optimum temperature for maximum pyrolytic
oil produced from Mahua seed thermal pyrolysis was decided on
2.2. Feedstock preparation the basis of highest weight percentage yield of the pyrolytic oil.

Fresh Mahua seeds were dried in sun for 10 h and then crushed 2.5. Characterization of Mahua bio-oil
and sieved to get particles of 0.55–1 mm size. Before performing
pyrolysis, the powdered seeds were preheated at 110 °C in hot 2.5.1. Water content and pH analysis
air oven for 2 h to remove free moisture content and they were Water content in the bio-oil was estimated using Aquamax KF
stored in airtight plastic containers. Oil Evaporator model 51000 as per ASTM method (D6304). 0.5 g
bio-oil was mixed in 10 mL dried hexane and shaken well till it dis-
2.3. Proximate and ultimate analyses solved. 1.0 mL aliquot was injected into the base oil of the oil evap-
orator. The liberated moisture was transferred into the titration
The proximate analyses of the Mahua seed and bio-char were vessel by the carrier gas where it was titrated coulometrically.
performed according to the ASTM D 3172-07a to evaluate for its The pH of the pyrolytic oil was determined by using Eutech
moisture, volatile, fixed carbon and ash contents. The ultimate water proof pH 510 (pH Spear) pH meter.
analyses for carbon, hydrogen, nitrogen, sulfur and oxygen weight
percentages of Mahua seed, bio-oil and bio-char were determined 2.5.2. Density, viscosity and calorific value estimation
from CHNSO elemental analyzer (Variael CUBE Germany). The The density determination of the pyrolytic oil was done by
major constituent of Mahua seed are hemicellulose, cellulose, lig- introducing a small volume (approximately 0.6 mL) of bio-oil sam-
nin and oil content which were also determined [3,16]. ple into an oscillation U shaped tube in a thermal bath at 15 °C as
 D. Pradhan et al. / Energy Conversion and Management 108 (2016) 529–538 531

spectroscopy (FTIR) using a Perkin Elmer FTIR at 8 cm
1 resolution

in the range of 400–4000 cm
1 using Najol mull. A small drop of
the oil was mounted on KBr pellet and the infra-red spectrum of
the bio-oil was taken.

2.5.5. 1H NMR analysis

1
H NMR (Proton nuclear magnetic resonance) spectra were
recorded by using a 400 MHz, BRUKER DPX-400, High-
performance digital FT-NMR spectrometer where chloroform-d
containing TMS (tetramethylsilane) used as the internal standard.

Fig. 1b. DTG plot of Mahua seed. 2.5.6. GC–MS analysis

Gas chromatography and mass spectroscopy (GC–MS) was per-
formed to quantitatively examine the elemental compounds in a
Table 2 bio-oil by using Agilent 7890B Network GC system that was pro-
Proximate and ultimate analyses of Mahua seed and bio-char. grammed at 70 °C for 3 min and then increased to 300 °C at
Characteristics Mahua seed Mahua bio-char 10 °C/min where the total GC run time was 25 min. The DB-5 ms
Proximate analysis (wt.%) column of diameter 0.250 lm and 30 m length was used where
Moisture content 8.6 5.14 1 lL bio-oil was injected into the column with the carrier gas
Volatile content 84 36.17 (Helium) at 1.5 mL/min flow rate. Chemical compounds present
Fixed Carbon 5.4 50.03 in bio-oil were ionized at 70 eV ionization energy, 230 °C ion
Ash content 2.0 8.66
sources temperature and were analyzed over a mass electron (m/
Ultimate analysis (wt.%) z) range of 40–700 (Kg/C). The chromatogram of the chemical com-
Carbon 61.24 78.12
Hydrogen 8.4 4.07
pounds at different retention time and respective mass spectra
Nitrogen 4.12 2.81 were plotted and compared against the spectral data with the
Sulfur 0.74 0.16 W9N11 MS library.
Oxygen 25.5 14.84
H/C molar ratio 1.64 0.63
O/C molar ratio 0.31 0.14
Empirical formula CH1.64N0.05S0.004O0.31 CH0.63N0.03O0.14
2.6. Characterization of bio-char
Gross Heating value (GHV) (MJ/kg) 26.69 26.053
Component analysis (as received)
Bulk density of the powdered materials was estimated from the
Hemicellulose 7.9 – ASTM D 1895 standard method. Mahua bio-char was suspended in
Lignin 29 – a 0.1 N KCl (neutral salt) solution at 1:10 (wt/wt) ratio. After
Cellulose 32.4 – 30 min of stirring in an incubator shaker at 25 °C and 127 rpm,
Oil content 31 –
the pH of the bio-char suspension was ascertained using Eutech
water proof pH 510 (pH Spear) pH meter. The calorific value of
bio-char was determined by using bomb calorimeter as per ASTM
per ASTM D 4052. The change in oscillating frequency caused by standard D 4809-95.
the change in the mass of the tube was correlated with the calibra- The physical morphology of the solid fuel particles was ana-
tion data to estimate the density. lyzed using scanning electron microscopy (SEM) with JEOL-JSM-
Bio-oil viscosity was determined using a dynamic shear 6480LV model at 15 kV accelerating voltage.
rheometer RHEOPLU/32v2.66 (Anton Paar) by following the cone The surface area of bio-char was assessed by nitrogen adsorp-
(dia 39.018 mm and length 60 mm) and cup (internal diameter tion at 77 K using an automatic adsorption instrument (Quanta
41.97) type geometry where accurately ±0.05 °C temperature was chrome Corporation, Autosorb 1C) which operates on the static
controlled with TC 30 temperature controller. volumetric technique. Prior to gas adsorption measurements, bio-
The calorific values of the Mahua seed and its pyrolytic products char was degassed in the vacuum chamber at 200 °C for 4 h to
were estimated using a bomb calorimeter (Model: Parr 6100 EE remove the adsorbed moisture or other impurities bounded to
digital bomb calorimeter) where 0.5 ± 0.05 g sample was placed the surface.
inside the bomb and burned in the presence of oxygen. An incre-
ment of ±0.01 °C accuracy was used to determine the GHV (Gross
heating value) as per ASTM D 4809-95.

2.5.3. Determination of distillation temperature

The distillation temperature of Mahua bio-oil was determined
from TGA using a thermogravimetric analyzer (NETZSCH STA 449
C). Pyrolytic oil of 20.046 mg was heated from 25 to 500 °C in
Al2O3 crucible at a heating rate of 20 °C/min. At 30 mL/min flow
rate argon was used to observe the evaporation study of the pyro-
lytic oil. The weight loss percentage was observed against
temperature.

2.5.4. FTIR characterization

The presence of organic functional groups of different chemicals
in the pyrolytic oil was determined by Fourier transform infrared Fig. 2a. Influence of temperature on pyrolysis product yields.
532 D. Pradhan et al. / Energy Conversion and Management 108 (2016) 529–538

Table 4
Comparison of distillation temperature ranges for Mahua bio-oil and diesel 2.

Distillation (%) Temperature (°C)

Mahua bio-oil Diesel 2
10 197 194
20 251 209
30 291 226
40 314 243
50 330 260
60 343 277
70 361 296
80 388 316
90 420 326
99.58 500 –

Fig. 2b. Mahua seed conversion efficiency with respect to temperature.

to approximately 137 °C in Fig. 1b. indicates the evaporation of
moisture from the biomass seed, and the decomposition of hemi-
Table 3
Ultimate analysis of Mahua bio-oil.
cellulose and cellulose took place at around 160–400 °C and 220–
400 °C respectively. The weight loss became constant after 400 °C
Elemental analysis (wt.%)
due to slow decomposition of lignin. As described earlier, lignin
Carbon 69.32 decomposes very slowly till 700 °C and its rapid decomposition
Hydrogen 9.12 of approximately 67 wt.% was observed at 850 °C [18]. However
Nitrogen 2.53
Sulfur 0.89
in the present study the degradation profile has been showed up
Oxygen 18.14 to 600 °C. Thus the solid residue at 600 °C signifies slight decompo-
H/C molar ratio 1.58 sition of lignin content. Hence, from the TGA and DTG graph, the
O/C molar ratio 0.19 active pyrolytic zone for Mahua seed was established in the tem-
Empirical formula CH1.58N0.03S0.005O0.19
perature range of 450–600 °C.
Calorific value (MJ/kg) 39.02

3.1.2. Characteristics of Mahua seed

3. Results and discussion
Proximate analysis provides the information on moisture con-
tent, volatile matter, fixed carbon and ash content whereas the
3.1. Properties of Mahua seed
ultimate analysis provides the elemental composition of carbon,
hydrogen, nitrogen, sulfur and oxygen percentages. Thus, the char-
3.1.1. Thermal degradation profile
acterization of raw biomass feed stock is very important to check
The thermal degradation profile of Mahua seed was ascertained
the suitability for thermochemical conversion. The quality of solid
by performing TGA which provides a correlation between the
biofuel was estimated by proximate analysis. The major criteria for
weight loss of Mahua seed and temperature. From Fig. 1a. where
biomass thermal pyrolysis is high volatile matter with low ash con-
it can be seen that the weight loss percentage increased with the
tent [11]. Table 2 shows the proximate and ultimate analyses of
temperature. At 20 °C/min heating rate, it was observed that the
Mahua seed and its bio-char after pyrolysis at 525 °C. The pyrolytic
thermal decomposition of Mahua seed started at around 135 °C
conversion efficiency and heating value of derived liquids are
and 82% of the conversion took place till 600 °C. The maximum
greatly influenced by the moisture content of the biomass. Mahua
conversion was observed between 200 and 400 °C after which
seed has a moisture continent of 8.6% which is on the same range
the decomposition rate became relatively constant. Biomass pyrol-
as of other seeds [8,9,11]. Therefore it has little effect on conver-
ysis exhibits three main stages of (i) moisture drying, (ii) main
sion efficiency. Mahua seed had a very high volatile matter of
degradation of the more unstable polymers and (iii) continuous
84%, after pyrolysis it drastically reduced to 36.17% in bio-char.
devolatilisation [17]. Differential thermogravimetric analysis
High volatile matter in the proximate analysis indicates that 84%
(DTG) vs temperature relation Fig. 1b. was established from the
effectiveness of seed on weight basis. Effectiveness is the total
TGA data to give a better representation of the conversion of
weight loss of sample at a given pyrolysis temperature or volatile
Mahua seed. The first peak observed from ambient temperature
matter conversion efficiency. Though the sample contains high
volatile matter and lignin content (29%) can’t be pyrolyzed fully
at 600 °C. From the above TGA analysis it was also observed that
only 82% weight of sample can be converted into liquid and non-
combustible gas at 600 °C. The lower amounts of fixed carbon
and ash make a positive effect during pyrolysis according to Moralı
and Sß ensöz [19]. The fixed carbon and ash contents of Mahua seed
is lower consequently yield of bio-oil is higher.
The ultimate analysis revealed that the Mahua seed contained
highest carbon content of 61.24% among the other elements like
oxygen, hydrogen, nitrogen and sulfur. The molar ratio (H/C, O/C)
of Mahua seed was 1.64 and 0.31 respectively and these ratios
were very close to that demonstrated by other researchers
[20,21]. The estimated chemical composition of Mahua seed and
bio-char was CH1.64N0.05S0.004O0.31 and CH0.63N0.03O0.14 respec-
tively. The oil content of Mahua seed is 31% hence its overall heat-
Fig. 3. Viscosity of Mahua bio-oil with temperature. ing value increases than that of its bio-char. These analyses provide
 D. Pradhan et al. / Energy Conversion and Management 108 (2016) 529–538 533

Fig. 4. FTIR spectra of Mahua bio-oil.

Table 5
FTIR functional group and the indicating compound of Mahua bio-oil.

Wave length range (cm
1) Frequency (cm
1) Functional group Type of vibration
3500–3300 3354.8 Phenol, carboxylic acid, water impurities OAH Stretching
2960–2850 2954.7 Alkane CAH Stretching
1740–1700 1705.4 Ketone C@O Stretching
1650–1580 1639.2, 1593.2 Alkenes, aromatics C@C stretching
1470–1350 1458,1377.3 Alkyne C„C stretching
1300–950 1262.2,1109.6 Esters and ethers CAO stretching
900–650 908.12 Mono and polycyclic substituted aromatics groups OAH bending

Table 6
1
H NMR results of the Mahua bio-oil.

Types of hydrogen Chemical shift (ppm) Bio-oil (mol % of hydrogen)

Aromatic 8.5–6.5 3.25
Phenolic (OH) or olefinic proton 6.5–5.0 2.07
CH3 CH2 and CH to an aromatic ring 3.3–2.0 10.87
CH2 and CHb to an aromatic ring (naphthenic) 2.0–1.6 5.76
b-CH3, CH2 and CH c to an aromatic ring 1.6–1.0 66.86
CH3 c or further from an aromatic ring 1–0.5 11.19

an effective way to assess the type and quality of the fuel after increasing temperature probably because of greater primary
which further experiments can be pursued. decomposition of Mahua seed or secondary decomposition of the
char residues with rising temperature. Which is also confirmed
3.1.3. Influence of temperature on pyrolysis yield through the increasing conversion efficiency with temperature as
Thermal pyrolysis experiments were carried out to determine shown in Fig. 2b. Shadangi and Mohanty have mentioned that tem-
the optimum temperature at which the bio-oil yield from Mahua perature had the positive contribution towards increase in conver-
seed was maximum. The pyrolysis yields of bio-oil, aqueous phase, sion [5]. The non-condensable gas increased from 18% to 28%, with
bio-char and non-condensable gases of Mahua seed with 0.55– increasing temperature mainly due to secondary decomposition of
1 mm particle sizes and temperature ranging from 450 to 600 °C pyrolysis vapors and bio-char at higher temperatures [8].
at 20 °C/min heating rate have been represented in Fig. 2a. It can
be seen from the graph that the bio-oil yield increased with tem- 3.2. Characterization of pyrolytic oil
perature and at 525 °C, the maximum yield of 49% was obtained
after which the yield percentage continued to decrease. The max- 3.2.1. Ultimate analysis
imum bio-oil yield at 525 °C can be attributed to thermal cracking, Table 3 represents the elemental or ultimate analysis of bio-oil
depolymerization and recondensation of secondary reactions [20]. which includes the quantitative determination of carbon, hydro-
The bio-char yield however, decreased from 26% to 14% with gen, nitrogen, sulfur, and oxygen. Heat from the combustion of
534 D. Pradhan et al. / Energy Conversion and Management 108 (2016) 529–538

Fig. 5. NMR spectra of Mahua bio-oil.

bio-oil was mostly from carbon and hydrogen burning. Its potential 3.2.3. Density, viscosity and calorific value
was determined from the elemental composition of products dur- The mass-volume relationship of the bio-oil is required to be
ing pyrolysis. The measurement of nitrogen and sulfur contents in established and thus, the density of the bio-oil is measured. It
the fuel composition is very crucial for environmental pollution as was 921.3 kg/m3 at 15 °C, which is a little denser than diesel. The
their oxides are formed during combustion/burning. Bio-oil water content in bio-oil affects the density by decreasing it. More-
derived from lignocellulosic materials consists of huge number of over, the viscosity also decreases in the presence of water content.
oxygen containing reactive functional groups which are mainly Generally, the pyrolytic bio-oils are very viscous and this limits
fragments of cellulose, hemicellulose, and lignin polymers. The less their utility as an alternate fuel for Internal Combustion (IC)
oxygen composition in bio-oil is probably due to the transforma- engines. Mahua seed bio-oil has somewhat higher viscosity than
tion of more oxygen to non-condensable gas. In order to produce diesel but it decreases with increasing temperature and shear rate.
potential bio-oil, the O/C molar ratio should be decreased and H/ The shear-rate-dependent viscosity at three different temperatures
C molar ratio should be increased. The H/C molar ratio of oil was (30 °C, 40 °C and 50 °C) is represented in Fig. 3. Viscosity variation
1.58 that lies between light and heavy petroleum oils. in bio-oil can intuitively reflect changes in its physical and chemi-
cal properties. The calorific value of Mahua seed bio-oil, as mea-
sured by bomb calorimeter was found to be 39.02 MJ/kg.
3.2.2. Water content and pH value However, the calorific value of petroleum fuel varies from 42 MJ/
The pyrolytic liquid consists of aqueous and oil phase which are kg to 46 MJ/kg. Thus, we assume that the presence of oxygen in
separated by gravity separation. During biomass pyrolysis water the bio-oil has lowered its calorific value.
content is formed due to dehydration of biomass. The partial com-
bustion reactions inside the pyrolysis reactor may also contribute
to the water content [22]. The bio-oil contains 1.1% of water which 3.2.4. Boiling point distribution
has no negative effect on the heating value whereas it enhances the The distillation temperature of bio-oil was appraised from TGA
fluidity/pumping and combustion/atomization [23,24]. analysis. The boiling point distribution of Mahua bio-oil compared
The pH of the pyrolytic bio-oil was estimated to be 4.8. Bio-oils with diesel 2 is shown in Table 4. The volatility of the bio-oil was
are usually acidic in nature and contain different amount of organic characterized with distillation temperature for combustion charac-
acids. Acidity causes corrosion of materials in the storage and those teristics of the diesel engine. Mahua bio-oil chemical composition
used for Internal Combustion (IC) engine applications. Mahua bio- is a mixture of various valuable chemicals and shows a wide range
oil contains organic acids like octanoic acid, octadecenoic acid and of boiling temperatures. The bio-oil starts boiling below 100 °C.
tetradecenoic acid. Slow heating of the bio-oil during distillation can cause polymer-
 D. Pradhan et al. / Energy Conversion and Management 108 (2016) 529–538 535

Fig. 6. GC–MS chromatogram of Mahua seed pyrolytic oil.

ization. It was found that 10% and 50% of distillation was possible groups. Furthermore, the absorption peak between 900 and
at 197 °C and 330 °C respectively, while 90% distillation at 420 °C. 650 cm
1 with OAH bending refer to the mono and polycyclic sub-
A maximum of 99.58% separation was possible at 500 °C. Thus, stituted aromatics groups. The significant abundance of aliphatic
Mahua bio-oil blends can be used for diesel engine applications. compounds along with few aromatics clearly suggests the presence
of cellulose, hemicellulose and lignin in Mahua seed [11,25,26].
This was again verified through the GC–MS analysis of the bio-oil.
3.2.5. Functional group determination
The FTIR spectrum of bio-oil obtained at 525 °C is shown in
Fig. 4, where the several peaks with strong, and medium intensities 3.2.6. 1HNMR analysis
of various bond types present in bio-oil is represented in Table 5. Percentage hydrogen distribution was computed on the basis of
The broad peak observed from 3600 cm
1 to 3200 cm
1 is caused chemical shift values from the 1H NMR spectra which is summa-
due to OAH stretching and mainly represents the presence of phe- rized in Table 6. Fig. 5 shows the 1H NMR spectrum of bio-oil which
nol, carboxylic acid or water impurities in bio-oil. The CAH stretch- provides the detailed information on aromatic, olefinic and alipha-
ing vibration from 3200 to 2800 cm
1 represented the presence of tic based on the proton type. Aromatic proton occurred in the
alkane. The major peak at 1705 cm
1 arises from the C@O stretch- chemical shift region of 8.5–6.5 ppm range and the amount of
ing vibrations and is in correspondence to the presence of ketone maximum proton attached to b-CH3, CH2 and CH c to an aromatic
groups. The C@C stretching vibration between 1650 and ring accounted to 66.86% in the chemical shift region of 1.6–
1580 cm
1 indicates the presence of alkene and aromatics. The 1.0 ppm. Moreover, 2.07% of olefinic proton was observed in the
peak C„C deformation vibration between 1470 and 1350 cm
1 region of 6.5–5.0 ppm. The 10.87% of proton attached to CH3CH2
determine the presence of alkyne groups. The peaks between and CH to an aromatic ring lied in the chemical shift region of
1300 and 950 cm
1 designate the esters and ethers due to the 3.3–2.0 ppm. These data are in agreement with various other
CAO stretching and deformation vibration of these functional research work [21,27,28].
536 D. Pradhan et al. / Energy Conversion and Management 108 (2016) 529–538

Table 7
GC–MS analysis of Mahua seed bio-oil.

RT (min) Peak area (%) Compound Molecular formula

5.444 0.14 4-Decane C10H20
5.748 0.24 D-Limonene C10H16
6.157 0.48 o-Cresol C7H8O
6.513 0.68 Benzenemethanol C7H8O
6.810 0.46 5-Undecene C11H22
6.952 0.82 n-Undecane C11H24
7.382 0.18 Cyclooctene C8H14
7.605 0.13 1-Hydroxy-2-ethylbenzene C8H10O
7.954 0.88 n-Pentyl benzene C11H16
8.266 0.35 Octanoic acid C8H16O2
8.467 0.44 1-Dodecene C12H24
8.593 0.66 n-Dodecane C12H26
8.994 0.37 1-Cycloheptene C7H12
9.537 0.51 Hexylbenzene C12H18
10.309 0.28 Trifluoroacetate C3F2O2
10.086 0.67 n-Tridecene C13H26
10.748 1.03 2-(4-Methylphenyl)cyclopentanone C12H14O
11.476 2.24 n-Tetradecane C14H30
12.768 3.84 Pentadecane C15H32
13.972 3.41 Hexadecane C16H34
15.123 5.16 n-Heptadecane C17H36
15.784 0.98 Tetradecanoic acid C14H22O2
16.185 1.38 n-Octadecane C18H38
17.263 2.37 Pentadecanenitrile C15H29N
18.080 11.79 Hexadecanoic acid C16H32O2
19.045 3.96 Cyano-8-pentadecene C16H29N
19.253 3.37 Heptadecanenitrile C17H33N
19.409 1.14 Octadecanoic acid, methyl ester C19H38O2
19.781 12.58 6-Octadecenoic acid C18H34O2
20.004 10.67 n-Octadecanoic acid C18H36O2
20.524 1.08 Cyclopentane, 1,10 -[3-(2-Cyclopentylethyl)-1,5-pentanediyl]bis- C22H40
21.512 1.09 9-Octadecenamide C18H35NO
21.705 1.20 Tetradecanamide C14H29NO
21.972 0.92 n-Methyloctadecanamide C19H39NO
23.005 0.31 Succinic acid, nonyl tetradec-11-enyl ester C27H50O4
23.948 0.68 N-Acetyldioctylamine C18H37NO
24.572 0.99 9-Tetradecenoic acid C14H26O2
25.828 2.72 1,10 30 ,10 -Terphenyl, 50 -phenyl- C24H18
27.343 0.63 Pyrrolo[3,2-c]dibenzofuran C14H13NO
28.450 0.78 1,3-Dimethyl-4-azaphenanthrene C15H13N
30.849 0.64 1,2,4-Benzenetricarboxylic acid, 4-dodecyl dimethyl ester C23H34O6

3.2.7. GC–MS analysis agent and as a non-drying oil for surface coatings [10]. The IUPAC
GC–MS analysis provides information regarding diversity of name of stearic acid is known as n-octadecenoic acid, is mainly
components present in bio-oil. In this study, the detected com- used for emulsifying agent and solubilizing agent in aerosol prod-
pounds were identified by searching the W9N11 MS library data- uct. But the purification of these fatty acids is limiting the applica-
base. More than 100 compounds were identified to be present in tion in laundry soaps or detergents. Some other aliphatic
the Mahua bio-oil by GC–MS analysis, the chromatogram is shown compounds, such as alkanes and alkenes were found in bio-oil,
in Fig. 6 among which the peaks with high degree of probability with relative composition of 17.6% and 6.3% respectively. Benzene
(P80%) and peaks areas around or greater than 0.1% are listed in and its derivatives constituted about 4.9%. The chemical composi-
Table 7. The compound which were identified in bio-oils instigated tion of Mahua seed bio-oil was ascertained to be that of straight
in consequence of the thermal cracking of cellulose, hemicellulose chain aliphatic carbon in the range of C7AC27 which is mixture of
and lignin in the biomass. gasoline and diesel fuel. Because of the existence of such various
Bio-oil consists of more than 300 different organic compound compounds in the Mahua bio-oil, it can be used as an alternative
because of their complexity nature [29]. Hence they were branched fuel and a chemical source.
into six major classes’ monoaromatics, polyaromatics, aliphatic,
heterocyclic, oxygenates and nitogenates which has been previ-
ously demonstrated by Nanda et al. [30]. The various prominent 3.3. Characterization of bio-char
organic products such as Acid, Alcohols, Ketones, Aldehydes, Esters,
Amines, Ethers, and Nitriles were found from most of the bio-oils. The principle of bio-char yield is due to slow pyrolysis of ligno-
Mahua pyrolytic oil consisted of various chemical groups such cellulosic materials. It can be used as cheap absorbent, carbon coat-
as alkanes, alkenes, branched hydrocarbon, saturated fatty acids ing, solid fuel, and soil amendment. Bio-char having high calorific
and their derivatives i.e., esters, amides and nitriles which were value with low sulfur content and carbon-rich fuel that is suitable
typically the primary products. The most significant compounds for direct fuel and household briquette production. The growing
in bio-oil are acid (Tetradecanoic acid, Hexadecanoic acid, Octade- interest of bio-char is due to its potential in carbon sequestration
cenoic acid, etc.) which had combined relative composition of 37%. and in improving soil health. Bio-char characterization was done
Out of these Hexadecanoic acid is used to produce soap/cosmetics to understand its potential for use as a solid fuel [31,32].
 D. Pradhan et al. / Energy Conversion and Management 108 (2016) 529–538 537

1.8 and other volatile compounds. The H/C and O/C molar ratios of bio-
1.6 Mahua seed char were calculated from the elemental composition and com-
1.4 pared with the original Mahua seed biomass. It was found that
Atomic H:C rao

1.2 bio-char fall within the region of coal in the Van Krevelen diagram
1 which shown in Fig. 7 [36]. The calorific value of bio-char was
0.8 found to be 26.053 MJ kg
1 which is more than that of coal. Hence,
0.6 Bio-char
it can be used as fuel in boiler (either alone or as a mixture with
0.4
biomass). Bio-char can also be used as a good source of solid fuel
0.2
for cooking and heating. Low levels of nitrogen in bio-char also
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
suggest low levels of NOX emission during combustion.
Atomic O:C rao
3.3.1. SEM and BET analysis of bio-char (morphological
Fig. 7. Mahua seed and its bio-char in Van Krevelen diagram.
characteristics)
Bio-char’s porous structural examination as observed under
scanning electron microscopy is represented in Fig. 8. Volatile mat-
Bulk density of bio-char reflects the flow consistency and pack-
ters escape during pyrolysis of biomass that left pores behind the
ing quantity of solid fuels. Ash and bulk density were estimated to
surface of the bio-char. The SEM images show heterogeneous dis-
be 8.66% and 833 Kg/m3 respectively.
tribution of macropores and a rough texture. The average pore
The pH of bio-char is an important property to be determined as
diameter of the bio-char surface was found to be 21.53 lm and
this changes the soil pH depending on the quantity of bio-char
12.51 lm. Highly porous bio-chars have more adsorption sites
added. KCl was used to enhance the properties of bio-char because
for ions and provide spaces for nutrients and water retention
it could release the exchangeable protons from bio-char into the
[19,37]. These findings were consistent with BET analysis for sur-
solution due to its ionic nature. The solution pH of bio-char was
face area measurement whereas the surface area of char is impor-
more alkaline as it was produced from pyrolysis with long resi-
tant like other physicochemical characteristics, the average surface
dence time. The pH of Mahua bio-char was 11.9 which is probably
area was found to be 13.2 m2/g. However, further activation of the
good for acidic soils. The soil pH of around 6.3–6.8 is the optimum
bio-char with acid, and alkaline its quality can improve and use for
range in terms of nutrient availability for most plants and is pre-
adsorption process. It may strongly affect the reactivity and com-
ferred by most beneficial soil bacteria [33]. Moreover, alkalinity
bustion behavior of char. Since the obtained bio-char from Mahua
can be influenced by three factors: organic functional groups, car-
seed pyrolysis is mainly macroporous with low surface area but it
bonates and inorganic alkalis [34] in order to meet up with the
could be used for the production of activated carbon after chemical
requirement of soil pH.
and physical activation.
The proximate and ultimate analyses of bio-char obtained by
pyrolysis of Mahua seed at 525 °C are shown in Table 2. Fixed car-
bon in bio-char was 9.3 times higher than the feedstock because 4. Conclusion
the lignin content (29%) present in the Mahua seed feedstock can-
not decompose fully at 525 °C and thus, increase the fixed carbon The pyrolysis of Mahua seeds was carried out in a semi-batch
content in bio-char. The ash content was higher in bio-char as com- reactor and a maximum of 49% bio-oil yield was obtained at
pared to raw biomass but less than that of standard Indian coal 525 °C and 20 °C/min heating rate under 30 cm3/min sweep gas
[35]. The non-volatile inorganic salts in Mahua seed might also flow rate. GC–MS results indicated that the bio-oil comprises more
contribute to the intensification of ash content. From ultimate aliphatic followed by aromatics and oxygenated compound. FTIR
analysis, it was inferred that carbon, the main element in bio- analysis determined that the oil was mainly composed of oxy-
char, increased in comparison to raw biomass, while oxygen and genated species. The Mahua bio-oil ascertained could be ranked
hydrogen content decreased. The high carbon content in bio-char as carbon chain range of C7AC27 which indicates that the bio-oil
indicates dehydration and decarboxylation reactions from thermal was the mixture of gasoline and diesel. However, the empirical for-
decomposition of biomass which results in the removal of oxygen mula of bio-oil derived was CH1.58N0.03S0.005O0.19 and H/C ratio of

Fig. 8. SEM images of Mahua bio-char with 500 and 750 magnification.
538 D. Pradhan et al. / Energy Conversion and Management 108 (2016) 529–538

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