Accepted Manuscript

Title: Detailed Characterization of bio-oil from pyrolysis of

non-edible seed-cakes by Fourier Transform Infrared
Spectroscopy (FTIR) and Gas Chromatography Mass
Spectrometry (GC-MS) techniques

Authors: Vatsala Sugumaran, Shanti Prakash, Emmandi

Ramu, Ajay Kumar Arora, Veena Bansal, Vivekanand
Kagdiyal, Deepak Saxena

PII: S1570-0232(17)30079-X
DOI: http://dx.doi.org/doi:10.1016/j.jchromb.2017.05.014
Reference: CHROMB 20603

To appear in: Journal of Chromatography B

Received date: 18-1-2017

Revised date: 9-5-2017
Accepted date: 11-5-2017

Please cite this article as: Vatsala Sugumaran, Shanti Prakash, Emmandi
Ramu, Ajay Kumar Arora, Veena Bansal, Vivekanand Kagdiyal, Deepak
Saxena, Detailed Characterization of bio-oil from pyrolysis of non-edible
seed-cakes by Fourier Transform Infrared Spectroscopy (FTIR) and Gas
Chromatography Mass Spectrometry (GC-MS) techniques, Journal of Chromatography
Bhttp://dx.doi.org/10.1016/j.jchromb.2017.05.014

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Highlights of the paper:

 Pyrolysis of jatropha and karanjia seed-cake carried out.

 Multiple solvent extractions done to reduce the complexity of the sample.

 FTIR analysis carried out for identifying the major functional groups.

 Detailed component analysis for unumabigous determination of more than 80

components and class-wise distribution of compounds in bio-oils presented.

1
Detailed Characterization of bio-oil from pyrolysis of non-edible seed-cakes

by Fourier Transform Infrared Spectroscopy (FTIR) and Gas

Chromatography Mass Spectrometry (GC-MS) techniques

Vatsala Sugumaran*, Shanti Prakash, Emmandi Ramu, Ajay Kumar Arora, Veena Bansal,

Vivekanand Kagdiyal and Deepak Saxena

Indian Oil Corporation Limited, R & D Centre, Sector 13, Faridabad 121007, Haryana

Corresponding author e-mail: sugumaranv@indianoil.in

2
ABSTRACT

Bio-oil obtained from pyrolysis is highly complicated mixture with valued chemicals. In order to

reduce the complexity for unambiguous characterization of components present in bio-oil,

solvent extractions using different solvents with increasing polarity have been adopted. The

fractions have been analyzed by Fourier transform infrared (FTIR) spectroscopy for identifying

the functional groups and Gas chromatography-mass spectrometry (GC-MS), for detailed

characterization of components present in various fractions, thereby providing in-depth

information at molecular level of various components in bio-oil. This paper reveals the potential

of the analytical techniques in identification and brings out the similarities as well as differences

in the components present in the bio-oil obtained from two non-edible oil seed-cakes, viz.,

Jatropha and Karanjia.

Key words: pyrolysis; bio-oil; jatropha seed-cake; karanjia seed-cake; FTIR; gas

chromatography mass spectrometry

3
1.0 INTRODUCTION

Biomass provides an abundant, inexpensive and renewable resource for its application as

chemical feedstock for producing bio-oil and emerges as an attractive alternative to conventional

fuels. Gasification and liquefaction of biomass through pyrolysis route have emerged as key

thermodynamic processes for conversion of biomass to liquid bio-fuel. The pyrolysed oil or bio-

oil is considered as new low cost, clean and green bio-energy, and an attractive option in place of

conventional fuel in the aspect of reducing environmental pollution. Bio-oil has advantage of

transport, storage, combustion, retrofitting and flexibility in production and marketing [1].

Applications of bio-oil is limited because of high acidity (pH 2.5), high viscosity, low volatility,

corrosiveness, immiscibility with fossil fuels, thermal instability and tendency to polymerize on

exposure to air and oxygen. However, bio-oil can be upgraded to fuel and chemicals that fit in

our current fuel and chemicals infrastructure. Hydrotreatment is an effective way to convert

unsaturated compounds into some stable ones, but having an established catalyst for this process

is still a challenge. Some of the upgradation techniques are catalytic cracking, Steam reforming

and emulsification [2-5]. NREL demonstrated reforming of bio-oil in a bench-scale fluidized

bed system using several commercial as well as custom-made catalysts and obtained a hydrogen

yield of 70% [6]. Biomass contains varying amount of cellulose, hemicelluloses and lignin, its

pyrolysis produces products that is sum of individual pyrolysis of the three components. Hence

the chemical nature of bio-oil is closely related to ratio of these components in biomass. Bio-oil

is a mixture of more than 300 compounds resulting from depolymerization of cellulose, hemi-

cellulose and lignin. Oxygen content and water content of bio-oil is in the range of 40-50% and

25-35% respectively. This results in low calorific value of around 16-18MJ kg-1[7-8]. It is

therefore necessary to get an insight of molecular composition of the crude pyrolysis oil and

4
upgraded products for optimizing the use of bio-oils, so obtained. Chemical composition of bio-

oil gives insight into its quality and stability. This information is crucial for development of

efficient catalytic upgradation processes to meet the required product properties.

Molecular-level characterization of bio-oil has been studied using different analytical techniques

like Gas chromatography-mass spectrometry (GCMS), Fourier transform infrared (FTIR)

spectroscopy, Nuclear magnetic resonance (NMR) spectroscopy and classical elemental analysis

[9-10]. Bio-oil obtained from pyrolysis of empty fruit bunches (EFB) of palm fruit was

characterized for various functional groups, using FTIR spectroscopy. Phenols, alcohols,

ketones, aldehydes, carboxylic acids, alkanes, alkenes and aromatics were identified in bio-oil

using characteristic IR stretching frequency in FTIR [11]. NMR spectroscopy has been used to

characterize fast pyrolysis bio-oils, energy crops and agricultural feedstocks [12].

GC-MS remains a preferred technique for the separation and identification of complex mixture

of components in bio-oil. Quadrupole GCMS has been used for characterization of bio-oil from

pyrolysis of switch-grass at different temperatures [13]. In the last decade comprehensive two

dimensional GC with improved chromatographic resolution in combination with Time of flight-

mass spectrometry (ToF-MS) with fast scanning abilities are used for separation and

identification of pyrolysis oil [14]. However, these instruments are expensive and spectral

libraries are fewer than for Quadrupole mass spectrometers. Moldoveanu et al. has developed a

direct pyrolysis technique for cellulose and identified more than 100 components with a

molecular weight range of 45 to 210 u including aldehydes, ketones, furans and other phenolic

derivatives [15]. Pyrolytic products from cellulose lignin and sewage were analyzed by 2D-GC-

ToF MS in the mass range of 40 to 300 u and over 1000 components have been identified and

further grouped into different classes [16]. Marsman et al has carried out orthogonal separation

5
by comprehensive two-dimensional gas chromatography of fast pyrolysis of Beech oil to

maximize chromatographic resolution and GC-quadrupole mass spectrometry has been used to

obtain structural information [17].

Characterization of intermediate pyrolysis oils derived from sewage sludge (SSPO) and

delinking sludge (DSPO) from paper industry residue with a view to study their use as fuel in

diesel engine has been reported [18]. Most of the important physical and chemical properties of

the oil were analyzed and compared with conventional diesel and bio-diesel fuels by Yanik et al

[19]. Water insoluble fractions of pyrolysed oil from three agricultural wastes - corncob, straw

and oreganum stalks at 500 0C in a fluidized bed reactor were analyzed by GC-MS and liquid

chromatography (LC) by Tsai et al [20]. Another interesting study underlying the chemistry of

thermochemical conversion systems and several aspects of pyrolysis has been investigated using
1
free-jet molecular-beam mass spectrometric sampling (MBMS) [21]. H and 13C NMR

spectroscopy were used for the identification of functional groups and gauging the aromatic

carbon content in the bio-oil for aromaticity and functional groups in bio-oil from hydrothermal

liquefaction of organic waste and Fourier-transform ion cyclotron resonance mass spectrometry

(FTICR-MS) having ultrahigh resolution and mass accuracy capability for describing aromatic

components [22]. Progressive extraction of bio-oil with various solvents based on solubility has

been adopted for classification of compounds [23].

Seed-cakes after removal of oil from plant seeds is generally used as manure, fodder or fuel.

Seed-cakes can be converted to fuel, energy and chemicals by thermo chemical processes like

pyrolysis. The advantages of this process over other process like biochemical process are

feedstock flexibility and conversion of lignin and carbohydrates [24-25]. Decomposition

products of jatropha waste, including husk, seed shell and branch have been investigated for

6
desirable organic compounds in the liquid and its characterization has been done using Py-

GC/MS [26]. An extensive liquid-liquid extraction approach has been adopted to separate the

components of bio-oil from jatropha curcas seed-cake and identification of components present

has been reported [27]. Although characterization of jatropha waste has been carried out,

detailed characterization of pyrolysed products of jatropha and karanjia seed-cake has not been

reported.

In the present study, pyrolysed bio-oil derived from Jatropha (JSCBO) and Karanjia seed-cake

bio-oil (KSCBO) have been fractionated by solvent extraction method using solvents of

increasing polarity in order to reduce the complexity of the oil for in-depth characterization of

components present in the extracted fractions. GPC analysis of the seed-cake and their fractions

were also analyzed by FTIR technique to identify the functionality and GCMS for detailed

components present in the individual fractions and further classified into classes depending on

their chemical nature.

2.0 EXPERIMENTAL

2.1 Pyrolysis:

Dried Jatropha and Karanjia seed-cake were crushed to particle size less than 1-2 mm in ball mill

and sieved. Thereafter the feedstock prepared was dried in oven at 100 0C to have moisture

content below 5%. The feed stock prepared was subjected to pyrolysis in a reactor of feed rate

of 20 kg/h. The pyrolysis was performed in temperature range of 460 to 500 0C. under nitrogen

atmosphere of flow 1-2 L/min for time period of 15-20 minutes. The pyrolysis experimental

conditions of temperature and time were optimized to obtain maximum bio-oil yield of ~30-40

wt. % biochar produced was in range of 40% and ~20% gas were produced. Two-stage cooling

was employed to obtain bio-oil with low moisture content. The bio-oil obtained under optimized

7
pyrolysis conditions had moisture content of 7-8%. Detailed physico-chemical property

evaluation was also carried out.

2.2 Materials

JSCBO and KSCBO for this study were obtained from pyrolysis of their respective seed-cakes.

The solvents used for extraction of bio-oil components were hexane (Hex), benzene (Benz),

dichloromethane (DCM), ethyl acetate (EA) and methanol (MeOH) of AR grade.

2.3 Solvent Extraction method.

2 grams of pyrolysed JSCBO and KSCBO samples were filtered using steel strainer of pore size

0.8µm. The filtered sample was washed twice with demineralized water to bio-oil ratio at 10%.

The water wash was found to have traces of short chain acids like formic and acetic acid in

insignificant amount. The water-insoluble fraction was then extracted with multiple solvents

with increasing polarity. Hexane, benzene, dichloromethane, ethyl acetate and methanol were

used for solvents extraction sequentially. The bio-oil was extracted sequentially twice with 30ml

of solvent in a ultrasonic bath for 20 mins for every solvent. The fractions were filtered with

Buchner funnel under vacuum. The water vapor from the filtrate sample was removed using

sodium sulfate. The filtrates were then carefully evaporated in rotavapor equipment to remove

the solvent. The evaporated sample fractions were weighed. The bio-oil fractions extracted in

each solvent was calculated using equation 1 given below:

(eq.1)

2.4 Gel Permeation Chromatography (GPC)

Viscotek gel permeation chromatograph equipment fitted with Triple Detector Array - UV-PDA,

RI, Viscosity detectors was used for analysis of bio-oil. Three Viscotek GPC columns T4000-

T2000-T1000 (polystyrene divinyl benzene) columns of dimension 300 x 8 mm were used

8
separation of different molecular weight of bio-oils. Column temperature was maintained at 35 0

C during the whole chromatographic run and RI (refractive index) detector was used for

detection. 1% solution of bio-oil in tetrahydrofuran (THF, HPLC grade from Spectrochem) was

prepared and 100 µl volume was injected in the injector port. THF was used as mobile phase

with flow rate of 1.0 ml/min. The GPC column was standardized using n-paraffin standards in

the range of 140-620 Da. The GPC data was processed using Omnisec software.

2.5 FTIR

FTIR spectra of bio-oil and their solvent fractions were recorded by placing small drop of the

sample on KBr plate. The acquisition parameters are wavelength range 4000-400cm-1,

resolution 4 cm-1, and 50 scans. Infrared spectrometer (DLATGS detector) IR Prestige-21 model

from Shimadzu Corp., Japan was used. Spectra were processed for base line correction, smooth

and peaks using IR Solution software.

2.6 Gas Chromatography Mass Spectrometry

Analysis of bio-oil fractions were carried out on Autospec Ultima High resolution mass

spectrometer coupled with Agilent 6890N Gas Chromatograph. The mass spectrometer was

tuned for experiments in the mass range of 50 to 500u. Perfluorokerosene (PFK) was used as

reference compound for calibration of masses. The magnet scan was set at 0.5 seconds/ decade

and interscan delay of 0.1 second. Ionization of samples in the mass spectrometer was carried

out using electron of 70eV. Data acquisition and processing were done using OPUS 3.6V

software and NIST mass spectral library was used for identification of components in the

samples.

Capillary column DB5 (30m x 0.25mm id, 0.32µm film thickness) was used for separation of

components in bio-oil fraction. The GC conditions set for the analysis are as follows:

9
Oven Temperature (Initial) : 60 0C (hold 3min)

Ramp rate I : 3 0C /min

Oven II Temperature : 100 0C (hold 1min)

Ramp rate II : 5 0C / min

Oven III Temperature (Final) : 300 0C (hold 1min)

Helium flow rate : 1.2 ml / min

Injector temperature : 300 0C

Interface temperature (splitless) : 225 0C

0.4µL of sample in solvent (respective solvents used for extraction) was injected through the

heated injector port of the gas chromatograph. Simultaneously, magnet scan and data acquisition

were initiated. For quantitative analysis peak area of individual components was considered.

3.0 RESULTS AND DISCUSSION

Published literature on fast pyrolysis of biomass indicates that pyrolysis produces 60–75 % w/w

of oily products (oil and other liquids) with 15–25% of solids (mainly biochar) and 10–20% of

gaseous phase depending on the feedstock used [28]. Different components, classified in groups

of organic acids, aldehydes, ketones, furans, phenolic compounds, and other sugar based

components has been identified in bio-oil derived from lignocellulosic feedstock [29]. Moisture

and ash contents of JSCBO and KSCBO used in the study are 8-10% and 0.05% respectively.

Bio-oil was obtained in the range of 16-20 wt. % for Jatropha and 30-40wt. % for Karanjia seed-

cake. Moisture and ash contents of JSCBO and KSCBO used in the study were 8 -10% and

0.05% respectively. Moisture content of the bio-oils samples were determined by ASTM D 95.

The ash content was determined by ASTM D 482 for the bio-oils. Since pyrolysis of the seed-

cakes produces bio-oil, pyrolytic char, gas and water, the bio-oils are usually associated with

10
some moisture, even after the removal by various methods [30]. Presence of nitrogen,

phosphorus and potassium has been reported in jatropha seed-cake and hence presence of 0.05 to

0.1% ash can be expected [31]. The recovered solvents from the rotavapour also analyzed by

GCMS technique did not show presence of any low boiling components of bio-oils. Table 1

provides details of physico-chemical properties of typical Jatropha and Karanjia seed-cake bio-

oil products. Figure 1 shows percentage weight of bio-oil fractions sequentially extracted with

each solvent of increasing polarity.

3.0 GPC

Overlay chromatogram of JSCBO and KSCBO is shown in (Fig S1, see Supporting Material)

GPC chromatogram of JSCBO and KSCBO showed one major component, constituting nearly

90% from the chromatogram peak area and in the molecular weight range of 300 to 350 daltons.

Higher molecular weight components were found to be around 10% in the molecular weight

range of 400 to 600 daltons. The GPC chromatograms showed the presence of 4 to5 components

based on separation of molecular weight.

3.1 Fourier Transfer Infrared (FTIR) analysis

Figure 2 shows the IR spectra of JSCBO solvent extracted fractions. Sample as such shows the

presence of phenol / alcohol (3288cm-1), carboxylic acid (1710cm-1) and amide (1660cm-1)

functional groups clearly. Hexane and benzene fractions of JSCBO showed enrichment of

phenols / alcohols (3288cm-1), amides (1660cm-1), aromatics / substituted aromatics (850 –

650cm-1) and low quantity of carboxylic acids, long chain olefin moieties (3005cm -1). The only

difference observed from the IR spectrum of EA and DCM fractions is due to presence of acid

moieties in the EA fraction. Figure 3 shows the IR spectra of KSCBO solvent extracted

fractions. Hexane, benzene, ethyl acetate and dichloromethane fractions of KSCBO shows

11
similar components like saturated / un-saturated fatty acid (1707 cm-1), amide (1660 cm-1) and

aromatics / substituted aromatics (800 – 650cm-1). Esters of fatty acids were present in hexane

fraction. Methanol fraction was also found to be rich in amide and phenols compared to other

fractions.

3.1 GCMS analysis

Detailed components analysis of Bio-oil fractions was carried out on the Autospec Ultima HR-

GCMS system. TIC chromatogram for each fraction was recorded as per GCMS conditions

explained in experimental section. Individual components in each fraction have been identified

using NIST mass spectral library, retention index and boiling point data of the compounds.

Table 2 and 3 represent the detailed component analysis of the compounds present in each

fraction of JSCBO and KSCBO. For quantitative analysis, peak area of individual components

was considered.

3.1.1 Hexane Fraction

From the total fraction weight percentage, around 32 wt. % of the JSCBO was extracted with

hexane and its total ion current (TIC) chromatogram is shown in Figure 4. GCMS analysis

shows the presence 34 compounds using NIST library. It has been confirmed that the major

components present in this fraction were methyl ester of fatty acid up to 12.8 and free fatty acids

up to 8.9 wt% respectively. GCMS analysis indicates presence of alkanes and alkenes in the

range of C14 –C20 in the concentration range of 0.7 and 0.6 wt. % respectively in this fraction.

Major fatty acids found in the mixture were C18:2, C18:1 and C16:0, whereas C20:0 was found

in lesser amounts. Figure 5 show the EI mass spectrum of C18: 1 acid present in the sample.

GCMS analysis of the fraction shows the presence of methyl ester of C18 fatty acids (FAME).

Presence of FAME in crude bio-oil composition is not common and has not been reported.

12
Therefore from the findings of GCMS analysis it may be assumed that certain fatty acids,

especially C18 acids have been converted to methyl esters during pyrolysis process, where

conditions are favorable for trans-esterification [28]. Presences of indole, C1 to C3-indoles upto

0.7 wt. % and C16 - C18 alkyl amides upto 0.6 wt. % were also identified in this fraction.

Presence of these nitrogen compounds in proteinaceous biomass has been reported earlier.

In case of KSCBO, around 42.0 wt.% of sample was extracted with hexane showed prominent

presence of fatty acid up to 27.0 wt. %, out of which around 4.0 wt. % represents methyl ester

converted fatty acids unlike in case of JSCBO, showing the presence of more fatty acid methyl

esters. Fatty acids in the range of C16 - C18 up to 23.0 wt. % and fatty acid methyl ester up to 3.9

wt. % were also identified in the fraction. The fatty acids observed in the C18 range were largely

unsaturated with single or double bond as in case of JSCBO, whereas methyl esters of the fatty

acids were in the wider range from C16 to C22. Alkanes in the carbon range C11-25 up to 3.2 wt%

and alkenes /alkynes in C11-19 up to 2.6% were observed. Long chain alkyl amide from C16 to C18

alkyl chains were also found in this fraction. Unlike in the case of hexane fraction of JSCBO, the

KSCBO fraction showed presence of only substituted phenols in the concentration range of 1.0

wt. % and presence of methoxy phenols were inconspicuous. This fraction also showed the

presence of fatty acid amides from C16 to C18 range as in the case of JSCBO. It was observed

from FTIR and MS studies that in addition to non-polar compounds, some polar compounds like

long alkyl chain fatty acids and amides were also found to be present in the hexane fraction that

behaved like non-polar compounds during extraction.

3.1.2 Benzene Fraction

Benzene extraction of total bio-oil sample was 28.4 wt. % in JSCBO. GCMS analyses of this

fraction also confirmed that C16:0, C18:0, C18:1 and C18:2 fatty acids, either in the form of free

13
acid or their methyl ester major component were present. From the TIC chromatogram, the

concentration of fatty acid was found to be in the range of 7.0 wt. %, of which hexadecanoic acid

as major one. The fatty acid in the methyl ester form was in the range of 8.1wt %, out of which

oleic and linoleic acid were almost 7.9 wt %. Phenols and methoxy phenols were identified in

up to 4.9 wt. %. The major component among the phenols was 4-ethyl-2-methoxy phenol, as

confirmed by mass spectrum. N-aromatics like indole, methyl and dimethyl indoles were present

up to 2.6 wt. %. Aromatic compounds like naphthalene and diphenyl propane were found to be

present in traces.

KSCBO showed C16 to C18 fatty acids as major class of compounds present in this fraction

constituting to 15.7 wt. %, out of the 29.6 wt. % total fraction weight. Additionally, it is observed

that 3.0 wt. % of fatty acids exists in the form of methyl esters. Long chain amide in C 16 to C18

carbon range makes up to 1.6% sample weight. Alkanes and alkenes in the concentration range

of 1.6 and 1.4 wt. % were also observed in this fraction. Aromatic hydrocarbons like lower alkyl

benzene in range from C3 - C7, naphthalenes and substituted phenols were present in low

concentrations. It was observed from the GCMS analysis that major quantity of alkanes, alkenes,

low molecular weight aromatics hydrocarbons and phenols has been extracted in hexane and

benzene fractions.

3.1.3 Dichloromethane fraction

12.0 and 10.5 wt. % of the bio-oil was extracted with DCM in the case of jatropha and karanjia

seed-cakes respectively. TIC chromatogram of the fractions showed the presence of phenols and

methoxy phenols with alkyl chain length from C1-C4 up to 5.5 wt. %. Methoxy phenols with this

alkyl chain length appear to be distributed in both benzene and DCM fraction. Fatty acids and

their methyl esters up to 2.6 and 1.1 wt. % respectively were indentified. Methyl, diethyl and

14
methoxy indoles up to 1.2 wt. % have also been found. This fraction of JSCBO showed presence

of oxy-aromatic compounds like dihydorbenzofuran and benzene diol up to 1.2 wt. %.

From the TIC chromatogram of dichloromethane fraction of KSCBO, it has been inferred that

fatty acid is present up to 8.3 wt%. From Table 3 and individual component analysis, it is

obvious that the presence of phenols and methoxy phenols is in very small amount, i.e., 0.4 wt %

as compared to that of JSCBO fraction containing 5.5 wt. % of the same components. This

fraction of KSCBO showed the presence of oxo-aromatic compounds, such as tetrahydroxy

naphtho [1,2-b]furan-dione showing molecular ion at m/z 262 and major fragment ion at m/z 160

in concentration range of 0.6 wt. % and another compound, i.e., 2-methylamino-3-(N,N-

methylphenylamino)-1,4napthaoquinone with major molecular ion at m/z 291 and fragment ion

at m/z 160 in traces. Probability of the presence of these compounds in the pyrolysed sample

may be due to breaking down and rearrangement of large lignin and protein molecules during

pyrolysis.

3.1.4 Ethyl Acetate fraction

Detailed compositional analysis of this fraction as inferred from the GCMS analysis showed the

presence of same components as found in the DCM fraction with variation in their intensities.

However, saturated hydrocarbons and lower phenols were found only in traces in the sample.

TIC chromatogram of JSCBO showed higher amount of FAME (3.7 wt. %), fatty acids up to 2.0

wt. % and phenols and methoxy phenols in concentration range of (2 wt. %) by weight.

Benzenediol and ethylbenzenediol were also present up to 1wt. % in the sample.

GCMS analysis of EA fraction of KSCBO showed the presence of fatty acids (1.2%) and amides

(0.3%), tetrahydroxy naphtho[1,2-b]furan-dione (0.6%) and 2-methylamino-3-(N,N-

15
methylphenylamino)-1,4 napthaoquinone in traces were identified from mass spectra of the

sample. Figure 1 shows the extraction of only 2 wt. % of the sample weight in EA.

3.1.5 Methanol Fraction

16.9 wt % of the JSCBO was extracted in MeOH. GCMS analysis of MeOH extracted bio-oil

showed major components as phenols. Total phenols in the fraction are determined as 8.4 wt %.

The fractions shows exclusive extraction of long chain pentadecenyl and pentadidecenyl phenols

as major constituent, amounting to 5.6, out of total 8.4 wt %. Figure 6 represents the EI

spectrum of pentadecenyl phenol in the sample. Pentadecanyl phenols are present in the range of

1.2 wt%. Other lower phenols in carbon range C6 to C9 are present in less concentration.

Tetrahydroxy naphtho[1,2-b]furan-dione and 2-methylamino-3-(N,N-methylphenylamino)- 1,4

napthaoquinone were indentified in the concentration range of 0.3 wt%. Octadecenamide

(m.wt. 282) and butyl-N-benzylamide (m/z 268) in the concentration of 1.2 and 0.8 wt %

respectively. 2.2 wt. % of methyl ester of fatty acid and 0.8 wt. % of fatty acids are the other

components identified in this fraction, along with 1.8 wt. % of other unidentified components.

15.4 wt % of the KSCBO was extracted with MeOH. Tetrahydroxy naphtho[1,2-b]furan-dione,

amounting to 6.4 wt % and 1.0 wt % of 2-methylamino-3-(N,N-methylphenylamino)-

1,4napthaoquinone were present. Other constituents of the fraction were free fatty acids along

with their amides and esters. About 0.8 wt % of components in JSCBO and KSCBO fractions

could not be identified.

Table 4 shows the comparison of class-wise distribution of components extracted in hexane,

benzene, dichloromethane, ethyl acetate and methanol solvents.

4.0 CONCLUSION

16
Each category of bio-oil needs a more critical protocol based separation for clear identification of

components present using various analytical techniques. In this work bio-oil fraction has been

characterized by FTIR and GCMS technique to provide in-depth information at molecular level

of components present. Fatty acids and their methyl ester along with amides (C16 to C18) were

predominantly found in hexane and benzene fractions. Valuable chemicals like phenols and

methoxy phenols were obtained in polar bio-oil fractions. Presence of long alkyl chain phenols

and oxygenated compounds were identified in methanol fractions of JSCBO and KSCBO

respectively.

17
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[15] S.C. Moldoveanu, J. Microcolumn Sep. 13 (2001) 102.
[16] A. Fullana, J. A. Contreras, R.C. Striebich, S.S. Sidhu, J. Anal. Appl. Pyrol. 74 (2005) 315.
[17] J.J. Marsman, J. Wildschut, F. Mahfud, H.J. Heeres, J. Chromatogr. A. 1150 (2007) 21.
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(2013) 247.
[19] J. Yanik, C. Kornmayer, M. Saglam, M. Yuksel, Fuel Process. Technol. 88 (2007) 942.
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D. Angelis, ChemSusChem. 6 (2013) 160.

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222.
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Sharma, J. Anal. Appl. Pyrol. 118 (2016) 202.
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19
Figure captions

Figure 1. Bio-oil fractions extracted with different solvent

Figure 2. Overlay FTIR spectra of JSCBO solvent fractions.

Figure 3. Overlay FTIR spectra of KSCBO solvent fractions.

Figure 4. EI mass spectrum of C18: 1 acid present in hexane fraction of JSCBO

Figure 5. TIC chromatogram of Hexane fraction of JSCBO

Figure 6. EI mass spectrum pentadecyl phenol present in MeOH fraction of JSCBO

Table titles
Table 1: Physico-chemical properties of bio-oils from Jatropha and Karania seed-cake
Table 2: Detailed component analysis of JSCBO solvent fractions by GCMS
Table 3: Detailed component analysis of KSCBO by GCMS
Table 4: Comparison of Compounds classes in hexane/benzene/DCM/EA/MEOH fractions of
JSCBO and KSCBO

20
Table 1: Physico-chemical properties of bio-oils from Jatropha and Karanjia seed-cake
S No Test Method Typical Results
1 Density @15C (gm/ml) ASTM D 4052 1.02 – 1.04
2 Metal Content (wt. %) ICAP Ca=15ppm,Mg=6ppm,
Zn=12ppm,
Ni=3ppm,Si=50ppm,other
metals<1ppm
3 Carbon Residue Content (wt. %) ASTM D 4530 9.65 – 9.95
(MCR) %wt.
4 Acid Number ASTM D664 91-100
5 Inorganic Acidity D974 Nil
6 Water Content % wt ASTM 95 8 – 10
7 Kinematic viscosity @400C (cSt) ASTM D445 207 – 210
8 Pour point Deg C ASTM D97 21 -250C
11 Ash content, %wt ASTM D-482 0.05 -0.1%
12 Calorific Value (MJ/kg) ASTM,D-240 33.2 - 37.0
14 Elemental Analysis (wt. %) ASTM D-5291
C 64.3 – 65.0
H 8.0 -10
N 3.9 – 4.0
O 21.2 -22.0

21
Table 2: Detailed component analysis of JSCBO solvent fractions by GCMS
M.
S.No. Components Formula M.wt Hex Benz DCM EA MeOH
%wt %wt %wt %wt %wt %wt
Methyl pentenone C6H10O 98 nd nd nd nd 0.2
1.
Methyl hydroxy pentanone C6H12O2 118 nd nd nd nd 0.1
2.
Phenol C6H6O 94 nd nd 0.9 0.3 nd
3.
4-methyl phenol C7H8O 108 0.2 0.1 0.2 0.1 0.3
4.
3-methyl phenol C7H8O 108 0.2 0.4 0.8 0.6 nd
5.
Methoxyphenol C7H8O2 124 1.0 0.9 0.7 nd nd
6.
Dimethyl aniline C8H11N 121 nd nd 0.2 nd nd
7.
Hydroxybenzyl alcohol C7H8O2 124 nd 0.1 nd nd nd
8.
Tetramethyl piperidinone C8H17NO 140 nd nd nd nd 0.6
9.
Methyl benzenenitrile/Indole C8H7N 117 nd 0.1 nd nd nd
10.
Dimethyl Phenol C8H10O 122 nd 0.1 nd nd nd
11.
2,4-dimethylphenol C8H10O 122 0.2 0.1 nd 0.1 nd
12.
2,4-ddimethylphenol C8H10O 122 nd 0.1 0.3 0.2 nd
13.
Ethylphenol C8H10O 122 nd nd nd nd 0.2
14.
Propylphenol C9H12O 136 nd 0.4 0.3 nd nd
15.
Napthalene C10H8 128 0.3 0.2 nd nd nd
16.
1,4-dimethoxybenzene C8H10O2 138 0.1 0.1 nd nd nd
17.
Methyl-methoxyphenol C8H10O2 138 0.1 0.3 0.3 nd nd
18.
Methyl-methoxyphenol C8H10O2 138 0.2 0.1 nd nd nd
19.
2,3-dihydrobenzofuran C8H8O 120 nd 0.1 0.2 nd 0.1
20.
Benzenediol C6H6O2 110 0.1 0.1 0.4 0.7 nd
21.
Benzenepropanenitrile C9H9N 131 nd 0.1 nd nd nd
22.
p-ethyl anisole C9H12O 136 nd nd 0.2 nd nd
23.
Propylphenol C9H12O 136 nd 0.1 nd nd nd
24.
4-methyl-2-methoxyphenol C9H12O2 152 0.7 0.6 0.5 nd nd
25.
2-methoxy-3-(1-methylethyl)pyrazine C8H12N2O 152 nd nd 0.2 0.2 nd
26.
4-methylbenzaldoxime C8H9NO 135 0.1 0.1 nd nd nd
27.
Indole C8H7N 131 nd 0.3 0.3 0.2 0.1
28.
Methylnapthalene C11H10 142 0.1 nd nd nd nd
29.

22
 Tetramethylphenol C10H14O 150 0.1 0.1 0.2 0.1 0.1
30.
Eugenol (isomer) C10H12O2 164 0.2 0.1 nd 0.1 nd
31.
Methylbenzenediols C7H8O2 124 nd 0.1 nd 0.1 nd
32.
Methoxy-propenylphenol C10H12O2 164 nd 0.1 0.5 nd nd
33.
Heptyl benzene C13H20 176 0.2 nd nd nd nd
34.
2,6-dimethoxy phenol C8H10O3 154 0.2 0.1 nd nd nd
35.
2-methoxy-4-propylphenol C10H14O2 166 nd 0.1 0.2 0.5 nd
36.
Dihydroxy phenyl acetamide C8H9NO3 167 nd 0.1 nd nd nd
37.
3-methylindole/3-methyl indolizine C9H9N 131 0.2 0.2 0.2 0.1 nd
38.
Tetradecene C14H28 196 0.1 nd nd nd nd
39.
Tetradecane C14H30 198 0.1 nd nd nd nd
40.
Eugenol (isomer-propenyl) C10H12O2 164 0.1 0.1 0.4 0.1 0.1
41.
Ethylbenzenediol C8H10O2 138 nd 0.1 nd 0.1 nd
42.
Eugenol (isomer-propenyl) C10H12O2 164 0.5 0.2 0.8 0.2 nd
43.
C-2 Indoles C10H11N 145 0.2 0.4 0.2 0.1 nd
44.
N-ethyl indole C10H11N 145 0.2 0.3 nd nd nd
45.
p-tert-butylcatechol C10H14O2 166 0.1 0.2 nd 0.1 nd
46.
Pentadecene C15H30 210 0.1 0.2 nd 0.1 nd
47.
Pentadecane C15H32 212 0.2 0.2 nd nd nd
48.
unidentifieds - - 0.1 0.4 nd nd nd
49.
Vanillyl methyl ketone C10H12O3 180 0.1 0.1 0.1 nd nd
50.
4-hydroxy-3-methoxybenzene C9H10O3
182 0.1 0.1 0.1 nd nd
51. acetic acid
1,1'-Ethylidinebisbenzene C14H14 182 nd nd 0.1 0.1 nd
52.
Methyl ester of dihydroxy phenyl C9H10O4
182 nd nd nd 0.2 nd
53. acetic acid
Trimethoxymethylbenzene C10H14O3 182 0.1 0.1 0.2 nd nd
54.
Hexenyl phenol C12H16O 176 0.1 nd nd nd 0.1
55.
Trimethylindole C11H13N 159 0.1 0.1 nd nd nd
56.
hexyl phenol C12H18O 176 0.1 nd nd nd 0.1
57.
Unidentified - - 0.3 0.2 nd nd nd
58.
Diphenyl propane C15H16 - - 0.3 nd 0.1 nd
59.
Unidentified - - 0.8 0.8 nd 0.1 nd
60.
Pyrazolo[5,1c][1,2,4]-benzotriazin-8-ol C9H6N4O 186 0.1 0.1 0.1 nd nd
61.

23
 Unidentifieds - - 0.0 0.7 nd nd nd
62.
Octenyl phenol C14H20O 204 nd nd nd nd 0.1
63.
Octyl phenol C14H22O 206 nd 0.4 nd nd 0.2
64.
Unidentifieds - - 0.1 0.5 nd nd nd
65.
Nonenyl phenol C15H22O 218 nd nd nd nd 0.1
66.
Nonyl phenol C15H24O 220 nd nd nd nd 0.1
67.
n-Nonadecane C19H40 268 0.3 nd nd nd 0.1
68.
Methyl ester of hexadecanoic acid C17H34O 270 0.4 0.1 nd nd nd
69.
Dibutyl phthalate C16H22O4 278 0.1 0.2 0.1 nd nd
70.
Hexadecanoic acid C16H32O2 256 6.9 4.1 2.3 2.0 0.2
71.
Dihydroxy benzoic acid C7H6O4 154 nd nd nd nd nd
72.
Eicosane C20H42 282 nd nd nd nd 0.1
73.
Hexadecanoic acid C16H32O2 256 nd nd nd nd 0.4
74.
Butyl-N-benzylamide C18H22NO 268 0.1 0.1 nd 0.1 0.8
75.
Unidentifieds N compounds - - 0.6 1.2 nd nd 0.3
76.
Aminodiphenylimidozole+Methyl C15H13N3
235/292 nd nd nd nd 0.1
77. ester of C18:3
Methyl ester of octadecadienoic -
- nd 0.6 nd nd nd
78. acid
Methyl ester of octadecadienoic C19H34O2
294 0.8 0.1 nd nd nd
79. acid
Methyl ester of octadecenoic acid C19H36O2 296 1.3 0.6 0.2 nd nd
80.
Methyl ester of octadecenoic acid C19H36O2 296 0.4 0.1 nd 0.1 nd
81.
Methyl ester of octadecanoic acid C19H38O2 298 0.3 0.1 nd nd 1.9
82.
Octadecadienoic/~20%octadecenoic
C18H32/34O2 280/282 9.6 6.4 0.7 3.6 0.4
83. acid
Hexadecanamide C16H33NO 255 nd nd 0.1 0.2 nd
84.
Octadecanoic acid C18H36O2 284 1.8 2.9 0.2 0.4 0.3
85.
Octadecanal C18H34O 266 0.3 0.1 nd nd nd
86.
Tridecyl phenol C19H32O 276 nd 0.1 nd nd 0.4
87.
Unidentifieds - - nd 0.5 nd nd nd
88.
Octadecenamide C18H35NO 281 0.2 0.2 0.1 0.1 1.6
89.
Octadecanamide C18H37NO 283 0.4 0.1 nd nd 0.3
90.
Arachadic acid C20:0 C20H40O2 312 0.4 nd nd nd nd
91.
Unidentifieds - - 0.1 0.2 nd nd 0.1
92.

24
 Penta-decenyl/decnyl
C21H34/30O 298 0.1 nd nd nd 0.8
93. phenol(C13:1&3)
Penta-decnyl/dienyl phenol
C21H34/32O 300/302 nd nd nd nd 4.8
94. (C15:1&2)
Penta-decanyl phenol (C15:0) C21H36O 304 nd nd nd nd 1.2
95.
Tetrahydroxy naptho[1,2-b]furan
C23H6O7 262 nd 0.1 nd nd 0.3
96. dione (T)
unidentified - - 0.1 0.1 nd nd 0.6
97.
Total 31.8 28.4 12.3 10.7 16.9
*Note: Hex=hexane, Benz=benzene, DCM=dichlorobenzene, EA=ethyl acetate, MeOH=methanol

25
 Table 3: Detailed component analysis of KSCBO by GCMS
S.No. Components M. formula M.wt Hex Benz DCM EA MeOH
%wt %wt %wt %wt %wt %wt
3-methyl phenol C7H8O 108 0.3 0.2 nd 0.1 nd
1.
4-methyl phenol C7H8O 108 0.2 0.2 0.3 nd nd
2.
Undecene C9H12 154 0.2 0.0 nd nd nd
3.
Naphthalene C8H10 128 0.1 0.2 nd nd nd
4.
Dodecene C12H24 168 0.2 0.1 nd nd nd
5.
Dodecane C12H26 170 0.3 0.1 nd nd nd
6.
Benzene propanenitrile C9H9N 131 nd 0.2 nd nd nd
7.
Methyl naphthalene C11H10 142 0.2 0.1 nd nd nd
8.
Indole C8H7N 131 nd 0.2 0.2 nd nd
9.
Tridecene C13H26 182 0.4 0.1 nd nd nd
10.
Tridecane C13H28 184 0.4 nd nd nd nd
11.
Bifuran C8H6O2 134 0.1 0.3 0.2 0.1 nd
12.
Heptyl benzene C13H20 176 0.1 0.2 nd nd nd
13.
3-Methyl-1H-Indole/3-me indolizine C9H9N 131 0.3 0.3 nd 0.1 nd
14.
Tetradecene C14H28 196 0.5 0.2 nd nd nd
15.
Tetradecane C14H30 198 0.4 nd nd nd nd
16.
unidentifieds - - 0.4 0.3 nd nd nd
17.
Pentadecene C15H30 210 0.2 0.2 nd nd nd
18.
Pentadecane C15H32 212 0.5 0.1 nd nd nd
19.
Ditertiarybutylphenol C14H22O 206 0.1 0.1 0.1 nd 0.2
20.
Dipentenylpyridine(T) C15H21N 215 0.2 0.3 0.1 nd nd
21.
Hexadecynes C16H30 222 0.2 nd nd nd nd
22.
Hexadecene C16H32 224 0.1 0.5 nd nd nd
23.
Hexadecane C16H34 226 0.4 0.3 nd nd nd
24.
Heptadecyne C17H32 236 0.3 0.1 nd nd nd
25.
Heptadecene C17H34 238 0.5 0.2 nd nd nd
26.
Methyl -2,4 ditertiary butyl phenol C15H24O 220 0.3 0.2 nd nd nd
27.
n-Heptadecane C17H36 240 0.4 0.4 nd nd nd
28.
C9H6N4O 186 0.2 0.1 nd nd nd
29. Pyrazolo[5,1-c]1,2,4]benzotriazin-8-ol
unidentifieds - nd 0.1 0.8 0.2 nd 0.1
30.

26
 Dimethyl ester of 1,4- C10H10O4 194 nd nd nd nd 0.4
31. benzenedicarboxylic acid
unidentified - nd 0.2 0.1 nd nd nd
32.
n-Nonadecane C19H38 266 0.1 0.3 nd nd 0.2
33.
unidentified C19H40 268 0.5 nd nd nd nd
34.
Methyl ester of hexadecanoic acid C17H34O 270 0.1 0.3 nd nd 0.2
35.
Trihydroxy benzopyranone C9H6O5 194 0.1 0.4 0.3 nd nd
36.
Dibutyl phthalate C16H22O4 278 nd 0.2 nd nd nd
37.
Hexadecanoic acid C16H32O2 256 7.0 5.7 1.6 0.3 2
38.
unidentified - nd 0.9 nd nd nd nd
39.
Methyl ester of C18:1 & 2 acid - nd 3.2 0.3 0.2 nd 0.9
40.
Hexadecenamide C16H33NO 255 nd nd nd nd 0.4
41.
Methyl ester of octadecenoic acids C19H36O2 296 nd 2.0 nd nd nd
42.
Methyl ester of octadecanoic acid C19H38O2 298 0.4 0.3 nd nd 0.3
43.
Octadecenoic acid C18H34O2 282 6.1 4.3 2.3 0.3 0.1
44.
Octadecadienoic acid C18H32O2 280 6.1 4.4 2.5 0.4 0.1
45.
Octadecanoic acid C18H34O2 284 3.8 1.3 1.9 0.2 0.0
46.
Ocatadecenamide C18H35NO 281 1.2 0.3 0.2 0.2 1.0
47.
Ocatadecanamide C18H35NO 283 0.8 0.4 nd nd 0.3
48.
unidentified - nd 0.2 0.1 nd nd nd
49.
n-C23H48 - nd 0.2 0.1 nd nd nd
50.
N-methyl octadecenamide C19H37NO 295 0.4 0.4 nd nd nd
51.
Unidentifieds - - nd nd nd nd 0.9
52.
n-C24H50 C24H50 338 0.2 0.1 nd nd 0.1
53.
N-methyl octadecenamide C19H37NO 295 0.3 0.3 nd 0.1 nd
54.
Unidentified - - 0.2 0.4 nd nd nd
55.
Methyl ester of docosanoic acid C23H46O2 354 0.2 0.1 nd nd 0.4
56.
C23H6O7 262 nd 0.4 0.6 0.2 6.4
57. Tetrahydroxy naphtho[1,2b]furandione(T)
2-methyl amino-3-(N,N-dimethyl
C18H16N2O2 291 0.4 0.4 0.1 0.2 1.0
58. phenylamino)-1,4naphthoquinone
Higher paraffin > C25 - - 0.2 0.1 nd nd nd
59.
Higher unidentified and components less
- - 1.5 0.9 0.2 nd 0.7
60. than 0.1%
Total 41.9 29.6 11.0 2.2 15.4
61.
*Note: Hex=hexane, Benz=benzene, DCM=dichlorobenzene, EA=ethyl acetate, MeOH=methanol

27
Table 4: Comparison of Compounds classes in hexane/benzene/DCM/EA/MEOH fractions of
JSCBO and KSCBO
Hexane Benzene DCM EA MeOH
Class-wise JSC KS JSC KSC JSC KSC JSC KSC JSC KSC
distribution BO C BO BO BO BO BO BO BO BO
(%wt) BO
Alkanes 0.7 3.2 0.4 1.6 nd nd 0.1 nd 0.1 0.3
Alkenes/ nd 2.6 nd 1.4 nd nd nd nd nd nd
alkynes
Aromatic 0.5 0.8 0.4 0.7 0.3 nd 0.2 nd nd nd
Hydrocarbon
Fatty acids 8.9 23.0 7.0 15.7 2.6 8.3 2.4 1.2 0.9 2.0
Methyl esters 12.8 3.9 8.1 3.0 1.1 0.2 3.7 nd 2.2 1.8
of Fatty acids
N-Aromatics 1.4 0.4 2.6 0.8 1.2 0.2 0.6 0.1 1.0 nd
Phenols/ 4.2 1.0 4.9 0.7 5.5 0.4 2.0 0.1 8.4 0.2
methoxy
phenols
Amides 0.6 2.8 0.5 1.6 0.2 0.2 0.4 0.3 2.7 1.7
Ketones/ 0.4 nd 0.3 nd 0.1 nd nd nd nd nd
aldehydes
Miscellaneous 0.2 0.9 0.5 1.7 1.2 1.2 1.2 0.3 0.6 6.8
hetero-compds
Unidentifieds 2.1 3.2 3.6 2.4 0.2 0.4 0.1 0.2 1.0 2.7
Total 31.8 41.8 28.3 29.6 12.4 10.9 10.7 2.2 16.9 15.5
Note: *nd= not detectable (<0.1%)

28