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Journal of Analytical and Applied Pyrolysis


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Effect of catalytic vapour cracking on fuel properties and composition


of castor seed pyrolytic oil
Mithelesh Koul a , Krushna Prasad Shadangi b , Kaustubha Mohanty a,
a
b

Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati 781039, India
Department of Chemical Engineering, Veer Surendra Sai University of Technology, Burla 768018, India

a r t i c l e

i n f o

Article history:
Received 22 January 2016
Received in revised form 26 April 2016
Accepted 30 April 2016
Available online xxx
Keywords:
Biooil
Catalytic vapour cracking
Castor seed
Fuel properties
Composition analysis

a b s t r a c t
In this work, catalytic upgrading was carried out to enhance the yield and quality of castor seed pyrolytic
oil. The inuence of catalytic vapour cracking of castor seed was performed over Kaolin, CaO and ZnO
catalysts at various weight percentage of loading. This study conrmed that the yield varied with catalyst
type and its amount of loading. The maximum pyrolysis yield of oil was obtained about 66.4 wt.%, 64.9 wt.%
and 65.8 wt.% at 15 wt.% CaO and Kaolin and 10 wt.% ZnO respectively. The effect of catalyst on fuel
properties were studied at that catalyst loading where the yield of pyrolytic liquid was higher. The fuel
properties of castor seed thermal and catalytic pyrolytic oil were compared. The cracking of castor seed
pyrolytic vapour over the bed of catalysts proved to enhance the fuel properties of pyrolytic oil for all
catalysts. In comparison with ZnO, CaO and Kaolin found to have signicant effect on enhancing the
fuel properties in terms of viscosity, pH, caloric value and pour point. It was observed that in catalytic
pyrolytic oil the number of acidic groups signicantly reduced as they got converted to esters compared
to thermal pyrolytic oil. The increase in the formation of nitriles and aromatics content in the catalytic
pyrolytic oil was also noticed which were comparatively less in the thermal pyrolytic oil.
2016 Elsevier B.V. All rights reserved.

1. Introduction
Crude biomass pyrolytic liquid is unstable and a mixture of
organic and aqueous phase. The organic phase pyrolytic liquid is a
mixture of various acids, oxygenated hydrocarbons, alkane, alkene,
alcohol, ketones, furan, various aromatics, levoglucosan along with
several nitrogenated compounds. Apart from these chemical compounds, water in the pyrolytic oil is a result of various pyrolysis
reactions. The presence of water, various oxygenated compounds
and acids reduces the stability as well as fuel quality. It is well
known that the formation of water is a byproduct of biomass
pyrolysis [1]. Usually, water is generated due the dehydration reaction which occurs at the initial stage of biomass pyrolysis. This
also depends on the initial moisture content and the oxygen content of the feed biomass. Besides this reason, water also forms
during the degradation of cellulose, hemicellulose at low temperature [1,2]. The presence of oxygen in the biomass reacts during
de-volatilization of cellulose which forms various oxygenated compounds. The volatilization of cellulose increases the porosity of the
biomass char particles which makes easy diffusion of oxygen into

Corresponding author.
E-mail address: kmohanty@iitg.ernet.in (K. Mohanty).

it. Since, lignin is less reactive with oxygen, most of the oxygenated
compounds produced during de-polymerization of total cellulose
[2]. The oxygenated compounds include carbonyl group of compounds such as aldehyde (RCHO), ketone (RCOR ), carboxylic acid
(RCOOH), ester (RCOOR ), amide (RCONR R ), acyl halides (RCOX)
and acid anhydrites ((RCO)2 O) along with the formation of gaseous
products, e.g. CO, CO2 ,CH4 [3,4]. However, it is quite difcult to nd
the actual reaction mechanism of cellulose pyrolysis. Levoglucosan
is one of such sugar compounds which are also formed by pyrolysis of cellulose. Lignin decomposition leads to the formation of
phenols and aromatic compounds such as styrene, ethyle benzene
and toluene due to the free-radical and ionic reaction pathways
during the pyrolysis of lignin [4,5]. The primary pyrolysis of lignin
results styrene, whereas the secondary decomposition of styrene
produce ethyle benzene and toluene [5]. Extractives present in
biomass also play a major role on the yield of organic liquid during pyrolysis of biomass. The extractive content is usually higher
in the oil rich biomass such as oil containing seeds in comparison
with woods, leaves, grass and other biomasses. Literature reveals
that more the extractives which is a composition of various fatty
acids, waxes, fats, resins, tannin, simple sugars, starches and pigment higher is yield of organic pyrolytic liquid [4,6]. Guo et al.
studied the inuence of extractives on the mechanism of biomass
pyrolysis and observed that decomposition of extractives formed

http://dx.doi.org/10.1016/j.jaap.2016.04.014
0165-2370/ 2016 Elsevier B.V. All rights reserved.

Please cite this article in press as: M. Koul, et al., Effect of catalytic vapour cracking on fuel properties and composition of castor seed
pyrolytic oil, J. Anal. Appl. Pyrol. (2016), http://dx.doi.org/10.1016/j.jaap.2016.04.014

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70

60

50

Yield wt. %

phenol, methanol, methane, aldehyde with fewer amounts of CO2


and water. However, extractive free biomass resulted in less organic
and acid yield and more water, CO, CO2 . It was conrmed that
the presence of extractive in biomass catalyze the formation of
more acids while its absence enhances the yield of water and CO2
[4]. Hence, biomass pyrolytic oil has complex composition. Since,
biomass pyrolytic oil can be used as an alternative fuel, the present
research aims to produce higher and better pyrolytic oil than char
and gaseous products. The yield and quality of pyrolytic oil depends
on feed stock types and other process parameters such as reactor used, temperature and carrier gas ow rate. Literature says
non-edible seeds are such biomass which contains high extractives compared to total cellulose and lignin. Thermal pyrolysis of
various non-edible seeds and their composition was reported elsewhere, which showed the non-edible seed pyrolytic oils were acidic
[710]. This acidic properties of the pyrolytic oil reduces its stability and also do not allow it to be use directly in combustion
engine. Therefore, upgrading of the pyrolytic oil is highly desirable. Catalytic cracking and catalytic cracking of biomass pyrolytic
vapours are some of the methods that can be used to enhance the
fuel properties of pyrolytic oil. Pyrolysis in presence of catalyst is
rmly known as catalytic pyrolysis. Catalytic pyrolysis is of two
types. One is known as in-situ process, where catalyst is mixed
with the feed biomass, whereas the other technique is ex-situ process. The ex-situ catalytic pyrolysis is known as catalytic vapour
cracking, where the pyrolytic vapour generated passes through a
bed of catalyst and cracking occurs. Both the catalytic processes
enhance the yield and quality of pyrolytic oil. The effects of various catalysts on biomass pyrolysis were studied and their positive
effects with respect to upgrading of pyrolytic oil are well documented [918]. In-situ catalytic pyrolysis of Mahua, Karanja and
Niger seed were carried out by Shadangi and Mohanty using various catalysts to enhance the yield of pyrolytic oil and fuel properties
[911]. The study conrmed that the use of catalyst enhanced the
fuel properties of pyrolytic oil, whereas the yield was more or less
equal with that of thermal pyrolysis process. Onay reported that
the yield and quality of pyrolytic oil from Pistacia khinjuk seed can
be enhanced using BP 3189 and Criterion-424 catalysts [13]. However, the decreased in the yield of pyrolytic oil on catalytic pyrolysis
of cotton seed with MgO was reported by Putun [14]. Hence, it is
conrmed that the yield and quality of pyrolytic oil varies with the
catalyst types. There are many literatures found on in-situ and exsitu catalytic pyrolysis of different biomass, however, a few were
noticed on non-edible oil seeds. Based on the literatures, it was
observed that catalytic vapour cracking can be used as one of the
upgrading techniques to enhance the liquid yield and quality.
In the present study catalytic vapour cracking of Castor seed was
studied using catalysts such as Kaolin, CaO and ZnO. The effect of
catalysts on yield and fuel properties of pyrolytic oil was studied
and compared with that of thermal pyrolysis reported elsewhere
[8].

oil
aqueous
total liquid
char
gas

(a)

40

30

20

10

0
5

10

15

Fig. 1. Effect of Kaolin on pyrolytic yield.

70

60

oil
aqueo us
total liquid
char
gas

50

(b)
40

30

20

10

0
5

10

15

20

Fig. 2. Effect of CaO on pyrolytic yield.

70

60

oil
aqu eou s
total liquid
cha r
gas

50

Castor seed used as raw material in this study were purchased


from Ganjam, Odisha, India. The seeds were separated from their
kernel and afterwards used as the feed for pyrolysis.
2.2. Catalysts used

Yield wt. %

2.1. Raw materials

25

Catalyst wt.%

(c)

2. Materials and methods

20

Catalyst wt. %

Yield wt. %

40

30

20

10

0
5

10

15

20

ca ta lyst w t %

Three catalysts namely Kaolin (Central Drug House (P) Ltd.,


India), CaO and ZnO (Loba Chemie Pvt. Ltd., India) were purchased
and used in the present study without any further treatment.

Fig. 3. Effect of ZnO on pyrolytic yield.

Please cite this article in press as: M. Koul, et al., Effect of catalytic vapour cracking on fuel properties and composition of castor seed
pyrolytic oil, J. Anal. Appl. Pyrol. (2016), http://dx.doi.org/10.1016/j.jaap.2016.04.014

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120

T h e rm a l
15 w t. % C aO
15 w t. % K a o lin
10 w t. % Z n O

110
100
90
80

%T

70
60
50
40
30
20
10
4 5 00

4 0 00

3 5 00

3 00 0

2 50 0

2 0 00

1 5 00

1 0 00

5 00

-1

W a v e n u m b e r (c m )
Fig. 4. FTIR analysis of thermal and catalytic pyrolytic oils.

Table 1
Fuel properties of catalytic pyrolytic oils.
Pyrolytic oil
Castor thermal [8]
Present Study

15 wt.% Kaolin
15 wt.% CaO
10 wt.% ZnO

Mahua 2:1CaO [9]


Niger 8:1 Kaolin [11]
Diesel [8]

pH

Viscosity (cSt.)

Water content (%)

Caloric value (MJ kg1 )

Cloud point ( C)

3.7
8.36
9.25
8.32
8.58
8.01

83
39
8.3
28
17.5
13.1
26

2.9
3.1
4.3
0.62
18.14
0

35.4
42.18
41.3
36.8
43.15
38.72
45

<5
6
7
1
3
6
40

Table 2
FTIR analysis of thermal and catalytic pyrolytic oils.
Wave number (cm1 )

Vibration

Functional groups

Pyrolytic oils
Thermal

15 wt.% Kaolin

15 wt.% CaO

10 wt.% ZnO

28603000
2243
17001720
14501470
1205
800920
710730

C
C
C
C
C

Alkanes
Acetylene group
Acids, Aldehydes, ketones, esters
Alkanes
Amines
Alkenes, alkynes
Alkyl halides

Yes
No
Yes
Yes
Yes
Yes
Yes

Yes
No
Yes
Yes
No
Yes
Yes

Yes
Yes
Yes
Yes
No
Yes
Yes

Yes
No
Yes
Yes
Yes
Yes
Yes

H stretch
C stretch
O stretch
H bending
N stretch
C H stretch
C X stretch

2.3. Pyrolysis experiment


Thermal pyrolysis of castor seed was carried out in the temperature range of 450600 C at the heating rate of 25 C min1
according to literature [8]. The study conrmed that 550 C was
the optimum temperature to produce for maximum yield of oil.
Hence, in the present study, xed bed catalytic vapour cracking of
castor seed was carried out at the same temperature (550 C). A
semi batch reactor of length 21 cm and id 6 cm used in the study
was made up of stainless steel whose one end was opened to collect the generated volatiles. Initially the reactor was lled with
about 40 g of castor seed. The distance between the biomass bed
and catalytic bed was kept constant at 2 cm by using glass wool.
The height of the catalytic bed was 0.3 cm. The catalysts used in
the study were CaO, Kaolin and ZnO. The catalysts loaded on the
glass wool were 5, 10, 15 and 20 wt.% of the feed. The reactor was
electrically heated at a rate of 25 C min1 using cylindrical furnace,
which was identical to the thermal pyrolysis as reported in litera-

ture [8]. The desirable temperature was attained by PID controller


coupled with the furnace. The generated volatiles from the seeds
were passed through the catalytic bed and condensed with the help
of ice water cooled condenser. The condensed liquid was collected
in a glass measuring cylinder and weighed. The pyrolytic liquid
was separated into oil and aqueous phase by means of a separating
funnel and weighed accordingly. The remaining material left after
pyrolysis was collected as char from the reactor after cooling.

2.4. Characterization of the pyrolytic oil


The fuel properties and chemical composition of the pyrolytic
oil obtained at the optimum catalytic conditions were studied.
The fuel properties such as viscosity, pH, caloric value and cloud
point were determined using standard methods reported elsewhere [911]. The viscosity of the pyrolytic oil was determined
at 25 C and 50 rpm using rheometer (HAKEE Rheostress 1) coupled with HAAKE DC-50 temperature controller. The data was

Please cite this article in press as: M. Koul, et al., Effect of catalytic vapour cracking on fuel properties and composition of castor seed
pyrolytic oil, J. Anal. Appl. Pyrol. (2016), http://dx.doi.org/10.1016/j.jaap.2016.04.014

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Table 3
GCMS analysis of 15 wt.% Kaolin catalytic oil.
Retention time
(min)

Area%

14.94
16.975
19.822
19.981
29.01
29.867
Total

0.218
0.908
33.056
0.701
1.365
0.473
36.721

10.404
13.482
15.465
23.881
24.442
27.226
17.077
Total

0.038
0.438
0.799
0.776
0.599
10.858
0.197
13.705

13.722
16.213
20.763
Total

1.364
0.262
4.265
5.891

15.343
15.179
21.957
26.985
28.222
Total

1.185
1.835
3.122
5.616
2.457
14.215

16.765
18.719
Total

4.097
0.976
5.073

18.472
20.962

0.718
0.923

Total

1.641

22.035
22.204
23

0.919
1.487
1.094

23.425
27.133
Total

0.83
2.314
3.144

12.119
13.876
18.392
26.362
25.107

0.753
0.545
6.435
4.804
0.686

Total

13.223

Compound

Mol. Weight

Esters
Cyclopropanecarboxylic acid, 3-phenylpropylester
Phosphorothioic acid, s-ester
10-undecenoic acid, butyl ester
10-undecenoic acid, butyl ester
Dasycarpidan-1-methanol, acetate (ester)
9-hexadecenoic acid, 9-octadecenyl ester, (z,z)-

204
382
240
240
326
504

Aromatics
Pyridine, 2-ethenyl
Pyridine, 2-propyl
1-methyl-4-[nitromethyl]-4-piperidinol
Phenol, 2,4,6-tris(1-methylethyl)2,5-bis(1-methyl-1-silacyclobutyl)-p-xylene
1,3,5-triazine, 2-allyloxy-4,6-di(1-pyperidyl)1h-indole, 2-aminomethyl

105
121
174
220
274
303
146

Amines
3-pyridinamine, 2-methyl
7-benzofuranamine, 2-methyl
Piperidine, 4,4 -(1,3-propanediyl)bis

108
147
210

Acids
Butanoic acid, 2-amino-4-(methylsulnyl)2-propanone, phenylhydrazone
Trans-2-dodecenoic acid
Oleic acid
Octadecenoic acid

165
148
198
282
282

Alkanes
Cyclohexasiloxane, dodecamethyl
Dodecane, 1-(methoxymethoxy)-

444
230

Amides
9-octadecenamide, (z)Aminoacetamide,
n-methyl-n-[4-(1-pyrrolidinyl)-2-butynyl]-

281
209

Alkanones
Oxacyclododecan-2-one
1-(4-methylcyclohexyl)imidazolidin-2-one
2h-2,4a-methanonaphthalen-8(5h)-one

184
182
220

Alkenes
3-chloro-1-triisobutylsilyloxyprop-2-ene
2,15-heptadecadiene, 9-(ethoxymethyl)-

290
294

Others
1-[n-aziridyl]propane-2-thiol
1-[n-aziridyl]propane-2-thiol
Divinylbis(cyclopropyl)silane
14-octadecenal
3-(1-ethyl-1-methyl-4-piperidin-1-yl-but-2-ynyloxy)propionitrile

collected at different intervals and the average value was taken


as viscosity of oil. The functional groups present in the pyrolytic
oil were determined using Excalibur Bio-Rad spectrophotometer
(Model FTS 3500 GX) in the range of 4004000 cm1 at a step size
of 4 cm1 . The Gas chromatographymass spectroscopy analysis
(GCMS) was carried out to determine the composition of pyrolytic
oils. The analysis was performed using Varian 450-GC coupled with
240-MS mass spectrometer. The GC column oven temperature was
initially programmed at 40 C for 0.5 min and then heated to 300 C
at rate of 10 C min1 . The sample for GCMS analysis was prepared
with methanol and exact 1 L of sample injected into the column.
Helium was used as the carrier gas at ow rate of 0.6 mL min1

117
117
164
266
248

where the total GC run time was 30 min. The MS ion source temperature was kept at 180 C and analysis was done in the m/z ratio
of 49700. Gas chromatogram obtained at different retention times
was analyzed with their respective mass spectra followed by the
NIST library software.
3. Results and discussion
3.1. Effect of catalyst on pyrolysis yield
The effects of various catalysts at different wt.% on the yield of
pyrolytic products are shown in Figs. 13. A little variation was

Please cite this article in press as: M. Koul, et al., Effect of catalytic vapour cracking on fuel properties and composition of castor seed
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Table 4
GCMS analysis of 15 wt.% CaO catalytic oil.
Retention time
(min)

Area%

12.117
15.458
16.755
16.97
18.065
19.633
19.809
26.961
27.113
28.962
29.842
Total

0.811
0.665
5.063
0.871
0.886
27.142
0.997
0.762
1.421
1.321
0.967
40.906

9.746
13.711
15.175
17.072

0.188
1.315
1.168
0.328

22.5
22.185
25.11

0.295
1.449
0.512

Total

5.255

20.754
20.954
Total

3.42
0.967
4.387

13.48

0.421

27.197

12.024

Total

12.445

18.458
18.707
21.897
27.668
28.202
Total

0.988
0.702
2.624
0.921
7.021
12.256

23.406
22.96

0.619
1.184

Total

1.803

22.024
Total

1.182
1.182

14.457
26.5
Total

0.215
0.577
0.792

26.352
Total

7.185
7.18

27.984
30.422
31.919
Total

0.693
0.219
0.331
1.243

18.37
19.047
21.056
24.482
Total

7.255
1.157
0.734
0.282
9.428

Compound

Mol. Weight

Esters
Phosphorothioic acid, S-ester
Phosphorothioic acid, S-ester
Phthalic acid, monoamide, N,N-dioctyl, propyl ester
4-Cyanobenzoic acid, hexadecyl ester
1,2,4-Trioxolane-2-octanoic acid, 5-octyl-,methyl ester
10-Undecenoic acid, butyl ester
10-Undecenoic acid, butyl ester
8,11-Octadecadienoic acid, methyl ester
10,13-Eicosadienoic acid, methyl ester
9-Hexadecenoic acid, 9-octadecenyl ester
9-Octadecenoic acid (Z)-, 9-octadecenyl ester, (Z)-

382
382
431
371
344
240
240
294
322
504
532

Aromatics
Pyridine, 3-ethyl
Pyrazine, 2,5-dimethyl
Pyridine, 4-pentyl
2-(6-Nitro-1H-benzoimidazol-2-ylmethylsulfanyl)benzothiazole
Pyridine, 4-undecyl
Benzenethiol, 2-amino
3-(1-Ethyl-1-methyl-4-piperidin-1-yl-but-2-ynyloxy)propionitrile
Amines
Piperidine, 4,4 -(1,3-propanediyl)bis
N-[3-[N-Aziridyl]propylidene]-2-[2-pyridyl]ethylamine
Amides
Acetamide,
N-pyridin-2-ylmethyl-2-(5-p-tolyltetrazol-2-yl)Acetamide, N-(3-cyano-4,5,6,7,8,9hexahydrocycloocta[b]thiophen-2-yl)
Acids
Hexadecenoic acid, Z-11Cis-10-Nonadecenoic acid
Undecanoic acid
Pentetic Acid
14-Pentadecenoic acid
Alkanones
Azabenzocyclohepten-8-one
1,4-Methanoazulen-7(1H)-one,
octahydro-1,5,5,8a-tetramethyl

107
108
149
342
233
125
248

210
203

308
248

254
296
186
393
240

234
220

Alkanals
4-Octadecenal

266

Alcohols
1,2-Nonadecanediol
2-Tetracosanol, acetate

300
396

Alkenes
2,15-Heptadecadiene, 9-(ethoxymethyl)-

294

Ethers
Dihydromorphine, di(trimehylsilyl) ether
Dihydromorphine, di(trimehylsilyl) ether
Dihydromorphine, di(trimehylsilyl) ether

431
431
431

Others
Divinylbis(cyclopropyl)silane
Silane, dimethyl(dimethylpentyloxysilyloxy)tetradecyloxy
Silane, dimethylpentyloxypentadecyloxy
Deoxyspergualin

164
432
372
387

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observed in the yield of pyrolytic products at all catalytic conditions. The total yield of pyrolytic liquid obtained at catalyst loading
was higher at 15 wt.% for kaolin (66.4 wt.%) and CaO (65.8 wt.%)
and 10 wt.% for ZnO (64.9 wt.%) respectively. In the previous study,
it was reported that thermal pyrolysis of castor seed produced
64.4 wt.% of the pyrolytic liquid [8]. This conrmed that catalytic
vapour cracking of castor seed increased the yield of pyrolytic liquid. However the yield of aqueous pyrolytic liquid was not reported
in the literature [8].
It was noticed that catalytic vapour cracking produced two
phase pyrolytic liquid such as organic phase (oil) and aqueous phase
(mostly water and water soluble chemicals). In the present study,
the major emphasis was given on the yield of pyrolytic oil other
than that of aqueous liquid. The yield of aqueous liquid was less
than 5% for each catalyst at all catalytic loadings. The yield of aqueous pyrolytic liquid was more for ZnO in comparison with CaO and
Kaolin. In general, the formation of aqueous product is attributed to
the dehydration reactions taking place during the pyrolysis [11,18].
This effect might be more prominent in presence of ZnO than the
other two catalysts which may be the reason for increased aqueous yield. Literatures reported that catalytic pyrolysis increased the
yield of water in pyrolytic oil [911,18]. The yield of pyrolytic oil
was of 63.8 wt.% for Kaolin, 64 wt.% for CaO and 61.2 wt.% for ZnO.
The result conrmed that catalytic vapour cracking with CaO at a
loading of 15 wt.% yielded higher pyrolytic oil compared to other
catalysts.
3.2. Characterization of pyrolytic oil
3.2.1. Fuel properties of pyrolytic oil
The fuel properties of catalytic pyrolytic oils are compared with
the thermal pyrolytic oil, diesel and kerosene and presented in
Table 1.
The analysis conrmed that catalytic cracking of castor seed
pyrolytic vapour for all the catalysts, increased the caloric value,
altered the pH and decreased the viscosity and pour point compared
to thermal pyrolysis. These effects were dissimilar with the catalyst
types. However, the most synergic catalytic effect was observed for
CaO which alter the pH from 3.7 to 9.25 and reduced the viscosity
and pour point from 83 to 8.3 cSt and 5 to 7 C respectively. The
change in pH may be due to conversion of the acid compounds
to ester and hydrocarbons by catalytic decarboxylation reaction
with CaO [911]. The decrease in viscosity may be attributed to
the increase in the formation of lighter compounds during catalytic pyrolysis. The catalytic effect also enhanced the caloric value
of the pyrolytic oil compared to thermal pyrolysis which may be
due to the removal of oxygen. The removal of oxygen compounds
might be the cause for the increase in the aqueous product. Among
all, catalysts, catalytic vapour cracking of castor seed with Kaolin
(15 wt.%) enhanced the caloric value to 42.18 MJ kg1 , which was
quite closer to diesel (45 MJ kg1 ). The increase in the caloric value
may be due to decrease of acidic groups and removal of oxygen
from the pyrolytic oil in the form of water [9,19]. Furthermore, the
effect of catalysts on the cold ow properties was also prominent
for all catalyst in comparison with thermal pyrolytic oil. Thus, it was
concluded that catalytic vapour cracking enhanced the fuel properties of the pyrolytic oil. This implied the possible use of the castor
catalytic pyrolytic oil as an alternative fuel.
3.2.2. Fourier transform infrared analysis (FTIR)
The FTIR spectra for the thermal and catalytic pyrolytic oils are
shown in Fig. 4 and the detailed analysis with respect to the wave
number and functional groups are deliberated in Table 2.
It was noticed that both the thermal and catalytic pyrolytic oils
comprised of similar groups of compounds with varying intensities.
The variation of intensities implied the change in concentration of

Table 5
GCMS analysis of 10 wt.% ZnO catalytic oil.
Retention
time (min)

Area%

Compound

9.747
15.177
16.728
22.473
27.187

0.249
1.126
7.479
0.587
13.937

Aromatics
Pyridine, 3-ethyl
Pyridine, 2-(3,3-dimethylbutyl)Thymolphthalein
3-cholestanol, 2-fromyl-3-benzyl
1,3,5-triazine,
2-allyloxy-4,6-di(1-pyperidyl)-

107
163
430
506
303

Total

23.378

20.743

3.792

Alkanes
3,7-diazabicyclo[3.3.1]nonane,
9,9-dimethyl-

154

Total

3.792

15.447

0.684

21.863
27.645
28.187
Total

1.727
0.963
8.506
11.88

16.971
17.064

0.845
0.628

19.479
19.557
19.712
21.054
22.269

13.215
3.482
2.126
1.086
0.464

24.472
Total

0.421
22.267

12.112
20.945

1.379
1.038

22.163

1.769

Total

4.186

19.041
23.4

2.41
2.339

26.735

1.097

Total

5.846

25.114

0.382

26.488
26.344

0.776
9.163

Total

10.321

18.692
22.016
Total

1.105
1.499
2.604

15.517
Total

0.359
0.359

18.373
18.458
27.104
Total

10.806
1.834
0.973
13.613

Acids
12-dimethylamino-10-oxododecanoic
acid
10-hydroxydecanoic acid
Hexadeconoic acid
Octadecenoic acid
Esters
4-cyanobenzoic acid, hexadecyl ester
Cis-10-heptadecenoic acid,
trimethylsilyl ester
10-undecenoic acid, butyl ester
10-undecenoic acid, butyl ester
10-undecenoic acid, butyl ester
Carboxylic acid, ethyl ester
1,2,4-trioxolane-2-octanoic acid,
5-octyl-,methyl ester
Oleic acid, eicosyl ester
Amines
1,4-butanediamine
N-[3-[n-aziridyl]propylidene]-2[2pyridyl]ethylamine
Benzenamine,
n-(6-bromo-n-hexanoyl)-4-[[(2thiazolyl)amino]sulfonyl]Alkanones
Androst-5-ene-16,17-dione
2-isopropylamino-6-methyl-6,7dihydro-9h-5-oxa-9azabenzocyclohepten-8-one
Androst-5-en-3-one,
19-acetoxy-4,4-dimethyl-, oxime
Alkenes
2,15-heptadecadiene,
9-(ethoxymethyl)17-pentatriacontene
2,15-heptadecadiene,
9-(ethoxymethyl)-

Mol.
Weight

257
188
240
282

371
340
240
240
240
402
344

88
203
431

448
234

373

294
490
294

Alkanals
8-octadecenal
8-octadecenal

266
266

Amides
9-octadecenamide, (z)-

281

Others
Divinylbis(cyclopropyl)silane
3,7-dimethyl-6-nonen-1-ol acetate
Z,z-3,15-octadecadien-1-ol acetate

164
212
308

Please cite this article in press as: M. Koul, et al., Effect of catalytic vapour cracking on fuel properties and composition of castor seed
pyrolytic oil, J. Anal. Appl. Pyrol. (2016), http://dx.doi.org/10.1016/j.jaap.2016.04.014

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JAAP-3713; No. of Pages 7

ARTICLE IN PRESS
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various compositions. It was observed that the peak obtained at


2243 cm1 owing to C C stretching vibrations only present in CaO
(15 wt.%) catalytic pyrolytic oil, which conrmed the presence of
alkyne groups of compounds. The presence of such groups was not
noticed in any catalytic and thermal pyrolytic oils. However, the
existence of amine groups at 2243 cm1 was attained for both thermal and ZnO catalytic (10 wt.%) pyrolytic oils. Excluding that, all the
catalytic pyrolytic oil and thermal pyrolytic oil contained carbonyl,
alkane and alkyl halides group of compounds. The presence of both
unsaturated and saturated hydrocarbons was also seen in all the
pyrolytic oils [911,20,21].

CaO had more effect on pH (9.2) and decrease in the viscosity up


to 8.3 cSt. However catalytic vapour cracking of castor seed with
Kaolin produced higher caloric value pyrolytic oil (42.18 MJ kg1 )
compared to thermal and other catalysts. The effect of ZnO was
found to be comparatively less compared to other catalysts. The
catalytic pyrolytic oils were found to possess higher aromatic and
ester compounds. The overall study conrmed that catalytic vapour
cracking can be followed to enhance the yield and fuel properties of pyrolytic oil. Catalytic pyrolytic oil was found to have closer
fuel properties to that of diesel and can be blended with diesel at
suitable proportions.

3.2.3. Gas chromatographymass spectrometry (GCMS) analysis


The composition of the catalytic pyrolytic oil obtained at the
optimum conditions was determined by GCMS analysis and presented in Tables 35. It was observed that the composition of
the pyrolytic oil varied signicantly with catalyst types. Literature reported castor seed thermal pyrolytic oil comprised of acids,
ketones and alkanes compounds [8]. The present study conrmed
that the composition of the catalytic pyrolytic oils was dissimilar to
that of thermal pyrolytic oil. The acid content of thermal pyrolytic
oil was about 69% which were signicantly reduced to about 14.2%,
12.26% and 11.88% by simultaneous formation of the esters. The
increase in the esters was 36.7% for Kaolin, 40.9% for CaO and 22.3%
for ZnO respectively. Thus, it was conrmed that all the three catalysts resulted in the thermal conversion of fatty acids to esters. This
may be the reason behind the basic nature of the catalytic pyrolytic
oils. The presence of alkane and its compounds were detected in
Kaolin (5%) and ZnO (3.8%) catalytic pyrolytic oil whereas no such
compounds were observed in CaO catalytic oil. The presence of aromatic compounds, mostly pyridine and its derivatives, was noticed
in all the pyrolytic oils. Catalytic vapour cracking with CaO produced least amount of aromatics about 5.25% whereas, Kaolin and
ZnO resulted 13.7% and 23.78% respectively. The formation of aromatics is attributed to the aromatization reactions undergone by
the low molecular weight hydrocarbons as well as deoxygenation
of oxygenated (non-phenolic) compounds [19]. The presence of
higher aromatic compounds in fuel oil is undesirable and eventually
results in the more soot formation owing to the increased carbon
content [20,22,23]. About 12.4% amide compounds were noticed
in the CaO catalytic oil which reduced to 1.6% in Kaolin and 0.3%
in ZnO pyrolysis oils respectively. The presence of higher alkanes
such as decane and its compounds was seen only in Kaolin catalytic
oils (5%) and thermal (1.7%) whereas they were absent in ZnO and
CaO pyrolytic oils. The increased alkane content in the pyrolytic oils
was found to have positive effect on the caloric value and cold ow
properties. The alkenes were found only in CaO (7%) and ZnO (10%)
catalytic pyrolytic oils whereas thermal pyrolysis oil contained a
minor amount (1.02%) of alkenes. Another notable compound divinyl-bi-silane (cyclopropyl) which was noticed in all the catalytic
pyrolytic oils but absent in the thermal oil. The GCMS analysis conrmed that the application of catalysts played a major role in the
composition as well as the fuel properties of the pyrolytic oils.

Acknowledgements

4. Conclusion
The study conrmed that catalytic vapour cracking increased
the yield and fuel properties of castor seed pyrolytic oil. All the catalyst used in the study had positive effect on the yield and quality
of pyrolytic oil. The maximum pyrolysis yield of oil was obtained
about 66.4 wt.%, 64.9 wt.% and 65.8 wt.% at 15 wt.% CaO and Kaolin
and 10 wt.% ZnO respectively. In comparison to Kaolin and ZnO,

Authors acknowledge the analytical facilities at the Central


Instrumental Facility (CIF), IIT Guwahati as well as the analytical
laboratory at Department of Chemical Engineering, IIT Guwahati.
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Please cite this article in press as: M. Koul, et al., Effect of catalytic vapour cracking on fuel properties and composition of castor seed
pyrolytic oil, J. Anal. Appl. Pyrol. (2016), http://dx.doi.org/10.1016/j.jaap.2016.04.014