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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. %
oil
aqueous
total liquid
char
gas
(a)
40
30
20
10
0
5
10
15
70
60
oil
aqueo us
total liquid
char
gas
50
(b)
40
30
20
10
0
5
10
15
20
70
60
oil
aqu eou s
total liquid
cha r
gas
50
Yield wt. %
25
Catalyst wt.%
(c)
20
Catalyst wt. %
Yield wt. %
40
30
20
10
0
5
10
15
20
ca ta lyst w t %
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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
pH
Viscosity (cSt.)
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
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4
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
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
pyrolytic oil, J. Anal. Appl. Pyrol. (2016), http://dx.doi.org/10.1016/j.jaap.2016.04.014
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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
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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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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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,
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