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Effect of catalytic vapour cracking on fuel properties and composition of castor seed pyrolytic oil
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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 influence of catalytic vapour cracking of castor seed was performed over Kaolin, CaO and ZnO catalysts at various weight percentage of loading. This study confirmed 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 significant effect on enhancing the fuel properties in terms of viscosity, pH, calorific value and pour point. It was observed that in catalytic pyrolytic oil the number of acidic groups significantly 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: [email protected] (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 difficult to find 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 influence of extractives on the mechanism of biomass pyrolysis and observed that decomposition of extractives formed
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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
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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 confirmed 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 flow 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 [7–10]. This acidic properties of the pyrolytic oil reduces it’s 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 firmly 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 [9–18]. 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 [9–11]. The study confirmed 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 confirmed 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. %
2
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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3
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
0
-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 (%)
Calorific value (MJ kg−1 )
Cloud point (◦ C)
3.7 8.36 9.25 8.32 8.58 8.01 –
83 39 8.3 28 17.5 13.1 2–6
– 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 (cm−1 )
Vibration
Functional groups
Pyrolytic oils Thermal
15 wt.% Kaolin
15 wt.% CaO
10 wt.% ZnO
2860–3000 2243 1700–1720 1450–1470 1205 800–920 710–730
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 450–600 ◦ C at the heating rate of 25 ◦ C min−1 according to literature [8]. The study confirmed that 550 ◦ C was the optimum temperature to produce for maximum yield of oil. Hence, in the present study, fixed 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 filled 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 min−1 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, calorific value and cloud point were determined using standard methods reported elsewhere [9–11]. 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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4 Table 3 GC–MS 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-(methylsulfinyl)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 400–4000 cm−1 at a step size of 4 cm−1 . The Gas chromatography–mass spectroscopy analysis (GC–MS) 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 min−1 . The sample for GC–MS analysis was prepared with methanol and exact 1 L of sample injected into the column. Helium was used as the carrier gas at flow rate of 0.6 mL min−1
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 49–700. 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. 1–3. 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 GC–MS 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 confirmed 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 [9–11,18]. The yield of pyrolytic oil was of 63.8 wt.% for Kaolin, 64 wt.% for CaO and 61.2 wt.% for ZnO. The result confirmed 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 confirmed that catalytic cracking of castor seed pyrolytic vapour for all the catalysts, increased the calorific 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 [9–11]. 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 calorific 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 calorific value to 42.18 MJ kg−1 , which was quite closer to diesel (45 MJ kg−1 ). The increase in the calorific 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 flow 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 GC–MS 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
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various compositions. It was observed that the peak obtained at 2243 cm−1 owing to C C stretching vibrations only present in CaO (15 wt.%) catalytic pyrolytic oil, which confirmed 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 cm−1 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 [9–11,20,21].
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 calorific value pyrolytic oil (42.18 MJ kg−1 ) 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 confirmed 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 chromatography–mass spectrometry (GC–MS) analysis The composition of the catalytic pyrolytic oil obtained at the optimum conditions was determined by GC–MS analysis and presented in Tables 3–5. It was observed that the composition of the pyrolytic oil varied significantly with catalyst types. Literature reported castor seed thermal pyrolytic oil comprised of acids, ketones and alkanes compounds [8]. The present study confirmed 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 significantly 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 confirmed 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 it’s 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 calorific value and cold flow 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 GC–MS analysis confirmed 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 confirmed 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. References [1] D. Mohan, C.U. Pittman Jr., P.H. Steele, Pyrolysis of Wood/Biomass for bio-oil: a critical review, Energy Fuel 20 (3) (2006) 848–889. [2] A. Gani, I. Naruse, Effect of cellulose and lignin content on pyrolysis and combustion characteristics for several types of biomass, Renew. Energy 32 (2007) 649–661. [3] P. Rutkowski, Pyrolysis of cellulose xylan and lignin with the K2 CO3 and ZnCl2 addition for bio-oil production, Fuel Process. Technol. 92 (2011) 517–522. [4] X. Guo, S. Wang, K. Wang, Q. Liu, Z. Luo, Influence of extractives on mechanism of biomass pyrolysis, J. Fuel Chem. Technol. 38 (1) (2010) 42–46. [5] P.F. Britt, A.C. Buchanan, B.K. Thomas, S.K. Lee, Pyrolysis mechanisms of lignin: surface-immobilized model compound investigation of acid-catalyzed and free-radical reaction pathways, J. Anal. Appl. Pyrolysis 33 (1995) 1–19. [6] K.P. Shadangi, K. Mohanty, Characterization of non-conventional oil containing seeds towards the production of bio-fuel, JRSE 5 (2013) 033111. [7] N.K. Nayan, S. Kumar, R.K. Singh, Production of the liquid fuel by thermal pyrolysis of neem seed, Fuel 103 (2013) 437–443. [8] R.K. Singh, K.P. Shadangi, Liquid fuel from Castor seeds by pyrolysis, Fuel 90 (2011) 2538–2544. [9] K.P. Shadangi, K. Mohanty, Comparison of yield and fuel properties of thermal and catalytic Mahua seed pyrolytic oil, Fuel 117 (2014) 372–380. [10] K.P. Shadangi, K. Mohanty, Thermal and catalytic pyrolysis of Karanja seed to produce liquid fuel, Fuel 115 (2014) 434–442. [11] K.P. Shadangi, K. Mohanty, Production and characterization of pyrolytic oil by catalytic pyrolysis of Niger seed, Fuel 126 (2014) 109–115. [12] D. Guo, S. Wua, B. Liu, X. Yin, Q. Yang, Catalytic effects of NaOH and Na2 CO3 additives on alkali lignin pyrolysis and gasification, Appl. Energy 95 (2012) 22–30. [13] O. Onay, Fast and catalytic pyrolysis of pistacia khinjuk seed in a well-swept fixed bed reactor, Fuel 86 (2007) 1452–1460. [14] E. Putun, Catalytic pyrolysis of biomass: effects of pyrolysis temperature, sweeping gas flow rate and MgO catalyst, Energy 35 (2010) 2761–2766. [15] M.I. Nokkosmaki, E.T. Kuoppala, E.A. Leppamaki, Catalytic conversion of biomass pyrolysis vapours with zinc oxide, J. Anal. Appl. Pyrolysis 55 (1) (2000) 119–131. [16] Y. Xu, T. Wang, M. Longlong, G. Chen, Upgrading of fast pyrolysis liquid fuel from biomass over Ru/c-Al2 O3 catalyst, Energy Convers. Manag. 55 (2012) 172–177. [17] Q. Zhang, J. Chang, T.J. Wang, X. Ying, Upgrading bio-oil over different solid catalysts, Energy Fuel 20 (2006) 2717–2720. [18] L. Zhou, H. Yang, H. Wu, M. Wang, D. Cheng, Catalytic pyrolysis of rice husk by mixing with zinc oxide: characterization of bio-oil and its rheological behavior, Fuel Process. Technol. 106 (2013) 385–391. [19] K. Smets, A. Roukaerts, J. Czech, G. Reggers, S. Schreurs, R. Carleer, J. Yperman, Slow catalytic pyrolysis of rapeseed cake: product yield and characterization of the pyrolysis liquid, Biomass Bioenergy 57 (2013) 180–190. [20] L. Zhongyang, W. Shurong, L. Yanfen, Z. Jinsong, G. Yueling, C. Kefa, Research on biomass fast pyrolysis for liquid fuel, Biomass Bioenergy 26 (2004) 455–462. [21] M. Koul, K.P. Shadangi, K. Mohanty, Thermo-chemical conversion of Kusum seed: a possible route to produce alternate fuel and chemicals, J. Anal. Appl. Pyrolysis 110 (2014) 291–296. [22] K.P. Shadangi, K. Mohanty, Effect of co-pyrolysis of Mahua seed and waste polystyrene on quality of liquid fuel, JRSE 6 (2014) 053142. [23] K.P. Shadangi, K. Mohanty, Co-pyrolysis of Karanja and Niger seeds with waste polystyrene to produce liquid fuel, Fuel 153 (2015) 492–498.
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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 influence of catalytic vapour cracking of castor seed was performed over Kaolin, CaO and ZnO catalysts at various weight percentage of loading. This study confirmed 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 significant effect on enhancing the fuel properties in terms of viscosity, pH, calorific value and pour point. It was observed that in catalytic pyrolytic oil the number of acidic groups significantly 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: [email protected] (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 difficult to find 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 influence of extractives on the mechanism of biomass pyrolysis and observed that decomposition of extractives formed
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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 confirmed 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 flow 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 [7–10]. This acidic properties of the pyrolytic oil reduces it’s 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 firmly 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 [9–18]. 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 [9–11]. The study confirmed 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 confirmed 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. %
2
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.
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3
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
0
-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 (%)
Calorific value (MJ kg−1 )
Cloud point (◦ C)
3.7 8.36 9.25 8.32 8.58 8.01 –
83 39 8.3 28 17.5 13.1 2–6
– 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 (cm−1 )
Vibration
Functional groups
Pyrolytic oils Thermal
15 wt.% Kaolin
15 wt.% CaO
10 wt.% ZnO
2860–3000 2243 1700–1720 1450–1470 1205 800–920 710–730
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 450–600 ◦ C at the heating rate of 25 ◦ C min−1 according to literature [8]. The study confirmed that 550 ◦ C was the optimum temperature to produce for maximum yield of oil. Hence, in the present study, fixed 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 filled 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 min−1 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, calorific value and cloud point were determined using standard methods reported elsewhere [9–11]. 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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4 Table 3 GC–MS 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-(methylsulfinyl)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 400–4000 cm−1 at a step size of 4 cm−1 . The Gas chromatography–mass spectroscopy analysis (GC–MS) 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 min−1 . The sample for GC–MS analysis was prepared with methanol and exact 1 L of sample injected into the column. Helium was used as the carrier gas at flow rate of 0.6 mL min−1
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 49–700. 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. 1–3. 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 GC–MS 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 confirmed 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 [9–11,18]. The yield of pyrolytic oil was of 63.8 wt.% for Kaolin, 64 wt.% for CaO and 61.2 wt.% for ZnO. The result confirmed 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 confirmed that catalytic cracking of castor seed pyrolytic vapour for all the catalysts, increased the calorific 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 [9–11]. 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 calorific 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 calorific value to 42.18 MJ kg−1 , which was quite closer to diesel (45 MJ kg−1 ). The increase in the calorific 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 flow 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 GC–MS 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
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various compositions. It was observed that the peak obtained at 2243 cm−1 owing to C C stretching vibrations only present in CaO (15 wt.%) catalytic pyrolytic oil, which confirmed 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 cm−1 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 [9–11,20,21].
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 calorific value pyrolytic oil (42.18 MJ kg−1 ) 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 confirmed 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 chromatography–mass spectrometry (GC–MS) analysis The composition of the catalytic pyrolytic oil obtained at the optimum conditions was determined by GC–MS analysis and presented in Tables 3–5. It was observed that the composition of the pyrolytic oil varied significantly with catalyst types. Literature reported castor seed thermal pyrolytic oil comprised of acids, ketones and alkanes compounds [8]. The present study confirmed 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 significantly 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 confirmed 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 it’s 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 calorific value and cold flow 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 GC–MS analysis confirmed 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 confirmed 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,
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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