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Journal of Analytical and Applied Pyrolysis 99 (2013) 122–129

Contents lists available at SciVerse ScienceDirect

Journal of Analytical and Applied Pyrolysis

journa l h o me page: www.elsev ier .com/ locate / jaap

tudies on cracking of Jatropha oil

helly Biswas ∗, D.K. Sharmaentre for Energy Studies, Indian Institute of Technology Delhi, New Delhi 110016, India

r t i c l e i n f o

rticle history:eceived 12 June 2012ccepted 16 October 2012vailable online 23 October 2012

eywords:racking

atropha oilineticson-isothermal

a b s t r a c t

Pyrolysis/cracking of non-edible plant seed oil Jatropha oil (JO) and the utilization of cracked liquidproduct as a transportation fuel have gained importance due to the growing demand of renewable fueloil source and depleting fossil fuel reserves. Thus, an attempt has been made to study the non-isothermalkinetics of JO cracking/pyrolysis using thermogravimetric analysis. The experiments were carried out atdifferent heating rates of 5, 10, 15 and 20 K min−1 under nitrogen atmosphere from ambient temperatureto 1073 K. The degradation of JO was found to occur in three steps. The main devolatilization of JO occursin the temperature region 623–753 K and the degradation is essentially complete in this zone. Kineticstudies using isoconversional Friedman’s plots obtained for JO degradation show the presence of tworegions of JO degradation. The average activation energy calculated for the first region was 114.49 kJ/mol

and for the second region was 221.88 kJ/mol. For better understanding of JO cracking, the cracking of JOwas also carried out in a batch reactor and the liquid, gaseous product and char obtained were analyzed.Both the methods revealed that there is a complete conversion of JO. The liquid product obtained from JOcracking was found to contain alkanes, alkenes, cycloalkanes and carboxylic acids. The gaseous productobtained consisted of methane, pentane, iso-butane and certain uncondensed components (greater thanC5 carbons). The char obtained had high carbon content and showed the presence of K, Mg, and Fe.

© 2012 Elsevier B.V. All rights reserved.

. Introduction

Renewable and sustainable production of biofuels has becomencreasingly sought after due to the increased demand, issueselated to environmental concerns and the depletion of petroleumeserves and the quality of crude oil [1–3]. Thus, the transportationuels derived from renewable sources, i.e. biomass or plant seed oiluch as edible palm oil, soyabean oil, sunflower oil [4–6] and non-dible such as cotton seed oil, rapeseed oil, karanja, Jatropha oil (JO)nd waste oils [7–16]. These vegetable oils are triglycerides, whichonsist of fatty acid chains connected via the carboxylic group to alycerol backbone. The main problems associated with the use ofhese vegetable oils as liquid fuels directly are their instability, highiscosity and formation of carbon deposits in parts of automobilengines (i.e. in diesel engines) [10]. The drawbacks of transesterifi-ation of these vegetable oils to derive biodiesel are the use of largemounts of methanol and formation of glycerol as a by-product10,17,18]. Thus, conversion of these vegetable oils to transporta-

ion fuels by cracking, catalytic cracking, and hydrocracking woulde a better substitute. Most of the research work on vegetable oilracking has been concentrated on edible oils such as palm oil [4,5]

∗ Corresponding author. Tel.: +91 99 58067120; fax: +91 11 26581121.E-mail address: shelly.biswas@gmail.com (S. Biswas).

165-2370/$ – see front matter © 2012 Elsevier B.V. All rights reserved.ttp://dx.doi.org/10.1016/j.jaap.2012.10.013

and sunflower oil [6]. But due to competition with its utilizationas a food product, it is required to carry out cracking of non-ediblevegetable oils to generate transportation fuels. Thus, Jatropha oilas a cracking feed needs to be studied in detail to understandits cracking mechanism. Hydroprocessing of Jatropha oil (JO) andits catalytic cracking has been studied by researchers [10,11]. Tounderstand the mechanism of JO cracking reactions, kinetic stud-ies become an important tool, which can be done by studying thenon-isothermal kinetics from TGA data. Thermogravimetric analy-sis data has been used as a powerful tool to investigate the thermaldegradation of different materials [19–23]. Different kinetics mod-els have been developed by several researchers [24–30] based onTGA data. To understand the kinetics of biomass, plastics, oil shaleresearchers have used different models based on different heatingrates (as single heating rate data can give very confusing results)[31–35]. Thus, there is a need to study the thermal cracking ofJO under non-isothermal TGA conditions for better understandingof the cracking kinetics of JO. Thus, this study was carried out tounderstand the non-isothermal kinetics of JO using TGA data. Thekinetic analysis of the cracking of JO can provide an insight into thecracking process. The cracking of JO was carried out in a batch reac-

tor under isothermal conditions, and the liquid, gaseous and solidproduct obtained was analyzed. The isothermal kinetic study wascarried out to analyze the effect of reaction conditions on activationenergy.

S. Biswas, D.K. Sharma / Journal of Analytical and Applied Pyrolysis 99 (2013) 122–129 123

Table 1Ultimate analysis of Jatropha oil, cracked liquid product and char.

Sample C H N S Oa Atomic H/C Atomic O/C Atomic S/C

JO 70.8 10.8 0 0 18.3 1.84 0.19 0Liquid product 73.6 11.4 0.07 0 14.9 1.86 0.15 0

2

2

Npptf2TtasttiUt

asor3wfuTs

IwpaSoTs

cna(oucwTfaspdla

Char 93.3 3.0 1.2 1.3

a By difference.

. Experimental

.1. Materials and equipment

Jatropha oil (JO) was procured from Jatropha Vikas Sansthan,ew Delhi. The ultimate analysis of JO along with that of liquidroduct and char obtained is presented in Table 1. TGA of the sam-le was carried out using a TA Q60 simultaneous TGA–DTA–DSChermogravimetric analyser under non-isothermal conditions. Dif-erent heating rates of 5 K min−1, 10 K min−1, 15 K min−1 and0 K min−1 were considered for study under nitrogen atmosphere.he temperature range studied was from an ambient temperatureo 1073 K under nitrogen flow at the flow rate of 100 ml/min. Themount of the sample used for study was about 10 mg for each runtudied at different ramp rates. The inert atmosphere was main-ained during pyrolysis of the sample by using nitrogen flow, sohat unwanted oxidation of sample can be avoided. As slow heat-ng rates are used thus, the heat transfer limitation can be ignored.nder these conditions, the mass loss and rate were recorded con-

inuously.Cracking of JO under isothermal conditions was carried out using

batch reactor under nitrogen atmosphere and atmospheric pres-ure. The flow of nitrogen was maintained at 120 ml/h for the coursef the reaction. About 5 g of the sample was used for the crackingeactions. The temperature range studied was 300 ◦C, 350 ◦C and75 ◦C. All the reactions were studied in triplicates. The reactionsere followed by the quantitative measurement of the products

ormed i.e. liquid product and char. The amount of gaseous prod-cts formed was calculated by difference, i.e. by material balance.he gaseous products produced were collected in a tedlar bag andubjected to GC analysis.

The structure of the liquid product obtained was studied usingR (Thermo Scientific Nicolet 6700) spectral studies and the peaks

ere defined by the instrument only after 120 scans. The liquidroduct obtained from cracking reaction of JO was also char-cterized by NMR spectral studies using the instrument Brukerpectrospin 300 NMR spectrometer. The solvent used for carryingut the NMR study was CDCl3 containing TMS as internal reference.he spectrum was recorded between 0 and 10 ppm for 1HNMRtudies and between 0 and 200 ppm for 13C NMR studies.

Liquid column chromatographic technique for separation of theracked liquid was also carried out. A 50 cm (length) × 1.1 cm (inter-al diameter) glass column fitted with a teflon stopcock was usednd was packed with a slurry of pretreated (oven dried) silica gel20 g) in petroleum ether. The cracked liquid (0.5 g) was adsorbedn silica gel (2 g). A plug of cotton wool was used to support the col-mn. The hexane fraction of the liquid product obtained from theracking of Jatropha oil was characterized using GC–MS. The GC–MSas performed by on the apparatus Thermo Trace GC ultra GC–MS.

he separation was conducted on a column of 25 m × 0.25 mm (ID)used silica capillary coated with DB-5. The oven programming wass follows 35 ◦C hold for 4 min, heated at 10 ◦C/min to 200 ◦C andubsequently at a rate of 4 ◦C/min to 280 ◦C (and held at the tem-

erature for 30 min). The injector temperature was 200 ◦C and theetector temperature was 280 ◦C. The gaseous product was ana-

yzed by GC Nucon GC. Char metal analysis was done by SEM-EDXnalysis using ZEISS EVO Series Scanning Electron Microscope EVO

1.1 0.39 0.01 0.005

50. The morphology of the char samples was investigated using SEM(ZEISS EVO Series Scanning Electron Microscope EVO 50). ScanningElectron Microscope EVO 50 has a resolution of 2.0 nm at 30 kV withmagnification range up to 1,000,000×. The ultimate analysis wasperformed using Elemental Vario EL Cube. The combustion tubetemperature used was 1150 ◦C and the reduction tube temperaturewas 850 ◦C. The oxygen flow was maintained at 2 mbar.

3. Result and discussion

3.1. Thermal degradation of JO using TGA

The thermogravimetric analysis and DTG curves for thermaldegradation of JO at different heating rates are shown in Fig. 1. Thedegradation of JO is found to occur in three steps. The TG curveshave shown that there is a slight mass loss occurring from ambientto about 493 K, which is due to loss of the water present in the JO,i.e. this zone signifies the drying of JO. The next step of degrada-tion takes place from 503 to 623 K. The main devolatilization of thematerial occurs in the next zone i.e. 623–753 K and the degradationis essentially complete in this zone. It was observed that the com-plete degradation of JO takes place without any residual mass beingleft. The DTG curve also shows that there are two peaks observed.The first peak would be due to the breakdown of the big triglyc-eride molecule into smaller organic molecules. The second peakcorresponds to the total devolatilization of the organic molecules.The pyrolysis characteristics of JO cracking from DTG curve is givenin Table 2.

3.2. Determination of kinetic parameters

The kinetic study of thermal decomposition is a very complexprocess involving a large number of reactions [30,32–35]. The rateof degradation reaction can be generally described by

dx

dt= K(T)f (x) (1)

where t is the time, T is the temperature and x is the extent ofconversion. An assumption is used according to which the temper-ature dependence of the rate constant K(T) can be separated fromthe reaction model, f(x). The temperature dependence of the rateconstant is introduced by replacing K(T) with Arrhenius equationas

dx

dt= A exp

(−E

RT

)f (x) (2)

where A the frequency factor and E, the activation energy arethe Arrhenius parameters and R is the gas constant. Under non-isothermal conditions in which samples are heated at a constantrate, the temperature dependence of Eq. (2) can be eliminated

through the trivial transformation as

dx

dt= A

ˇexp

(−E

RT

)f (x) (3)

124 S. Biswas, D.K. Sharma / Journal of Analytical and Applied Pyrolysis 99 (2013) 122–129

Fig. 1. TG curves of JO at different heating rates. Inset corresponding DTG curves.

Table 2Cracking characteristics for JO from DTG curve.

Sample Heating rate (K min−1) Temperature (K)

Tonset Tmax1 Tmax2 Tend

5 463 673(10.48%/min) 543(0.76%/min) 933

[

l

Ws(m

tfibrtlwtaoeowdicts

increases, the cracking of JO oils proceeds to completion with about73% liquid yield, 26% gaseous product and about less than 1% char.The liquid product obtained was characterized by using FTIR, NMR,liquid column chromatography and GC–MS. The ultimate analysis

Table 3Kinetic parameter for pyrolysis of JO.

First Second

%Conversion E (kJ/mol) %Conversion E (kJ/mol)

0.01 100.02 0.2 173.660.02 111.23 0.3 187.280.03 105.27 0.4 202.750.04 51.70 0.5 181.540.05 175.03 0.6 128.720.06 136.86 0.7 340.77

JO10 473

15 493

20 493

The differential isoconversional method suggested by Friedman30] is based on Eq. (3) in logarithmic form leads to:

ndx

dt= ln Af (x) +

(−E

R

) (1T

)(4)

hen ln(dx/dt) vs. 1/T is plotted for different conversion levels atraight line is obtained and the slope of the line corresponds to− E/R), thus the activation energy can be calculated for the given

aterial.Isoconversional Friedman’s plots obtained for JO oil degrada-

ion are shown in Fig. 2. The plots clearly depict two regions, therst region (0.01 < x < 0.1) corresponds to the breakdown of theig triglyceride molecule into smaller molecules and the secondegion (0.2 < x < 0.9) corresponds to the complete degradation ofhe smaller organic molecules. The average activation energy calcu-ated for the first region was 114.49 kJ/mol and for the second region

as 221.88 kJ/mol (Table 3). These results depict the existence ofwo different processes in the degradation or pyrolysis of JO. Theverage activation energy calculated for the complete degradationf JO was 168.18 kJ/mol which is in agreement with the activationnergy obtained for plant seed oil (palm oil) [36]. The mechanismf thermal degradation of JO involves chain-series reaction, whichas found to vary with temperature. Oxidation was the principalecomposition step for JO cracking [37]. The bond energy for break-

ng of C C (353 kJ/mol) and C H (285 kJ/mol) bonds was higher asompared to the activation energy calculated [38,39]. This indicateshat breakdown of the triglyceride molecules is dependent on thetructure of the molecule and its thermolabile nature.

683(16.14%/min) 543(1.61%/min) 853683(21.31%/min) 563(2.28%/min) 823703(30.76%/min) 553(3.112%/min) 1053

3.3. Thermal cracking of JO in a batch reactor

The results of JO cracking in a batch reactor are presented inFig. 3. The thermal cracking has been carried out at 300 ◦C, 350 ◦Cand 375 ◦C. The cracking of JO at 300 ◦C indicates that there is notmuch reaction that has taken place, and unreacted JO oil is leftbehind even as we go increasing the time of reaction from 2 minto 10 min. The results of thermal cracking of JO at 375 ◦C indicatethat there was a complete conversion of the JO to liquid, gaseousproducts and char. The effect of time on the cracking of JO oil ispresented in Fig. 4. It was observed that as the time of cracking

0.07 107.99 0.8 316.540.09 117.01 0.9 243.730.1 125.34Mean 114.49 Mean 221.88

S. Biswas, D.K. Sharma / Journal of Analytical and Applied Pyrolysis 99 (2013) 122–129 125

-2

-1

0

1

2

3

4

0.0013 0.0014 0.0015 0.0016 0.0017 0.0018 0.0019 0.002 0.0021 0.0022

Ln

(d

x/d

t)

1/T

JO

0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.09 0.1

0.

plot

otdca

c

Fr

0.2 0.3 0.4 0.5

Fig. 2. Friedman

f the cracked liquid has been presented in Table 1. It was observedhat the atomic H/C ratio has increased and the atomic O/C ratio hasecreased as compared to that of the raw JO seed oil. Thus, this indi-ates that there is removal of oxygenates during cracking process

long with formation of more aliphatic components.

Distinct absorption bands from FTIR of cracked liquid from JOracking (Table 4) show the presence of CH3 and CH2 (2925 cm−1),

-20

0

20

40

60

80

100

120

275 295 315 335 355 375 395

Pro

du

ct d

istr

ibu

tio

n (

%)

Temperature of reaction (oC) for 5min reaction time

Product yield from cracking JO

Liquid (%) Char (%) Gaseous product (%) unreacted (%)

-20

0

20

40

60

80

100

120

275 295 315 335 355 375 395

Pro

du

ct d

istr

ibu

tio

n (

%)

Temperature of reaction (oC) for 10min reaction time

Product yield from cracking of JO

Liquid (%) Char (%) Gaseous product (%) unreacted (%)

a

b

ig. 3. Effect of temperature on the product distribution of JO cracking in a batcheactor.

6 0.7 0.8 0.9

for JO pyrolysis.

the C O ester (1710 cm−1), and C O stretch (1170 cm−1) of estergroups.

Definition of the 1H and 13C NMR chemical shifts [40] for hydro-carbons and structural parameters derived for liquid product fromJO cracking are shown in Table 5. The liquid product obtainedfrom the cracking of JO at 375 ◦C indicates the presence of 88%aliphatic hydrogen. However, the aliphatic hydrogen distributionwas mainly H�+� (68%) and H� and HCH3 8.37% and 11.46% respec-tively (Table 5). The liquid product of JO cracking contained 91%aliphatic carbon and 6.9% aromatic carbon. The classification of var-ious types of carbon is presented in Table 5. The liquid productshowed the presence of 5.19% protonated aromatic carbon. Signalof carbon atoms corresponding to the long paraffinic straight chain(14.1, 22.8, 29.9, 32 ppm) were prominent in the 13C NMR spectraof the cracked oil.

Liquid column chromatographic technique for separation of thecracked liquid into aliphatic, aromatics, oxygenated compoundsand polar compounds were carried out. The sequence and amountof solvents used for fractionating the different classes of com-pounds, and the amount of compounds fractionated are presentedin Table 6. It was observed that about 86% aliphatic, 3% aromaticsand oxygenated aromatics and 10% polar components were present

in the cracked liquid.

The GC–MS of the liquid product obtained is shown in Fig. 5.The liquid product obtained consists of various components as

Table 4FTIR absorption peaks for the liquid product obtained from JO cracking.

Absorption peak cm−1 Assignment

2925(s) C H stretch alkanes2855(s) C H stretch alkanes1710(s) C O stretch, esters1459(m) C H bend alkanes1374(w) C H rock alkanes1285(m) Wagging mode of the CH2 group1170(w) C O stretch alcohols, carboxylic acids, esters, ethers1114(w) C C skeletal stretching modes

963(m) C C skeletal stretching modes723(m) C H rock alkanes

126 S. Biswas, D.K. Sharma / Journal of Analytical and Applied Pyrolysis 99 (2013) 122–129

Table 5Structural parameters (derived from 1H and 13C NMR data) of the liquid products obtained from cracking of JO.

Parameters Chemical shift Liquid product (%) Definition

HA 9.0–6.0 4.95 % aromatic protonsHS 4.0–0.5 88.54 % aliphatic protonsH� 4.0–2.0 8.37 % CH3, CH2 and CH protons � to aromatic ringH�+� 2.0–1.0 68.71 % CH2 and CH protons of alkyl chains � or further to ring and CH3 protons � to the ringHCH3 1.0–0.5 11.46 % CH3 protons of alkyl chains � or further from aromatic ring or CH3 of saturated compoundsCS 10.0–50.0 91.2 % saturated aliphatic carbonsCP� 14.1 8.42 % carbon of terminal methyl group of alkyl chain � CH3 (CH2)n (n ≥ 4)CP� 22.7 8.28 % carbon of CH2 group � to terminal methyl of alkyl chain with n ≥ 4CPn 29.6–30.1 23.39 % carbon of � or higher of alkyl chain CH3 CH2 CH2 (CH2)n CH2 CH2

CP� 32 7.11 % carbon of � CH2 in CH3 (CH2)� CH2 (CH2)n

CA 100–150 6.9 % aromatic carbonCAH 100–130 5.19 % protonated carbonCAI 129.2–132.5 6.29 % bridgedhead internal aromatic carbonH/C [(2CS + CA)/(CS + CA)] 1.93 Hydrogen to carbon ratioRA (1 + CAI/2) 2.15 No. of aromatic rings per average molesACL 2CP/CP˛ 11.21 Average chain length

(a). Product distribution at 300oC

(b). Product distribution at 350 ºC

(c). Product distribution at 375oC

-20

0

20

40

60

80

100

0 5 10 15

Pro

du

ct d

istr

ibu

tio

n (

%)

Time of reaction (min)

Product yield from cracking of JO at 300oC

Liquid unreacted Gaseous product

-20

0

20

40

60

80

100

0 2 4 6 8 10 12

Pro

du

ct d

istr

ibu

tio

n (

%)

Time of reaction (min)

Product yield from cracking of JO at 350oC

Liquid Char Gaseous product

-20

0

20

40

60

80

100

0 2 4 6 8 10 12

Pro

du

ct d

istr

ibu

tio

n (

%)

Time of reaction (min)

Product yield from cracking of JO at 375oC

Liquid Char Gaseous product

Fig. 4. Effect of reaction time on the product distribution of JO cracking in a batchreactor.

Table 6Chemical class fractionation of the cracked oil from JO cracking from liquid columnchromatography.

Volume of solvent Solvent Fraction % composition

50 ml Hexane Aliphatics 86.2

50 ml Toluene Aromatics 1.0250 ml Ethyl acetate Oxygenated aromatics 2.150 ml Methanol Polar compounds 10.6

presented in Table 7. It was observed that the liquid productconsisted of the class of organic compounds such as alkanes,alkenes, cycloalkanes and carboxylic acids. From the GC–MS ofthe hexane fraction of the liquid product, it was concluded thatthe triglyceride molecule undergoes dehydration ( H2O), decar-boxylation ( CO2), decarbonylation ( CO), recombination andrearrangement reactions [41], to generate different hydrocarbons.

The liquid product obtained in this study has been com-pared with those reported in literature for other vegetable oils[6,9,13,42–53] (Fig. 6). It was observed that the values of liquidproduct as obtained in the present study (73%) is comparable withthose reported for soybean oil [42,43], rapeseed oil [44] under ther-mal cracking conditions.

The gaseous product formed consisted of methane, pentane,iso-butane and certain uncondensed components (greater than C5carbons) as presented in Table 8.

The morphology of the JO char was done using SEM analysis(Fig. 7.) and it was found that the char obtained had a smooth tex-

ture. From ultimate analysis of the char (Table 1) it was observedthat the H/C ratio obtained was less than 1 indicating that the charformed was aromatic in nature. Carbon content obtained for thechar was high, which indicated that the char could be used as an

Table 7Compounds present in the cracked liquid product of JO.

Compound Molecular formula RT Probability m/z

2-Methylpentane C6H14 3.04 89.76 863-Methylpentane C6H14 3.22 35.51 86Cyclohexane C6H12 3.94 82.22 842-Methyl-1-pentene C6H12 4.49 51.32 842-Ethyl-3-methyl-1-butene C7H14 9.84 29.30 98Nonane C9H20 10.05 68.57 128Cyclotetradecane C14H28 14.20 51.39 224Capric acid C10H20O2 17.24 48.41 172Docosane C22H46 20.34 47.28 310Cyclohexadecae C16H32 21.68 38.32 224Pentadecane C15H32 23.37 54.95 212Palmitic acid C16H32O2 28.83 92.83 256Stearyl alcohol C18H38O 30.60 24.89 270Linoleic acid C18H32O2 32.68 62.62 280

S. Biswas, D.K. Sharma / Journal of Analytical and Applied Pyrolysis 99 (2013) 122–129 127

Fig. 5. GC–MS data for liquid product of JO.

vari

ap

3

m

TC

Fig. 6. Comparison of liquid product obtained from

ctivated carbon source. EDX analysis of the JO char shows theresence of K, Mg, and Fe.

.4. Isothermal kinetics using Arrhenius model fitting

The intensive kinetics for decomposition/cracking of a solidaterial follows the rate expression [54]

dx

dt= k(1 − x)n (5)

able 8omposition of gases formed by JO cracking.

Component % distribution

Methane 10.1Pentane 9.9Iso-butane 10.1>C5 69.8

ous plant seed oils with that of the present study.

when integrated the equation becomes

F(x) = − ln(1 − x) = kt(n = 1) (6)

and

F(x) = (1 − x)1−n − 1n − 1

= kt(n /= 1) (7)

where fractional conversion of

ln k = ln A −(

E

RT

)(8)

where x is the fractional conversion of the material/fractional lossin weight, n is the order of the reaction, k is the rate constant, Eis the activation energy of the reaction, R is the gas constant, T is

temperature and A is the frequency factor.

To calculate the value of k the plot F(x) verses t (time) is drawnto get a straight line. The slope of the line corresponds to the valueof k. By using this method the value of k is obtained at different

128 S. Biswas, D.K. Sharma / Journal of Analytical and Applied Pyrolysis 99 (2013) 122–129

Fig. 7. SEM image and EDX obtained for the char sample from JO cracking.

Table 9Activation energy, frequency factor and order obtained for JO cracking using Arrhenius model fitting under isothermal conditions.

Substance Rate constant Activation energy (kJ/mol) Frequency factor (/s) Order (n)

116

totEmwcvam

4

o

K300 K350 K375

JO 0.005 0.048 0.078

emperatures. The values of E and A can be obtained from the plotf ln k verses 1/T. The slope of the straight line obtained correspondso the activation energy E and the intercept gives the value of A. The

for cracking of JO was obtained to be 116.78 kJ/mol from isother-al kinetic study using Arrhenius model fitting (Table 9). Thus, itas observed that the method (i.e. isothermal and non-isothermal

onditions) of finding activation energy leads to a difference in thealues of activation energy obtained. This could be due to erroneousssumptions and ambiguous evaluation of the different reactionodels [55].

. Conclusions

Cracking of Jatropha oil is complex process consisting of vari-us steps. From the TG/DTG curve, it is clear that the pyrolysis or

.69 2.31 × 108 0

degradation takes place in three steps. The main components ofdegradation take place in two steps as observed from DTG curveand even the Friedman curves have also suggested the presencetwo phases/steps of reaction for cracking of JO oil. The thermalcracking carried out in the reactor as well as TGA pyrolysis sug-gests the complete conversion of JO oil during cracking process.However, the activation energy obtained from isothermal, andnon-isothermal kinetic studies were found to give different val-ues. The liquid products obtained from the reactor cracking, revealthat the liquid product obtained consisted of different hydrocar-bon fractions i.e. aliphatic, aromatic, oxygenated aromatics and

polar compounds, which can be used as a feasible source for trans-portation fuel. The gaseous product formed consisted of methane,pentane, iso-butane and certain uncondensed components (greaterthan C5 carbons). The char formed was aromatic in nature, with

tical a

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S. Biswas, D.K. Sharma / Journal of Analy

igh carbon content and thus it could be used as an activated carbonource.

eferences

[1] G.W. Huber, S. Iborra, A. Corma, Synthesis of transportation fuels from biomass:chemistry, catalyst and engineering, Chemical Reviews 106 (2006) 4044–4098.

[2] G.W. Huber, A. Corma, Synergies between bio- and oil refineries for the pro-duction of fuels from biomass, Angewandte Chemie International Edition 46(2007) 7184–7201.

[3] A. Demirbas, Progress and recent trends in biofuels, Progress in Energy andCombustion Science 33 (2007) 1–18.

[4] P. Tamunaidu, S. Bhatia, Catalytic cracking of palm oil for the productionof biofuels: optimization studies, Bioresource Technology 98 (18) (2007)3593–3601.

[5] T.L. Chew, S. Bhatia, Effect of catalyst additives on the production of biofuelsfrom palm oil cracking in a transport riser reactor, Bioresource Technology 100(2009) 2540–2545.

[6] T.A. Ngo, J. Kim, S.K. Kim, S.S. Kim, Pyrolysis of soybean oil with H-ZSM5 (Proton-exchange of Zeolite Socony Mobil #5) and MCM41 (Mobil Composition ofMatter No. 41) catalysts in a fixed-bed reactor, Energy 35 (2010) 2723–2728.

[7] T.V.M. Rao, M.M. Clavero, M. Makkee, Effective gasoline production strategiesby catalytic cracking of rapeseed vegetable oil in refinery conditions, Chem-SusChem 3 (7) (2010) 807–810.

[8] P. Simácek, D. Kubicka, G. Sebor, M. Pospísil, Hydroprocessed rapeseed oil as asource of hydrocarbon-based biodiesel, Fuel 88 (2009) 456–460.

[9] X. Dupain, D.J. Casta, C.J. Schaverien, M. Makke, J.A. Moulijin, Cracking of arapeseed vegetable oil under FCC conditions, Applied Catalysis B 72 (2007)44–61.

10] R. Kumar, B.S. Rana, R. Tiwari, D. Verma, R. Kumar, R.K. Joshi, M.O. Garg, A.K.Sinha, Hydroprocessing of jatropha oil and its mixtures with gas oil, GreenChemistry 12 (2010) 2232–2239.

11] E. Buzetzki, K. Sidorova, Z. Cvengrosova, J. Cvengros, Effect of oil type on prod-ucts obtained by cracking oils and fats, Fuel Processing Technology 92 (2011)2041–2047.

12] X. Junming, J. Jianchun, C. Jie, S. Yunjuan, Biofuel production from catalyticcracking of woody oils, Bioresource Technology 101 (2010) 5586–5591.

13] H. Li, B. Shen, J.C. Kabalu, M. Nchare, Enhancing the production of biofuels fromcottonseed oil by fixed-fluidized bed catalytic cracking, Renewable Energy 34(2009) 1033–1039.

14] W. Charusiri, W. Yongchareon, T. Vitidsant, Conversion of used vegetable oils toliquid fuels and chemical over HZSM-5, sulphated zirconia and hybrid catalyst,Korean Journal of Chemical Engineering 23 (2006) 349–355.

15] S. Biswas, D.K. Sharma, Synergistic co-processing/co-cracking ofjatropha oil, petroleum vacuum residue, and high density polyeth-ylene, Journal of Renewable Sustainable Energy 4 (043112) (2012),http://dx.doi.org/10.1063/1.4737924.

16] S. Biswas, P. Mohanty, D.K. Sharma, Studies on synergism in thecracking and co-cracking of jatropha oil, vacuum residue and high den-sity polyethylene: kinetics analysis, Fuel Processing Technology (2012),http://dx.doi.org/10.1016/j.fuproc.2012.10.001.

17] J.T. Kloprogge, L.V. Doung, R.L. Frost, A review of the synthesis and characteri-sation of pillared clays and related porous materials for cracking of vegetableoils to produce biofuels, Environmental Geology 45 (2005) 967–981.

18] F. Ma, M.A. Hanna, Biodiesel production: a review, Bioresource Technology 70(1999) 1–15.

19] V. Lorey, D. Cancellieri, E. Leoni, J.L. Rossi, Kinetic study of forest fuels by TGA:model-free kinetic approach for the prediction of phenomena, ThermochimicaActa 497 (2010) 1–6.

20] N. Mominou, S.B. Xian, X. Jiaoliang, Studies on coprocessing vacuum residue oilwith plastics using thermogravimetric analysis, Petroleum Science and Tech-nology 27 (2009) 588–596.

21] B. Gornicka, L. Gorecki, TGA/DTG/DSC investigation of thermal ageing effectson polyamide–imide enamel, Journal of Thermal Analysis and Calorimetry 101(2010) 647–650.

22] F.A. López, A.L.R. Merce, F.J. Alguacil, A. López-Delgado, A kinetic study on thethermal behaviour of chitosan, Journal of Thermal Analysis and Calorimetry 91(2008) 633–639.

23] W.W. Sulkowski, A. Danch, M. Moczynski, A. Radon, A. Sulkowska, J. Borek,Thermogravimetric study of rubber waste-polyurethane composites, Journalof Thermal Analysis and Calorimetry 78 (2004) 905–921.

24] A.V. Coats, J.P. Redfern, Kinetic parameters from thermogravimetric data,Nature 201 (1964) 68–69.

25] C.D. Doyle, Kinetic analysis of thermogravimetric data, Journal of Applied Poly-mer Science 5 (1961) 285–292.

26] T.V. Lee, S.R. Beck, A new integral approximation formula for kinetic analysis

of nonisothermal TGA data, AIChE Journal 30 (1984) 517–519.

27] H. Flynn, L.A. Wall, A quick, direct method for the determination of activationenergy from thermogravimetric, Polymer Letters 4 (1966) 323–342.

28] T. Ozawa, A new method of analyzing thermogravimetric data, Bulletin of theChemical Society of Japan 38 (1965) 1881–1891.

[

nd Applied Pyrolysis 99 (2013) 122–129 129

29] H.E. Kissinger, Reactions kinetics in differential thermal analysis, AnalyticalChemistry 29 (1957) 1702–1706.

30] H.L. Friedman, Kinetics of thermal degradation of char-forming plastics fromthermogravimetry. Application to a phenolic, Journal of Polymer Science PartC 6 (1964) 183–195.

31] S. Vyazovkin, C.A. Wright, Model-free and model-fitting approaches to kineticanalysis of isothermal and nonisothermal data, Thermochimica Acta 340/341(1999) 53–68.

32] A. Aboulkas, K. El Harfi, Study of the kinetics and mechanisms of thermaldecomposition of Moroccan Tarfaya oil shale and its kerogen, Oil Shale 25 (4)(2008) 426–443.

33] A. Aboulkas, K. El Harfi, M. Nadifiyine, A. El Bouadili, Thermogravimetriccharacteristics and kinetic of co-pyrolysis of olive residue with high densitypolyethylene, Journal of Thermal Analysis and Calorimetry 91 (2008) 737–743.

34] A. Aboulkas, K. El Harfi, A. El Bouadili, M. Nadifiyine, Study of the pyrolysisof Moroccan oil shale with poly(ethylene terephthalate), Journal of ThermalAnalysis and Calorimetry 100 (2010) 323–330.

35] D. Choudhary, R.C. Borah, R.L. Goswammi, H.P. Sharmah, P.G. Rao, Non-isothermal thermogravimetric pyrolysis kinetics of waste petroleum refinerysludge by isoconversional approach, Journal of Thermal Analysis and Calorime-try 89 (2007) 965–970.

36] W.B. Wan Nik, F.N. Ani, H.H. Masjuki, Thermal stability evaluation of palmoil as energy transport media, Energy Conversion and Management 46 (2005)2198–2215.

37] R.A. Oderinde, I.A. Ajayi, A. Adewuyi, Characterization of seed and seed oil ofHura crepitants and the kinetics of degradation of the oil during heating, Elec-tronic Journal of Environmental Agricultural and Food Chemistry 8 (3) (2009)201–208.

38] A. Osmont, L. Catoire, I. Gokalp, M.T. Swihart, Thermochemistry of C C andC H bond breaking in fatty acid methyl esters, Energy and Fuels 21 (2007)2027–2032.

39] A.M. El-Nahas, M.V. Navarro, J.M. Simmie, J.W. Bozzelli, H.J. Curran, S. Dooley,W. Metcalfe, Enthalpies of formation, bond dissociation energies and reactionpaths for the decomposition of model biofuels: ethyl propanoate and methylbutanoate, Journal of Physical Chemistry A 111 (2007) 3727–3739.

40] M. Ahmaruzzaman, D.K. Sharma, Characterization of liquid products obtainedfrom cocracking of petroleum vacuum residue with plastics, Energy and Fuels21 (1) (2006) 2498–2503.

41] M.K. Figueiredo, G.A. Romeiro, R.V.S. Silva, P.A. Pinto, R.N. Damasceno, L.A.d’Avila, A.P. Franco, Pyrolysis oil from fruit and cake of Jatropha curcas pro-duced using a low temperature conversion (LTC) process: analysis of a pyrolysisoil-diesel blend, Energy and Power Engineering 3 (2011) 332–338.

42] D.G. Lima, V.C.D. Soares, E.B. Ribeiro, D.A. Carvalho, E.C.V. Cardoso, F.C. Rassi,Diesel-like fuel obtained by pyrolysis of vegetable oils, Journal of Analytical andApplied Pyrolysis 71 (2004) 987–996.

43] V. Wiggers, H. Meier, A. Wisniewski, A. Barros, M. Maciel, Biofuels from contin-uous fast pyrolysis of soybeanoil: a pilot plant study, Bioresource Technology100 (2009) 6570–6577.

44] O. Onay, O.M. Kochar, Pyrolysis of rapeseed in a free fall reactor for productionof bio oil, Fuel 85 (2006) 1921–1928.

45] Y. Luo, I. Ahmed, A. Kubatova, J. Stavova, T. Aulich, S.M. Sadrameli, The ther-mal cracking of soybean/canola oils and their methyl esters, Fuel ProcessingTechnology 91 (2010) 613–617.

46] F.A. Twaiq, N.A.M. Zabidi, S. Bhatia, Catalytic conversion of palm oil to hydro-carbons: performance of various zeolite catalysts, Industrial and EngineeringChemistry Research 38 (1999) 3230–3237.

47] S.P.R. Katikaneni, J.D. Adjaye, N.N. Bakhshi, Performance of aluminophosphatemolecular sieve catalysts for the production of hydrocarbons from wood-derived and vegetable oils, Energy and Fuels 9 (1995) 1065–1078.

48] R.O. Idem, S.P.R. Katikaneni, N.N. Bakhshi, Catalytic conversion of canolaoil tofuels and chemicals: roles of catalyst acidity, basicity and shape selectivity onproduct distribution, Fuel Processing Technology 51 (1997) 101–125.

49] J. Liu, C. Liu, G. Zhou, S. Shen, L. Rong, Hydrotreatment of Jatropha oil overNiMoLa/Al2O3 catalyst, Green Chemistry 14 (2012) 2499–2505.

50] L. Dandik, H.A. Aksoy, A. Erdem-Senatalar, Catalytic conversion of used oil tohydrocarbon fuels in a fractionating pyrolysis reactor, Energy and Fuels 12 (6)(1998) 1148–1152.

51] F.A. Twaiq, N.A.M. Zabidi, A.R. Mohamed, S. Bhatia, Catalytic conversion ofpalm oil over mesoporous aluminosilicate MCM-41 for the production of liquidhydrocarbon fuels, Fuel Processing Technology 84 (1–3) (2003) 105–120.

52] C.M.R. Prado, N.R.A. Filho, Production and characterization of the biofuelsobtained by thermal cracking and thermal catalytic cracking of vegetable oils,Journal of Analytical and Applied Pyrolysis 86 (2009) 338–347.

53] E. Buzetzki, K. Sidorová, Z. Cvengrosová, A. Kaszonyi, J. Cvengros, The influenceof zeolite catalysts on the products of rapeseed oil cracking, Fuel ProcessingTechnology 92 (2011) 1623–1631.

54] M. Ahmaruzzaman, D.K. Sharma, Coprocessing of petroleum vacuum residue

with plastics, coal, and biomass and its synergistic effects, Energy and Fuels 21(2) (2007) 891–897.

55] S. Vyazovkin, C.A. Wight, Isothermal and non-isothermal kinetics of thermallystimulated reactions of solids, International Reviews in Physical Chemistry 17(3) (1998) 407–433.