b i o m a s s a n d b i o e n e r g y x x x ( 2 0 1 3 ) 1 e4
Available online at www.sciencedirect.com
http://www.elsevier.com/locate/biombioe
Short communication
Biodiesel production from Jatropha curcas L. oil using Lemna perpusilla Torrey ash as heterogeneous catalyst Ashish Pratap Singh Chouhan, Anil Kumar Sarma* Sardar Swaran Singh National Institute of Renewable Energy, Jalandhar-Kapurthala Road, Kapurthala, Punjab 144601, India
article info
abstract
Article history:
Refined Jatropha curcas L. oil (JCO) and methanol were used as the reactants for the trans-
Received 25 October 2012
esterification reactions in a Radleys reactor in the presence of a heterogeneous ash catalyst
Received in revised form
derived from the waste aquatic plant Lemna perpusilla Torrey. Physical characterization of
28 January 2013
the catalyst showed partly crystalline behaviour and a moderate surface area 9.622 m2 g1.
Accepted 4 February 2013
The L. perpusilla Torrey ashes obtained from traditional combustion method were further
Available online xxx
calcined at 550 5 C before use. In addition to other non-metal and metallic constitutes the ash contains 11.3% potassium which attributed to its catalytic behaviour. The cumu-
Keywords:
lative mass fraction of 89.43% of the oil was converted to biodiesel at 65 5 C in 5 h at
Jatropha curcas L. oil (JCO)
1:9 M ratio of oil to alcohol with 5% of the ash as catalyst. The biodiesel (FAME) so obtained
Lemna perpusilla Torrey ash
were characterized using appropriate ASTM methods and found within the defined stan-
Heterogeneous catalyst
dard limits. The catalyst could be reused upto 3-times but there is a reduction of efficacy by
FAME
about 25% for 3rd consecutive batch reaction. The activation energy was calculated for
Gas chromatograph analysis
FAME and found to be 29.49 kJ mol1. ª 2013 Elsevier Ltd. All rights reserved.
Biodiesel is a renewable liquid fuel made from the vegetable oils (i.e. edible, non-edible and waste frying oil), animal fats and algae biomass via transesterification reaction. This is a promising liquid fuel for the near future because of its biodegradable, renewable, nontoxic, eco-friendly, neutral green house and toxic emissions nature. Jatropha curcas L. oil (JCO) is gaining invested interest due to the easy availability, low production cost and above all the emphasis of Govt. of India for Jatropha (Ratanjot in Hindi) mission. The catalyst plays vital role during the transesterification reaction which could be either homogeneous or heterogeneous. Selection of a suitable catalyst for economic production is also an area of research. Biodiesel production using waste material based
heterogeneous catalyst is gaining focus in recent years due to easy availability and waste disposal concerns [1]. Their production and processing are easy and farmer friendly. Toda et al. [2] reported a sugar based carbon catalyst prepared by incineration of commercial-grade sugar. In this work, the authors investigated the transesterification of refined JCO using methanol as reactants and catalyst prepared from Lemna perpusilla Torrey. Physicochemical characterization of the catalyst and their suitability during transesterification, quality tests of the biodiesel obtained and the kinetic parameters are also reported herewith. L. perpusilla Torrey is a very small aquatic weed which grows naturally in the water surface of ponds and other water
* Corresponding author. SSS-NIRE, Biofuel Division, 12 KM Stone, Jalandhar Kapurthala Road, Wadala Kalan, Kapurthala, Punjab 144601, India. Tel.: þ91 1822255543. E-mail addresses:
[email protected] (A.P.S. Chouhan),
[email protected] (A.K. Sarma). 0961-9534/$ e see front matter ª 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.biombioe.2013.02.009
Please cite this article in press as: Chouhan APS, Sarma AK, Biodiesel production from Jatropha curcas L. oil using Lemna perpusilla Torrey ash as heterogeneous catalyst, Biomass and Bioenergy (2013), http://dx.doi.org/10.1016/j.biombioe.2013.02.009
2
b i o m a s s a n d b i o e n e r g y x x x ( 2 0 1 3 ) 1 e4
accumulating bodies throughout India and most parts of Asia and Latin America as shown in the Fig. 1. The L. perpusilla Torrey plants (about 3 months old) required for this study were collected from a pond of depth 1.1 m located in Sipajhar (Longitude 91.88 E, Latitude 26.40 N) Assam, India using specially made thread net. These were dried in open sunlight for three days to remove the initial moisture and were stored in polyethene bags. Further, these were carried to the laboratory and dried in an oven at 50 C for 72-hours. The moisture content was determined from the green sample and found to be 95.5% of the original mass. After complete drying these were burnt in open air to produce ash. These ashes were further calcined in a furnace at 550 5 C temperature for 2 h. After the calcinations these ashes were stored as catalyst in corked glass vessel. The metallic and non-metallic constituents were measured using standard procedure and presented in Table 1. The thermograms of the prepared catalyst was studied (TGDTA, Perkin Elmer, model STA 6000) at a temperature range 30e1000 C, heating rate 10 C min1 and constant flow of nitrogen and air at a rate 20 ml min1 to observe the decomposition under air and nitrogen medium. TGA was used to determine the thermal and oxidative stability of the catalyst. It shows how much the catalyst degrades above its prepared temperature (550 C). This stability is required for reactivation (calcination) of the catalyst during subsequent application [3]. The thermograms for the weight loss with respect to temperature have been presented in Fig. 2 which shows noticeable weight loss between 550 and 950 C. It has been observed that 5% of the initial mass was lost in air environment while the loss was 6% under nitrogen medium at 950 C. This may be attributed to oxidation mass increase of some component of the catalyst by 1% in air environment. The decrease of mass of the catalyst is mainly due to the oxidation of carbonaceous materials and release of CO, CO2 etc. Catalyst surface area, pore size and pore volume were measured using the BET surface area analyser of Quantachrome instrument manufactured by Nova. The BET surface area of the catalyst treated at 550 C was found to be 9.622 m2 g1, total pore volume 2.170 108 m3 g1 for pores smaller than 7.382 108 m (Radius) at P/P0 equal to 0.98682 and pore size expressed as average pore radius was equal to 4.512 109 m. Catalyst particle size and structural analysis were studied using XRD (Instrument made by Expert-Pro).
The sharp peaks in 2ө between 20 and 30, 37, 40e41, 50e51 and at 60 show (Fig. 3) the presence of crystalline phases while the major parts are amorphous in nature. All these properties unveil that the L. perpusilla Torrey ash could be a moderately good catalyst for transesterification reaction. The J. curcas ripe seeds were collected from the plantations of Sardar Swaran Singh National Institute of Renewable Energy (Longitude 75.439 E, Latitude 31.355 N), Kapurthala, Punjab, India in September, 2011. First, seeds were dried in the open sunlight for 3-days and then dried in an oven at 50 C for another 3-days. After the drying, the seed kernels were removed from the seeds separating the husk and shell. Seed kernels were milled before using in a solvent extraction unit (Soxhlet apparatus). The solvent and other chemicals used were of analytical grade. These were procured from commercial sources and used as such without further treatment. Extraction of oil was carried out by solvent extraction method using hexane and petroleum ether (40e60 C) as solvent in a Soxhlet extractor. The extraction process continued for 8 h in each batch till the colour of the solvent in the capillary was found similar to the original. The solvent was removed at 45e50 C at 2.25 104 Pa using a rotary vacuum evaporator (Heydolph, Germany) to yield 35% mass fraction JCO from the seed kernel. Petroleum ether (bp 40e60 C), hexane and diethyl ether were tried separately to examine the amount of oil extraction. After the extraction it was found that petroleum ether is a better solvent as compared to the hexane and diethyl ether that are least suitable. The density of the oil is 919 kg m3 at 20 C, acid value is 7.46 mg KOH g1 oil which is equivalent to about 3.7% free fatty acid content. This oil was later washed with 1% KOH solution and then with warm water 5e6 times to remove the free fatty acids and dried which has been named as refined JCO. Initially, the transesterification reaction was carried out in separate sealed vials of 10 ml capacity using 1, 3, 5 and 7% ash catalyst and 1% KOH respectively, in 1: 9 M ratio of oil to alcohol heating in an oven at 65 5 C for 24 h. It was observed from the analysis that 5% and 7% ash catalyst showed equivalent conversion efficacy to that of 1% KOH of analytical grade. A mixture of oil in methanol (1.3 l) and the catalyst (5%) were placed in a Radleys reactor at 65 5 C under constant stirring (68.07 rad s1)for 5 h. After the completion of the transesterification reaction raw biodiesel was separated from
Fig. 1 e Lemna perpusilla Torrey plants (A); mixed with Pistia stratiotes Linn Araceae (B). Please cite this article in press as: Chouhan APS, Sarma AK, Biodiesel production from Jatropha curcas L. oil using Lemna perpusilla Torrey ash as heterogeneous catalyst, Biomass and Bioenergy (2013), http://dx.doi.org/10.1016/j.biombioe.2013.02.009
b i o m a s s a n d b i o e n e r g y x x x ( 2 0 1 3 ) 1 e4
3
Table 1 e Metallic and non-metallic concentration in the Lemna perpusilla Torrey ash. Parameters
Concentration
Specification
Chloride (%) Carbonate (%)
1.10 ND (MDL: 2 mg kg1) 0.53 11.32 3.77 6.35 5.10 82.51
AOAC 915.01
Sodium (%) Potassium (%) Lead (mg kg1) Cobalt (mg kg1) Carbon (%) Silica (various forms) (%)
AOAC 975.03
TGA method
the glycerol layer using a separator flask. The ester layer was further placed in the rotary evaporator for separating the unreacted methanol from the biodiesel. The ester was later washed with hot water to remove the glycerol and dried in the oven at 105 C and using Na2SO4. The catalyst was separated by gravity from the glycerolewater phase and washed with petroleum ether and calcined at 550 C for 1 h and reused. The FAME was later centrifuged at 15 C and 418.88 rad s1 for 10 min to separate the traces of catalyst and glycerol present. Pure biodiesel was later used for the gas chromatograph (GC) analysis to determine the percent conversion of fatty acid methyl ester (FAME). The FAME conversions, expressed as mass percentage were calculated from the GC profile presented in Fig. 4 using the following formula as per procedure EN 14103 using an Agilent make GC, %FAME conversion ¼ X
P
hX i ðA AEIÞ=AEI ðWEI=WÞ 100
A ¼ Total peak area from C6 : 0 to C24 : 1
AEI ¼ Peak area corresponding to nonadecanoic acid methyl ester WEI ¼ Weight (mg) of nonadecanoic acid methyl ester being used as internal standard W ¼ Weight ðmgÞ of the sample The cumulative mass fraction of JCO consist in its composition 16.90% methyl palmitate, 32.31% methyl linoleate, 38.07% methyl oleate, 8.57% methyl stearate and 0.2% methyl
Fig. 2 e Thermograms of catalyst in nitrogen and air environment.
Fig. 3 e XRD pattern of the catalyst.
arachidate. The oleic acid is the major fatty acid followed by linoleic acid, palmitic acid and stearic acid in JCO, comprising of about 25.8% unsaturated and 70.4% saturated fatty acids. The cumulative percentage conversion of oil to FAME in Radleys reactor was found to be 89.43%. The details regarding conversion of refined JCO to FAME have been presented in Table 2. However, in the second and third round of reaction the mass fraction conversion of oil to FAME was decreased and reached at 67% and 57%, respectively. This clearly demonstrate that although a heterogeneous catalyst it is better to replace the same for each batch as the cost factor is negligible and can be easily obtained by the farmer from waste materials. The density and API gravity of the oil at 15 C are found to be 919 kg m3 and 920 kg m3, respectively. The density of the FAME is 891 kg m3 at 15 C which shows the reduction of the density to the standard compatible for biodiesel. The kinematic viscosity of JCO at 40 C is 34 mm2 s1 while for biodiesel it is 6.8 mm2 s1, a fourfold decrease which is slightly higher than the specified standards for B100 biodiesel stock as per ASTM methods (6 mm2 s1). The catalyst leaching was observed in the crude FAME layers which were potassium 12.32 mg kg1 and sodium 3.8 mg kg1. However, after the washing and centrifugation, the metal concentration in the FAME obtained have been found within the prescribed EN standard which is equal to 4 mg kg1. The other fuel properties of the FAME have been presented in Table 3.
Fig. 4 e Gas chromatograph of fatty acid methyl ester obtained from JCO using Lemna perpusilla Torrey ash as catalyst (EN 14103).
Please cite this article in press as: Chouhan APS, Sarma AK, Biodiesel production from Jatropha curcas L. oil using Lemna perpusilla Torrey ash as heterogeneous catalyst, Biomass and Bioenergy (2013), http://dx.doi.org/10.1016/j.biombioe.2013.02.009
4
b i o m a s s a n d b i o e n e r g y x x x ( 2 0 1 3 ) 1 e4
Table 2 e Fatty acid profile of refined Jatropha curcas oil (JCO) and the corresponding FAME (Radleys reactor). IUPAC name of the identified fatty acid
Refined JCO (mass fraction, %)
FAME (mass fraction, %)
Tetradecanoic acid (C14:0) Hexadecanoic acid (C16:0) Octadeconoic acid (C18:0) cis,cis-9, 12-octadecadienoic acid (C18:2) Icosanoic acid (C20:0) (C18:1) cis-9-octadecenoic acid Total
0.06
0.06
16.90
15.59
8.57
7.03
32.31
31.61
0.24 38.07
0.17 35.97
96.15
89.43
Table 3 e Properties of the of refined JCO and FAME. Refined JCO
FAME
Density at 15 C (kg m3) Specific gravity at 15 C (kg m3) API density (kg m3) IBP/FBP ( C) Distillation characteristics: mass fraction recovery (at 340, 360, 365 and 367 C)
919 920 920
Flash point, ( C) Calorific value (MJ kg1) Viscosity @ 40 C (mm2 s1) Acid value (mg KOH g1) Rams bottom carbon residue% Copper strip corrosion Oxidation stability at 110 C, h, min Sulphur content (mg kg1) Sodium (mg kg1) Potassium (mg kg1) Total (Na þ K) Glycerol% Monoglycerides% Diglycerides% Triglycerides% Total glycerol (free plus bound)%
115 36.0 34 7.4 1.6 1a
891 892 892 250/431 18.9 24.3 82.1 91.3 108 37.100 6.800 0.000 0.300 1a 1.1 10 ND 4.0 4.0 0.351 0.190 0.000 0.020 0.560
ND ND ND e e e e e
1 dx A Ea ¼ ln 1 x dT b RT
ln
Properties
e e
The kinetic study for determination of Arrhenius factor (A), rate constant (k) and activation energy (E ) was conducted using thermograms obtained from the thermo-gravimetric analysis (TGA) analysis of the FAME within temperature range 30e1000 C, at constant flow of nitrogen 20 ml min1 and heating rate 10 C min1. The rate of conversion, dx/dt for TGA experiment at constant rate of temperature change, was calculated using the following equation:
The IBP/FBP of the biodiesel obtained was 250/431 C. The cumulative mass fraction of FAME recovered by temperature is 18.9% at 340 C and 101 kPa pressure which attained 91.3% at 367 C and 101 kPa pressure. The pour point of FAME was found to be 0 C. The copper strip corrosion test showed a value (1a) for both oil and biodiesel. The unconverted triglyceride, diglyceride, monoglyceride and glycerol available in the biodiesel were also determined from the GC profile as per EN 14106.
The plot of ½ð1=ð1 xÞÞðdx=dTÞ versus 1/T should give a straight line with slope (Ea/RT) from which the activation energy, Ea can be calculated [3]; where Ea ¼ activation energy, kJ mol1, A ¼ pre-exponential factor or frequency factor, min1, R ¼ gas constant 8.314 J mol1 K1, T ¼ Absolute temperature (K), k is expressed as the specific reaction rate or rate constant, which is assumed to be only a function of temperature for liquid systems. The Arrhenius factor, rate constant and activation energy were calculated and found 46.81, 0.1 and 29.49 kJ mol1, respectively. This is very much similar to earlier reported literature [4]. L. perpusilla Torrey ash has been used first time as a heterogeneous catalyst for the biodiesel production to the best of the authors’ knowledge. As a heterogeneous catalyst L. perpusilla Torrey ash is suitable due to the non-corrosive, environmentally benign and present fewer disposal problems. It can be easily separated from the biodiesel prepared from the refined JCO and can be regarded as a moderately good heterogeneous catalyst.
Acknowledgement The authors express sincere thanks to Prof VK Rattan, Punjab University for XRD and BET analysis, concerned authority of IOCL Jalandhar and IOCL Faridabad for some of the fuel property evaluation and MNRE, Govt of India for financial grants (Sanction F No. 7/144/2009-NT dt. 01.10.2010).
references
[1] Sharma M, Khan AA, Puri SK, Tuli DK. Wood ash as a potential heterogeneous catalyst for biodiesel synthesis. Biomass Bioenerg 2012;41(6):94e106. [2] Toda M, Takagaki A, Okamura M, Kondo JN, Hayashi S, Domen K, et al. Green chemistry: biodiesel made with sugar catalyst. Nature 2005;438(7065):178. [3] Coughlan B, Narayanan S, McCann WA, Carroll WM. Ruthenium zeolite catalysts: a characterization by gas adsorption, thermogravimetry and catalytic activity for the hydrogenation of benzene. J Catal 1977;49(1):97e108. [4] Jain S, Sharma MP. Correlation development between the oxidation and thermal stability of biodiesel. Fuel 2012; 102(Sp. issue):354e8.
Please cite this article in press as: Chouhan APS, Sarma AK, Biodiesel production from Jatropha curcas L. oil using Lemna perpusilla Torrey ash as heterogeneous catalyst, Biomass and Bioenergy (2013), http://dx.doi.org/10.1016/j.biombioe.2013.02.009
