Nanocrystalline KeCaO for the transesterification of a variety of feedstocks: Structure, kinetics and catalytic properties Dinesh Kumar, Amjad Ali* School of Chemistry and Biochemistry, Thapar University, Bhadson Road, Patiala, Punjab 147004, India article info Article history: Received 11 June 2011 Received in revised form 22 June 2012 Accepted 30 June 2012 Available online 11 August 2012 Keywords: Solid catalyst Transesterification Homogeneous contribution 1 H NMR spectroscopy KoroseNowak criterion abstract The work presented in current manuscript demonstrated the preparation of potassium ion impregnated calcium oxide in nano particle form and its application as solid catalyst for the transesterification of a variety of triglycerides. The catalyst was characterized by powder X- ray diffraction, scanning electron and transmission electron microscopic, BET surface area measurement, and Hammett indicator studies in order to establish the effect of K þ impreg- nation on catalyst structure, particle size, surface morphology, and basic strength. The catalyst prepared by impregnating a mass fraction of 3.5% K þ in CaO was found to exist as w40 nm sized particles, and same was employed in present study as solid catalyst for the transesterification of a variety of feedstocks viz., mutton fat, soybean, virgin cotton seed, waste cotton seed, castor, karanja and jatropha oil. Under optimized conditions, KeCaO was found to yield 98 2% fatty acid methyl esters (FAMEs) from the employed feedstocks, and showed a high tolerance to the free fatty acid and moisture contents. A pseudo first order kinetic model was applied to evaluate the kinetic parameters and under optimized condi- tions first order rate constant and activation energy was found to be 0.062 min 1 and 54 kJ mol 1 , respectively. The KoroseNowak criterion test has been employed to demonstrate that measured catalytic activity was independent of the influence of transport phenomenon. Finally, few physicochemical properties of the FAMEs prepared from waste cotton seed oil, karanja oil and jatropha oils have been studied and compared with European standards. ª 2012 Elsevier Ltd. All rights reserved. 1. Introduction The continuously decreasing fossil fuel resources, increasing petroleum crude oil price and the environmental concerns have increased the interest in renewable fuels, such as bio- diesel, in recent past [1]. Fatty acid methyl esters (FAMEs), commonly known as biodiesel, are a non toxic, biodegradable, eco-friendly and renewable substitute for conventional diesel fuel. Combustion of the biodiesel in engines causes signifi- cantly lesser emission of particulates, unburnt hydrocarbons, carbon monoxide, carbon dioxide and SO x than conventional diesel fuels [2,3]. Transesterification reaction of the naturally occurring triglycerides (animal fat or vegetable oils) with short chain alcohols (e.g., MeOH and EtOH) in the presence of homogeneous catalysts such as strong bases (e.g., NaOH, KOH, NaOMe and KOMe) [4,5] or acids (e.g., HCl and H 2 SO 4 ) [6] is the most common method for biodiesel production. The trans- esterification reactions catalysed by alkali catalysts were found to proceed more rapidly than acid catalysed one and hence, don’t require harsh reaction conditions. However, the use of homogeneous alkali catalyst presents several disad- vantages viz., their non recyclability and deactivation by high moisture (mass fraction > 0.3%) and free fatty acid (mass fraction > 0.5%) contents in feedstock. Further, the use of * Corresponding author. Tel.: þ91 175 2393832; fax: þ91 175 2364498, þ91 175 2393005. E-mail addresses: [email protected], [email protected](A. Ali). Available online at www.sciencedirect.com http://www.elsevier.com/locate/biombioe biomass and bioenergy 46 (2012) 459 e468 0961-9534/$ e see front matter ª 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.biombioe.2012.06.040
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Nanocrystalline K–CaO for the transesterification of a variety of feedstocks: Structure, kinetics and catalytic properties
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b i om a s s a n d b i o e n e r g y 4 6 ( 2 0 1 2 ) 4 5 9e4 6 8
Available online at w
http: / /www.elsevier .com/locate/biombioe
Nanocrystalline KeCaO for the transesterification of a varietyof feedstocks: Structure, kinetics and catalytic properties
Dinesh Kumar, Amjad Ali*
School of Chemistry and Biochemistry, Thapar University, Bhadson Road, Patiala, Punjab 147004, India
Table 4 e Physicochemical properties of the FAMEsprepared from WCO (FCO), KO (FKO) and JO (FJO).
S. no. Parameters FCO FKO FJO EN 14214 Testmethod
1. Ester
content
(%)
>99 >99 >99 96.5 1H NMR
2. Flash
point (�C)110 115 100 100e170 ASTM
D 93
3. Pour
point (�C)6 5 �1 e ASTM
D 2500
4. Kinematic
viscosity
at 40 �C
3.94 6 4.5 1.9e6.0 ASTM
D 445
5. Calorific
value
(MJ kg�1)
40 25 39 e IS 1350
P:2
6. Ash (%) 0.02 0.02 0.01 0.02 ASTM
D 874
7. Density at
31 �C(g mL�1)
0.80 0.89 0.87 0.86e0.89 IS 1448
P:32
8. Water (%) 0.05 0.05 0.5 0.5 ASTM
D 2709
9. Iodine value 84 86 90 <120 EN 14111
10. Acid KOH
value
(g kg�1)
0.1 0.5 0.3 0.8 ASTM
D 664
11. K/Ca
(mg kg�1)
200/
4500
300/
4400
300/
4600
<5000
(total
metal)
ASTM
D 1318
b i om a s s a n d b i o e n e r g y 4 6 ( 2 0 1 2 ) 4 5 9e4 6 8 467
4. Conclusions
In present work prepared, 3.5eKeCaO, was found to exist in
the form of w40 nm size particles as revealed by powder XRD
and TEM techniques. The same was found to be an effective
catalyst for the transesterification of a variety of feedstock
having upto mass fraction of 10.26% and 8.4% of moisture and
FFA contents, respectively. Under optimized reaction condi-
tions (methanol to oil molar ratio of 12:1, catalyst concentra-
tion 7.5%, and at 65 �C) the transesterification of the waste
cotton seed oil is a pseudo first order reaction and the observed
first order rate constant and activation energy for the same
reaction was found 0.062 min�1 and 54 kJ mol�1, respectively.
The catalyst has been recovered and recycled for three
consecutive reaction cycles with the partial loss of the activity
after every catalytic run. The lixiviation study supports the
negligible homogenous contribution in catalytic activity, and
KN test also demonstrates that catalytic activity is free from
transport phenomenon. Few physicochemical properties of
the FAMEs prepared from the waste cotton seed, karanja and
jatropha oils have also been studied, and observed valueswere
found within the limits of EN 14214 specifications.
Acknowledgement
We acknowledge the financial support from CSIR, New Delhi
(gs1) (Ref. No.: 01(2503)/11/EMR-II). We also thank SAIF (Panjab
University) for powder XRD, NMR and TEM, and Matter Lab
(Thapar University) for FESEM studies.
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