69-73
TI Journals
ISSN:
2306-6474
Copyright 2015. All rights reserved for TI Journals.
Tushar D. Patil
Department of Oil Technology, University Institute of Chemical Technology, North Maharashtra University, Jalgaon -425 001 (Maharashtra), India.
Ghayas A. Usmani
Department of Oil Technology, University Institute of Chemical Technology, North Maharashtra University, Jalgaon -425 001 (Maharashtra), India.
Hansraj V. Patil
Department of Oil Technology, University Institute of Chemical Technology, North Maharashtra University, Jalgaon -425 001 (Maharashtra), India.
Namrata B. Pawar
Department of Oil Technology, University Institute of Chemical Technology, North Maharashtra University, Jalgaon -425 001 (Maharashtra), India.
*Corresponding author: pawan.dm@gmaill.com
Keywords
Abstract
Microwave synthesis
Palm oil
Anionic surfactant
CMC
Kraft Point
The trans-esterification of palm oil was carried out under microwave irradiation to prepare Palm oil methyl
ester (POME). The sulfonation of POME was carried out at refrigerated condition using chlorosulfonic acid
as a sulfonating agent. The resulting product after subsequent purification was neutralized with alkali to
yield anionic surfactant, methyl ester sodium sulfonate (MESS). The synthesized surfactant was
characterized by FTIR, 1H-NMR and 13C-NMR spectral techniques. The performance properties of
surfactant such as critical micelle concentration, kraft point, emulsifying power and foaming ability were
determined using standard methods.
1.
Introduction
Anionic surfactants are kind of important products for utilization in various industrial applications due to their excellent detergency performance
[1] and it accounts for more than 60 % of the total world production of surface active species [2]. Previously surfactants were been prepared
from the precursor materials of petroleum origin [3-6]. However, with rising petroleum prices and great concern towards environmental issues
have gained momentum to substitute the synthetic petroleum based surfactants with bio-compatible surfactants [7]. The plant oil based
oleochemicals have been used as intermediates to prepare the finished products such as anionic surfactants [8-10]. Among the several reported
anionic surfactants, the ester sulfonate derived from renewable oil source has attracted the researchers because of its suitability to replace the
conventional linear alkyl benzene sulfonates (LABS), an active constituent in detergent formulation [11,12]. The methyl ester sulfonate (MES)
as anionic surfactant offers better wetting and cleaning properties at low cost and is considered environment friendly due to its biodegradable
nature [13,14]. An extensive research has been published giving the methods of MES preparation and possible applications [8,13,15-20].
In present study, an effort is made to utilize Palm oil as renewable source for preparation of MES. The cold sulfonation of ester followed with
alkali neutralization was the designed pathway to obtain the product. Besides, the process optimization for fatty methyl ester synthesis was done
using microwave irradiation technique which reduced the reaction time and gave better yield. The prepared Palm oil based methyl ester sodium
sulfonate (MESS) was characterized using spectral techniques and standard methods.
2.
Experimental Procedure
2.1. Materials
Refined Palm oil was procured from local general store. The chemicals and reagents used in the study were of analytical grade, and were
purchased from Merck, Mumbai. The sulfonating agent, chlorosulfonic acid was obtained from Sisco Chem., Mumbai.
2.2. Microwave assisted synthesis of MESS
2.2.1 Preparation of methyl ester
The trans-esterification was performed with a stoichiometric amount of Palm oil (0.1851 mol) and solvent methanol (1.125 mol) along with
alkali catalyst (KOH, 1.0 wt. % of oil) placed in a 250 cc three necked round bottom flask equipped with motor stirrer. The whole assembly was
placed in a microwave digester unit (MAS-II, SINIO MODEL) with irradiation power set at 300 W. The reaction mixture was heated to 60 oC
under microwave irradiation to enhance the rate of reaction. The reaction was stopped after 10 min of irradiation and the completion of transesterification reaction was confirmed by formation of methyl ester (ME) as determined using TLC technique. Two layer of mixture formed
thereof was separated by gravity separation to obtained the methyl ester and glycerol. The methyl ester separated was washed with deionized
water till stable pH near to neutral was achieved and further subjected to vacuum distillation for elimination of any residual moisture from the
ester product. The liquid ester was clear with light amber color and was comparatively less viscous from the precursor Palm oil.
Pawan Devidas Meshram *, Tushar D Patil, Ghayas A Usmani, Hansraj V Patil, Namrata B Pawar
70
CH2-OH
CH2-COOR1
KOH
R2OOC-HC
3 CH3-OH
CH2-COOR3
Triglycerides
Methanol
3R-CH2-COOCH3
+ CH-OH
CH2-OH
Methyl Ester
Glycerol
R= C16H34 (Palmitic)
+ ClSO3H
Chlorosulfonic
Acid
0 oC, 4 hrs
R-CH-COOCH3
HCl
ClSO3H
Methyl ester
sodium sulfonate
3.
71
Novel Microwave Assisted Synthesis of Anionic Methyl Ester Sulfonate Based on Renewable Source
International Journal of Engineering Sciences Vol(4), No (6), June, 2015.
Pawan Devidas Meshram *, Tushar D Patil, Ghayas A Usmani, Hansraj V Patil, Namrata B Pawar
72
73
Novel Microwave Assisted Synthesis of Anionic Methyl Ester Sulfonate Based on Renewable Source
International Journal of Engineering Sciences Vol(4), No (6), June, 2015.
4.
MESS Conc.
(g/L)
EP
(min)
Wetting time
(sec)
Foam volume
(ml) at 300 sec
0.01
19
48
0.02
16
125
85
0.03
12
14
161
123
0.05
38
468
196
Conclusion
The renewable source, Palm oil was successfully utilized for preparation of methyl ester sodium sulfonate (MESS). A novel microwave assisted
reaction mechanism was established to reduce the production time and to obtain high yield of product. The synthesis of the ester sulfonate was
confirmed using FTIR and NMR spectral techniques. The synthesized ester sulfonate as an anionic surfactant showed fairly low CMC value
(0.0005 mol/L) corresponding to the surface tension value of 32.6 dynes/cm, and Kraft point was noted to be 35 oC. The SEM micrographs
illustrated the plate and rod shape like structures of the ester sulfonate. The results for various performance tests were obtained using standard
methods which showed suitability of the prepared ester sulfonate as effective wetting, foaming and emulsifying agent. Thus, the ester sulfonate
can find its place in various chemical industries such paint, polymer, textile and particularly in detergents for its active properties.
Acknowledgements
The authors are very much thankful to the TEQIP-II, funded by MHRD, Government of India, Delhi (India) for providing financial support to
carry out this work. Authors also acknowledge the support extended by SAIF, Punjab University, Chandigarh for sample characterization.
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