Esterification of free fatty acids with supercritical methanol for biodiesel production and related kinetic study

RSC Advances ◽  
2015 ◽  
Vol 5 (64) ◽  
pp. 52072-52078 ◽  
Author(s):  
Tianwei Jin ◽  
Bin Wang ◽  
Jinhui Zeng ◽  
Chun Yang ◽  
Yuqi Wang ◽  
...  

The interaction of raw material ratio, reaction temperature and reaction time on the esterification reaction of free fatty acids, and a kinetic analysis of it.

2019 ◽  
Vol 13 (4) ◽  
pp. 464-474 ◽  
Author(s):  
Youzhou Jiao ◽  
Yahe Mei ◽  
Le Wang ◽  
Jiaao Liu ◽  
Zhiping Zhang ◽  
...  

The innocuous utilization of diseased swine carcasses is a key issue in reducing environmental pollution and ensuring safety in animal husbandry. In this study, by using fat from diseased swine carcasses as raw materials, response surface experiments were conducted to investigate the influences of reaction time, catalyst concentration, reaction temperature, and methanol/oil molar ratio on the biodiesel purity and the optimum conditions for biodiesel production were determined. Furthermore, three-dimensional (3D) ultrasound assistance was adopted and kinetic analysis was performed. The results show that the influencing factors on biodiesel purity, in descending order, were determined to be reaction temperature > catalyst concentration > reaction time > methanol/oil molar ratio. Moreover, the maximum biodiesel purity was 93.7% under the following optimal conditions: catalyst concentration of 5.0 wt%; reaction temperature of 68 °C; methanol/oil molar ratio of 10:1; reaction time of 37 h. When 3D ultrasound assistance was adopted, the maximum biodiesel purity of 98.1% was obtained for the reaction process of 8 h under the ultrasound power and frequency of 500 W and 20 kHz, respectively. And the esterification reaction time was significantly reduced, compared to without ultrasound assistance. The results of kinetic analysis demonstrate that the reaction rate constants of the ultrasound group were 4.45–5.52 times greater than that of the control group. And the activation energy for the ultrasound group was 25.58 kJ/mol, which is 22.81% lower than that of the control group. This study will help to conduct large-batch biodiesel production from diseased swine carcasses in the future.


2014 ◽  
Vol 69 (3) ◽  
Author(s):  
Hazir Farouk ◽  
Mohammad Nazri Mohd Jaafar ◽  
A. E. Atabani

A two step-transesterification process was adopted to produce biodiesel from crude jatropha oil in lab scale and pilot plant. The crude jatropha oil used was sourced with high different level of free fatty acids. The first sample (FFA=4.5%) was subjected to pretreatment step under reaction condition of 0.225 v/v sulfuric acid (H2SO4), 6:1 w/w methanol (MeOH) to oil mole ratio, reaction temperature of 65°C, and 180 min of reaction time. Meanwhile, the second jatropha oil sample (FFA=8%) was subjected to pretreatment process in pilot plant under reaction condition of 0.225 v/v sulfuric acid (H2SO4), 4.5:1 w/w methanol (MeOH) to oil mole ratio, reaction temperature of 65°C, and 180 min of reaction time. Moreover, the esterifies oil from both jatropha oil samples was subjected to alkaline base step using base-catalyst process parameters of 1.2 w/w potassium hydroxide (KOH), 4.5:1 w/w methanol to oil mole ratio, reaction temperature of 60°C, and 120 min of reaction time. The final biodiesel yield obtained was 82% and 90% from the first and the second jatropha oil sample respectively. The basic physiochemical properties of the jatropha methyl ester produced from both jatropha oil samples were found to be within the ASTM D6751 specified limits.


2015 ◽  
Vol 781 ◽  
pp. 655-658 ◽  
Author(s):  
Thakun Sawiwat ◽  
Somjai Kajorncheappunngam

Synthesis of biodiesel from rubber seed oil using a supercritical methanol was investigated under various reaction conditions (220 - 300°C, 80 - 180 bar) with reaction time of 1-15 min and oil:methanol molar ratio of 1:20 - 1:60. Free fatty acid methyl esters (FAMEs) content were analyzed by gas chromatography-mass spectroscopy (GC-MS). Most properties of produced biodiesel were in good agreement with biodiesel standard (EN 14214). The maximum FAME yield of 86.90% was obtained at 260°C, 160 bar, 5 min reaction time using oil:methanol molar ratio of 1:40. The result showed the acid value of rubber seed oil decreased to 0.58 mgKOH/g from initial 24 mgKOH/g to. It could be concluded from this findings that crude rubber seed oil is a promising alternative raw material for biodiesel synthesis via supercritical methanol tranesterification.


2010 ◽  
Vol 07 (13) ◽  
pp. 30-32
Author(s):  
Luis Alcides Brandini DE BONI ◽  
Eduardo GOLDANI

Several raw materials have been used in the biodiesel production since the implementation of the National Program of Production and Use of Biodiesel through the Brazilian Law 11.097 of January 13th 2005. The most common way used to produce this biofuel is the transesterification reaction which, among others features, requires a raw material with low acidity level. When this condition is not reached, the esterification reaction is alternatively used to convert free fatty acids into mono alkyl esters. Sulfuric acid is one of the catalysts that can be used in the esterification reaction which, therefore, can react with the alcohol generating dimethylsulfate. The aim of this technical report is to discuss the chemical reactions involved when the esterification reaction is used and the effects that this may cause, such as exposure to carcinogenic products.


2010 ◽  
Vol 51 (5) ◽  
pp. 1055-1059 ◽  
Author(s):  
R. Alenezi ◽  
G.A. Leeke ◽  
J.M. Winterbottom ◽  
R.C.D. Santos ◽  
A.R. Khan

2016 ◽  
Vol 709 ◽  
pp. 57-60
Author(s):  
Fei Ling Pua ◽  
Kah Thong Looi ◽  
Shamala Gowri Krishnan ◽  
Sharifah Nabihah

In recent years, attention has been drawn to produce heterogeneous catalyst to replace homogeneous catalyst in biodiesel industry. This study was focused on the synthesis of three different types of alginate based heterogeneous catalyst (Ferric-alginate, Copper-alginate, and Nickel alginate) and the effect of the catalyst on esterification of oleic acid. Morphology and elemental analysis was conducted to investigate the properties of the catalyst. The new heterogeneous catalysts were used to catalyze the esterification of oleic acid at reaction temperature of 60°C and 2 hours reaction time. Fe-alginate has achieved the highest free fatty acids (FFAs) conversation rate of 82.03%. The results and findings proved that transition metal-alginate heterogeneous catalyst has the potential and ability to esterify the free fatty acids prior biodiesel production from high free fatty acids feedstock.


2011 ◽  
Vol 343-344 ◽  
pp. 222-226
Author(s):  
Xiang Yu Li ◽  
Jian Chun Jiang ◽  
Kui Wang ◽  
Ke Li ◽  
Yi Wei Gao

The preparation and production technology of biodiesel was explained in this paper. The transesterification mechanism was discussed from the synthesis reaction of biodiesel. Then the synthetic effects on the reaction were investigated such as water of the raw material oil, free fatty acids, temperature, pressure, catalyst, reaction time, alcohol-oil ratios, the mixing degree of raw materials and other aspects. The best synthetic technology was obtained.


2018 ◽  
Vol 5 (9) ◽  
pp. 180672 ◽  
Author(s):  
Benyong Han ◽  
Wudi Zhang ◽  
Fang Yin ◽  
Shiqing Liu ◽  
Xingling Zhao ◽  
...  

Methyl laurate was synthesized from lauric acid (LA) and methanol via an esterification reaction using ionic liquids (ILs) as catalysts. The efficiencies of three different catalysts, 1-methylimidazole hydrogen sulfate ([Hmim]HSO 4 ), 1-methyl-2-pyrrolidonium hydrogen sulfate ([Hnmp]HSO 4 ) and H 2 SO 4 , were compared. The effect of the methanol/LA molar ratio, reaction temperature, reaction time and catalyst dosage on the esterification rate of LA was investigated by single-factor experiments. Based on the single-factor experiments, the esterification of LA and methanol was optimized using response surface methodology. The results showed that the most effective catalyst was the IL [Hnmp]HSO 4 . The optimal conditions were as follows: [Hnmp]HSO 4 dosage of 5.23%, methanol/LA molar ratio of 7.68 : 1, reaction time of 2.27 h and reaction temperature of 70°C. Under these conditions, the LA conversion of the esterification reached 98.58%. A kinetic study indicated that the esterification was a second-order reaction with an activation energy and a frequency factor of 68.45 kJ mol −1 and 1.9189 × 10 9 min −1 , respectively. The catalytic activity of [Hnmp]HSO 4 remained high after five cycles.


Author(s):  
Nurul Asmawati Roslan ◽  
Mohammad Haniff Che Hasnan ◽  
Norhayati Abdullah ◽  
Syamsul Bahari Abdullah ◽  
Sumaiya Zainal Abidin

<p>The exploration of non-edible oils as a feedstock has been positively affect the economic viability of biodiesel production.  Due to the high level of free fatty acid (FFA) in non-edible oils, esterification is needed to remove the acidity to the minimum level before base-catalyzed transesterification.  In this study, 1-hexyl-3-methylimidazolium hydrogen sulphate (HMIMHSO<sub>4</sub>) was self-synthesized and compared with the commercialized ionic liquid, 1-butyl-3-methylimidazolium hydrogen sulphate (BMIMHSO<sub>4</sub>). HMIMHSO<sub>4</sub> and BMIMHSO<sub>4</sub> were characterized by <sup>1</sup>H NMR prior to use in the esterification reaction. The reaction was carried out in a batch reactor and variables such as types of alcohol, oil: alcohol molar ratio, temperature and types of stirring were investigated. The highest conversion for each catalyst was achieved using ethanol as a solvent at the condition of 343 K reaction temperature, 12:1 alcohol to oil ratio in 8 h reaction time. BMIMHSO<sub>4</sub> showed higher conversion (98%) as compared to HMIMHSO<sub>4</sub> with only 82% conversion. Clearly, BMIMHSO<sub>4</sub> shows considerable potential to reduce the FFA in the feedstock as it is exhibit excellent catalytic activity due to lower alkyl chain of BMIMHSO<sub>4</sub> compared to HMIMHSO<sub>4</sub>. Copyright © 2016 BCREC GROUP. All rights reserved</p><p><em>Received: 21<sup>st</sup> January 2016; Revised: 29<sup>th</sup> February 2016; Accepted: 6<sup>th</sup> March 2016</em></p><strong>How to Cite:</strong> Roslan, N.A.,  Che Hasnan M.H., Abdullah, N., Abdullah, S.B., Abidin, S.Z. (2016). A Preliminary Study: Esterification of Free Fatty Acids (FFA) in Artificially Modified Feedstock Using Ionic Liquids as Catalysts. <em>Bulletin of Chemical Reaction Engineering &amp; Catalysis</em>, 11 (2): 182-191 (doi:10.9767/bcrec.11.2.549.182-190)<p><strong>Permalink/DOI:</strong> <a href="http://dx.doi.org/10.9767/bcrec.11.2.549.182-190">http://dx.doi.org/10.9767/bcrec.11.2.549.182-190</a></p>


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