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Procedia Engineering 148 (2016) 473 – 478

4th International Conference on Process Engineering and Advanced Materials

Isopropanolysis of Cottonseed Oil to Biodiesel via Potassium Hydroxide

Catalyst

Fatah H. Alhassana,*, Yoshimitsu Uemuraa

a
Centre for biofuel and biochemical research, Universiti Teknologi PETRONAS, 32610 Bandar Seri Iskandar, Perak Darul Ridzuan, Malaysia

Abstract

Biofuel from plant oils have attracted a great attention as replacements for conventional diesel to decrease reliance on fossil based-oil and offer an
eco-friendly fuel. The transesterification reaction of cottonseed oil with isopropyl alcohol using potassium hydroxide as catalyst has been
deliberated for the production of biodiesel. The objective of this study is to find the best condition for the production of isopropyl esters of
cottonseed oil. The reaction parameters used are isopropyl alcohol/cottonseed oil molar ratio (6:1 up to 30:1 in interval of 3), catalyst amount (0.5–
2.5 wt. %) and heating events of (50–80°C) while the duration of the procedure and the stirring power are fixed at 2 hour and 600 rpm, respectively.
However, about 98.9% of fatty acid isopropyl esters was obtained at the best conditions of 2h, 600 rpm, 1.5% catalyst concentration, 70 oC
temperature of the reaction and 1:24 as cottonseed oil to isopropyl alcohol molar ratio.
©
© 2016
2016 The
The Authors.
Authors. Published by Elsevier
Published by Elsevier Ltd.
Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of ICPEAM 2016.
Peer-review under responsibility of the organizing committee of ICPEAM 2016
Keywords: Isopropanolysis; Cottonseed oil; FAIPE’s

1.0 Introduction

Biodiesel is a renewable fuel produced from edible and non-edible vegetable oils and animal fats, which is suggested to substitute a
substantial proportion of fossil diesel in this century. It is a non-toxic, biodegradable fuel with less emissions, improved lubrication
properties and can be blended in specific ratio with conventional diesel. Recently, the best relevant method for decreasing the
viscosity of triglycerides is transesterification reaction which includes the conversion of edible and non-edible feedstock with an
alkyl alcohol to yield biodiesel and glycerine. Stoichiometrically transesterification reaction needs a molar ratio of 1:3 of oil to
alcohol for the production of biodiesel to the glycerine in molar ratio of three to one via using the homogeneous or heterogeneous
acidic and basic catalyst [1]. Nevertheless, in preparation a larger molar ratio of triglycerides to alcohol is essential for gaining a
better alkyl esters yield. Additional factors disturbing transesterification process are: amount and kind of catalysts, temperature and
duration of transesterification, level of (FFA’s) and amount of moisture in feedstock [1, 2]. The suggested concentration of
homogeneous basic catalyst for transesterification reaction is between 0.5 and 2.0% (w/w) of the triglycerides.

* Corresponding author. Tel.: 0060103090625; fax: 006053687649.

E-mail address: fathelrahman.el@Petronas.com.my

1877-7058 © 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of ICPEAM 2016
doi:10.1016/j.proeng.2016.06.475
474 Fatah H. Alhassan and Yoshimitsu Uemura / Procedia Engineering 148 (2016) 473 – 478

The cottonseed oil is obtained from the cotton plant via the mechanical pressure of seeds after the cotton lint has been removed.
Almost, the physico-chemical properties of cotton seed oil be similar to those of the main plant oils that as well have, heterogeneous
constituents of the triacylglycerol’s (TAG) [3].
The transesterification process utilizing cotton seed oil as feedstock has been reported in the literature. Moreover, the
transesterification reaction of cotton seed oil with potassium hydroxide as catalyst employed the microwave radiation for biodiesel
synthesis has been also discussed[4]. While, other researchers [1] described the transesterification reaction of cotton seed oil using
heterogeneous acids catalysts.
To the best of our knowledge, the assessment of the best reaction variables for the production of biodiesel from cotton seed oil using
isopropyl alcohol and potassium hydroxide as catalyst has not so far been studied. Therefore, the main aim of this study was to find
the best factors for the making a biodiesel based isopropanol (FAIPE’s) which expected to be 7- 10% more than FAME’s due to their
heavier molecular weight and hence, compensates for the increased budget of biodiesel industry.

2. Materials and Method

2.1. Materials

Sample (around 3L) of cottonseed oil was purchased from Sudanese Arab Company for vegetable oils limited / Sudan. Isopropanol,
n-hexane, anhydrous sodium sulfate were obtained from Merck (Darmstadt, Germany), while potassium hydroxide was of R&M
marketing Essex , U.K.Whole chemicals employed were analytical reagent grade.

2.2. Experimental procedure

Transesterification reactions were performed using a 250 ml round bottom flask attached to a condenser and a magnetic stirrer. The
agitation is fixed to 600 rpm to improve the miscibility of the reactants.
Initially the desired quantity of cotton seed oil was weighed in the reactor and subsequently placed in a fixed heating bath skilled of
keeping the heating events of the reaction to around ±0.1. The potassium hydroxide catalyst was dissolved in the isopropyl alcohol
and the resultant mixture was transferred to the heated oil in the reactor. The reaction time was set up once the potassium
hydroxide/isopropanol mixture was added to the three-necked round bottom flask at a required temperature and it continual for two
hours. Finally, the mixture of the products was placed for separation, permitting glycerine to detach via settling in a period of 4 hours
h. Once glycerine is taken out the isopropanol was removed by evaporation while isopropyl esters were cleaned with warm distil H2O
to get rid of potassium hydroxide, glycerol and isopropanol residuals. The conversion of cotton seed oil into isopropyl ester was
evaluated using A Shimadzu HPLC system equipped with Lab-solutions lite software version 5.5 beside a column having a length of
150mm and outer diameter10 mm was used for all analyses, while the detector is a differential refractive detector (RID-10A) held at
forty oC. A 1:30 ratio of a mixture of isopropyl esters in n-hexane is employed to find the response. The mobile phase was a mixture
of n-hexane and 2-propanol [5]. However, the flow rate of the mobile phase is adjusted at 1.0 mL/min and quantity of 20 µL is
injected each time. The Triglycerides conversion was calculated according to the equation (1):

Triglycerides conversion = (1- {x/w}) X 100 (1)

Whereas
x is the peak area of triglycerides in ester sample
w is peak area of triglycerides in the feedstock.

3. Results and discussion

The cottonseed oil used had free fatty acid level of 0.45% and saponification number of 199.0 mg KOH/g. The impacts of several
reaction parameters on the transesterification process of the feedstock used with 2-propanol have been assessed. Among parameters
considered influencing a transesterification process are the KOH concentration, cottonseed oil to 2-propanol molar ratio and the
reaction temperature.

3.1. Effect of catalyst concentration

Fig. 1 shows the effect of catalyst concentration on conversion of cotton seed oil to an ester. As it has been clearly shown in figure 1,
the smallest concentration of potassium hydroxide (0.5%) was not operative to drive the transesterification towards a completion.
Likewise, the conversion did not improve by increasing the concentration of potassium hydroxide. In same manner, when the
concentration of potassium hydroxide increased to more than 2% there was reduction in the rate of the conversion. This decrease in
 Fatah H. Alhassan and Yoshimitsu Uemura / Procedia Engineering 148 (2016) 473 – 478 475

the rate of conversion can be ascribed to the production of soap and glycerin. These results come to an agreement with the outcomes
confirmed that the generation of potassium salts as result of increasing the potassium hydroxide concentration, makes the mixture of
starting materials more viscous hence, dropping the conversion rate [6, 7]. Adding more quantity of potassium hydroxide catalyst
results in the generation of suspension, increasing the viscosity of the reactants mixture which might be finally hinders the glycerol
recovery and complicate the separation of the biodiesel [8]. Thus, 1.5% potassium hydroxide is a best concentration essential for
effective transesterification reaction of cotton seed oil with isopropanol[9].

Fig. 1. Effect of catalyst concentration at 2h, isopropyl alcohol/oil molar ratio of 9:1, 80 oC temperature of the reaction and stirring speed of 600 rpm

3.2. Effect of reaction temperature

Fig. 2 shows the Influences of temperature on the conversion of feedstock, while other parameters used are molar ratio of
isopropanol/triglycerides (9:1), 1% potassium hydroxide, time 2h and stirring 600rpm. The results in Fig. 2 reveal that at 50 and
70°C, the conversion efficiency was enhanced, respectively. When the temperature of the reaction was raised to 80 °C, the rate of the
conversion was decreased which can be due to the lost in amount of isopropanol. Therefore, specifying that the conversion of
feedstock is substantially impacted by the heating events of the reaction as discussed previously [10-12].
476 Fatah H. Alhassan and Yoshimitsu Uemura / Procedia Engineering 148 (2016) 473 – 478

Fig. 2. Effect of Temperature of the reaction at 2h, catalyst concentration of 1%, alcohol to oil molar ratio of 9:1 and stirring speed of 600 rpm,

3.3. Effect of isopropyl alcohol/cotton seed oil molar ratio

Stoichiometrically the production of biodiesel via transesterification process needs 3 mol of alcohol to react with one mol of oil to
produce three mole of biodiesel in addition to one mole of glycerol. Nonetheless, transesterification reaction is an equilibrium
process in which an additional alcohol is essential for effective completion of transesterification. In this paper the molar ratios of
triglycerides to isopropyl alcohol used were 1:6 up to 1:30. The conversion of triglycerides versus molar ratio of isopropyl alcohol/
cotton seed oil are revealed in Fig.3. A rise of triglycerides/2-propanol stoichiometric ratio from 1:6 up to 1:24 shown positive
impacts on the the conversion of oil (Fig. 3). An increase in the molar ratio over the stoichiometric ratio caused an improved in the
conversion rate [12, 13] and might confirm complete transesterification. Nevertheless, more increase in isopropanol to cotton seed oil
molar ratio (30:1) exhibited slight impacts on conversion rate. Hence, a best molar ratio of isopropyl alcohol /cotton seed oil in this
study to yield best isopropyl esters (98.9%) from cottonseed oil was found to be 24:1.
 Fatah H. Alhassan and Yoshimitsu Uemura / Procedia Engineering 148 (2016) 473 – 478 477

Fig. 3. Effect of alcohol to oil molar ratio at 2h, 1.5% catalyst concentration, 70 oC temperature of the reaction and stirring speed of 600 rpm

3.4. Comparison of the finding with previous similar study

The production of biodiesel via isopropanolysis reported so far using different feed stocks and achieving vary contents of isopropyl
esters at different conditions. L.liu et al., for example conducted the isopropanolysis of Camellia oil using immobilized lipase which
gave an ester content of 89.83% [14]. On the other hand, Paul s et al., , studied the production of biodiesel based 2-propanol from two
different feestocks and found that a 1:20 molar ratio of feedstock to 2-propanol and 1wt.% as concentration of the catalyst was the
most effective way to produce an isopropyl esters without mentioned the other parameters like time and temperature and how much
the content of the esters[15]. A Bouaid et al., have carried out statistical approach study for the synthesis of the isopropyl esters using
sunflower oil via enzymatic catalyst and they achieved only maximum conversion of 84% at temperature of 71 oC, 7% catalyst
concentration and 1:3 molar ratio of 2-propanol to triglycerides[16]. The optimum conditions for this study are comparable to the
other isopropanolysis methods. Although the molar ratio of 2-propanol to the triglycerides is slightly higher than the reported, a
higher fatty acid isopropyl esters content was obtained in a shorter reaction time.

4. Conclusion

The conversion of cotton seed oil to biodiesel has been done via isopropyl alcohol and potassium hydroxide as the homogeneous
basic catalyst. The best parameters for highest conversion of cotton seed oil into biodiesel were found to be catalyst concentration
1.5%, temperature of the reaction 70 °C, 24:1 isopropanol to oil molar ratio, 2 hour reaction time and 600 rpm stirring power. The
aforesaid best condition gave cotton seed oil isopropyl esters of about (98.9%) and cotton seed oil methyl esters of (71.9%, at T =65
o
C) which confirms that the fatty acid isopropyl esters yield is a highest compared to that of the fatty acid methyl esters. The next
stage of this work is utilization of this optimum conditions to study the important fuel properties of fatty acid isopropyl esters and
compare with ASTM D6751 and EN 14214 standards.
478 Fatah H. Alhassan and Yoshimitsu Uemura / Procedia Engineering 148 (2016) 473 – 478

Acknowledgement

With a great thanks we would like to acknowledge the financial funding from Mitsubishi/0153AB D07 Cost Centre and also agreat
thanks to Universiti Teknologi PETRONAS for providing a congenial work environment and state – of- the-art research facilities.

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