Sunteți pe pagina 1din 8

Applied Catalysis A: General 476 (2014) 26–33

Applied Catalysis A: General 476 (2014) 26–33 Contents lists available at ScienceDirect Applied Catalysis A:

Contents lists available at ScienceDirect

Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

General journal homepage: www.elsevier.com/locate/apcata Biodiesel production via transesterification of palm olein

Biodiesel production via transesterification of palm olein using sodium phosphate as a heterogeneous catalyst

Khritsayaporn Thinnakorn , Jirdsak Tscheikuna

Oleochemical Laboratory, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Phayathai Road, Pathumwan, Bangkok 10330, Thailand

Phayathai Road, Pathumwan, Bangkok 10330, Thailand a r t i c l e i n f

a r t i c

l e

i n f o

Article history:

Received 13 November 2013 Received in revised form 7 February 2014 Accepted 8 February 2014 Available online 17 February 2014

Keywords:

Transesterification

Palm olein

Heterogeneous catalyst

Sodium phosphate

a b s t r a c t

The production of Fatty Acid Methyl Esters (FAMEs) via the transesterification reaction of palm olein and methanol using sodium phosphate (Na 3 PO 4 ) as a heterogeneous catalyst has been investigated. This study determined the influence of various parameters, such as the methanol to oil molar ratio, the operating temperature, the amount of catalyst, and the presence of water and free fatty acid in the raw materials, on the rate of reaction. The study demonstrated that Na 3 PO 4 can be used effectively as a heterogeneous catalyst in transesterification process. It was determined that increasing the methanol to oil molar ratio results in an increase in equilibrium conversion. A molar ratio of methanol to oil of 18:1 provides the fastest rates of reaction and the highest FAME content. The operating temperatures have a strong effect on FAME yield; increasing the reaction temperature tends to accelerate the rate of reaction but reduces the glycerol by-product quality. Under the study conditions, with a methanol to oil molar ratio of 18:1 and a reaction temperature of 210 C 98.5% FAME yield was obtained within 30 min with only 1 wt.% of Na 3 PO 4 . When a large excess of methanol was used, the experimental results agreed with the irreversible 1st order kinetic model, while the activation energy was found to be 32.59 kJ/mol palm olein. © 2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

27

2. Experiment

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

27

2.1. Materials

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

27

2.2. Transesterification

reaction

 

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

28

2.3. Analysis

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

28

3. Results

and

discussion

 

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

29

3.1. Transesterification

reaction using Na 3 PO 4

 

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

29

3.2. the molar

Effect

of

ratio of methanol

to

oil

 

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

29

Effect

of

3.3. reaction

temperature

 

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

30

Effect

of

3.4. mass

ratio of catalyst

to

oil

 

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

30

3.5. the water and free fatty acid (FFAs) content in oil

Effect

of

 

30

3.6. solubility

Catalyst

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

31

3.7. of

Kinetics

transesterification

 

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

31

4. Conclusions

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

32

References

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

32

Corresponding author. Tel.: +66 2 2186878; fax: +66 2 2186880. E-mail addresses: khrits@yahoo.com, thinna1@hotmail.com (K. Thinnakorn).

http://dx.doi.org/10.1016/j.apcata.2014.02.016

0926-860X/© 2014 Elsevier B.V. All rights reserved.

K. Thinnakorn, J. Tscheikuna / Applied Catalysis A: General 476 (2014) 26–33

27

1. Introduction

Biodiesel or fatty acid methyl esters (FAMEs) produced by the transesterification of vegetable oil or animal fats with methanol

is used as a renewable diesel fuel. Biodiesel has similar proper-

ties to petroleum-based diesel but has several advantages, such as being biodegradable and producing less harmful gas emissions and particulate matter content. The conventional production pro- cess for biodiesel uses homogeneous catalysts and excess methanol to attain high yields, with the reaction products being FAME and glycerin. The most commonly used and most active catalysts are homogeneous alkaline catalysts such as NaOH, KOH, and their methoxides (NaOCH 3 , KOCH 3 ) [1]. The production process obtains high FAME yields (>98%) within a short reaction time at low temper- ature. However, these processes generate large amounts of waste water from the washing step. Moreover, the glycerin by-product from this reaction is not pure and must go through a complex

purification process before use in industrial cosmetics [2,3]. Several types of catalysts have been developed for FAME pro- duction to reduce the environmental impact. A homogeneous acid-catalysed process can reduce environmental problems from

highest activity but dissolved on the biodiesel during the reac- tion because the mechanism of these catalysts are transformed to methoxide ion [17,18]. High-activity catalysts partially dissolved, and reutilisation of the catalyst without regeneration has shown a loss of efficiency. However, if the catalyst is not soluble or less soluble, it will take a long time to obtain a high yield. For example, CaO was a good catalyst in the transesterification reaction and had low solubility, but the reaction time was up to 20 h to obtain an 80% yield of the FAME product [19]. However, the development of heterogeneous catalysts has to be based on high activity and good stability. One way to reduce the catalyst dissolution under the reaction conditions is to prepare the active components on stable mate- rials, such as supported catalysts, to reduce the leaching of the active components and increase the surface area of the reaction. Moreover, the separation of the catalyst from the reaction products is easier than in powder form. Many researchers have investi- gated various active compounds on supported catalysts [20–24]. However, the long reaction time is maintained due to the internal diffusion of the large triglyceride molecule into the catalyst pores

[25].

waste water emission, but acid catalysts require a high alcohol to oil molar ratio and a long reaction time to complete the conversion [4].

Normally, accelerating the rate of reaction of a heterogeneous system can be achieved with an increase in the amount of alcohol and catalyst used [12,26,27]. This can also be performed by increas- ing the reaction temperature [11,17,28,29]. The ability of CaO to catalyse transesterification was quite weak under ambient temper- ature, and the yield of methyl ester was only 5% over 3 h. However, when the reaction temperature was increased to 252 C, the reac- tion was completed within 6 min [30,31]. Transesterification is an endothermic reaction, so increasing the reaction temperatures will accelerate the reaction rate and reduce the amount of catalyst used while generating a high product yield. Among these base catalysts, Na 3 PO 4 appears to be a promising candidate to develop for the transesterification reaction because it has high activity, is insoluble in reactants, and inexpensive. Nor- mally, it is mainly used as fertiliser in agriculture. It can be reused in many times, which makes it easier to handle than homoge- neous catalysts and more environmentally friendly. Na 3 PO 4 has been shown to be a potential catalyst with both high activity and good stability for the transesterification reaction [10,32,33]. It could be used in a continuous production process. In the present work, Na 3 PO 4 -catalysed transesterification reaction of palm olein and methanol was investigated. The variables affecting the methyl ester yield during the transesterification of palm olein and methanol, such as the molar ratio of methanol/oil, the amounts of catalyst, and the reaction temperature, were studied. Moreover, the pres- ence of water and free fatty acid contents in raw materials was also studied in this research.

2. Experiment

A

supercritical process is an alternative method for a non-catalytic

transesterification reaction. The reaction completes within a short time, but requires high temperature (350–400 C) and high pres- sure (45–65 MPa) [5]. Enzymatic processes [6] and ion-exchange resins [7] have been the focus of interest in recent years. Because enzymes can tolerate free fatty acid and water contents in oils while avoiding soap formation, purification of biodiesel and glycerin is thus easier than with the other methods. However, enzymes are expensive and ion-exchange resins require a long reaction time to obtain high product yields. A production process using a heterogeneous catalyst is an alter- native that solves these problems. It produces biodiesel in a more environmentally friendly manner because the catalyst does not dis- solve into the products; it can easily be separated from the product by filtration at the end of the reaction. Thus, the catalyst does not require a water-washing step and can be reused several times. Con- sequently, transesterification with a heterogeneous catalyst has the potential to be developed for use in a continuous production process. Currently, only one industrial application of the heteroge- neous base catalysts developed by the French Institute of Petroleum (IFP) has been reported. This process, using a spinel mixed of Zn and Al oxide as a solid base, operated at 200–250 C [8]. On a labo- ratory scale, the development of heterogeneous catalysts has been extensively investigated, with many catalysts being studied and tested in the transesterification of various types of oils and alcohols. The most widely used catalysts were alkaline and alkaline-earth compounds, such as metal oxides, carbonates, phosphates, and the catalysts prepared on supported catalysts [9–12]. The major problem with a heterogeneous catalyst is the slow reaction rate due to the problem of mass transfer resistance of the 3 phases (oil, methanol, and catalyst), which are not soluble in each other. Strong mechanical stirring and a long reaction time are required to obtain a high product yield [13]. Additionally, it was found that there is leaching of active species into the reac- tion mixture after the reaction. Thus, the reusability of catalysts without regeneration has been shown to be less than ideal. Many studies have reported on the effect of partial dissolution of catalysts into the product where they act as homogeneous catalysts, but the result requires complex separation [14,15]. It has been reported that highly active solid catalysts, such as K 2 CO 3 , dissolve readily into products, and high yields (98%) were obtained within 120 min, but it was found that 55 wt.% had dissolved [16]. The same was true for metal oxides such as SrO, CaO, ZnO, TiO 2 , and ZrO 2 . SrO showed

2.1. Materials

The refined palm olein used in this research was purchased from the market. Industrial-grade methanol (purity: 99.86 wt.%) was used as the reactant in this research. Na 3 PO 4 ·12H 2 O (labora- tory grade) was used as the catalyst. Prior to the transesterification reaction, the catalyst was dried in an oven at 120 C for 24 h and then calcined in a muffle furnace at 500 C for 5 h. The powder particle diameter of the calcined Na 3 PO 4 was determined through with a particle size analyser and ranged from 200 to 250 m. The basic strength (H ) of the catalyst as determined using the Hammett

indicator method was 15 < H < 18.4 [34,35].

The palm olein used in this research was analysed for its phys- ical properties and fatty acid compositions. The results are shown

28

K. Thinnakorn, J. Tscheikuna / Applied Catalysis A: General 476 (2014) 26–33

Table 1 Physical properties of palm olein.

Physical properties

Acid value (mg KOH /g) Saponification value (mg KOH /g) Moisture content (wt.%) Molecular weight (g/mol)

 

0.358

197.946

0.104

850.76

Table 2 Fatty acid composition of palm olein.

 

Name

Structure

Composition (wt.%)

Lauric

12:0

0.53

Myristic

14:0

1.04

Palmitic

16:0

38.67

Palmitoleic

16:1

0.23

Stearic

18:0

4.10

Oleic

18:1

42.90

Linoleic

18:2

10.92

Linolenic

18:3

0.24

Arachidic

20:0

0.35

Behenic

22:0

0.80

Erucic

22:1

0.22

Total Saturated

45.49

Total Unsaturated

54.51

in Table 1 and Table 2, respectively. The results show that the fatty acid composition of the palm olein varied within the range of C12:0–C22:1 and that the major fatty acid components in the palm olein were palmitic and oleic acids. The total saturated fatty acids in the palm oil was 45.49 wt.%, while the total unsaturated fatty acids was 54.51 wt.%. The amount of unsaturated and satu- rated oils had an effect on the fuel properties, especially because the presence of saturated fatty acids lowers the cloud point.

2.2. Transesterification reaction

The experiments were conducted in a 2-litre stainless-steel autoclave equipped with a variable speed agitator (50–1500 rpm). The reactor could be heated while the temperature was controlled by a jacketed heating element. The reactor pressure was maintained at 800 psi with nitrogen gas. The calcined sodium phosphate cat- alyst was first put in a stainless steel basket that was placed in the middle of the reactor vessel. Palm olein was put into the reac- tor in predetermined amounts, and the feed bomb was filled with methanol. The system was then purged with nitrogen. Next, the reactor was heated to the desired temperature while the liquid was stirred at a constant speed of 600 rpm. When the reactor reached the reaction temperature, methanol was fed into the reactor. Sam- ples were taken at specific times, dipped into cold water to stop the reaction, and then separated in a centrifugal separator. The prod- uct was separated and washed with warm water. The samples were analysed for FAME content using gas chromatography. A schematic diagram of the experimental set up is shown in Fig. 1.

2.3. Analysis

The FAME products were analysed by gas chromatography (Variance 3800). A polar capillary column (Agilent, HP-Innowax 20 M) with an internal diameter of 0.32 m, a length of 30 m, a film thickness of 0.25 m, and a Flame Ionisation Detector (FID) were used. Helium was used as the carrier gas at a pressure of 10 psig. The injector and detector temperature were set at 260 C and 230 C, respectively. The programmed temperature was set for an initial temperature of 80 C for 5 min, and then the rate was increased with the heating rate set at 20 C/min up to a final temperature of 230 C where it was held for 5 min. Methyl decanoate, which was used as an internal standard, was mixed with heptane to prepare a stock solution. After a sample was accurately weighted, an internal standard stock solution was added to the sample. The FAME

standard stock solution was added to the sample. The FAME Fig. 1. Schematic diagram of the

Fig. 1. Schematic diagram of the experimental set up for the transesterification process.

K. Thinnakorn, J. Tscheikuna / Applied Catalysis A: General 476 (2014) 26–33

29

/ Applied Catalysis A: General 476 (2014) 26–33 29 Scheme 1. Transesterification of palm olein with

Scheme 1. Transesterification of palm olein with methanol.

content was defined as the ratio of the weight of FAME determined by the GC to the weight of the oil used, as shown in Eq. (1).

Yield of FAME =

Wt. of FAME (g) (g) × 100%

Wt. of Palm Oil used

(1)

The FAME content was calculated using the compensated nor-

malisation method with internal standardisation. A standard FAME

mix (C8–C24) from Supelco was used to identify the peaks at differ-

ent retention times and to correct the peak area using the response

factors of the compound. Error was separated into analytical error

and

experimental error. The analytical error was checked by repeat-

ing

the process 7 times and was found to be less than 1.5% on

average (at 95% confidence error). The experimental error was determined by repeating the experiment 3 times. The errors are shown in the experimental results.

3. Results and discussion

3.1. Transesterification reaction using Na 3 PO 4

Sodium phosphate-catalysed transesterification at a low tem- perature has been studied previously [32,33]. However, the reaction mechanism of the Na 3 PO 4 -catalysed transesterification

reaction is not explained well. In a homogeneous system, the alkox-

ide

group (NaOCH 3 , KOCH 3 ) attacks the carbonyl carbon atom of

the

triglyceride molecules to form fatty acid methyl ester [36,37].

Many studies assumed a similar mechanism in the case of a hetero- geneous Bronsted base catalyst, such as basic zeolite [37], which formed catalytic species of homogeneous alkoxide. The formation of alkoxide groups is also a fundamental step for heterogeneous basic catalysts [17,38–40]. In this work, the transesterification of palm olein and methanol catalysed by Na 3 PO 4 can be described as similarity to process using a heterogeneous Bronsted basic catalyst [41]. Triglyceride reacts with three moles of methanol to give 3 moles of fatty acid methyl ester and one mole of glycerine through reversible reac- tions. The transesterification of palm olein with methanol is shown in Scheme 1. This reaction involves 3 steps that take place simultaneously. Diasakou [42] proposed that triglycerides react with methanol to produce diglycerides, and then diglycerides react to produce mono- glycerides. Finally, monoglycerides react with methanol to yield

glycerin as a by-product. At each reaction step, one molecule of the methyl ester is produced for each molecule of methanol consumed. The analytical results showed that no side reactions occurred

and

that the reaction products, FAME and glycerine, collected from

the

reaction appeared to be clean and transparent. The FAME

products derived from the reaction were analysed by gas chro- matography. Prior analytical research reported only the yield of

FAME, which ignores the complex diglyceride and monoglyceride intermediates. Fig. 2 shows a gas chromatogram of the FAMEs in the product sample, methyl laurate (C12:0), methyl myris-

tate (14:0), methyl palmitate (16:0), methyl palmitoleate (C16:1),

methyl stearate (18:0), methyl oleate (18:1), methyl linoleate (C18:2), methyl linolenate (C18:3), methyl arachidate (C20:0),

methyl behenate (C22:0), and methyl erucate (C22:1), sequentially.

The results show that the amount of product corresponds to the

results show that the amount of product corresponds to the Fig. 2. Gas chromatogram of fatty

Fig. 2. Gas chromatogram of fatty acid methyl esters (FAME) in a product sample.

proportion of fatty acid content in the palm olein raw material, as seen in Table 2.

3.2. Effect of the molar ratio of methanol to oil

The molar ratio of alcohol to oil is one of the most important variables affecting transesterification reactions. In this study, the effect of stoichiometric methanol/oil molar ratios of 3:1–24:1 on the FAME yield was investigated. All experiments were conducted at a reaction temperature of 190 C with 0.5 wt.% Na 3 PO 4 . The for- mation of FAME with different ratios of methanol as a function of time is shown in Fig. 3. It can be seen that the reaction proceeds rapidly with an increase in the molar ratio of methanol to oil from 3:1 to 18:1. A higher molar ratio drastically increases the FAME content over time. However, the reaction is limited by the mass transport of methanol to the oil phase. At molar ratios of higher than 18:1, the FAME contents are almost identical because further increases in methanol do not affect the reaction rate. Transesterification is a chemical equilibrium reaction. An excess of methanol compared to oil is generally used to drive the reaction forward, thus producing higher yields of methyl esters. However, eventually the amount of methanol had no effect on the reaction rate [43]. One fact to consider is that methanol and oil are insoluble in each other at molar ratios higher than 3:1. In the case of a solid catalyst, the existence of 3 phases at the initiation of the reaction limits contact between the reactant and the catalyst. It can be con- cluded that the concentration of the alcohol has to balance between the rate of diffusion by the formation of two phases of fluid, and the shifting of the reaction towards products [41]. This research shows that 18:1 is the appropriate proportion for maximum yield.

that 18:1 is the appropriate proportion for maximum yield. Fig. 3. Effect of the molar ratio

Fig. 3. Effect of the molar ratio of methanol to oil on FAME yield. Molar ratio of methanol to oil 3:1–24:1. Temperature: 190 C. Amount of Na 3 PO 4 :0.5 wt.%.

30

K. Thinnakorn, J. Tscheikuna / Applied Catalysis A: General 476 (2014) 26–33

Tscheikuna / Applied Catalysis A: General 476 (2014) 26–33 Fig. 4. Effect of reaction temperature on

Fig. 4. Effect of reaction temperature on FAME yield. Temperature: 190–250 C. Molar ratio of methanol to oil: 18:1. Amount of Na 3 PO 4 :0.5 wt.%.

to oil: 18:1. Amount of Na 3 PO 4 :0.5 wt.%. Fig. 5. Effect of the

Fig. 5. Effect of the mass ratio of catalyst to oil on FAME yield. Amount of Na 3 PO 4 :

0.0–1.0 wt.%. Temperature: 210 C. Molar ratio of methanol to oil: 18:1.

However, while higher methanol to oil molar ratios interfere with the separation of glycerol, methanol with its polar hydroxyl group can also work as an emulsifier at the same time [44].

3.3. Effect of reaction temperature

Reaction temperature strongly affects the reaction rate. To study the effect of the reaction temperature, the experiment was per- formed at temperatures from of 190 to 250 C. The molar ratio of methanol to oil was fixed at a value of 18:1 with 0.5 wt.% Na 3 PO 4 . Fig. 4 shows the effect of reaction temperature on FAME yield. It was observed that the reaction rate increased with increasing reac- tion temperature. At a reaction temperature of 210 C, the FAME content reached equilibrium within 30 min. At a reaction temper- ature of 250 C, the reaction proceeded very quickly, and complete conversion of oil was observed within a 20 min period. However, it was observed that the glycerol product under these conditions exhibited a darker colour than the samples obtained at lower tem- peratures. Transesterification is an endothermic reaction, so increasing the reaction temperature favours higher product yields. At high tem- peratures, non-polar triglycerides can dissolve well in methanol to form a single phase of methanol and oil, resulting in an increase in FAME content [9]. To quantify the effects of the reaction temper- ature on FAME content and calculate the activation energy of the transesterification reaction with Na 3 PO 4 , the experimental results were interpreted in terms of the kinetics of converting palm olein to methyl esters. The results are shown in the next section.

3.4. Effect of mass ratio of catalyst to oil

The role of the catalyst is very important to promoting the rate of reaction. The effect of the mass ratio of the catalyst to oil was determined based on comparison with a non-catalytic reaction under the same conditions. Although the transesterification reac- tion occurs at temperatures approximately 200 C, the reaction is very slow, and the formation of desired esters is not selective due to incomplete alcoholysis of glyceride derivatives [42,45]. In this research, the effect of different amounts of catalyst, varying from 0.0 to 1.0 wt.% of oil, were examined. The molar ratio of methanol to oil was 18:1 with a reaction temperature of 210 C. The results are shown in Fig. 5. It is clear that the transesterification reaction of palm olein and methanol must be a catalysed reaction. Small amounts of FAME were detected when there was no catalyst in the reactor. When only a small amount of Na 3 PO 4