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Investigation of the factors affecting the progress of base-catalyzed

transesterification of rapeseed oil to biodiesel FAME

Article  in  Fuel Processing Technology · February 2015

DOI: 10.1016/j.fuproc.2014.09.013

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 Fuel Processing Technology 130 (2015) 127–135

Contents lists available at ScienceDirect

Fuel Processing Technology

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

Investigation of the factors affecting the progress of base-catalyzed

transesterification of rapeseed oil to biodiesel FAME
James Pullen, Khizer Saeed ⁎
Low Carbon Energy Research Group, School of Computing, Engineering and Mathematics, University of Brighton, Lewes Road, Brighton BN2 4GJ, United Kingdom

a r t i c l e i n f o a b s t r a c t

Article history: Conventional base-catalyzed transesterification method for large scale biodiesel FAME production is affected by a
Received 19 March 2014 number experimental factors. This work investigates, quantifies and establishes the effects of catalyst type,
Received in revised form 9 September 2014 number of reaction stages, the free fatty acid (FFA) and water content of the reactants on the progress of rapeseed
Accepted 10 September 2014
base-catalyzed transesterification under the optimized reaction conditions used in scale-up production. Firstly,
Available online xxxx
the efficacy of different alkaline-base catalysts: sodium hydroxide (NaOH), potassium hydroxide (KOH), and so-
Keywords:
dium methoxide (CH3ONa) were investigated and compared. The order of catalyst efficacy was found to be
Biodiesel NaOH N CH3ONa N KOH at 1% m/m concentration: NaOH was most potent achieving the highest conversion to
Fatty acid methyl esters (FAME) FAME in the shortest time. The effect of performing a 2 stage base-catalyzed reaction, where glycerol was
Transesterification removed prior to a second reaction stage, was investigated to determine any increase in the overall conversion
Catalyst to FAME relative to the single stage process. The effects of increasing the reactant FFA and water content on
completeness of transesterification using 1% m/m NaOH were also studied. End-product FAME content was sig-
nificantly reduced at N 5% m/m acid content (acid value N 10 mg KOH/g). Above ~7% m/m acid (~14 mg KOH/g),
the reaction was stopped due to excessive soap/gel formation. The FAME content was not especially sensitive to
reactant water contamination. Only at a water level of N 6000 ppm was the FAME content.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction chemical reaction known as transesterification, which converts TAG and

alcohol into fatty acid alkyl esters (FAAE), forming glycerol as
Biodiesel is a renewable replacement for petro-diesel that is co-product, according to the well established reaction as presented in
biodegradable, less toxic and can reduce harmful tailpipe combustion Fig. 1. The alkoxide anion (R′O−) generated by the base catalyst drives
emissions (CO2, CO, UHC and PM) relative to petro-diesel [1]. Biodiesel the reaction, as discussed by [4–6]. Methanol (CH3OH) is typically used,
is miscible with petro-diesel, compatible with fuel delivery infrastruc- yielding fatty acid methyl esters (FAME). The transesterification re-
ture, has high flashpoint for safer handling, and can be used in standard action is a sequence of three consecutive and reversible reactions
diesel engines requiring no engine modification. Biodiesel also offers in which di-acylgylcerols (DG) and mono-acylglycerols (MG) are
improved lubricity over certain low-sulfur petro-diesels and thus formed as intermediates. The reaction proceeds stepwise via DG
can help reduce wear of engine components [2]. Running diesel- and MG, with a fatty acid alkyl ester being formed in each step [7,
engine equipment on biodiesel can be beneficial in terms of environ- 8], as shown below:
mental impact and energy security. In Europe, biodiesel should meet
0 
0 
the fuel quality standard known as EN 14214 [3] to be approved for Alcohol R OH þ TriglycerideðTAGÞ←→Alkyl ester R COOR
use in diesel engines; limits are imposed on a range of important þ DiglycerideðDGÞ
fuel properties, including: purity, combustion properties and fuel
stability.
0 
0 
Biodiesel is produced mainly from plant-seed oils: rapeseed in Europe, Alcohol R OH þ DiglycerideðDGÞ←→Alkyl ester R COOR
soybean in USA and also more generally from used cooking oil (UCO), þ MonoglycerideðMGÞ
though it can be derived from a wide range of other seed oils, animal
fats and even certain lipid-rich algal species. The main molecular compo-
0 
0 
nent of oils and fats are Triglycerides, also known as Triacylglycerols Alcohol R OH þ MonoglycerideðMGÞ←→Alkyl ester R COOR
(TAG). Biodiesel is conventionally made via the alkaline-base catalyzed þ GlycerolðG F Þ:

⁎ Corresponding author. Tel.: +44 1273 642304; fax: +44 1273 642405. In practice, the starting oil/fat is heated and vigorously mixed with a
E-mail address: k.saeed@brighton.ac.uk (K. Saeed). solution of base-catalyst and methanol usually for around 1 h, under

http://dx.doi.org/10.1016/j.fuproc.2014.09.013
0378-3820/© 2014 Elsevier B.V. All rights reserved.
128 J. Pullen, K. Saeed / Fuel Processing Technology 130 (2015) 127–135

Fig. 1. Reaction scheme for alkaline-base catalyzed transesterification, where R′ is a short alkyl group of an alcohol (e.g. methanol CH3), R″ is a long-chain alkyl group (fatty acid chain), and
R′O−is the alkoxide anion generated by the base catalyst which drives the reaction.

atmosphere and below methanol boiling point (65 °C). The product is
allowed to settle before it is purified by decanting glycerol and final
washing [9].
The transesterification reaction must be sufficiently complete and the
FAME purified in order to meet fuel quality standards, such as the
European standard EN 14214, which requires biodiesel FAME content
N96.5% m/m. The main purpose of transesterification is primarily to
reduce viscosity of TAG to a value much closer to that of conventional
petro-diesel. Without converting TAG to FAME, the high viscosity of
TAG results in poor atomization upon injection into the combustion
chamber and leads to operational problems in diesel engines, such as de-
posit formation on engine parts, and eventual engine failure [10]. Though
some engines can be designed or modified to use untransesterified TAG,
the vast majority of engines require lower-viscosity fuel [2].
Previous authors including Knothe et al. [2], Ma and Hanna [4],
Meher et al. [5], Sharma et al. [11], Srivastava and Prasad [12] have iden-
tified that most important factors that influence transesterification and
determine completeness of conversion of TAG to FAME are catalyst type
and concentration, molar ratio of alcohol to oil, reaction temperature,
reaction time, mixing intensity, and reactant purity (particularly water
content and levels of free fatty acids present in the oil).
Several studies have examined the effects of these factors on
transesterification of vegetable oils using alkaline catalyst to determine
the optimum reaction conditions. Relevant studies have been
performed by Darnoko and Cheryan [7], Martínez et al. [13,14], Leung
and Guo [15], Issariyakul et al.[16], Meng et al. [17], Phan and Phan
[18], Rashid et al. [19], Bautista [20], Ramos [21]. Table 1summarizes
optimum conditions for transesterification reported by these authors.

Table 1
Optimum conditions for transesterification reported by various authors.

Author reference Reported optimum Other conditions

held constant
Catalyst type Catalyst Alcohol:oil Temp Time
(% m/m) by oil mass molar ratio (°C) (min)

Darnoko and Cheryan [7] 1.0–1.2 KOH 65 Palm oil

6:1 methanol:oil
90 min
KOH
Vicente et al. [13] NaOH (fastest at 1.0% m/m) 1.5 KOH Sunflower
1.0 NaOH 65 °C
600 rpm
6:1 methanol:oil
Leung and Guo [15] NaOH achieved highest ester 1.1 NaOH, 6:1 60 N15 UCO methanol
conversion, NaOCH3 made less soap 1.3 CH3ONa Constant mixing
1.5 KOH
Leung and Guo [15] 1.0 NaOH 7:1 60 N15 Canola methanol
Constant mixing
Vicente et al. [14] 1.3 KOH 6:1 25 Sunflower oil
Methanol
60 min
Rashid et al.[19] NaOH 1.0 NaOH 6:1 60 Sunflower oil
600 rpm
120 min
Meng et al. [17] 1.0 NaOH 6:1 50–60 60 UCO
Methanol
NaOH
Phan and Phan [18] 0.75–1.0 KOH 7:1–8:1 50 UCO
Methanol
30 °C
0.75% m/m KOH
Bautista et al. [20] 1.3 KOH 30 UCO
Methanol
KOH
1 h reaction
700 rpm stir speed,
6:1 methanol:oil
 J. Pullen, K. Saeed / Fuel Processing Technology 130 (2015) 127–135
Fig. 2. Reaction scheme showing the hydrolysis of esters and saponification of fatty acids, where R″ = fatty acid chain, R′ = short alkyl group.
Despite some variation in optimum conditions reported, in general, a
fixed molar ratio of 6:1 methanol:oil was widely the optimum.
Increased temperature promoted base-catalyzed transesterification,
which was most efficient near the boiling point of the alcohol. Excessive
bubbling/vaporization of the alcohol (close to or above boiling pt.)
adversely affected the reaction. Methanolysis at or above 60 °C but
lower than the alcohol boiling point, generally brought the reaction to
completion faster than at lower temperatures. More than 60 min
reaction time generally achieved little improvement in yield, and
under favorable conditions, the reaction was complete in shorter times.
The feedstock free fatty acid (FFA) content can significantly affect
the transesterification progress. Used cooking oils (UCO) typically
contain 2–7% FFA, animal fats can contain 5–30% FFA, and some low
quality feedstocks, such as trap grease, can approach 100% FFA [2].
When alkaline base-catalyst is added to high FFA content feedstocks,
the FFA (R″OOH) react with the alkali to form soap and water (a process
known as saponification), as shown in the reaction scheme of Fig. 2. Less
catalyst is consumed forming less water and soap in base-catalyzed
transesterification of oil/fat feedstocks containing low levels of FFA.
According to Ma and Hanna [4], the oil should ideally have an acid
value less than 1 (mg NaOH/g). Knothe et al. [2] reported that for
feedstocks containing up to ~ 5% FFA, transesterification can still be
alkali catalyzed, though additional catalyst must be added to
compensate for the catalyst lost to soap formation. After the base-
catalyst has neutralized FFA to soap, the soap created is either removed
(decanted) with the glycerol phase or washed out of alkyl esters e.g. by
subsequent purification steps (water or dry washing). For feedstocks
with FFA levels N 5%, alkali catalyst consumption is said to become
excessive with soap and water formation that inhibits separation of
glycerol from esters and contributes to emulsion formation during
washing. For high FFA content feedstocks, acid-catalyzed esterifcation
of FFA to alkyl esters becomes necessary as a pre-stage to the
base-catalyzed transesterification, as performed by Wang et al. [22].
Increased feedstock FFA content therefore negatively affects
base-catalyzed transesterification, due to saponification and catalyst
loss, and completeness of base-catalyzed transesterification improves
with lower FFA content of the starting oil. Complete transesterification
is hence relatively easier to achieve with fresh, refined (low FFA) oil,
than with used cooking oil (UCO) of higher FFA content.
Elimination of water from the starting reactants is also important, as
the transesterification reaction can be slower or even stopped by the
presence of water [23]. This is because water results in the hydrolysis
of esters and glycerides to FFA, as shown in Fig. 2. However, water
content of reactants was not always reported in literature studies of
transesterification (Table 1).
Relatively few studies have examined the effects of water and free
fatty acid (FFA) contamination on base-catalyzed transesterification.
The effects of free fatty acids and water on the transesterification of
beef tallow with methanol were described by Ma and Hanna [4], who
reported that the water content of beef tallow should be kept below
0.06% m/m (600 ppm) and free fatty acid content of beef tallow should
be kept below 0.5% m/m in order to get the best conversion. They
concluded that water content was a more critical variable in the
129
transesterification process than were free fatty acids. Issariyakul et al.
[16] studied transesterification of fresh Canola oil and UCO mixtures,
with methanol and ethanol, catalyzed by KOH. Various ratios of Canola
(acid value = 0.4 mg KOH/g) and UCO (2.5 mg KOH/g) were prepared.
They observed that ester conversion tended to increase with more
Canola in the oil mixture, so that addition of fresh oil to the UCO helped
to improve ester yield. For example, the methyl ester conversion
increased steadily from 92 to 95% for 100% UCO to 100% Canola respec-
tively. Bautista [20] studied UCO methanolysis with KOH catalyst to
measure ester yield (% m/m). The FFA content of the starting UCO was
varied (3, 1.88, or 0.76% m/m) and results showed increasing FFA
content negatively affected FAME purity, due to greater saponification
and catalyst loss.
Generally, studies reported that optimum conditions for
transesterification strongly depended on the purity of the feedstock
oil. Complete alcoholysis with refined (high purity) oil was relatively
easier to achieve than with (lower purity) UCO. For example,
methanolysis of 10 different refined oils carried out by Ramos et al.
[21] under standard reaction conditions achieved N96.5% m/m ester
conversion for all 10 of the oils. Values ranged between 96.9% m/m
(lowest) for soybean and 99.8% for corn oil (highest). In contrast in
other studies, ester conversion for UCO was typically lower than
96.5% m/m. Leung and Guo [15]reported that optimum conversion for
UCO was 94.6% m/m. Meng et al. [17] reported that optimum conver-
sion of UCO was 89.8% m/m.
These studies clearly established that increased FFA content
negatively affected FAME conversion. However, the water content of
reactants — particularly the water content of feedstock oils — was not
always reported in literature studies. Of those studies reviewed above,
only two reported the water content of the starting oil. Moreover, the
effect of contaminant water on ester conversion, relative to the effect
of increased FFA content is not well described in the literature. Further
work is thus warranted that would examine the effects of increasing
contaminant FFA and water levels on ester conversion.
Sodium hydroxide (NaOH), potassium hydroxide (KOH), and
sodium methoxide (CH3ONa) are usually the most cost-effective and
hence commonly investigated base-catalysts for transesterification.
The hydroxide anion reacts with alcohol (R′OH); forming equilibrium
with alkoxide (RO−) and water (H2O) [4–6]according to Eq. (1).
0 − −
R OHþ OH ←→ RO þ H2 O
: ð1Þ
Alcohol hydroxide Alkoxide water
The alkoxide is a stronger base than the hydroxide anion and is a
better catalyst of the transesterification reaction, increasing the reaction
rate. Thus when hydroxides are used as catalyst, water is an undesired
by-product of the alkoxide generation stage; the formed water would
ideally be removed.
Alkaline metal alkoxide catalyst (e.g. sodium methoxide CH3ONa)
dissociates in solution with the reactant alcohol to form the alkoxide
anion and metal cation directly; thus avoiding production of water,
according to Eq. (2)[4–6]. Knothe et al. [2] reported that the use of
alkaline metal alkoxides results in glycerol of higher purity and offers
130 J. Pullen, K. Saeed / Fuel Processing Technology 130 (2015) 127–135
advantages in terms of safety and convenience of handling, by not
having to perform the exothermic reaction of hydroxide with alcohol.
− þ
CH3 ONa ←→ CH3 O þ Na : ð2Þ
Molecular weights of respective catalysts are: 54.04 g/mol for
CH3ONa, 40.01 g/mol for NaOH, and 56.11 g/mol for KOH. Thus
CH3ONa is 35% heavier, and KOH is 40% heavier than NaOH on a molar
basis. According to Eqs. (1) and (2) above, 1 mol of catalyst generates
1 mol of the alkoxide anion so that catalysts might be assumed equally
efficacious on a molar basis. The order of molecular weights infers that
the order of efficacy by mass would be NaOH N CH3ONa N KOH.
Vicente et al. [13] found that the order of catalyst efficacy at 1.0% m/m
(by weight of oil) for sunflower oil was NaOH N KOH N CH3ONaN CH3OK,
although, 1.5% m/m KOH N 1.0% NaOH. Whereas Rashid et al. [19] found
that the efficacy order at 1.0% m/m for sunflower oil was
NaOH N CH3OK N KOH N CH3ONa. Leung and Guo [15] found that for
UCO the order was NaOH N CH3ONa N KOH. NaOH was consistently the
superior catalyst, in agreement with the order of efficacy suggested by
catalyst molecular weights, and the optimum NaOH concentration by
mass widely reported was 1.0% m/m. From Table 1, general optimum
conditions were: 6:1 methanol:oil molar ratio, 1% m/m NaOH catalyst,
60 °C reaction temperature, 60 min reaction time, and N600 rpm stir
speed.
However, the order of catalyst efficacy (behind NaOH in the first
place) was less clear. The relative performance of alkaline metal
alkoxide catalyst doesn't appear to be clearly established. Ma and
Hanna [4] commented that CH3ONa tended to be more effective than
NaOH, because the water produced upon mixing NaOH and the alcohol
can lead to increased saponification. Similarly, Demirbas [24] stated that
alkaline metal alkoxides were the most active catalysts though they
require the absence of water, which makes them inappropriate for
typical industrial processes. Inferring that for alkaline metal alkoxides
to be better catalysts, the reactants must be sufficiently anhydrous.
A study that examines base-catalyst performance at equivalent
concentrations, while controlling the amount of contaminant water in
the reactants appears warranted, in order to more confidently define
the order of catalyst efficacy. Transesterification could also be carried
out in two (or more) stages; where part of the alcohol and catalyst is
mixed with the oil in a first stage reaction, followed by glycerol removal,
followed by a second reaction stage where the remaining catalyst and
alcohol are added, before once again decanting glycerol. This technique
is not widely reported in the literature though according to Knothe et al.
[2]it can provide a more complete reaction using less alcohol than single
step method to still achieve high ester conversion; with potential cost
savings for producers. Investigation appears lacking and would seem
called for.
The aim of the present work was to experimentally compare the
performance of base-catalysts (NaOH, KOH and CH3ONa) at equal
concentration (% m/m) in order to better establish the relative efficacy
of these catalysts. A further aim was to examine whether 2-stage
transesterification could yield higher ester conversion, compared to a
single stage process. And lastly, the aim was to investigate the relative
effect of increasing FFA content in the oil, and increasing reactant
water contamination on the completeness of transesterification of
rapeseed oil
2. Experimental procedure
Transesterification trials comparing base-catalysts (NaOH, KOH and
CH3ONa) were performed using refined rapeseed oil and anhydrous
methanol. Analytical grade methanol (N 99.5% purity) and catalyst
materials: sodium hydroxide (N 98% purity) pellets, potassium
hydroxide (N86%) pellets, sodium methoxide (CH3ONa) solution
30 wt.% pure in methanol (Acros Organics–Fisher Scientific Ltd.) were
used. The water content of both the rapeseed oil and methanol used
was b200 ppm, measured by titration with a Karl Fischer Coulometer
(KFC) [mg/kg], according to the standard method EN ISO 12937 [25],
supplied by Metrohm Ltd., Herisau/Switzerland. The acid value of the
rapeseed oil was 0.21 mg KOH/g, measured by titration with potassium
hydroxide solution [mg KOH/g], according to the method EN 14104[27]
using an 809 Titrando, auto-titrator, Metrohm Ltd., Herisau/
Switzerland. Each catalyst was tested in turn, at 1% m/m concentration
by weight of oil in order to establish the relative efficacy of each. Second,
catalyst concentration was increased to 1.35% for CH3ONa, and 1.4 (% m/
m) for KOH by weight of oil since CH3ONa is 35% heavier, and KOH is
40% heavier than NaOH on a molar basis. Consistent reaction conditions
were maintained in all trials (6:1 methanol:oil molar ratio, 60 °C
reaction temperature, 60 min reaction time, and 600 rpm stir speed).
Each experiment was undertaken at least four times to establish the repro-
ducibility and repeatability in experiments, and to achieve statistical reli-
ability of the experimental data obtained from the experiments. In each
reaction process, at least four samples were withdrawn from the reaction
(25 ml aliquots) for each of the following time steps: 5, 10, 20, 40 and
6 min, to determine the reaction progress. After each withdrawal, a few
drops of dilute acid (HCL, 37% aqueous solution) were added to each sample
to neutralize the alkaline catalyst and stop the reaction except for the
60 minute sample. All four samples obtained at different time steps were
left to settle overnight. Residual glycerol was decanted from the separat-
ing funnel contents, before esters were ‘dry-washed’, by filtering under
gravity through ion-exchange resin (Purolite PD206A) until pH neutral.
Esters were then also purified by washing with warm distilled water.
Effluent water was decanted and the sample was dried by gentle
heating (50 °C) and open to-air stirring in a beaker, evaporating
residual moisture. Water content of the dried sample was reduced to
b500 ppm, checked using a KFC, before being stored in an airtight jar
prior to analysis. For each 25 ml sample collected in a vial, the upper
phase of methyl ester was drawn off using a pipette, leaving the lower
glycerol phase and in-between the layer of precipitated salt (neutraliza-
tion product). Esters were ‘dry-washed’ as above, using a small amount
of fresh Purolite, before being dried to b500 ppm water content by
heating (70 °C) and open to-air stirring in a beaker; evaporating
residual alcohol and moisture. 250 mg of each methyl ester sample
was weighed (+/−0.0001 g) into a 10 ml brown-glass vial, to which
5 ml of methyl heptadecanoate in n-heptane (10 mg/ml solution) —
internal standard was added using a pipette ready for GC analysis,
described below. A three-necked glass reaction vessel of 1 l was used
for the analysis.
Gas chromatography (GC) method BS EN 14103[26] was used for
the determination of FAME content (% m/m) for each sample, using a
DB-WAX capillary column coated with a polyethylene glycol stationary
phase of length 30 m, internal diameter of 0.32 mm, and film thickness
of 0.25 μm. The GC system was an Agilent 7890A equipped with a split/
splitless injector, flame ionization detector (FID), data log PC with
ChemStation software, supplied by Agilent Technologies UK Limited.
GC method parameters were set according to Table 2. A reference
mixture (AOCS No. 3, F.A.M.E. RM-3 mixture — Sigma Aldrich) was
first run in order to determine retention times for respective methyl
esters (C14–C24:1). Integration was carried out from the methyl
myristate (C14) peak up to that of (C24:1) taking all peaks into consid-
eration including minor ones. Chromatogram results were analyzed to
Table 2
EN 14103 method parameters (BSI 2003 [26]).
Injector Split flow ratio: 80:1, 250 °C injector temperature, 1.0 μl sample
injection volume
Gas flow N2, 1.5 ml/min, constant flow mode
Column DB-WAX, polyethylene glycol stationary phase, length 30 m, i.d.
0.32 mm, film thickness 0.25 μm
Oven 210 °C hold 9 min, ramp 20 °C/min, to 230 °C and hold for 10 min
Detector FID, 300 °C, H2 40 ml/min, Air 400 ml/min, make up (N2) 40 ml/min,
 J. Pullen, K. Saeed / Fuel Processing Technology 130 (2015) 127–135 131

99
EN 14214 requirement >96.5%
98

97

FAME content (%m/m)

96

95

94

93

92

91

90
0 10 20 30 40 50 60
Reaction time (minutes)
CH3ONa NaOH KOH

Fig. 3. FAME content (% m/m) versus reaction time (min) for catalyst trials at 1% m/m concentration.

obtain peak area data for respective alkyl ester components. Each
prepared sample was injected and analyzed in duplicate. FAME content,
CFAME (% m/m) was calculated from integration results for a particular
determination according to Eq. (3), and the average FAME content
from duplicate determinations was recorded.
X 
A −AEI CEI  VEI
CFAME ¼   100%
AEI m was transferred to a separating funnel and purified for any remaining
where, ΣA is the sum of all methyl ester peak areas from C14 to C 24:1,
AEI is peak area for methyl heptadecanoate (internal standard), CEI is
concentration (mg/ml) of the methyl heptadecanoate solution
(10 mg/ml), VEI is volume (ml) of the methyl heptadecanoate solution
used (5 ml) and ‘m’ is precise mass (mg) of the FAME sample.
Two-stage transesterification was carried out, using essentially the
same conditions/procedure as outlined above. One 2-stage trial was car-
ried out with 1% m/m NaOH, and another with 1% m/m CH3ONa. In the
first reaction stage, 80% vol. of the alcohol/catalyst solution was added
to the oil. After 30 min reaction time, the mixture was transferred to a
separating funnel and allowed to settle for 10 min before glycerol was
decanted. With some of the glycerol removed, the product was then
transferred back into the reaction vessel and the remaining 20%
alcohol/catalyst solution was added, and the reaction continued for
20 min. In the 2-stage reaction, samples (25 ml) were withdrawn for
ð3Þ analysis at 5, 10, 20, 30, 45, and 55 min. After 60 min, the final product
water and catalyst impurities as discussed above.
The effect of increasing FFA content in the oil on completeness of
transesterification was further investigated by adding oleic acid to rape-
seed oil. Oleic acid (Fisher Scientific Ltd.) was weighed (+/−0.0001 g)
into a beaker and rapeseed oil was added to bring the total sample mass
to 320 g (+/−0.1 g). The acid value (mg KOH/g) of the resulting oleic
acid/rapeseed oil blend was measured by method EN 14104. Ten blends
were prepared and respective transesterification trials were carried out.
In each trial the proportion of oleic acid that was mixed with the

99
EN 14214 requirement >96.5%
98

97
FAME content (%m/m)

96

95

94

93

92

91

90
0 10 20 30 40 50 60
Reaction time (minutes)
CH3ONa NaOH KOH

Fig. 4. FAME content (% m/m) versus reaction time (min) for catalyst trials at respective concentrations of 1.0 NaOH, 1.35 CH3ONa, and 1.4 (% m/m) KOH by weight of oil.
132 J. Pullen, K. Saeed / Fuel Processing Technology 130 (2015) 127–135

101
100
99

FAME content (%m/m)

98
97
96
95
94
93
92
91
90
89
0 10 20 30 40 50 60
Reaction time (minutes)
1%m/m NaOH, 2stage 1%m/m NaOH, 1 stage

Fig. 5. FAME content (% m/m) versus reaction time (min) for single-stage and two-stage transesterification using NaOH at 1% m/m concentration.

rapeseed oil was increased: 0, 0.6, 3.4, 5.1, 5.4, 5.7, 6.0, 6.9, 7.4, and 10.3
(% m/m). Each acidified test oil was transesterified by essentially the
same procedure described above (stages 1. to 10.), except that samples
were not taken for analysis during the reaction (stages 6. and 9. were
not performed) i.e. CFAME (% m/m) was only measured for the end
product. Consistent reaction conditions were maintained in all trials
(single-stage reaction, 1% m/m NaOH catalyst, 6:1 methanol:oil molar
ratio, 60 °C reaction temperature, 60 min reaction time, and 600 rpm
stir speed). Two used cooking oils (UCO obtained from a local biodiesel
manufacturer), were also transesterified by this method for comparison.
Each UCO was first dried by heating (80 °C) and open to-air stirring in a
beaker, evaporating residual moisture, and allowed to cool before acid
value was measured. UCO#1 acid value was 5.31, while UCO#2 was
10.15 mg KOH/g.
The effect of increasing water contamination on completeness of
transesterification of rapeseed oil was also investigated. The initial water
content (ppm) of the test materials was measured by KFC (4 replicate av-
erages) to be 183 ppm (Woil) for rapeseed oil, and 133 ppm (Wmeth) for
methanol. Eight (otherwise identical) transesterification trials were car-
ried out, where rapeseed oil was transesterified (stages 1. to 10. above)
and CFAME (% m/m) was measured for the end product. Consistent reaction
conditions were maintained in all trials (1% m/m NaOH catalyst, 6:1 meth-
anol:oil molar ratio, 60 °C reaction temperature, 60 min reaction time, and
600 rpm stir speed), except a measured amount of water (+/−0.0001 g)
was also added to reactant methanol prior to adding the NaOH catalyst.
Contaminant water was added to the methanol rather than to the oil, in
order to prevent water evaporation before the start of the reaction. In
each trial, 300 g rapeseed oil was accurately weighed (moil +/− 0.1 g)

101
100
99
FAME content (%m/m)

98
97
96
95
94
93
92
91
90
89
0 10 20 30 40 50 60
Reaction time (minutes)
1%m/m CH3ONa, 2stage 1%m/m CH3ONa, 1stage

Fig. 6. FAME content (% m/m) versus reaction time (min) for single-stage and two-stage transesterification using CH3ONa at 1% m/m concentration.
 J. Pullen, K. Saeed / Fuel Processing Technology 130 (2015) 127–135 133

Table 3 3. Results and discussion

FAME content results from transesterification trials of UCO and oleic acid/rapeseed oil
blends.
The difference between the duplicate determination results for
Trial reference Oleic acid Acid value FAME content CFAME did not exceed 0.93% m/m, and the average difference was
(% m/m) (mg KOH/g) (% m/m) 0.23% m/m. Fig. 3 shows how FAME content increased with reaction
T0 0.0 0.21 97.1 time for each of the catalyst trials at 1% m/m concentration. NaOH was
T1 0.6 1.36 96.9 clearly the best catalyst achieving the highest conversion to FAME in
T2 3.4 7.08 96.7
the shortest time, so that the order of efficacy at 1% m/m concentration
T3 5.1 10.53 89.6
T4 5.4 11.09 82.2 was NaOH N CH3ONa N KOH. The final FAME content for each catalyst
T5 5.7 12.16 78.1 test is plotted at 60 min (Fig. 3), and this was attained after allowing
T6 6.0 13.92 50.0 the reaction product to settle overnight. Because the residual catalyst
T7 6.9 14.13 4.2 was not neutralized with acid, a very slow reaction continued during
T8 7.4 15.85 3.8
overnight settling period at the prevailing ambient conditions. For KOH
T9 10.3 21.03 3.9
UCO#1 – 5.31 94.1 and CH3ONa, the final FAME content was significantly improved
UCO#2 – 10.15 93.3 compared to the samples taken at 40 min. These results showed that
all three catalysts achieved N 96.5% conversion, though 1% m/m
CH3ONa and KOH were relatively slower.After transferring the reaction
product to the separating funnel, phase separation of glycerol occurred
into the reactor. Next, 65.5 g methanol (mmeth +/− 0.0001 g) was and the concentration of glycerol in solution with the methyl esters
weighed, the reading was tared and drops of water were added decreased. According to Le Chatelier's principle, the subtraction of
(mwater +/− 0.0001 g). The water content (ppm) of the aggregated glycerol causes the reaction to oppose the change and favor the product
reactants was calculated according to Eq. (4). side, driving more complete conversion to FAME. Hence allowing the
un-neutralized product to settle probably helped achieve greater
conversion to FAME.
As discussed above, the catalysts might be assumed (hypothesis)
w  mmeth þ Woil  moil þ mwater equally efficacious on a molar basis. CH3ONa is 35% heavier, and KOH
Wreactants ¼
meth
 ð4Þ
mmeth þ moil þ mwater  10−6 is 40% heavier than NaOH on a molar basis. Fig. 4 shows how FAME
content increased with reaction time for each of the catalyst trials at
respective concentrations of 1.0 NaOH, 1.35 CH3ONa, and 1.4 (% m/m)
wheremmeth, moil is mass in kg, mwater is mass in mg, and W is water KOH by weight of oil. Comparing Figs. 3 and 4, the performance of
content (mg/kg). CH3ONa and KOH was relatively improved at increased concentration,
The amount of water (mwater) that was added to the methanol in and there was no significant difference between NaOH and CH3ONa.
each trial, was (approx to 1 s.f.): 0, 0.5, 1, 1.5, 2, 2.5, 3.5, and 4 g. The Though KOH still achieved relatively slower conversion to FAME, so
chemical composition analysis of each sample was done at least two that the order of efficacy was NaOH ≈ CH3ONa N KOH. The increased
times in gas chromatography. It was observed that repeatability and concentration of CH3ONa and KOH (Fig. 4) made little difference to
reproducibility of experiments were accurately achieved by this exercise. the final FAME content plotted at 60 min, attained after overnight set-
This approach was a step advance inthat the single typical single measure- tling. After 40 min of the CH3ONa test (Fig. 4), FAME content dropped
ments adopted in GC analysis were reported in most biodiesel literature. slightly below the value measured at 20 min, but this may be due to
This has ensured statistical relevance, validity and accuracy of the GC measurement error and may not be significant. The reason KOH was
analysis data obtained and presented in this work. relatively slower at 1.4% m/m, was most probably due to the lower

100

90

80
FAME content (%m/m)

70

60

50

40

30

20

10

0
0 5 10 15 20 25
Oil Acid Value (mg KOH/g)
UCO Oleic acid/ Rapeseed oil blend

Fig. 7. FAME content (% m/m) versus oil acid value (";mg KOH/g) for single-stage transesterification of UCO and oleic acid/rapeseed blends, using NaOH at 1% m/m concentration.
134 J. Pullen, K. Saeed / Fuel Processing Technology 130 (2015) 127–135
100
99
98
FAME content (%m/m)
97
96
95
94
93
92
91
90
0 2000
Fig. 8. FAME content (% m/m) versus aggregated reactants water content (ppm) for single-stage transesterification of rapeseed oil, using NaOH at 1% m/m concentration.
purity of the KOH pellets (N86%). In comparison, the NaOH pellet purity
was (N 98%). The CH3ONa was 30 wt.% pure in methanol solution. The
quantity of catalyst used was calculated by weight of oil (300 g), so
that the molar amounts of respective catalysts used can be approxi-
mately calculated as follows:
o NaOH: 1% m/m = 3 g × 98% purity = 2.94 g pure NaOH =
0.0735 mol NaOH
o KOH: 1.4% m/m = 4.2 g × 86% purity = 3.61 g pure KOH =
0.0644 mol KOH
o CH3ONa: 1.35% m/m = 4.05 g = 0.0750 mol CH3ONa
i.e. In terms of the molar amounts of respective catalysts used, number
of moles were for NaOH ≈ CH3ONa N KOH, explaining why KOH was
relatively slower.
Fig. 5 compares results from trials of single-stage and two-stage
transesterification using NaOH at 1% m/m concentration. Fig. 6 shows
results using CH3ONa at 1% m/m concentration. In the 2 stage process,
80% vol. of the alcohol/catalyst solution was added to the oil in the
first reaction stage, explaining why the reaction was slower relative to
the single-stage during the first 30 min of the reaction. After the
first-stage reaction product (glycerol) had been decanted, and the
remaining 20% alcohol/catalyst had been added, the sample withdrawn
at 45 min showed greater FAME content than the single-stage final
product. Removal of glycerol helped shift the reaction further to the
product side according to the Le Chatelier's principle. The 2 stage
process significantly improved transesterification completeness and
increased reaction speed, relative to the single-stage. FAME content of
both 2-stage final products (plotted at 60 min) were calculated to be
N100% m/m, which indicated complete conversion although also some
measurement error. As a calibration check, duplicate samples of methyl
myristate N 99% purity (Acros Organics), were also analyzed. The results
for CFAME were 100.9% and 100.3% indicating a slight overshoot
measurement error. However, any calculation overshoot value is taken
as indicating 100% or full conversion.
Figs. 3–6 all show evidence of reversibility to some extent in
transesterification reaction process. Two-stage reactions are used to
overcome this reversibility by creating favorable equilibrium to push
the reaction toward the products. Interesting observation can be seen
from Figs. 3–6 that in that the FAME yield drops down significantly
after the elapse of certain reaction time period due to the triggering of
the reaction reversibility. Introduction of two-stage reaction process
4000 6000 8000 10000 12000
Water content of reactants (ppm)
was found to eliminate the reversibility process leading to the better
FAME yield.
Table 3 compares results from the transesterification trials of UCO
and oleic acid/rapeseed oil blends, showing the effect of increasing the
oil FFA content on the completeness of transesterification. For each
trial (T0-9), the proportion of oleic acid (% m/m) blended with rapeseed
oil is shown, along with the measured acid value of the blend.
FAME content (% m/m) was measured for the end product of
transesterification, as described above. From Table 3, it can be seen
that each acid value measured was approximately twice the oleic acid
content (apart from T0). This is because 1 mol of KOH neutralizes
1 mol of oleic acid, and 1 g KOH (1/56.1 mol) neutralises 5.03 g oleic
acid (of molecular weight = 282.5 g/mol). Therefore, 1 mg KOH/g
(1 g KOH/1000 g) corresponds to oleic acid content of 0.503% m/m.
Fig. 7 shows graphically how end-product FAME content was
reduced by increasing the FFA content of the rapeseed oil. The results
indicated that N 5% m/m acid content (N 10 mg KOH/g) and FAME con-
tent was significantly reduced. Above ~ 7% m/m (~14 mg KOH/g), the
reaction was stopped due to excessive soap/gel formation.
Fig. 8 shows how the end-product FAME content was reduced by
increasing the level of water contamination. However, the results
showed that FAME content was not especially sensitive to water
contamination. Even at quite high levels of water contamination,
N10,000 ppm (N 1% m/m), 94.5% m/m content was achieved; which
was better than that achieved for dry UCO (Table 3). In none of the trials
was the reaction stopped due to excessive soap/gel formation. Only at a
water level of N6000 ppm was FAME content noticeably affected.
4. Conclusions
1. Experiments showed that optimum conditions for transesterification
(methanolysis) were: 6:1 methanol:oil molar ratio, 1% m/m NaOH
catalyst, 60 °C reaction temperature, 60 min reaction time, and
N 600 rpm stir speed.
2. Experiments showed that the optimum catalyst type was NaOH since
the order of catalyst efficacy at 1% m/m concentration was
NaOH N CH3ONa N KOH.
3. At respective concentrations of 1.0 (% m/m) NaOH, 1.35(% m/m),
CH3ONa, and 1.4 (% m/m) KOH, the order of catalyst efficacy was
NaOH ≈ CH3ONa N KOH, where KOH was slower probably due to
lower purity of the KOH pellets.
 J. Pullen, K. Saeed / Fuel Processing Technology 130 (2015) 127–135
4. All three catalysts consistently achieved N 96.5% m/m FAME content
for transesterification of refined rapeseed oil after allowing the un-
neutralized product to settle overnight. Only 1% m/m NaOH and
1.35% m/m CH3ONa (single-stage) achieved N96.5% in under
40 min reaction time.
5. Two-stage transesterification increased conversion to FAME relative
to the single-stage process, since the removal of glycerol shifted the
reaction further to the product side according to the Le Chatelier's
principle.
6. Increased FFA content of the oil caused end-product FAME con-
tent to be significantly reduced above N5% m/m FFA content
(N10 mg KOH/g), and N7% m/m (N14 mg KOH/g) the reaction
was stopped due to excessive soap/gel formation.
7. End-product FAME content was not especially sensitive to water
contamination. Even with high levels of water at N10,000 ppm,
better FAME content was achieved than with dry UCO. Also, high
levels of water did not cause the reaction to stop due to soap/gel
formation.
8. Oil FFA content would appear to be the more critical feedstock oil
quality parameter, compared to the water content. Only at a water
level of N6000 ppm was FAME content noticeably affected.
Acknowledgements
The authors wish to express thanks to Rye Biofuels Ltd. (UK) and the
Engineering and Physical Sciences Research Council (EPSRC) (EP/
F022840/1) of the United Kingdom for their support.
References
[1] R.L. McCormick, A. Williams, et al., Effects of biodiesel blends on vehicle emissions,
Milestone Report, NREL/MP-540-405542006.
[2] G. Knothe, J. Van Gerpen, et al., The Biodiesel Handbook, AOCS Press, Urbana, Illinois,
2005.
[3] BSI, BS EN 14214:2008 + A1:2009, Automotive fuels — Fatty Acid Methyl Esters
(FAME) for Diesel Engines — Requirements and Test Methods, Standards Policy
and Strategy Committee, British Standards Institute, 2008.
[4] F. Ma, M.A. Hanna, Biodiesel production: a review, Bioresource Technology 70
(1) (1999) 1–15.
[5] L.C. Meher, D. Vidya Sagar, et al., Technical aspects of biodiesel production by
transesterification — a review, Renewable and Sustainable Energy Reviews 10
(3) (2006) 248–268.
View publication stats
135
[6] J.M. Encinar, J.F. González, et al., Ethanolysis of used frying oil. Biodiesel preparation
and characterization, Fuel Processing Technology 88 (5) (2007) 513–522.
[7] D. Darnoko, M. Cheryan, Kinetics of palm oil transesterification in a batch reactor,
JAOCS 77 (12) (2000) 1263–1267.
[8] Kondo Fukuda, et al., Biodiesel fuel production by transesterification of oils, Journal
of Bioscience and Bioengineering 92 (5) (2001) 405–416.
[9] M. Slinn, K. Kendall, Developing the reaction kinetics for a biodiesel reactor,
Bioresource Technology 100 (2009) 2324–2327.
[10] C.D. Bannister, C. Chuck, et al., Oxidative stability of biodiesel fuel, Proceedings of the
Institution of Mechanical Engineers. Part D, Journal of Automobile Engineering D1
(2010) 99–114.
[11] Y.C. Sharma, B. Singh, et al., Advancements in development and characterization of
biodiesel: a review, Fuel 87 (12) (2008) 2355–2373.
[12] A. Srivastava, R. Prasad, Triglycerides-based diesel fuels, Renewable and Sustainable
Energy Reviews 4 (2) (2000) 111–133.
[13] G. Vicente, M. Martínez, et al., Integrated biodiesel production: a comparison of
different homogeneous catalysts systems, Bioresource Technology 92 (3) (2004)
297–305.
[14] G. Vicente, M. Martínez, et al., Optimisation of integrated biodiesel production. Part
I. A study of the biodiesel purity and yield, Bioresource Technology 98 (9) (2007)
1724–1733.
[15] D.Y.C. Leung, Y. Guo, Transesterification of neat and used frying oil: optimization for
biodiesel production, Fuel Processing Technology 87 (10) (2006) 883–890.
[16] T. Issariyakul, M.G. Kulkarni, et al., Biodiesel production from mixtures of canola oil
and used cooking oil, Chemical Engineering Journal 140 (1–3) (2008) 77–85.
[17] X. Meng, G. Chen, et al., Biodiesel production from waste cooking oil via alkali catalyst
and its engine test, Fuel Processing Technology 89 (9) (2008) 851–857.
[18] A.N. Phan, T.M. Phan, Biodiesel production from waste cooking oils, Fuel 87 (2008)
3490–3496.
[19] U. Rashid, F. Anwar, et al., Production of sunflower oil methyl esters by optimized
alkali-catalyzed methanolysis, Biomass and Bioenergy 32 (12) (2008) 1202–1205.
[20] L.F. Bautista, G. Vicente, et al., Optimisation of FAME production from waste cooking
oil for biodiesel use, Biomass and Bioenergy 33 (5) (2009) 862–872.
[21] M.J. Ramos, C.M. Fernández, et al., Influence of fatty acid composition of raw
materials on biodiesel properties, Bioresource Technology 100 (1) (2009) 261–268.
[22] Y. Wang, P.L.S. Ou, et al., Preparation of biodiesel from waste cooking oil via
two-step catalyzed process, Energy Conversion and Management 48 (1) (2007)
184–188.
[23] J. Kwiecien, M. Hájek, et al., Combined effect of water and KOH on rapeseed oil
methanolysis, Bioresource Technology 101 (9) (2010) 3121–3125.
[24] A. Demirbas, Comparison of transesterification methods for production of biodiesel
from vegetable oils and fats, Energy Conversion and Management 49 (1) (2008)
125–130.
[25] BSI, BS EN ISO 12937:2001, determination of water content — coulometric Karl
Fischer titration method, British Standard Test Method, BSi, 2001.
[26] BSI, BS EN 14103:2003, Fat and Oil Derivatives — Fatty Acid Methyl Esters (FAME) —
Determination of Ester and Linolenic Acid Methyl Ester Contents, Standards Policy
and Strategy Committee, British Standards Institute, 2003.
[27] BSI, BS EN 14104:2003, Fat and Oil Derivatives — Fatty Acid Methyl Esters (FAME) —
Determination of Acid Value, Standards Policy and Strategy Committee, British
Standards Institute, 2003.