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Esterification of Free Fatty Acids in Used Cooking Oil Using Ion-

Exchange Resins as Catalysts: An Efficient Pretreatment Method for
Biodiesel Feedstock
Sumaiya Zainal Abidin,†,‡ Kathleen F. Haigh,† and Basudeb Saha*,§

Department of Chemical Engineering, Loughborough University, Loughborough, Leicestershire, LE11 3TU, United Kingdom

Faculty of Chemical and Natural Resources Engineering, Universiti Malaysia Pahang, Lebuhraya Tun Razak, 26300 Gambang,
Kuantan, Pahang Darul Makmur, Malaysia
Department of Applied Science, Faculty of Engineering, Science and the Built Environment, London South Bank University,
London, SE1 0AA, United Kingdom

ABSTRACT: The esterification of used cooking oil (UCO) with methanol was studied using different types of ion-exchange
resins, that is, Purolite D5081, Purolite D5082, and Amberlyst 36. Several catalyst characterization analyses (elemental analysis,
surface area measurement, particle size distribution analysis, scanning electron microscopy analysis, true density measurement,
and acid capacity analysis) have been conducted in the screening stage. Of all of the catalysts investigated, Purolite D5081 resin
showed the best catalytic performance and was selected for further experimental studies. The esterification process was carried
out in a jacketed stirred batch reactor for 8 h. Elimination of mass transfer resistances and the effect of catalyst loading (0.5−1.5%
w/w), reaction temperature (50−65 °C), and methanol to UCO feed mole ratio (4:1−12:1) on the conversion of FFAs were
investigated. The highest FFAs conversion was found to be 92%, at a catalyst loading of 1.25% w/w, 60 °C reaction temperature,
6:1 methanol to UCO molar ratio, and stirring speed of 475 rpm. During the reusability study, the conversion of catalyst dropped
by 8−10% after each reutilization cycle. Several experiments have been conducted through the homogeneous contribution study,
and the results confirmed that both resin pore blockage and sulfur leaching are dominant factors that decrease the catalytic
performance of Purolite D5081 ion-exchange resin.

1. INTRODUCTION convert the triglycerides into a mixture of esters and glycerine,

A majority of the world’s energy is supplied through in the presence of a catalyst and alcohol. In recent years, the
petrochemical sources, coal, and natural gases. However, with major obstacle for biodiesel’s commercialization from vegetable
a high energy demand from various sectors, global warming, an oil is the high cost of raw feedstock. Therefore, cheap nonedible
unstable price, and finite availability of petroleum-based oil as vegetable oil, animal fats, and waste oils have been found to be
well as environmental pollution due to the widespread use of effective feedstock replacements to reduce the cost of
fossil fuels make the petroleum-based energy unreliable. The biodiesel.5−10 According to Balat,11 the price of used cooking
world energy forum has also predicted that, in less than 10 oil (UCO) is 2.5−3.5 times cheaper than that of virgin
decades, fossil-based oil, including coal and natural gases, will vegetable oils; thus it can significantly reduce the production
be depleted.1 Therefore, it is increasingly necessary to develop cost of biodiesel. However, these oils contain a significant
renewable energy resources to replace the traditional sources. amount of free fatty acids (FFAs); for example, crude mahua oil
Vegetable oil has become one of the most popular feedstocks contains about 13−20% FFAs,12,13 crude jatropha oil contains
for renewable fuel nowadays and is widely available from a about 12−14% FFAs,14,15 crude tobacco seeds oil contains
variety of sources. Biodiesel, in particular, has the following about 17% FFAs,16 crude Zanthoxylum bungeanum seed oil
advantages over diesel fuel: it produces less smoke and (ZSO) contains about 25% FFAs,17 and waste oil contains 6−
particulates, has higher cetane numbers, produces lower carbon 15% by weight of FFAs.18,19 Oils and fats with a high FFAs
monoxide and hydrocarbon emissions, is biodegradable and content cannot be directly used in a base-catalyzed trans-
nontoxic, and provides better performance in engine lubricity as esterification reaction. A study by Naik et al.20 showed a
compared to conventional diesel fuels.2 Conversely, depending significant drop in the conversion of ester when the FFAs
on the sources of feedstock, they present other technical content was above 2%. The FFAs react with the alkali catalyst
challenges such as low volatility, high pour points, high cloud to form soap. The saponification process forms a stable
points and high cold filter plugging temperatures, elevated NOx emulsion and leads to difficulties in process separation and
emissions, and incomplete combustion.3,4 There is also a major reutilization of catalyst. In addition, it also creates a significant
concern regarding the unfavorable cold flow properties of
biodiesel as it tends to gel (freeze) at lower temperature, thus Received: March 21, 2012
affecting the driveability of biodiesel vehicles.4 Revised: October 4, 2012
Transesterification is the most popular method to produce Accepted: October 17, 2012
biodiesel. It follows three consecutive equilibrium reactions that Published: October 17, 2012

© 2012 American Chemical Society 14653 | Ind. Eng. Chem. Res. 2012, 51, 14653−14664
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amount of toxic wastewater through the neutralization process. resins on the FFAs conversion was carried out in the screening
Several studies on the utilization of waste oils as raw material stage. Ion-exchange resin with the highest conversion of FFAs
have been conducted,21,22 and it has been found that high yield was chosen for further experimental studies. Mass transfer
is achieved using a two-step synthesis of biodiesel. The first step resistances as well as the effect of catalyst loading, reaction
is the pretreatment step (esterification process) required to temperature, and methanol to UCO molar ratio on the
reduce the amount of FFAs in the feedstock before being conversion of FFAs have been studied. Analysis of FFAs has
subjected to a transesterification reaction, that is, the second been carried out using the ASTM D974 standard titration
step. method.
Currently, most biodiesel processes use homogeneous acid
catalysts (e.g., sulphuric acid, hydrochloric acid) to esterify 2. EXPERIMENTAL METHODS
FFAs in waste oils because they are effective and soluble in
methanol. These homogeneous catalysts have a number of 2.1. Materials. The UCO was supplied by Greenfuel Oil
drawbacks: corrosion of equipment, existence of side reactions, Co. Limited, UK. The UCO has an acid value of approximately
generation of a substantial amount of wastewater, a high 12.2 mg KOH/g and a FFAs value of approximately 6.1%.
production cost due to additional equipment/reagents for Methanol (>99.5% purity), 2-propanol, toluene, 0.1 M
separation/neutralization processes, and difficulties in catalyst volumetric standard hydrochloric acid, 0.1 M of volumetric
recovery.23,24 The use of heterogeneous catalysts has proven to standard sodium hydroxide, 0.1 M standardized solution of
simplify the production and purification processes because they potassium hydroxide in 2-propanol, p-naphtholbenzein, methyl
can be easily separated from the reaction mixture. This allows red, and n-hexane (≥99% purity) were purchased from Sigma
multiple usage of the catalyst through regeneration, resulting in Aldrich, UK and Fisher Scientific, UK and were used as
a reduction in waste and a reduction in the environmental received. Pure standards of fatty acid methyl ester (methyl
impact. palmitate, methyl heptadecanoate, methyl stearate, methyl
Heterogeneous catalysts can be classified into several oleate, methyl linoleate, methyl linolenate) were purchased
different categories, single and mixed metal oxides, hydro- from Sigma Aldrich, UK with over than 99% purity. Ion-
talcites, heteropolyacids, ion-exchange resins, zeolites, sulph- exchange resin catalysts (Purolite D5081 and Purolite D5082)
ated metal oxides, and organic acid catalysts. Ion-exchange were supplied by Purolite International Limited, and Amberlyst
resins are more popular because they can catalyze the reaction 36 was purchased from Sigma Aldrich, UK. These resins were
using mild conditions due to the high concentration of acid pretreated before being used as the reaction catalysts. The
sites.25 Most of the ion-exchange resins used in biodiesel pretreatment method used in this research work is a common
production are based on cross-linked polystyrene-divinyl method used by most researchers in esterification of FFAs
benzene copolymers bearing the sulfonic acid group using ion-exchange resins.31−35 Basically, dry catalyst does not
(−SO3H). In the past few years, several studies have been require any pretreatment as the active sites are already free and
reported on the development of ion-exchange resins as catalyst available on the resin’s surface and inside the pores, whereas the
in the biodiesel process.16,26,27 Cation-exchange resins are wet catalyst usually goes through the preconditioning process
preferable in esterification reaction as they offer better with solvent, is rinsed, and then dried in an oven for a certain
selectivity toward the desired products.28,29 Ö zbay et al.30 period of time.31 All wet resins were immersed in methanol
reported the esterification of FFAs in waste cooking oil using overnight and pretreated with the same solvent under
various types of ion-exchange resin catalysts, but the FFAs ultrasonic condition. The process takes about 8−10 cycles of
conversion was relatively very low, with a conversion of about rinsing steps to ensure that all impurities are totally removed
45.7% at the optimum conditions (20% v/v methanol, 60 °C, (the color of filtrate turned from light brownish to colorless
2% w/w catalyst, 180 min). On the other hand, a study by Feng solution). During this washing process, the conductivity of the
et al.26 showed a 90% conversion of FFAs when a cation- residual solution was recorded, and the process continues until
exchange resin, NKC-9, was used as the catalyst in biodiesel the conductivity of the residual solution is approximately the
esterification. The optimized conditions were achieved in 3 h same with the solvent (methanol). Finally, resins were dried in
using 18% w/w catalyst and 66 °C reaction temperature. a vacuum oven at 100 °C for 6 h to completely remove water
In this study, the utilization of ion-exchange resins in the and methanol. All other chemicals used were analytical reagent
pretreatment stage of the UCO has been explored, using novel grade.
catalysts Purolite D5081 and Purolite D5082. These catalysts 2.2. Used Cooking Oil (UCO) and Product Character-
were chosen because they were developed specifically for the ization. 2.2.1. Average Molecular Mass Determination:
esterification of edible oil for biodiesel production. This work Analysis of Fatty Acid Composition in the UCO. The fatty
has been conducted in collaboration with Purolite International acids bonded to the glycerine backbone vary depending on the
Limited for possible commercialization of these catalysts. oil type, and as a result an average molecular mass is generally
Previously, Amberlyst BD20 resin has been proposed as the determined on the basis of the fatty acid composition of the oil.
comparison catalyst, but due to commercial reasons, Rohm and Average molecular mass was calculated by multiplying the mass
Haas were not able to supply it and recommended Amberlyst fractions of fatty acids presence in the oil with the individual
36 as an alternative. The main goal of this research work is to molecular mass of each fatty acids involved. The determination
identify the best catalyst for esterification process and to of fatty acid composition was done by converting the
determine the optimum conditions for the esterification process triglycerides to glycerine and fatty acid methyl ester (FAME)
prior to the transesterification. Several catalyst characterization through a methylation or hydrolysis process.36 Derivatization
analyses (elemental analysis, surface area measurement, particle through the methylation process has been widely used to
size distribution analysis, scanning electron microscopy analysis, characterize lipid fractions in fats and oil.37,38 It is a well-
true density measurement, and acid capacity analysis) were accepted characterization method because of the robustness
conducted, and comparison between various ion-exchange and reproducibility of the chromatographic data. These
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methods are also cheaper in terms of reagent usage and do not Brunauer−Emmett−Teller (BET) method was used to
require expensive equipment. calculate the surface area.
In this study, the sample was prepared using methods in 2.3.3. True Density Measurement. The true density (ρt) of
European Union (EU) Regulation,39 and the results were the sample was measured using a Micromeritics helium
verified using British Standard Institution (BSI) standard pycnometer 1305. Samples with known mass (m) were placed
method, EN ISO 12966-2:2011.40 Derivatisation process begins into the pycnometer cell. After that, a constant flow of helium
by weighing 100 mg of UCO in a 20 mL screw-cap test tube or gas was introduced into the cell several times to ensure that
reaction vial. Next, the UCO was dissolved in 10 mL of n- void spaces between the particles were filled by helium gas. The
hexane. 100 μL of 2 N potassium hydroxide was added to the actual volume of sample (v) was calculated on the basis of the
reaction vial together with 100 mL of methanol. The tube or known parameters, that is, cell volume, expansion medium
vial was closed and mixed vigorously for 60 s. The sample was volume, and the charge pressure before and after expansion.
then transferred into a conical bottom tube for centrifugation Finally, the true density of particles was determined using the
process. This process takes about 10 min with 16 000 rpm standard formula: true density, ρt = (m/v). All samples were
rotational speed. The upper layer, the clear supernatant, was measured in duplicate, and the error was less than 1%.
analyzed by GC−MS (GC−MS Hewlett-Packard HP-6890), 2.3.4. Particle Size Distribution (PSD) Analysis. Particle size
with DB-WAX (J&W Scientific) capillary column, 30 m length distribution (PSD) analysis was performed with a Coulter LS
and 0.25 mm inner diameter, and packed with polyethylene 130 Particle Analyzer with particle size measurement over the
glycol (0.25 μm film thickness). Helium was used as a carrier range 0.1−1000 μm. The Fraunhofer optical model was used
gas at a constant flow rate of 1.1 mL/min. The amount of for the measurement of the distribution pattern. The
sample injected was 1 μL. The temperature of the injector and equipment operating parameters were set to record the
detector was 250 °C. The initial oven temperature was 70 °C background measurement for 60 s followed by sample
held for 2 min, programmed at 40 °C/min to 210 °C, measurement for 60 s. The samples were then introduced
programmed at 7 °C/min to 230 °C, final temperature held for into the dispersion module with isopropyl alcohol as the
11 min. Methyl heptadecanoate was used as the internal solvent, and a total of two measurement cycles were carried out
standard. for each sample and the average was taken as the final result.
2.2.2. Free Fatty Acids (FFAs) Analysis. The acid value of the 2.3.5. Acid Capacity Analysis. Acid capacity determination
UCO was determined using ASTM D974, which was was conducted using a conventional titration method. The
specifically used to determine the acidic or basic constituents analysis took place in a 50 mL Erlenmeyer flask with the ion-
in highly colored fats and oils. The determination of acid or exchange resins (∼0.5 g) contacted with 50 mL of 0.1 M of
base number was carried out by dissolving the sample in a volumetric standard sodium hydroxide. The flasks were sealed
mixture of toluene, 2-propanol, and a small amount of water to with Parafilm and shaken for 72 h in an orbital shaker. After
form a single phase solution. The resulting solution was then that, the solution was filtered, and 5 mL aliquots were back-
titrated at room temperature with an alcoholic base solution, titrated with 0.1 M volumetric standard hydrochloric acid using
and the end point is detected by changes of the indicator, p- methyl red as an indicator. All samples were analyzed in
naphtholbenzein, color from orange to green. The conversion duplicate, and the error was less than 3%.
of FFAs was calculated using the following equation: 2.3.6. Scanning Electron Microscopy (SEM) Analysis. A
scanning electron microscope (Carl Zeiss (Leo/Cambridge)
CA 0 − CA Stereoscan360) was used to study the morphology of the ion-
conversion of FFAs, XA =
CA 0 exchange resins. The pretreated catalysts were preconditioned
(drying at 100 °C for 6 h and stored in desiccators) prior to
where CA0 is the initial concentration of FFAs of the mixture analysis to eliminate moisture. After that, the samples were
(i.e., at time t = 0) and CA is the concentration of FFAs at any mounted on a metal stub using a carbon conductive pad, and
time t. silver metals were placed at both sides of the samples to act as a
2.3. Catalyst Characterization. 2.3.1. Elemental Analysis. conductor. Finally, the samples were coated with gold under
Carbon, hydrogen, and nitrogen determination was carried out vacuum condition in an argon atmosphere prior to observation.
using an Exeter Analytical CE440 C, H, N analyzer. It works by 2.4. Experimental Method. The esterification process was
combusting the sample in pure oxygen with tin as a catalyst. carried out in a four-neck 1000 mL cylindrical jacketed-glass
Any sulfur, phosphorus, or halogens were removed and excess reactor, equipped with a mechanical stirrer, sampling outlet,
oxygen was reduced, leaving only CO2, H2O, and N2 as the and reflux condenser to prevent the loss of reactant due to
combustion products. These gases are then analyzed for vaporisation. Heating was achieved by circulating water from a
quantity using a system of detectors and scrubbers. The sulfur water bath and through the reactor, and a thermocouple was
determination was carried out separately using oxygen flask used for temperature monitoring. Figure 1 shows the
combustion analysis, followed by a titration. All of the results experimental setup of the reaction process, and Schemes 1
were reported in weight percentage of carbon, nitrogen, and 2 shows the reaction scheme of the process.
hydrogen, and sulfur, and the residual was assumed to be A specified amount of UCO and methanol was added to the
oxygen. All samples for elemental analysis were analyzed in reactor, and the stirring and heating of the reaction mixtures
duplicate, and the error was less than 3%. were started. When the reactor reached the required temper-
2.3.2. Surface Area Measurement. Surface area, pore ature, catalyst was added, and this point was taken as the zero
volume, and average pore diameter were determined from the time for the reaction. The samples were periodically taken from
nitrogen adsorption and desorption isotherms using a Micro- the reactor for FFAs analysis. After 8 h, the reaction mixture
meritics ASAP 2020 surface analyzer. The samples were was transferred to a separation funnel and allowed to settle
degassed at a two-stage temperature ramping, followed by overnight to form two layers; the top layer consisted of excess
sample analysis at −195.15 °C using nitrogen gas. The methanol and its impurities, whereas the bottom layer was
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Scheme 2. Reaction Scheme for the Esterification Process:

Conversion of FFAs to FAMEa

R1 represents the fatty acid group.

and used catalysts were tested for SEM, SEM-EDX, acid

capacity, and elemental analyses.
Figure 1. Experimental setup for the reaction process. An investigation into the homogeneous contribution was
carried out to establish if sulfonic acid groups were leached
during the reaction process. The process flow diagram for the
mainly unreacted UCO together with traces of methanol, reusability study is summarized in Figure 2. It was done by
glycerine, esters, and the remaining catalyst. The bottom layer reacting fresh methanol with unused pretreated catalyst for 8 h
was withdrawn from the separating funnel together with the at 60 °C and 475 rpm stirring speed. After that, the catalyst was
catalyst, and the retained catalyst was washed, dried, and stored filtered, and the solution was used in the subsequent reaction
for further experimental work. Studies on the mass transfer with fresh UCO (6:1 methanol:UCO molar ratio), in the
resistance as well as the effect of methanol to UCO molar ratio absence of any catalyst. This is referred to as the first cycle of
(4:1, 6:1, 9:1, 12:1), catalyst loading (0.5, 0.75, 1, 1.25, 1.5% w/ homogeneous contribution study. The filtered catalyst was
w), and reaction temperature (50, 55, 60, 62, 65 °C) have been dried in the vacuum oven for 6 h (100 °C), and this catalyst
conducted. was then used for an experiment with fresh methanol and fresh
In terms of the reproducibility of experimental data, selected UCO at optimum condition to monitor the conversion trend as
experiments have been repeated three times, and it was found a result of the catalyst being treated with methanol. This result
that there was a 1−2% difference in the results. Therefore, it was plotted as the first cycle of the methanol treated catalyst
was assumed that a similar error applies to all results. In study.
addition, a blank run without catalyst has been performed, and The spent catalyst from the previous methanol treated
there was no conversion of FFAs after 8 h of reaction time. catalyst experiment was washed thoroughly with methanol
Therefore, it was concluded that the esterification of FFAs using an ultrasonic bath until there was no evidence of UCO
occurs only due to the presence of the catalyst. contamination. The catalyst was filtered and dried in a vacuum
2.5. Reusability Study Including an Investigation of oven at 100 °C for 6 h. The experimental work proceeded to
Homogenous Contribution. A detailed reusability study of the second homogeneous cycle, where the reaction took place
Purolite D5081 catalyst with the highest conversion was between the fresh methanol and used catalyst. The used catalyst
conducted to determine the catalyst life span. The first phase of was the same catalyst used in the first cycle of homogeneous
this work was to investigate the effect of reusing the same batch contribution study and the first cycle of methanol treated
of a catalyst for a number of cycles on the conversion of FFAs. catalyst study. The filtered solution from the methanol−catalyst
For this purpose, used catalyst was washed with methanol with reaction was added to fresh UCO (6:1 methanol:UCO molar
the aid of an ultrasonic bath until there were no traces of oil ratio) without the presence of catalyst, and the FFAs
and colorless solution was obtained. During this washing conversion was monitored. The result was plotted as the
process, the conductivity of the residual solution was recorded, second cycle of the homogeneous contribution study. The used
and the process continues until the conductivity of the residual catalyst obtained from the methanol−catalyst reaction was
solution is approximately the same with the solvent dried (100 °C, 6 h) and introduced to fresh UCO and fresh
(methanol). The washed catalyst was filtered and dried in a methanol. By using the optimum reaction parameters, the
vacuum oven at 100 °C for 6 h. The reusability study was esterification was conducted, and the second cycle of methanol
carried out under the optimum process conditions. The fresh treated catalyst data was plotted.

Scheme 1. General Reaction Scheme for Biodiesel Productiona

R1, R2, and R3 represent the fatty acids groups attached to the backbone of triglycerides.

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Figure 2. Process flow diagram for catalyst reusability study.

Figure 3. Chromatogram of the derivatized UCO.

3. RESULTS AND DISCUSSION The retention times for each individual component are as
3.1. GC−MS Analysis of Derivatized Used Cooking Oil follows: methyl palmitate (C16:0) appeared at 8.324 min
(UCO). Figure 3 shows a typical chromatogram of the retention time, methyl heptadecanoate (C17:0, reference
derivatized UCO. From the chromatogram, six different standard) at 8.950 min, methyl stearate (C18:0) at 9.712
components (including the reference standard) were identified. min, methyl oleate (C18:1) at 9.914 min, methyl linoleate
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(C18:2) at 10.349 min, and finally methyl linolenate (C18:3) at Table 3. Properties and Characteristics of Various Ion-
11.005 min. As the methylation process converts fatty acids to Exchange Resins
methyl esters through derivatization method, it could be
catalyst properties Purolite D5081 Purolite D5082 Amberlyst 36
concluded that there were five main components present in
UCO, the palmitic acid, stearic acid, oleic acid, linoleic acid, and physical appearance black spherical black spherical black spherical
beads beads beads
linolenic acid.
matrix hyper-cross- hyper-cross- macroporous
The response factor for each component was determined linked linked
using the calibration of individual standards. The predeter- cross-linking level highly cross- highly cross- medium cross-
mined response factor was then used to determine the fatty acid linked linked linked
composition of the sample. By calculating the mass fractions of particle size
each fatty acid, the average molecular mass of the fatty acids distribution (μm)
could be easily calculated and will be further used to determine 10%> 638.6 806.8 741.1
the methanol to UCO molar ratio.17 The fatty acids 50%> 496.5 644.8 575.8
composition is summarized in Table 1. These data clearly 90%> 396.4 482.1 341.1
nitrogen BET
BET surface area 514.18 459.62 30.0
Table 1. Percent Composition of Fatty Acid in Used (m2/g)
Cooking Oil (UCO) total pore volume 0.47 0.36 0.19
component % composition (w/w)
average pore 36.9 31.4 254.2
palmitic acid (C16:0) 11.34 diameter (Å)
stearic acid (C18:0) 3.18 true density (g/cm3) 1.311 1.375 1.568
oleic acid (C18:1) 43.95 acid capacity 1.59 1.79 5.00
linoleic acid (C18:2) 36.44 (mmol/g)
linolenic acid (C18:3) 5.09 swelling (media: negligible negligible negligible

show that oleic and linoleic acids comprise more than 80% of Purolite D5082 (459.6 m2/g) and Amberlyst 36 (30 m2/g).
the total fatty acids in the sample. Using the European Union Table 3 also shows that Purolite D5081 has the largest pore
(EU) Regulation39 method, the average molecular mass of fatty volume (0.47 cm3/g) among all of the resins analyzed.
acids is 278.11 g/mol. The reliability of the previous standard 3.2.3. True Density Measurement and Particle Size
method was verified by analyzing the sample according to the Distribution Analysis. The measured true densities for all
British Standard Institution (BSI) method, EN ISO 12966- resins are as follows: 1.311, 1.375, and 1.568 g/cm3 for Purolite
2:2011.40 It was found that the results were very similar and the D5081, Purolite D5082, and Amberlyst 36, respectively.
average molecular mass of fatty acids obtained using the second Purolite D5082 and Amberlyst 36 have a similar distribution
method was 277.93 g/mol. Therefore, it can be concluded that of particle size, whereas Purolite D5081 has slightly smaller
both methods are comparable. particles, and this information is shown in Figure 4. Amberlyst
3.2. Catalyst Characterization. 3.2.1. Elemental Analysis.
The results for elemental analysis are presented in Table 2. For

Table 2. Elemental Analysis for Ion-Exchange Resinsa

catalyst %C %H %N %S % Ob
Purolite D5081 77.04 5.32 0.95 4.09 12.61
Purolite D5082 68.87 4.44 0.13 5.92 20.65
Amberlyst 36 42.18 4.10 0.10 18.27 35.35
All percentages are in w/w %. bOxygen by difference.

all ion-exchange resins, it was assumed that the only other

species present was oxygen. Oxygen cannot be measured by
elemental analysis, and, therefore, the percentage of oxygen
content was determined by the difference from the total weight
percentage of other elements (i.e., carbon, hydrogen, nitrogen, Figure 4. Particle size distribution of ion-exchange resins catalysts.
and sulfur). For cation-exchange resins, the polymer structure
consists of carbon, hydrogen, sulfur, and oxygen elements.
There was an unexpected presence of nitrogen in the cation- 36 has the widest size distribution, with particle ranges between
exchange resins, and the value was less than 1%. In this case, 100 and 900 μm and a secondary peak. The two resins from
nitrogen was assumed to be a contaminant in the sample. It can Purolite have narrower distributions, where the range lies
be seen from Table 2 that Amberlyst 36 has the highest between 375 and 900 μm for Purolite D5082 and 280 and 800
percentage of oxygen and sulfur as compared to the other μm for Purolite D5081. Chemical and physical characteristics
resins. for all resins are summarized in Table 3.
3.2.2. Surface Area Measurement. The results for surface 3.3. Optimization of Esterification Process in a
area, average pore diameter, and total volume are presented in Jacketed Batch Reactor. 3.3.1. Screening of Ion-Exchange
Table 3. Purolite D5081 catalyst shows the highest Brunauer− Resins. To identify the best of the three ion-exchange resins for
Emmett−Teller (BET) surface area (514.2 m2/g), followed by further experimental work, all three resins, Purolite D5081,
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Purolite D5082, and Amberlyst 36, were evaluated under the reach the equilibrium. However, these catalysts are highly
same reaction conditions, that is, at 1% w/w of catalyst loading, porous, and as a result this effect is very small when compared
6:1 methanol to UCO molar ratio, 60 °C reaction temperature, to the effect of the catalysts pore volume.
and 350 rpm impeller stirring speed. From Figure 5, it can be Although Amberlyst 36 has the highest sulfur content and
the largest average pore diameter, the result from the
esterification reaction (Figure 5) shows that Amberlyst 36 has
the lowest conversion as compared to Purolite D5081 and
D5082 resins. This is because Amberlyst 36 has the lowest
specific surface area and lowest pore volume as compared to the
Purolite resins, and, therefore, there are less active catalytic sites
available for the reaction to occur. The level of DVB cross-
linking also contributes significantly to the level of FFAs
conversion. From Figure 5, it could be seen that resins with
high DVB cross-linking (Purolite D5081 and D5082) result in
higher FFAs conversion as compared to lower DVB cross-
linking resin (Amberlyst 36). The FT-IR analysis has also been
carried out, and there was no noticeable change of functional
groups for all of the resin samples, and, therefore, these results
are not presented in this Article. The FT-IR results also indicate
Figure 5. Effects of different types of ion-exchange resins on FFAs that sulfur was present only in sulfonic acid functional group.
conversion (experimental conditions: molar ratio (methanol:UCO), Because Purolite D5081 showed the best catalytic performance,
6:1; catalyst loading, 1% w/w; stirring speed, 350 rpm; reaction
it was used for further experimental work.
temperature, 60 °C).
3.3.2. Investigation on the Effect of Mass Transfer
seen that, after 8 h, Purolite D5081 resin achieved the highest Resistance. There are two types of mass transfer resistances
FFAs conversion of ∼88%, while Purolite D5082 and involved in ion-exchange catalysis. The first is external mass
Amberlyst 36 achieved FFAs conversion of ∼78% and ∼30%, transfer resistance, which takes place across the solid−liquid
respectively. interface, while the second is the internal mass transfer
The differences in the properties of various resins, that is, resistance, associated with the differences in particle size
surface area measurement, elemental analysis, and acid capacity distribution of the catalysts. Mixing is one of the key factors to
analysis, can be used to explain the differences in catalytic optimize the production of biodiesel as it increases the
activity (Tables 3−5). These analyses show that even though interaction between the reactants (methanol and UCO) and
the catalyst, predominantly at the early stage of the reaction.
Table 4. Elemental Analysis for Fresh and Used Ion- However, after the reaction mixture reaches the stage where the
Exchange Resinsa reactant and the catalyst are well-mixed (e.g., there is sufficient
contact between the catalyst and the reactant), there is no
catalyst %C %H %N %S % Ob additional benefit from increasing the stirring speed. This
fresh D5081 77.04 5.32 0.95 4.09 12.61 phenomenon is due to the external mass transfer resistances.
used D5081c 77.41 5.69 0.93 3.32 12.66 To investigate the influence of external mass transfer
fresh D5082 68.87 4.44 0.13 5.92 20.65 resistance, three different stirring rates were investigated for
used D5082c 69.07 4.53 0.03 5.41 20.97 the reaction process, and the conversion patterns were
fresh Amberlyst 36 42.18 4.10 0.10 18.27 35.35 observed. Figure 6 shows the trend for FFAs conversion of
used Amberlyst 36c 42.18 4.19 0.10 18.17 35.36 Purolite D5081 for three levels of impeller agitation speed, that
All percentages are in w/w %. bOxygen by difference. cWashing after is, 350, 475, and 600 rpm. The FFAs conversion between the
first cycle reaction.

Table 5. Acid Capacity for Fresh and Used Ion-Exchange

catalyst fresh resin (mmol/g) used resin (mmol/g)
D5081 1.59 1.39
D5082 1.79 1.59
Amberlyst 36 5.00 4.99

Purolite D5081 has the lowest sulfur content (Table 4), it

exhibits the highest BET surface area and total pore volume,
which means that there are more accessible active sites for the
reaction to occur, and hence it reaches the equilibrium at a
faster rate. In addition, the particle size distribution results
(Figure 4) show that Purolite D5081 has the smallest average Figure 6. Effect of different stirring speed on the FFAs conversion −
particle size, which leads to a larger external surface area as external mass transfer resistance (experimental conditions: catalyst,
compared to the other resins. A larger surface area may Purolite D5081; molar ratio (methanol:UCO), 6:1; catalyst loading,
contribute to a faster reaction rate and shorten the time to 1.25% w/w; reaction temperature, 60 °C).

14659 | Ind. Eng. Chem. Res. 2012, 51, 14653−14664

Industrial & Engineering Chemistry Research Article

selected stirring rates gave almost an identical trend with less

than 2% difference when the agitation speed increased from
350 to 600 rpm. As the stirring speed only has a small impact
on the FFAs conversion, it was confirmed that there was no
evidence of external mass transfer resistance in the esterification
Internal mass transfer resistance refers to resistance of
movement of reactant inside the pores of the catalyst. To
investigate the occurrence of internal mass transfer resistance, a
set of experiments were conducted using various ranges of
particle sizes, and this method has been widely used in the
catalytic reaction process.18,35,41−44 Figure 7 shows the effect of

Figure 8. Effect of different catalyst loading on the FFAs conversion

(experimental conditions: catalyst, Purolite D5081; stirring speed, 350
rpm; reaction temperature, 60 °C; molar ratio (methanol:UCO), 6:1).

the catalyst loading increases, the number of active catalytic

sites increases, and a shorter time is required to reach
equilibrium. Variation in catalyst loading also has an effect on
the final conversion of FFAs with the difference between the
highest and the lowest catalyst loading of about 10%. At a low
catalyst concentration (<1% w/w), the difference in the
conversion was significant. However, as catalyst loading was
increased (≥1.25% w/w), the trends were less significant. This
phenomenon indicates that as the percentage of resin increases,
Figure 7. Effect of different resin size on the FFAs conversion − the conversion increases. However, as the number of catalytic
internal mass transfer resistance (experimental conditions: catalyst, sites increases (≥1.25% w/w catalyst loading), the benefits are
Purolite D5081; stirring speed, 475 rpm; catalyst loading, 1.25% w/w; reduced as there are sufficient active catalytic sites in the
reaction temperature, 60 °C; molar ratio (methanol:UCO), 6:1). reactant molecules to catalyze the reaction. In the case of the
system investigated, it was found that once the catalyst loading
different PSD on the FFAs conversion. From Figure 7, it can be increased to 1.25% w/w, there were sufficient catalyst sites for
seen that 280−800 μm particle range gives a slightly higher this particular reaction. As a result, 1.25% w/w loading was
conversion as compared to the other two particle ranges. This is chosen as the optimum catalyst loading and was used for all
because this range, that is, 280−800 μm, covers a wide range of further experimental work.
particles, and therefore the possibility of having smaller particles 3.3.4. Effect of Reaction Temperature. The choice of
is higher. This leads to a higher conversion of FFAs as smaller temperature range was determined by the findings of Leung
particles have shorter pore channels and a larger area of the and Guo.45 They investigated the effect of temperature on the
pores is accessible by the reactant molecules. To support this biodiesel process, and the results showed that any temperatures
argument, a comparison was made between 600−710 and higher than 50 °C have a negative impact on the virgin oils but
425−500 μm range catalyst particles, and it was found that the had a positive impact for waste oils. Esterification was
conversion for 600−710 μm particle size was slightly lower investigated at different temperatures (50, 55, 60, 62, 65 °C),
than 425−500 μm particle size in the first 5 h of reaction. and the results are shown in Figure 9. It has been observed that
Nevertheless, the conversions of FFAs for all three particle
ranges were approximately the same at the end of the 8 h
reaction. This finding proved the previous theory that smaller
catalyst particles contribute to a larger accessible surface area
and thus increase the FFAs conversion. However, the difference
between each range was very small (less than ±2%), and the
final conversions were approximately the same. Hence, the
effect of internal mass transfer limitation can be eliminated. As a
conclusion, stirring speed of 350 rpm and above was selected
for subsequent experiments as there was no external mass
transfer resistance above this speed limit and the Purolite
D5081 resin was used without sieving.
3.3.3. Effect of Catalyst Loading. The effect of catalyst
loading is shown in Figure 8. The reaction temperature was set
at 60 °C with 6:1 methanol to UCO molar ratio, and the
reaction took approximately 8 h to reach equilibrium. The
result shows that the conversion is greatly influenced by the Figure 9. Effect of different reaction temperatures on FFAs conversion
amount of catalyst, especially at the early stage of the (experimental conditions: catalyst, Purolite D5081; stirring speed, 350
esterification reaction. This is attributed to the fact that as rpm; catalyst loading, 1.25% w/w; molar ratio (methanol:UCO), 6:1).

14660 | Ind. Eng. Chem. Res. 2012, 51, 14653−14664

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increasing temperatures lead to reduction in the viscosity of costs, a molar ratio of 6:1 (methanol:UCO) was chosen as the
UCO, which enhances the contact between the methanol and optimum molar ratio for the esterification reaction.
UCO leading to a higher conversion of FFAs. The highest 3.4. Catalyst Reusability Study. A series of reactions,
conversion was obtained at 65 °C. A decrease in the volume of using the same batch of Purolite D5081 catalyst, were carried
the reaction mixture was observed when the temperature out at optimum process conditions, that is, 1.25% w/w catalyst
reached the boiling point of methanol, 64.7 °C. It was expected loading, 333 K reaction temperature, 6:1 methanol to UCO
that there will be some changes to the system when this feed mole ratio, and 475 rpm stirring speed, to determine the
temperature is reached, with more methanol present in the catalyst life span. The results are shown in Figure 11, and from
headspace of the reactor as vapor. Liu et al.46 also claimed that
beyond 65 °C, methanol started to vaporize rapidly, forming a
large number of bubbles to form foam and resulting in a
decrease in FFAs conversion. Generally, in a typical biodiesel
reaction process, low temperature will result in lower
conversion, while higher temperatures lead to excessive
methanol loss due to evaporation. After consideration of the
safety issues, cost implications, and the conversion trends for
each temperature, the optimum reaction temperature was
found to be 60 °C.
3.3.5. Effect of Methanol to UCO Molar Ratio. Figure 10
shows the effect of methanol to UCO molar ratio on the

Figure 11. Reusability study on Purolite D5081 ion-exchange resins

(experimental conditions: catalyst, Purolite D5081; stirring speed, 475
rpm; catalyst loading, 1.25% w/w; reaction temperature, 60 °C; molar
ratio (methanol:UCO), 6:1).

these data it can be seen that the conversion decreased by

approximately 8−10% per cycle (e.g., fresh catalyst gives ∼92%
conversion, the first cycle gives ∼84% conversion, and the
second cycle gives ∼73% conversion). Potential reasons for the
loss of activity include contamination of the external or internal
surface of the catalyst and sulfur leaching.
Scanning electron microscopy (SEM) analysis was used to
Figure 10. Effect of different molar ratio (methanol:UCO) on the investigate the effect of cleaning regimes on the surface of the
FFAs conversion (experimental conditions: catalyst, Purolite D5081; ion-exchange resin catalysts. Purolite D5081 was cleaned by
catalyst loading, 1.25% w/w; stirring speed, 350 rpm; reaction placing the catalyst in a flask of methanol, which was
temperature, 60 °C). subsequently placed in an ultrasonic bath, and the method is
detailed in section 2.5. To determine the effect of ultra-
conversion of FFAs. The reaction temperature was set at 60 °C, sonication, Purolite D5082 was cleaned using methanol but
at 350 rpm stirrer speed with 8 h reaction time. The molar without ultrasonication. A series of SEM images are shown in
ratios were calculated on the basis of the molecular mass of Figure 12, which show the comparison of fresh and used
average fatty acid composition. From Figure 10, it can be seen catalyst (after the first run) as well as comparing the effect of
that the conversion increased slightly with an increase in cleaning regimes. Figure 12a and b shows a sample of Purolite
methanol to UCO molar ratio. However, the conversion D5081 before and after esterification, and it can be seen that
differences between the molar ratios were less noticeable, giving there is no trace of UCO on the surface of the used catalyst in
about 2% increments in conversion as the molar ratio increases. Figure 12b. Figure 12c and d shows a sample of Purolite D5082
In comparison, a ratio of 4:1 has a comparably lower initial before and after esterification, and in this case it can be seen
conversion as compared to the other three molar ratios. This that there is UCO present on the surface of the catalyst,
will be due to insufficient methanol in the mixture to force the indicating incomplete washing of the catalyst. This observation
reaction, leading to longer reaction time to reach equilibrium. fits with the results of the elemental analysis for used D5082
The reaction time can be shortened using a higher methanol to (Table 4), which shows there is a slight increase in residual
UCO molar ratio; however, the costs will be higher due to carbon. On this basis it was decided that ultrasonication was
higher methanol recovery requirements. A high molar ratio also needed as part of the cleaning process to ensure UCO was
leads to difficulties in the separation process and thus hinders removed from the surface of the catalyst.
separation by gravity.47 Furthermore, this situation, that is, high Contamination of the internal surface of the catalyst could
molar ratio, could also increase the solubility of glycerine, and possibly result from the resin pore blockage, either by the
thus reduces the yield of FAME as glycerol remains in the presence of metal ions in the UCO or by the blockage by the
pretreated UCO phase. Excess methanol also could drive the UCO residue itself. An energy-dispersive X-ray spectroscopy
combination of methyl ester and glycerine to monoglycerides, (EDX) analysis of fresh and used Purolite D5081 catalysts has
which increases the viscosity of the reaction mixture.46 Taking been conducted, and a trace amount of metal was found on the
into account the safety issues and the capital and operating catalyst. The amount of sodium and iron content was very
14661 | Ind. Eng. Chem. Res. 2012, 51, 14653−14664
Industrial & Engineering Chemistry Research Article

Figure 13. Study on the homogeneous contribution of Purolite D5081

ion-exchange resins (experimental conditions: catalyst, Purolite
D5081; stirring speed, 475 rpm; reaction temperature, 60 °C; molar
ratio (methanol:UCO), 6:1).
Figure 12. SEM analysis of Purolite catalysts taken at 5000×
magnification: (a) and (b) show Purolite D5081 before and after result clearly shows there was a significant FFAs conversion for
the esterification process, and (c) and (d) show Purolite D5082 before the first cycle of homogeneous contribution study. This
and after esterification process. confirms the occurrence of sulfonic acid group leaching,
believed to be due to the detachment of sulfonic acid group
similar for both fresh and used Purolite D5081 catalysts from the catalyst surface, followed by the hydrolysis of sulfonic
(∼0.20% and ∼0.15%). In the used Purolite D5081 catalyst, a acid species with water to form homogeneous species. Data for
trace amount of calcium ions was found (approximately 0.012− the second cycle show after the first homogeneous contribution
0.10%). Given that only a trace amount of metal was found on cycle that conversion is very low, indicating that there is no
the surface of the catalyst, it has been concluded that the metal further leaching of the sulfonic acid group into methanol in
ion impurities in UCO do not contribute to the deactivation of subsequent cycles.
Purolite D5081 catalyst. In addition, the catalyst deactivation has also been
It was found that the mass of catalyst increased slightly after investigated using the catalyst that was previously filtered
each reaction cycle, and it has been assumed that this was due from the methanol solution. The results are summarized in
to the presence of triglycerides, proteins, trace amount of Figure 14. From the figure, it could be seen that the conversion
phospholipids, and other impurities in UCO that could
potentially foul Purolite D5081 catalyst. The BET analysis
showed that Purolite D5081 resin has the highest total pore
volume of 0.47 cm3/g, which was slightly higher than other
conventional ion-exchange resins. This means it is possible for
the triglycerides, proteins, and a trace amount of phospholipids
molecules to be retained within the resin catalyst, and they may
contribute to pore blockage. This may also reduce the
accessibility of the active catalyst sites and may lead to higher
internal mass transfer resistance and finally contribute to
decreasing catalytic activity.
Sulfur leaching occurs due to the detachment of sulfonic acid
group from the polymer matrix. Water is one of the products
formed during the esterification reaction, and in theory it could
hydrolyze sulfonic acid groups to form homogeneous sulphuric
acid. An elemental analysis was carried out to determine the Figure 14. Study on the methanol treated catalyst deactivation
level of sulfur within various resin samples, and the results are (experimental conditions: catalyst, Purolite D5081; catalyst loading,
shown in Table 4. Fresh D5081 resin had a sulfur content of 1.25% w/w; stirring speed, 475 rpm; reaction temperature, 60 °C;
4.1%, and after the first reaction cycle this decreased by nearly molar ratio (methanol:UCO), 6:1).
20% to 3.3%. Ion-exchange capacity results in Table 5 show a
decrease of acid capacity for fresh and used catalyst of for the second cycle was slightly lower as compared to the first
approximately 13%. This indicates that sulfur leaching cycle. This was solely due to the blockage of large molecules of
contributes to the reduction in catalytic activity of Purolite UCO molecules as the data from Figure 13 show that the
D5081 catalyst. leaching of sulfonic acid was negligible during the second cycle
To further investigate the leaching of homogeneous species of the reaction.
in the reaction mixture and UCO blockage within the resin Figure 15 shows the comparison between the reusability
pores, several sets of experiments have been carried out. The study and methanol treated catalyst study. The difference in
experimental work and the process flow diagram have been FFAs conversion between the fresh catalyst and first methanol
detailed in section 2.5 and Figure 2, respectively. Figure 13 treated catalyst cycle is believed to be due to leaching of
shows the conversion of FFAs during the uncatalyzed reaction sulfonic acid groups. This is because both experiments were
between the treated-methanol solution and UCO, and this conducted at the same experimental parameters; the only
14662 | Ind. Eng. Chem. Res. 2012, 51, 14653−14664
Industrial & Engineering Chemistry Research


Corresponding Author
*Tel.: +44 (0) 2078157190. Fax: +44 (0) 2078157699. E-mail:
The authors declare no competing financial interest.

We gratefully acknowledge Purolite International Ltd. (late Dr.
Jim Dale and Mr. Brian Windsor) for kindly supplying the
catalysts for this research work and GreenFuel Oil Co. Ltd. for
supplying the UCO. We also would like to thank EPSRC
funding for the Ph.D. Scholarship to K.F.H. and Universiti
Malaysia Pahang and Malaysian Government for the Ph.D.
Figure 15. Comparison between the reusability study and the
scholarship to S.Z.A.

methanol treated catalyst study (experimental conditions: catalyst,
Purolite D5081; stirring speed, 475 rpm; catalyst loading, 1.25% w/w;
reaction temperature, 60 °C; molar ratio (methanol:UCO), 6:1).
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