BIODIESEL PRODUCTION

FROM LOW GRADE OIL

FEEDSTOCKS
Stphane Dumas

MASTER OF CHEMISTRY
Training report MC412

April 4th to
August
29th

Internship supervisor: Professor Flora Ng

University of Waterloo
Canada
1

ACKNOWLEDGEMENTS

First of all, I would like to thank my research supervisor, Professor Flora Ng, who
accepted me in her group, welcomed me with goodness and helped me find a
good residence to live here in Waterloo. I would also like to thank my colleagues,
Larry Liu, Lu Dong, Chau Mai, Aashish Gaurav, for their support and co-operation
during the work.
Also, I would not be there without the help of my university, University Pierre and
Marie Curie, especially Anne-Lise Dhimane in charge of international mobility who
offered me the chance to live this amazing life experience in Canada. Im very
thankful to the Chemistry department and to the FSDIE (Fonds de Solidarit et de
Dveloppement des Initiatives Etudiantes) for their financial assistances.

TABLE OF CONTENTS

INTRODUCTION
2

PART 1 :
1.1) BIODIESEL AND BITUMEN
1.2) CONVERSION OF GLYCEROL
1.3) PROCESSES MODELING

AND CATALYST IMPROVEMENT

PART 2 : EXPERIMENTAL SECTION

2.1) MATERIALS
2.2) EQUIPMENT
2.3) PROCEDURES
2.3.1) BIODIESEL PRODUCTION
2.3.2) CATALYST PREPARATION
2.3.3) CATALYST CHARACTERIZATIONS
PART 3 : RESULTS AND DISCUSSION
3.1) THE HANDLING OF EXPERIMENTAL DATA
3.2) KINETIC ANALYSIS
3.2.1) TRANSESTERIFICATION
3.2.2) ESTERIFICATION
3.2.3) ACTIVATION ENERGY
3.3) FACTORS INFLUENCING CATALYTIC ACTIVITY
3.3.2) AMOUNT OF FREE FATTY ACIDS ADDED TO CANOLA OIL
3.3.3) NATURE OF FREE FATTY ACIDS ADDED TO CANOLA OIL
3.4) COMPARISON YELLOW GREASE / CANOLA OIL
3.5) CATALYSTS PROPERTIES
CONCLUSION
GLOSSARY
BIBLIOGRAPHY
APPENDIXES

INTRODUCTION
3

The University of Waterloo is ranked as one of the top ten universities in Canada.
It is particularly famous for its engineering program and researches which,
according to 2013 ARWU (Academic Ranking of World Universities) rankings, are
ranked 43rd in the world and second in Canada. Within the Chemical Engineering
Department, Professor Flora Ngs group works on nanocatalysts and green
chemistry processes such as bitumen upgrading and biodiesel production.
Counting the internship students, there are around ten people working daily in the
group in three different laboratories.
Biodiesel is a renewable alternative fuel, a theoretically inexhaustible source of
energy, composed of a mixture of different fatty acid methyl esters (FAME). It can
be made from vegetable oil, waste cooking oil, algae oil or animal fats which
contain mainly triglycerides (TG), and for some of them, free fatty acids (FFA):

Triglyceride

Free fatty acids (satured or

insaturated)

Biodiesel is biodegradable, non-toxic and has similar chemical and physical

properties than those of petroleum diesel (see Appendix Table 1) hence it is
possible to totally substitute the fossil diesel by biodiesel, named B100 for 100%
of biodiesel, or make different blends such as B20 which is petroleum diesel with
20% biodiesel [1]. Furthermore, thanks to its 11% content oxygen by weight,
biodiesel contributes to reduce greenhouse gas emissions by emitting around
50% less carbon monoxide and particles, and 70% fewer unburned hydrocarbons
than conventional diesel [2]. As shown in Figure 1 (see Appendix), even blended
with petroleum diesel, biodiesel significantly reduces emissions.
However, compared to the petroleum diesel market, its commercialization
remains a challenge because of the high cost of raw materials especially the
refined vegetable oils which represent about 80% of the biodiesel production cost
[3]
. The current way of producing biodiesel at large scale is based on the
transesterification of highly refined oils using methanol and NaOH as basic
4

catalyst through homogeneous catalysis. This process allows fast kinetics with low
pressure and temperature conditions, but the catalyst used is sensitive to water
and FFA content in the feedstock due to the following reactions:

The soap produced in the above reaction hinders the product separation process
due to the formation of an emulsion. In addition, the hydrolysis reaction
contributes to a lower yield of biodiesel [4] [5]. Therefore, some costly processing
upstreams are required to obtain very pure anhydrous feedstock oil containing
less than 0.5% of FFA which make the process less competitive [1] [3].
To overcome this economic issue, cheaper feedstocks such as waste cooking oils,
animal fats and some non-edible vegetable oils seem to be a credible alternative
to the conventional way of making biodiesel. However, these kinds of feedstocks
contain a significant amount of FFA and water, so the use of another process,
without the drawbacks mentioned above, is necessary. Heterogeneous acidic
catalysis appears to be one of the best solutions, indeed solid acid catalysts offer
many advantages [1] [3] [6]:

Insensitive to
FFA
Can be reused

Catalyze
esterification
and
transesterificati
on
simultaneously
Higher quality
of biodiesel and
glycerol
produced

Non toxic

Ease of catalyst
separation

For this process, two simultaneous reactions occur in the reactor i.e
transesterification of TG and esterification of FFA. Both are reversible reactions,
that is why methanol, a low cost alcohol, is added in excess in order to shift the
equilibrium toward biodiesel production. As illustrated in Figure 2 (see Appendix),
transesterification requires three steps which give respectively diglyceride (DG),
monoglyceride (MG) and finally glycerol. One molecule of TG is converted into
three molecules of FAME and one molecule of glycerol [5] [7]. Glycerol, the
byproduct of transesterification, is especially used in the cosmetic industries or
can be transformed into 1,2-propandiol, a more valuable product, so that the
whole process of biodiesel production becomes more economically attractive. The
second reaction involves FFA which is esterified into FAME and water. As shown in
the equation above, water is responsible for the hydrolysis of biodiesel hence the
reaction rate is slowed, that is the only disadvantage of using this method [3].
The focus of this research is to study simultaneous transesterification and
esterification kinetics for yellow grease with methanol and develop a kinetic
model suitable for application in process modeling and simulation of biodiesel
process configurations.
In order to build a viable process model, this report will focus on kinetic analysis of
biodiesel produced from low grade feedstocks in a single step through
heterogenenous acidic catalysis. Furthermore, factors influencing the activity of
the catalyst such as nature and amount of FFA added to feedstock will also be
studied. The catalyst used for all the experiments was a heteropolyacid (HPA),
silicotungstic acid (STA), supported on alumina. Indeed, when dispersed over a
6

large surface area, this ecofriendly insoluble solid offers high catalytic activity and
high thermal stability [8]. This report also includes an overview of the catalysts
properties.

PART 1: PROFESSOR NGS GROUP

Professor Flora Ng is a chemical engineering professor at the University of
Waterloo as well as a research group leader working on the three topics below. In
the past, she worked in partnership with BP Chemicals, UK, helping making a new
process called Avada which won an award for the Best Green Chemistry and
Engineering Process from the U.K. Institute of Chemical Engineers in 2002. She
was elected a Fellow of the Royal Scoiety of Canada in 2007. In 2008, she was
given the title of University Professor, only 14 professors at the University have
this prestigious title. She won the Chemical Institute of Canadas Catalysis Award
7

in 2008 and the Green Chemistry and Engineering award in 2013. She has served
as President of the Catalysis Society in Canada, President of the Catalysis
Foundation and represented Canada to International Association of Catalysis
Societies.
1.1) BIODIESEL AND BITUMEN
Two kind of green energy processes are developed: the upgrade of oil sands
bitumen, and a process to create biodiesel from waste oils. The purpose of both
processes is to produce clean transportation fuels which are more energy efficient
and hence reduce the carbon footprint.
1.2) CONVERSION OF GLYCEROL AND CATALYST IMPROVEMENT
The byproduct of biodiesel reaction is also an important part of the research
within Professor Ngs group. Indeed, two PhD students (equivalent to doctorate
in France) are working on the upgrading of glycerol to other value added
chemicals through a heterogeneous catalytic hydrogenation process. That is why
they also develop solid catalysts using different supports such as platinium or
palladium. The analytical techniques used for catalyst characterization are
numerous: thermogravimetric analysis (TGA), temperature programmed
desorption (TPD), X-ray diffraction (XRD), Fourier transform infrared spectroscopy
(FT-IR)
1.3) PROCESSES MODELING
For the purpose of offering viable solutions to industrials, another PhD student
focuses his researches on the process design via AspenPlus or HYSYS. These two
softwares enable the simulation of the economic feasibility of each process but
they require all the data obtained from the experiments performed in the lab.
Therefore, the entire group works together, everyone help each other and so is
more productive.

PART 2: EXPERIMENTAL SECTION

8

2.1) MATERIALS
During the five months of internship, two different feedstocks have been used.
The first one is yellow grease which comes from used cooking oils from
restaurants hence it contains plant and animal fats. Before being converted into
biodiesel, waste cooking oils are collected and purified by rendering companies
to eliminate solid contaminants and water. The product thus obtained is called
yellow grease. Since yellow grease contains FFA up to 15%, its cost remains by far
lower than refined vegetable oils usually used for biodiesel production [9]. The
second one is canola oil, an edible vegetable oil containing less than 1.2% of FFA,
especially a very small amount of saturated FFA [10] (see Appendix Table 2).
According to the Canola Concil of Canada, this low level of FFA contributes to
lower the temperature at which small crystals form in canola biodiesel, resulting
in a better behavior in cold weather. Moreover, it has oxidative stability which
allows reduction of engine deposits. Despite these advantages, we can see in the
Figure 3 (see Appendix) that the use of canola oil as biodiesel feedstock is
significantly decreasing these last three years, unlike yellow grease which is
increasing every year [11].
Canola oil was obtained from a local grocery shop. Yellow grease was purchased
from a specialized company. Methanol (purity 99.9%), heptane (purity 99%), 2propanol (purity 99.9%), toluene (purity 99.9%), 0.1M KOH (volumetric standard,
in isopropanol), p-naphtholbenzein, methyl heptadecanoate, palmitic acid (purity
98%) were procured from Sigma-Aldrich, USA. Oleic acid (purity 99%) was
obtained from Alfa Aesar, USA. The silicotungstic acid, also called HSiW, with the
chemical formula H4O40SiW12, was purchased from Sigma-Aldrich, USA.
2.2) EQUIPMENT
The experiments were performed in a fully automated high-pressure and hightemperature batch autoclave reactor (PARR Instrument). As illustrated in Figure 4
(see Appendix), this equipment allows controlling temperature, pressure and
stirring. Furthermore, samples can be taken at anytime from a specific valve
outlet.
A gas chromatograph (GC) Agilent 7890A equipped with a flame-ionization
detector has been used for the analysis of FAME following the EN 14103* method
9

using conditions listed in Table 3 (see Appendix). This method allows to quantify
FAME between C14:0* and C24:1 by the relative responses to a single compound methyl heptadecanoate (C17:0). For this calibration, a biodiesel standard mixture
was prepared by the dilution 1.25 g of methyl heptadecanoate in 250 mL of
heptane. 1 mL of this biodiesel standard was added each 50 mg of sample taken
from the batch autoclave.
*cf. glossary
2.3) PROCEDURES
2.3.1) BIODIESEL

PRODUCTION

Three different types of experiments have been carried out as follows:

Yellow grease as feedstock: undergoes both

transesterification simultaneously to produce biodiesel.

Crude canola oil as feedstock, approximated to be composed 100% of TG:

undergoes only transesterification to produce biodiesel.

Oil feedstock models with high FFA content (canola oil mixed with 10 to 20%
of palmitic acid and canola oil mixed with 10% of oleic acid): undergo both
esterification and transesterification simultaneously to produce biodiesel.

esterification

and

The studies were carried out following the optimized reaction conditions
presented in the paper written by Aijaz Baig and Flora Ng [3], which uses 1:27
oil/alcohol molar ratio and 3 wt% catalyst. Feedstock oil, optionally FFA, catalyst
and methanol were respectively added in the 300 mL Parr reactor. Each
experiment was performed at 150, 170 or 190C for 23 hours. The kinetics of the
reaction were determined and the activation energy calculated for both
transesterification and esterification. The reactor was pressurized by nitrogen at
350 psi to keep the reactants in the liquid phase and stirred at 600 rpm. When the
reaction mixture attained the desired temperature, samples were taken at regular
time intervals to follow the kinetic of the reaction. For all samples, two phases
were observed after centrifugation: the top layer contained mainly glycerol and
methanol which has not reacted (subsequently called methanol phase), the
bottom layer contained mainly biodiesel (subsequently called biodiesel phase).
Then, as illustrated in Figure 5 in Appendix, the two phases were separated,
filtrated to remove catalyst residues, and analyzed by GC. FAME present in both
phases were quantified by comparing the peak areas with those of the standards.
10

Meanwhile, acid number of each biodiesel phase (bottom layer) was determined
through a colorimetric titration which allows measuring the amount of FFA in order
to follow the kinetics of esterification. Acid number is the quantity of base
required to neutralize the acidic constituents in 1 g of sample. The unit is
milligram of KOH per gram and it is calculated using this formula:
Vblank represents the volume of KOH needed
to change the color of the titration solvent
(toluene/isopropanol/water) without
sample.

Reproducibility of results was ensured by repeating an experiment (canola oil with

10% palmitic acid).

2.3.2) CATALYST

PREPARATION

The STA, highly soluble in water, was anchored onto high-surface area alumina by
a wet impregnation method, dried at 125C and finally calcined under nitrogen
atmosphere at desired temperature for two hours.
A wet impregnation method, as shown in Figure 6, involves dissolution of STA in a
specific volume of distilled water, after what the insoluble support is added to the
solution. At this moment begins the capillary action which brings the solution
containing the STA into the pores of alumina. Then, the mixture is dried and
calcined in order to evaporate the water and fix the active phase onto the support
via hydrogen bonds [12]. The catalyst thus obtained (STA/Al2O3) is an insoluble solid
acid.

11

Figure 6. Wet impregnation method

2.3.3) CATALYST

CHARACTERIZATIONS

At the end of each experiment, the used catalyst remaining in the reactor was
collected and dried at 90C to evaporate the methanol. X-ray diffraction (XRD)
measurements were carried out using a Bruker D8 FOCUS, operated with a Nifiltered Cu K radiation source at 40kV and 40mA. The support, the fresh catalyst
STA/Al2O3 and one used catalyst were analyzed. Thermogravimetric analyses
(TGA) were performed on a TA Instruments Q500. Fresh and used catalysts were
heated in the temperature range 40C to 600C under nitrogen atmosphere with a
temperature ramp of 10C/min.

PART 3: RESULTS AND DISCUSSION

3.1) THE HANDLING OF EXPERIMENTAL DATA

12

Experimental data was treated as follows: (a) based on the amount of FAME
determined from GC analysis and the acid number determined from titration,
kinetic models for the transesterification and esterification reactions were
developed. (b) From the kinetic models, the rate constants for the
transesterification reaction and esterification reaction were determined at
different temperatures. (c) The activation energies were determined using the
rate constants determined at different temperatures. The effect of different FFA,
palmitic acid and oleic acid on the esterification reaction was studied. A
comparison between the rate constants for the conversion of canola oil and yellow
grease to biodiesel may provide information for future experiments. Finally, the
catalyst, whether fresh or recovered, were studied through two analytical
techniques: XRD and TGA.
As shown in Figure 7 in the Appendix, chromatograms in our analysis conditions
allow us to see the retention time (min), the peak area (pA.s) and the name
related to each compound between C14:0 and C24:1 found in the sample. The
FAME content, also called ester content, can be therefore calculated based on the
peak
area
using
the
following
formula:

After
getting data from the experiments, acid number of biodiesel phase as well as
ester content (weight%) of biodiesel phase and methanol phase are plotted
versus time which give the graph in Figure 8. In addition, the reaction rate (wt%
per minute) of simultaneous transesterification and esterification can be found by
plotting the gradient of the first points versus time as shown in Figure 9. A kinetic
study was performed to find out the transesterification and esterification rate
constants at three different temperatures and the corresponding activation
energies.

13

35
30
25

Biodiesel phase (Ester content wt.%)

Methanol phase (Ester content wt.%)

20
15
10

Acid number of biodiesel phase (mg of KOH/g)

5
0
0

200

400

600

800

1000

1200

1400

1600

Figure
8. Example of graph obtained from the experimental data

f(x)
9 =
R = 0
8
f(x) = 0.01x + 5.47
7
R = 0.72
6 Biodiesel phase (Ester content wt.%)

Rate = 0.0807 wt
%/min
Linear (Biodiesel phase (Ester content wt.%))

5
4
3
Methanol phase (Ester content wt.%)

Linear (Methanol phase (Ester content wt.%))

1
0
0

50

100

150

200

250

300

Figure
9. Rate of formation of biodiesel in both phases

14

3.2) KINETIC ANALYSIS

3.2.1) TRANSESTERIFICATION

As the methanol is introduced in excess, 1:27 oil/alcohol molar ratio, the

equilibrium is shifted toward biodiesel production and the rate law is expected to
follow a pseudo first order dependence with respect to the concentration of TG. In
order to find the rate constant of transesterification (k 1) of TG, the crude canola oil
appears the best feedstock because it contains a very low amount of FFA. In this
study, the crude canola oil is approximated to be composed of 100% of TG and
0% of FFA, thus it undergoes only transesterification. In Figure 10 (see Appendix)
is demonstrated how to calculate transesterification and esterification as first
order reaction. Conversion of TG is determined using the biodiesel wt% obtained
from GC analysis and the initial wt% of oil.

conversion

MWoil
Biodiesel( wt%)

Initial(wt %) of oil 3MWbiodiesel

Molecular weight of
the most common
TG in canola oil
(triolein)

As illustrated below, the plot of -ln (1-conversion) versus reaction time shows a
linear relationship. This indicates that the transesterification of TG follows first
order dependence with respect of time. The opposite of ln (1-conversion) is
plotted to obtain a rising curve. The slope of this line represents the
transesterification rate constant k 1 and its unit is min-1. As one set of experiment
was conducted at 150, 170 and 190C, three differents k 1 were obtained,
respectively 0.0005, 0.0014 and 0.0039 min-1, so that the activation energy of
transesterification (Ea trans) could be determined.

15

1.6

190C

1.4

Crude canola

1.2
1

-ln (1-conversion)
0.8
0.6
0.4

k1 = 0.0039
min-1

0.2
0
0

50

100

150Time200

250

300

(min
11. Example of k1 determination: crude canola oil at 190C

350

400

Figure

3.2.2) ESTERIFICATION

Now, a fixed amount of FFA, 10 or 20 wt%, is initially added in the reactor with the
usual reactants (canola oil, methanol, catalyst). Esterification of FFA occurs with a
large excess of methanol. Therefore, as the transesterification, the equilibrium is
shifted toward biodiesel production and it is considered a pseudo first order
reaction. The progress of esterification of FFA to FAME can be monitored through
the decrease in the acid number. Hence the k 2 value can be determined for each
experiment. As illustrated below, the plot of ln (acid number) of the first points
versus reaction time shows a linear relationship. This indicates that the
esterification of FFA follows first order dependence with respect of time. Like the
transesterification, k2 (min-1) is the slope of the line and three different values of k 2
will be found in order to get the activation energy of esterification (Ea ester).

16

12

190C

10

Canola +10%
FFA

k2 = 0.0182
min-1

6
4
2
0

f(x) =
0 R = 0

50

100

150

200

250

300

Figure 12. Example k2 determination: canola oil +10% FFA at 190C

3.2.3) ACTIVATION ENERGY
The activation energy is calculated using the Arrhenius equation approach:
Where k is the rate constant, Ea the activation energy, R
the gas constant, T the temperature and A the Arrhenius
constant (or pre-exponential factor).
The activation energy was determined by plotting the logarithm of the rate
constant as a function of the inverse of temperature in Kelvin. As shown in Figures
13 and 14 (see Appendix), an accurate linear regression (R 2 = 0.99) allowed to
find the slope of the line which represents E a/R. Through a simple calculation, the
activation energy of both reactions was then determined.
A lower activation energy generally facilitates a reaction to occur. It has been
found that Ea trans (83.56 kJ/mol) is much higher than E a ester (48.83 kJ/mol).
Esterification is therefore kinetically favored over transesterification in the case of
temperatures between 150 and 190C. However, the ratio of rate constant (see
Appendix Table 4) shows a significant decrease in the experiment performed at
190C.
3.3) FACTORS INFLUENCING CATALYTIC ACTIVITY
17

3.3.1) AMOUNT OF FREE FATTY ACIDS ADDED TO CANOLA OIL

Firstly, three different experiments with canola oil as feedstock are compared:
pure canola oil, canola oil with an initial 10 wt% of palmitic acid (PA), canola oil
with an initial 20 wt% of PA. PA is a saturated FFA consisting of sixteen carbons
and was in solid form, undissolved in the mixture, when introduced in the reactor.
Since methanol phase contains only a small amount of biodiesel produced during
the reaction, the following three graphs represent the ester content (wt%) of
biodiesel phase as a function of time for temperatures of 150, 170 and 190C.
45
40
35
30
25
Pure canola

20

Canola +10% palmitic acid

Canola + 20% plamitic acid

15
10
5
0
0

200

400

600

800

1000

1200

1400

1600

60
50
40
30

Pure canola

Canola + 10% palmitic acid

Canola + 20% palmitic acid

20
10
0
0

200

18

400

600

800

1000

1200

1400

1600

80
70
60
50
40

Pure canola

Canola +10% palmitic acid

Canola oil + 20% palmitic acid

30
20
10
0
0

200

400

600

800

1000

1200

1400

1600

Figure
15. Influence of amount of FFA on biodiesel yield at different temperatures
Biodiesel yield: It can be noted for experiments performed with FFA that there is
presence of biodiesel at 0 min. This is due to the fact that esterification, which is
faster than transesterification, has already started prior to the first sample being
taken, i.e once temperature reaches the reaction temperature. The results
obtained show an increase of biodiesel yield with temperature. However, it seems
that the initial amount of PA in canola oil does not play a predominant role on
ester content when temperature is above 170C. Furthermore, at 190C biodiesel
yields tend toward the same value, 70 wt%, regardless if canola oil contains or not
PA. There are differents behaviors at 150C because transesterification has not
reached the equilibrium conversion yet due to its low rate constant. The reason
why results are far from acceptable yields is because:
-Eleven samples of 5 mL were taken to study the kinetics hence a decrease of
reactants in the reactor.
-A small part of the biodiesel content, around 10 wt% for the last sample, is in the
methanol phase.

19

30
25
20

Acid number (mg of

KOH/g) 15 yellow grease

canola oil +20% palmitic acid

canola oil +10% palmitic acid

10

3.76

1.43
0.69

0
0

200

400

600

800

1000

1200

1400

1600

25
20
15
10

yellow grease

canola oil +20% palmitic acid

canola oil +10% palmitic acid

2.27
1.95

0
0

200

20

400

600

800

1000

1200

1.16
1400

1600

25
20
15
yellow grease

10

canola oil +20% palmitic acid

canola oil +10% palmitic acid

3.01
2.56

0
0

200

400

600

800

1000

1200

1.75
1400

1600

Figure
16. Influence of amount of FFA on acid number at different temperatures
The previous three graphs represent the acid number (mg of KOH/g) of biodiesel
phase as a function of time for temperatures of 150, 170 and 190C.
Acid number: It can be easily observed through the gradients that the higher the
temperature, the faster is the conversion of FFA. Acid numbers of crude canola oil
was not measured because the acid number is too low (around zero). Also, at
190C the initial acid number of canola oil containing 20 wt% of PA is lower than
experiments performed at 150 and 170C due to the fact that the speed of
esterification increases with temperature. For canola oil experiments, the final
acid number increases with temperature. Acid number is directly proportional to
the FFA concentration. Therefore, high temperature conditions shift the
equilibrium of esterification towards FFA production, which is highly undesirable
because it inhibits the reaction.
Kinetics: As seen in Table 5, Ea ester decreases (54.95 to 39.15 kJ/mol) when
initial amount of PA increases. Also, a higher percentage of PA added to canola oil
significantly increases the reaction rate and, to a lesser extent, the biodiesel yield
depending at which temperature the experiment is performed. Therefore,
reactions with canola oil containing FFA are thermodynamically and kinetically
favored over those performed with crude canola oil. In addition, low final acid
numbers show that nearly all FFA are consumed during the reaction. These results
demonstrate that activity of STA/Al2O3 is not affected with high percentages of
FFA.
21

3.3.2) NATURE OF FREE FATTY ACIDS ADDED TO CANOLA OIL

This second parameter is studied through experiments carried out with canola oil
containing 10% of PA and canola oil containing 10% of oleic acid (OA). OA is an
unsaturated FFA consisting of eighteen carbons with one carbon-carbon double
bond and was in liquid form when initially introduced in the reactor (dissolved in
the mixture). The discussion will follow the same way as in 3.3.1).
35
30
25
20
Canola +10% PA

15

Canola +10% OA

10
5
0
0

200

400

600

800

1000

1200

1400

1600

60
50
40
30

Canola +10% PA

Canola +10% OA

20
10
0
0

200

22

400

600

800

1000

1200

1400

1600

80
70
60
50
40

Canola +10% PA

Canola +10% OA

30
20
10
0
0

200

400

600

800

1000

1200

1400

1600

Figure
17. Influence of nature of FFA on biodiesel yield at different temperatures
Biodiesel yield: The two profiles are quite similar especially at the beginning of
each experiment. The experiments performed with PA give a higher final ester
yield but not very far from those performed with OA. Hence, one can assume that
the nature of FFA in canola oil does not play a predominant role on ester yield, but
further experiments with other FFA need to be conducted to validate this
hypothesis. In other words, the carbon-carbon double bond of oleic acid does not
influence the catalyst activity.
16
14
12
10
8

Canola +10% PA

Canola +10% OA

6
4

1.25

0.69

0
0

200

23

400

600

800

1000

1200

1400

1600

14
12
10
8
Canola +10% PA

Canola +10% OA

1.69
1.16

2
0
0

200

400

600

800

1000

1200

1400

1600

14
12
10
8
Canola +10% PA

Canola +10% OA

2.56

2
0
0

200

400

600

800

1000

1200

1400

1600

Figure
18. Influence of nature of FFA on acid number at different temperatures
Acid number: Acid number profiles are similar as well. At 190C, final acid
numbers are exactly the same. In addition, as observed in 3.3.1), the final acid
number increases with temperature which indicates hydrolysis of esters into FFA.

24

0
0

1/Temperature
0
0
(Kelvin)

-1
-2

ln (kester)
-3
-4

150
0
C

Ea ester (Canola +10% PA) =

54.95 kJ/mol
Canola + 10% PA

Ea ester (Canola +10% OA)

=30.06 kJ/mol

Canola + 10% OA

-5
-6

Figure
19. Comparison of esterification activation energies
Kinetics: A comparison of Ea ester between the two experiments (Figure 19)
shows a difference of 25 kJ/mol, thus esterification of OA in canola oil is kinetically
favored over the experiment with PA. But it is important to note that reactions
carried out above 150C have a higher reaction rate in the case of canola oil
containing 10 wt% of PA. For instance, with this STA/Al 2O3 catalyst, it will be
preferable to perform reaction below 150C if the feedstock used for biodiesel
production contains more OA than PA. This may change depending on the type of
catalyst and the amount of FFA present in the feedstock.
3.4) COMPARISON YELLOW GREASE / CANOLA OIL
Another purpose of this internship was to make a model of yellow grease with
canola oil by adding different percentages of FFA, because composition and
amount of FFA into the yellow grease bought is not known.
Results obtained show that experiments with yellow grease gave lower biodiesel
yields, lower reaction rates as well as lower esterification rate constants (see
Appendix Figure 20 and Table 5) compared to all the experiments conducted using
canola oil containing high initial amount of FFA. However, as seen in Figure 20, the
behavior of simultaneaous transesterification and esterification of yellow grease in
the first hundred minutes is quite similar to canola oil containing 10 wt% of FFA.
Also, initial acid numbers of yellow grease and canola oil containing 20 wt% of PA
25

are quite close. This confirms an initial amount of FFA in this waste cooking oil
comprised between 10 and 20 wt%.
An interesting difference with canola oil experiments is that the final acid number
of yellow grease (see above Figure 16) decreases with temperature. Furthermore,
acid number is directly proportional to the FFA concentration. Therefore, referring
to the esterification reaction shown in Figure 2 (reaction b), temperature shifts the
equilibrium towards biodiesel production.
3.5) CATALYSTS PROPERTIES
HPA are strong Brnsted acids, they catalyze a wide variety of reactions due to
their Keggin structure: [XM12O40]n-, nH+. This primary structure, as illustrated
below, corresponds to a cluster where the central atom (X) is bonded to oxygen
atoms through a tetrahedral arrangement. This tetrahedron is surrounded by
twelve oxygen octahedra containing the metal in high oxidation state. In the case
of STA the heteroatom X is silica, the metal M is tungsten and n is equal to four.
Hence to respect the principle of electroneutrality there are four acidic protons
coming from water which are probably bonded to the terminal oxygens forming
H5O2+ bridges [13]. When dispersed onto a support possessing pores such as
alumina, heteropolyacids have several advantages: high thermal stability, high
surface area, high catalytic activity and selectivity, easy separation from a
reaction mixture and possible reuse [8].

26

Figure 21. Primary structure of Keggin ion

Catalyst properties of fresh as well as recycled STA/Al 2O3 were analyzed using the
following two analytical techniques:
-XRD: Figure 22 shows the XRD patterns for alumina, fresh STA/Al 2O3 and a spent
STA/Al2O3 which is a mixture of the recovered catalysts from the following two
experiments;
1) 190C, canola oil containing 10 wt% of PA
2) 190C, canola oil containing 20 wt% of PA
It can be noted that the support does not have sharp diffraction peaks, this
indicates an absence of crystallinity. So the alumina is amorphous and by
referencing to literature the weak peak at 67 (2) attests this support
corresponds to -alumina [14].

27

The presence of a wide weak peak at 33 (2) reflects the slight crystallinity of
fresh STA onto the support. The peak of alumina at 67 (2) still appears on
catalyst graphs. This confirms a reasonable dispersion of STA over the surface of
the support despite the presence of some agglomerates. Moreover, graphs of
fresh and recycled catalysts are nearly similar. So, STA/Al 2O3 does not undergo a
structural change during the reaction hence it is stable at 190C. Residual
hydrocarbons produced from the reaction can get trapped in the catalysts pores,
which explains the large peaks at 8 and 20 (2).

Figure
22. XRD patterns of support, fresh catalyst, spent catalyst

-TGA: Figures 23 shows the TGA patterns for fresh and all recycled STA/Al 2O3.
Weight of samples heated is recorded as a function of time. This analytical
technique will help determine the conditons for removing residues from the
recycled STA/Al2O3. It can be noted that nearly all used catalysts have the same
profile: three regions of mass loss where most of the residues are decomposed
between 170C and 400C (see Figure 24).
28

It is interesting to note a mass loss of 37% and 30% for yellow grease
experiments, performed at 190C and 170C, reflecting a greater proportion of
residues in the catalyst. This is probably due to the presence of numerous species
inside the yellow grease which adsorbed on the catalyst during the reaction.
Therefore, this may explain low yields and reaction rates for yellow grease
experiments in batch autoclave. Also, comparing the spent catalysts 2), 5) and 9)
in Figure 23a, one can conclude that at 150C the catalyst is less contamined
during reactions performed with canola oil containing FFA than crude canola oil.
100
95
90
85
80
75
70
65
60
55
0

100

200

300

400

500

600

700

Figure
23. TGA patterns of fresh and spent catalysts

29

100
95
90
85

1)
2)
3)
4)

80
75

Canola
Canola
Canola
Canola

oil
oil
oil
oil

+10% PA
+10% PA
+20%
+10%

70
65

7) Yellow grease
8) Canola oil +10%
9) Canola oil
10) Yellow grease

60
55
0

100

200

300

400

500

Figure 23a. Detailed TGA patterns of spent catalysts

30

600

700

Yellow grease at
170C

Figure
24. TGA patterns of spent catalyst from yellow grease experiment at 170C

CONCLUSION
The kinetics of transesterification and esterification follow first order dependence
for each reaction and will be used for process modeling and simulation. It has
been found that, in our conditions, esterification is up to eleven times faster than
transesterification and that the solid acid catalyst is not deactivated by the high
FFA content. In fact, experiments with highest biodiesel yields and reaction rates
were those performed using canola oil containing 20 wt% of PA. Presence of
saturated and unsaturated fatty acids in the canola feedstock oil apparently does
not affect yields and reaction rates. However, further experiments will be carried
out using linoleic acid as FFA which contains two carbon-carbon double bonds.
With the kinetic parameters found such as rate constants and activation energies,
99.9% pure biodiesel as well as 99.9% pure glycerol can be produced from yellow
grease according to modelling using AspenPlus in Professor Ngs research group. A
31

paper will be written gathering kinetic analyses, process modeling and catalyst
characterization for biodiesel production through heterogeneous acidic atalysis.
On a personal note, this five-month internship has been doubtless the best
experience of my life. The most exciting challenges were to cimatize myself to a
new environment with different customs and speaking only English. Admittedly,
the first weeks were quite difficult because of the language barrier, knowing no
one and the learning of lab equipment such as the batch autoclave. But the fact
to work on a subject which captivates me as well as being in a group full of
friendly people helped me to quickly improve myself. In addition, writing this
report in English and reading scientific papers contributed to expand my writing
skills. Also, as Waterloo is a student city, I had the opportunity to meet people
from all around the world hence discovering different cultures. In conclusion I
would say that despite the overall cost of this internship, I have been able to gain
valuable work experience while improving my standard of English.

32

GLOSSARY
C14:0 means that there are 14 carbons in the fatty acid chain and zero
carbon-carbon double bond:

DG = diglyceride(s)
Ea trans = activation energy of transesterification
Ea ester = activation energy of esterification
EN 14103 = fat and oil derivatives FAME determination of ester and
linolenic acid methyl ester content, European Committee for
Standardization
FAME = fatty acid methyl ester(s)
FFA = free fatty acid(s)
GC = gas chromatograph
HPA = heteropolyacid(s)
STA = silicotungstic acid (HSiW)
STA/Al2O3 = silicotungstic acid anchored to alumina
MG = monoglyceride(s)
OA = oleic acid
PA = palmitic acid
TG = triglyceride(s)
TGA = thermogravimetric analysis
33

XRD = X-ray diffraction

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August 7th 2014).
34

[13] Bardin, B.B.; Bordawekar, S.V.; Neurock, M.; Davis, R.J. J. Phys. Chem. B 1998,
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[14] Rauwel, E.; Galeckas, A.; Rauwel, P.; Nilsen, O.; Walmsley, J.C.; Rytter, E.;
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APPENDIXES
Properties

Biodiesel

Petroleum
diesel

Density at 20C
0.88
0.85

35

Units