OPTIMIZATION OF ALKALI-CATALYSED

BIODIESEL PRODUCTION FROM USED COOKING

OIL THROUGH TRANSESTERIFICATION AND
OZONE TECHNOLOGY UNDER RESPONSE
SURFACE METHODOLOGY
E. Creencia1, FN. Dumas2, J. Ligutom3, E. Llanos4, and B. Pugate5

Department of Chemical Engineering and Technology, Mindanao State University-Iligan Institute of

Technology, A. Bonifacio Avenue, Tibanga, 9200 Iligan City, Philippines,
Email: eul212@yahoo.com1, niquee9ner@gmail.com2, jenny.ligutom19@gmail.com3,
ellaine.llanos@gmail.com4, brianpugate@gmail.com5

Received: July 15, 2014

Abstract
The used cooking oil has high potential to produce renewable, cheap and clean-burning
diesel substitute. The oil sample was introduced to two separate processes for the
production of biodiesel. With a fresh volume of used oil for each, the first process was
standard transesterification, and the second process was ozonolysis-coupled
transesterification. The second reaction was done to verify any comparable difference
between biodiesel achieved without ozone and biodiesel synthesized through ozonolysis.
In the first set-up, the reaction was carried out using a simple batch reactor that
contained a mixture of used cooking oil, ethanol, and dissolved sodium hydroxide. In the
second set-up, the batch reactor was modified with an inlet for the ozone coming from the
ozone generator, and an outlet for the excess ozone leading to a potassium iodide trap.
Here the independent variables were temperature, molar ratio of ethanol to oil, and length
of time of ozone exposure. The operating conditions for the reaction with and without
ozone were determined through Response Surface Methodology (RSM). Samples from
each set up were obtained and then analyzed through gas chromatography.
Results showed that sole transesterification produced long-chain ethyl esters such as ethyl
caproate, ethyl laurate, ethyl palmitate, and ethyl octadecanoate. The transesterification
with ozonolysis produced short-chain ethyl ester products which were ethyl laurate, ethyl
isomyristate, and ethyl palmitolate. The former reaction had its best yield at 60°C and 1:4
molar ratio of ethanol to oil, while the latter had best yield at 40°C, 1:6 molar ratio of
ethanol to oil, and 80 minutes of exposure to ozone. All products of the reaction with
ozone comparably had higher biodiesel yield with an added advantage of shorter-chain
esters which allow more control over the flow properties of the biodiesel. The ozonolysis
reaction succeeded in attempting to produce a satisfactory diesel substitute.

Keywords: Biodiesel, Ozonolysis, Response Surface Methodology, Transesterification, Used

Cooking Oil
Introduction
The world’s massive fuel consumption despite unstable sources or reserves contributes to
economic crisis. This condition is highly inevitable because fuel usage permeates almost
all human activities. This entails a demand of around 18.4 litres per day.[1] Meanwhile, the
fossil fuel resources continuously diminish because they are non-renewable. The apparent
scarcity of petroleum reserves results to steep price hikes of fuels like crude oil. This in
turn appears to be one of the major problems in certain regions of the world. Furthermore,
the increasing demand for fossil fuels exacerbates environmental concerns such as higher
carbon dioxide and greenhouse emission and more seriously – global warming. For these
reasons, the researchers aim to design an alternative fuel that is not only cheap but can also
alleviate environmental deterioration.
Biodiesel is one of the biofuels considered to be a renewable source of fuel. Several
studies show that biodiesel is a very promising fuel alternative because it does not require
engine modification, is more biodegradable, and is ten times less poisonous than the
ordinary diesel oil.[2] Hence, biodiesel usage is environmentally friendly because of its
reduced carbon dioxide emission to the atmosphere. It can contribute to assuage of global
warming.
Animal fats and plant lipids can be used as biodiesel source. However, utilization of
human nutrition sources can cause food crisis due to its limited availability and consequent
price increase. Therefore, most researchers use non-edible oil or waste cooking oil (WCO),
which can be acquired at no charge, as feedstock for producing biodiesel. The use of waste
edible oils can reduce the cost of biodiesel production as much as 60 to 90 percent.[3]
Every year, billions of gallons of waste vegetable oil are produced mainly from
industrial deep fat fryers found in potato processing plants, food factories, restaurants, and
fast-food establishments. Improper disposal of those WCO decreases water stream quality
and contaminates sewage systems. Hence, alternative disposal methods to convert these
waste products to high value products need to be developed. Producing biodiesel is one of
the recycling options that is technically feasible, environmentally acceptable, economically
competitive, and readily available. Various methods for the synthesis of biodiesel are used
nowadays. Among these, transesterification is an attractive and widely accepted technique.
Another, which is less prominent, is the use of ozone technology. The simultaneous
reactions of these two methods can be used to efficiently produce biodiesel.
The optimal operating conditions are ideally characterized through Response
Surface Methodology (RSM). This is a statistical tool that is proven helpful in studying the
interaction between the independent variables on response variables thereby producing
optimized results of the biodiesel produced.
The main purpose of this study is to produce a potential alternative fuel – biodiesel.
This product will not only make use of the resource that has been present in excess for a
long time but will also produce less pollutant fuel. The rising demand and increasing cost
of energy can also be aided by producing a promising alternative fuel that is cheap, clean
and eco-friendly. The scarcity of fossil fuels in the near future, together with concerns over
the consequences of dependency of this type of resource, is also addressed.
The focus of this study is to determine the most favorable condition for the
production of biodiesel using used cooking oil. This will be established through the
statistical analysis of the process variables using the Response Surface Methodology. The
effect of the process (independent) variables on the ozonolysis and the transesterification
products will also be rationalized accordingly. However, this paper does not include
thorough exploration of physical and chemical properties such as viscosity, density, cetane
number, pour point, and flame point of the biodiesel product.
Objective
The main objective of the study is to produce biodiesel from waste cooking oil through
transesterification and ozone technology. Specifically, the study aims to:
 determine the fatty acid composition of waste cooking oil using Gas
Chromatography;
 determine the optimal operating condition for synthesis of biodiesel using Response
Surface Methodology (RSM) applied to the three independent process variables:
reaction temperature (40°C to 60°C), molar ratio of oil to ethanol (1:4 to 1:6), and
ozone exposure (80 minutes to 110 minutes);
 validate the ethyl ester content of the biodiesel product using Gas Chromatography;
 evaluate the effect of independent variables on ozonolysis and transesterification
products through the results of RSM.

Materials and Methods

Materials
The raw material used for the experiment was obtained from a local restaurant in Iligan
City, Lanao del Norte. The used cooking oil was filtered to separate the visible impurities
such as solid residues from the oil feedstock used in the experiment. All the chemicals used
for transesterification and ozonolysis reactions such as ethanol and sodium hydroxide were
of analytical grade (AR). Ozone was generated from atmospheric oxygen gas through an
ozone generator (Sheng Han Ozonizer with a capacity of 200mg/hr).

Methods
In transesterification, oil feedstock was charged into the reactor equipped with magnetic
stirrer and hotplate and was heated to a specified temperature with constant stirring at 750
rpm. The alkali catalyst was prepared by dissolving the sodium hydroxide pellet (1 g
NaOH) to 50 mL ethanol then the solution was added to the oil feedstock. The temperature
and molar ratio of ethanol to the used cooking oil was varied according to the experimental
design. After the reaction, the solution was allowed to cool and settle overnight in a
separatory funnel where ethyl ester (biodiesel) and glycerine separated.
The glycerine layer was decanted and the ethyl ester layer was washed with tap
water about three times to dissolve and remove excess alcohol compounds until the water
was clear and neutral. Finally, the ethyl ester content in the biodiesel product was
determined through Gas Chromatography. A schematic diagram for the transesterification
process is described in Figure 1. In Ozonolysis, the experimental setup used was the same
as that in the transesterification reaction, except that ozone was injected continuously as the
reaction proceeded with a defined reaction time. The gas was generated through an
Ozonizer that produced ozone from oxygen gas at 200 mg per hour. Tubes were used to
deliver ozone gas to the reactor containing the mixture of used cooking oil, ethanol and
catalyst. The exit port of the reactor was connected into a potassium iodide solution trap in
order to trap unreacted ozone. The reaction was run at varying temperatures, molar ratio,
and time of exposure to ozone which were varied according to the experimental design
Figure 2 shows the schematic diagram of the simultaneous transesterification and
ozonolysis process.
 Figure 1. Schematic diagram of transesterification set-up

Figure 2. Schematic diagram of ozonolysis set-up

Experimental Design
The design used to optimize the operating conditions was by Second-Order Response
Surface or Central Composite Design (CCD). CCD works efficiently for quadratic models
but cannot support full cubic graphs. [4]
This research focuses on the effect of three independent variables: reaction
temperature, molar ratio of ethanol to oil and ozone exposure of the sample. These design
variables were evaluated at two responses: percent yield without ozone (response 1) and
percent yield with ozone (response 2). The three independent variables were studied and
optimized.

Response Optimization
The response surface analyses focused on modeling process. The optimization of the
measured responses indicates areas in the design region where the process is likely to give
desirable results. The selection of appropriate model for each response was followed by
finding a set of operating conditions that optimize all responses or keep them at desired
ranges. In this study, the variables were criticized based on how they affect the percent
yield of the biodiesel product. A useful approach to multiple responses is to use the
simultaneous optimization technique by Derringer and Suich (1980) called as desirability
functions.[5]

Results and Discussions

Gas Chromatography was used to determine the fatty acid content in the used cooking oil,
the result of which is shown in Table 2.[6][7]

Table 2.1 Fatty Acid Composition of Used Cooking Oil

Saturated fatty acid Composition (wt%)
Lauric acid (C12:0) 0.89
Myristic acid (C14:0) 1.40
Palmitic acid (C16:0) 40.95
Stearic acid (C18:0) 4.46
Unsaturated fatty acid Composition (wt%)
Oleic acid (C18:1) 38.55
Linoleic acid (C18:2) 11.15
Percentages may not add to 100% due to rounding of values and other constituents are not listed
The result shows that the oil has 47.7% saturated fatty acid and 49.7% unsaturated
fatty acid. Palmitic acid is the major fatty acid of used cooking oil followed by oleic acid, a
monosaturated fatty acid, and linoleic acid, a polysaturated fatty acid. The chromatographic
profile of these fatty acids is presented in Figure 3. As analyzed by Bruker Scion 456
GC/MS, the data was based on the sample used. This data does not have significant
difference from the data previously reported from literature. It is important to determine the
fatty acid composition of oil because it affects the performance of biodiesel in engines.
Saturation increases the cloud point, cetane number and improved stability, while
polyunsaturation reduces these properties.[8]

Figure 3. Gas Chromatogram of Used Cooking Oil Sample

Summary of Results
The responses are summarized at Table 3 where the data for percent yield for
transesterification reaction (without Ozone) and ozonolysis reaction (with Ozone) are
tabulated.

Table 3. CCD and Response Variables

Molar Ratio Ozone Response 1 Response 2
Temperature
Run of Oil to Exposure, %yield % yield With
°C
Ethanol mins Without Ozone Ozone

1 40 1:6 80.0 86.42 90.33

2 50 1:5 120.0 82.01 85.62
3 35 1:5 95.0 79.12 83.02
4 60 1:6 80.0 88.02 86.50
5 50 1:65 90.0 82.01 85.21
6 50 1:5 70.0 82.01 85.40
7 50 1:5 100.0 82.01 84.20
8 60 1:4 80.0 88.50 81.55
9 40 1:4 110.0 78.43 85.50
10 65 1:5 95.0 87.01 82.01
11 60 1:4 110.0 88.50 81.30
12 50 1:5 80.0 88.01 85.01
13 60 1:6 110.0 88.02 87.95
14 40 1:4 80.0 78.43 89.04
15 50 1:5 95.0 81.72 84.10
16 40 1:6 110.0 86.42 87.40
17 50 1:35 95.0 79.04 85.71
18 50 1:5 70.0 81.72 85.90
19 50 1:5 95.0 81.72 83.75
20 60 1:4 80.0 85.07 79.91

The analysis of variance (ANOVA) for the response data was evaluated. In the
transesterification process, the result showed that the quadratic model was significant. It
also showed that the model terms, temperature and molar ratio were both significant model
terms that have notable effect to the responses.

For ozonolysis, the result showed that the model was also significant. The analysis
of variance result showed that temperature and molar ratio were significant linear terms;
temperature-molar ratio and temperature-ozone exposure relationships were significant
interaction terms, and molar ratio is a significant quadratic term.
Model Graph and Effect of Independent Variables of Response 1

Figure 4. % Yield without ozone versus molar ratio and temperature

The results show that the percent yield of transesterification increased significantly
with increasing reaction temperature and molar ratio hence higher long chain fatty acid
ethyl ester produced. There is also a dramatic decrease of percent yield observed with
decreasing temperature and molar ratio. This condition is expected because the rate of
transesterification reaction will increase with increasing reaction time that can be deduced
from its reaction kinetics. If the reaction temperature rises, the rate constant increases as is
based on Arrhenius Law.[10] Figure 4 shows the quadratic model graph of molar ratio and
temperature with constant ozone exposure at 95 minutes.
Model Graph and Effect of Independent Variables of Response 2

Figure 5. % Yield with ozone versus temperature and molar ratio

The experimental set-up that is introduced with ozone converts the unsaturated fatty
acid content of the oil to short chain fatty acid ethyl ester. This conversion increases with
high molar ratio and decreased reaction temperature. The percent yield decreases at low
molar ratio and higher reaction temperature. The ozonolysis reaction requires high ozone
solubility in the oil; hence higher temperature will reduce the amount of ozone and impair
the ability to crack double bonds in unsaturated fatty acids. Figure 5 shows the quadratic
model graph of reaction temperature and molar ratio versus percent yield of ozonolysis
product.
 Figure 6. % Yield with ozone versus ozone exposure and temperature

Figure 6 shows that the ozonolysis product increased significantly at lower reaction
temperature and low exposure to ozone. This is evident in the experimental data gathered
at 40°C and 80 minutes ozone exposure at run number 1. There is also considerable
increase in yield with increased ozone exposure but not as high as the percent yield
obtained at lower ozone exposure. However, the percent yield decreases significantly at
higher temperature and low ozone exposure. The model graph below shows the percent
yield with ozone versus ozone exposure and temperature at constant molar ratio of ethanol
to oil at 1:5.

Figure 7. % Yield with ozone versus ozone exposure and molar ratio

The results show that there is an increased ozonolysis product with increased molar
ratio of ethanol to oil. On the other hand, the yield decreased significantly at higher ozone
exposure and lower molar ratio. The experimental data of highest yield at 90.33% is
obtained at 80 minutes ozone exposure and 1:6 molar ratio of oil to ethanol. The yield
slightly increased with lower molar ratio and lower exposure to ozone. Figure 7 shows the
quadratic graph of percent yield with ozone exposure and molar ratio at constant
temperature at 50°C.
Gas Chromatogram Results

Figure 8. Gas Chromatogram Transesterification Product of Used Cooking Oil

(a) Capric acid, ethyl ester, (b) Lauric acid, methyl ester, (c) Lauric acid, ethyl ester, (d)
Methyl isomyristate, (e) Myristic acid, ethyl ester, (f) Palmitic acid, methyl ester, (g)
Palmitic acid, ethyl ester, (h) trans-Vaccenic acid, methyl ester, (i) 9-Octadecenoic acid,
ethyl ester, (j) Octadecanoic acid, 17-methyl-, methyl ester

Figure 9. Gas Chromatogram of Ozonolysis Product of Used Cooking Oil

(a) Methyl laurate, (b) Methyl isomyristate, (c) Methyl palmitolate, (d) Methyl palmitate,
(e) Methyl octadeca-9,12-dienoate, (f) Methyl trans-9-octadecenoate, (g) Methyl eicosa-
5,8,11,14,17-pentaenoate, (h) Methyl 9-eicosenoate, (i) Methyl 4,7,10,13,16,19-
docosahexaenoate, (j) Dodecanoic acid, 1-(hydroxymethyl)-1,2-ethanediyl ester
The transesterification product of highest yield was analyzed through Gas
Chromatography. Results showed that the saturated fatty acids in the used cooking oil were
effectively converted to long chain fatty acid ethyl esters (ethyl laurate, ethyl myristate,
ethyl palmitate, and ethyl stearate) as shown in the major peaks of chromatogram.
The results obtained by this study showed that there were peaks detected that were
the same with the gas chromatogram results of transesterification product by Farooq et al.
(2009) and Nakpong et al. (2013). The results of the previous literature were compared to
the study of the researchers and there had been compounds that were common to both
biodiesel produced.
The chromatogram of ozonolysis product revealed that the unsaturated fatty acid
content of the used cooking oil was converted to short chain fatty acid ethyl ester. This is
evident on Figure 8b where there are small peaks detected in the chromatogram. The
sample used in the analysis was run under 40°C, 1:6 molar ratio of ethanol to oil and 80
minutes exposure to ozone. It was chosen to be the sample analyzed because it obtained the
highest from its specified parameter.
The biodiesel produced from ozonolysis was also compared with the gas
chromatogram results of other studies. The peaks detected for the result of gas
chromatogram by Purwanto et al. (2013) shows compounds that were common to the both
produced biodiesel.[11]

Optimization of Biodiesel Synthesis using Ozone

The optimal operating condition used for the synthesis of biodiesel was determined by the
highest percent yield of ethyl ester product from ozonolysis and transesterification
reactions. An experiment was done to confirm the effect obtained by optimization at 40°C,
1:6 molar ratio of ethanol to ozone and 80 minutes ozone exposure. Results reveal that the
percent yield of simultaneous transesterification and ozonolysis reaction increases by
1.89% from 90.33 to 92.22 percent.

ACKNOWLEDGMENT
The fulfillment of this thesis paper required the invaluable help of many different people,
in their different ways. The researchers would like to extend profound gratitude to the
following people who gave us the determination to pursue this study and to make it
possible. First and foremost to our considerate thesis adviser, ASEAN Engr. Eulalio C.
Creencia, to whom we are exceedingly thankful for his great efforts of supervising and
leading us to accomplish this fine work. To our mentors, Dr. Maria Sheila K. Ramos and
Engr. Ralf Ruffel Abarca, to whom we are thankful for their exemplary guidance and
support for helping us in choosing a research topic and for assisting us in our statistical
method used. And lastly to the MSU-IIT Chemistry Department, to which we are deeply
touched and grateful for their sincerity and kindness for giving us the opportunity of using
their newfangled Gas Chromatography equipment and generously providing us the free
expense of analyzing our samples.

CONCLUSION
This study had been successful in producing biodiesel from waste cooking oil by
transesterification and ozonolysis reactions. The use of RSM in determining the optimum
conditions was an effective method in studying the influence of the input variables on the
response variables. The use of RSM had also been both resourceful and time-saving since
the number of experimental runs was reduced. The chromatogram of ozonolysis product
revealed that the unsaturated fatty acid content of the used cooking oil was converted to
short chain fatty acid ethyl ester. The highest yield obtained for the transesterification
reaction (Response 1) was 88.5% at 60°C operating temperature and 1:4 molar ratio of
ethanol to oil. On the other hand, the highest yield for the ozonolysis reaction (Response 2)
was 90.33% at 40°C, 1:6 molar ratio of ethanol to oil and 80 minutes of exposure to ozone.

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