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Optimization of Conversion of Waste Cooking Oil Into Biodiesel
Optimization of Conversion of Waste Cooking Oil Into Biodiesel
into Biodiesel
MACIVER.
dustinchen@gmail.com
Also Blue Apple Biodiesel Company for the supply of waste cooking oil as well as
Abstract……………………..……………………………………………… page 6
Introductory…………….…………….……………………………………. page 8
1. Literature review…….………………………………………………….…page 8
1.2 Concise Documentary Research of Biodiesel from 1937 till Present….…. page 8
2.1 Why Biodiesel can be used as Surrogate Fuel for Diesel Engines……….. page 15
2.4 Advantages and Limitations of both Virgin Vegetable Oils and Waste Cooking Oils
Project…………………………………………………………………………page 20
Project - Why GC and Relative Viscosity and other Parameters are chosen to Evaluate
2. Equipment………………………………………………………………… page 26
11.2 Safety…………………………………………………………………….page 36
11.4 GC analysis………………………………………………………………page 37
5.1 Calibration curves and equations for the three methyl esters…………... page 52
5.2 The calibration equations generated by Excel above were used to calculate the
concentration of each of biodiesel sample and concentration data are listed in the tables
6 IR experiment……………………………………………………………. page 68
Conclusion……………………………………………………………… page 74
Optimized method of biodiesel production using waste cooking oil was achieved and is
References……………………………………………………………… page 77
Waste cooking oil with high free fatty acid content was used as the feedstock for
laboratory biodiesel production. In the optimised production method acidic value was
measured using the BP method before water was removed by heating it to 35°C and
The conversion of the free fatty acid and triglyceride into methyl esters was performed
in two stages:
1. The first stage was acidic esterification. Between 0.5 and 1.0% of free fatty
acid by weight of sulphuric acid was used as an acidic catalyst. Between 1:15
and 1:30 molar ratio of free fatty acid and methanol was mixed and heated to
finish the acidic esterification stage. The free fatty acid was converted to
methyl esters.
Between 1:6 and 1:10 molar ratio of triglyceride was mixed with methanol,
The amounts of sulphuric acid, sodium hydroxide and methanol were variables which
were controlled in examining the conversion rate of methyl esters. The optimized
method was obtained by monitoring the concentrations of total methyl esters in the
biodiesel samples. Viscosity and cloud point were important properties of the
using biodiesel samples from a local company as the control group and comparing
them to lab biodiesel samples. Minitab's 2 samples t test was used as the statistic
method to evaluate the important properties of cloud point, relative viscosity and
1. Literature review
Biodiesel vegetable oils, animal fats and used cooking oil; mostly including
triglycerides and free fatty acid and other small amounts of impurities [5].
Historically, since the diesel engine inventor Rudolf Diesel [4] used peanut oil as his
machine’s first fuel supply, there have been many trials to use plant oils as biofuel
notably during World War II. In some countries vegetable oils were used as
conducted as early as 1853 by scientists E. Duffy and J. Patrick [4], many years before
Present
31st August 1937 when G. Chavanne of the University of Brussels (Belgium) [4] was
granted a patent licence for the alcoholysis (aka transesterification) of vegetable oils
using ethanol or methanol with the purpose of separating the fatty acids from the
glycerol by means of replacing the glycerol with short linear alcohols. It was the
The petroleum crisis of the 1970s was the first point in time when energy prices hit the
global economy and this phenomenon was repeated in the early 1990s and again in the
present day. [10] On 17th June 2008 oil prices soared to over 140 US dollars per barrel
More recently, in 1982 during the oil embargo on South Africa, it was reported in
Brazil that Caterpillar had made use of a 10% mix of vegetable oils along with 90%
adjustment [22].
In 1983 rapeseed oil was studied as a contemporary alternative to diesel fuel due to its
high yield of oil (45%). [20]. A blend of 25% sunflower oil and 75% of fossil diesel
Schwab et al. used safflower oil as biodiesel in 1988 using pyrolysis technology; the
components produced being determined by GC-MS [23]. Copra oil and palm oil were
Beef tallow was tested as a source to make biodiesel using transesterification with
methanol in 1994 [24]. Jackson and King reported a direct metholysis of triglycerides
using an immobilized lipase in flowing supercritical carbon dioxide with corn oil as the
source in 1996[31].
Using enzymes as catalysts to alcoholise soybean oil with methanol and ethanol was
Japan, as a country, has a scarcity of oil and other resources and Japanese scientists are
vegetable oils into biodiesel. The water and free fatty acids contents do not greatly
affect the soap formation which is a negative factor in the viscosity of biodiesel. This
sources to make biodiesel. Mustafa Balat et al., [3] 2008 compiled a clear and well
Vegetable oil Palmitic Stearic Palmitoleic Oleic Linolei Ricinic 12- Other
16:0 18:0 16:1 18:1 c 18:2 OH-oleic acids
Tallow 29.0 24.5 - 44.5 - - -
Coconut oil 5.0 3.0 - 6.0 - - 65.0
Olive oil 14.6 - - 75.4 10.0 - -
Groundnut oil 8.5 6.0 - 51.6 26.0 - -
Cotton oil 28.6 0.9 0.1 13.0 57.2 - 0.02
Corn oil 6.0 2.0 - 44.0 48.0 - -
Soybean oil 11.0 2.0 - 20.0 64.0 - 3.0
Hazelnut kernel 4.9 2.6 0.2 81.4 10.5 - 0.3
Poppy seed 12.6 4.0 0.1 22.3 60.2 - 0.8
Rapeseed 3.5 0.9 0.1 54.1 22.3 - 9.1
Safflower seed 7.3 1.9 0.1 13.5 77.0 - 0.2
Sunflower seed 6.4 2.9 0.1 17.7 72.8 - 0.1
Castor oil - 3.0 3.0 3.0 1.2 89.5 0.3
Investigating vegetable oils to make biodiesel has been pursued for almost a century
now and the first actual use of biodiesel was reported in 1937 in the Belgian Congo.
Chavanne, made ethyl ester of palm oil using acid as a catalyst. However since the
first energy crisis came to the media’s attention in late 1970s more considerable
research has been carried out on vegetable oils as diesel fuel. The first International
Conference on Plant and Vegetable Oils as fuels was organised in Gargo, North
Dakota in August 1982. The primary concerns discussed were the cost of making
biodiesel, the effects of biodiesel on engine performance & durability and biodiesel
A diesel fleet was powered by filtered frying oil by Anon in 1982 when a mix of 95%
used cooking oil and 5% diesel fuel were tested. Records show that there were no
coking or carbon build-up problems with the engines except that the lubricating oil
became contaminated. The researchers later concluded that it was beneficial to change
There have been more recent experiments of biodiesel usage in diesel engines. In 1983,
degummed and dewaxed sunflower oils were tested using a single cylinder pre-
combustion chamber engine [27]. The long term performance was monitored using a
fuel blend of 75% unrefined mechanically expelled soybean oil and 25% diesel fuel
but this failed after 90 hours of engine run due to a 670% increase in the lubricating oil
viscosity [28]. Schelick et al. evaluated a 2.59 L, 3 cylinder 2600 series Ford diesel
engine’s performance with soybean and sunflower oil mixed with number 2 diesel at
the ratio of 25:75 by volume; the engine worked constantly throughout the 200 hour
assessment. However carbon deposits on all combustion chamber parts were recorded
as overly high and so prohibited the use of this blend of diesel fuel. Soybean oil was
thermally decomposed and distilled in air and nitrogen sparged with standard ASTM
distillation equipment to lower the viscosity [23]. Still later, a new catalytic procedure
for the cracking of vegetable oils to produce biodiesel fuels was studied [19].
There has been considerable development of more advanced technology and theories in
biodiesel production although most of this has been used for commercial purposes.
Biodiesel production has increasingly and has steadily been promoted since the early
1990s as a means to respond to the fast growing levels of energy demand. With the
technology and research will become more important around the world.
Yet in real commercial practice there are still huge barriers to biodiesel technology for
practical use. Almost all the experiments and commercial production show that the
cost of biodiesel is between 1½ and four times the cost of conventional diesel. The
main barrier is the expense of the plant oils which normally account for 65 - 90% of
the overall cost of biodiesel production. Mounting food price inflation will only add to
In recent years many researchers have employed different approaches to reduce the
cost of sources used to make biodiesel and seek alternatives to virgin plant oils. In
Germany, due to recycling laws and regulations, it is relatively cheap and efficient to
make biodiesel with waste cooking oils. This approach hugely cuts the cost in making
biodiesel. Some research papers claim that using waste cooking oil could cut the price
from 75% of the total cost down to around 20%. In America there are some recycling
companies which collect and process waste cooking oil and they classify this oil as
yellow grease and brown grease based loosely on how much FFA it contains. These
Leandro et al. in 2007 [11] produced some research on using defective coffee beans in
labs as a cheap source to make biodiesel and this technology may be worthy of further
commercial proposition.
Production
recent decades and this places the biodiesel business in an encouraging position for
many environmental friendly policies, countries and industries. Efforts have been
(EBB), [12]. Germany is the prime mover with over 50% of the total EU production
[13]. Brazil and United States are another two important players in the biodiesel
industry. Two factors have led the EU to become the world leader in biodiesel
production; [14]. One is the reform of the Common Agricultural Policy (CAP), a
supranational and domestically oriented farm policy for EU member countries, adopted
in 1992 and implemented in 1993-1994[15]. The second factor is high fuel taxes which
have enabled indirect subsidies for biofuel production through limited or full
exemption of the fuel excise tax. In February 1994 the European Parliament adopted a
renewable sources such as new and or used vegetable oils (yellow grease), animal fats
(brown grease); sources which can be generated in large quantities annually. Various
studies show that fossil fuels might be depleted in the next 100 years at present
Unlike the EU most biodiesel made in the United States is from virgin plant oils such
as rapeseed, sunflower seed and soybean. Rapeseed oil is probably the most widely
used source since it is planted extensively in farms in the United States and research
has shown that there is a low percentage of free fatty acid contained in rapeseed oil
which is a positive factor for producing good quality biodiesel. Some RBD (refined,
bleached and deodorized) [18] virgin plant oils are understood to contain less than
0.5% of free fatty acid and this makes it an ideal source for producing good quality
biodiesel. However, using virgin plant oils raises questions over food price inflation
and the impact on global hunger. Food price inflation leads to more expensive
While the United States mainly uses virgin oils the European Union predominately
exploits used cooking oil and animal fats to make biodiesel. Reportedly Germany has
the largest biodiesel industry with an estimated 43% of the world’s production in 2006.
German production jumped from 1·67 to 2·66 million tons between 2005 and 2006
when it was estimated that 42% of the world’s total biodiesel production was
accounted for by the country [3]. Other EU countries have also significantly increased
production including France, Italy and the United Kingdom. There are EU laws and
regulations for classification and for collections of different recycled wastes and these
make it easier to collect cleaner used cooking oil which should contain less free fatty
Marine algae came to note as a biodiesel production source due primarily to their
economical farming cost and reduced competition with plant land thus lessening any
fatty acid composition of ten marine algae from Australian waters [29]. It was reported
TLC, GC-MS technologies were used to separate and determine the free fatty acid
content after the treatment with H2S and appropriate work up conditions to convert
fatty acid to methyl esters. Donghui Song et al., investigated oil bearing microalgae
for biodiesel production and suggested in their conclusions that algae breeding farms
should strengthen their trade with oil refining companies[30]. These conclusions also
2.1 Why Biodiesel can be used as Surrogate Fuel for Diesel Engines
and cleaner fuel. Some research has been reported in the Biodiesel Production
magazine. In that report they concluded that biodiesel’s overall lifecycle emissions of
carbon dioxide (a major greenhouse gas) from biodiesel are 78% lower than from
petroleum diesel. Also, overall emissions of carbon monoxide were likewise reduced
by 35%. The study also found that biodiesel reduces the sulphur oxides (major
components of acid rain) which are 8% lower than from traditional diesel. Many other
as surrogate diesel energy is that their viscosity and energy efficiency ratios are
engines in vehicles. However there are still a few barriers to using biodiesel as routine
diesel (whose cloud point is also higher than petroleum) so in cold climates biodiesel
might gel and interfere with the engine functioning. The other main drawback is that
biodiesel viscosity is higher than that of diesel so the tank injection of vehicles and
some other small parts might need to be maintained more regularly to reduce poor
functional performance.
Considerable efforts have been made to develop derivatives of vegetable and animal
fat oils which approximate the physiochemical properties of conventional diesel. Most
vegetable and animal oils without proper derivatization would have much higher
viscosity than fossil diesel and this renders it impossible to use as fuel in diesel engines
the viscosity of the biodiesel production. In fact transesterification is one of the four
main methods to reduce the viscosity of vegetable oils. The other three major
derivatives of vegetable oils as diesel fuels have also been developed and studied.
ethanol; 25% of sunflower oil and 75% of diesel were blended as diesel [8].
the compounds of shorter chain alkanes, alkenes carboxylic acids etc, which
with a short chain alcohol in order to derivatize the triglycerides and fatty acid
The main components of biodiesel are free fatty acid methyl esters which are
derivatized from free fatty acids. The most common free fatty acids in soybean oil and
animal fats are palmitic(16:0), stearic, (18:0), oleic, (18:1), linoleic (18:2) and linolenic
(18:3). There is much less free fatty acid content in virgin vegetable oils and some
rapeseed oil contains less than 0.5%. The highest percentage of oil content in
vegetables is triglyceride; also termed as triolein. Free fatty acids and water content
are two major negative factors to producing good quality biodiesel as they promote
formation soaps and gels when employing basic catalysts. Manufacturers therefore
prefer to use virgin oil such as rapeseed to make biodiesel due to its consistent quality
and because only a single basic transesterification process is needed and it becomes
When making biodiesel from cooking oils or animal fats a major challenge is their
relative high content of free fatty acids which easily form soap and gel making
separation of the product and free fatty acids difficult. It can also have an effect on the
For waste cooking oil to make biodiesel there is one more step needed after water
removal - either the free fatty acid is distilled or it is derivatized to methyl esters by
acidic esterification:
Virgin vegetable oils are more widely used in biodiesel production because of their
comparative consistent quality compared to animal fat or waste cooking oil. Its
is its high cost which leads to the biodiesel price of about 1.5 to 3 times that of fossil
Animal fat and waste cooking oils seem more viable due to their meagre cost however
they contain more water and free fatty acid (some up to 50%) [1]which makes their
Water has to be removed from feedstock, then acidic esterification is used to derivatize
free fatty acid to methyl esters, then basic transesterification is used to derivatize
triglycerides into methyl esters and glycerol. Feedstock such as waste cooking oil
quality is not consistent and may contain many other impurities which make this
continuously produce biodiesel in industry using low grade waste cooking oil as
feedstock. The quality control of this type of product is variable since it involves more
steps to transesterify the triglyceride and free fatty acid into methyl ester. This is a
Although there are more complex steps in producing biodiesel from waste cooking oil
it is possible to improve the quality of the end product by optimizing the production
process. For a certain biodiesel company which has a stable feedstock supply it is
possible to design a standard operation procedure to control the quality of the biodiesel
There has been little research published on the optimization of the biodiesel production
method for quality control in industrial practice. This is the main rationale in carrying
A foolproof method to make good economic biodiesel with waste cooking oil was
a) Water removal: heat the waste cooking oil to about 60 deg C in a settling tank
oil, and mix with 1 ml of 95% H2SO4 by 1 litre of oil - heat and stir then let the
c) Basic transesterification: mix 1 litre of oil with 2.6% v/m sodium methoxide
d) The reaction solution separates into two obvious layers. The top layer is
usually yellow or light brown colour methyl ester. The bottom layer is dark
brown colour and is mostly triglycerine with other minor components such as
biodiesel produced. Then settle for 24 hours until the biodiesel turns a light
yellow colour
The optimization process of this foolproof method to make biodiesel was designed to
separating free fatty acid esters because free fatty acids are volatile under the high
temperature oven and capillary column. GC has excellent separation power because of
the long narrow column. So, even with many impurities existing in the production
from waste cooking oil, it shows a clear narrow peak which is very accurate and is
Infrared (IR) technology is also used to identify the different test batches and so
The monitoring of free fatty acid value can be done before the acidic transesterification
process e.g. according to BP titration method and is helpful to calculate how much
Batch production would be needed to control the quality of the final biodiesel product.
The aims and objectives of this research were to optimize this simple foolproof method
research can be carried out; a standard operating procedure (SOP) could be configured
In this research the biodiesel production method was mainly based on the one provided
by Aleks Kac at the link mentioned above. [1] However some reliable technology
sources were also referenced from Biodiesel Production Technology released by the
National Renewable Energy Laboratory operated for the U.S. Department of Energy
Office of Energy Efficiency and Renewable Energy. That report was published
During preparatory study using other research papers it was evident that several
variations were fundamental to optimise biodiesel production. These included the use
of different basic catalysts, molar ratio of methanol to oil and proper temperature
control.
spectrometry. The purpose and objective of this project was to evaluate the
reproducibility of this batch biodiesel production method and to optimize it with some
Methyl ester concentration and viscosity are two important parameters to evaluate the
biodiesel production samples in this method. The gas chromatography machine was
used with eight different methyl esters including palmitic, stearic, oleic, linoleic and
linolenic. The GC results of these standard methyl esters helped to identify the methyl
esters in the biodiesel batches. Standards also help to determine the concentration of
the methyl esters in the lab biodiesel. The concentration levels of methyl esters gave
an idea of the conversion rate of the waste cooking oil into methyl esters and by
comparing different batches it could be concluded which method was the optimized
The relative viscosity of the different batches of biodiesel were tested and the results
measured against each other and also compared to the results from the Apple Fuels
biodiesel company samples. This company’s customer base is mainly taxi drivers who
are often concerned about engine performance when using the product. Viscosity is
1. Materials
Waste cooking oils were provided by the Apple Fuels biodiesel company of
Glasgow. These were obtained from local eateries such as fish & chip shops
HPLC grade ethyl acetate and 95-98% sulphuric acid were provided by the
Sigma-Aldrich Company Ltd, The Old Brickyard New Road, Gillinghan SP8
Gas chromatography was carried out using a Hewlett Packard 5890 series II instrument
fitted with an AS800 autosampler and a FID detector. The instrument was fitted with a
Rtx Stabiliwax column 30 m x 0.25 mm i.d. x 0.25µm film (Thames Restek, UK).
The following GC conditions were used: Oven on equilibrium time: 0.5 min., injector
230 °C, detector 250 °C, FID detection frequency: 10 Hz, Runtime: 22 min. Oven
2.2 IR Spectrometry:
Heating blocks were provided by Corning Hot Plate and Bibby Sterilin Ltd.
A viscosity measuring U tube was from Volac Brand, serial no 5925 BS.U. M3.
Flasks, magnet stirring bars and thermometer were provided by Strathclyde University
After eliminating the solid non oil contaminants the waste oil was put in a deep V
shape settling flask and heated to a temperature of approximately 60 deg C which was
maintained for 30 minutes. This was then left to settle for 24 hours to allow the water
present in the sample to mass at the bottom of the flask. This action helped to
maximize the useful oil and 10% at the bottom of the flask was always discarded to
The acid value of the waste cooking oil was determined in order to estimate the free
fatty acid content and give an idea of how much acid catalyst and methanol would be
needed to push the acid esterification chemical towards methyl ester production. In
earlier published research it was recommended that 0.5 - 1.5% (based on the weight of
free fatty acid in the oil) of pure (95-98%) sulphuric acid should be used as a catalyst.
Acid value titration method was used according to BP monograph. The method is
described here:
neutralise the free fatty acid in 1g of the substance when determined by the
of the substance being examined (10g) and was mixed with 50 ml of a mixture
of equal volumes of ethanol (96%) and ether which had been neutralised with
indicator. When the substance was completely dissolved it was titrated with
volume, in ml, of potassium hydroxide solution required and w was the weight,
in g of substance taken.
5.Preparation of Biodiesel
For each production batch of biodiesel in these experiments about 100ml of waste
cooking oil was used in a conical flask with a tight fitting stopper.
The waste oil was heated to 35 deg C on the laboratory heating block until all the
solids liquefied and the temperature was then maintained between 35 and 50 deg C.
Sulphuric acid (95 – 98%) was used in the batches at levels varying between 0.1ml and
0.3ml per100ml oil. In the opening few experiments the sulphuric acid was first added
to the oil but this technique scorched some of the oil and discoloured it to a dark brown.
Earlier research had suggested that this could reduce the catalytic function so, in later
experiments, the sulphuric acid was first mixed with methanol before adding to the
waste cooking oil. After adding the methanol / sulphuric acid solution to the waste
cooking oil magnetic stirring bars were used to mix the solvents until they became
murky. This was then heated to about 35 deg C for between 1 and 2 hours. Stirring
continued throughout this process and for a further hour before the mix was left to
settle overnight.
esterification stage was maintained at 0.5 to 1.5% of the free fatty content by weight as
It was suggested in previously published research papers that the methanol to oil molar
ratio was best between 10:1 to 40:1 and that 80ml of methanol was used per litre of oil.
However no mention was made of the amount of free fatty acid which might be
contained in the spent cooking oils which fluctuated a great deal due the varying
Other variables which could impinge on the outcome include heat and mixing. A
higher temperature or a faster stirring rate may push the acidic esterification equation
Methanol can be absorbed through skin and can damage the eyes and clothing.
Evaporation of methanol could also affect the acidic esterification process as well as
polluting the laboratory atmosphere and causing harm to personnel. Care was
therefore taken to properly and securely fit the stopper to the flask.
95-98% sulphuric acid is a highly corrosive substance so protective glasses were worn
when carrying out these experiments and a running water source was nearby.
Great care was taken to steer clear of the heating blocks and the wearing of protective
a. Weigh 15.035g of sodium hydroxide and mix with 500ml of HPLC grade pure
methanol in a 500ml flask, then the ultra sonic bath was used to assist in the
concentration for this sodium methoxide stock solution was 30.1mg of sodium
b. Sodium hydroxide (20.06 g) was weighed and mixed with 500ml of HPLC
grade methanol in a 500 ml flask, and then ultra sonic was used to dissolve the
sodium hydroxide in the solvent for 30 minutes. Concentration for this sodium
c. Sodium hydroxide (13.335 g) was weighed and mixed with 250ml of HPLC
grade pure methanol in a 250 ml flask, and then ultra sonic was used to dissolve
the sodium hydroxide in the solvent for 30 minutes. The concentration for this
methanol.
d. Potassium hydroxide (4.218g) was weighed and mixed with 100ml of HPLC
grade pure methanol in a 100 ml flask, and then ultra sonication was used to
1) Each batch of oil mixture was heated to temperatures which were controlled
between 55 and 70 deg C for the whole of this basic transesterification stage.
for another ½ to 2 hours using the same lowest speed of the magnetic stirring
bars to facilitate the settling of biodiesel and glycerine layers while settling.
6. Methanol Recovery
In order to keep the costs to a minimum it was decided to recover the un-reacted
methanol from the biodiesel. A Rotavapor R-3000 was used to evaporate the un-
reacted methanol and running water generated the vacuum condition in the pipe of the
the flask of biodiesel was rotated at a constant slow speed. Three lots of un-reacted
methanol were reclaimed taking between 20 and 30 minutes to finish each methanol
recovery process.
7. Separation
Following the basic transesterification process and any methanol evaporation the
resultant biodiesels were left to lie for at least 8 hours or, in the main, overnight.
Separation funnels were used to separate the top (methyl ester) and bottom (glycerol)
layers of the biodiesel samples. Two layers could clearly be seen in the successful
basic transesterified biodiesel samples. The top layer was mainly composed of free
fatty acid methyl esters. The bottom deposit was mostly made up of glycerol, salts,
soap, other impurities and excess methanol as it is a very polar compound i.e. it
partitions more with polar glycerol as opposed to the non-polar methyl esters. The
density of the methyl esters is less than the bottom glycerol and soap etc layer.
1ml of 10% phosphoric acid was added to one of the biodiesel samples in an attempt to
neutralize the excess basic catalyst in the oil. This was to facilitate the extraction of
the glycerol in the bottom layer for recycling purposes. This was not of significance in
this project as the quantities of the test samples were too small and made it impractical
to collect the glycerol from the bottom layer. There would also have been many
The top methyl ester layer was separated and removed from every production sample.
The water washing process was then used on some of the biodiesel batches. Only one
of the biodiesel samples was neutralised with 10% phosphoric acid as the original
One part water was used with three parts of the top layer (methyl esters) biodiesel for
washing. Warm water was used to help combat formation of any solids as the cloud
9. Viscosity Tests
After the washing process, a viscosity U tube was used to measure the relative
thickness of the biodiesel samples. A dropper was used to transfer each biodiesel test
sample to this U shaped tube which was filled to the same mark for each analysis. It
was then noted exactly how long it took for the sample to drop to a lower mark through
a capillary pipe connecting to the opposite side of the U tube. This time was the
quoted relative viscosity value. All the biodiesel samples were subject to this test and
the control group was a sample from the local Glasgow biodiesel company. The
shorter the time taken to drop to the low mark, the lesser the sample’s relative viscosity.
The viscosity U tube has similar characteristics to an hourglass so the resultant values
cannot be assumed to be absolute. Even so, care should be taken to make best use of
the resource. This can be achieved by standardising the fixing of the U tube at the
same position, in a regular temperature and, if possible, in the water bath tank. The
information obtained was relative data; used to compare the comparative viscosity of
standards for biodiesel quality and more precise testing apparatus is available for the
manufacturing situation.
Cloud point might reflect two important properties of biodiesel. A high cloud point
could be caused by too much saturated fatty acid methyl ester in biodiesel. It may
additionally be more stable in storage and have a reduced probability for oxidization.
However it invariably creates additional problems for many diesel engines. Larger
amounts of saturated fatty acid methyl esters in biodiesel raises the cloud point and it
can easily clog the diesel engine and injection cylinder resulting in a machine with
cloud point for this project. The biodiesel samples were moved to flasks which were
set in large beakers full of ice. A thermometer was used to monitor the point when
crystals of biodiesel formed and that temperature was recorded. There may be some
inaccuracy with this method of measuring the cloud point because the test was carried
readings.
Biodiesel samples from the local Glasgow biodiesel company were used as the control
group to compare the biodiesel samples made in batches of waste cooking oil in the
laboratory.
The basic production method for biodiesel using waste cooking oil was acquired from
http://journeytoforever.org/biodiesel_aleksnew.html
Ten weeks of experiments were carried out with the objective to optimize biodiesel
production from waste cooking oil based on this particular method. Several important
variables were reviewed and monitored for the purpose of working out a definite and
reliable method to recycle the discarded cooking oil and provide functional biodiesel.
The spent cooking oils had been collected from various eateries, fish and chip shops,
Chinese restaurants etc. The waste oils had been pre-treated by basic filtering to
reduce contaminants.
solutions were prepared and completely dissolved then left to settle overnight before
their use for basic transesterification. The application of this alkali methoxide was
biodiesel production.
Sodium methoxide (CH3ONa) was chosen ahead of sodium hydroxide (NaOH) and
11.2 Safety
Sodium hydroxide and potassium hydroxide pellets are highly caustic substances.
Methanol can be absorbed through the skin and is a serious contaminant to eyes
therefore a lab coat, gloves and protective glasses must be worn when preparing these
Several variables were adjusted and monitored during each minor modification in order
to optimize the method. Experience gained from this experiment was that warm water
was beneficial for bathing the biodiesel oil before separating with the funnel. Because
there is too much saturated free fatty acid methyl esters in the oil samples the bottom
layer can easily become solid even at room temperature after settling for a long time.
It would be difficult to separate the top and bottom layers with the funnel once it partly
solidified. Both the top and bottom layers of each biodiesel sample were stored in
optimize the method. However this could not be strictly and accurately managed due
to heating block limitations. Likewise in some production batches heating and stirring
Potassium methoxide was used in just one of the batch biodiesel production samples.
The processes using the potassium methoxide were exactly the same as for the sodium
11.4 GC Analysis
Using GC 8 different free fatty acid methyl esters were identified according to their
retention time which was based on their molecular weight (table 2).
Before testing any of the biodiesel samples a repeat (x5) injection of the same free fatty
acid methyl ester standard solution was run to test precision. Then a five point
calibration series of eight free fatty acid methyl esters mixed standard solution was also
run to test the reliability of the GC performance and accuracy. Microsoft Excel was
methanol,
were trickled into the mixture oil and the sample was then examined using the GC.
The major free fatty acid methyl esters peak areas were monitored in the GC
chromatogram. This monitoring finished at the point when there was no change in
peak area reading of the GC machine. It was assumed that the reaction reached its
During the basic transesterification stage different batches of biodiesel production were
amounts of soap and gel formation which made the biodiesel/glycerol layers difficult
to separate. The remaining 24 samples were seen with a clear liquid top layer which
indicated biodiesel since its density was lower than the bottom layer which contained
order to achieve a better conversion rate of biodiesel from waste cooking oil. After
each measured change of these variants every biodiesel sample was run with GC. Peak
areas of major methyl esters were collected and compared to previous runs until there
was no growth in the peak area value. This indicated that the conversion rate of waste
runs were used to monitor the optimization of the biodiesel production method.
Sequence runs were set up in every GC run through the GC machine operating
software ChromQuest version 3.0. The vial labels were double checked and
coordinated with the ChromQuest sequence run order control and the positions on the
GC injection panel.
As a standard operational procedure that a blank and the mixed methyl esters standard
solutions should be run prior to analysing every batch of biodiesel sample solution on
the GC machine. In this research project both mixed standard methyl esters solutions
and biodiesel sample solutions from the local biodiesel company were used as control
groups.
The mixed standard methyl esters solution was used to help identify the methyl esters
in the biodiesel samples based on their retention time under the same GC method and
conditions. A calibration series was also run for the purpose of quantification of the
Biodiesel samples from the numerous experiments were tested using a Jasco-4200
FTIR with Pike Technologies MIRACLE IR machine. The samples were tested under
Diamond ATR condition and, since they were in liquid state, these tests were used to
identify the free fatty acid methyl esters. There was an inadequate amount of standard
free fatty acid methyl esters for IR test in this project so IR spectrometry of standard
methyl esters was acquired from the chemistry reference book Beilstein. The results
In the report published by National Renewable Energy Laboratory for the U.S.
comprised of mono-alkyl esters of long chain fatty acids derived from vegetable oils or
Biodiesel can be used as B100 which means pure 100% alcoholised mono alkyl esters
of long chain fatty acid. It can be blended with conventional diesel when a mix of 20%
biodiesel with 80% fossil diesel is termed B20. A combination of 5% biodiesel with
organization which has set the property requirements, testing criteria and quality
control methods for biodiesel B100. This is known as ASTM6751 [2] and some of the
Water and sediment is a test which determines the volume of free water and
range 1.0 to 4.1 mm2/s and densities in the range of 700 to 900 kg/m3.
Sulphated ash is the residue remaining after a sample has been carbonized.
The storage stability standard for B100 is still in the development stage within the
ASTM process.
The acid values of different feedstock sources were tested and, during this project, the
parameters below were monitored to evaluate the quality of the biodiesel lab batches,
30 batches consisting of 100ml of waste cooking oil were produced in the experiments.
27 batches produced biodiesel but 3 were unsuccessful due to excessive soap formation
In the results and discussion section the biodiesel samples made in the lab were
labelled as:
labelled:
Acid values of the waste cooking oils were tested according to BP monograph. Most
of the batches were from the same oil source with the exception of those labelled 6A,
The acid values were percentages, by weight, of free fatty acid in the waste cooking oil
feedstock. This was a good indicator in calculating how much acidic catalyst was
0.5% and 1.5% of the weight of the free fatty acid as amount of acidic catalyst was
used in the acidic esterification stage in the biodiesel production from used cooking oil.
It was important to calculate the free fatty acid content before the acidic esterification
stage because the waste cooking oil quality varied greatly from batch to batch.
Previous experiments showed up to 50% content of free fatty acid in the waste cooking
catalyst needed for different feedstocks can be calculated based on acid value [1].
At this stage the correct amount of acidic catalyst, in proportion to the amount of free
fatty acid methyl esters, was crucial to optimising the production of quality biodiesel
3.Cloud point
Cloud point: is the temperature at which a cloud of wax crystals first appears in a
liquid when it is cooled down under conditions prescribed in this test method. This
Batch 1A 1B 1C 1D 2A 2B 3A 3B 4A
Cloud point 11°C 12°C 11°C 12°C 12°C 12°C 11°C 12°C 11°C
Batch 4B 4C 5A 5B 6A 6B 6C 6D 7A
Cloud point 12°C 11°C 11°C 12°C 11°C 12°C 13°C 13°C 11°C
Batch 8A 8B 8C 8D 8E 9A 9B 9C 9D
Cloud point 11°C 12°C 11°C 12°C 11°C 11°C 12°C 12°C 11°C
Batch 10A S1 S2 S3 S4 S5
Cloud point 11°C 10°C 11°C 11°C 11°C 12°C
Table 5: Cloud point of lab biodiesel group classed into 3 groups (°C)
Tables 5 and 6 above show that the mean value of the biodiesel batches cloud point
was slightly different from that of the local biodiesel company’s control group samples
How the cloud point of different groups of biodiesel would affect the performance of
Minitab statistical software was used to calculate the cloud points of the biodiesel
samples made in the lab and compare them with the control group samples from the
13.0
12.5
12.0
Data
11.5
11.0
10.5
10.0
Two-Sample T-Test and CI: cloud point lab Batches biodiesel, cloud point
Controlled group
Using the 5% level, the value of 2.571 was found in the t-table under column 0.025 and
across row DF=5. Since t=1.69 does lie in the range -2.571 to +2.571 we conclude that
the result was not significant. The mean cloud point of controlled group biodiesel
samples and lab batches biodiesel samples may well be the same.
The cloud points of two failed biodiesel samples were not tested as excessive soap
The cloud point experiments were controlled manually using constant equipment and
conditions. However there was room for uncontrolled errors such as variations in
room temperature, deviations in test times and system errors with the thermometer etc.
The number of unsaturated free fatty acid chains in the biodiesel should affect the
cloud point readings; the more unsaturated chain fatty acid esters in the biodiesel the
lower the cloud point. This was confirmed by the biodiesel samples from the local
methyl stearate (18:1) compared to the other lab biodiesel production samples.
Waste cooking oil which has been heated to a high temperature has a higher proportion
by weight of polymers than virgin vegetable oil and this can affect the cloud point of
the final product; more polymers result in a higher cloud point. This is why 90% of
industrial biodiesel is manufactured from virgin vegetable oil and diesel from used
4.Relative Viscosity
A U tube was the equipment used to measure the relative viscosity. The time taken for
the biodiesel to drop to the same mark on the U tube was measured in minutes and
seconds as the measure of relative viscosity. Both the controlled group of biodiesel
This experiment’s readings were relative and not absolute values. The purpose of the
Batch 1A 1B 1C 1D 2A 2B 3A 3B 4A
Relative viscosity 13’56” 12’26” 12’25” 12’03” 11’51” 12’35” 12’30” 14’06” 12’17”
Batch 4B 4C 5A 5B 6A 6B 6C 6D 7A
Relative viscosity 12’28” 11’34” 12’02” 13’16” 13’31” 11’35” 9’38” 9’23” 8’18”
Batch 8A 8B 8C 8D 8E 9A 9B 9C 9D
Relative viscosity 10’59” 10’58” 9’09” failed 10’23” 12’05” 11’15” 12’04 9’24”
Batch 10A S1 S2 S3 S4 S5
Relative viscosity 10’14” 12’39” 11’21” 13’03” 12’35” 11’57”
The relative viscosity data for both groups were analysed by Minitab
14
13
12
Data
11
10
batches produced in the lab was lower than the mean value of relative viscosity of
90 Mean StDev N AD P
12.16 0.6556 6 0.373 0.288
80 11.36 1.436 26 0.648 0.081
70
Percent
60
50
40
30
20
10
1
6 8 10 12 14 16
Data
The trend in the plot is roughly linear and most of the data lies within the confidence
Variable Q3 Maximum
On close examination, using the 5% level, the value of 2.11 was found in the t-table
under column 0.025 and across row DF=17. Since t=2.06 does lie in the range -2.11 to
+2.11 we conclude that the result was not significant. The mean relative viscosities of
controlled group biodiesel samples and lab biodiesel samples may well be the same.
Based on the measured mean value it was clear that the lab biodiesel batches had
marginally better viscosity test results. A concern over the results from the local
biodiesel company samples was the relative small number of tests; more samples being
Viscosity of the biodiesel is closely related to the concentration of the methyl esters.
Higher levels of methyl esters concentration resulted in better conversion rates of used
cooking oil into biodiesel. Also, high content of unsaturated fatty acids in the biodiesel
lowered the viscosity. In some of the biodiesel samples excess methanol was not
evaporated; this might possibly reduce the relative viscosity reading as well. It is
commonly accepted that methanol is a very polar molecule so most of the excess
methanol would be partitioned to the bottom layer of glycerine instead of the top
chains in the biodiesel; the more unsaturated free fatty acid chain in biodiesel the less
time for the relative viscosity measurement. In a small number of published research
revealed the correlation between the conversion rate of biodiesel production using
waste cooking oil and its viscosity. Viscosity monitoring can play an important role in
The type of methyl esters in used cooking oil derived biodiesel can fluctuate because
the quality of feedstock varies from batch to batch. There were also some polymer
triglycerides formed during high temperature cooking which were difficult to detect by
research papers noted that these polymer forms of triglyceride can be hard to alcoholise
into alkyl esters. In every biodiesel sample tested with GC there were three peaks
identified by testing an 8 standard methyl esters mixture using the same GC method
according their retention time. Three identified methyl esters were methyl palmitate
(C16:0), methyl stearate (C18:0) and methyl oleate (C18:1). There were some other
small peaks present in the gas chromatogram but these were ignored as insignificant.
For the convenience of quantification only these three methyl esters concentrations
were determined and compared. These three peaks of methyl palmitate (C16:0),
methyl stearate (C18:0), and methyl oleate (C18:0) were monitored in GC and used to
evaluate the optimization method of the biodiesel production. The three peak area
readings were converted into concentrations with calibration curves prepared using
up their total value was assumed to indicate the degree of conversion of free fatty acid
and triglyceride into methyl esters. The concentrations from the controlled group were
The optimized method of biodiesel production using waste cooking oils was obtained
by monitoring the methyl esters’ peak area with GC runs. In order to get precise and
convincing results every biodiesel sample solution concentration prepared for GC was
within the range of the calibration curve. The biodiesel sample solutions were diluted
with HPLC grade ethyl acetate solvent before they were run in the GC machine.
Calibration equations were then used to determine the actual concentration of the
5.1 Calibration curves and equations for the three methyl esters
The calibration curves were plotted for the three methyl esters. They were found to be
linear over the range 0.25-1 mg/ml. The calibration curves are shown in figures 3-5
and the data used to plot the curves is given in tables 8-10.
600000
500000
peak area
400000
300000
200000
100000
0
0 0.2 0.4 0.6 0.8 1 1.2
concentration
Optimisation of Conversion of Waste Cooking Oil into Biodiesel
Page 53 of 80
5.1.3 Methyl stearate (18:0) calibration equation
600000
500000
peak area
400000
300000
200000
100000
0
0 0.2 0.4 0.6 0.8 1 1.2
concentration
Table 13: Concentration of methyl esters of biodiesel samples from local company.
Control Group
Biodiesel C16:0 (mg/ml) C18:0 (mg/ml) C18:1 (mg/ml) Total (mg/ml)
Figure 12: Biodiesel sample 1 (controlled group from local company) gas
chromatography (4.375mg/ml)
equation. Then concentration of the three methyl esters were summed and used for
comparison with other samples. It was evident that the amounts of 16:0 were higher in
the test batches which had high levels of free fatty acid. It was apparent that only 70-
80% of the composition of the oil could be accounted for by methyl esters. Both
mathematical and statistical methods were used to evaluate the optimized method of
The total concentrations of methyl esters were compared after the acidic esterification,
0.8
c
o 0.7
n
c 0.6
e
n 0.5
t
0.4
r
a 0.3
t
i 0.2
o
n 0.1
0
C 16:0(mg/ml) C 18:0(mg/ml) C 18:1(mg/ml) total(mg/ml)
Acidic esterification stage 0.0053 0.0044 0.001 0.0107
Basic transesterification stage 0.0798 0.0662 0.0981 0.2441
Optimized stage 0.2625 0.2112 0.3025 0.7742
from table 15 and figure 16 above. After each of the three stages of biodiesel
production all the samples were monitored with GC. These results demonstrate that
the optimized method had the highest conversion rate. There were only small amounts
of methyl esters created after the acidic esterification stage and the conversion rate of
methyl esters after the basic transesterification from the original method was also
unsatisfactory. This is deduced from the readings and more statistical evaluation will
be discussed later.
The relative conversion rate of methyl esters at the optimized stage was assumed to be
Table 17: Methyl esters concentration after the acidic esterification stage (group
labelled as conc1)
labeled as conc2)
Table 19: Methyl esters concentration after optimized method stage (group labelled as
conc3)
Minitab statistical software was used to evaluate the different groups of data above.
Using the 5% level, the value of 12.706 was found in the t-table under column 0.025
and across row DF=1. Since t=-9.98 does lie in the range -12.706to +12.706 we
of biodiesel samples after acidic esterification and biodiesel samples after the original
Using the 5% level the value of 3.182 was found in the t-table under column 0.025 and
across row DF=1. Since t=-40.71 does not lie in the range -3.182 to +3.182 we
conclude that the result was significant. The mean concentration of methyl esters of
biodiesel samples after acidic esterification and biodiesel samples after optimized
and across row DF=1. Since t=-15.33 does not lie in the range -12.076 to +12.076 we
conclude that the result was significant. The mean concentration of methyl esters of
biodiesel samples after basic transesterification and biodiesel samples after optimized
Minitab was used as statistic software to evaluate the two data groups in table 18.
Median
0.69140
0.75255
Variable Q3 Maximum
0.85
0.80
Data
0.75
0.70
0.65
0.60
controlled group lab batches
90 Mean StDev N AD P
0.6923 0.01651 5 0.189 0.796
80 0.7545 0.04743 24 0.534 0.154
70
Percent
60
50
40
30
20
10
1
0.60 0.65 0.70 0.75 0.80 0.85 0.90
Data
Both boxplot and probability plot of two groups showed the data was normally
distributed. 2 sample t-test was used to evaluate the lab experiment results.
Using the 5% level, the value of 2.093 was found in the t-table under column 0.025 and
across row DF=19. Since t=-5.11 does not lie in the range -2.093 to +2.093 we
controlled group biodiesel samples and lab batches biodiesel samples was not the same;
the yield of methyl esters was higher in the batches prepared in the lab using the
optimised method.
6 IR Experiment
Every biodiesel sample was examined with the IR machine; the finger print region of
the IR spectrum was compared for each biodiesel sample. All the peaks of the bands in
the 900-1500cm-1 region were carefully checked and compared. They were very
similar between samples and along with the GC identification run based on standard
methyl esters, it is possible to be confident that these materials can be identified as the
Rovatary evaporation was used to remove any excess methanol in the lab produced
biodiesel samples. Excess methanol was evaporated of three lab biodiesel samples.
Rovac was set at the condition: water bath temperature at 55°C, rotate at 100rpm
evaporation time 30 minutes. A balance was used to weigh the difference of the
Table 21: Weight difference of biodiesel samples before and after evaporation
The data in table 21 shows that more excess methanol was evaporated from biodiesel
sample 2B and 3B. These results matched with the low conversion rate of methyl
esters based on the GC experiments when lower conversion rates resulted in greater
Some of the other biodiesel samples were evaporated and unexpectedly turned solid.
More methanol was mixed with these solid biodiesel samples and stirred however they
This problem had been discussed and explored in earlier research papers. One
possibility was that, because the saturated methyl esters take over the majority of
biodiesel even at room temperature after evaporating the surplus methanol. This
hypothesis raises the prospect for further research in order to explain the formation of
solid biodiesel at room temperature. Alternatively the saturated methyl esters may
exist in different polymorphic forms and heating interconverts between a low melting
and a high melting form. Such a conversion might have implications for long term
storage.
production
Table 22 shows some of the variations in the production methodology along with the
yield of fatty acid methyl esters in the samples. The table was reordered according to
the values of total methyl esters concentrations in the right column. The best yield of
methyl esters may not reflect the optimised method as other factors such as methanol
requirement may reduce the viability. There was clearly a best possible set of
cooking oil
There were thirty biodiesel samples produced and three of these failed due to excessive
soap formation leading to low methyl esters conversion rates and an excess of gel
made it difficult to separate the top and bottom layers. It was thought that the cause for
this unsuccessful biodiesel production very likely occurred during the acidic
used during the acidic esterification stage for every 100 ml of waste cooking oil but,
noticeably, this method did not work properly because of too much soap development.
Based on the optimised method, developed later, it was recommended that at least 12
ml of methanol for every 100 ml of waste cooking oil feedstock should be used at this
stage. Despite this three production samples still failed, possibly, due equipment
limitations resulting in them not being heated or stirred accurately. This could be the
Three groups of methyl esters were analysed by GC for their methyl esters
concentration:
Minitab’s 2 samples t-test method was used to evaluate the results and, according to
the statistic assessment, we can conclude that the optimized stage of biodiesel
production produced a better conversion rate of methyl esters than the other two stages.
Five controlled group samples and twenty four lab produced samples of biodiesel were
studied for their important properties such as cloud point and relative viscosity using
Minitab statistical software. The data was analysed with 2 sample t-test and the results
sample groups.
The methyl esters concentration of controlled groups and lab groups biodiesel were
their methyl esters concentration. NaOH as a basic catalyst generated a better methyl
esters conversion rate than KOH. We can conclude that the optimised method of lab
biodiesel production group has a better methyl esters conversion rate than the current
commercial method. The balance of the composition was the main unresolved issue
resolved by NMR.
Step1: Examine the acid value of waste cooking oil feedstock using BP method;
Step 2: Heat the waste cooking oil (100ml) to 60°C and maintain the temperature for
about half an hour then settle the oil over night to eradicate water
Step 3: Acidic esterification stage: Heat the oil to between 35 and 45°C; add 0.5-
1.0% by weight of free fatty acid (calculated by step one) of sulphuric acid to the oil
(100ml). Then add 1:15 to1:20 molar ratio of oil to methanol to the heated oil while
constantly stirring at the speed about 500 rpm. Keep heating for at least an hour before
Step 5: Basic esterification. Heat the mixed oil to 60°C. Add first half of 16 - 18%
by weight of waste cooking oil of sodium methoxide to the oil. Maintain the heat
while stirring at a slower speed for 5 minutes. Then add another half of sodium
methoxide. Maintain heat while stirring for another 30 to 60 minutes before turning
Step 6: Separate the top layer and bottom layer with a separating funnel
Step 7: Washing: Use warm water of one third the volume of biodiesel and wash
three times before letting the biodiesel settle for future use.
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Balat Sila Science and Energy Unlimited Company, University Mahallesi, Tranbzon,
November 2001Fuels
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