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0 History of biodiesel
Rudolf Diesel, the inventor of the first compression-ignition (CI) engine, once said that "the use
of vegetable oils for engine fuels may seem insignificant today but such oils may become, in the
course of time, as important as petroleum and the coal-tar products of the present time." He was
indeed right because nowadays biodiesel is one of the greatest alternative sources of renewable
fuel. The discovery of transesterification of 9 vegetable oil in 1853 by scientists E. Duffy and J.
Patrick gave way to the invention of biodiesel fuel. Rudolf Diesel's prime model, a single 10 ft (3
m) iron cylinder with a flywheel at its base, ran on its own power for the first time in Augsburg,
Germany on August 10, 1893. In remembrance of this event, August 10 has been declared
"International Biodiesel Day". This engine stood as an example of Diesel's vision because it was
powered by peanut oil a biofuel, though not biodiesel, since it was not transesterified. He
believed that the utilization of biomass fuel was the real future of his engine. In 1979, more than a
century later after the discovery of the first transesterification of vegetable oil, South Africa
initiated the use of transesterifi8ed sunflower oil, and refined it to diesel fuel standards, By 1983
the process for producing fuel-quality, engine-tested biodiesel was completed and published
internationally. An Austrian company, Gaskoks, obtained the technology from the South African
Agricultural Engineers; the company erected the first biodiesel pilot plant in November 1987, and
the first industrial-scale plant in April 1989 (with a capacity of 30,000 tons of rapeseed per annum).
Throughout the 1990s, plants were opened in many European countries, including the Czech
Republic, Germany and Sweden. France launched local production of biodiesel fuel (referred to
as diester) from rapeseed oil, which is mixed into regular diesel fuel at a level of 5%, and into the
diesel fuel used by some captive fleets (e.g. public transportation) at a level of 30%. During the
same period, nations in other parts of world also saw 10 local production of biodiesel starting up:
by 1998 the Austrian Biofuels Institute had identified 21 countries with commercial biodiesel
projects. In September of 2005 Minnesota became the first U.S. state to mandate that all diesel fuel
sold in the state contain part biodiesel, requiring a content of at least 2% biodiesel. In Asia,
Chemrez Technologies Inc. is the the biggest and most modern biodiesel facility, which started its
operation on May 2006. This biodiesel plant is actually located here in the Philippines, which in
fact manufactures coco-biodiesel in particular. Chemrez Technolologies Inc. produces 60, 000
metric tons of Bio-Active (the brand name of their coco-biodiesel) premium biodiesel per annum.
The first public recognition of transesterification technology became a patent asset on 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 earliest account of the production as well as the terminology
biodiesel. 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 Optimisation of
Conversion of Waste Cooking Oil into Biodiesel Page 9 of 80 and look set to injure the global
economy by triggering significant food inflation and the resultant poverty to vulnerable sways of
the populace. 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% traditional
diesel to maintain the performance of engines without alteration or 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 was then tested in 1986. [21]
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 cracked with
SiO2/Al2O3 as catalysts in experimentation in the course of 1993 [19]. Beef tallow was tested as
a source to make biodiesel using transesterification with methanol in 1994 [24]. Jackson and King
carbon dioxide with corn oil as the source in 1996[31]. Using enzymes as catalysts to alcoholise
soybean oil with methanol and ethanol was investigated commercially by Bernardes [25]. Japan,
as a country, has a scarcity of oil and other resources and Japanese scientists are therefore
is an effective and clean technology for transesterifying 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 is however still too costly for the commercial energy market.
Many other different vegetable oils and feedstocks have been explored by scientists as sources to
make biodiesel. Mustafa Balat et al., [3] 2008 compiled a clear and well organized table to describe
different vegetables main FFA contents in Energy Conversion and Management magazine in
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 medias
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 Optimisation
of Conversion of Waste Cooking Oil into Biodiesel Page 11 of 80 preparation specifications and
additives. Oil production, oilseed processing and extraction were also discussed at that meeting
[26]. 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 the lubrication oil every 4,000 - 4,500
miles. 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 precombustion
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 engines 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 Optimisation of Conversion of Waste Cooking Oil into Biodiesel Page 12 of 80
price of petroleum repeatedly hitting historical highs this year biodiesel production, 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 1 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 the outlay of making biodiesel with virgin vegetable oils. 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 companies then sell it on to customers
including biodiesel production companies according to sundry pricing policies. 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 consideration in coffee producing
2.1 biodiesel
2.1.1 Applications
Biodiesel can be used in pure form (B100) or may be blended with petroleum diesel at any
concentration in most modern diesel engines. It has higher lubricity index compared to petrodiesel
is an advantage and can contribute to longer fuel injector life. However, biodiesel is a better solvent
than petrodiesel, and has been known to break down deposits of residue in the fuel lines of vehicles
that have previously been run on petrodiesel. As a result, fuel filters and injectors may become
clogged with particulates if a quick transition to pure biodiesel is made, as biodiesel cleans the
engine in the process. It is, therefore, recommended to change the fuel filter within 600- 800 miles
after first switching to a biodiesel blend. 18 Pure unblended biodiesel can be poured straight into
the tank of any diesel vehicle. As with normal diesel, low-temperature biodiesel is sold during
winter months to prevent viscosity problems. Some older diesel engines still have natural rubber
parts which will be affected by biodiesel, but in practice these rubber parts should have been
replaced long ago. Biodiesel is used by millions of car owners in Europe (particularly Germany).
Research sponsored by petroleum producers has found petroleum diesel to be better for car engines
than biodiesel. This has been disputed by independent bodies, including for example the
Volkswagen environmental awareness division, who note that biodiesel reduces engine wear.
Biodiesel has also been noted to be linked to premature injection pump failures. While many
vehicles have been using biodiesel for many years without ill effect, the correlation between
several cases of pump failure and biodiesel cannot be dismissed. Pure biodiesel produced 'at home'
is in use by thousands of drivers who have not experienced failure, however. The fact remains that
biodiesel has been widely available at gas stations for less than a decade, and will hence carry
more risk than older fuels. Biodiesel sold publicly is held to high standards set by national
standards bodies.).
General Advantages
It has a higher gel point. B100 (100% biodiesel) gets slushy a little
under 32F. But B20 (20% biodiesel, 80% regular diesel - more
regular diesel, the gel point can be lowered further with additives
areas).
Some of the advantages of using biodiesel as a replacement for diesel fuel are
[14]:
Degrades more rapidly than diesel fuel, minimizing the environmental consequences
of biofuel spills.
Lower emissions of contaminants: carbon monoxide, particulate matter, polycyclic
May be blended with diesel fuel at any proportion; both fuels may be mixed
It is the only alternative fuel that can be used in a conventional diesel engine,
without modifications.
Used cooking oils and fat residues from meat processing may be used as raw
materials.
There are certain disadvantages of using biodiesel as a replacement for diesel fuel
that must be taken into consideration:
Slightly higher fuel consumption due to the lower calorific value of biodiesel.
Higher freezing point than diesel fuel. This may be inconvenient in cold
climates.
It is less stable than diesel fuel, and therefore long-term storage (more than six
May degrade plastic and natural rubber gaskets and hoses when used in pure
Teflon
components is recommended.
It dissolves the deposits of sediments and other contaminants from diesel fuel in
storage tanks and fuel lines, which then are flushed away by the biofuel into the
engine, where they can cause problems in the valves and injection systems. In
recommended.
this testing:
lower.
least 90%.
The properties of biodiesel can be grouped by multiple criteria. The most important are those that
influence the processes taking place in the engine (ignition qualities, ease of starting, formation
and burning of the fuel-air mixture, exhaust gas formation and quality www.intechopen.com
Biodiesel Quality, Standards and Properties 13 and the heating value, etc.), cold weather properties
(cloud point, pour point and cold filter plugging point), transport and depositing (oxidative and
hydrolytic stability, flash point, induction period, microbial contamination, filterability limit
temperature, etc.), wear of engine parts (lubricity, cleaning effect, viscosity, compatibility with
Quality is a prerequisite for the long-term success (successful use, without technical
problems) of a biofuel. Biodiesel quality depends on several factors that reflect its chemical and
physical characteristics. The quality of biodiesel can be influenced by a number of factors: the
quality of the feedstock; the fatty acid composition of the parent vegetable oil or animal fat; the
production process and the other materials used in this process; the postproduction parameters;
and the handling and storage. Given the fact that most current diesel engines are designed to be
powered by diesel fuel, the physicochemical properties of biodiesel should be similar to those of
diesel oil. This chapter presents the main standards on commercial biodiesel quality adopted in
different regions of the world and the importance and significance of the main properties that are
regulated (cetane number, density, viscosity, low-temperature performances, flash point, water
content, etc.) and unregulated (elemetal composition, fatty acid methyl and ethyl esters
composition, heating value, lubricity, etc.). Properties of fatty acid methyl and ethyl esters obtained
from different feedstocks1 are presented based mainly on data published in the specialized
Biodiesel standardization
The main criterion of biodiesel quality is the inclusion of its physical and chemical properties into
the requirements of the adequate standard. Quality standards for biodiesel are continuously
updated, due to the evolution of compression ignition engines, everstricter emission standards,
reevaluation of the eligibility of feedstocks used for the production of biodiesel, etc. The current
standards for regulating the quality of biodiesel on the market are based on a variety of factors
which vary from region to region, including characteristics of the existing diesel fuel standards,
the predominance of the types of diesel engines most common in the region, the emissions
regulations governing those engines, the development stage and the climatic properties of the
region/country where it is produced and/or used, and not least, the purpose and motivation for the
use of biodiesel (European Commission, 2007). In Europe the fleet of cars equipped with diesel
engines is considerable, while in the United States of America and Brazil diesel engines are
specifically used in trucks. The most common feedstocks used are rapeseed and sunflower oil in
Europe, soybean oil and waste vegetable oil in the USA and Canada, soybean oil in South America,
palm, jatropha and coconut oil in Asia, palm oil and soybean oil in Australia and waste vegetable
oil and animal fat in New Zealand. It is therefore not surprising that there are some significant
differences among the regional standards, a universal quality specification of biodiesel is, and will
be impossible. Table 1 presents a list of the most important biodiesel quality standards in the world,
while in Tables 2-9 specifications of the imposed limits for the main properties of biodiesel and
the required test methods are presented. Country/Area Specifications Title EU EN 14213 Heating
fuels - Fatty acid methyl esters (FAME) - Requirements and test methods EU EN 14214 EN 14214
Automotive fuels - Fatty acid methyl esters (FAME) for diesel engines - Requirements and test
methods U.S. ASTM D 6751 ASTM D6751 - 11a Standard Specification for B
The properties of biodiesel can be grouped by multiple criteria. The most important are those that
influence the processes taking place in the engine (ignition qualities, ease of starting, formation
and burning of the fuel-air mixture, exhaust gas formation and quality www.intechopen.com
Biodiesel Quality, Standards and Properties 13 and the heating value, etc.), cold weather properties
(cloud point, pour point and cold filter plugging point), transport and depositing (oxidative and
hydrolytic stability, flash point, induction period, microbial contamination, filterability limit
temperature, etc.), wear of engine parts (lubricity, cleaning effect, viscosity, compatibility with
Density of biodiesel
Fuel density () is the mass of unit volume, measured in a vacuum. Since density is strongly
influenced by temperature, the quality standards state the determination of density at 15 C. Fuel
density directly affects fuel performance, as some of the engine properties, such as cetane number,
heating value and viscosity are strongly connected to density. The density of the fuel also affects
the quality of atomization and combustion. As diesel engine fuel systems (the pump and the
injectors) meter the fuel by volume, modification of the density affects the fuel mass that reaches
the combustion chamber, and thus the energy content of the fuel dose, altering the fuel/air ratio
and the engines power. Knowing the density is also necessary in the manufacturing, storage,
account in the design of these processes. The density of esters depends on the molar mass, the free
fatty acid content, the water content www.intechopen.com 18 Biodiesel Quality, Emissions and
By-Products and the temperature. Density values determined for pure esters are presented in Table
14 and for different biodiesel feedstock are listed in Table 13. The density of biodiesel is typically
higher than that of diesel fuel and is dependent on fatty acid composition and purity. As biodiesel
is made up of a small number of methyl or ethyl esters that have very similar densities, the density
of biodiesel varies between tight limits. Contamination of the biodiesel significantly affects its
Viscosity of biodiesel
The viscosity of liquid fuels is their property to resist the relative movement tendency of their
composing layers due to intermolecular attraction forces (viscosity is the reverse of fluidity).
Viscosity is one of the most important properties of biodiesel. Viscosity influences the ease of
starting the engine, the spray quality, the size of the particles (drops), the penetration of the injected
jet and the quality of the fuel-air mixture combustion (Alptekin and Canakci 2009). Fuel viscosity
has both an upper and a lower limit. The fuel with a too low viscosity provides a very fine spray,
the drops having a very low mass and speed. This leads to insufficient penetration and the
formation of black smoke specific to combustion in the absence of oxygen (near the injector)
(Baga et al., 2003). A too viscous biodiesel leads to the formation of too big drops, which will
penetrate to the wall opposite to the injector. The cylinder surface being cold, it will interrupt the
combustion reaction and blue smoke will form (intermediate combustion product consisting of
aldehydes and acids with pungent odor) (Baga et al., 2003). Incomplete combustion results in
lower engine power. Too high viscosity leads to the increase of combustion chamber deposits and
the increase of the needed fuel pumping energy, as well as the increased wear of the pump and the
injector elements due to higher mechanical effort. Too high viscosity also causes operational
problems at low temperatures because the viscosity increases with decreasing temperature (for
influences the lubricity of the fuel as some elements of the fuel system can only be lubricated by
the fuel (pumps and injectors). Due to the presence of the electronegative oxygen, biodiesel is
more polar than diesel fuel; as a result, the viscosity of biodiesel is higher than that of diesel fuel.
The viscosity of pure ethyl esters are higher then viscosity of methyl esters (Table 14). The
Generally, all fuels for CIE may cause starting problems at low temperatures, due to worsening of
the fuels flow properties at those temperatures. The cause of these problems is the formation of
small crystals suspended in the liquid phase, which can clog fuel filters partially or totally. Because
of the sedimentation of these crystals on the inner walls of the fuel systems pipes, the flow section
through the pipes is reduced, causing poor engine fueling. In extreme situations, when low
temperatures persist longer (e.g. overnight), the fuel system can be completely blocked by the
solidified fuel. The cloud flow performances of the fuels can be characterized by the could point
(CP), the pour point (PP), the cold filter plugging point (CFPP) and viscosity (). An alternative
to CFPP is the low-temperature flow test (LTFT). Recently, the U.S. introduced a new method for
assessing the cold flow properties of biodiesel, called cold soak filtration test (CSFT).
The cloud point (CP) is the temperature at which crystals first start to form in the fuel. The cloud
point is reached when the temperature of the biodiesel is low enough to cause wax crystals to
precipitate. Initially, cooling temperatures cause the formation of the solid wax crystal nuclei that
are submicron in scale and invisible to the human eye. Further decrease of temperature causes
these crystals to grow. The temperature at which crystals become visible (the crystals diameter
0.5 m) is defined as the cloud point because the crystals form a cloudy suspension. Below the CP
these crystals might plug filters or drop to the bottom of a storage tank. The CP is the most
commonly used measure of low-temperature operability of the fuel. The biodiesel cloud point is
typically higher than the cloud point of conventional diesel. The cloud point of biodiesel depends
on the nature of the feedstock it was obtained from (Table 15) (Barabs & Todoru, 2010; Fan et
The pour point is the temperature at which the fuel contains so many agglomerated crystals that it
is essentially a gel and will no longer flow. This occurs if the temperature of the biodiesel drops
below CP, when the microcrystals merge and form large clusters, which may disrupt the flow of
the biodiesel through the pipes of the engines fuel system. Similarly to the cloud point, the pour
point values also depend on the feedstock the biodiesel was produced from (see Table 15). Pour
point values are between -15 C (REE and YMEE) and 16 C (PME). Although CP and PP are
relatively easily determined, they only provide indicative values for the minimum temperature at
which the fuel can be used. While at cloud point the fuel can still be used in acceptable conditions,
at pour point this is no longer possible. In other words, cloud point overestimates minimum
The flash point is the minimum temperature calculated to a barometric pressure of 101.3 kPa at
which the fuel will ignite (flash) on application of an ignition source under specified conditions. It
is used to classify fuels for transport, storage and distribution according to hazard level. The flash
point does not affect the combustion directly; higher values make fuels safer with regard to storage,
fuel handling and transportation. FP varies inversely with the fuels volatility. For biodiesel the
minimum flash point is 93 C in the United States, 100 C in Brazil and 120 C in Europe.
Biodiesels flash point decreases rapidly as the amount of residual (un-reacted) alcohol increases
(methanols flash point is 1112 C, and ethanols is 1314 C). Thus, measuring the biodiesel
flash point helps indicate the presence of methanol or ethanol. For example, the presence of 0.5%
methanol in biodiesel reduces biodiesel flash point from 170 C to 50 C. If flash point is used to
determine the methanol content, the ASTM standard imposes for it a minimum value of 130 C.
This limit may be considered too severe, because at the maximum permissible concentration of
methanol of 0.2% w/w biodiesel flash point drops below 130 C. The flash point of biodiesel
produced from various feedstocks are presented in Table 17 (Anastopoulos et al., 2009; Barabs
& Todoru, 2010; Barabs et al., 2010; Chuepeng &Komintarachat, 2010; Pinyaphong et al., 2011;
Acid value
The acid value (AV), also called neutralization number or acid number is the mass of potassium
hydroxide (KOH) in milligrams that is required to neutralize the acidic constituents in one gram
of sample. The acid value determination is used to quantify the presence of acid moieties in a
biodiesel sample. In a typical procedure, a known amount of sample dissolved in organic solvent
is titrated with a solution of potassium hydroxide with known concentration and with
residual mineral acids from the production process, 2) residual free fatty acid from the hydrolysis
process or the post- hydrolysis process of the esters and 3) oxidation byproducts in the form of
other organic acids (Berthiaume & Tremblay, 2006). This parameter is a direct measure of the
content of free fatty acids, thus the corrosiveness of the fuel, of filter clogging and the presence of
water in the biodiesel. A too high amount of free glycerin can cause functioning problems at
reduced temperatures and fuel filter clogging. This parameter can also be used to measure the
freshness of the biodiesel. Fuel that has oxidized after long-term storage will probably have a
Iodine value
The iodine value (IV) or iodine number was introduced in biodiesel quality standards for
evaluating their stability to oxidation. The IV is a measurement of total unsaturation of fatty acids
measured in g iodine/100 g of biodiesel sample, when formally adding iodine to the double bonds.
Biodiesel with high IV is easily oxidized in contact with air. The iodine value highly depends on
the nature and ester composition of the feedstocks used in biodiesel production. Therefore the IV
is limited in various regions of the world depending on the specific conditions: 120 in Europe and
Japan, 130 in Europe for biodiesel as heating oil, 140 in South Africa, in Brazil it is not limited
and in the U.S., Australia and India it is not included in the quality standard (it would exclude
feedstocks like sunflower and soybean oil). Biodiesel with high IV tends to polymerize and form
deposits on injector nozzles, piston rings and piston ring grooves. The tendency of polymerization
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
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].
Page 17 of 80
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
Transesterification is the general term used to describe the important class of organic reactions
where an ester is transformed into another through interchange of the alkoxy moiety. When the
original ester is reacted with an alcohol, the transesterification process is called alcoholysis
(Scheme 1)1. In this review, the term transesterification will be used as synonymous for alcoholysis
of carboxylic esters, in agreement with most publications in this field. The transesterification is an
equilibrium reaction and the transformation occurs essentially by mixing the reactants. However,
the presence of a catalyst (typically a strong acid or base) accelerates considerably the adjustment
of the equilibrium. In order to achieve a high yield of the ester, the alcohol has to be used in excess.
The applicability of transesterification is not restricted to laboratory scale. Several relevant
industrial processes use this reaction to produce different types of compounds1. An example is the
catalyst (Scheme 2)2. Furthermore, a large number of acrylic acid derivatives is produced by
transesterification of methyl acrylate with different alcohols, in the presence of acid catalysts3-6.
If the alcohol and the ester groups are present in the same molecule simple lactones7,8 or
transesterification reactions can be found in the literature, in which metal alkoxides11-16, aluminum
catalysts.
Transesterification of Vegetable Oils
In the transesterification of vegetable oils, a triglyceride reacts with an alcohol in the presence of
a strong acid or base, producing a mixture of fatty acids alkyl esters and glycerol25,26 (Scheme 4).
The overall process is a sequence of three consecutive and reversible reactions, in which di- and
triglyceride and 3 mol of the alcohol. However, an excess of the alcohol is used to increase the
yields of the alkyl esters and to allow its phase separation from the glycerol formed.
Several aspects, including the type of catalyst (alkaline or acid), alcohol/vegetable oil molar ratio,
temperature, purity of the reactants (mainly water content) and free fatty acid content have an
influence on the course of the transesterification and will be discussed below, based on the type of
catalyst used.
Acid-Catalyzed Processes
sulfuric acids26,28,29. These catalysts give very high yields in alkyl esters, but the reactions are slow,
requiring, tipically, temperatures above 100 C and more than 3 h to reach complete conversion30.
Pryde et al.26 showed that the methanolysis of soybean oil, in the presence of 1 mol% of H2SO4,
with an alcohol/oil molar ratio of 30:1 at 65 C, takes 50 h to reach complete conversion of the
vegetable oil (> 99%), while the butanolysis (at 117 C) and ethanolysis (at 78 C), using the same
The alcohol/vegetable oil molar ratio is one of the main factors that influences the
transesterification. An excess of the alcohol favors the formation of the products. On the other
hand, an excessive amount of alcohol makes the recovery of the glycerol difficult, so that the ideal
for a monoglyceride. However, it can be extended to di- and triglycerides31. The protonation of the
carbonyl group of the ester leads to the carbocation II which, after a nucleophilic attack of the
alcohol, produces the tetrahedral intermediate III, which eliminates glycerol to form the new ester
According to this mechanism, carboxylic acids can be formed by reaction of the carbocation II
with water present in the reaction mixture. This suggests that an acid-catalyzed transesterification
should be carried out in the absence of water, in order to avoid the competitive formation of
Base-Catalyzed Processes
The base-catalyzed transesterification of vegetable oils proceeds faster than the acid-catalyzed
reaction26,30. Due to this reason, together with the fact that the alkaline catalysts are less corrosives
than acidic compounds, industrial processes usually favor base catalysts, such as alkaline metal
The first step (Eq. 1) is the reaction of the base with the alcohol, producing an alkoxide and the
protonated catalyst. The nucleophilic attack of the alkoxide at the carbonyl group of the
triglyceride generates a tetrahedral intermediate (Eq. 2)11,40, from which the alkyl ester and the
corresponding anion of the diglyceride are formed (Eq. 3). The latter deprotonates the catalyst,
thus regenerating the active species (Eq. 4), which is now able to react with a second molecule of
the alcohol, starting another catalytic cycle. Diglycerides and monoglycerides are converted by the
they give very high yields (> 98%) in short reaction times (30 min) even if they are applied at low
molar concentrations (0.5 mol%). However, they require the absence of water which makes them
inappropriate for typical industrial processes30. Alkaline metal hydroxides (KOH and NaOH) are
cheaper than metal alkoxides, but less active. Nevertheless, they are a good alternative since they
can give the same high conversions of vegetable oils just by increasing the catalyst concentration
to 1 or 2 mol%. However, even if a water-free alcohol/oil mixture is used, some water is produced
in the system by the reaction of the hydroxide with the alcohol. The presence of water gives rise
to hydrolysis of some of the produced ester, with consequent soap formation (Scheme 7). This
undesirable saponification reaction reduces the ester yields and considerably difficults the recovery
Potassium carbonate, used in a concentration of 2 or 3 mol% gives high yields of fatty acid alkyl
esters and reduces the soap formation38. This can be explained by the formation of bicarbonate
instead of water (Scheme 8), which does not hydrolyse the esters.
heterogenize them on organic polymers. Schuchardt et al. tested principally cellulose and
poly(styrene/divinylbenzene), but also polyuretanes and other organic polymers allow the suitable
incorporation of guanidines. The heterogenization of guanidines on organic polymers and their use
microcrystalline cellulose activated by cyanuric chloride at the C-6 position (Scheme 11). After
deprotonation of the guanidinium salt formed, the guanidine-containing cellulose shows a slightly
reduced activity, compared to guanidine in homogeneous phase, giving a conversion of 30% after
1 h, when used at 5 mol%68. This guanidine-containing cellulose was used in a continuous reactor
containing 100 g of the catalyst. An alcohol/oil mixture of 2:1 was pumped at 60 C with a rate of
0.48 L/h. In the first hour the methyl esters were obtained with high yields and the phase separation
was quick69. After this, however, the reaction was incomplete and the phase separation difficult.
This could be due either to leaching of the catalyst or to its irreversible protonation. As no leaching
polystyrenes was investigated70. The guanidine-containing polymers (Scheme 12) were used in the
transesterification of soybean oil with methanol in several consecutive catalytic cycles. The
and II) showed a slightly lower activity than their homogeneous analogues but allowed the same
high conversions after prolonged reaction times. However, they slowly leached from the polymers,
allowing only nine catalytic cycles. The guanidines heterogenized on linear polystyrene with the
use of a 'spacer-arm' (polymers III, IV), were less active. Polymer V, which is symmetrically
substituted showed an activity as high as polymer I. When another methyl group was introduced
(polymer VI) its activity was slightly reduced. Furthermore, all polymers with a 'spacer-arm'
suffered substitution reactions during the recycling experiments to form inactive hexasubstituted
guanidinium compounds. A summary of the catalytic performance of these polymers is shown in
Table 4.
The lower activity of the guanidine-containing polymers I and II, when compared to their
homogeneous analogues, is probably due to the hydrophobicity of the polymer chain which
reduces the concentration of the methanol at the active sites. However, at prolonged reaction times,
the efficiency of the anchored catalysts is practically the same. The use of a 'spacer-arm' (polymers
III-VI) was expected to improve the performance of the heterogenized catalyst. However, polymer
IV showed the same activity as polymer II and polymer III was even less active than polymer I70.
Despite less active than their homogeneous analogues, all polymer-containing guanidines could
be reused in several consecutive reaction cycles70. However, a loss of activity was observed,
mainly due to leaching of the anchored base from the polymers, as mentioned above. Polymers I
and II have the guanidine moiety bound to the benzylic CH2 group of the polystyrene. After the
protonation of the base, the electrophilic character of the methylene group is increased, thus
becoming more susceptible to nucleophilic attack by methoxide ions present in the reaction
medium. This attack results in the removal of the guanidine moiety from the polymer as shown in
Scheme 13. The leaching of the guanidines from the other polymers follows a similar mechanism.
For the polymers containing a 'spacer-arm', there is an additional factor that accelerates the
deactivation of the supported catalysts. The anchored bases can react with electrophilic functional
groups which are further away on the polymer chain, producing inactive hexasubstituted
hexasubstituted guanidinium compounds, which should give doubly anchored active guanidines
activity in the addition reaction of benzaldehyde to acetone71. However, its activity in the
transesterification of vegetable oils is low (14% conversion after 5 h72), as the diffusion of the
triglycerides through the channels of the Y zeolite is slow due to steric hindrance.
Characteristics of Alcohols Used in Biodiesel Production Alcohols that can be used in biodiesel
production are those with short chains, including methanol, ethanol, butanol, and amylic alcohol.
The most widely used alcohols are methanol (CH3OH) and ethanol (C2H5OH) because of their
low cost and properties. Methanol is often preferred to ethanol in spite of its high toxicity because
its use in biodiesel production requires simpler technology; excess alcohol may be recovered at a
low cost and higher reaction speeds are reached. The comparison between the two alcohols is
summarized in Box 2.2. It must be remembered that in order for biodiesel to be a fully renewable
fuel, it should be obtained from vegetable oils and animal fats, together with an alcohol that is
produced from biomass, such as bioethanol, instead of being a petrochemical product. Several
countries are carrying out research towards this objective, such as Spain and Brazil. H C OH H C
2.3 Biodiesel Production Process Biodiesel is produced from vegetable oils or animal fats and an
alcohol, through a transesterification reaction [1, 2, 4, 5]. This chemical reaction converts an ester
(vegetable oil or animal fat) into a mixture of esters of the fatty acids that makes up the oil (or fat).
Biodiesel is obtained from the purification of the mixture of fatty acid methyl esters (FAME). A
catalyst is used to accelerate the reaction (Fig. 2.5). According to the catalyst used,
transesterification can be basic, acidic or enzymatic, the former being the most frequently used, as
indicated in Box 2.3. A generic transesterification reaction is presented in Eq. (2.1); RCOOR0
mixture and cat a catalyst: RCOOR0 R00OH , cat R0 OH RCOOR00 2:1 When methanol
is the alcohol used in the transesterification process, the product of the reaction is a mixture of
methyl esters; similarly, if ethanol were Box 2.2 Most Important Alcohols Used in Biodiesel
Production Methanol. Most widely used, in spite of its toxicity. It is a substance of petrochemical
origin. Ethanol. Less used, requires more complex production technology and the reaction speeds
Alcohol-catalyst mixing
Chemical reaction
The content of free fatty acids, water and non-saponificable substances are key parameters to
achieve high conversion efficiency in the transesterification reaction. The use of basic catalysts in
triglycerides with high content of free fatty acids is not advisable [18], since part of the latter reacts
with the catalyst to form soaps. In consequence, part of the catalyst is spent, and it is no longer
available for transesterification. In summary the efficiency of the reaction diminishes with the
increase of the acidity of the oil; basic transesterification is viable if the content of free fatty acids
(FFAs) is less than 2%. In the case of highly acidic raw materials (animal fats from cattle, poultry,
pork; vegetable oils from cotton, coconut, most used oils, etc.) an acid transesterification [19] is
necessary as a preliminary stage, to reduce the level of FFAs to the above-mentioned value.
Besides having low humidity and acid content, it is important that the oil presents a low level of
non-saponificable substances. If the latter were to be present in significant amounts and soluble in
biodiesel, it would reduce the level of esters in the product, making it difficult to comply with the
minimum ester content required by the standards. The AOCS standards [20] list the required
properties of oils. Anyway, the properties required by the oils are finally determined by the
biodiesel industry in each country. For instance, in Argentina the oils for biodiesel production
usually have: Acidity level \0.1 mg KOH/g Humidity \500 ppm Peroxide index\10 meq/kg
Alcohol-Catalyst Mixing
The alcohol used for biodiesel production must be mixed with the catalyst before adding the oil.
The mixture is stirred until the catalyst is completely dissolved in the alcohol. It must be noted that
the alcohol must be water-free (anhydrous) for the reasons explained in the previous paragraph.
Sodium and potassium hydroxides are among the most widely used basic catalysts. For production
Of course, due caution must be exercised, and all applicable safety regulations must be followed,
when working with methanol, hydroxides and methoxides, independently of the production scale.
The alcohol-to-oil volume ratio, R, is another key variable of the transesteri- fication process. The
stoichiometric ratio (Fig. 2.5) requires 1 mol of oil to react with 3 mol of alcohol, to obtain 3 mol
of fatty acids methyl esters (FAME) and 1 mol of glycerin. However, since the reaction is
reversible, excess alcohol as a reactant will shift the equilibrium to the right side of the equation,
increasing the amount of products (as it may be inferred from Le Chateliers principle). Although
a high alcohol-to-oil ratio does not alter the properties of FAME, it will make the separation of
biodiesel from glycerin more difficult, since it will increase the solubility of the former in the latter.
Usually, a 100% alcohol excess is used in practice, that is, 6 mol of alcohol per mole of oil. This
corresponds to a 1:4 alcohol-to-oil volume ratio (R = 0.25). The relation between the dielectric
properties of FAME and the alcohol-to-oil ratio, R, will be discussed in Chap. 7. Finally, it must
be noted that the necessary amount of catalyst is determined taking into account the acidity of the
oil, by titration.
Chemical Reaction
The chemical reaction takes place when the oil is mixed with the alkoxide (alcoholcatalyst mix)
described in the previous paragraph. This requires certain conditions [17, 21] of time, temperature
and stirring. Since alcohols and oils do not mix at room temperature, the chemical reaction is
usually carried out at a higher temperature and under continuous stirring, to increase the mass
transfer between the phases. Usually, emulsions form during the course of the reaction; these are
much easier and quicker to destabilize when methanol is used, in comparison to ethanol [22]. Due
to the greater stability of emulsions formed, difficulties arise in the phase separation and
purification of biodiesel when ethanol is used in the reaction. The transesterification process may
be carried out at different temperatures. For the same reaction time, the conversion is greater at
higher temperatures. Since the boiling point of methanol is approximately 68C (341 K), the
temperature for transesterification at atmospheric pressure is usually in the range between 50 and
60C. It is very useful to know the chemical composition of the mixture during the reaction; then,
if the reaction mechanism and kinetics are known, the process can be optimized. However, the
determination of the mixture composition is not easy, since more than a hundred substances are
known to be present [23]. For instance, for biodiesel production from rapeseed oil (whose main
SFAs are palmitic, oleic, linoleic and linolenic) and methanol, with potassium hydroxide as a
water, etc. The studies on this subject [24, 25] indicate the following general guidelines: For
longer reaction times, the concentration of triglycerides diminishes the concentration of esters,
increases and the concentration of mono- and diglycerides increases to a maximum and then
decreases. Most of the chemical reaction takes place during the first minutes. The absence of
mono- and diglycerides at the beginning of the chemical reaction and the increase and reduction
of their concentration during the reaction confirm that the production of esters from the
triglycerides takes place in three steps, as represented in the equations below: TG MOH ! KOH
MOH indicates methanol, ME are the methyl esters, TG, DG and MG are tri-, di- and
Several methods, with different levels of equipment complexity and training requirements, have
been devised to analyze samples that are mixtures of fatty acids and esters from mono-, di-, and
triglycerides obtained from transesterification of vegetable oils. A list is presented in Box. 2.5. It
must be noted that thin layer chromatography (TLC) provides essentially qualitative information
about the sample composition, as distinct from the other methods in Box 2.5, that can be used for
quantitative analysis. However, the simplicity, speed and low cost of TLC make it quite attractive
as a technique for process optimization and routine checks, especially in small- and medium-scale
Catalysts
The catalysts used for the transesterification of triglycerides may be classified as basic, acid or
enzymatic, as indicated in Box 2.3 [38, 39]. Basic catalysts include sodium hydroxide (NaOH),
potassium hydroxide (KOH), carbonates and their corresponding alcoxides (for instance, sodium
methoxide or ethoxide). There are many references on basic catalysts in the scientific literature
[26, 4051]. Acid catalysts include sulfuric acid, sulfonic acids and hydrochloric acid; their use
has been less studied [26, 5257]. Heterogeneous catalysts that have been considered for biodiesel
production include enzymes [39], titanium silicates [58], and compounds from alkaline earth
metals [59], anion exchange resins [59] and guanidines in organic polymers [60]. Lipases are the
The separation of reaction products takes place by decantation: the mixture of fatty acids methyl
esters (FAME) separates from glycerin forming two phases, since they have different densities;
the two phases begin to form immediately after the stirring of the mixture is stopped. Due to their
different chemical affinities, most of the catalyst and excess alcohol will concentrate in the lower
phase (glycerin), while most of the mono-, di-, and triglycerides will concentrate in the upper phase
(FAME). Once the interphase is clearly and completely defined, the two phases may be physically
separated. It must be noted that if decantation takes place due to the action of gravity alone, it will
take several hours to complete. This constitutes a bottleneck in the production process, and in
consequence the exit stream from the transesterification reactor is split into several containers.
Centrifugation is a faster, albeit more expensive alternative. After the separation of glycerin, the
FAME mixture contains impurities such as remnants of alcohol, catalyst and mono-, di-, and
triglycerides. These impurities confer undesirable characteristics to FAME, for instance, increased
cloud point and pour point, lower flash point, etc. In consequence a purification process is
necessary for the final product to comply with standards. This will be discussed in the next section.
Purification of the Reaction Products
The mixture of fatty acids methyl esters (FAME) obtained from the transesteri- fication reaction
must be purified in order to comply with established quality standards for biodiesel. Therefore,
FAME must be washed, neutralized and dried. Successive washing steps with water remove the
remains of methanol, catalyst and glycerin, since these contaminants are water-soluble. Care must
be taken to avoid the formation of emulsions during the washing steps, since they would reduce
the efficiency of the process. The first washing step is carried out with acidified water, to neutralize
the mixture of esters. Then, two additional washing steps are made with water only. Finally the
traces of water must be eliminated by a drying step. After drying, the purified product is ready for
process described above is the use of ion exchange resins or silicates. Glycerin as obtained from
the chemical reaction is not of high quality and has no commercial value. Therefore, it must be
purified after the phase separation. This is not economically viable in small scale production, due
to the small glycerin yield. However, purification is a very interesting alternative for large-scale
production plants, since, in addition to the high quality glycerin, part of the methanol is recovered
for reutilization in the transesterification reaction (both from FAME and glycerin), and thus
lowering biodiesel production costs. The steady increase of biodiesel production is fostering
research for novel uses of glycerin in the production of high-value-added products. It must be
noted that the stages of the biodiesel production process (summarized in Box 2.4) are the same for
all the production scales (laboratory, pilot plant, 22 2 Introduction to Biodiesel Production small-
, medium-, and large-scale industrial). However, the necessary equipment will be significantly
different [2].
2.4 Plam kernel oil as a feedstock for Biodiesel Production
Oil palm [11] is a tropical plant that reaches a height of 2025 m with a life cycle of about 25
years. Full production is reached 8 years after planting. Two kinds of oil are obtained from the
fruit: palm oil proper, from the pulp, and palm kernel oil, from the nut of the fruit (after oil
extraction, palm kernel cake is used as livestock food). Several high oil-yield varieties have been
developed. Indonesia and Malaysia are the leading producers. International demand for palm oil
has increased steadily during the past years, the oil being used for cooking, and as a raw material
for margarine production and as an additive for butter and bakery products. It is important to
remark that pure palm oil is semisolid at room temperature (2022C), and in many applications is
Palm kernel oil (PKO) is one lauric vegetable oil (Table I) in Nigeria, which had hitherto been
underutilized as edible oil. Available records however ranked Nigeria as one of the world
producers of palm kernel. Between 1995 and 1998, Nigerias share in the world production of
palm kernel were 0.27, 0.26 and 0.25 million metric ton for 1995/96, 1996/97 and 1997/98
production seasons respectively. This record placed Nigeria next to Malaysia and Indonesia, and
ahead of PKO producing countries like Cote divore, Colombia, Thailand, Zaire and Equador
(Alamu et al., 2007a, b). Limited studies were however found in the literature on production and
testing of biodiesel from Nigerian lauric oils. Abigor et al. (2000) produced biodiesel from palm
kernel oil and coconut oil by transesterification of the oils with different alcohols using PS30 lipase
catalyst. From a few recent works published on this subject, potassium hydroxide catalyst was
used for the transesterification process (Alamu et al., 2007a, b; Alamu et al., 2008). In this work,
biodiesel was produced through transesterification of PKO with ethanol using NaOH (alkali)
catalyst. The PKO biodiesel produced was further characterized as alternative diesel fuel through
ASTM standard tests for basic fuel properties such as specific gravity, viscosity, pour point and
cloud point.
Characterization of Catalyzed