Chapter 18

Biodiesel

The energy in biomass doesn’t come for free, you have to use
fertilizers. You have the plowing of the field and even by plowing
the field you will need power. I have read that for 1 hectare 100
liters of diesel will be needed. If the scope of the land is the
production of biodiesel, 1/10 will be lost just for the plowing of
the field.
Michel Hartmut, Nobel Prize in Chemistry in 1988.

18.1 Fundamentals of Biodiesel Production

Biodiesel is sometimes considered as a renewable transportation fuel, and it is nor-

mally produced from vegetable oils and animal fats even if it can be produced from
other sources such as waste cooking oils (Phan and Phan 2008). Biodiesel is consist-
ing of fatty acid methyl esters (FAME) (Hoekman et al. 2012) and because of this
composition required, it will be more understood why they are produced by vegetable
oils. In the following explanations, the author of this book encourages the reader in
considering also more advanced textbooks of organic chemistry (Jones and Fleming
2014) in order to understand the terminology used here.
Vegetable oils present a series of positive aspects that make them suitable for
biodiesel production. More in particular:
• are rich in neutral triacylglycerols (TAG);
• can be rich in free fatty acids (FFA).
Non-conventional sources of these two categories of compounds are, for instance,
non-edible vegetable oils (for instance, Jatropha oil and Polanga oil) or animal fat
wastes (AFWs) (Pollardo et al. 2018) (for instance, chicken fat and white grease).
These feedstocks are characterized with high free fatty acids and water.
As mentioned previously, biodiesel is constituted mainly by FAME, however, the
composition can still vary quite largely when considering the process conditions and
the feedstock utilized. In addition, catalysis plays a fundamental role in biodiesel
production.

© Springer Nature Switzerland AG 2019 253

C. De Blasio, Fundamentals of Biofuels Engineering and Technology,
Green Energy and Technology, https://doi.org/10.1007/978-3-030-11599-9_18
254 18 Biodiesel

In regard to the biodiesel composition, Table 18.1 is derived with data from Knothe
(2005) and Hoekman et al. (2012) and only the main esters are reported here. This
is done to demonstrate that, even if the composition of biodiesel is restricted to only
some compounds, there is still a variety of them (Table 18.1).
The main reactions taking place during the biodiesel production aim at the for-
mation of fatty acid esters (characterized by the group –OOR). If the feedstock is
rich in neutral triacylglycerols (TAG), we have the following reaction:
Catalyst
Triacylglycerol (TAG) + 3R OH ←→ 3R COOR + C3 H5 (OH)3 (18.1)

the component 3R COOR is our fatty acid ester and in addition, glycerol is produced
by this process. Notice that the terms R and R are referred here to carbon chains
(CH3 –CH2 –CH2 – …).
The catalysts can be KOH, NaOH, or H2 SO4 . If vegetable oils are rich in free
fatty acids (Gebremariam and Marchetti 2018), FFA, we have:
Acid Catalyst
RCOOH (FFA) + R OH ←→ RCOOR + H2 O (18.2)

where the catalyst is commonly HCl or H2 SO4 and RCOOR is an alkyl ester. In
transesterification, the biodiesel is obtained by the reaction of a vegetable oil with
an alcohol, in the presence of a catalyst, to give monoalkyl esters.
The overall reaction is represented in Fig. 18.1.
Free fatty acids are formed when oils are treated at high temperatures where
they undergo an oxidation process. Side reactions in the production of biodiesel are
saponification and hydrolysis, and they are represented, respectively, by:
 
RCOOH + NaOH (or KOH) ↔ R COONa+ or R COOK+ + H2 O (18.3)

Base catalyst
RCOOR + H2 O ←→ RCOOH + R OH (18.4)

Fig. 18.1 Reaction of a vegetable oil with an alcohol. Adapted from Lotero et al. (2005)
Table 18.1 Main esters of biodiesel in reference to different kinds of feedstock used
Ester Camelina Canola Coconut Corn Jatropha Palm Rapeseed Safflower Soy Sunflower Tallow Yellow
grease
Lauric 47.7
(dode-
canoic);
12:0
Myristic 18.5
(tetrade-
canoic);
14:0
Palmitic 11.5 14.9 42.5 11.6 24.3
(hexade-
canoic);
16:0
Stearic 18.2
18.1 Fundamentals of Biodiesel Production

(octade-
canoic);
18:0
Methyl 16.8 60.4 26.6 40.4 41.3 59.5 14.2 23.7 21.7 42.2 44.6
octade-
cenoate
(methyl
oleate);
18:1
Methyl 17.0 21.2 58.7 36.2 21.5 74.3 53.8 66.3 25.1
octadeca-
dienoate
(linoleate);
18:2
Methyl 35.6 9.6 8.4
octadeca-
trienoate
(linole-
nate);
18:3
Values in % of FAME composition
255
256 18 Biodiesel

It is referred in literature that when acid-catalyzed reactions occur, the saponification

is greatly reduced (Gebremariam and Marchetti 2018). On the other hand, when free
fatty acids (FFAs) (ROOH is the acidic group) are present in the feedstock, then
there could be the formation of soaps, and this is due to a possible excess of the
catalyst itself. The reaction of saponification due to an excess of base catalyst is also
described in Fig. 18.2.
The formation of soaps is very negative for separation processes, the viscos-
ity will increase for example. In waste oil, the amount of FFA suggested is not
very high and around 1 wt% (Kumar Tiwari et al. 2007). While the FFA reduces
the quality of the feedstock, water is eliminated by centrifugation to an acceptable
level of 0.5% (wt).
Fatty acids directly affect the main parameters of the biodiesel which are:

• the cloud point (the minimum temperature at which small solid crystals can be
observed when the temperature of the sample is decreased);
• the cold filter plugging point (the temperature at which the fuel filter plugs due to
crystals and solid components);
• the pour point (the minimum temperature at which the fuel is actually moving
sufficiently, it becomes a gel).

For the sake of comprehension, we remember here that the structure of a carboxylic
acid is represented in Fig. 18.3.
In Fig. 18.3, it is possible to notice that this molecule has some parts which are
nucleophile (attract protons) while, on the other hand, there are also electrophile
parts (which attract electrons). It is quite important to reason on these sites of the
molecules to understand and design possible reaction routes. For this reason, more
information on the meaning of ionization potential and electron affinity will be given
in the following sections.

Fig. 18.2 FFA reaction with a base catalyst and formation of soap

Fig. 18.3 Carboxylic acid

representation. Adapted from
Jones and Fleming (2014)
18.2 Ionization Potential and Electron Affinity of an Element 257

18.2 Ionization Potential and Electron Affinity

of an Element

The ionization potential is the energy required to subtract one electron from the atom
to form a cation (the easiest electron is the one situated at the upper orbital level),
this is measured in electron Volt, eV, which is equivalent to 1 V·1.6 × 10−19 C, and
this has the dimensions of Joule. Remember also that 1 V = 1 J/1 C and that the
Coulomb is actually the measure of the charge (the electrons).
The electron affinity is, on the other hand, the energy released when the electron
is added to an atom. Some values for the ionization potential of some elements are
given in Table 18.2 adapted from Jones and Fleming (2014).
While an example of nucleophilic substitution is given in Fig. 18.4.
To be noticed that in Fig. 18.4, the N–H group has more negative charge on the N
atom, and therefore the H atom will have a more positive charge. On the other hand,

Table 18.2 Examples of ionization potential and electron affinities (in brackets)
H He
13.60 24.59
(0.75)
Li Be B C N O F Ne
5.39 0.32 8.30 11.26 14.53 13.62 17.42 21.56
(0.62) (0.24) (1.27) (1.47) (3.34)
Na Mg Al Si P S Cl Ar
5.14 7.65 5.99 8.15 10.49 10.36 12.97 15.75
(0.55) (0.46) (1.24) (0.77) (2.08) (3.61
Values are in eV

Fig. 18.4 Nucleophilic substitution between N–H and C–OH groups

258 18 Biodiesel

Fig. 18.5 Formation of the tetrahedral intermediate in the esterification of hydroxyl acids. Adapted
from Jones and Fleming (2014)

Fig. 18.6 All steps in Fischer esterification. Adapted from Jones and Fleming (2014)

the group C–OH has a more negative charge on the OH part and therefore this part
will have more possibility to react with the H atom of the N–H group.
The formation of the tetrahedral intermediate in the esterification of hydroxyl
acids proceeds as shown in Fig. 18.5.
Consider the periodic table with the electron affinities, note that oxygen has an
electron affinity higher than carbon; for this reason, the alcohol will bound on the
carbon and not on the oxygen.
All steps in Fischer esterification are demonstrated in Fig. 18.6.
The ion RH2 O+ goes to R–OH which is a stable compound. The reaction with the
alkoxide group (− OR) is reversible and catalytic, while the reaction of the hydroxide
group (− OH) is not reversible and not catalytic (Fig. 18.7).
18.2 Ionization Potential and Electron Affinity of an Element 259

Fig. 18.7 Reaction involving the alkoxide group (− OR) and the hydroxide group (− OH). Adapted
from Jones and Fleming (2014)

The hydrogen from the hydroxyl acid cannot just be replaced by the R of the alko-
hyde; because, an acid when loses the hydrogen is actually stabilized by resonance.
Remember that R is referring to the carbon chain (CH3 –CH2 …).
As a summary and as referred previously, the catalysts used in the process of
biodiesel production are mainly alkaline:

• NaOH
• KOH.

And, they are involved in the reactions:

CH3 O− Na+ → CH3 O− + Na+ (18.5)

NaOH + CH3 OH ↔ CH3 O− + H2 O + Na+ (18.6)

 
Here, we notice the formation of the methoxide ions CH3 O− , and they are strong
nucleophiles and attach the glyceride molecules.

18.3 Base-Catalyzed Production of Biodiesel

When base catalysts are used in the production of biodiesel, the reaction mechanisms
are illustrated as follows. The base catalysts create an alkoxide ion, BH+ . In this way,
the alkyl ion, RO− , will attack directly the double bond of the carboxylic group.

ROH + B ↔ RO− + BH+ (18.7)

The alkyl ion attack on the double bond of the triglyceride is demonstrated in
Fig. 18.8.
Notice that the RO– ion is a nucleophile. As an example, here, the formation of
the methoxide ion from a base catalyst and an alcohol is demonstrated:
260 18 Biodiesel

CH3 O− Na+ → CH3 O− + Na+ (18.8)

NaOH + CH3 OH ↔ CH3 O− + H2 O + Na+ (18.9)

In particular, the methoxide ion (the one with the methyl group) is a strong nucle-
ophile, which means that it is able to link at lower electrophile carbon.

18.4 Acid-Catalyzed Production of Biodiesel

When an acid will be adopted as catalyzer, the attack on the original triglyceride is
shown in Fig. 18.9.
Acid catalysts do not show measurable susceptibility to FFA as previously men-
tioned; however, remember that, there has to be a limit in FFA content. In case, we

Fig. 18.8 Catalyst alkoxide ion and attach on the carboxylic group. Adapted from Lotero et al.
(2005)
18.4 Acid-Catalyzed Production of Biodiesel 261

consider here an alcohol described by R4 OH (see Fig. 18.9), this would be a nucle-
ophile because it can give some electrons to the cation. Nucleophiles are also called
Lewis bases. If R4 is the methoxide ion, then this will be the methyl ester we want,
the carbonyl oxygen becomes more electrophilic, and this is because obtains a plus
charge, and this makes more easy to host the OH group of the alcohol.
An example of homogeneous acid-catalyzed process for biodiesel production is
given in Fig. 18.10.
As an example of biodiesel production from waste cooking oils (WCO), it will
be reported here the alkali-catalyzed transesterification of waste cooking oils. The
composition of waste cooking oils is demonstrated in Table 18.3.
In this particular study, the temperature of the experiments was 30, 50, or 70 °C.
While the residence time was 20, 40, 60, 90, or 120 min, the molar ratio of methanol
and WCO was from 5:1 to 12:1. The amount of KOH catalyst was 0.5–1.5 wt% of
the WCO.
The transesterification is commonly carried out with an extra amount of alcohol
in order to shift the equilibrium to the proposed product, methyl ester.

Fig. 18.9 Acid-catalyzed reactions on the triglyceride. R1, R2, and R3 are carbon chains of the
fatty acids, while R4 is an alkyl group of the alcohol. Adapted from Lotero et al. (2005)
262 18 Biodiesel

Fig. 18.10 Example of homogeneous acid-catalyzed process for biodiesel production

Table 18.3 Composition of Component g/100 g of total fatty acid methyl ester
waste cooking oils (WCO)
C6:0 0
C8:0 8.82
C10:0 6.21
C12:0 44.65
C14:0 16.31
C15:0 0.00
C16:0 10.59
C16:1 0
C17:0 0
C18:0 3.29
C18:1 8.17
C18:2 1.96
C18:3 0
C20:0 0
C20:1 0
Adapted from Phan and Phan (2008)

Table 18.4 reports a comparison between waste cooking oil and diesel. It is possi-
ble to notice that obviously waste cooking oils are not suitable for an engine, however,
they do have good technical properties.
Methanol concentration has an effect on the conversion of biodiesel; as a matter
of fact, the conversion to biodiesel can be up to 20% in case the concentration of
methanol goes from five to twelve times the concentration of waste cooking oils.
The temperature also affects the conversion of waste cooking oils to biodiesel;
it is reported in the literature that if the concentration of KOH is 0.75 and the
methanol/WCO ratio is 8:1, then the highest conversion has been noticed at 50 °C
(Lotero et al. 2005).
18.5 More Detailed Process Description for Alkali-Catalyzed … 263

Table 18.4 Properties of Parameter WCO Biodiesel

waste cooking oils and diesel
Acid number (mg KOH/g) 2.36 0.11
Iodine number (mg KOH/g) 13.20 –
Saponification number (mg KOH/g) 268.22 –
Density (g/cm3 ) 0.92 0.83
Flash point (°C) 269 69
Cloud point (°C) 21 0
Pour point (°C) 18 <12
Viscosity at 40 °C (mm2 /s) 30.05 3.53
Adapted from Phan and Phan (2008)

Fig. 18.11 A more detailed flow diagram for biodiesel production by a homogeneous alkali-
catalyzed process. Adapted from Apostolakou et al. (2009)

18.5 More Detailed Process Description

for Alkali-Catalyzed Biodiesel Production

Previous studies on biodiesel production and the different alternatives available have
been performed. It has been concluded that the alkali-catalyzed process for biodiesel
production is the most favorable in terms of its economy (Marchetti et al. 2008) and
that heterogeneous-catalyzed processes are also favorable. For this reason, the case
of alkali-catalyzed biodiesel production will be described in more details here. The
process is demonstrated in Fig. 18.11.
The demonstrated process is mostly suitable for oils that have a low content in
FFA, like rapeseed oil. The oil and the related catalyst are sent to a transesterification
264 18 Biodiesel

reactor together with methanol. As mentioned, diverse catalysts could be used in

this stage and to give one example, sodium methoxide could be used (KoohiKamali
et al. 2012); however, also other types of catalysts are utilized as well. The effluent
from the transesterification reactor is sent to a centrifuge where the esterificated
fraction is sent to a second reactor. The glycerol is separated from this fraction
and sent to a mixing tank. The same operation is basically achieved into the second
transesterification reactor, and the obtained product is then sent to the washing process
where the biodiesel fraction is processed with water and hydrochloric acid. The
fraction containing soaps or salts, methanol, water, glycerol, and FFA is sent to a
mixing tank, while the remaining biodiesel (which contains a small fraction of water)
is sent to a flash tank unit where the refined biodiesel is then separated.
The fraction with the highest amount of glycerol and coming from the transesteri-
fication reactors is sent, together with the fraction coming from the washing process,
to be mixed and the separation of FFA occurs by centrifugation with the help of
HCl solution. The derived glycerol and methanol stream is then adjusted for its pH
values with NaOH and sent to a glycerol recovery column where the glycerol is
finally separated. The effluent stream with the highest amount of methanol is sent to
a methanol recovery column where it is separated.

References

Apostolakou, A. A., Kookos, I. K., Marazioti, C., & Angelopoulos, K. C. (2009). Techno-economic
analysis of a biodiesel production process from vegetable oils. Fuel Processing Technology, 90,
1023–1031. https://doi.org/10.1016/j.fuproc.2009.04.017.
Gebremariam, S. N., & Marchetti, J. M. (2018). Biodiesel production through sulfuric acid catalyzed
transesterification of acidic oil: Techno economic feasibility of different process alternatives.
Energy Conversion and Management, 174, 639–648. https://doi.org/10.1016/j.enconman.2018.
08.078.
Hoekman, S. K., Broch, A., Robbins, C., Ceniceros, E., & Natarajan, M. (2012). Review of biodiesel
composition, properties, and specifications. Renewable and Sustainable Energy Reviews, 16,
143–169. https://doi.org/10.1016/j.rser.2011.07.143.
Jones, M., & Fleming, S. A. (2014). Organic chemistry (5th ed.). W. W. Norton & Company.
Knothe, G. (2005). Dependence of biodiesel fuel properties on the structure of fatty acid alkyl esters.
Fuel Processing Technology Biodiesel Processing and Production, 86, 1059–1070. https://doi.
org/10.1016/j.fuproc.2004.11.002.
KoohiKamali, S., Tan, C. P., & Ling, T. C. (2012). Optimization of sunflower oil transesterification
process using sodium methoxide. The Scientific World Journal, 2012, 8 pages. https://doi.org/10.
1100/2012/475027.
Kumar Tiwari, A., Kumar, A., & Raheman, H. (2007). Biodiesel production from jatropha oil
(Jatropha curcas) with high free fatty acids: An optimized process. Biomass and Bioenergy, 31,
569–575. https://doi.org/10.1016/j.biombioe.2007.03.003.
Lotero, E., Liu, Y., Lopez, D. E., Suwannakarn, K., Bruce, D. A., & Goodwin, J. G. (2005). Synthesis
of biodiesel via acid catalysis. Industrial and Engineering Chemistry Research, 44, 5353–5363.
Marchetti, J. M., Miguel, V. U., & Errazu, A. F. (2008). Techno-economic study of different alter-
natives for biodiesel production. Fuel Processing Technology, 89, 740–748. https://doi.org/10.
1016/j.fuproc.2008.01.007.
References 265

Phan, A. N., & Phan, T. M. (2008). Biodiesel production from waste cooking oils. Fuel, 87,
3490–3496. https://doi.org/10.1016/j.fuel.2008.07.008.
Pollardo, A. A., Lee, H., Lee, D., Kim, S., & Kim, J. (2018). Solvent effect on the enzymatic
production of biodiesel from waste animal fat. Journal of Cleaner Production, 185, 382–388.
https://doi.org/10.1016/j.jclepro.2018.02.210.