Renewable and Sustainable Energy Reviews 54 (2016) 74–83

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

The Used Cooking Oil-to-biodiesel chain in Europe assessment

of best practices and environmental performance
T.D. Tsoutsos a,n, S. Tournaki a, O. Paraíba b, S.D. Kaminaris a
a
Renewable and Sustainable Energy Lab, School of Environmental Engineering-Technical University of Crete, Kounoupidiana, GR-73100 Chania, Greece
b
Energy Agency of Arrábida, Avenida Belo Horizonte, Ed. Escarpas Santos Nicolau, 2910-422 Setúbal, Portugal

art ic l e i nf o a b s t r a c t

Article history: Inappropriate disposal of Used Cooking Oils (UCOs) can generate major problems, such as the operational
Received 20 March 2015 problems occurring in wastewater treatment plants when discharged into sewerage systems. In this
Received in revised form paper the best methods to process the UCO-to-biodiesel chain are reviewed putting emphasis on the
1 June 2015
most critical technical and practical guidelines including best practices, quality characteristics of the
Accepted 18 September 2015
collected UCO, potential implications, environmental performance and risks, and at the same time
Available online 11 November 2015
highlighting the strong and weak points of each analyzed route. The most common transesterification
Keywords: processes (homogeneous-catalyzed, heterogeneous-catalyzed, enzymatic, supercritical methanol, non-
Biodiesel catalyzed) are evaluated according to environmental, technical, health and safety, market and EU policy
Used Cooking Oil
criteria.
Transesterification
& 2015 Elsevier Ltd. All rights reserved.
Best practices
Environmental impact

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
2. Existing processing technologies and practices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
2.1. Biodiesel producing procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
2.2. Common practices in transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
2.2.1. Homogeneous-catalyzed transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
2.2.2. Heterogeneous-catalyzed transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
2.2.3. Enzyme-catalyzed transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
2.2.4. Non-catalyzed transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3. Crucial issues concerning the most common production practices and biodiesel distribution methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
4. Environmental impact analysis of UCO-to-biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
5. Comparison of main biodiesel production processes using UCOs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82

1. Introduction accounting for nearly 80% of the total biofuel production in

Compared with petroleum-based diesel, biodiesel has con-
siderable environmental and economic advantages [1]. Studies
present that the biodiesel burning emits, on average, 48% less CO;
47% less particulate material and 67% less HCs [2–4]. The European
biodiesel market is one of the largest throughout the world
n
Corresponding author. Tel.: þ 30 2821037825; fax: þ 30 2821037861.
E-mail address: theocharis.tsoutsos@enveng.tuc.gr (T.D. Tsoutsos).
European Union (EU). Actually, the EU biodiesel market is the
largest one globally and, in addition, the third-largest global bio-
fuel market. Both biodiesel production and consumption have
increased in the past decade in the European market (Table 1) [5].
By exploiting local resources to produce biodiesel exist economic
benefits for the rural areas by creating jobs, the process industry
by creating added value from raw sources and for the State by
income taxes and reduction of the country’s dependency on crude
oil imports [6].

http://dx.doi.org/10.1016/j.rser.2015.09.039
1364-0321/& 2015 Elsevier Ltd. All rights reserved.
 T.D. Tsoutsos et al. / Renewable and Sustainable Energy Reviews 54 (2016) 74–83 75

Table 1
EU Biodiesel production and capacity [5].

YEAR 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014

EU biodiesel production (kts) 1065 1034 1933.4 3183.4 4890 5713 7755 9046 9570 8607 8927 10,367 N/A
EU biodiesel production capacity (kts) N/A 2048 2246 4228 6069 10,289 16,000 20,909 21,904 22,117 23,538 24,216 23,093

16000
14000
12000
10000
8000
6000
4000
2000
0

*estimation

Fig. 1. Biofuel consumption for transport in the EU-28 (ktoe) [7].

Table 2
Production capacity of the main EU biodiesel producers in Europe in 2013 (ts) [6].

Company Country Number of plants in 2013 Production capacity in 2013 (ts)

Diester Industrie & Diester Industrie International (Sofiproteol) France France (5),Germany (1), 2,500,000
Italy (1), Belgium (1)
Neste Oil Finland Finland (2), Netherlands (1) 1,180,000
Biopetrol Industries Switzerland Germany (2), Netherlands (1) 1,000,000
ADM Biodiesel Germany Germany (3) 975,000
Infnita (Musim Mas) Spain Spain (2) 900,000
Marseglia Group (Ital Green Oil and Ital Bi Oil) Italy Italy (2) 560,000
Verbio AG Germany Germany (2) 450,000
Cargill/Agravis Germany Germany (2) 250,000
Petrotec Germany Germany (2), Spain (1) 185,000

The EU has supported the increase of biofuel consumption in
transport as means of reducing the emissions of Greenhouse Gases
(GHGs), as well as supporting the security of energy supply, techno-
logical development, economic development at regional scale and job
creation. Fig. 1 shows the biofuels consumption in transport in EU.
The major actors in the EU biodiesel market are shown in
Table 2,[7]. Since 2009, all EU Member States (MS) have been sub-
ject to the Renewable Energy Directive (RED) [8], which requires MS
to comply with a target of 10% of renewable energy in the transport
sector by 2020, the majority deriving from biofuels, predominantly
biodiesel. The EU is, also, committed to reduce GHG emissions to
80–95% below 1990 levels by 2050. The “Energy Roadmap 2050”
adopted on 15 December 2011 [9] provides directions towards a
future European sustainable energy system. Furthermore, according
to the Communication of 8 March 2011, “A Roadmap for moving to a
competitive low carbon economy in 2050" [10] the EU should
prepare for cutbacks in its domestic GHG emissions by 40% by 2030,
and by 80% by 2050, calculated with respect to 1990 levels. Sectoral
strategies should accompany this roadmap supporting technologi-
cal innovations.
The exploitation of Used Cooking Oils (UCOs) to produce bio-
diesel is in line with the RED, covering GHGs, biodiversity and
carbon stock. UCOs and tallow (excluding category 3 tallow) use
the EC default value for ‘waste vegetable and animal oil’. For the
use of the UCOs in the fatty acid methyl esters (FAME) production
the Carbon Saving is 83% [11] to 85% [12,13].
UCO is a waste produced in the domestic sector, canteens,
hotels, restaurants and food industry, existing in edible vegetable
oil, which is used for frying food. Inappropriate disposal of UCO
may generate major problems, such as operational problems
occurring in wastewater treatment plants when discharged into
sewerage systems [14].
A Strengths, Weaknesses, Opportunities and Threats (SWOT)
Analysis of Sustainable Management of UCOs is given below
(Table 3).
This paper displays the best methods to process the UCO-to-
biodiesel chain putting emphasis on the most critical technical and
practical guidelines including best practices, quality characteristics
of the collected UCO, potential implications, environmental perfor-
mance and risks, highlighting the strong and weak points of each
analyzed route. Based on the field work, as well the verification of
the existing literature done during the project period the most
common transesterification processes (homogeneous-catalyzed,
heterogeneous-catalyzed, enzymatic, supercritical methanol, non-
catalyzed) are evaluated according to environmental, technical,
health and safety, market, EU policy criteria.
2. Existing processing technologies and practices
2.1. Biodiesel producing procedure
Biodiesel can be blended with petrodiesel at any percentage even
though pure biodiesel ('B100') is equally suitable for diesel engines.
Either primary (i.e. straight or virgin) oils or secondary (used) oils can
be used with no discernible difference in the product. Fig. 2 shows the
76 T.D. Tsoutsos et al. / Renewable and Sustainable Energy Reviews 54 (2016) 74–83

process of converting used cooking oils into biodiesel fuel. Technically,
the methods for producing biodiesel from UCO do not differ from
conventional transesterification processes using alkaline, acid and
enzymatic catalysts.
Methanol (MeOH) is the normally used alcohol in the process
due to its low cost, physical and chemical advantages. Homo-
geneous basic catalysts are the most widely used in the industry as
they accelerate the process and achieve milder reaction conditions,
either using discontinuously (batch) or continuously systems. After
the reaction, the glycerol is separated either by settling or cen-
trifuging; the organic phase (biodiesel) is then purified before being
used as diesel fuel in compliance with the EN14214 Standard and
other national quality standards and technical norms.
The advantages and disadvantages of the transesterification
method are summarized in Table 4, as reported in relevant studies
and research reports.
2.2. Common practices in transesterification
Transesterification is a relatively simple process that produces
biodiesel and Fatty Acid Ethyl Esters (FAEE), according to the
standards EN 14214 for Europe and ASTM D 6751-12 for USA.
The most common processes are:

 Classic transesterification process, Homogeneous-catalyzed

Table 3
SWOT Analysis of Sustainable Management of UCOs.
Sustainable Management of UCOs
Strengths
EU legislation on biodiesel
The existing sustainable management
know-how
Improvement of quality of local
environment
Low cost of management for local authorities
New jobs creation
Opportunity
Active participation of citizens – they become
more active in other waste management
issues
Positive environmental profile for local
authorities – can lead to access to envir-
onmental funding, etc.
Positive political profile – increased
acceptance levels from citizens
Table 4
Advantages and disadvantages of the transesterification method.
Processing method: transesterification
Weaknesses
UCOs are not regarded as an
important waste stream by
local authorities
Organization and networking is
required
Constant information and sen-
sitization campaigns is needed
Threats
Can work only if it is accepted
by citizens
Low participation levels from
citizens
transesterification.
 Heterogeneous-catalyzed transesterification.
 Enzymatic, Enzyme-catalyzed transesterification.
 Supercritical MeOH, Non-catalyzed transesterification.
2.2.1. Homogeneous-catalyzed transesterification
This is the most frequent process with the most commonly
used catalysts: KOH and NaOH. Acid catalysts (H2SO4, RSO3H,
H3PO4 and HCl) are also used with lower efficiency than the base
catalysts.
Base catalysts provide the further advantage of the lower cost.
It is important to note that the FFA content in the base feedstock is
essential for this process, because high FFA concentrations need
supplementary amounts of catalyst and accelerates the soap for-
mation through saponification. Fig. 3 presents schematically the
full alkali process of FAME from UCO.
For the purpose of this paper, in order to identify the best
homogeneous catalysts for the esterification process of UCO, sev-
eral studies have been reviewed. The studies, mostly, suggest the
use of an excess amount of KOH. Others promote the use of
methoxide catalysts as the lack of hydroxide radical in their
structure reduces the amount of soaps by inhibition of the sapo-
nification reaction. Usually, they refer to Potassium or to Sodium
methoxide catalysts [15–18].

Advantage Disadvantage 2.2.2. Heterogeneous-catalyzed transesterification

Fuel properties are closer to
diesel
High conversion efficiency
Low cost
Suitable for industrialized
production
Low FFA and water content are required (for
base catalyst)
Pollutants are produced because products
must be neutralized and washed
Accompanied by side reactions
Recently, several researchers and industrial processes manu-
facturers have started to pay more attention to heterogeneous
catalysts due to their higher biodiesel yield, higher glycerol purity
and easier catalyst separation and recovery. This process makes
headway because it is cheaper, safer, and environmentally
friendly; also it does not require a washing step for the crude ester.
Moreover, heterogeneous catalysts are preferred over homogenous

Fig. 2. Indicative flowchart of the biodiesel producing procedure.

 T.D. Tsoutsos et al. / Renewable and Sustainable Energy Reviews 54 (2016) 74–83 77

Fig. 3. Production of FAME from UCO by alkali process.

Table 5
Biodiesel production from UCO using heterogeneous catalysts.

Oil Catalyst Catalyst Alcohol Process Ester

amount molar yield
(%wt) ratio Temperature (°C) Time (h) (%)

UCO Sr/ZrO2 2.7 29:1 115.5 2.82 79.7

ZS/Si 3.0 6:1 200 10 81.0
SO42  / 3.0 9:1 200 5 92.0
TiO2–
SiO2

Fig. 4. Enzymatic production of FAME.

catalysts in biodiesel production from UCO because saponification

and hydrolysis reactions are eliminated. The heterogeneous cata-
lysts are divided, as are the homogeneous ones, in two groups:
acidic and basic. Table 5 presents the “performance” of selective
heterogeneous catalysts for the transesterification of UCO [19–20].

2.2.3. Enzyme-catalyzed transesterification

It must be noticed here that this method is not yet fully
industrially available. A flowchart of the typical enzymatic pro-
duction of FAME is presented in Fig. 4.
The methods are presented in Fig. 5 and compared in Table 6 [21].
The use of enzymes provides the advantage of the tolerance in
the water concentration in the oil and the avoidance of undesired
FFA saponification. In addition the reaction of transesterification
takes place in lower pressure and temperature, therefore mini-
mizing the energy consumption. On the contrary, the enzyme is
more expensive, there is inhibition by MeOH, long reaction time is
required and the glycerol is adsorbed on the enzyme surface [22].
2.2.4. Non-catalyzed transesterification
This, not yet industrial method uses MeOH under supercritical
conditions. The supercritical transesterification has some advan-
tages over the conventional process, due to the absence of catalyst,
the easier separation of products, the faster reaction rate and the
elimination of the effects of the high content of FFA and of the
excess of water. However, obviously, the method requires high
reaction conditions (temperature and pressure), as well as a large
amount of alcohol. As a result of the supercritical, the energy
required is high and the capital cost increased [23–25]. Typical
flowchart of the proposed procedure is presented in Fig. 6 [26].
According to Table 7, the original optimal conditions – defined as
yielding the highest extent of reaction as over 90% triglyceride
conversion or over 96% alkyl esters content – were temperatures
between 300 and 350 °C, pressures within 20–35 MPa, alcohol to
oil molar ratio ranging from 40:1 to 42:1 and reaction time of
5–30 min, for both MeOH and Ethanol (EtOH) [27]. These para-
meters, which are referred to as the original supercritical transes-
terification parameters, were used to study the implication of each
Fig. 5. Comparison of steps involved in the immobilization of extracellular and
intracellular lipase enzymes.
parameter, the chemical kinetics, the phase behavior and the
techno-economic feasibility of the process.
Among the general operating parameters mentioned above, reac-
tion temperature is considered to be the major determinant of the
reaction's efficiency. In parallel, in cases that maximum alkyl ester
content is required for biodiesel production, the higher operating
temperatures generate thermal cracking reaction. This reaction is the
chemical limitation of supercritical transesterification, which creates
negative effect on the proportion of alkyl esters obtained in the pro-
duct. Explaining the above limitations it must be mentioned that the
European Standard EN14214, requires over 96.5% esters content, so
the thermal cracking of polyunsaturated fatty acids can be a serious
barrier. According to several studies, if the reaction temperature is
over 300 °C and the reaction time over 15 min, the methyl linoleate
content in FAME decreases by approximately 10% compared to the
level in the feedstock [28]. Additionally, the high temperature and
pressure requires both an expensive reactor and a sophisticated
energy and safety management. The high ratio of alcohol/oil results in
a large energy consumption in the reactants pre-heating stage and in
the recycling process. Especially the high amount of alcohol in the
produced biodiesel mix lows down the phase of biodiesel–glycerol
separation. As a result these parameters generate higher capital costs
78 T.D. Tsoutsos et al. / Renewable and Sustainable Energy Reviews 54 (2016) 74–83

than the novel catalytic methods, especially for the reactor and pump.

Cost of production
In order to increase the technical and economic feasibility of super-
critical transesterification, further studies are required in the direction
of optimizing the operating parameters of this process.

Moderate

Moderate
High

High
High
High

High
High

High
Low
3. Crucial issues concerning the most common production

Combined use of Lipozyme TL IM and Novozyme 435 along with tert-butanol as solvent
Stepwise addition MeOH and preincubation of enzyme in methyl oleate and soyabean practices and biodiesel distribution methods

Stepwise addition of MeOH and removal of glycerol using the solvent, iso-propanol
A novel acyl acceptor, methyl acetate which had no inhibitory effects was used
Biodiesel is highly biodegradable and has minimal toxicity; it
can replace petrodiesel often including internal combustion
engines without major modifications [29]. A slight decrease of the
engine’s performance is reported with almost zero emissions of
Stepwise addition of MeOH and removal of glycerol by dialysis

chemical substances, such as sulfates and aromatic compounds

Butanol was used as an acyl acceptor and no solvent was used

that are destructive to the environment. Some technical problems

concerning biodiesel include low-temperature properties, stability
during storage and slightly increased NOx exhaust emissions.
Ethyl acetate having no inhibitory effects was used

Marketing issues with biodiesel include economics and the

inadequacy of vegetable oil or fat to replace a small share of the
petrodiesel market.
The production of biodiesel from UCO is expected to be more
critical in the future due to its low cost and wide availability,
tert-BuOH was used as a solvent

however the following critical issues must be taken into account

[30].
Stepwise addition of MeOH

Stepwise addition of MeOH

To begin, UCO requires several pretreatment steps in order to

Conversion (%) Technique employed

eliminate solid impurities and to reduce FFA and water content. In

the pretreatment process washing, centrifugation, flash evapora-
tion, and acid esterification are included. MeOH is used in the
transesterification process because of its wide availability, low cost
and high activity. In contrast, EtOH is more soluble in oil, so it
enhances mass transfer within the system. Thus, a MeOH–EtOH
oil

mixture was proposed to combine the advantages of both alcohols.

In the UCO-to-biodiesel chain a challenge between base homo-
genous and heterogeneous catalysts is established.
A brief assessment based of the basic advantages and dis-
90–93

91.3

advantages of the above processes are illustrated in Table 8.

90
90

92
98
95
97

97

97

The production of UCO is a complex process involving several

Methyl acetate
Acyl acceptor

reactions that affects the components; the fatty materials are used
Ethyl acetate

as a frying medium which are the Triglycerides (TG), and the

Comparison of tasks in the enzymatic production of biodiesel for extracellular lipase [26].

components of the unsaponifiable fraction (sterols, tocopherols,

MeOH
MeOH

MeOH
MeOH

MeOH
Novozyme 435 & Lipozyme TL IM MeOH
MeOH
BuOH

carotenes, etc.). Basically three types of reaction take places during

the forming process:

 Oxidation reactions.
 Hydrolysis of triglycerides.
 Polymerization of triglycerides.
Novozyme 435
Novozyme 435

Novozyme 435
Novozyme 435
Novozyme 435
Novozyme 435

Novozyme 435
Novozyme 435

The various products of these reactions may be grouped as

P. flourescens

shown in Table 9.
Enzyme

The main characteristics of UCOs in relation to their safety are [31]:

 The transfer of liposoluble compounds from the food to the

Cotton seed oil,

frying oil, which allows the liposoluble contaminants in the

Sunflower oil
Watanabe et al. (2000) Vegetable oil
Samukawa et al. (2000) Soyabean oil

Soyabean oil
Soyabean oil
Rapeseed oil

Jatropha oil

food to be transferred to the cooking oil. It should also be

pointed out that as successive batches of food are placed in the
Triolein

oil, these substances will become concentrated.

UCO
Oil

 The transfer of water from the food to the frying oil. This is a
determinant of its degradation reactions. It is also important to
Shimada et al. (2002)

consider the remaining water concentrations in UCOs collected

Royon et al. (2007)
Modi et al. (2007)
Bako et al. (2002)

for subsequent recycling.

Iso et al. (2001)

Du et al. (2004)
Xu et al. (2004)
Developer/year


Li et al. (2006)

Formation of volatile compounds in the oil, at low concentra-

tions; they provide the typical aromas and flavors in the fried
products, avoiding however high concentrations.
Table 6

 Considerable degradation concerning their composition of the

cooking oil, as a result of different reactions. The importance
 T.D. Tsoutsos et al. / Renewable and Sustainable Energy Reviews 54 (2016) 74–83 79

Fig. 6. Supercritical transesterification process for UCO conversion to biodiesel.

Table 7
Reaction parameters and optimal conditions of supercritical transesterification for various oil types and alcohols.

Developer/year Oil type Alcohol temp. P (MPa) Alcohol/oil Reaction time Reactor (size/type) Extent of reaction
(mole/mole) (min)

Bunyakiat et al. Coconut and palm MeOH, 350 °C 19 42:1 7–15 251 mL 95% Methyl ester
(2006) kernel Continuous reaction in a content
tubular vesicle
Demirbas (2002) Hazelnut kernel and MeOH, 350 °C Not reported 41:1 5 100 mL 95% Methyl ester
cottonseed Batch content
Rathore and Madras Palm and groundnut MeOH, 400 °C 20 50:1 30 11 mL 95% Triglyceride
(2007) Batch conversion
Sawangkeaw et al. Palm kernel MeOH, 350 °C 20 42:1 30 250 mL 95% Methyl ester
(2007) Batch content
Saka and Kusdiana Rapeseed MeOH, 350°C 45 42:1 4 5 mL 98% Methyl ester
(2001) Batch content
Minami and Saka Rapeseed MeOH, 350 °C 20 42:1 30 200 mL Continuous reaction 87% Methyl ester
(2006) in a tubular vesicle content
Yin et al. (2008) Soybean MeOH, 350 °C 20 42:1 30 250 mL Batch 95% Methyl ester
content
Madras et al. (2004) Sunflower MeOH and 20 40:1 30 8 mL Batch 97% Triglyceride
EtOH, 400 °C conversion
Vieitez et al. (2011) Castor EtOH, 300 °C 20 40:1 Not reported 42 mL Continuous reaction 75% Ethyl esters
in a tubular vesicle content
Silva et al. (2007) Soybean EtOH, 350 °C 20 40:1 15 42 mL Continuous reaction 80% Triglyceride
in a tubular vesicle conversion
Balat (2008) Sunflower EtOH, 280 °C Not reported 40:1 5 100 mL Batch 80% Ethyl esters
content

Table 8 Table 9
Advantages and disadvantages of the transesterification processes. Results of frying.

Process Advantages Disadvantages Reaction Results

Homogeneous-catalyzed Acceptable reac- Sensitive to FFA Oxidation reactions Fixed oxidation compounds (oxidized TG,
transesterification tion time Use of water epoxides, etc.)
Easy Glycerol quality Volatiles (hexanal, pentane, 2,4-decadienal,
Heterogeneous-catalyzed Not so sensitive to Expensive pentanol, etc.)
transesterification FFA Oxidized oligomers
Use of water Longer reaction time Sterol oxides
Glycerol quality Hydrolysis of triglycerides Free fatty acids (FFA)
Enzyme-catalyzed Not so sensitive to Very expensive Diglycerides (DG)
transesterification FFA Monoglycerides (MG)
Use of water Polymerization of triglycerides Non-polar dimers
Glycerol quality Longer reaction time Other non-polar oligomers
Supercritical MeOH Not so sensitive to Very expensive
FFA
Use of water The main harmful effects of the oil’s degradation compounds
Glycerol quality Use of energy
are presented in Table 10 below:
It is obvious that these compounds engender toxic effects, so
regarding safety of use in feeds is enormous and should be the created toxicity value is the sum of all the substances present
taken into account. in a sample. The UCOs can be toxic, so they must be handled in the
same way.
Biodiesel distribution includes activities in the storage infra-
structure, the blending, the quality assurance and the
80 T.D. Tsoutsos et al. / Renewable and Sustainable Energy Reviews 54 (2016) 74–83

Table 10
Harmful effects of the oil's degradation compounds.

Degradation compounds Severity Toxic effects

Hydroperoxides Low, only at low temperatures Enzymatic dysfunction of the intestinal mucosa
Induction of colon cellular proliferation
Epoxides, TG and Oxidized FAcids Moderate (low temp.) Hepatic hypertrophy
Hepatic enzymatic dysfunction
Secondary compounds Moderate–High Hepatoxicity
Mutagenicity
Oxidized cyclic monomers Moderate–Low especially at high temperature Reduced growth and death
Non-oxidized dimers and Oligomers Moderate–High at 200 °C and low oxygen concentration Diarrhea
Oxidized dimers Predominant at high temperature with excess of oxygen Reduced growth
Oxidized oligomers Predominant at high temperature with excess of oxygen Reduced growth
Oxysterols Variable Atherogenicity
Cytotoxicity/Mutagenicity

Fig. 7. Indicative flowchart of the biodiesel distribution steps.

Table 11 Table 12
Assessment of the biodiesel distribution methods. The environmental impact per 1 t biodiesel production from UCO [31,32]

Destination Advantages Disadvantages Impact categories [32] Adapted from Units

[33]
Refineries Constant buyer Oligopsony controlling the
More constant rules market Abiotic Depletion 5.51 0.01 kg Sb eq
Distributor Selection of the best Sensitive market depend- Global Warming 299.60 299.52 kg CO2 eq
prices and trade ing on national policies Potential
agreements Ozone Layer Depletion 5.80  10  5 4.31  10  5 kg CFC 11 eq
Transport Companies Selection of the best Risk for black market and Human toxicity 106.97 62.73 kg 1,4 dichlor-
and Gas Stations prices and trade tax evasion obenzene eq
agreements Fresh Water Aquatic 19.18 51.75 kg 1,4 dichlor-
Ecotoxicity obenzene eq
Marine Aquatic 1.39  105 1.76  105 kg 1,4 dichlor-
transportation methods/means. In other words, it involves the Ecotoxicity obenzene eq
Terrestrial ecotoxicity 0.52 0.95 kg 1,4 dichlor-
steps and provisions required to transfer the biodiesel from the
obenzene eq
producer to the marketplace or to the refinery for blending. Fig. 7 Photochemical 0.08 12.47 kg C2H4 eq
indicates the stages which should be considered in the biodiesel oxidation
distribution process. Acidification 1.39 1.21 kg SO2 eq
A comparison of the three main distribution methods is pre- Eutrophication 0.10 0.40 kg PO4 eq

sented in Table 11.

4. Environmental impact analysis of UCO-to-biodiesel
UCOs have been gaining prominence for biodiesel production
due to its’ potential to improve the environmental performance of
biodiesel produced with biomass.
The current integrated management of UCOs is shown in Fig. 8.
The environmental impact of 1 t biodiesel production from UCO
has the following impacts to the following ten (10) categories as
depict in Table 12 [32,33] The system assumes that UCO is a waste
product, which means that its production does not use up any
additional material or energy inputs and has no impact on the
environment. For this reason, the UCO itself is not included in the
assessment.
In an environmental perspective, the UCOs collection and
delivery has a positive environmental impact as it avoids deposi-
tion of the UCOs in landfills or its discharge in the sewer system.
When sent to the sewer system that causes many problems in the
operation of the wastewater treatment plants as far as efficiency
and operational costs (e.g. significant decrease in the maintenance
costs). Most Life Cycle Assessment (LCA) studies of biodiesel from
UCOs have showed that the UCOs collection and delivery had a
small contribution to the overall impacts [6].
In the same direction, are also the results from a thermoeconomic
analysis [34], according to which the energy return of energy
investment would be increased to 69 and the renewability to 98.7%.
The results show that biodiesel from UCO is by far the most sus-
tainable biodiesel from the viewpoint of the use of fossil resources.
UCO pretreatment and transesterification are the stages that
have the highest impact compared to the other categories,
accounting for between 10% and 90% of the impacts investigated.
The impacts associated with collection and delivery of UCO are
negligible observing the other processes.
The biggest factor contributing to Global Warming Potential
(GWP) is transesterification, but the GWP of UCO Pre-treatment is
also significant. When it comes to terrestrial ecotoxicity, the single
largest contributory factor comes from the transesterification.
The factor that contributes most to acidification and photo-
chemical oxidation is transesterification for 57% and 75%, respec-
tively, caused by emissions during combustion. The stage of the
 T.D. Tsoutsos et al. / Renewable and Sustainable Energy Reviews 54 (2016) 74–83 81

Fresh Vegetable Oil

FOOD
HOUSEHOLDS
INDUSTRY

Intermediate
Recycling Center
Collection of UCO
Containers
Emissions
UCO
Solid
WASTEWATER Pretreatment of UCO
Wastewater Wastes
Treatment

UCO

Delivery of UCO Emissions

WATER
UCO
Transesterification Fatty Acid Methyl Ester

UCO

Reactants Glycerol
Additives Emissions
Fertilizers

Fig. 8. Overall production of FAME from UCO.

biodiesel process that contributes most to human toxicity and
eutrophication is also transesterification, accounting for 66% and
63%, respectively. The human toxicity emanate come mostly from
the emission of volatile organic compounds during sugarcane
harvesting (burning). The greatest eutrophication impact comes
from the waste produced during distillation (vinasse).
5. Comparison of main biodiesel production processes using
UCOs
The evaluation criteria of main biodiesel production processes
using UCOs (chapter 2) are:
 Environmental
 Technical
 Health and safety
 Market Opportunities and Barriers
 Harmonization with EU Directive and Sustainability
 Climate/Geographical Parameters
The results of the above mentioned comparative analysis are
shown at Table 13.
The supercritical process always generated a higher impact on
the environment, due to the requirement of large amounts of
MeOH during the reaction and consequently the energy expendi-
ture in MeOH recirculation. In order to make the supercritical
MeOH process feasible, from an environmental point of view, the
distillation column in the MeOH recovery process has to be
replaced with a different less energy-intensive process technology.
Alternatively, it remains to be confirmed whether the promising
results of the two-stage supercritical process, with reduced oper-
ating pressure, temperature and MeOH to oil ratios, will be reliably
translated into industrial scale production [35].
Obviously acid, alkali, or enzymatic catalyzed and supercritical
transesterifications are alternative approaches that have been used
for biodiesel production having both pros and cons. Amongst them
the type of feed stock is the most critical factor in the production
of biodiesel. It is essential to understand that UCO can decrease
biodiesel production costs. On the other hand, the shortage of UCO
in EU may lead in imports, therefore the price of obtaining the raw
material may be higher in the future. However, the cooking pro-
cess influences negatively the oil properties and can create dif-
ferent types of impurities in the oil, as well as increasing the FFA
and water oil content. Hence, these obstacles increase the pur-
ification and separation costs in the downstream biodiesel
production.
The transesterification with alkali catalysts is the most common
conventional method for biodiesel production. However this
method causes serious problems in the purification part since they
are highly sensitive to FFA and water content in the UCO. On the
contrary the acid catalyzed process is not sensitive to FFA and
water content like base catalysts, with the only drawback that the
production process is slower.
The utilization of enzymatic catalysts proved very promising,
but since the catalysts are expensive, this process is not, yet, sui-
table for industrial production of biodiesel [36]. Furthermore, the
supercritical method requires high temperature and pressure,
making the process, yet, neither economical nor environmentally
friendly.
Therefore, scientists focus on the utilization of heterogeneous
acid and base catalysts in biodiesel production since the catalysts
82 T.D. Tsoutsos et al. / Renewable and Sustainable Energy Reviews 54 (2016) 74–83

can be reused many times, making it an environmentally friendly

graphical Parameters

Moderate dependent

Moderate dependent
practice. In a continuous process the reusability of the catalysts is

High dependent

High dependent
Climate/Geo-
the most important property making them economical for
industrial production. Hence, in order to reduce production costs,
reaction time, catalyst and alcohol requirements in transester-
ification reactions have demonstrated various processes such as
membrane reactor, reactive distillation, reactive absorption,
microwave, and ultrasonic. These processes increase the quality
Covering the EU Directive on

Covering the EU Directive on

Covering the EU Directive on

Covering the EU Directive on

Directive and Sustainability

and quantity of FAME for applications to diesel engines without

Harmonization with EU

Sustainability (Medium

Sustainability (Medium

Sustainability (Medium

Sustainability (Medium
any engine modification.
Realistically, for the current time, the use of homogenous cat-
alysts is the optimum way for the UCO-to-biodiesel chain. The
following essential considerations must be taken into account:
covering)

covering)

covering)

covering)
1. KOH catalyst is less effective than the sodium based catalysts. A
catalyst concentration of 0.8 (wt%) for UCOs ensures that visc-
osity is within the limits, but then purity is lower than the
High reaction time (Med-

minimum required according to the European biodiesel stan-

Large amounts of energy.
Increasing market share.

Increased production of

Increased production of

Increased production of
methylesters (Medium

dard EN 14214. Since at the highest catalyst concentrations

Not proved industrial
Market Opportunities and

production (Medium
purity was generally very close to the limit, better results are
Low quality (Low

expected by increasing the catalyst concentration [36].

ium negative)
methylesters.

methylesters.

2. Kinematic viscosity and methyl ester content are considered as

High costs.
High costs

High costs
negative)

negative)

negative)

the most important properties to evaluate which catalyst type

and concentration is proper.
Barriers

3. MeOH, being cheaper, is the commonly used alcohol during

transesterification reaction.
Normal (Medium

Normal (Medium

Normal (Medium

(Low positive)
Health and

positive)

positive)

positive)

6. Conclusions
safety

UCOs-to-biodiesel chain is a dynamic activity in EU with

essential economic and environmental benefits. Through the col-
Established technology

lection of different types of UCOs, the cost of biodiesel is con-

Longer time reaction

(Under development
High glycerin purity

siderably reduced and the negative impact of the waste oil dis-
(Well established

(Less established

(Less established

posal in the environment are minimized. The most common

Technology)

technology)

technology)

technology)

methods to process the UCO-to-biodiesel chain have been

Technical

reviewed, putting emphasis on the critical technical and practical

guidelines as well as highlighting the strong and weak points of
each analyzed route. As expected the results indicate that trans-
esterification reaction is the "heart" of full chain, therefore its
requirement for large amounts of MeOH during the
reaction and consequently the energy expenditure
Higher impact on the environment, because of its

optimization is critical for the full chain feasibility.

Low to normal glycerin purity (Medium positive)

Normal or triacetylglycerol as byproduct) (High

Poor quality of glycerin (Medium positive)

in MeOH recirculation in the recycle loop.

Large amounts of energy. (Low positive)

Acknowledgments
Waste water and saponified products

The authors and all the consortium partners are grateful to the
EACI executives for their support and helpful cooperation. This
Evaluation criteria of examined biodiesel production processes.

publication is supported by the European Commission under the

Intelligent Energy-Europe Programme, within the framework of
Evaluation criteria

the project RecOil-Promotion of used Cooking Oil recycling for

No waste water.
No waste water

No waste water
Environmental

sustainable biodiesel production, Contract number: IEE/11/091/

SI2.616369. The sole responsibility for the content of this paper
lies with the authors. It does not necessarily reflect the opinion of
positive

the European Union. The European Commission is not responsible

for any use that may be made of the information contained
therein.
Heterogeneous-catalyzed
Homogeneous-catalyzed

transesterification.
transesterification

transesterification

Supercritical MeOH

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