Fatty Acid Ethyl Esters

Fatty acid ethyl esters
Carlo Hamelinck Ecofys

Sigurd Schober Graz University
Martin Mittelbach Graz University
Julien Verolet Iterg
Bart Dehue Ecofys
BIOScopes

Final report for Lot 3a of the Bioscopes project

Authors:
Carlo Hamelinck (Ecofys) Lot 3a coordinator
Sigurd Schober (Graz University)
Martin Mittelbach (Graz University)
Julien Verolet (Iterg)
Bart Dehue (Ecofys)

Publication date:
June 2007

BIOScopes:
Biodiesel Improvement On Standards, Coordination of Producers and Ethanol Studies

EC project TREN/D2/44-LOT 3/S07.54848

The European BIOScopes project is carried out by Ecofys for the European Commissions
Directorate-General Energy and Transport, in cooperation with AGQM, EBB, NEN, University of
Graz, Atrax, ITERG, Abengoa, SSOG, ASG, ADM, Ecotraffic, BAFF, LACCO, UNGDA, LBB,
O2Diesel, and VTT.

BIOScopes is concerned with the improvement of the EN 14214 biodiesel quality standard, and the
increased use of bioethanol in the diesel market.

The following reports have been published:
Lot 2: Heavy-duty ethanol engines
Lot 3a: Fatty acid ethyl esters (FAEE)
Lot 3b: Ethanol-diesel blends

Contact information:
For information concerning the BIOScopes project please contact Mr. Eric van den Heuvel:
E.vandenheuvel@ecofys.nl, +31 (0) 30 2807851

For more information concerning this study and report please contact Carlo Hamelinck:
C.Hamelinck@ecofys.nl, +31 (0) 30 2808496

Prefa Prefa Prefa Preface ce ce ce
Road transport has a significant share in the overall greenhouse gas emissions of the EU. These
emissions are still expected to increase in the near future. Therefore the European Commission has set
out ambitions to attain a 20% market share of alternative fuels to the transport sector by 2020. Biofuels
will play an important role in reaching that ambition. Recently the European leaders have confirmed
the ambitions on climate change by setting strict 2020 targets for greenhouse gas emission reduction
(30%), share of renewables (20%) and the share of biofuels in the transport sector (10%).

The current EU transport sector is characterized by a growing share of diesel, at the cost of the
gasoline share. Increasing the contribution of biofuels to the desired levels will be a challenge: various
limitations still exist, hindering an optimal market introduction.

The current fuel quality standards only allow 5 vol-% fuels to be blended in conventional fuels.
Developments in fuel performance and emission requirements, as well as engine developments might
require revision of existing standards, among which the EN14214 biodiesel standard. Currently the
biodiesel standard is rapeseed focused and might need be adapted due to growing targets and needs for
diversification of the supply sources, while maintaining within fuel quality and engine performance
boundaries.

The growing ethanol production facilities are faced with a decreasing market share for gasoline, while
the growing diesel market even creates a surplus of gasoline. Ethanol replacing gasoline even further
creates a surplus of gasoline. Export to the USA might be less attractive due to the USAs plans for
biofuels (mainly ethanol) contribution, with lower need for gasoline. All in all, it seems worthwhile to
explore the opportunities to use ethanol in the EU diesel market: i) diesel engines running on neat
ethanol; ii) bioethanol-diesel blends; and iii) replacing methanol by ethanol in the production process
of biodiesel.

Commissioned by the European Commission, the BIOScopes project has reviewed these new biofuel
opportunities. The underlying documents reports, on basis of a thorough analysis and review, provide
you with an update on the actual opportunities and will support the European Commission in their
future activities to accelerate the market introduction of biofuels.

Eric van den Heuvel


Carlo Hamelinck Ecofys
Sigurd Schober Graz University
Martin Mittelbach Graz University
Julien Verolet Iterg
Bart Dehue Ecofys

BIOScopes
Fatty acid ethyl esters v

BIOScopes
Glossary Glossary Glossary Glossary
CFPP Cold Filter Plugging Point, item of the biodiesel quality standard
CO
2
Carbon dioxide
CP Cloud Point, item of the biodiesel quality standard
DME DiMethylEther, alternative fuel
EN14214 European quality standard for FAME
ETBE Ethyl-Tertiary-Butyl-Ether, an octane improving additive to gasoline
FAEE Fatty Acid Ethyl Ester, biodiesel from esterification of fatty acids with ethanol
FAME Fatty Acid Methyl Ester, biodiesel from esterification of fatty acids with methanol
GHG Greenhouse gas
HC Hydrocarbons, emission of hydrocarbon compounds, dangerous for health
LCA Life Cycle Assessment
NO
x
Nitrogen oxide
PM Particle Matter, emission of small particles, dangerous for health
PP Pour Point, item of the biodiesel quality standard
RME Rapeseed Methyl Ester, common biodiesel from rapeseed
RPM Rounds per minute
TAEE Tertiary Amyl Ethyl Ether, an oxygenate to gasoline

Fatty acid ethyl esters vi

BIOScopes
Executive s Executive s Executive s Executive summary ummary ummary ummary
There is a clear European goal to increase the amount of biofuels applied in the transportation sector,
both to decrease greenhouse gas emissions from this sector and to make it less dependent on fossil oil.

Common options are biodiesel replacing diesel and bioethanol replacing gasoline. Biodiesel currently
receives much more attention than ethanol, mainly because of the much lower production costs and
because of the growing demand for diesel replacing fuels. However, with the prospects that the
production of biodiesel from oil crops could slow down at some moment and that the production of
bioethanol becomes more and more attractive, it is valuable to know the opportunities for using
ethanol in the diesel sector. One option is to use ethanol in the production of biodiesel or so-called
Fatty Acid Ethyl Ester (FAEE), thereby replacing the fossil component methanol.

This study aims to shed light on the production technology of FAEE, its technical quality and
suitability for application as automotive fuel, its well-to-wheel and end-use environmental
performance, and its production costs.

The main findings of this study are:
Technically and chemically, FAEE production is very comparable to FAME production.
Therefore, existing biodiesel methyl ester plants have the technical possibilities to produce
FAEE without major retrofitting problems.
Practical experience on the production of FAEE is limited mainly on funded studies and a few
demonstration projects. Brazil, as producer of the cheapest ethanol, has some experiences with
FAEE production and at least one biodiesel factory is claimed to be capable of producing FAEE.
The fuel quality parameters are expected to generally be in line with the European biodiesel
standard EN14214, except that the analytical methods would have to be adopted for ethyl ester
application.
There is not enough (recent) insight in the application of FAEE in engines in comparison with
FAME application. Based on limited information, it is expected that FAME and FAEE have a
very similar performance.
Application of FAEE offers generally larger benefits in terms of well-to-wheel energy efficiency
than in terms of GHG emissions. This is caused by the fact that methanol production is rather
energy intensive, but as methanol is rich in hydrogen the greenhouse gas penalty is limited.
FAEE produced from sugar cane ethanol and with utilisation of a larger fraction of palm oil
could perform much better on the greenhouse gas balance than FAME from rapeseed, especially
because of the high yields per hectare for those crops. Unfavourable land-use changes, however,
can completely turn this picture upside-down.
Fatty acid ethyl esters vii

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Production costs for FAEE are generally higher than for FAME. In Brazil, however, we expect
that FAEE can be directly more economically attractive than FAME. If methanol prices
continue to increase faster than ethanol prices in the coming years, FAEE production can
become an alternative to FAME from the economic point of view.
The almost non-existing production capacity of FAEE in comparison with the success of FAME
is currently mainly due to the higher price of methanol in comparison with ethanol and the fact
that the increased environmental performance does not lead to a higher economic value.

Fatty acid ethyl esters viii

BIOScopes
Contents Contents Contents Contents
Preface i i i
Gl ossary v
Execut i ve summary vi
Cont ent s vi i i
1 Int roducti on 1
1.1 Background 1
1.2 Objective 2
1.3 Methodology and reading advice 2
2 Producti on of FAEE 3
2.1 Introduction 3
2.2 Catalysts 4
2.3 Transesterification Conditions 5
2.4 Alcohol - Requirements 6
2.5 Glycerol Quality 6
2.6 Retrofitting FAME into FAEE Plants 7
2.7 Practical production experience 7
3 Qual i t y aspects of FAEE 9
3.1 Fuel properties 9
3.2 Engine application 10
Fatty acid ethyl esters ix

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4 Envi ronmental performance of FAEE 12
4.1 End-use emissions, toxicity and biodegradibility 12
4.2 GHG performance and energy efficiency 13
5 Economi c anal ysi s of FAEE 22
5.1 Base-line: FAME production costs 22
5.2 FAEE production costs 23
5.3 Conclusions 27
6 Concl usi ons 28
6.1 Technical aspects 28
6.2 Quality aspects of FAEE 28
6.3 Sustainability aspects 29
6.4 Economic aspects 29
7 References 30
Annex A Feedstock producti on 33
A.1 Oil palm fruits 33
A.2 Rapeseed 33
A.3 Wheat and straw 34
A.4 Sugar cane 34
Annex B Conversi on t o bi ofuel s 35
B.1 Biodiesel from palm oil 35
B.2 Biodiesel from rapeseed 36
B.3 Ethanol from wheat 37
B.4 Ethanol from sugar cane 38
Annex C Generi c data 39
C.1 Transportation distances 39
Annex D Ethanol f racti on i n bi odi esel 40
Fatty acid ethyl esters x

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Annex E Det ai l ed energy ef fi ci ency of FAEE pal m oi l -
wheat 41
Annex F Li t erat ure survey (Graz Uni versi t y) 42
F.1 General Considerations 42
F.2 Production of FAEE: 42
F.3 Experience with FAEE 53
F.4 Summary 68
F.5 References 69
Annex G Theoret i cal Anal ysi s of Techni cal
Bot t l enecks and Sol ut i ons (Graz Uni versi t y) 75
G.1 Introduction 75
G.2 Transesterification Technology 76
G.3 FAME versus FAEE Quality Parameters 78
G.4 Engine Applications and Experience 79
G.5 Summary 81
G.6 References 82
Annex H Economi c Issues Rel ated t o FAEE (Graz
Uni versi t y) 84
Annex I Laborat ory t ests and l i terature survey
(It erg) 92
I.1 Description of the project technical objectives 92
I.2 Summary of Work performed 92
I.3 Homogeneous catalyse 92
I.4 Heterogeneous catalyse 98
I.5 Enzymatic catalyse 102
I.6 General comments and conclusion 104

Fatty acid ethyl esters 1

BIOScopes
1 11 1 Introduction Introduction Introduction Introduction
1.1 1.1 1.1 1.1 Background Background Background Background
There is a clear European goal to increase the amount of biofuels applied in the transportation sector,
both to decrease greenhouse gas emissions from this sector and to make it less dependent on fossil oil.

Both for diesel and for gasoline, there are biofuel alternatives. Currently the most common biofuels
are biodiesel replacing diesel, and ethanol or ethanol derived ETBE replacing gasoline. Both biodiesel
and bioethanol can in principle be made from broad ranges of feedstock. Both biofuels may play an
important role in the future European automotive fuel supply. Ethanol could also be produced from
lignocellulose biomass, which makes it an interesting transition biofuel. Nevertheless, biodiesel
currently receives much more attention, mainly because of the much lower production costs and
because of the growing demand for diesel replacing fuels.

With further developments in the bioethanol production technology, and with the utilisation of cheaper
feedstock over time, the price of ethanol is expected to decrease. The amounts of ethanol that could be
produced from food industry waste streams and lignocellulose biomass are huge. At the same time,
feedstock limitations
1
and sustainability concerns may well increase the price of vegetable oils. These
developments could bring ethanol and biodiesel at more equal price levels in several years.

The diesel consumption in the EU is estimated to be about 70 % of all fuels used for road transport.
Despite the increasing demand, refineries cannot further increase their diesel over gasoline product
ratio. This means that there is a clear demand for alternative fuels that can be used as a substitute for
diesel. With the prospect that the production of biodiesel from oil crops could indeed slow down and
the production of bioethanol becomes more and more attractive, it is valuable to know the
opportunities for using ethanol in the diesel sector. Commissioned by the European Commission, the
BIOScopes project reviewed these opportunities in three separate reports:
Use of neat ethanol in adapted diesel engines (LOT2)
Blend ethanol in regular diesel (LOT3b)
Use ethanol in the production of biodiesel (LOT3a)

1
The current European quality standard for biodiesel, EN14214, is historically based on rapeseed oil derived
biodiesel. The fractions of palm oil and soybean oil that could be used to produce biodiesel of
sufficient quality are therefore limited to some 20 - 40 % of the feedstock.

BIOScopes
1.2 1.2 1.2 1.2 Objective Objective Objective Objective
The LOT3a part of the BIOScopes project aims to study the use of ethanol instead of methanol in the
production of biodiesel. In other words, the production of Fatty Acid Ethyl Ester (FAEE) is compared
to the more common production of Fatty Acid Methyl Ester (FAME). This means that several
questions must be answered:
How does it work, what are the (technical) bottlenecks and how can these be overcome?
Will the product be acceptable in terms of quality and safety?
What are the environmental benefits or drawbacks?
What are the economic benefits or drawbacks?
How do these aspects compare to those of other biofuel alternatives and to those of fossil fuels?
What are the prospects for such processes in the present and future biofuels market?
1.3 1.3 1.3 1.3 M MM Methodology ethodology ethodology ethodology and reading advice and reading advice and reading advice and reading advice
In order to answer the questions above, several tasks have been performed. The following list also
indicates where in the underlying report each item is dealt with.
The conversion technology for biodiesel using ethanol is analysed in
detail. This starts from theoretical expectations based on the differences
with biodiesel production using methanol, actual experience on laboratory
scale, and limited experience on commercial scale. The technical problems
actually faced and those expected for large-scale application are discussed
and also the possible solutions to overcome these problems
Chapter 2
The technical quality that can be expected for biodiesel produced by using
ethanol is discussed and compared with that of biodiesel from methanol
Chapter 3
The end-use impacts from the use of FAEE are discussed. The well-to-
wheel energy and greenhouse gas emission balances of FAEE and FAME
are compared for several feedstock options
Chapter 4
The production costs of FAEE are compared with that of FAME,
reckoning with the necessary adaptations in the production process and the
allowance for other feedstock
Chapter 5
Finally, the outcomes from all the tasks are discussed in a broader
perspective
Chapter 6

More extensive background information, necessary to carry out the tasks described above, can be
found in the Annexes:
An extensive literature survey was performed on experiences and research
in Europe and beyond
Annex F
An analysis of the technical bottlenecks and possible solutions Annex G
Several gaps in the knowledge on using ethanol in the conversion to
biodiesel were covered by the performance of synthesis experiments
Annex I
Generic data is used for the calculations of energy and greenhouse gas
balances
Annex A, B and C


BIOScopes
2 22 2 Production of FAEE Production of FAEE Production of FAEE Production of FAEE
The main technical issues associated with the production of Fatty Acid Ethyl Ester are described,
mainly based on academic literature and laboratory experience. There is only limited large-scale
commercial experience.
2.1 2.1 2.1 2.1 Introduction Introduction Introduction Introduction
The production of biodiesel from fats and oils occurs according to the transesterification reaction
presented in Figure 2-1. In principle, the transesterification reaction can be performed with methanol
as well as with ethanol, to produce the corresponding fatty acid methyl and ethyl esters respectively.
However, currently, almost all biodiesel produced worldwide is coming from transesterification of oils
with methanol.

O
II
3 R` - O C R +
O
II
CH
2
O C - R
O
II
CH O C R + 3 R`OH
O
II
CH
2
O C - R
CH
2
OH
CH OH
CH
2
OH
Triacylglycerol
(Vegetable oil)
Alcohol Alkyl ester
(Biodiesel)
Glycerine

Fi gur e 2-1. The t r ansest eri f i cat i on reacti on. R i s a mi xt ure of vari ous f at t y aci d chai ns
(Knothe, et al . 2004).

Transesterification of oils with ethanol is possible, but methanol is generally cheaper, the production
technology with ethanol is better known and further developed and accepted quality specifications
exist for FAME. However, due to the increasing production volumes of ethanol, decreasing prices and
the increasing demand of alternative fuels, biodiesel production with ethanol as the alcohol may
become more important in the nearer future.


BIOScopes
The main technical differences between the production of FAEE and FAME reside in:
Choice and amount of catalyst
Transesterification conditions
Conversion rate
Alcohol requirements
Glycerol quality

All these aspects are evaluated more detailed in this chapter, based on practical experiences from
laboratory trials as well as on reported data. There are some technologies for the production of FAEE
available (see literature survey in Annex F) but the main problem is, that it is not possible to evaluate
such processes from the technical side because currently no industrial scale biodiesel ethyl ester plant
is running worldwide. Even small-scale plants, which operate for example in Brazil, did not give
detailed information on their process conditions and upcoming problems during operation. Therefore,
all the problems or differences compared to classical methyl ester production, as described in this
chapter, are based on different laboratory experiments and pilot plants.
2.2 2.2 2.2 2.2 Catalysts Catalysts Catalysts Catalysts
From a technical point of view the most promising and investigated technology will be based on
alkaline catalysts whether in form of sodium or potassium hydroxides or in form of sodium or
potassium alkoholates. Such alkoholates can be either methoxides or ethoxides. In fact, the amount of
the catalysts cannot be specified generally but the evaluation of all reported material indicated that the
amount would be slightly higher than compared to methyl ester production. These aspects should be
taken into consideration from the economic point of view. Furthermore, ethoxides will be more
expensive than methoxides and it is not easy to elicit if ethoxides will be available in sufficient
amounts on the market.

The trials of Iterg (Annex I) showed that the best conversion rates and fastest kinetics were obtained
with sodium methoxides. Potassium hydroxide leads to significantly lower reaction rates. Also, the
phase separation was much better when sodium methoxides was used in comparison with potassium
hydroxide.

Other options for catalysts that can be used for transesterification are either acid or enzymatic
catalysts. The use of acids would have the advantage that undesirable soap formation
2
would not take
place. Soaps not only represent a direct loss of ester, but also inhibit the separation of the biodiesel
from the glycerine fraction. As acid catalysts in principle all kinds of strong inorganic acids can be
used: H
2
SO
4
, H
3
PO
4
, HCl, or organic acids like p-toluene-sulfonic acid. The concentration of water
has to be less than 0.5%. Investigations showed that with acid catalysis high conversion rates are
possible. Nevertheless, longer reaction times are required than for alkaline catalysts. From the

2
In the presence of water, base catalysts can react with free fatty acids or with already formed esters to form
soap (saponification).

BIOScopes
economic point of view, long reaction times should be avoided so therefore it is hard to argue if acid
catalyzed transesterification for ethyl ester production will be an option for technical implementation.

The evaluation of literature data of the past years showed that numerous articles are published
reporting investigations of enzyme-based transesterification. Different kinds of enzymes from varying
sources are able to transesterify fats and oils into biodiesel with high yields and even high quality.
Probably most of such enzymes are able to show similar transesterification behaviour when used for
fatty acid ethyl ester production. Basically, several authors reported such evaluations but compared to
FAME only few data is available. However, all enzyme-type transesterification reactions with
methanol as well as ethanol are currently at experimental state. Due to the high prices of the enzymes
from the commercial point of view, such technologies will not be used for large-scale biodiesel
production in the near future. Probably this might be changing if enzymes are available at reasonable
prices but as already mentioned, currently enzymes suitable for biodiesel production (in fact the
cheapest ones) are 10 times more expensive than classical alkaline catalysts.

The Iterg experiments showed that after enzymatic hydrolysis, the glycerol layer was very pure in
glycerides. Therefore, the purification of glycerol could be done by a simple distillation step. Also, a
neutralisation step is not necessary because enzymatic catalyse produces no soaps.
2.3 2.3 2.3 2.3 Transesterification Conditions Transesterification Conditions Transesterification Conditions Transesterification Conditions
The conditions of transesterification of fats and oils with ethanol are generally comparable to the
conditions of classical biodiesel production processes. Transesterification can be performed with batch
type processes as well as semi-continuous or continuously. Plant modification aspects, to switch from
methyl ester to ethyl ester production, are evaluated in Section 2.6.

The differences in conditions in comparison to methyl ester production are typically caused by
chemical effects. Increasing the temperature up to 70 C during transesterification would result in
higher ester yields and faster reaction time (Feuge and Gros 1949). At such temperatures evaporation
of ethanol has to be suppressed. Higher pressure and intensive agitation are required. Other authors
reported similar behaviour at even lower temperatures (Chowdhury and Mukherji 1954). Slightly
higher amounts of catalyst are recommended, in comparison to methyl ester production, otherwise the
ester yields would be too low. The overall kinetics of ethyl ester production are comparable or even
slightly better than those of methyl ester production, due to better ethanol solubility in the oil
(Gauglitz and Lehman 1963). Thus, reaction time, catalyst amount and reaction temperature are the
most influencing factors on the velocity of the reaction and therefore have to be optimized for
production.

Phase separation is a major hurdle in ethyl ester production. The main reason for this is the far better
solubility of ethanol in the ethyl ester phase when compared to methanol. Another important reason is
that saponification during ethanolysis has been found to be more critical than during methanolysis
(Glass 1963). Also increasing reaction temperature could have an influence on saponification reactions
(Chowdhury and Mukherji 1954). Generally, phase separation of glycerol possibly requires

BIOScopes
modifications compared to classical biodiesel processes. A possible way for separation of water-
soluble substances would be a neutralization step by addition of inorganic acids like HCl. Other acids
reported (acetic acid, H
2
SO
4
, H
3
PO
4
) will form emulsions that can only be separated by addition of
20% NaCl solution (Chowdhury and Mukherji 1954; Feuge and Gros 1949; Freedman, et al. 1984).
Another option for better glycerol separation would be the addition of purified glycerol to the reaction
mixture (Szpiz, et al. 1984). Furthermore, the use of ion exchange resigns in order to get better phase
separation behavior has also been discussed (Johnson 1981; Stern, et al. 1985).
2.4 2.4 2.4 2.4 Alcohol Alcohol Alcohol Alcohol - -- - Requirements Requirements Requirements Requirements
Many authors have reported on the negative influence of water on transesterification (Christie 1992;
Freedman, et al. 1984; Gauglitz and Lehman 1963; Glass 1963; Korus, et al. 1993; Romano 1982;
Schwab, et al. 1987; Wright, et al. 1949). In fact, water content is a limiting factor of vegetable oils as
well but the water content of the feedstock can be decreased by appropriate oil pre-treatment. Another
problem is water presence in the alcohol since different ethanol qualities are available. The use of
technical or industrial grade ethanol with water contents up to 5% or even higher would be from
commercial side the best opportunity because such alcohols would be available in large amounts
against low costs. However, the use of such ethanol has to be strictly avoided. Most of the
transesterification technologies suitable for ethyl ester production need highly purified ethanol with
less than 0.5% water.

Iterg trials (Annex I) have shown that an significant excess alcohol is required for the reaction. In
homogeneous catalysis, an excess of 50 % increases both the conversion rate and the phase separation,
while an excess of only 20 % reduced the conversion rate. It is not clear how this compares to
methanol use in FAME production. However, it must be realised that ethanol is a bigger molecule than
methanol. This implies that if the same alcohol/oil ratio is to be used, the reactor volume has to be
increased by 9 % (see Annex I.3).
2.5 2.5 2.5 2.5 Glycerol Quality Glycerol Quality Glycerol Quality Glycerol Quality
The evaluated data did not yield information about changes in glycerol quality from FAEE production
compared to that of FAME production. However, due to the better solubility of ethanol in fatty acid
ethyl esters technical problems might occur during phase separation. This means that probably higher
amounts of by-product would be found in the glycerol layer and therefore the technical glycerol
conditioning and purification steps would need modifications. These effects were not observed in the
experiments of Iterg, where it is concluded that purification of glycerol from FAEE production is quite
similar to purification of glycerol from FAME production (homogenous catalyse).

Ethanol removal during the different processing and purification steps is more energy consuming due
to the higher boiling point of ethanol compared to methanol.

BIOScopes
2.6 2.6 2.6 2.6 Retrofitting FAME into FAEE Plants Retrofitting FAME into FAEE Plants Retrofitting FAME into FAEE Plants Retrofitting FAME into FAEE Plants
Technically and chemically, FAEE production is very comparable to FAME production. Therefore,
existing biodiesel methyl ester plants have the technical possibilities to produce FAEE without major
retrofitting problems. However, some technical aspects will need to be modified.

Especially, possible problems with phase separation of ethyl esters from glycerol could require an
additional processing step (e.g. centrifugation or input of glycerol or acids for better phase separation).
Furthermore, in order to guarantee high conversion rates in combination with minimum losses of
chemicals used for transesterification, each piece of equipment would need to be optimised for ethanol
purification coming from the process. It has been mentioned that an excess of ethanol (with high
purity) is necessary for high conversion of the oils. During process, this ethanol excess will be
contaminated with process water. In order to reuse the ethanol, it has to be recycled and purified which
would require additional equipment and therefore additional investment costs. For retrofitting existing
FAME plants to FAEE production, this equipment might represent the major part of the additional
invests.

Additional problems might occur but cannot be evaluated generally. In fact, most technologies for
ethyl ester production are based on classical biodiesel processing used for FAME. Especially batch
type processing of ethyl esters has been extensively investigated and therefore have a higher potential
for early retrofitting than large continuous processes.

The most obvious and important barrier for ethyl ester production is the commercial aspect which will
be more detailed evaluated in chapter 3.4 and 3.5. Higher prices for ethanol compared to methanol and
additional energy input for processing and ethanol recovery discourage FAME producers to switch to
FAEE production. The environmental advantages of FAEE use in comparison with FAME are limited
(Chapter 4). Additionally, still missing quality standards for FAEE will have negative influences on
customers and engine manufacturers.
2.7 2.7 2.7 2.7 P PP Practical p ractical p ractical p ractical production roduction roduction roduction experience experience experience experience
Practical experience using FAEE as a fuel is limited mainly on funded studies and a few
demonstration projects. Brazil produces the cheapest ethanol and has some experiences with FAEE
production. However, it is not clear if FAEE is currently being produced in Brazil. Information from
the Brazilian biodiesel institution led to the result that most of them are producing mainly FAME due
to technical problem when switching to FAEE (see Annex F.3).

Large-scale commercial production of FAEE has not been tested yet. The recently constructed plant of
Usina Barralcool S.A. is the first biodiesel plant integrated with an ethanol plant designed for the
production also of ethyl ester. However, although the Brazilian biodiesel program recommends the
production through the ethyl route, it did not make it mandatory and, therefore, the market will have to
define the technology to be used.


BIOScopes
Additionally, many of the classified pilot-scale plants in USA and Brazil have been used within
funded projects for practical experience investigations on technology and engine tests and have been
dismantled or closed after the projects end. So therefore it was not possible to get confidential data on
currently running FAEE biodiesel plants world-wide, the quantities being produced and the quality
(due to non-existing FAEE standards). This is also valid for the situation in Europe, where no
industrial scale FAEE plant is working. However, a mid-scale plant nearby Set (France) is projected
which possibly should produce FAEE but this information could not be verified.

Due to the missing interest of customers, missing incentives and missing quality monitoring system,
large-scale FAEE production is practically non-existing. The only production facilities operating have
lab-scale or pilot-scale character. Of course, some of them are able to produce FAEE in small scale but
no information is available on the effective production amount.


BIOScopes
3 33 3 Quality Quality Quality Quality aspects aspects aspects aspects of FAEE of FAEE of FAEE of FAEE
Both the measurable fuel quality aspects of fatty acid ethyl esters in relation to the existing biodiesel
standard and its behaviour as a fuel in engines are important criteria for a successful market
introduction.
3.1 3.1 3.1 3.1 Fuel properties Fuel properties Fuel properties Fuel properties
Fatty acid ethyl esters have very similar chemically behaviour compared to the corresponding methyl
esters. Although in both cases, process technology, used feedstocks, alcohol, and catalysts are similar,
the resulting esters would have some differences concerning quality parameters according EN14214.
Such differences can be classified either into changes of values resulting or induced by the ethyl ester
group and differences of analytical determination methods. Parameters affected directly by the use of
ethanol for production are:
Viscosity: which might be significantly higher than compared to methyl esters. Basically most
vegetable oil ethyl esters would have viscosities below or nearby the current EN14214
specification limit but some of them (e.g. castor oil ethyl esters) would be far above the limit. In
fact, such higher viscosities would be one of the most critical argumentation points especially
for car manufacturers and engine producers in order to successfully introduce such a fuel.
Density: only slight or even negligible increases are expected but within specification limits.
Flash Point: higher than compared to methyl esters but in fact depending on process technology
for ethanol removal.
Distillation Characteristics: would differ from methyl esters due to the higher boiling points of
ethyl esters. For European specifications this parameter is not important but it is included in
other National standards (e.g. U.S.).
Carbon Residue: expected to be slightly higher but should be definitely within the given limits.
Oxidation Stability: not many data and experience available but first reports showed comparable
or even slightly higher oxidation stabilities of ethyl esters.
Low Temperature Behaviour: similar situation than mentioned on oxidation stability. Not many
data available but the fatty acid ethyl esters should have better low temperature behaviour
(CFPP/PP/CP). However, the differences will be in best case only some C.

Additional influences or changes of the mentioned parameters will be strongly dependent on the
technology used for production.

Furthermore, even some of the analytical methods of EN14124 have to be adopted for ethyl ester
application. Most of the current methods can be used without further modifications but especially the
ester specific methods have to be re-evaluated or even new designed. Concrete actions have to be set
on: ester content method (EN14103), linolenic acid ester content (EN14103), polyunsaturated fatty

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acid esters content (currently no existing method), methanol (ethanol) content (EN14110), mono-, di-,
and triglyceride content (EN14105), and iodine value if calculated on unsaturated fatty acid ester
content.
3.2 3.2 3.2 3.2 Engine application Engine application Engine application Engine application
Apart from production technology and actual quality standards, the behaviour of FAEE as a fuel in
engines is an important criterion for a successful market introduction. Compared to FAME where lots
of studies, reports, and data on engine and driving performance as well as on exhaust emission
behaviour are available, only few data exist about the use of ethyl esters. Especially data that give a
direct comparison between the behaviour of ethyl esters, methyl esters and diesel fuel are very rare.

The reason is that there has not been such an insistent need on ethyl esters so far. Furthermore, due to
missing large-scale production plants for ethyl esters, there are also no big fleet programs. Therefore,
most of the existing data is limited to short-term engine tests or long-term tests with only few vehicles.
In fact, most of the investigations have been carried out in USA where different investigations have
been undertaken mainly by the University of Idaho. These initiatives included, besides research on
production technology, also the corresponding evaluation of the engine behaviour of fatty acid ethyl
esters.

One project tested a biodiesel fuel prepared from ethanol and waste French-fry oil (Peterson, et al.
1995). This so called HySEE (hydrogenated soybean oil ethyl ester) fuel was screened in an 300h
engine durability test. At the end of the test, the engines were dissembled and inspected for evaluation
of the effect of the fuel on engine components, especially for coking of the so-called pintle injector,
pre-combustion chamber and piston ring grooves. In comparison to Number 2 Diesel fuel, the use of
HySEE increased the coking by a factor 3, but that was still considered low. Engine power and torque
were each reduced by about 5%. The average fuel consumption on a mass basis was about 7% higher.
The differences in fuel consumption and power reflect the differences in heat of combustion and
density between the two fuels. The emissions of hydrocarbon, carbon monoxide and nitrogen oxides
decreased significantly. More detailed results are given in Annex G.4. Unfortunately, it is impossible
to estimate from these results how FAEE would perform in comparison with FAME.

Similar results were obtained in an earlier project of the University of Idaho (1994) dealing with the
production and testing of ethyl and methyl esters. Methyl and ethyl esters of four renewable fuels
(canola, rapeseed, soybean oil, and beef tallow) were processed, characterized and performance tested.
Most of the results in this study focus on the differences between biodiesel and regular diesel, or the
FAEE and FAME performed the same. However, it was concluded that ethyl esters produced higher
levels of injector coking than the methyl esters did (details in Annex G.4).

Later a vehicle test with an 1994 Dodge 2500 pickup fuelled with ethyl esters of rapeseed oil was
carried out (Nimcevic, et al. 2000). A total distance of 14.069 km has been covered and engine
performance and emission behaviour have been monitored. Also this test showed significant emission

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reductions for hydrocarbon, carbon monoxide and nitrogen oxides, and significant reductions of power
and fuel economy (details in Annex G.4).

The results of these three reports indicate that ethyl esters of vegetable oils lead to comparable results
known for FAME. It should be noted that the mentioned investigations have been performed with
biodiesel produced in lab or even pilot scale and that due to missing specifications especially for ethyl
esters at that time the quality of the tested fuels (given in the reports) would not fit current EN14214
specification limits and therefore the results obtained of the engine tests might be influenced by this
varying quality. Several additional engine and performance tests have been carried out since then (see
also Annex F.3). These tests were on a small-scale and had demonstration character and in general
they led to comparable results (performance as well as emission characteristics) with earlier projects.

The mentioned results indicate only that the engine performance is very comparable to results obtained
for FAME so far. We assume that this is mainly caused by the context of those projects to compare
biodiesels with diesel and not with among each other.


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4 44 4 Environmental performance of FAEE Environmental performance of FAEE Environmental performance of FAEE Environmental performance of FAEE
The production of biodiesel with ethanol instead of methanol has been put forward as an
opportunity to increase the environmental performance of biodiesel. This chapter analyses the
environmental performance of the production and use of FAEE compared to that of FAME and
fossil diesel. The first section gives an overview of results found in literature with respect to NO
x
,
particulate emissions, toxicity and biodegradability. The second section makes a detailed analysis of
the well-to-wheel energy efficiency and GHG-balance of FAEE versus FAME and fossil diesel.
4.1 4.1 4.1 4.1 End End End End- -- -use emissions, use emissions, use emissions, use emissions, toxicity and biodegradibility toxicity and biodegradibility toxicity and biodegradibility toxicity and biodegradibility
Apart from the well-to-wheel greenhouse gas performance and energy use (Section 4.2), some more
general environmental aspects of biodiesel, with special focus on FAEE, deserve attention.

Environmental and health effects of biodiesel were for example examined by Reece et al. (1996).
According to several tests reported by them, biodiesel is nontoxic and biodegradable, resulting in less
potential hazard to animals, humans, and the aquatic environment.

A special focus on environmental effects of rapeseed oil ethyl ester was put by Makareviciene and
Janulis (2003). Exhaust emission tests were conducted on rapeseed oil methyl esters, rapeseed oil ethyl
esters and fossil diesel fuel as well as on their mixtures. Results showed that when considering
emissions of nitrogen oxides (NO
x
), carbon monoxide (CO) and smoke density, rapeseed oil ethyl
ester had less negative effect on the environment in comparison with that of rapeseed oil methyl ester.
When fuelled with rapeseed oil ethyl ester, the emissions of NO
x
showed an increase of 8.3% over
those of fossil diesel fuel. When operated on 25-50% bio-ester mixed with fossil diesel fuel, NO
x

emissions marginally decreased. When fuelled with pure rapeseed oil ethyl ester, HC emissions
decreased by 53%, CO emissions by 7.2% and smoke density 72.6% when compared with emissions
when fossil diesel fuel was used. Rapeseed oil ethyl ester was more rapidly biodegradable in aqua
environment when compared with rapeseed oil methyl ester and especially with fossil diesel fuel.
During a standard 21 day period, 97.7% of rapeseed oil methyl ester, 98% of rapeseed oil ethyl ester
and only 61.3% of fossil diesel fuel were biologically decomposed.

Comparable investigations on ethyl esters of pongamia oil were done by Chandraju and Prathima
(2003). The use of the ethyl ester of a non-edible oil and its performance in blends for diesel engines
was studied. The results showed a 14 to 17% mileage improvement and 65 to 71% smoke reduction on
using pure ethyl ester of pongamia oil (EEPO) and an EEPO 10% blend in diesel. Compared to diesel,
the EEPO 10% blend shows 71% reduction of exhaust emissions. Pure EEPO is the best alternative
fuel compared to high-speed diesel (HSD) due to its high calorific value and oily nature, which leads
to smooth operation of the engine.

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Knothe and Dunn (1998) report that most harmful exhaust emissions are reduced when replacing
diesel with biodiesel. However, some technical problems are still associated with the reduction of
nitrogen oxides exhaust emissions to meet increasingly stringent environmental regulations. Cetane-
improving additives decrease NO
x
emissions from regular diesel and could also be suitable to further
reduce nitrogen oxide emissions from biodiesel.

It seems that the effect especially on nitrogen oxides emissions is ambiguous, as some studies (refer to
Section 3.2) report significant emission decreases while others show some increase. This difference in
conclusions could be caused by the improvements made in engine technology, which would suggest
that the comparative advantage of biodiesel over diesel has disappeared over the last decade.

More details on the various studies are included in the survey in Annex F.3.
4.2 4.2 4.2 4.2 GHG performance and energy efficiency GHG performance and energy efficiency GHG performance and energy efficiency GHG performance and energy efficiency
Introd Introd Introd Introduction and methodology uction and methodology uction and methodology uction and methodology
This section analyses the effects of replacing methanol by ethanol on the GHG balance and energy
efficiency of biodiesel. For this purpose, first the energy efficiency and GHG balance of Fatty Acid
Methyl Esther (FAME) is calculated. This is done for two different oil feedstocks that represent two
extremes in terms of energy efficiency and GHG balance: palm oil and rapeseed. The purpose of
analysing different types of FAME with varying GHG balances is to determine to what extent the
effects of replacing methanol by ethanol depends on the oil feedstock. It is thereby expected that the
performance of most biodiesel produced from vegetable oils will fall within the rapeseed palm oil
range in terms of GHG balance and energy efficiency.

Having determined the energy efficiency and GHG balance of FAME, it will next be analysed what
the effects are of substituting methanol by ethanol by determining the energy efficiency and GHG
balance for Fatty Acid Ethyl Esters (FAEE) based on the same oil feedstocks. In doing so, a choice has
to be made on the feedstock that is used to produce the ethanol as this influences the energy efficiency
and GHG balance of the ethanol and thereby of the resulting FAEE. Again, two extremes were chosen
to give a performance range: ethanol from European wheat and ethanol from Brazilian sugar cane.

Together this creates the following six scenarios which will be analysed on their GHG and energy
balance, see Table 4-1. The performance of these six scenarios will also be compared to fossil diesel.
The GHG balance and energy efficiency in this analysis are based on economic allocation.


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Tabl e 4-1. Di f f er ent bi odi esel scenari os anal ysed i n thi s study on t hei r ef f ect on GHG-
bal ance and ener gy ef f i ci ency.
Bio-oil Feedstock FAME (Reference) FAEE-wheat FAEE-sugar cane

Rapeseed FAME-rapeseed FAEE-rapeseed-wheat FAEE-rapeseed-sugar cane
Palm oil FAME-palm oil FAEE-palm oil-wheat FAEE-palm oil-sugar cane

Based on the resulting GHG performance and energy efficiency of both FAME and FAEE conclusions
are drawn on the effects of replacing methanol by ethanol in the production of biodiesel.
Results base case scenario: FAME Results base case scenario: FAME Results base case scenario: FAME Results base case scenario: FAME
E n e r g y e f f i c i e n c y E n e r g y e f f i c i e n c y E n e r g y e f f i c i e n c y E n e r g y e f f i c i e n c y
The energy efficiencies of FAME from rapeseed and palm oil are shown in Figure 4-1. In this figure
the following categories can be distinguished:
Feedstock production (dark green): this includes all fossil energy consumption related to
feedstock production such as fertilizer production and application, diesel consumption by
agricultural machines, etc.
Waste products (light green): this category was especially introduced to capture the methane
emissions caused by waste water from palm oil mills. This category is therefore only used in the
GHG balance and not in the energy efficiency.
Feedstock transport (light blue): this includes the fossil energy consumption from transporting
the feedstock to the processing plant (crushing plant for bio-oil).
Bio-oil (purple): this includes the fossil energy consumption from the processing plant. In the
processing plant the oil is expelled out of the oilseeds.
Transportation of bio-oil (yellow): this includes the fossil energy consumption from transporting
the pressed oil to the biodiesel factory.
Transesterification (red): this includes all fossil energy consumption related to the
transesterification of the bio-oil together with methanol to biodiesel. This does not include the
energy content of the methanol or the energy required to produce the ethanol.
Fuel distribution (dark blue): this includes the fossil energy consumption related to transporting
the biodiesel to the fuel station.
End-use direct (dark gray): this includes the fossil energy contained in the final fuel. For FAME
this refers to the methanol fraction in the biodiesel. For fossil diesel this is the full energy
content of the diesel (1 MJ/MJ).
End-use indirect (light gray): this refers to the energy required to produce and transport the
fossil energy in the final fuel. As can be seen from Figure 4-1 methanol has a relatively poor
energy efficiency with 1.9 MJ
fossil
/MJ
methanol
(38.08 MJ/kg methanol (Elsayed, et al. 2003)).


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0.00
0.20
0.40
0.60
0.80
1.00
1.20
FAME rapeseed FAME palm oil Reference diesel
M
J

f
o
s
s
i
l

/

M
J

f
u
e
l
End-use direct
End-use indirect
Fuel distribution
Transesterification
Transport bio-oil/ethanol
Bio-oil & ethanol production
Feedstock transport
Waste products
Feedstock production

Fi gur e 4-1. Ener gy ef f i ci ency of sel ect ed FAME compared t o di esel .

As can be seen from Figure 4-1, both FAME-rapeseed and FAME-palm oil have a significantly better
energy efficiency than diesel: respectively 0.42 and 0.20 MJ
fossil
/MJ
biodiesel
compared to 1.14 for diesel.
Thereby FAME-palm oil uses more than 50% less fossil fuel than FAME-rapeseed. The main reasons
for the large difference between FAME-palm oil and FAME-rapeseed are:
Feedstock production (green in Figure 4-1):
Fertilizers: palm oil has a very high oil yield per ha per year compared to rapeseed while
at the same time it requires less fertilizer per ha per year. The amount of fertilizer needed
per unit of palm oil is therefore significantly lower than the amount needed per unit of
rapeseed oil. The result is a fossil energy consumption for fertilizers of 0.024
MJ
fossil
/MJ
biodiesel
versus 0.082 MJ
fossil
/MJ
biodiesel
for palm oil and rapeseed respectively.
Machinery: palm oil harvesting is mainly done manually while rapeseed production is
heavily mechanised. The result is a fossil energy consumption for machinery of 0.003
MJ
fossil
/MJ
biodiesel
versus 0.070 MJ
fossil
/MJ
biodiesel
for palm oil and rapeseed respectively
3

Extraction (purple in Figure 4-1):
Palm oil extraction is mostly done by mills which use (almost) 100% palm oil by-products
as a fuel source, thereby not consuming any fossil fuel in the process. Oil extraction from
rapeseed instead consumes 0.091 MJ
fossil
/MJ
biodiesel
.

It should be stated explicitly here that this study treats the methanol fraction in FAME as fossil energy
and that FAME can thus not be considered a 100% biofuel. This statement deviates from the EU
directive on biofuels which treats FAME as 100% biofuel.

3
Note than even for rapeseed production, which is heavily mechanised, fossil energy consumption is dominated
by fertilizers and not by machinery (0.082 MJfossil/MJbiodiesel for fertilizer versus 0.070 MJfossil/MJbiodiesel
for machinery).

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G H G G H G G H G G H G - -- - p e r f o r m a n c e p e r f o r m a n c e p e r f o r m a n c e p e r f o r m a n c e
The GHG-performance of FAME-palm oil and FAME-rapeseed are significantly better than that of
diesel but the benefits are smaller than for the energy efficiency, see Figure 4-2. The main reason for
this is the N
2
O emissions from fertilizers, which is a very powerful GHG. As with the energy
efficiency, FAME-palm oil brings significantly larger benefits than FAME-rapeseed. GHG benefits of
FAME compared to diesel are 36% and 64% respectively for FAME rapeseed and FAME palm oil. In
addition to the observations mentioned above for the energy efficiency, the following observations are
important for the GHG-emissions:
Feedstock production (dark green in Figure 4-1): because palm oil requires significantly less N-
fertilizer input per unit of oil than rapeseed, and N-fertilizers cause N
2
O emission, the GHG-
emissions of palm oil feedstock production are several times lower than for rapeseed.
Waste products (light green in Figure 4-1): the palm oil milling process generates Palm Oil Mill
Effluent which is treated in ponds, thereby emitting the powerful GHG methane. As can be seen
from Figure 4-2, methane emissions from POME almost equal the total GHG-emissions of palm
oil feedstock-production.

0.0000
0.0100
0.0200
0.0300
0.0400
0.0500
0.0600
0.0700
0.0800
0.0900
FAME rapeseed FAME palm oil Reference diesel
G
H
G
-
e
m
i
s
s
i
o
n
s

(
k
g

C
O
2

e
q
u
i
v
a
l
e
n
t
/
M
J

f
u
e
l
)
End-use direct
End-use indirect
Fuel distribution
Transesterification
Feedstock transport
Waste products

Fi gur e 4-2. GHG-emi ssi ons of sel ect ed FAME compar ed t o di esel .
Results of replacing methanol by eth Results of replacing methanol by eth Results of replacing methanol by eth Results of replacing methanol by etha aa anol nol nol nol
E n e r g y e f f i c i e n c y E n e r g y e f f i c i e n c y E n e r g y e f f i c i e n c y E n e r g y e f f i c i e n c y
The effects of replacing methanol by ethanol on the energy efficiency of biodiesel is depicted in
Figure 4-3 and Figure 4-4. In the case of biodiesel from rapeseed the benefits of FAEE compared to
FAME are respectively 12% and 23% of the total fossil energy consumption for FAEE-rapeseed-
wheat and FAEE-rapeseed-sugar cane. In other words, the savings on fossil energy are twice as large
if ethanol from sugar cane is used in stead of ethanol from wheat.


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For biodiesel from palm oil the relative effects are larger because of the lower absolute fossil energy
consumption and GHG-emissions of palm oil derived biodiesel. For FAEE-palm oil-wheat and for
FAEE-palm oil-sugar cane respectively 21% and 44% less fossil fuel is consumed than for FAME-
palm oil.

The most important differences between FAME and FAEE in the energy efficiency are:
Methanol: No methanol (a fossil fuel) is consumed in FAEE which directly saves both the direct
and indirect energy consumption of ethanol in the end-use (the light gray and dark gray areas in
Figure 4-3 and Figure 4-4).
Ethanol:
The ethanol which replaces the methanol needs to be produced. Basically two feedstocks
now have to be produced: the vegetable oil and the ethanol. This increases the fossil
energy consumption in the following categories: feedstock production, feedstock
transport, bio-oil & ethanol production, and transport of bio-oil/ethanol.
Sugar cane outperforms wheat in both the feedstock production and the ethanol
production stage: Sugar cane production requires less fertilizer than wheat production, and
the sugar cane ethanol plant is powered by sugar cane residues.
FAEE requires less bio-oil input per kg of biodiesel than FAME.
Ethanol has a higher molecular weight than methanol: 46 instead of 32. Assuming a
constant molecular ratio of alcohol to bio-oil, the production of FAEE requires more
ethanol (kg
ethanol
/kg
biodiesel
) than FAME requires methanol (kg
methanol
/kg
biodiesel
). Similarly,
the production of FAEE requires less bio-oil (kgbio-oil/kg
biodiesel
) than FAME requires
methanol (kgbio-oil/kg
biodiesel
)
4
.

The effect that this has on the energy efficiency depends
on the energy efficiency of the ethanol compared to the energy efficiency of the bio-oil
which it replaces. For example, rapeseed feedstock production is less energy efficient than
sugar cane feedstock production. This means that the replacement of rapeseed oil by sugar
cane ethanol has a positive effect on the energy efficiency. This can be seen in Figure 4-3
where the energy consumption for feedstock production for FAEE-rapeseed-sugar-cane is
lower than for FAME-rapeseed while FAEE-rapeseed-sugar-cane clearly requires more
feedstock production than FAME (FAEE-rapeseed-sugar-cane requires the production of
both rapeseed and sugar cane while FAME-rapeseed only requires rapeseed production).
The opposite is true for FAEE-palm-oil-wheat. Feedstock production for ethanol from
wheat has a lower energy efficiency than feedstock production for palm oil. Therefore the
displacement effect of palm oil by ethanol from wheat has a negative effect on the energy
efficiency. Toghether with the fact that FAEE requires two feedstocks to be produced and
FAME only one, this leads to a significantly higher energy consumption for feedstock
production for FAEE-palm-oil-wheat compared to FAME-palm-oil. A detailed graph
showing the relative contribution of the bio-oil and ethanol fraction to the total energy
consumption of the resulting biodiesel is included in Annex E.

4
The quantitative differences in bio-oil and alcohol requirements are described in Annex D.


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For the transesterification process no good data was available for FAEE. The assumption made is that
the transesterification process is similar for FAME and FAEE.
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
FAME rapeseed FAEE rapeseed-wheat FAEE rapeseed-sugar
cane
M
J

f
o
s
s
i
l

/

M
J

f
u
e
l
End-use direct
End-use indirect
Fuel distribution
Transesterification
Feedstock transport
Waste products

Fi gur e 4-3. Ener gy ef f i ci ency of FAEE ver sus FAME fr om r apeseed.
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
cane
M
J

f
o
s
s
i
l

/

M
J

f
u
e
l
End-use direct
End-use indirect
Fuel distribution
Transesterification
Feedstock transport
Waste products

Fi gur e 4-4. Ener gy ef f i ci ency of FAEE ver sus FAME fr om pal m oi l .


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G H G G H G G H G G H G - -- - b a l a n c e b a l a n c e b a l a n c e b a l a n c e
The effects of replacing methanol by ethanol on the GHG-balance are less positive than the effects on
the energy efficiency.
For rapeseed derived biodiesel respectively 7% and 13% less GHG-emissions are caused by
FAEE-wheat and FAEE-sugar cane compared to FAME.
For palm oil derived biodiesel these figures are 9% and 21% respectively. The small effect on
the GHG-balance of FAEE-wheat compared to FAME for palm oil derived biodiesel is caused
by the relative bad energy efficiency of ethanol from wheat.
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
FAME rapeseed FAEE rapeseed-
wheat
FAEE rapeseed-
sugar cane
G
H
G
-
e
m
i
s
s
i
o
n
s

(
k
g

C
O
2

e
q
u
i
v
a
l
e
n
t
/
M
J

f
u
e
l
)
End-use direct
End-use indirect
Fuel distribution
Transesterification
Feedstock transport
Waste products

Fi gur e 4-5. GHG bal ance of FAEE compar ed t o FAME f rom r apeseed.
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
cane
G
H
G
-
e
m
i
s
s
i
o
n
s

(
k
g

C
O
2

e
q
u
i
v
a
l
e
n
t
/
M
J

f
u
e
l
)
End-use direct
End-use indirect
Fuel distribution
Transesterification
Feedstock transport
Waste products

Fi gur e 4-6. GHG bal ance of FAEE compar ed t o FAME f rom pal m oi l .


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The reasons for the modest benefits in GHG balance compared to the benefits in energy efficiency can
be explained by:
Methanol emissions make up a large fraction of the total energy consumption of FAME and
only a small fraction of GHG emissions of FAME. Therefore the potential gains for GHG by
replacing methanol are also smaller.
The main activities responsible for the GHG emissions of biodiesel, bio-oil feedstock
production and methane emissions from POME, are not affected by the replacement of methanol
by ethanol (or only to a very limited extent).
One of the main causes of GHG-emissions in the production of biodiesel are N
2
O-emissions
from N-fertilizers needed for feedstock production. Replacing methanol by ethanol requires the
production of a second feedstock, for ethanol production, which increases N
2
O-emissions from
fertilizer usage. The size of this effect depends on the amount of fertilizer needed for the
cultivation of the ethanol feedstock: thereby wheat requires significantly more N-fertilizer per
unit of ethanol than sugar cane.
Conclusions Conclusions Conclusions Conclusions
Replacing methanol by ethanol has a positive effect on both the energy efficiency and the GHG-
balance of the resulting bio-diesel. As can be seen from Table 4-2, the relative benefits in the energy
efficiency depend on the feedstock of both the bio-oil and the ethanol. The relative benefits in energy
efficiency are larger for biodiesel made from bio-oils with a high energy efficiency such as palm oil.
Furthermore, for a given bio-oil feedstock the benefits in energy efficiency vary widely depending on
the ethanol feedstock used. Thereby ethanol from sugar cane provides significantly larger benefits in
energy efficiency than ethanol from wheat.
Tabl e 4-2. Ener gy ef f i ci ency gai ns of FAEE compar ed t o FAME dependi ng on t he oi l and
et hanol f eedst ock. Ener gy ef f i ci enci es of FAME ar e 0. 42 and 0. 20
MJf o s s i l /MJbi o di e s el f or FAME rapeseed and FAME pal m oi l r espect i vel y,
compar ed t o 1. 14 f or di esel .
Rapeseed Palm oil

Wheat 12% 21%
Sugar cane 23% 44%

The positive effects on the GHG-emissions are more moderate, see Table 4-3. Again relative benefits
are higher for palm oil than for rapeseed. GHG benefits are roughly twice as large when ethanol from
sugar cane is used in stead of ethanol from wheat.
Tabl e 4-3. GHG bal ance gai ns of FAEE compar ed t o FAME dependi ng on t he oi l and
et hanol f eedst ock. Compared t o di esel FAME emi t s 36% and 64% l ess
GHG s f or FAME rapeseed and FAME pal m oi l r espect i vel y.
Rapeseed Palm oil

Wheat 7% 9%
Sugar cane 13% 21%


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Overall, it can be concluded that the choice in ethanol feedstock has a large influence on both the
energy efficiency and GHG-benefits of FAEE over FAME. Ethanol from wheat thereby offers only
moderate GHG-benefits compared to FAME. Furthermore, when compared to FAME, FAEE offers
generally larger benefits in terms of energy efficiency than in terms of GHG emissions.

The largest gains seem to be possible if the somewhat better cold-flow properties of FAEE allow for
utilisation of higher fractions of palm oil, where FAME would include more rapeseed oil. It must
however be noted that palm oil, if produced in an unsustainable way, could have negative side-effects
for sustainability in general and for the greenhouse gas balance in particular, which could counteract
5

the positive effects summarised in Table 4-3.

5
Current work by Ecofys, CE and E4Tech in projects for the Dutch and UK government respectively, indicates
the possibly large impact from soil carbon stock change on the well-to-wheel greenhouse gas balance
in case of supply chains that include unfavourable land-use changes.

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5 55 5 Economic Economic Economic Economic analysis of FAEE analysis of FAEE analysis of FAEE analysis of FAEE
The production costs of FAEE are compared to that of FAME. The analysis starts by describing the
reference situation: the production costs of FAME. Next, the differences in the production process
of FAEE versus FAME will be described and their effect on the production costs are analysed.
5.1 5.1 5.1 5.1 Base Base Base Base- -- -line: FAME production costs line: FAME production costs line: FAME production costs line: FAME production costs
In the production costs of FAME we distinguish the following components:
Costs of bio-oil: the main ingredient of FAME and as we will see the main cost component in
the production of FAME. We have used a mix of 85% rapeseed and 15% palm oil for our
calculations.
Costs of alcohol: methanol in the case of FAME.
Costs of catalyst: Sodium methoxide is the common catalyst for FAME production and will be
used in our analysis.
Costs of energy: for consistency reasons we use the energy input requirements for the
production of biodiesel which are also used for the greenhouse gas balance made for FAME in
this study.
Income from glycerol
Capital costs
Maintenance costs
Labour costs

The values used in this analysis are summarised in Table 5-1.
Tabl e 5-1. Input par amet ers used f or cal cul at i on of FAME pr oducti on cost s.
Component Parameter Value Unit

Bio-oil Rapeseed oil costs
1)
640

/tonne
RBD palm oil costs
1)
406

/tonne
Requirement
8)
1.0526

kg oil/kg FAME
Alcohol Methanol costs
2)
250

/tonne
Requirement
8)
0.109

kg methanol/kg FAME
Catalyst Sodium Methoxide costs
3)
700

/tonne
Glycerine Value Glycerine
1)
350 /tonne
Requirement
8)
0.10

kg glycerine/kg FAME
Energy Electricity costs
7)
0.017

/MJ
Natural Gas costs
6)
0.0056

/MJ
Fuel Oil costs
5)
0.017

/MJ
Labour 150,000 tonne/y plant
4)
0.3% of total prod. costs

Maintenance 150,000 tonne/y plant
4)
3% of investment / year
Specific investment 150,000 tonne/y plant
4)
67

/annual ton biodiesel
Payback Economic life time 10 years
Discount rate 10%

1)
Oil World (2006).
2)
ICIS (2006)
3,4)
Based on confidential benchmark analyses performed by Ecofys.

BIOScopes
5)
Based on a price of 0.60 per litre, energy content of 42 MJ/kg and a density of 835 kg/m
3
.
6)
Based on a price of 20 /MWh (Statkraft, 2006)
7)
Based on a price of 61 /MWh (Statkraft 2006)
8)
Elsayed (2003)

The resulting costs for the production of FAME are 0.61 /l biodiesel (including revenues from
glycerine) and are shown in Figure 5-1. What can be seen from this figure is that the bio-oil feedstock
makes up the majority of the biodiesel costs with 89% of total costs. The costs of methanol make up
around 4% of total costs as do energy costs. Fixed capital costs, labour costs, catalyst costs and
maintenance costs all constitute a minority fraction of total biodiesel costs.
5.2 5.2 5.2 5.2 FAEE production costs FAEE production costs FAEE production costs FAEE production costs
General principles General principles General principles General principles
The economic calculation of ethyl ester production should give an idea on costs which might be
arising for producers and investors interested in this kind of alternative fuel production. In fact, the
scenarios given in this section represent only rough calculations, influenced by many different
parameters that cannot be included as exact values but only as assessments based on already existing
-0.10
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
FAME
e
u
r
o

/

l

b
i
o
d
i
e
s
e
l
Capital costs
Maintenance costs
Labor
Energy costs
Catalyst
Alcohol
Bi Oil
Glycerine

89.0%
0.3%
0.3%
1.5%
4.1%
1.0%
3.8%

Fi gur e 5-1. FAME pr oduct i on cost s i n Eur o per l i t r e bi odi esel and per centage of t ot al
cost s. In t he l ef t gr aph t he benef i ts f r om gl ycer i ne have been subtr act ed
f r om t he cost s of the bi o oi l i n order t o have a corr ect represent at i on of t he
t ot al cost pr i ce of bi odi esel . In t he ri ght f i gur e, the f r act i on of total cost s
has been obt ai ned by di vi di ng t he cost s of t he component by t he t ot al cost s
wi t hout subt r act i ng t he gl yceri ne benef i t s f rom t he t ot al cost s: ot her wi se
t he t ot al cost s woul d amount to mor e t han 100%.

BIOScopes
experience and technology. So therefore, different ancillary conditions had to be set in order to enable
and guarantee a comprehensive cost calculation:
Technology: As already mentioned, experience with large-scale ethyl ester production is
currently not available. Only pilot-scale and small scale production plants have been operated so
far. Therefore, the scenario for the calculation of production costs is based on available practical
experience and on most promising technology suitable for ethyl ester production even in large
scale. This means in detail that such kind of production plant will be running on classical
biodiesel process including two-step batch transesterification of the oil, typically washing and
purification steps for the produced biodiesel, glycerol processing and fertilizer production as by-
products. Classical alkaline transesterification using KOH as catalyst is used.
Alcohol: the Ethanol used for transesterification must be of high purity. Anhydrous alcohol is
therefore selected for the calculation.
Additional invests for ethyl ester production: Within the cost calculation, especially this part is
very difficult to evaluate due to missing experience and references. Additional costs for energy
(ethanol recovery etc.) are estimated being 5%. More invests for the additional technology and
equipment necessary for the biodiesel plant are set on 25%. These invests include mainly the
ethanol recycling path. An excess of ethanol is necessary for the production of the ester. For
ethanol reuse, the alcohol has to be purified again to guarantee anhydrous quality.
Alcohol price scenarios: Different scenarios are included in the calculation. A comparison of
different ethanol prices world-wide is kept as well as differences of methanol prices for a direct
comparison. Furthermore, due to increasing methanol prices during the last months a critical
value for methanol has been calculated. This price indicates equal costs for biodiesel production
of FAEE chain as well as FAME.
Parameters for FAEE production Parameters for FAEE production Parameters for FAEE production Parameters for FAEE production
The technical analysis of FAEE production made clear how the process and its mass and energy
balances are changed in comparison with FAME production. This leads to the following changes to
the production cost parameters:
Bio-oil requirement: 1.0047 kg oil/kg biodiesel is used instead of 1.0053 because of the higher
molecular weight of ethanol compared to methanol which leads to a substitution of oil by
ethanol by weight in FAEE: see Annex D.
Alcohol requirement: 0.150 kg ethanol/kg biodiesel instead of 0.109. Again due to the
difference in molecular weight between methanol and ethanol, see Annex D.
Energy consumption increases with +5%. This is to compensate for the additional energy
requirements from the recovery of ethanol which has a higher boiling point.
Investment costs are estimated to increase with +15%. While much of the production of FAME
and FAEE is similar, FAEE will require additional equipment to purify the ethanol which is
recovered from the process.
The ethanol price in the EU is estimated at 700 /tonne (refer to Figure 5-3).
Oil feedstock: two options have been analysed
One in which the oil feedstock remains the same: e.g. 85% rapeseed and 15% palm oil.

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One in which the expected improvements in cold flow properties are exploited to increase
the fraction of palm oil to 25% (rest is rapeseed oil). This is done to illustrate the potential
positive effects on the economics of FAEE if it indeed proves to have better cold flow
properties because of which cheaper feedstock such as palm oil can be used in larger
quantities.
The other production cost parameters (such as catalyst and labour) as well as the parameters for
glycerine revenues have been assumed to remain the same as with the production of FAME.
Note that all these parameters which are kept constant have only a very limited influence on the
total price of biodiesel.
Results Results Results Results
The results are shown in Figure 5-2. The main findings are:
Overall costs for FAEE production are modestly higher than that of FAME production. The
integral costs of FAEE with the same feedstock is 0.66 /l compared to 0.61 /l for FAME
(7.7% higher costs).
If the better cold flow properties of FAEE indeed allow for a 10% higher palm oil fraction in the
feedstock mix, the integral costs of FAEE are reduced to 0.64 /l (4.3% higher costs than
FAME). The cheaper oil feedstock mix thus reduces the gap between the costs of FAEE
compared to that of FAME, but FAEE remains more expensive.
The main differences between FAME and FAEE are obviously caused by the higher costs of the
-0.100
0.000
0.100
0.200
0.300
0.400
0.500
0.600
0.700
FAME FAEE FAEE (cheaper bio-oil)
e
u
r
o

/

l

b
i
o
d
i
e
s
e
l
Capital costs
Maintenance costs
Labor
Energy costs
Catalyst
Alcohol
Bi Oil
Glycerine

Fi gur e 5-2. Cost s FAME and FAEE. For FAEE a scenar i o has been comput ed i n
whi ch the oi l f eedst ock r emai ns t he same as i n FAME and a
scenar i o i n whi ch t he oi l f eedst ock i ncl udes more pal m oi l (25%
i nst ead of 15%), whi ch i s possi bl e due t o t he expected
i mpr ovement s i n col d f l ow pr oper ti es i n FAEE.

BIOScopes
ethanol compared to methanol. Part of the increased alcohol costs is caused by the higher price
of ethanol in comparison to methanol. Note that another part of the increase in the costs of the
alcohol are caused by a displacement of bio-oil by ethanol (on weight basis) in the production of
FAEE because of the higher molecular weight of ethanol compared to methanol (the extent of
this replacement is calculated in Annex D). This is also the reason why the oil feedstock costs
are lower for FAEE, even if the same oil feedstock mix is used: simply less bio-oil is needed per
litre of biodiesel in the production of FAEE compared to FAME.
The other changes in the production parameters have a rather limited effect on the total biodiesel
price:
The overall effect of a 5% increase in energy consumption barely increases the total costs.
The overall effect of a 15% increase in investment barely increases total costs.
Impact of methanol and ethanol prices Impact of methanol and ethanol prices Impact of methanol and ethanol prices Impact of methanol and ethanol prices
The results of the economic analysis have clearly shown that the price of the ethanol compared to the
price of methanol is the most important factor driving the difference in costs between FAME and
FAEE with ethanol prices being almost triple the price of methanol in this economic analysis.
However, the price of ethanol depends strongly on the geographical location and fluctuates strongly
over time see Figure 5-3. Methanol prices have been more constant over time but witnessed a sharp
increase recently. Current (January 2007) methanol prices are 420 /MT compared to 250 /MT six
months ago.

0
100
200
300
400
500
600
700
800
900
1000
0
1
-
0
1
-
2
0
0
4
2
9
-
0
6
-
2
0
0
4
2
6
-
1
2
-
2
0
0
4
2
4
-
0
6
-
2
0
0
5
2
1
-
1
2
-
2
0
0
5
1
9
-
0
6
-
2
0
0
6
1
6
-
1
2
-
2
0
0
6
1
4
-
0
6
-
2
0
0
7

/

t
o
n
n
e
Methanol Europe
Ethanol USA

Fi gur e 5-3. Met hanol and f uel ethanol pr i ce devel opment i n the l ast 3 years (Oxy-Fuel
2006, 2007; Met hanex).

BIOScopes
To illustrate the effects of price changes in methanol and ethanol, several scenarios have been
analysed at which FAEE is competitive in price to FAME:
At a methanol price of 250 /MT, FAEE has the same costs as FAME at a fuel-ethanol price of
348 /MT, or half todays EU fuel-ethanol prices.
At a methanol price of 420 /MT (January 2007), FAEE has the same costs as FAME at a fuel-
ethanol price of 472 /MT, which is still substantially below the average price in the EU of
around 700 /MT in January 2007 (ICIS 2007, http://www.icispricing.com/).
If the higher methanol price (420 /MT) is combined with a cheaper oil feedstock mix for FAEE
(25% palm oil in stead of 15%), FAEE becomes competitive to FAME at a fuel-ethanol price of
629 /MT, which is only 10% under todays EU prices.
Brazilian fuel-ethanol price forecast for 2007 is 1.18 $/Gallon (Fapri 2006, U.S. and World
Agricultural Outlook, Food and Agricultural Policy Research Institute) or 240 /MT
6
. Assuming
similar oil feedstock mixes for FAEE and FAME and production costs similar to the EU
scenario, this makes FAEE competitive to FAME at a methanol price of 101 /MT, far below
current prices levels.
5.3 5.3 5.3 5.3 Conclusions Conclusions Conclusions Conclusions
At 2006-level commodity prices, FAEE costs are 0.66 /l compared to 0.61 /l for FAME (7.7%
higher costs). The difference is mainly caused by the higher cost of using ethanol compared to using
methanol. This, in turn is caused by a combination of both the higher prices of fuel-ethanol on itself,
and by the fact that more ethanol (by mass) is needed in the production of FAEE than methanol is
needed in the production of FAME.

However, methanol prices have risen sharp recently and at todays methanol prices the costs of FAME
increase to 0.63 /l, or only 5% below the costs of FAEE. This indicates that if methanol prices
increase faster than ethanol prices in the coming years, FAEE production can become an alternative to
FAME from the economic point of view. In countries with lower fuel-ethanol prices such as Brazil
FAEE can be more economic than FAME: assuming a similar biodiesel cost structure as in the EU,
Brazilian FAEE is more economic than FAME at methanol prices higher than 100 /MT (which is
substantially below todays market prices of over 400 /MT).

Finally, FAEE may offer opportunities to increase the fraction of cheaper bio-oil feedstocks in case the
cold flow properties of FAEE are better compared to FAME. At todays methanol and fuel-ethanol
prices, an increase in the fraction of palm oil from 15% to 25% makes FAEE economic to FAME at an
fuel-ethanol price of 630 /MT: only 10% below todays EU price-level. Note, however, that the
improvement of the cold-flow properties seems to be limited, see Section 3.1.

6
Assuming an exchange rate of 0.77 US $/ (exchange rate at 23-1-2007).

BIOScopes
6 66 6 Conclusions Conclusions Conclusions Conclusions
6.1 6.1 6.1 6.1 Technical aspects Technical aspects Technical aspects Technical aspects
Technically and chemically, FAEE production is very comparable to FAME production. Therefore,
existing biodiesel methyl ester plants have the technical possibilities to produce FAEE without major
retrofitting problems. However, some technical aspects will need to be modified.

From a technical point of view the most promising and investigated technology will be based on
alkaline catalysts whether in form of sodium or potassium hydroxides or in form of sodium or
potassium alkoholates (most likely methoxides). Furthermore reaction time, catalyst amount and
reaction temperature are the most influencing factors on the velocity of the reaction and therefore have
to be optimized for production. Phase separation is a major hurdle in ethyl ester production. The main
reasons being the far better solubility of ethanol in the ethyl ester phase in comparison to methanol and
increased risk for saponification (formation of soaps).

Practical experience using FAEE as a fuel is limited mainly on funded studies and a few
demonstration projects. Brazil produces the cheapest ethanol and has some experiences with FAEE
production. It was not possible to get confidential data on currently running FAEE biodiesel plants
world-wide. Due to the missing interest of customers, missing incentives and missing quality
monitoring system, large-scale FAEE production is practically non-existing. The only production
facilities operating have lab-scale or pilot-scale character. Of course, some of them are able to produce
FAEE in small scale but no information is available on the effective production amount.
6.2 6.2 6.2 6.2 Quality aspects of FAEE Quality aspects of FAEE Quality aspects of FAEE Quality aspects of FAEE
Both the measurable fuel quality aspects of fatty acid ethyl esters in relation to the existing biodiesel
standard and its behaviour as a fuel in engines are important criteria for a successful market
introduction. Fatty acid ethyl esters have very similar chemically behaviour compared to the
corresponding methyl esters. Some differences can be expected on parameters relevant for the
EN14214, such as a significantly higher but still acceptable viscosity and somewhat lower cold flow
properties.

Not much is known about the application of FAEE in engines in comparison with FAME application,
since most (older) studies that did deal with FAEE compared its performance to regular diesel. The
few useful studies indicated that FAME and FAEE may have very similar performance, but there is
possibly some increased coking on engine parts.

BIOScopes
6.3 6.3 6.3 6.3 Sustainability aspects Sustainability aspects Sustainability aspects Sustainability aspects
The choice in ethanol feedstock has a large influence on both the energy efficiency and greenhouse
gas benefits of FAEE over FAME. Ethanol from wheat thereby offers only moderate greenhouse gas
benefits compared to FAME, while ethanol from sugar cane has the potential to significantly improve
the well-to-wheel greenhouse gas balance.

When compared to FAME, FAEE offers generally larger benefits in terms of energy efficiency than in
terms of GHG emissions.

In the final comparison, it was shown that FAEE produced from sugar cane ethanol and with
utilisation of a large fraction of palm oil could perform much better on the greenhouse gas balance
than FAME from rapeseed. This was especially caused by the high yields per hectare that can be
realised for sugar cane and palm oil. It must, however, be noted that if the palm oil is produced in an
unsustainable way, this positive effect could be completely counteracted.
6.4 6.4 6.4 6.4 Economic Economic Economic Economic aspects aspects aspects aspects
At 2006-level commodity prices, FAEE costs are about 8 % higher than FAME costs, because of
higher prices of fuel-ethanol compared to methanol. However, methanol prices have risen sharp
recently. If methanol prices continue to increase faster than ethanol prices in the coming years, FAEE
production can become an alternative to FAME from the economic point of view.

In countries with lower fuel-ethanol prices such as Brazil FAEE can be directly more economic than
FAME.

The slightly better cold-flow properties of FAEE in comparison with FAME allows for more
utilisation of cheaper vegetable oils like palm oil which could improve the production costs of FAEE
and make FAEE more competitive.


BIOScopes
7 77 7 References References References References
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Chemical & Environmental Research, 12: 289-293.
Chowdhury DK and Mukherji BK, 1954, Ethanolysis of vegetable oils using sodium hydroxide as
catalyst, I, Effect of ethanol and catalyst concentration and soap formation, Journal of the Indian
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Chowdhury DK and Mukherji BK, 1954, Ethanolysis of vegetable oils using sodium hydroxide as
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Wageningen the Netherlands.
Elsayed MA, Matthews R and Mortimer ND, 2003, Carbon and energy balances for a range of
biofuels options, Sheffield Hallam University/Resources Research Unit, Sheffield UK.
FAO, 2001, Fertiliser use by crop, United Nations Food and Agricultural Service >Land and water
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Feuge RO and Gros AT, 1949, Modification of vegetable oils, VII, Alkali catalyzed interesterification
of peanut oil with ethanol, Journal of the American Oil Chemists' Society, 26: 97-103.
Freedman B, Pryde EH and Mounts TL, 1984, Variables affecting the yields of fatty esters from
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Gauglitz EH and Lehman LW, 1963, The preparation of alkyl esters from highly unsaturated
triglycerides, Journal of the American Oil Chemists' Society, 40: 197-198.

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Glass RL, 1963, Alcoholysis, saponification and the preparation of fatty acid methyl esters, Lipids, 6:
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GTZ, 1997, Environmental management guideline for the palm oil industry, Deutsche Gesellschaft fr
Techniche Zusammenarbeit (GTZ), Bangkok Thailand.
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ICIS, 2006, ICIS Pricing, FOB Rotterdam, Q3 2006, www.icispricing.com.
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Korus RA, Hoffmann DS, Bam N, Petersom CL and Drown DC, 1993, Transesterification process to
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Canada.
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Annex A Feedstock producti on
Factual information on the production of feedstock was previously summarised in Ecofys
Participative LCA on biofuels (Hamelinck and van den Broek 2005), and Future scenarios for
biofuels (Hamelinck and Hoogwijk 2006).
A.1 A.1 A.1 A.1 Oil palm fruits Oil palm fruits Oil palm fruits Oil palm fruits
Tabl e A-1. Pr oduct i on of pal m oi l f r ui t i n Asi a.

Yields
1)

Fresh Fruit Bunches
No co-product

19.2 tonne/ha/yr
Energy and materials
Energy
2)

Fertiliser
3)

500 MJ/ha/yr
98 kg N/ha/yr
38 kg P2O5/ha/yr
146 kg K2O/ha/yr

1)
A Fresh Fruit Bunch (FFB) can contain from 1,000 to 3,000 individual fruits, together weighing 10 to
20 kilograms. Every mature oil palm tree produces several bunches per year. The fruit bunches yield
per hectare is 10 to 35 tonnes per hectare (van Gelder 2004). FAO reports that the average yield for
palm oil in Asia is 19.2 tonne/ha/yr (FAO 2006).
2)
0.5 GJ/ha/yr (Dehue 2006). The Malaysian Palm Oil Board mentions a total energy input of 6.14
GJ/ha/year for machinery, based on a study of 1991. Dehue cites FAO that the energy input should
rather be 500 MJ/ha/yr. This is significantly lower than soy or rape which seems plausible since palm
oil is harvested and fertilized by hand.
3)
Palm oil production requires less fertiliser per unit of output than other oilseed crops (WWF 2005).
On average, every hectare of mature oil palm plantation needs 1.6 tonne of fertiliser per year (Metro
Spectrum 2006), part of this is in the form of empty fruit bunches. Young oil palms require 5.2 to 14
kg N/rai/yr, adult oil palms require 18 to 25.6 kg N/rai/yr, old oil palms require > 32.6 kg N/rai/yr
(2.5 rai = 1 acre = 0.4047 ha) (GTZ 1997). We apply the average fertiliser use for palm oil in Asia as
reported by FAO (FAO 2001).

A.2 A.2 A.2 A.2 Rapeseed Rapeseed Rapeseed Rapeseed
Tabl e A-2. Pr oduct i on of r apeseed and str aw i n Eur ope.

Yields
1)

Rapeseed
Straw

3.4 tonne/ha/yr
2.6 tonne/ha/yr
Diesel
2)
Fertiliser
3)

4610 MJ/ha/year (at yield 3.3 tonne/ha/yr)
146 kg N/ha/year
40 kg P2O5/ha/yr
63 kg K2O/ha/yr

1)
Rapeseed 3300 kg/ha/yr minus 6 kg/ha/yr for sowing (PAV 2000). Range is 2.2 4.08 tonne/ha/yr
in Ecofys fact-finding study (Van den Broek, et al. 2003). Straw yield 2.5 tonne/ha/yr (Croezen and
Kampman 2005) 2.78 (Elsayed, et al. 2003). FAO reports that the average yield for rapeseed in
Europe is 3.4 tonne/ha/yr. The straw yield is corrected accordingly (assumed 2.5/3.3 times the
rapeseed yield).

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2)
Machinery uses about 130 litre diesel/ha/yr (PAV 2000), or 4.61 GJ direct energy. Elsayed (Elsayed,
et al. 2003) reports 2.39 GJ/ha/yr. We apply the value from PAV and correct the energy requirement
for the actual yield applied.
3)
Fertiliser use 180 kg N/ha/yr in CAN (Calcium Ammonium Nitrate) (PAV 2000), up to 196 kg N/ha/yr
(Elsayed, et al. 2003). We apply the average fertiliser use for soybean production in South America
as reported by FAO (FAO 2001).
A.3 A.3 A.3 A.3 Wheat and straw Wheat and straw Wheat and straw Wheat and straw
Tabl e A-3. Pr oduct i on of wheat and st r aw i n Eur ope.

Yields
Wheat
1)

Straw

5.59 tonne/ha/yr
2.99 tonne/ha/yr
Machinery
2)

Fertiliser
3)

2,597 MJ/ha/year
95.4 kg N/ha/yr
34.3 kg P2O5/ha/yr
27.4 kg K2O/ha/yr

1)
Netherlands: 8.4 tonne/ha/yr, minus 175 kg/ha/yr for sowing (PAV 2000). Range 5.42 9
tonne/ha/yr in Ecofys Fact-finding study (Van den Broek, et al. 2003) or 8 tonne/ha (Elsayed, et al.
2003). FAO reports that the average yield for wheat in Europe is 5.59 tonne/ha/yr. The straw yield is
assumed 4.4/8.23 times the wheat yield.
2)
From KWIN, machinery use, to achieve the yield mentioned for the Netherlands, sums up to 87 litre
diesel/ha/yr, or about 3.9 GJ/ha/yr. This number is corrected for the lower yield per hectare.
2)
Netherlands 205 kg N/ha/yr in the form of CAN (nitrate synthetic fertiliser. Sheffield reports 52.5 kg
N/ha/year. We apply the average fertiliser use for wheat production in Europe as reported by FAO
(FAO 2001).

A.4 A.4 A.4 A.4 Sugar cane Sugar cane Sugar cane Sugar cane
Tabl e A-4. Pr oduct i on of sugar cane i n South Amer i ca.

Yields
Sugarcane stalks
1)

69.5 tonne/ha/yr (73 % moist)
Machinery
2)

Fertiliser
3)

1779 MJ/ha/yr
84.6 kg N/ha/yr
55.7 kg P2O5/ha/yr
86.3 kg K2O/ha/yr

1)
Damen (Damen 2001) describes the production of ethanol from sugar cane in Brazil for the short and
longer term. The yield per plot is 90 tonne/ha, but there are 5 cuts in 6 years, so that the effective
yield is 75 tonnefresh/ha/yr. The sugar cane contains 73 % moist. In about 2021 the yield is expected
to be 120 tonnefresh/ha. With transgenic variations, irrigation, and better harvesting machines, the
yields could even be higher. The energy content of sugarcane stalks is 17.35 GJHHV/tonnedry (Damen
2001). In the long term, Damen suggests that trash that is now left in the field is also harvested to
produce electricity via BIG CC technology. This is not taken into account in the present study,
because the future economic value of the trash is unknown. FAO reports that the average yield for
sugar cane in South America is 69.5 tonne/ha/yr.
2)
Total first order energy input for cultivation, harvesting and baling is 1918 MJ/ha/yr for a yield of 75
tonnefresh/ha/yr, or 25.6 MJ/tonne sugar cane stalks.
3)
According to Damen (Damen 2001), fertiliser inputs are 90 kg N/ha/yr 4 out of 6 years, 50 kg
P2O5/ha/yr once per 6 years and 80 kg K2O/ha/yr once per 6 years. We apply the average fertiliser
use for sugar cane production in South America as reported by FAO (FAO 2001).

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Annex B Conversi on to bi ofuel s
B.1 B.1 B.1 B.1 Biodiesel fr Biodiesel fr Biodiesel fr Biodiesel from palm oil om palm oil om palm oil om palm oil
Tabl e B-1. Conver si on of Fr esh Fr ui t Bunches t o r efi ned pal m oi l (van Gel der 2004).
Fur t her conversi on of bi o- oi l t o bi odi esel i s assumed as f or r apeseed oi l
(Tabl e B-2).
Milling, pressing and kernel crushing
Yield
1)

Crude palm oil
Palm kernel oil
Palm kernel meal

0.1790 kg/kg FFB
0.0219 kg/kg FFB
0.0260 kg/kg FFB
Energy and Materials
2)
Methane emission from POME
CO2 emissions from POME

1.906 kg/tonne FFB
16.038 kg/tonne FFB

Refining, Bleaching, deodorising
3)
Unknown

1)
Related to a FFB yield of 19.2 tonne/ha (FAO 2006a) and a CPO yield of 3.44 ton/ha (FAO 2006a) an
oil extraction rate of 17.9% is obtained. Palm kernel oil yield and palm kernel meal yield are from
(Dehue, 2006).
2)
The electrical and steam requirements of the palm oil production are 20-25 kWh and 0.73 tonne
steam per tonne of FFB. The boilers are fuelled with shells and fibre, and thus no net energy input is
required (Damen and Faaij 2003). The palm oil mill effluent is drained to lagoons and leads to
emission of biogas. The emissions from POME are based on (Yacob, 2005). The methane emission
could be avoided rather easily and used for extra energy generation.
3)
Unknown, we assume this is small.

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B.2 B.2 B.2 B.2 Biodiesel from rapeseed Biodiesel from rapeseed Biodiesel from rapeseed Biodiesel from rapeseed
Tabl e B-2. Rapeseed to bi odi esel conver si on; par amet er s f or LCA anal ysi s (El sayed, et
al . 2003, appendi x B) .
Drying from moisture content 15 % 9 %
Yield
Dried rapeseed
No co-products

0.94 kg/kg raw rapeseed
Fuel oil

305 MJ/tonne dried rapeseed

Storage
1)

Electricity

11.6 kWh/tonne dried rapeseed

Solvent extraction
Yield
crude rapeseed oil
rapeseed meal animal feed

0.4 kg/kg dried rapeseed
0.6 kg/kg dried rapeseed
Natural gas
2)

Electricity

Hexane
3)

1790 MJ/tonne oil extracted
84 kWhe/tonne oil extracted
2.5 kg/tonne oil extracted

Refining
Yield
Refined oil
No co-products

0.98 kg/kg oil extracted
Electricity
Natural gas
Heavy Fuel oil
Light Fuel oil
Phosphoric acid

Smectite

3.1 kWhe/tonne refined rapeseed oil
178 MJ/tonne refined rapeseed oil
1 kg/tonne refined rapeseed oil
6 kg/tonne refined rapeseed oil

Esterification
Yield
Biodiesel
Crude glycerine

0.95 kg /kg refined oil
0.095 kg/kg refined oil
Electricity
Natural gas
Heavy fuel oil
Light fuel oil
Caustic soda (50 % concentration)
Methanol

23 kWh/tonne biodiesel
1402 MJ/tonne biodiesel
12 kg/tonne biodiesel
109 kg/tonne biodiesel

Plant construction and maintenance
Direct energy
Indirect energy


1)
Mainly cooling energy.
2)
Solvent extraction consumes steam, generated from natural gas 716 kg steam/tonne crude rapeseed
oil, and 2.5 MJ natural gas/kg steam (Elsayed, et al. 2003).


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B.3 B.3 B.3 B.3 Ethanol from wheat Ethanol from wheat Ethanol from wheat Ethanol from wheat
Tabl e B-3. Et hanol product i on f r om wheat (El sayed, et al . 2003, appendi x R).
Drying from mc 16 3 %
Yields
Dried wheat grains
No co-products

0.86 kg/kg fresh wheat grains
Fuel oil

661 MJ/tonne dried wheat grains

Storage
Electricity
1)

11.6 kWh/tonne dried wheat grains

Milling
Yields
Course powder flour
Bran

0.96 kg /kg dried wheat grains
0.040 kg /kg dried wheat grains
Electricity
2)

12.8 kWh/tonne course powder flour

Hydrolysis, fermentation, distillation, and stillage drying
Yields
Raw ethanol (94 %)
DDGS animal feed

0.36 kg/kg course powder flour (short term)
0.52 kg/kg course powder flour
Natural gas
3)

11081 MJ/tonne raw ethanol (short term)

Dehydration
Yields
Ethanol (100 %)

0.95 kg/kg raw ethanol
Natural gas
4)

35.1 MJ/tonne ethanol

Plant construction and maintenance
Direct energy
Indirect energy

3 MJ/tonne ethanol
179 MJ/tonne ethanol

1)
Mainly cooling energy (Elsayed, et al. 2003).
2)
12.3 kWh/tonne dried wheat grains (Elsayed, et al. 2003).
3)
Steam consumption for the entire plant requires 3862.5 MJ natural gas/tonne dried wheat grain, with
99.7 % in hydrolysis, fermentation, distillation, and stillage drying (Elsayed, et al. 2003).
4)
0.3 % of the total steam consumption (Elsayed, et al. 2003).


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B.4 B.4 B.4 B.4 Ethanol from sugar cane Ethanol from sugar cane Ethanol from sugar cane Ethanol from sugar cane
Tabl e B-4. Pr oduct i on of et hanol f r om sugar cane (Damen 2001).
Ethanol production from sugar cane
Yields
1)

Ethanol
Electricity

0.067 kg/kg sugar cane stalks
21.50 kWh/tonne sugar cane stalks
Energy and materials none

1)
Includes cane crushing, hydrolysis, fermentation and distillation, and electricity co-generation. The
system boundary includes the use of co-products for the production of heat or electricity. In the short
term, excess bagasse is available, but we have assumed that it has no value.


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Annex C Generi c dat a
C.1 C.1 C.1 C.1 Tran Tran Tran Transportation distances sportation distances sportation distances sportation distances

Tabl e C-1. Tr ansport at i on di st ances.
Feedstock Transport distance
feedstock
Transport distance bio-oil /
ethanol
Transport distance biofuel
Rapeseed
1)
truck 260 450
Palm oil
2)
truck
ship
5 100
15,500
100
Sugar cane
3)
truck
Ship
50 250
10,000
100
Wheat
2)
260 450
1)
Elsayed 2003. As Elsayed gives no transport distance for the rapeseed oil and wheat it is assumed
that the 450 km covers both rapeseed oil/wheat and final biofuel transportation.
2)
Damen 2003 gives distances for feedstock and crude palm oil transportation distances. Final biofuel
transport is assumed 100 km.
3)
Toyota 2004 gives a maximum distance of 50 km for sugar cane transport. Transportation distances
for ethanol are an estimation based on transportation from Brazil to Rotterdam. Final fuel
transportation is assumed to be 100 km.


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Annex D Et hanol fracti on i n bi odi esel
The fraction of ethanol in biodiesel is not the same as the fraction of methanol in biodiesel. The reason
for this is the higher molecular weight and LHV of ethanol compared to methanol.

Elsayed (2003) gives the following equation for FAME production:

1 kg tri-glycerine + 0.104 kg methanol = 0.950 FAME + 0.095 glycerine + 0.059 losses.

The ratio of molecular weight of ethanol versus methanol is 46/32.

Assuming an equal molecular ratio of methanol to tri-glycerine equals the molecular ratio of ethanol to
tri-glycerine in the production of biodiesel as well as equal losses the resulting equation for the
production of FAEE becomes:

1 kg tri-glycerine + 0.149 kg ethanol = 0.995 FAEE + 0.095 glycerine + 0.059 losses.

It is furthermore assumed that the energy content of FAME and FAEE are similar. While this certainly
will not be exactly correct, it does seem a reasonable assumption because:
it is in line with the finding from the literature study
the two main effects cancel each other out:
ethanol has a higher energy content than methanol: increasing the energy content of
FAEE compared to FAME
FAEE contains less bio-oil and more alcohol compared to FAME: decreasing the energy
content of FAEE compared to FAME (because the energy content of ethanol is lower than
the energy content of bio-oil).


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Annex E Detai l ed energy effi ci ency of FAEE pal m
oi l -wheat

0.0000
0.0500
0.1000
0.1500
0.2000
0.2500
E
n
e
r
g
y

u
s
e

(
M
J
/
M
J
)
End-use direct
End-use indirect
Fuel distribution
Transesterification
Extraction
Feedstock transport
Waste products
End-use direct 0.0503 0.0000 0.0000 0.0000
End-use indirect 0.0465 0.0000 0.0000 0.0000
Fuel distribution 0.0023 0.0023 0.0023 0.0000
Transesterification 0.0541 0.0543 0.0543 0.0000
Transport bio-oil/ethanol 0.0186 0.0194 0.0178 0.0016
Extraction 0.0000 0.0435 0.0000 0.0435
Feedstock transport 0.0005 0.0027 0.0005 0.0022
Waste products 0.0000 0.0000 0.0000 0.0000
Feedstock production 0.0270 0.0364 0.0259 0.0105
FAME palm oil FAEE palm oil-wheat bio-oil part ethanol part

Fi gur e 7-1 Det ai l ed represent at i on of t he energy ef f i ci ency of FAEE pal m oi l -wheat .
Whi l e FAEE has a l ower energy ef f i ci ency t han FAME, par t of t he benef i t s of
f or egoi ng t he met hanol consumpt i on ar e cancel l ed out by t he i ncrease i n
ener gy consumpt i on f or wheat cul t i vat i on, transpor t and conver si on t o
et hanol . Not e t hat the ener gy consumpt i on r el at ed t o pal m oi l pr oduct i on i s
sl i ght l y l ower i n the case of FAEE t han f or FAME. Thi s can be expl ai ned by
t he f act t hat FAEE contai ns sl i ght l y l ess bi o-oi l compar ed t o FAME due t o
t he hi gher mol ecul ar wei ght of et hanol compar ed t o met hanol : see al so
Annex D.


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Annex F Li terat ure survey
(Graz Uni versi ty)
F.1 F.1 F.1 F.1 General Considerations General Considerations General Considerations General Considerations
The aim of this literature study is, to give a comprehensive review on existing knowledge and data in
the field of Fatty Acid Ethyl Ester (FAEE) production and their use. Furthermore, a comparison to
classical Fatty Acid Methyl Ester (FAME, biodiesel) applications should be elaborated. Special focus
should be on differences in production technology, quality, and practical behavior of FAEE versus
FAME and also in comparison to diesel fuel.

However, when searching the literature on FAEE, the number of published data is conspicuously
much less than compared to that on FAME. The reason is clearly understandable due to the
tremendous boom of FAME within the last decade. Furthermore, legal frameworks, standardization
processes, public acceptance, and increasing biodiesel demands led to intensive research programs in
this field. Concerning FAEE the research is mainly based on basic production technologies and few
engine applications and endurance tests. Especially the use of FAEE in engines is by far not all-
embracing investigated. Reasons for this lack of data are widespread. It has been found very early
that transesterification of vegetable oils and fats with ethanol would be more sophisticated than
compared to FAME production. Especially if the product should have comparable high ester contents
as required by the, at that time, upcoming different quality standards, problems occurred. Furthermore,
differences in transesterification conditions (temperature, catalyst, catalyst amount) have been
identified. Including missing frameworks and acceptance of engine manufacturers, absence of quality
standards for FAEE and lower manufacture costs for FAME, the research in this field of alternative
fuels can be declared as not very attractive for researchers in the last decades. Of course this does not
mean that nothing has been done so far but should explain the big difference of available literature in
this field. This is also from the historical point of view an interesting fact, because the first published
data which can be interpreted as a step towards alternative fuel development were on FAEE
1,2,3
.
F.2 F.2 F.2 F.2 Production of FAEE: Production of FAEE: Production of FAEE: Production of FAEE:
For the production of FAEE, in principle the same technological approaches than used for FAME
production can be used. Therefore, the ester production can be performed via classical alkaline
catalysis using alkaline hydroxides or corresponding alkoxides, by acid catalyzed esterification and
transesterification using strong inorganic acids like sulfuric or phosphoric acid, by heterogeneous
catalysis using e.g. group II metal oxides or carbonates, by biotechnological approaches using
enzymes, as well as under supercritical conditions. But compared to FAME production, processing of
vegetable oils and fats into FAEE is more difficult especially if high ethyl ester yields are required.
The esterification and transesterification behavior is mainly influenced by the better solubility of
ethanol in the oil, by problems of phase separation of the glycerol layer (additionally affected by soap

BIOScopes
formation of free fatty acids), by the temperature and reaction time which have to be increased for
better processing, as well as by different alcohol : oil ratios, alcohol purity and higher catalyst
amounts. Detailed additionally information can be found in paragraph 2.1. Moreover, FAEE are being
produced only in lab-scale or pilot plants so far and therefore the practical experience of industrial
processing in large scale is still outstanding. Therefore the critical evaluation of suitable process
technologies is based on patents and published literature on this topic and should give an idea on
promising approaches for FAEE production which might be introduced in near future.

An interesting process for the continuous production of fatty acid ethyl esters via catalytic hydrolysis
and esterification of glyceridic oils is described by Dias de Moreas E Silva
4
. The process for the
manufacture of fatty acid ethyl esters, which may be used as biodiesel fuel, is achieved in two steps:
(1) through the catalytic hydrolysis of the glyceridic oils at approx. 60/1 atm., glycerol and free fatty
acids are obtained; and (2) the free fatty acid are catalytically esterified with hydrated ethyl alcohol.
These 2 reactions occur in two separate columns each 1.0-m high and packed with the heterogeneous
catalyst calcium and magnesium oxide (CaO.MgO) stones, being 1/15 the size of the column diameter.
Any vegetable oil is emulsified very finely with water at 60C and poured in the top of the first
cylinder, which is packed with the stones as the heterogeneous catalyst. The mixture flows through the
stones in the column splitting by hydrolysis the molecules of glyceryl esters and separating the fatty
acids from the glycerol and both products are collected at the column base and separated by density
difference. Both products are collected at the column base and separated by density difference. The
fatty acids separated from the glycerol are mixed with hydrated ethyl alcohol at a 1:2 ratio and poured
in the second column, which is packed with calcium and magnesium oxide stones ( 10 mm in size).
The dimension of the stones is at most 1/15 the column diameter. The mixture flows through the
packed stones through the bottom of the second column where the fatty acid ethyl esters are separated
by density from the water resulting in the dehydration reaction and the ethyl monoester (biodiesel) is
dissolved in excess alcohol. The solution of fatty acid ethyl ester in the excess alcohol is separated by
fractionated distillation recovering the hydrated ethyl alcohol and the fatty acid ethyl ester free from
the ethyl alcohol. Of course no quality parameters are described but due to recovery of the ethyl ester
via distillation, the product should have high purity at high ester contents.

Likewise, a continuous process for the transesterification of glycerides with lower alcohols is
published by Assmann et al.
5
. The process for the continuous preparation of alkyl esters, especially
methyl esters, comprises the 2-step conversion of glycerides (free fatty acid content <1%) with lower
alcohols, especially MeOH, in the presence of a homogeneous alkaline catalyst; the glycerol formed is
removed in each step. The reaction mixture passes in each step through a tube reactor and a separator.
The Reynolds No. (Re) of the flow is most preferably >10,000. Neutralized rape oil was passed
through a tube reactor at 150 L/h at 75C and 3 bars, and MeOH and NaOEt were added and glycerol
was removed after the 1st step; the ratio of oil to MeOH was 0.2 in the 1st step and 0.04 in the 2nd
step (Re = 2700). Conversion in the 1st step was 90% and the overall conversion was 98%.

Higher temperatures and pressures are used for the continuous process developed by Assmann et al.
6
.
The continuous process for producing lower esters is performed at temperatures of up to 100C and

BIOScopes
pressures of up to 10 bar by reacting, in an at least two-stage process, fatty acid triglycerides having an
acid value less than 1 with a lower alcohol in the presence of a homogeneous alkaline catalyst,
whereby the resulting glycerin is separated after the first stage. In order to be able to perform the
process with a high yield as well as with reduced maintenance, investment and energy costs than is the
case in the state of the art: the reaction mix, in each stage, passes only once through a reactor and
downstream static separator; tube reactors are used as reactors; and the Reynolds number of the
reaction mixture flow is greater than 2300.

A more sophisticated approach is given by Rohr
7
, using animal and vegetable oil residues as
feedstock. This method includes separation of insolubles, esterification of free fatty acids and
subsequent transesterification of the glycerides. The process consists on treatment of alcohol
(methanol or ethanol) dispersion of oil processing sludges by saponification of fatty acids and
triglycerides with strong base (NaOH or KOH); separation of insoluble org. compounds, e.g., lecithins
by filtration; reaction of soaps with strong mineral acids to generate free org. acids and insoluble salts
that are separated by filtration; heating of the alcohol-acid solution to effect esterification;
neutralization of residual mineral acid and separation of salts; distillation of residual alcohol; and
centrifugation and final separation to isolate the final esters that meet international specifications for
biodiesel. The strong mineral acids are selected from H
2
SO
4
, H
3
PO
4
, HNO
3
, HCl; the esterification is
carried out under reflux at 65-90C in the presence of strong acids; the neutralization base is selected
from Ca(OH)
2
, CaO, NaHCO
3
, and CaCO
3
. The distillation of residual alcohol is carried out at
atmospheric pressure or under vacuum at 40-90C and the esters are also distilled under pressure of 3-
760 mm Hg at 60-200C. Soybean oil refining sludges (1 kg) were solubilized in 5 kg ethanol and
saponified under reflux in the presence of 40 g NaOH 50% aq. solution; the product was heated up to
ethanol reflux temperature and the reaction was allowed to proceed for 30-90 min to obtain the sodium
soaps. The alcohol product mixture was filtered and lecithins were recovered for eventual use; the
alcohol solution was heated again for 30 - 90 min. after addition of 240 g concentrated H
2
SO
4
, the
resulting Na
2
SO
4
was separated by filtration and the solution was heated for 30-90 min for
esterification to take place. After neutralization with Ca(OH)
2
the alcoholic solution contained soy
fatty acid ethyl esters, ethanol was separated by distillation and the esters were subjected to
centrifugation to remove insoluble residues and final purification by distillation under vacuum
produced 556.4 g esters meeting Biodiesel specifications.

Hansen de Almeida used group 1A metal alkoholates as catalysts for the transesterification of soybean
oil with ethanol
8
, and Hilion et al. used spinel-type zinc aluminates
9
. Two types of biofuels, especially
biodiesel, are produced from triglyceride starting materials by an initial transesterification of the
glyceride with methanol or ethanol, to produce fatty acid methyl esters or ethyl esters, followed by
etherification of the by-product glycerin with excess C4-12-olefins, to produce the corresponding
mixture of monoethers, diethers, and triethers of glycerin as the second biofuel. Transesterification is
carried out over a spinel-type zinc aluminate, consisting of ZnAl
2
O
4
.xZnO.yAl
2
O
3
(x and y = 0-2);
etherification catalysts are typically acidic cation-exchange resins (e.g., Amberlyst 15).


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Vitoro invented an esterification process for the production of fatty acid alkyl esters
10
. In an agitating
container/vessel or in a similarly working homogenization apparatus with defined retention time, a
mixture of free fatty acid or a fatty acid-triglyceride mixture is mixed with an alcohol with a mono- or
bicyclic alkyl aromatic hydrocarbon in the presence 30-85% sulfuric acid at 25-80C is
(trans)esterified and the product separated. Additionally, process flow diagrams are presented.

On the other hand transesterification reaction can be carried out also in a high-pressure reaction vessel
as shown by Alves
11
. Animal or vegetable fatty acids, saturated or unsaturated, are reacted with a C1-5
alcohol, preferably ethanol, in the presence of a catalyst or co-catalyst, such as a base, an acid, and
enzyme or lipase, preferably potassium hydroxide. The transesterification vessel is a high-pressure
bomb into which the materials are injected; the reaction products are immediately separated into a
small fraction containing glycerin and a larger fraction containing the monoester. The esters are
produced with a high conversion index in an extremely short time.

For processing of oils in supercritical fluids without further catalysts or by using of enzymes, a method
is proposed by Madras et al.
12
. In this work, the transesterification of sunflower oil was investigated in
supercritical methanol and supercritical ethanol at various temperatures (200-400 C) at 200 bar. The
rate coefficients and the activation energies of the reaction were also determined. Biodiesel was also
enzymically synthesized in supercritical carbon dioxide. The effect of enzyme loading, oil to alcohol
ratio, reaction time and temperature was investigated. While nearly complete conversions were
obtained for the thermal reactions in supercritical methanol and ethanol, only 30% conversions were
obtained in the enzyme-catalyzed reactions in supercritical carbon dioxide.

Ethyl esters can be also obtained via single-phase base-catalyzed Ethanolysis of vegetable oils as done
by Zhou, Konar, and Boocock
13
. The effects of alcohol/oil molar ratio, base concentration, and
temperature on the single-phase base-catalyzed ethanolysis of sunflower and canola oils to produce
biodiesel were determined. The use of THF as co-solvent, as well as higher than usual
alcohol/substrate molar ratios, prevented glycerol separation. This allowed each reaction to reach
equilibrium rather than just steady-state conditions. High conversions of oil decreased the
concentrations of monoglyceride (MG) and diglyceride (DG) surfactants in the products and thereby
mitigated the formation of emulsions usually associated with ethanolysis reactions. An alcohol/oil
molar ratio of 25:1 with the necessary amount of co-solvent gave optimal results. At this molar ratio,
despite equilibrium, being achieved, ethanolysis, unlike methanolysis, did not quite produce biodiesel-
standard material, the MG content being .approximately 1.5%. For methanolysis and 1-butanolysis,
the corresponding values were 0.6 and 2.0% respectively. The use of 1.4% KOH (equivalent to 1.0%
NaOH) led to ethanolysis equilibrium within 6-7 min at 23C rather than 15 min when only 1.0% was
used. At 60C, equilibrium was reached within 2 min. Soybean and canola oils behaved similarly.

A combination of oil extraction coupled with in-situ alcoholysis is described by different research
groups. Ozgul-Yucel and Turkay prepared monoalkylesters from rice bran oil
14
. Extraction and in situ
esterification of rice bran oil with ethanol were investigated by studying the effects of rice bran oil
FFA content and water content of ethanol. Ethyl ester formation in the ethanol phase increased as FFA

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content increased. Neutral oil solubility in this phase fell considerably, resulting in a high ethyl ester
content. The decrease of the water content in ethanol led to an increase in neutral oil solubility in
ethanol and promoted the equilibrium of reaction to ethyl-ester formation, resulting in lower FFA
content of the product. The main factor that affected yield and monoester content when using high-
acidity bran and various monohydroxy alcohols was the solubility of neutral oil in alcohol. The highest
monoester content was obtained with methanol.

This specific method can be also demonstrated on rapeseed as done by Erdmann and Krause
15
. The
idea of work is the combination of the recovery of oil and the transesterification by ethanol as well as
solvent and partner for transesterification. In this report was investigated the possibility of the direct
transesterification of oils extracted by ethanol in a small technical range to produce an ethylester of
rape oil. The use of different solvents ant the transesterification of pure substances was investigated,
too. The transesterification by methanol shows better results than the transesterification by ethanol.
The transesterification after the extraction by ethanol is possible. Water and undesirable fatty
materials, however, have a negative influence on the transesterification of the mixture (oil/ethanol).
Also the results of the investigations show the use of the solvent extraction by ethanol will influence
the qualities of the coarse meal. Consequently it is possible to produce ethyl ester of rape oil as well as
chemical raw materials for technical, cosmetical and pharmaceutical purposes. Up to now the costs of
this process for production of ethyl esters are very high.

Similar results on other feedstocks were obtained by Lago et al.
16
. Samples of crushed and partially
dried soy beans, groundnuts and rapeseeds were extracted semi-continuously with commercial 99.5%
ethanol and the solutions separated into oil-rich and ethanol-rich miscellas. The oil-rich
miscellas were transesterified with ethanol using sodium hydroxide as catalyst, the separation of
glycerol and soaps formed during the reaction together with the excess of ethanol being achieved by
addition of 25 % of glycerol based on the weight of oil followed by the recovery of the by-products.
The fatty acids derived from soaps were converted into ethyl esters and the ethanol-rich miscellas
used for the extraction of new lots of seeds, thus making possible the transformation of practically all
glycerides into ethyl esters and reducing the energy requirements of the process to a minimum.

Soybean oil in-situ Alcoholysis was investigated by Kildira et al
17
. In-situ alcoholysis of soybean oil
with methanol, ethanol, n-propanol, and n-butanol was investigated, as well as the extraction of the oil
with these solvents, to explain the progress of in-situ alcoholysis and to determine the parameters that
affect this reaction. Because methanol is a poor solvent for soybean oil, the amount of oil dissolved in
methanol and converted to methyl esters was low after in-situ alcoholysis. Ethyl, propyl, and butyl
esters of soybean fatty acids could be obtained in high yields from in-situ alcoholysis of soybean oil
with these alcohols. In-situ alcoholysis proceeded through dissolution and alcoholysis of triglycerides
successively, and the overall reaction rate was determined by the extraction and alcoholysis rates. The
parameters, affecting yield and purity of the product esters, were mainly those that favor extraction
rate.


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Kahlil and Leite described an integrated process for producing biodiesel from oleaginous seeds,
preferably castor bean seeds, comprising a transesterification reaction where the seeds themselves
react with anhydrous ethyl alcohol in the presence of an alkaline catalyst
18
. The resulting ethyl esters
are then separated by decantation and neutralized and used as fuel for diesel engines, co-solvents for
diesel and gasoline mixtures with anhydrous or hydrated ethyl alcohol. The solid fractions may be
used as fertilizers, for feeding cattle and as a raw material for producing ethyl alcohol.

The mentioned processes all have in common that they did not give any additional information about
quality parameters of FAEE. A process for making high purified fatty acid lower alkyl esters is
described by Kenneally and Gansmuller
19
. The process for the synthesis of high purity fatty acid lower
alkyl esters comprise the steps of: (a) converting a fatty acid source to a product mixture comprising
lower alkyl esters and by-products; (b) water-washing the product mixture at elevated temperature and
elevated pressure to remove by-products; and (c) fractionally distilling the water-washed product
mixture to obtain high purity fatty acid lower alkyl esters. At least a portion of the fatty acids have
from about 20 to about 24 carbon atoms. The high purity lower alkyl esters have an acid value no
greater than about 1.0.

A more detailed information on fuel properties of rapeseed oil ethyl ester is given by Gudriniece et
al.
20
. Biodiesel fuel (REE) had been produced from rapeseed oil and absolute ethanol in the presence
of potassium hydroxide with 95-96% from mass of rapeseed oil yield. REE is suitable for the using in
diesel engines as pure or as mixture with fossil diesel fuel. Additional and more detailed information
of the different preparation characteristics and properties is given by Lang et al.
21
. Methyl, ethyl, 2-
propyl and butyl esters were prepared from canola and linseed oils through transesterification using
KOH and/or sodium alkoxides as catalysts. In addition, methyl and ethyl esters were prepared from
rapeseed and sunflower oils using the same catalysts. Chemical composition of the esters was
determined by HPLC for the class of lipids and by GC for fatty acid compositions. The bio-diesel
esters were characterized for their physical and fuel properties including density, viscosity, iodine
value, acid value, cloud point, pure point, gross heat of combustion and volatility. Methyl and ethyl
esters prepared from a particular vegetable oil had similar viscosities, cloud points and pour points,
whereas methyl, ethyl, 2-propyl and butyl esters derived from a particular vegetable oil had similar
gross heating values. However, their densities, which were 27% higher than those of diesel fuels,
statistically decreased in the order of methyl ~ 2-propyl>ethyl>butyl esters. Butyl esters showed
reduced cloud points (6C to 10C) and pour points (13C to 16C) similar to those of summer
diesel fuel having cloud and pour points of 8C and 15C, respectively. The viscosities of bio-
diesels (3.37.6104 Pa s at 40C) were much less than those of pure oils (22.445.1104 Pa s at
40C) and were twice those of summer and winter diesel fuels (3.50 and 1.72104 Pa s at 40C), and
their gross heat contents of approximately 40 MJ/kg were 11% less than those of diesel fuels (45
MJ/kg). For different esters from the same vegetable oil, methyl esters were the most volatile, and the
volatility decreased as the alkyl group grew bulkier. However, the bio-diesels were considerably less
volatile than the conventional diesel fuels. This study is comparable to the work done by Encinar et
al.
22
, studying transesterification behavior and properties of Cynara cardunculus oil. A study was
made of the transesterification reaction of Cynara cardunculus L. oil by ethanol, using sodium

BIOScopes
hydroxide and potassium hydroxide as catalysts. The objective of the work was to characterize the
ethyl esters for use as biodiesel in compression ignition motors. The operation variables employed
were temperature (25-75C), catalyst type (sodium hydroxide and potassium hydroxide), catalyst
concentration (0.25-1.5%), and ethanol/oil molar ratio (3:1-15:1). Oil mass (200 g), reaction time (120
min), and alcohol type (ethanol) were fixed as common parameters in all the experiments. The
evolution of the process was followed by gas chromatography, determining the concentration of the
ethyl esters at different reaction times. The biodiesel was characterized by determining its density,
viscosity, high heating value, Cetane index, cloud and pour points, characteristics of distillation, and
flash and combustion points according to ISO norms. The biodiesel with the best properties was
obtained using an ethanol/oil molar ratio of 12:1, sodium hydroxide as catalyst (1%) and 75C temp.
This biodiesel has very similar properties to those of No. 2 diesel fuel.

Similar results have been found on preliminary investigations on biofuel characteristics of tigernut
(Cyperus esculentus) oil by Barminas et al.
23
. Laboratory scale experiments were carried out to
produce and characterize biofuel from tigernut (Cyperus esculentus) oil. Transesterification of tigernut
oil afforded methyl and ethyl esters, which had fuel properties similar to common biofuels, hence
tigernut could be utilized as an alternative renewable energy resource.

As already mentioned, FAEE production technology needs characteristic tuning when compared to
FAME production. Several authors have referred to necessary changes e.g. of reaction temperature,
reaction time, catalyst amount and so on (see 2.1.). In order to obtain high quality products (however
the quality cannot by controlled by appropriate FAEE standards but is based on FAME experience)
different optimization studies and scenarios have been reported. Nimecevic et al. give an idea on the
transesterification behavior of rapeseed oil with lower aliphatic alcohols
24
. Rapeseed oil esters with
C1-4 alcohols were prepared in simple batch mode using an alkali (KOH) or acid (H
2
SO
4
) catalyst.
The transesterification reaction conditions were optimized in order to obtain high yields of esters of
the quality defined by standards for biodiesel fuels and for a short reaction time. Under these
conditions it was possible to prepare only the methyl and ethyl esters catalyzed by KOH. Pr and Bu
esters were obtained only under acid catalysis conditions. The reaction catalyzed by H
2
SO
4
was
successfully accelerated using slightly higher catalyst concentrations at the boiling points of the
alcohols used. Iso-Pr and iso-Bu alcohols reacted more slowly than their linear isomers, while tert-Bu
alcohol did not react at all. It was also possible to transesterify rapeseed oil using a mixture of alcohols
characteristic of the end products of some fermentation processes (e.g., the acetone-butanol
fermentation). A simple calculation was made which showed that, because of the higher price of
longer-chain alcohols and because of the more intensive energy input during production of the esters
of these alcohols, they are economically unfavorable as biodiesel fuels when compared with the Me
ester.

This work can be expanded by investigations done by Korus et al., who also included economic
assessments to their work
25
. A process for the production of the ethyl ester of winter rape (EEWR) for
use as a biodiesel fuel has been studied. The essential part of the process is the transesterification of
rape oil with ethanol, in the presence of a catalyst, to yield the ethyl ester of rape oil as a product and

BIOScopes
glycerin as a by-product. Experiments have been performed to determine the optimum conditions for
the preparation of EEWR. The process variables were. 1) temperature, 2) catalyst, 3) rate of agitation,
4) water content of the alcohol used, and 5) the amount of excess alcohol used. The optimum
conditions were: 1) room temperature, 2) 0.5% sodium methoxide or 1% potassium hydroxide catalyst
by weight of rapeseed oil, 3) extremely vigorous agitation with some splashing during the initial phase
of the reaction and agitation was not necessary after the reaction mixture became homogeneous, 4)
absolute ethanol was necessary for high conversion, and 5) 50% excess ethanol with NaOCH3 or
100% excess with KOH gave a maximum conversion. Viscosity, cloud point and pour point of the
EEWR were measured. A preliminary break-even cost for the commercial production of EEWR was
found to be $0.55/liter ($2.08/U.S. gallon).

Additionally inputs concerning biodiesel production via acid catalysis came from Canakci and Van
Gerpen
26
. Especially conversion of low cost feedstocks such as used frying oils is complicated if the
oils contain large amounts of free fatty acids that will form soaps with alkaline catalysts. The soaps
can prevent separation of the biodiesel from the glycerin fraction. Alternative processes are available
that use an acid catalyst. The objective of this study was to investigate the effect of process variables
on acid-catalyzed transesterification. The molar ratio of alcohol, reaction temperature, catalyst
amount, reaction time, water content, and free fatty acids were investigated to determine the best
strategy for producing biodiesel. Food grade soybean oil was used to prepare esters using excess
methanol and sulphuric acid as a catalyst. To compare the effect of different alcohol types on ester
formation, methanol, ethanol, 2-propanol, and n-butanol were compared. The American Oil Chemists
Society Method Ca 14-56 was used to measure the biodiesels total glycerin amount as an indicator of
the completeness of the reaction. It was found that acid catalysis can provide high conversion rates but
much longer times are required than for alkaline catalysts. The acid catalyst also requires the
concentration of water to be less than 0.5%, which is about the same as is required for alkaline
catalysts. Water formed by the esterification of free fatty acids limited their presence in the oil to 5%.

Optimization of a batch type ethyl ester process was done by Peterson et al.
27
. To accomplish this
conversion, raw rapeseed oil is treated at room temperature with ethyl alcohol in the presence of
potassium hydroxide as a catalyst. During the process, the glycerol which is produced is insoluble in
the ester product, and being heavier, settles out carrying most of the dissolved KOH catalyst with it.

Upon initial settling, some of the undesirable, emulsion-forming by-products may remain in the ester
layer, causing problems in the washing stage. It was discovered (by tracking the process with a
glycerol determination) that most of these products could be removed by simply re-stirring the
glycerol into the ester, adding water and letting the mixture settle out again. After draining off the
glycerol/water layer, the product (ethyl ester) can be easily water-washed to remove residual alcohol
and potassium.
Moreover, the production of FAEE from grease can also be optimized as demonstrated by Wu et al.
28
.
Response surface methodology (RSM) was employed to optimize reaction parameters-temperature,
time, level of lipase, mole ratio of reactants-in the PS-30 lipase-catalyzed transesterification reaction
of grease to ethyl esters using 95% ethanol. The regression equation obtained by a modified central

BIOScopes
composite design of RSM predicted optimal reaction conditions of 38.4C, 2.47 h, 13.7 wt% lipase
(PS-30), and a mole ratio of grease to ethanol of 1:6.6. Under these conditions the predicted optimal
percentage ethyl ester yield was 85.4%. Subsequent experiments using the predicted parameter
combinations indicated a trend where experimental percentage yields of ethyl ester were consistently
lower than predicted values. In an effort to improve the experimental yield of esters, a second portion
of PS-30 lipase was added without success; however, the addition of 5% SP435 one hour after the start
of the initial reaction increased the yield of esters to >96%. Neither lipase PS-30 nor lipase SP435
alone, however, gave the RSM-predicted yield of ethyl esters.

Another approach based on the optimization of alkaline transesterification of soybean oil and castor oil
came from de Oliveira et al.
29
. This article reports experimental data on the production of fatty acid
ethyl esters from refined and degummed soybean oil and castor oil using NaOH as catalyst. The
variables investigated were temperature (30-70 degrees C), reaction time (1-3 h), catalyst
concentration (0.5-1.5 w/wt%), and oil-to-ethanol molar ratio (1:3-1:9). The effects of process
variables on the reaction conversion as well as the optimum experimental conditions are presented.
The results show that conversions >95% were achieved for all systems investigated. In general, an
increase in reaction temperature, reaction time, and in oil-to-ethanol molar ratio led to an enhancement
in reaction conversion, whereas an opposite trend was verified with respect to catalyst concentration.

An important information on the influence of water (which e.g. is typically high in technical grade
ethanol) on reaction kinetics of transesterification of cottonseed oil is given by Bikou et al.
30
.
Cottonseed oil appears as a promising candidate for manufacturing biodiesel fuel. A kinetic model for
the transesterification of a cottonseed oil with ethanol in the presence of water is proposed. The effect
of water content in the reacting mixture on the transesterification reaction is studied. The dependence
of the equilibrium constants and reaction rate constants on the water content is presented. Equilibrium
was reached within <30 min reaction time in all cases. The increase of the water content results in
decrease of the conversion level of the oil. By increasing the ethanol/oil ratio the conversion of
triglyceride increases and the concentration of mono- and diglyceride in the product mixtures are
reduced.

Another approach for optimization of reaction yields for ethyl ester production from soybean oil was
designed by Zagonel et al.
31
. Soybean oil ethyl esters were produced by transesterification of crude
soybean oil with ethanol and KOH catalyst. Reaction conditions were determined using a two level,
three variable 23 experimental design of molar alcohol.:oil ratio, catalyst concentration and reaction
temperature. The ethyl esters are to be used as biodiesel substitute fuel and were successfully tested in
diesel engines. The conditions were adequate for the transesterification of waste cooking oil also. Size
exclusion chromatography and FTIR were used to monitor reaction yields and both methods were in
agreement.

Optimization can also be performed on enzymatic production of esters which has been evaluated also
by de Oliveira et al.
32
. They studied the production of fatty acid ethyl esters from castor oil using n-
hexane as solvent and two commercial lipases, Novozym 435 and Lipozyme IM, as catalysts. For this

BIOScopes
purpose, a Taguchi experimental design was adopted considering the following variables: temperature
(35-65 degrees C), water (0-10 wt/wt%), and enzyme (5-20 wt/wt%) concentrations and oil-to-ethanol
molar ratio (1:3 to 1:10). An empirical model was then built so as to assess the main and cross-
variable effects on the reaction conversion and also to maximize biodiesel production for each
enzyme. For the system containing Novozym 435 as catalyst the maximum conversion obtained was
81.4% at 65 degrees C, enzyme concentration of 20 wt/wt%, water concentration of 0 wt/wt%, and oil-
to-ethanol molar ratio of 1:10. When the catalyst was Lipozyme IM, a conversion as high as 98% was
obtained at 65 degrees C, enzyme concentration of 20 wt/wt%, water concentration of 0 wt/wt%, and
oil-to-ethanol molar ratio of 1:3.

Especially on enzymatic production of fatty acid esters much work has been done by several groups.
From the economical point of view these investigations have similar bottlenecks compared to FAME
production by enzymes. Generally, such processes are currently too costly due to the high prices of the
enzymes. Nevertheless, this technology might become more attractive in future if the trend of
decreasing enzyme prices will prolong. Therefore findings on enzymatic ester production are included
in this report.

The production of biodiesel by lipase catalyzed transesterification of different Nigerian lauric rich oils
was the aim of studies of Abigor et al.
33
. Fatty acids esters were produced from two Nigerian lauric
oils, palm kernel oil and coconut oil, by transesterification of the oils with different alcohols using
PS30 lipase as a catalyst. In the conversion of palm kernel oil to alkyl esters (biodiesel), ethanol gave
the highest conversion of 72%, t-butanol 62%, l-butanol 42%, n-propanol 42% and iso-propanol 24%,
while only 15% methyl ester was observed with methanol. With coconut oil, l-butanol and iso-butanol
achieved 40% conversion, l-butanol 16% and ethanol 35%, while only traces of methyl esters were
observed using methanol. Studies on some fuel properties of palm kernel oil and its biodiesel showed
that palm kernel oil had a viscosity of 32.40 mm
2
/s, a cloud point of 28C and a pour point of 22C,
while its biodiesel fuel had a viscosity of 9.33 mm
2
/s, a cloud point of 12C and a pour point of 8C.
Coconut oil had a viscosity of 28.58 mm
2
/s, a cloud point of 27C and a pour point of 20C, while its
biodiesel fuel had a viscosity of 7.34 mm
2
/s, a cloud point of 5C and a pour point of 8C. Some of
the fuel properties compared favorably with international biodiesel specifications.

Based on enzyme catalyzed alcoholysis with methanol the results of Shimada et al. could be
successfully used also for ethanolysis reactions
34
. Biodiesel fuel (fatty acid methyl esters; FAMEs) can
be produced by methanolysis of waste edible oil with a lipase. The degree of methanolysis was low in
reaction systems so far reported, and the lipase catalyst could not be reused in spite of using
immobilized enzyme. They clarified that this problem was due to the irreversible inactivation of the
lipase by contact with insoluble methanol (MeOH). Based on this result, they developed a stepwise
methanolysis system with immobilized Candida antarctica lipase. Two-step batch methanolysis was
most effective for the production of biodiesel fuel from waste oil: the first-step reaction was conducted
in the presence of 1/3 molar equivalent of MeOH for the stoichiometric amount, and the second-step
reaction was performed by adding 2/3 molar equivalent of MeOH. If the immobilized carrier is
destroyed by agitation in a reactor with impeller, three-step flow reaction will be available: the first-

BIOScopes
step substrates were waste oil and 1/3 molar equivalent of MeOH; the second-step, the first-step eluate
and 1/3 molar equivalent of MeOH; the third-step, the second-step eluate and 1/3 molar equivalent of
MeOH. The conversion of waste oil to biodiesel fuel reached >90% in the two reaction systems, and
the lipase catalyst could be used for >100 days without decrease of the activity. The stepwise
alcoholysis could successfully be applied to ethanolysis of tuna oil.

Very early Mittelbach studied the lipase catalyzed alkoholysis of sunflower oil even with ethanol
35
.
Lipase-catalyzed alcoholysis of sunflower oil underanhydrous conditions was examined. Lipase from
Pseudomonas fluorescens and 2 immobilized enzymes from Mucor miehei and a Candida sp. Gave
sufficient conversion with petroleum ether as the solvent, even when methanol and ethanol were used.
The overall content of tri-, di- and monoglycerides, as well as the corresponding alkyl esters, was
measured. Because pseudomonas lipase led to almost quantitative esterification, further studies were
carried out with that enzyme varying the amounts of enzyme or the alcohols. Acceptable conversions
were achieved even without solvent. Reaction rates of alcoholysis with 5 homologous alcohols, with
or without the addition of water, were measured, and in all cases the reaction rates increased with
higher chain length of the alcohol. In the case of methanol the highest rate was obtained without any
addition of water, but a significantly higher rate was observed with 96% ethanol as opposed to
absolute ethanol. The main advantages of lipase-catalyzed, non-aqueous alcoholysis as compared to
classical procedures are the mild reaction conditions, the isolation of glycerine without further
purification and without the formation of chemical waste, and the ability of lipases to catalyze the
esterification of free fatty acids.

Additional experiments on sunflower oil Ethanolysis in solvent free medium were carried out by Selmi
and Thomas
36
. The ethanolysis of sunflower oil (SFO) with Lipozyme (immobilized 1,3-specific
Mucor miehei lipase) in a medium solely composed of substrates was investigated. The effects of
oil/ethanol molar ration, temperature, added water content, and amount of enzyme were analyzed. The
optimal values were, respectively, 1:3, 50C, 0% (vol/vol), and 0.4 g of Lipozyme per 5.7 mmol of
SFO. The use of immobilized lipase made the reuse of enzyme feasible, and the enzyme could be
recovered easily from the reaction mixture and recycled to reduce the cost of catalyst. In the last three
consecutive runs of enzyme reuse, the final conversion yield of SFO from ethanolysis with added
silica gel support was higher than that obtained from ethanolysis under standard conditions. The
lipase-catalyzed alcoholytic reactions is potentially useful in the production of alkyl esters of specific
interest.

Besides pure vegetable oils tallow and grease can also be transesterified successfully using
immobilized lipases as shown by Hsu et al.
37
. The lipase-catalyzed synthesis of alkyl esters from
tallow and grease using Pseudomonas cepacia lipase (PS-30) immobilized within a phyllosilicate sol-
gel matrix was investigated. The effects of the presence of alcohol and of the amount of enzyme used
were studied. The matrix-immobilized PS-30 lipase effectively converted grease and tallow to ethyl
esters in greater than 95% yield when using ethanol. The final conversion of grease or tallow to alkyl
esters was aided by the addition of molecular sieves (0.4 wt% of substrates) to the reaction mixture.
The matrix-immobilized PS-30 enzyme was easily recovered and could be reused at least five times

BIOScopes
without losing its activity. Accordingly, the phyllosilicate sol-gel immobilized PS-30 lipase is
potentially useful for the economic production of biodiesel fuel.

Additionally, enzymatic production of esters can also be used via ethanolysis of fish oil for the
preparation of poly-unsaturated fatty acids (PUFA) used for nutritional applications as described by
Haraldsson et al.
38
. The objective of this study was to investigate the use of lipases as catalysts for
producing concentrates of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) form fish oil
as an alternative to conventional chemical procedures. Transesterification of fish oil with ethanol was
conducted under anhydrous solvent-free conditions with a stoichiometric amount of ethanol. Among
the 17 lipases tested, the results showed that Pseudomonas lipases hat the highest activity toward the
saturated and monounsaturated fatty acids in the fish oil, much lower activity toward EPA und DHA
and, at the same time, good tolerance toward the anhydrous alcoholic conditions. With 10 wt% of
lipase, based on weight of the fish oil triacylglycerol substrate (15% EPA and 9% DHA initial
content), a 50% conversion into ethyl esters was obtained in 24 h at 20C, in which time the bulk of
the saturated and monounsaturated fatty acids reacted, leaving the long-chain n-3 polyunsaturated fatty
acids unreacted in the residual mixture as mono-, di-, and triacyglycerols. This mixture comprised
approximately 50% EPA + DHA. Total recovery of DHA and EPA was high, over 80% for DHA and
more than 90% for EPA. The observed fatty acid selectivity, favoring DHA as a substrate, was most
unusual because most lipases favor EPA.

Similar results on this topic were simultaneously patented by Bertoli et al.
39
. A composition
concentrated in ethyl esters of polyunsaturated fatty acids is prepared by mixing a refined oil rich in
polyunsaturated fatty acids with ethanol in the presence of a catalyst to obtain an ethanolyzate
containing a glycerol phase and a fatty acid ethyl ester phase. The fatty acid ethyl ester phase is
separated from the glycerol phase and mixed with urea and ethanol to form a mixture, which is cooled
to form a liquid phase containing fatty acid ethyl esters and a solid phase containing insoluble
inclusion complexes. The liquid phase is separated from the solid phase to obtain a fraction enriched
in ethyl esters of polyunsaturated fatty acids.

Prior to that, Bertoli et al. investigated the use of urea for the preparation concentrates of ethyl esters
of poly-unsaturated fatty acids
40
. The concentrates of ethyl esters of polyunsaturated fatty acids, e.g.,
-linolenic acid (I), eicosapentaenoic acid, or docosahexaenoic acid, are prepared by ethanolysis of an
oil (e.g., I-containing oil from Borago officinalis seeds), addition of urea which forms inclusion
complexes with the ethyl esters, separation of the ester-rich liquid phase, refining of the liquid phase,
and addition of an antioxidant.
F.3 F.3 F.3 F.3 Experience with FAEE Experience with FAEE Experience with FAEE Experience with FAEE
Practical experience using FAEE as a fuel is limited mainly on demonstration projects and funded
studies. Long time experiences, comparable with the situation in Europe where FAME is used since
many years, are still outstanding. Expectable information from Brazil which should have traditionally
long experiences with FAEE and therefore would be the most promising market for FAEE production
could not be verified due to the already unclear situation if FAEE is currently being produced. In fact a
roadmap for the commercial use of biofuels has been established (Federal Law No. 11.097 from

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January of 2005). The time schedule under this Law was later modified (September 2005), so that it
will be mandatory to add 2% mixture (B2) of biodiesel to conventional diesel from January 1
st
, 2006.
The obligation is restricted to biodiesel volume produced by companies which have obtained the
Social Seal. This means a potential market of about 800 Million liters of biodiesel per year. From 2013
on, a further mandatory step of 5% mixture (B5) will be considered, meaning a firm market of 2.4
Billion liters per year. However, it is considered an immense challenge to reach those volumes of
production with the required quality to the end-consumer. Furthermore, the production of biodiesel in
Brazil is currently limited mainly on the production of FAME. Generally, the small amounts of FAEE
already produced world-wide enabled only limited practical experience. Therefore, the results of these
tests have only representative character and should be used as basis for further research activities as
long as legal frameworks and measures on standardization have been set. Without having uniform
FAEE quality limits, comparable results on practical experience will not be possible.
Environmental Aspects on FAEE Environmental Aspects on FAEE Environmental Aspects on FAEE Environmental Aspects on FAEE
Before summarizing the different experiences on FAEE behavior and performance, some general
environmental aspects of fatty acid esters with special focus on FAEE might be useful. Several authors
have reported on this topic and will be therefore included in this survey. Of course this overview is not
complete because much information on FAEE is hidden within numerous FAME reports. However,
most of these reports mentioned here include general considerations on this specific topic and should
build the connection to the upcoming paragraph, discussing the different experiences when FAEE is
used as fuel.

Schmiedl gives an comprehensive review on biofuels properties and experience with their use
41
. The
European Union wants to promote the use of renewable raw materials also in the traffic sector in order
to meet the internationally committed reduction of carbon dioxide emissions. At the same time a new
market shall be created for farming and jobs shall be secured. Fatty acid methyl esters in the diesel
market and ethanol and ethyl tert-butyl ether (ETBE) in gasoline are discussed as compounds that can
be produced from renewable raw materials and be applied as fuels in the short term. This literature
survey deals with the extent of CO
2
/greenhouse gas emission reductions, the availability of biofuels
and summarizes the economical and technical experiences obtained so far with their application. The
use of pure vegetable oils, dimethylether and pyrolysis oil is also briefly covered. If biodiesel (in
Germany normally rape seed methyl ester, RME) is used, problems result especially from storage over
a long period of time. Fatty acid methyl esters are prone to oxidation and to contact with water. In the
presence of water they may decompose by hydrolysis and show microbial attack. In the car industry
metals and elastomers have to be used that are compatible with fatty acid methyl esters. In general
there is still a lack of sufficient experience in everyday use. Therefore the car manufacturers are
reluctant to use biodiesel in cars due to its possible technical risks. Already today ethanol and ethyl
tert-butyl ether, a compound very similar to methyl tert-butyl ether, are used internationally in limited
amounts as fuel components. Therefore the technology is available to modify existing cars so that they
become compatible with these oxygenates. With alcohol containing gasolines problems may arise
from the formation of a water-alcohol phase. At high alcohol concentrations the engines have to be
adapted to the changed combustion parameters. The emissions of carbon monoxide, hydrocarbons and

BIOScopes
polycyclic aromatic hydrocarbons decrease if biodiesel, ethanol and ETBE are used, emissions of
nitrogen oxides in most cases increase slightly. The volumetric fuel consumption normally increases,
if biofuels are used.

Iglinski et al.
42
. later on expanded this review given by Schmidl
41
. Nowadays, the crude oil and its
derivatives are the main sources of energy. The oil crisis of 70s has clearly shown that the world
reserves are limited. The fast development of the transport contributes substantially to the increase of
the ecological threaten, mainly by the emission of CO
2
. The introduction and use of the renewable
biofuels becomes a must, both from the economical and ecological point of view. European Union and
governments of many countries are looking more favourably on biofuels following destabilization of
the crude oil market (e.g. Directive 2003/87/CE). Bioethanol, ETBE and TAEE ethers, methyl and
ethyl esters of higher fatty acids are the most known biofuels or biocomponents. The use of biofuels
shifts the energetic equilibrium toward the safer side and it leads to the substantial decrease of the
greenhouse gasses emission. Paper reviews the most popular biofuels applied nowadays. The
physicochemical properties of biofuels are presented. Ethanol dehydratation by the pervaporation is
presented and compared with entrained distillation and molecular sieves technologies. The
transesterification of vegetable oils is presented as a technology to produce biodiesel. The ecological
advantages of the use of biofuels are also pointed out. For instance 4% of ethanol in the fuel decreases
the emission of carbon monoxide (CO) by 8% and NO
x
by 33%.

More general are the comments of Knothe and Dunn, reviewing possible uses of vegetable oils
43
. The
review is based on the use of vegetable oil-based diesel fuels, particularly in the form of esters
(biodiesel). Topics discussed include sources and production of such fuels, general comparison of
fuels from vegetable oils and animal fats, process economics, regulatory issues, history and
development, combustion of and emissions from biodiesel fuels, properties of biodiesel (e.g., low-
temp. properties and storage stability), blending with conventional diesel fuels, transesterification, use
of waste vegetable oils, pyrolyzed vegetable oils, use of microemulsions, and outlook for biodiesel
fuels. Although vegetable oil-based fuels cannot replace all petroleum-based diesel fuels, they play an
important role among the alternative fuels and contribute to the goal of energy independence and
security.

Environmental and health effects were examined by Reece et al.
44
. Biodiesel fuels are reported to be
nontoxic and biodegradable, resulting in less potential hazard to animals, humans, and the aquatic
environment. Acute oral, acute dermal, and acute aquatic toxicity tests, and biodegradability with
rapeseed methyl ester (RME), rapeseed ethyl ester (REE), and blends of each with diesel fuel are
reported. Acute oral toxicity tests were conducted with albino rats; acute dermal toxicity tests were
conducted with albino rabbits at WIL Research Laboratories in Ashland, Ohio. Acute aquatic toxicity
tests were performed by CH
2
M Hill in Corvallis, Oregon, with Daphnia magna and rainbow trout.
Biodegradability tests were conducted at the University of Idaho. LD50 (the point at which 50% have
died and 50% are still alive determined by interpolation) values for each tested substance were >5,000
mg/kg when administered once orally and >2,000 mg/kg administered once for 24 h to the clipped,
intact skin of male and female albino rabbits. LC50 values for acute aquatic toxicity with Daphnia

BIOScopes
magma in ppm were 3.7 for table salt, 1.43 for 2-D, 23 for RME, and 99 for REE. An LD50 was not
determined for the rainbow trout study. Biodegradability tests showed that ethyl and methyl esters of
rapeseed oil degrades more rapidly than sugar, which was 90% degraded after 23 days. Diesel fuel was
26% degraded after 23 days.

Special focus on environmental effects of rapeseed oil ethyl ester was put by Makareviciene and
Janulis
45
. Exhaust emission tests were conducted on rapeseed oil methyl esters, rapeseed oil ethyl
esters and fossil diesel fuel as well as on their mixtures. Results showed that when considering
emissions of nitrogen oxides (NO
x
), carbon monoxide (CO) and smoke density, rapeseed oil ethyl
ester had less negative effect on the environment in comparison with that of rapeseed oil methyl ester.
When fueled with rapeseed oil ethyl ester, the emissions of NO
x
showed an increase of 8.3% over
those of fossil diesel fuel. When operated on 25-50% bio-ester mixed with fossil diesel fuel, NO
x

emissions marginally decreased. When fueled with pure rapeseed oil ethyl ester, HC emissions
decreased by 53%, CO emissions by 7.2% and smoke density 72.6% when compared with emissions
when fossil diesel fuel was used. Carbon dioxide (CO
2
) emissions, which cause greenhouse effect,
decreased by 782.87 g/kWh when rapeseed oil ethyl ester was used and by 782.26 g/kWh when
rapeseed oil methyl ester was used instead of fossil diesel fuel. Rapeseed oil ethyl ester was more
rapidly biodegradable in aqua environment when compared with rapeseed oil methyl ester and
especially with fossil diesel fuel. During a standard 21 day period, 97.7% of rapeseed oil methyl ester,
98% of rapeseed oil ethyl ester and only 61.3% of fossil diesel fuel were biologically decomposed.

Comparable investigations on ethyl esters of Pongamia (Honge) oil were done by Chandraju and
Prathima
46
. The use of the ethyl ester of a non-edible oil and its performance in blends for diesel
engines was studied. The results showed a 14-16.6% mileage improvement and 65-70.5% smoke
reduction on using pure ethyl ester of pongamia oil (E.E.P.O.) and a E.E.P.O.-10% blend. Compared
to diesel, the E.E.P.O. (10% blend) shows 70.5% reduction of exhaust emissions. Pure E.E.P.O. is the
best alternative fuel compared to high speed diesel (HSD) due to its high calorific value and oily
nature which leads to smooth operation of the engine. There is not much information about the usage
of ethyl ester of pongamia oil in this way and the usage of ethyl fatty esters as an oxygenated, low-S,
green fuel, was studied as an ecol.-safe fuel for diesel replacement in compression ignition engines.
Upgrading the fuel is achieved by blending with HSD up to 10% or as a substitute and this results in a
decrease of ash (0.009%) for pure E.E.P.O. and a 14-16% improvement in mileage, without diesel
engine modification.

Additional aspects are given by Knothe and Dunn
47
. In fact biodiesel is an attractive alternative fuel
for use in diesel engines since it provides engine performance comparable to conventional diesel fuel
(middle distillates, petrodiesel) while reducing most harmful exhaust emissions. However, some
technical problems are still associated with the use of biodiesel fuels. One problem is the reduction of
nitrogen oxides (NO
x
) exhaust emissions to meet increasingly stringent environmental regulations.
Cetane-improving additives decrease NO
x
emissions from petrodiesel. Cetane improvers with different
effects on various fatty compounds were identified, possibly enabling tailoring of the Cetane improver
to the major fatty compound in a biodiesel fuel. These effects depend on the Cetane improver and

BIOScopes
structural features of fatty compounds such as number and position of double bonds as well as number
of CH
2
groups. Some Cetane No. trends were altered. Compounds formed in the phase of fuel
injection into the combustion chamber prior to ignition (pre-combustion) were evaluated. Low Cetane
Nos. of pre-combustion species may explain differing Cetane Nos. of fatty compounds. Another major
problem is the relatively poor low-temperature flow properties with respect to petrodiesel. To improve
these properties of biodiesel, treatment with cold-flow improving additives and winterization were
studied as possible solutions. Results from cloud point (CP) and cold filter plugging point (CFPP)
measurements gave a linear correlation between these two parameters. With this correlation, results
from additive treatment and winterization of biodiesel were compared primarily with respect to CP.
Although treatment with cold-flow improvers reduced the pour point (PP) of biodiesel, these additives
did not greatly affect CP. Similar results were obtained for blends treated with additives. Winterization
reduced CP of biodiesel to a value comparable to that of petrodiesel. Although winterization
significantly reduced resistance to auto-oxidation, it does not compromise fuel quality of methyl
soyate regarding current standard fuel specifications for biodiesel.
Engine Experience Engine Experience Engine Experience Engine Experience
Initially it has been mentioned, that the research activities in the field of ethyl ester production are
much less than compared to that of methyl ester. As a consequence, it is not unexpected that only few
data and studies on ethyl ester use exist. Nevertheless, the upcoming cited references will represent an
adequate profile on FAEE behavior when used in combustion engines. Observable trends in engine
performance and emission characteristics compared to FAME as well as diesel fuel should be
identifiable. In this context the comprehensive comparison of engine emissions of different fuel types
conducted by the National Renewable Energy Laboratory (NREL) will highlight these trends
48
. Within
a study, NREL investigated various biodiesel fuels produced from waste oils. As a part of this study,
data on emissions on the Environmental Protection Agency (EPA) heavy-duty transient cycle have
been measured to demonstrate the sensitivity of engine emissions to biodiesel ester composition. The
objective of the investigation was to determine the effect of biodiesel source material and ester
molecular structure (number of double bonds and chain length) on particulate matter (PM), nitrogen
oxides (NO
x
), and certain unregulated pollutants. Testing included a series of fuels consisting of nearly
pure fatty acid esters with different chain lengths and numbers of double bonds, as well as a number of
fuels from practical feedstocks. A detailed analysis of the data was performed in an effort to determine
how fuel chemistry and fuel properties correlate with the increase in NO
x
emissions observed for many
biodiesels here, and in most previous studies.

In total, 28 neat biodiesels and four B-20 blends (with EPA certification diesel) were tested. Seven
fuels prepared from various natural feedstocks were obtained from the Institute of Gas Technology
(IGT), and three of these were tested as B-20 blends. A methyl ester biodiesel prepared from
soapstock was supplied by the Agricultural Research Service (ARS) and tested neat and as a B-20
blend. Twenty fuels were prepared at the Colorado School of Mines (CSM), primarily from nearly
pure (or technical grade) fatty acids. Nevertheless, many of these fuels were not as pure as was
originally intended because of high levels of impurities in the feedstocks. These fuels covered a very
wide range of realistic feedstocks as well as systematically varying chemical properties such as fatty

BIOScopes
acid chain length and number of double bonds in the fatty acid chain. Fuels were analyzed for a wide
range of properties including water and sediment, free and total glycerine, iodine number, peroxide
value, acid number, Cetane Number, density, kinematic viscosity, gross heating value, and carbon,
hydrogen, and oxygen content. The specific fatty acid esters present in the fuels were also determined
by GC/MS analysis. Regulated pollutant emissions, along with certain non-regulated pollutants, were
measured on a 1991 DDC Series 60 engine via the heavy-duty transient test (40 CFR Part 86 Subpart
N). Emissions from biodiesel fuels were bracketed with emissions for EPA certification diesel. This
allows comparison with a conventional diesel, and most importantly, a measure of engine drift.
Volatile organic fraction, PM sulfate, and emissions of certain aldehydes were measured for many of
the fuels. Samples for biological activity analysis by the University of California at Davis were
collected.

All fuels prepared at CSM met water and sediment specifications as well as free and total glycerine
specifications (with the exception of one fuel produced with high glycerine value on purpose). Not all
fuels met the acid number specification, in particular fuels with a high stearate content as these were
not liquid at or near room temperature making acid removal difficult. Fuels prepared by IGT met the
water and sediment specifications immediately after synthesis based on analyses supplied by IGT.
However, problems associated with water were evident when these fuels were received at CSM,
indicating that the hygroscopic character of these esters can create problems during storage and
transport. Other properties are generally in good agreement with literature values.

Certification fuel runs exhibited a mean NO
x
emission level of 4.59 g/bhp-h (+/-0.053) with no
significant drift over the four month test program. PM emissions averaged 0.261 g/bhp-h (+/-0.019). A
small downward drift in PM emissions was evident (11% over the course of the project). Thus, no
correction for drift was applied to the NO
x
emissions data but a small correction was applied to PM.
Testing the biodiesels produced from natural sources (supplied by IGT and ARS) indicated that PM
emissions did not depend on molecular structure but were dependent on the oxygen content of the fuel
only. All fuels reduced PM relative to certification diesel. NO
x
emissions varied considerably with
biodiesel feedstock but all increased NO
x
relative to certification diesel. The most highly unsaturated
fuels (canola, soy, and soapstock) produced the highest NO
x
emissions. Soy and soapstock biodiesels
produced very similar emissions, as expected. Btu based fuel economy was the same for all biodiesels
and certification fuel.

For the fuels prepared from nearly pure esters, all reduced PM relative to certification diesel but the
PM reduction was not proportional to oxygen content in all cases. Almost all of these fuels increased
NO
x
relative to certification fuel. The exceptions were the highly saturated esters methyl palmitate,
methyl laurate, ethyl and methyl stearate, and ethyl ester of hydrogenated soybean oil. No consistent
difference in emissions was observed between ethyl and methyl esters of the same feedstock. High
peroxide value (1800), acid number, and glycerine content had no effect on regulated pollutant
emissions in this short-term study. These out-of-spec fuel properties may cause fouling or storage and
handling problems in longer-term studies.


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The VOF emission for certification fuel (5.5% of 0.261 g/bhp-h PM) is 0.0144 g/bhp-h. For the
biodiesels on average (21.4% of 0.07 g/bhp-h), it is 0.0150 g/bhp-h (results for biodiesels from real-
world feedstocks). Neat biodiesel contains no sulfur and so sulfate emissions are significantly less for
these fuels. Aldehyde emissions from the various biodiesels are not significantly different from
aldehydes emissions from certification diesel fuel.

Regression analysis of the results indicated that emissions could be correlated by one parameter. PM
reduction was proportional to oxygen content for biodiesels with a Cetane Number of greater than
about 45 (density greater than 0.89). For fuels with Cetane Number less than 45, PM reduction was
less. NO
x
emissions were also well correlated with a single parameter, either density or cetane number
(which were highly correlated with each other). The results suggest that neat biodiesels with Cetane
Numbers greater than about 68 may produce NO
x
emissions equal to or less than certification fuel. The
impact of molecular structure is implicit in either the density or Cetane Number. More saturated esters
have higher Cetane Numbers and lower densities than less saturated esters. Thus, the lower the iodine
number, the lower the NO
x
emissions. These conclusions apply to natural Cetane Number, the impact
of Cetane enhancing additives may be different. Data collected also demonstrate the effect of chain
length. The density of shorter chain length saturated esters is greater than longer chain saturated esters
and the NO
x
emission is greater. Note that methyl laurate (12 carbon fatty acid chain), with Cetane
Number 61.2 and density 0.873, is NO
x
neutral compared to certification fuel. The important
conclusion is that fuel chemistry is at the root the fuel properties that effect emissions, and in
particular the increased NO
x
emissions observed for many biodiesel fuels.

It is important to note that the results presented here are engine specific. Other engines and
calibrations will probably give similar results. The impact of the NO
x
/PM tradeoff for specific diesel
engines will change the overall results but probably not the trends. The NO
x
behavior of biodiesel
blends is complex. Insufficient physical property data are available to characterize the effect of
blending at this time, although provisionally for 25 blends a linear combination of NO
x
emissions
seems appropriate. The effect of oxygen on particulate matter is well characterized by considering
only the oxygen content of the blend. This conclusion appears to be robust.

Further tests of ethyl esters from waste vegetable oils have been conducted by Al-Widyan, Tashtoush
and Abu-Quadais
49
. This study was initiated to investigate the potential of ethyl ester used as
vegetable oil (VO; biodiesel) to substitute oil-based diesel fuel. The fuels tested were several
ester/diesel blends including 100% ester in addition to diesel fuel, which served as the baseline fuel.
Variable-speed tests were run on all fuels on a standard test rig o a single-cylinder, direct-injection
diesel engine. Tests were conducted to compare these blends with the baseline local diesel fuel in
terms of engine performance and exhaust emissions. The results indicated that the blends burned more
efficiently with less specific fuel consumption, and therefore, resulted in higher engine thermal
efficiency. Furthermore, the blends produced less carbon monoxide and unburned hydrocarbons than
diesel fuel. The 100% ester fuel and the blend of 75:25 ester/diesel gave the best performance while
the 50:50 blend consistently resulted in the lowest amounts of emissions over the whole speed range
tested.

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These investigations have been prolonged by the authors by including the combustion performance in
a water-cooled furnace of ethyl esters from waste vegetable oils
50
. The feasibility of using this
renewable and low cost fuel as raw material for diesel fuel replacement in industrial residential heating
boilers was studied. The combustion performance and emissions of used palm oil ethyl ester
(biodiesel) were compared to baseline diesel fuel in a H
2
O-cooled furnace. The combustion efficiency,
c, and exhaust temperature, Texh, as well as the common pollutants and emissions were tested over a
wide range of air/fuel ratios from very lean to very rich (10:1-20:1). All tests were conducted at 2
different energy inputs for both fuels. At the lower energy rate, c and Texh for biodiesel were 66%
and 600 respectively with the corresponding values for diesel being 56% and 560. At the higher
energy input, biodiesel combustion performance deteriorated and was inferior to diesel fuel due to its
high viscosity, density and low volatility. Biodiesel emitted less pollutants at both energy levels over
the range of air/fuel ratios tested.

The efficiencies of various esters of fatty acids as diesel fuel have been tested by Klopfstein and
Walker
51
. Methyl esters of commercial grades of lauric, myristic, palmitic, stearic, linoleic and
linolenic acids, as well as ethyl and butyl esters of oleic acid, were burned in a diesel engine to
determine their efficiencies as fuels. Triolein and some common vegetable oils were burned as
comparison fuels and No. 2 diesel fuel was used as a control. The fuels were tested in a single-cylinder
direct-injection engine running at rated speed and load in short-term, performance engine tests.
Specific fuel consumption and thermal efficiencies of the engine burning these fuels were then
determined. Among the methyl esters of the saturated acids, thermal efficiency was inversely related
to chain length of the fatty acid. Introduction of a double bond resulted in increased efficiency. Further
increases in unsaturation had negligible effects on thermal efficiencies. Ethyl oleate had the highest
thermal efficiency and butyl oleate had the lowest thermal efficiency of any of the ester fuels tested.
Most of the ester fuels produced higher thermal efficiencies than died No. 2 diesel fuel. Triolein
produced the lowest specific fuel consumption of the triglyceride fuels and peanut oil produced the
lowest specific fuel consumption of the vegetable oils. The data suggest that ethyl esters of
monounsaturated or short-chain fatty acids should make good alternative fuels and that they should be
further evaluated in long-term engine tests.

Early tests with different ethyl and methyl esters have been carried out at the University of Idaho in
1994
52
. Test quantities of ethyl and methyl esters of four renewable fuels were processed,
characterized and performance tested. Canola, rapeseed, soybean oils, and beef tallow were the
feedstocks for the methyl and ethyl esters. Previous results have shown methyl esters to be a suitable
replacement for diesel fuel; however, much less has been known about the ethyl esters. A complete set
of fuel properties and a comparison of each fuel in engine performance tests are reported. The study
examines short term engine tests with both methyl and ethyl ester fuels compared to number 2 diesel
fuel (D2). Three engine performance tests were conducted including an engine mapping procedure, an
injector coking screening test, and an engine power study.


BIOScopes
The gross heat contents of the biodiesel fuels, on a mass basis, were 9 to 13 percent lower than D2.
The viscosities of biodiesel were twice that of diesel. The cloud and pour points of D2 were
significantly lower than the biodiesel fuels. The biodiesel fuels produced slightly lower power and
torque and higher fuel consumption than D2.

In general, the physical and chemical properties and the performance of ethyl esters were comparable
to those of the methyl esters. Ethyl and methyl esters have almost the same heat content. The viscosity
of the ethyl esters is slightly higher and the cloud and pour points are slightly lower than those of the
methyl esters. Engine tests demonstrated that methyl esters produced slightly higher power and torque
than ethyl esters. Fuel consumption when using the methyl and ethyl esters are nearly identical. Some
desirable attributes of the ethyl esters over methyl esters were: significantly lower smoke opacity,
lower exhaust temperatures, and lower pour point. The ethyl esters tended to have more injector
coking than the methyl esters and the ethyl esters had a higher glycerol content than the methyl esters.
This indicates also that missing quality standards for FAEE lead to difficulties when interpreting
results of engine tests where fuels have been used which have different quality characteristics.

These tests have been prolonged at the University of Idaho and first long duration engine tests have
been carried out
53
. During this one year test an on-road vehicle was driven coast-to-coast on biodiesel
for a total of 14,068 km(8742 mi.). As part of this on-road testing, the vehicle was tested for emissions
on a chassis dynamometer at the LA-MTA emissions test facility in Los Angeles, California. Tests
included HC, CO, CO
2
, NO
x
, and PM. The two cycles used in the tests included a modified arterial
cycle and the EPA cycle for heavy duty vehicles. Biodiesel research has included producing both
methyl and ethyl esters from tallow, canola, soybean oil and rapeseed oil. These eight fuels have been
subjected to fuel characterization tests according to the ASAE proposed Engineering Practice,
Reporting of Fuel Properties when Testing Diesel Engines with Alternative Fuels Derived from Biol.
Materials, X552; and short term injector coking tests and performance tests in a turbocharged, DI, CI
engine. Two-hundred hour EMA endurance tests in 3-cylinder, DI, CI engines have additionally been
carried out. The testing program has been accomplished by a case study with an vehicle test fuelled
with ethyl esters of rapeseed oil
54
. A 1994 Dodge 2500 turbocharged and inter-cooled diesel pickup
fuelled with 100% ethyl ester of rapeseed oil was driven by personnel representing the University of
Idaho, Agricultural Engineering Department from Moscow, Idaho to Los Angeles, California and back
to Moscow and then from Moscow to Ocean City, Maryland, east of Washington, D.C. and back to
Moscow, Idaho. These trips covered a total of 14,069 km (8742 miles). The truck averaged 7.76 km/l
(18.7 mile/gal) using 1772 l (468 gal) of ethyl ester of rapeseed oil fuel. No problems or unusual
events were encountered with the trucks operation. The truck was completely unmodified as to the
engine and fuel system. The fuel required for the trip was all processed in the Agricultural Engineering
Laboratory at the University of Idaho and was carried on-board as no refuelling facilities were
available away from Moscow, Idaho. This is believed to be the first coast-to-coast and back run on
100% biodiesel.

The performance of ethyl esters from rapeseed oil have also been tested by Megahed, Abdallah and
Nabil
55
. Esters of rapeseed oil with MeOH and EtOH were prepared using KOH or H
2
SO
4
catalysts.

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The volumetric ratio, alcohol:oil was 2:1 and the catalyst concentration was 5%. The esterification rate
was faster with the acidic catalyst. The esterified products were tested for their fuel properties
(calorific value, flash point, viscosity, and pour point) and compared to those of standard diesel fuel.
These esters are advantageous compared to diesel fuel since they are S-free and their combustion in an
engine will not produce acidic S oxides. They also do not contain non-combustible substances whose
deposition may cause abrasion of engine parts. Other fuel properties are more or less similar to those
of standard fuel. This implies less corrosion of engine parts as well as less pollution of the
environment. The performance of a 4-cylinder diesel engine fuelled with these esters was compared to
the performance with standard diesel fuel. The brake specific fuel consumption was lower and the
thermal efficiency was higher with rapeseed oil esters.

Additional information cane be obtained from the investigations carried out by Thompson et al.
56
. This
project was designed to determine the extent of deterioration of rape methyl ester (RME) and rape
ethyl ester (REE) in storage. The study involved triplicate samples of RME and REE stored in glass
and steel containers at room temperature (inside) and at the local ambient outdoor temperatures
(outside). The study was conducted for 24 months. At the beginning of the study and at three-month
intervals, samples were taken for measurement of peroxide value, acid value, density, viscosity, and
heat of combustion. At the conclusion of the study, engine performance tests were conducted with the
two year stored REE and RME, new REE and RME, and low sulfur diesel reference fuel. On the
average, the esters increased over time in all of the previously mentioned properties with the exception
of heat of combustion, which decreased. Regression models are presented to predict the deterioration
with time. Engine power varied less than 2% for both biodiesel fuels compared to the stored
counterparts while smoke density decreased 3.2% for the stored RME and increased 17.5% for stored
REE.

Ethyl esters of sunflower oil have also been tested. Their behaviour when fuelled into vehicles was
evaluated by Zahrer, Magahed and Kinawy
57
. Chemical modification of the sunflower oil was done by
catalyzed esterification with short chain alcohols being methyl and ethyl alcohols. The modified
products were then evaluated according to their fuel properties as compared to diesel fuel. The fuel
properties considered were viscosity, pour point, calorific value, flash point, and Cetane No. in
addition to some other properties. The performance of a diesel engine was tested when fuelled with a
50% blend of diesel oil and the oil methyl ester, a 50% blend of diesel oil and the oil ethyl ester, and
when fuelled with diesel oil. The tested parameters were the brake-specific fuel consumption and
brake thermal efficiency. The results of engine testing proved that the engine performance was best
using a 50% blend of diesel oil and the oil methyl ester. The brake-specific fuel consumption using
this blend was 0.24 kg/BHp compared to 0.26 kg/BHp using diesel oil. The brake thermal efficiency
using that oil blend was 37.6% compared to 31% with diesel oil.

Methyl and ethyl esters of soybean oil have been studied by Clark et al.
58
. The ethyl and methyl esters
of soybean oil with commercial diesel fuel additives revealed fuel properties that compared very well
with diesel fuel, with the exception of gum formation, which manifested itself in problems with the
plugging of fuel filters. Engine performance using soybean ester differed little from engine

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performance with diesel fuel. A slight power loss combined with an increase in fuel consumption was
experienced with the esters, primarily because of the lower heating value of the esters than for diesel
fuel. Emissions for the 2 fuels were similar, with nitrous oxide emissions higher for the esters.
Measurements of engine wear and fuel-injection system tests showed no abnormal characteristics for
any of the fuels after the 200-hr tests. Engine deposits were comparable in amount, but slightly
different in color and texture, with the methyl ester engine experiencing greater carbon and varnish
deposits on the pistons.

Performance and emission studies of mahua oil (Madhuca Indica) ethyl esters were done by Puhan,
Vedaraman and Sankaranarayanan
59
. Mahua oil ethyl esters were prepared by transesterification using
sulfuric acid (H
2
SO
4
) as catalyst and tested in a 4-stroke direct injection natural aspirated diesel
engine. Tests were carried out at constant speed of 1500 rev/min at different brake mean effective
pressures. Brake thermal efficiency of Mahua oil ethyl ester (MOEE) was comparable with diesel and
26.36% for diesel whereas 26.42% for MOEE. Emissions of carbon monoxide, hydrocarbons, oxides
of nitrogen and Bosch smoke no. were reduced around 58, 63, 12 and 70%, respectively, in case of
MOEE compared to diesel. The flash point and fire points were .apprx.100C higher for the biodiesel
than for No. diesel fuel. Based on this study, MOEE can be used a substitute for diesel in diesel
engine.

Ethyl esters of honge oil and palm oil blends with diesel in heavy duty vehicles were tested by
Chandraju and Prathima
60
. The blends of ethyl esters of pongamia oil (Honge oil) and palm oil are
prepared by blending/mixing esters directly 10-20% by vol. with diesel (HSD) and the results were
quite encouraging leading to 21% mileage improvement in honge oil ester diesel (HOED) 10% blend
compared to palm oil ester diesel (POED) 10% blend. But both are the selective improvement blends
compared to diesel. Thus HOED 10% shows 72% improvement and considerable reduction of exhaust
emissions compared to 64% improvement in POED 10%. The best performance blend compared to
HSD is HOED, and it has high calorific value, one of the oil derivatives leading to smooth drive of the
vehicle/engine causing less wear and tear.

Concerning blends with mineral diesel Dobrev patented a corresponding method
61
. A vegetable oil
(especially sunflower oil) is subjected to transesterification with 20-30 vol.% MeOH or EtOH in the
presence of 0.6-0.9 wt.% alkali metal hydroxide catalyst (e.g., NaOH or KOH) for 8 h at 50-70C and
atmospheric pressure. After separation of glycerol, the resulting fatty esters are rinsed with water or an
inorganic acid to remove the catalyst. The purified esters 5-40 wt.% are added to conventional diesel
fuel containing <0.3 wt.% S at 30-50C.

Information of the impact of biodiesel source material and chemical structure on emission of criteria
pollutants can be opbtained from the work of McCormick et al.
62
. In this study they examined
biodiesels produced from a variety of real-world feedstocks as well as pure (tech. grade) fatty acid
methyl and ethyl esters for emissions performance in a heavy-duty truck engine. The objective was to
understand the impact of biodiesel chemical structure, specifically fatty acid chain length and no. of
double bonds, on emissions of NO
x
and particulate matter (PM). A group of seven biodiesels produced

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from real-world feedstocks and 14 produced from pure fatty acids were tested in a heavy-duty truck
engine using the U.S. heavy-duty federal test procedure (transient test). It was found that the molecular
structure of biodiesel can have a substantial impact on emissions. The properties of density, Cetane
No., and Iodine No. were found to be highly correlated with one another. For neat biodiesels, PM
emissions were essentially const. at about 0.07 g/bhp-h for all biodiesels as long as d. was less than
0.89 g/cm
3
or Cetane No. was greater than about 45. NO
x
emissions increased with increasing fuel
density or decreasing fuel Cetane No. Increasing the number of double bonds, quantified as Iodine
No., correlated with increasing emissions of NO
x
. Thus the increased NO
x
observed for some fuels
cannot be explained by the NO
x
/PM tradeoff and is therefore not driven by thermal NO formation. For
fully saturated fatty acid chains the NO
x
emission increased with decreasing chain length for tests
using 18, 16, and 12 carbon chain molecules. Additionally, there was no significant difference in NO
x

or PM emissions for the methyl and ethyl esters of identical fatty acids.

Specific data on the speed of sound and isenotropic bulk modulus of biodiesel are given by Tat et al.
63
.
This study presents the results of measurements of the speed of sound and the isentropic bulk modulus
for methyl and ethyl esters of fatty acids from soybean oil and compares them with No. 1 and No. 2
diesel fuel. Data are presented at 21 1C and for pressures from atmospheric to 34.74 MPa. The
results indicate that the speed of sound and bulk modulus of the monoesters of soybean oil are higher
than those for diesel fuel and these can cause changes in the fuel injection timing of diesel engines.
Linear equations were used to fit the data as a function of pressure, and the correlation constants are
given.

Summarizing all the reported engine and performance tests it can be pointed out that FAEE show
comparable emission and performance characteristics when compared to FAME and therefore similar
beneficial effects of biodiesel especially in emission characteristics can be attested. However,
differences and discrepancies are not easy to clarify mainly due to the varying feedstock sources as
well as not uniform FAEE quality. Therefore it would be necessary to carry out additional engine tests
(especially long time tests) with FAEE of uniform quality. This emphasizes again the priority of the
development and implementation of a suitable uniform FAEE quality standard.
FAEE Properties FAEE Properties FAEE Properties FAEE Properties
FAEE specific parameters and the differences to FAME will be discussed in chapter 2.1.3.
Furthermore, different ethyl ester specific properties have been also investigated partially from other
points of view. These results can be interpreted as additional inputs on the development of a uniform
FAEE quality standard. One overall critical parameter (also valid for FAME) is the low temperature
operability. Especially biodiesel from feedstocks with higher contents of saturated fatty acids is known
for its poor low temperature behavior. Therefore the production of a biodiesel fuel with improved
properties at low temperature would be helpful. Delgado investigated a possible approach on this
topic
64
. He patented a procedure to generate biodiesel fuels with improved properties at low
temperature by the transesterification of triglycerides with alcohols (e.g., MeOH or EtOH), optionally
in the presence of MeOAc or EtOAc and an inert solvent, to produce Me or Et esters of fatty acids,
glycerin, and, where appropriate, glycerin triacetate, followed by separation of crude glycerin that is

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reacted with aldehydes, ketones, and/or AcOH or MeOAc or EtOAc to produce acetals, cetals, and/or
glycerin acetate. The acetals, cetals, and/or glycerin acetate are mixed with Me or Et esters of fatty
acids in concentrations of approx. 0.5-20 wt.% to obtain a biodiesel with improved properties at low
temperatures.

Other processes are described for the production of low pour point palm diesel particularly but not
exclusively via esterification of C18, C18:1 and C18:2 mixed fatty acids with methanol or ethanol, or
fractional distillation of methyl or ethyl esters of palm oil, palm kernel oil and palm oil products, or
fractional distillation of methyl or ethyl esters of palm oil, palm kernel oil and palm oil products,
followed by crystallization, or crystallization of methyl or ethyl esters of palm oil, palm kernel oil and
palm oil products, or crystallization of methyl or ethyl esters of palm oil, palm kernel oil and palm oil
products, followed by fractional distillation by May et al.
65
.

In this context, also data on composition of an additive and methods for improved lubrication, pour
point and fuel performance are published by Ritter
66
. The additive includes polyalphaolefin (PAO), a
calcium source, and one or more oils from, or components derived from, beans, seeds, or roots, such
as castor oil, jojoba oil, rape (canola) seed oil, palm oil, sunflower oil, soybean oil, etc. The preferred
composition of matter comprises a calcium source, PAO, castor oil, jojoba oil, and a soy methyl ester
and/or rape seed methyl or ethyl ester. The additive may be used in fuels that improve combustion
engine performance in terms of efficiency and emissions. The additive may be used in lubricants that
improve performance of both ferrous and nonferrous metal components of engines, guns, or other
machinery. The additive also may be used in cutting fluids for machining and fabrication. Used in
conjunction with other additives, embodiments of the invention may be used to lower pour points in
oils, esters and other similar products.

Other biodiesel fuel additives are described by Bradin
67
. The fuel additive composition includes fatty
acid alkyl esters and glyceryl ethers, and an alternative fuel composition that includes the fuel additive
composition. Also provided is a method for preparing the fuel additive composition and the alternative
fuel composition. In one embodiment, the fuel additive composition is prepared by esterifying free
fatty acids and etherifying glycerol with one or more olefins in the presence of an acid catalyst. In one
embodiment, the fuel additive composition can be thermally cracked under conditions of increased
temp. and/or pressure in the presence of a Lewis acid catalyst. In another embodiment, the fuel
additive composition is hydrocracked. The resulting fuel additive composition can be blended with
diesel fuel to produce an alternative fuel composition. In one embodiment, the alternative fuel
composition includes approximately 25-95% diesel fuel and approximately 5-75% of the fuel additive
composition.

Cetane numbers of fatty acid esters have also been investigated. Branched and straight-chain fatty acid
esters have been studied by Knothe, Mathaeus and Ryan
68
. In this work, the Cetane Nos. of 29 samples
of straight-chain and branched C1-C4 esters as well as 2-ethylhexyl esters of various common fatty
acids were determined. The Cetane Nos. of these esters are not significantly affected by branching in
the alcohol moiety. Therefore, branched esters, which improve the cold-flow properties of biodiesel,

BIOScopes
can be employed without greatly influencing ignition properties compared to the more common
methyl esters. Unsaturation in the fatty acid chain was again the most significant factor causing lower
Cetane Nos. Cetane Nos. were determined in an ignition quality tester (IQT) which is a newly
developed, automated rapid method using only small amounts of material. The IQT is as applicable to
biodiesel and its components as previous cetane-testing methods.

An possible explanation for different Cetane numbers of fatty acids and esters in this context is given
by Knothe, Marvin and Ryan
69
. Fatty acids of C18 chain length and their methyl, ethyl, propyl, and
butyl esters were injected into an constant-volume combustion apparatus suitable for collecting
material from the fuel spray prior to the onset of ignition. The collected material from this pre-
combustion phase of the injection event was analyzed by gas chromatography-mass spectrometry.
Compounds identified as forming during the pre-combustion phase were straight-chain and branched
alkanes, alkenes, and cyclic hydrocarbons, and aldehydes, ketones, esters, substituted benzenes, and
other species, such as furans. Some of the compound formed during pre-combustion have low Cetane
Nos. (CN). Low-cetane aromatic compounds were found more prominently for more unsaturated fatty
compounds.

The influence of various oxygenated compounds o the Cetane numbers of fatty acids and esters was
investigated by Knothe, Bagby and Ryan
70
. The ignition delay times of four C18 fatty acids of varying
unsaturation and their methyl, ethyl, propyl, and butyl esters were determined in a Constant Volume
Combustion Apparatus (CVCA). These values were used to calculate some preliminary relative
Cetane Nos. (CN). The CN range from 80.1 for butyl stearate to 20.4 for linolenic acid. In fatty
compound, there are positive correlations between CN and the number. of CH
2
groups as well as
between CN and the saturation of the hydrocarbon chains. In addition, the CN of numerous
oxygenated compounds with different functional groups were determined. These compounds are
possible Cetane-improving additives in biodiesel and perhaps for petroleum-based diesel fuel. One
neat material had ignition delay characteristics suggesting a CN of 234. These compounds were
investigated in different concentrations with the various fatty compounds. The effectivity of these
compounds varied with concentration, some being more effective at higher concentrations, some at
lower concentrations. The compounds had different effects on diesel fuel. One selected compound
markedly enhanced the CN of acids in contrast to the esters.

On the other hand experiments on oxidative stability which is an other crucial quality parameter, of
ethyl esters were performed by Ferrari et al.
71
. The oxidative stability of biodiesel manufactured by
ethanolysis of: (1) neutralized, refined, soybean frying oil waste and (2) partially hydrogenated
soybean frying oil waste was determined. Evaluation of the oxidative stability was conducted in an
automated "Rancimat" device, at 100C and 105C in an air flow of 20 L/h. The fatty acid
composition was determined by GC and the iodine value (as a measure of unsaturation) was
calculated. Even though the neutralized, refined and waste frying soybean oils presented close
comparable iodine values, the derived biodiesel presented different oxidative stabilities. The biodiesel
from neutralized soybean oil presented greater stability, followed by the refined oil and the frying
waste oil. Due to the natural antioxidants in its composition, the neutralized soybean oil promoted a

BIOScopes
larger oxidative stability of the produced biodiesel. During the deodorization process, the vegetable
oils lose part of these antioxidants, therefore the biodiesel from refined soybean oil presented a
reduced stability. The thermal process degrades the antioxidants, thus the biodiesel from frying waste
oil resulted in lower stability, the same occurring with the biodiesel from partially hydrogenated waste
oil, even though having lower iodine values than the other.

Studies on volatility and boiling points of biodiesel from vegetable oils and tallow were done by
Goodrum
72
. Quality control of fuel-related properties of biodiesel, such as volatility, is needed to
obtain consistent engine performance by fuel users. The vapour pressures and boiling points of
selected methyl esters and vegetable oils are proposed as quality control metrics for biodiesel. This
type of data was obtained by a rapid new method using thermogravimetry analysis (TGA). One
atmosphere boiling points (bps) and temperature-dependent vapor pressures from 1 atm down to 5.332
kPa (40 mM Hg) were measured for methyl and ethyl esters of rapeseed oil, canola oil, soybean oil,
and tallow. Boiling points (1 atm) ranged from 340 to 375C. Methyl and ethyl esters of a given oil
differ by .apprx.5C in bps. These results are discussed in terms of the fatty acid composition of the
esters and oils. Calibrations showed that the TGA/laser orifice capsule method gave accuracy of 5%.

Allen et al. developed a method for predicting the viscosity of biodiesel fuels from their fatty acid
ester composition
73
. Viscosity is one of the most significant properties to affect the utilization of
biodiesel fuels. A method is presented, which has been verified experimentally for predicting the
viscosities of biodiesel fuels from the knowledge of their fatty acid composition. The applicability of a
logarithmic mixture equation was verified using controlled mixtures of saturated fatty acid esters and
natural biodiesel. Several binary, ternary and quaternary mixtures of fatty acid ethyl ester (FAEE) gas
chromatography. (GC) standards were formulated. Their viscosities were predicted from their
component values and were within 3.7% of their measured values. The fatty acid compositions of six
typical oils were simulated by mixing fatty acid methyl ester (FAME) standards in appropriate
amounts. Viscosities of these mixtures were also predicted within 2.1% of their measured values.
Five biodiesel types were produced from natural oils and the logarithmic equation was applied to
predict their viscosities. An average prediction error of 3% was obtained for these samples. The
viscosities of fifteen biodiesel types were then predicted based on their fatty acid composition as
published in the literature and were found to vary as much as 100% This is most likely a principal
contributing factor to the variation in performance of some biodiesel fuel types. The viscosity of
biodiesel fuels reduce considerably with increase in unsaturation. Contamination with small amounts
of glycerides significantly affects the viscosity of biodiesel fuels.

The same authors also reported a method for predicting the surface tension of biodiesel fuels from
their fatty acid ester composition
74
. Surface tension, which plays a role in atomization, has lacked
attention compared to other biodiesel properties. The paper presents a method to predict the surface
tension of biodiesel fuels based on the fatty acid composition. Several binary, ternary, and quaternary
mixtures of fatty acid ethyl ester gas chromatography (GC) standards were prepared, and it was found
that a mass-average equation predicted the surface tension of these mixtures within 3.5% of their
measured values. Six complex mixtures of fatty acid methyl ester GC standards that simulated typical

BIOScopes
oils used as biodiesel fuels were also prepared. For these complex mixtures the predicted surface
tensions of the mixtures, calculated from a mass-average equation, were 2-6% higher than the
measured values. A mass-average equation was developed in which a weighted surface tension for the
individual components was used, and it was found that this method predicted the surface tension of the
simulated oils within 4.5% of their measured values. Five natural vegetable oils were used to produce
biodiesel fuels by the transesterification process. The predicted surface tensions of these fuels were all
within 3.5% of their measured values. The surface tensions of 15 biodiesel types were then predicted,
based on their fatty acid composition as published in the literature. These results show that the
differences in surface tension between biodiesel types are not the main cause of the reported
differences in engine tests.
Ethyl Ester Production Facilities Ethyl Ester Production Facilities Ethyl Ester Production Facilities Ethyl Ester Production Facilities
Due to the missing interest of customers and non-existing quality monitoring system, FAEE
production world-wide especially in large scale can be classified as already not existing. The only
production facilities operating have lab-scale or even pilot scale character. Of course some of them are
able to produce FAEE in small scale but no information is available on the effective production
amount. This is valid especially for the situation in Brazil where most of the FAEE production plants
are located. But information from the Brazilian biodiesel institution led to the result that most of them
are producing mainly FAME due to technical problem when switching to FAEE. Large-scale
commercial production of FAEE has not been tested yet, in fact one 50,000 t/y plant (USINA
BARRALCOOL) is currently under execution. However, since the Brazilian biodiesel program
recommends the production through the ethyl route but did not make it mandatory, the market will
have to define the technology to be used, especially for the first phase of the industrial and
technological development. Additionally, many of the classified pilot-scale plants in USA and Brazil
have been used within funded projects for practical experience investigations on technology and
engine tests and have been dismantled or closed after the projects end. So therefore it was not possible
to get confidential data on currently running FAEE biodiesel plants world-wide, the quantities being
produced and the quality (due to non-existing FAEE standards). This is also valid for the situation in
Europe, where no industrial scale FAEE plant is working. However, a mid-scale plant nearby Set
(France) is projected which possibly should produce FAEE but this information could not be verified.
F.4 F.4 F.4 F.4 Summary Summary Summary Summary
Literature evaluation on the main aspects for implementation of FAEE in the near future led to
following conclusions:

Production: The first step for industrial scale implementation of FAEE production technology will be
based on traditional biodiesel technologies. This means that esterification and transesterification of
vegetable oils or fats will be done by alkaline or acid catalyzed reaction pathways. Other appropriate
technologies like enzyme based or by heterogeneous catalysis are currently too costly. Modifications
on process have to be done when FAEE should be produced. Catalyst amount, alcohol excess, reaction
temperature and time have to be optimized. Furthermore, the transesterification reaction requires high
purity of the alcohol which in case of ethanol recycling (out of the process) would need additional
invests for the ethanol purification. However, due to missing experience with large scale FAEE

BIOScopes
production facilities (in fact some are currently under construction) all the mentioned aspects cannot
be analyzed more detailed. It is recommended to re-evaluate the given information again if
information of the practical experience of large scale FAEE production facilities is available.

Experience: Several investigations on the practical behavior of FAEE in automotives have been
carried out. All studies in common showed the similarity of FAEE compared to FAME when used as
fuel. This includes engine performance as well as emission characteristics with all pros and cons (e.g.
less emissions, higher consumption etc.). However, the results showed general trends but cannot be
interpreted (compared) directly. They are affected by the use of different fuel qualities during the
different tests and also by the small number of long time engine tests carried out. This means that
additional engine and performance tests should be carried out in order to guarantee trustable and
comparable results. However, before such tests can be carried out an uniform quality assurance
instrumentation on FAEE have to be installed. This should point out again the urgency for appropriate
FAEE standards which have to be developed based on already existing experience on FAME as well
as FAEE.

Production, Quality, and Quantity: Most of the currently running FAEE plants have pilot or small
scale character. In fact, several have been installed for the different studies on the engine performance
with FAEE. Most of them have been dismantled after the projects ended. Unclear is the situation of
FAEE production in Brazil. Generally, it can be stated that only few of the different small and mid-
scale production facilities in Brazil are able to produce FAEE but information on quality and quantity
could not be obtained with high confidence. However, the Brazilian biofuels market will be further
increased and FAEE production facilities besides FAME production will be established also
influenced by the availability of large amounts of ethanol at low prices.
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Low Pour Point for Cold Climate Countries. U.S. Pat. Appl. Publ. (2004), 7 pp, Cont.-in-part of U.S.
Ser. No. 440,169. US 2004231236.

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[66] C. Ritter: Composition and Methods for Improved Lubrication, Pour Point, and Fuel
Performance. PCT Int. Appl. (2006), 25 pp. WO 2006032012.
[67] D.S. Bradin: Biodiesel Fuel Additives Containing Fatty Acid Alkyl Esters and Glyceryl Ethers.
U.S. (1996), 6 pp. US 5578090 A 19961126.
[68] G. Knothe, A.C. Matheaus, T.W. Ryan: Cetane Numbers of Branched and Straight-chain Fatty
Esters Determined in an Ignition Quality Tester. Fuel (2003), 82, 971-975.
[69] G. Knothe, M.O. Marvin, T.W. Ryan: Precombustion of Fatty Acids and Esters of Biodiesel. A
Possible Explanation for Differing Cetane Numbers. JAOCS (1998), 75, 1007-1013.
[70] G. Knothe, M.O. Bagby, T.W. Ryan: The Influence of Various Oxygenated Compounds on the
Cetane Numbers of Fatty Acids and Esters. Liquid Fuel and Industrial Products from Renewable
Resources, Proceedings of the Liquid Fuel Conference, 3rd, Nashville, Sept. 15 -17, 1996 (1996), 54-
58.
[71] A.R. Ferrari, O. da Silva, V. Oliveira, A. Scabio: Oxidative Stability of Biodiesel from Soybean
Oil Fatty Acid Ethyl Esters. Scientia Agricola (Piracicaba, Brazil) (2005), 62, 291-295.
[72] J.W. Goodrum: Volatility and Boiling Points of Biodiesel from Vegetable Oils and Tallow.
Biomass and Bioenergy (2002), 22, 205-211.
[73] C.A.W. Allen, K.C. Watts, R.G. Ackman, M.J. Pegg: Predicting the Viscosity of Biodiesel Fuels
from their Fatty Acid Ester Composition. Fuel (1999), 78, 1319-1326.
[74] C.A.W. Allen, K.C. Watts, R.G. Ackman: Predicting the Surface Tension of Biodiesel Fuels from
their Fatty Acid Composition. JAOCS (1999), 76, 317-323.


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Annex G Theoreti cal Anal ysi s of Techni cal
Bottl enecks and Sol uti ons
(Graz Uni versi ty)
G.1 G.1 G.1 G.1 Introduction Introduction Introduction Introduction
Generally, transesterification reactions of fats and oils can be performed in principle with methanol as
well as ethanol to produce the corresponding fatty acid methyl and ethyl esters respectively. Currently,
almost all biodiesel produced worldwide is coming from transesterification of oils with methanol.
Main reasons are of course the lower price of the methanol as well as the currant production
technology, existing specifications for FAME as well as the public acceptance of this product.
However, due to the increasing production values of ethanol and the increasing demand of alternative
fuels, biodiesel production with ethanol as alcohol will probably become more important in the nearer
future.

As already mentioned transesterification of oils with ethanol is possible but compared to methanol
some problems or differences might occur. Some authors reporting problems with phase separation
after ethanolysis reaction
1,2
, whereas most authors concerning separation did not give any information
at all. Furthermore, the evaluation of the optimum reaction temperature led to differing results. As an
example, for sunflower oil transesterification a reaction temperature of 50C has been examined
3
,
whereas on the other hand for other oils different optima have been found
4
. On the other hand, an
excess of ethanol abs. (500%) and an amount of 1% sodium-methoxide as catalyst led to ester content
of 83.5% at reaction temperature of 83C
5
. Furthermore, formation of gels in the reaction admixture
could be observed. So these examples should demonstrate that several problems or differences to
classical transesterification with methanol are possible.

Besides alkaline catalyzed ethanolysis, acid catalysis has also being reported
6,20,21
. While alkaline
catalysis mostly lead to lower transformation rates compared to methanolysis, acid catalyzed
ethanolysis reactions led to higher ester contents than compared to methanolysis
7
. Also combinations
of acid and alkaline catalyzed reactions have been investigated
8
. On acid catalyzed reactions a
separation of saturated fatty acids have been observed
6
and acid values of the ethyl esters 3x higher
than at the corresponding methyl esters have been reported
9
. Up to now, also only few investigations
have been made on the use of technical grade ethanol containing several % of water
8,10
. All these
investigations showed insufficient results. This can be also stated for experiments with acid catalyzed
in situ transesterifications
11
.

All these mentioned aspects will be evaluated more detailed in the upcoming chapters based on
practical experiences from laboratory trials as well as reported data.

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G.2 G.2 G.2 G.2 Transester Transester Transester Transesterification Technology ification Technology ification Technology ification Technology
Based on reported data
3
experiments with alkaline catalyzed transesterification of sunflower oil with
stoichiometric amounts or even small excess of ethanol led to insufficient transesterification rates.
Furthermore, ethanolysis with catalyst amounts comparable to methanolysis reactions showed
insufficient results. Also reaction time and temperature had strong impacts on reaction yields. Finally,
also the type of catalyst, hydroxide versus ethoxide and the purity of the used ethanol significantly
influence reaction rates and yields. So therefore a lot of different modifications and optimization steps
are necessary to obtain high reaction rates to produce ethyl esters with required ester contents 96.5
%. Of course such technologies are available (see literature survey task 3.1.) but the problem is, that it
is not possible to evaluate such processes from the technical side because currently no industrial scale
biodiesel ethyl ester plant is running worldwide. However, even small scale plants which operated e.g.
in Brazil did not give detailed information on their process conditions and upcoming problems during
operation. So therefore all the described problems or differences compared to classical methyl ester
production are based on different laboratory experiments and pilot plants.
Catalysts Catalysts Catalysts Catalysts
From technical aspects the most promising and investigated technology will be based on alkaline
catalysts whether in form of sodium or potassium hydroxides or in form of sodium or potassium
alkoholates. Such alkoholates can be either methoxides or ethoxides. In fact the amount of the
catalysts cannot be specified generally but the evaluation of all reported material indicated that the
amount would be slightly higher than compared to methyl ester production. These aspects should be
taken into consideration from the economic point of view. Furthermore, ethoxides will be more
expensive than methoxides and it is also not easy to elicit if ethoxides will be available in sufficient
amounts on the market.

Other options for catalysts that can be used for transesterification are either acid catalysts or of
enzymatic type. Acids would have the advantage that saponification of free fatty acids in the oil would
not take place. These soaps can prevent separation of the biodiesel from the glycerin fraction. As acid
catalysts in principle all kinds of strong inorganic acids e.g. H
2
SO
4
, H
3
PO
4
, HCl, or organic acids like
p-toluene-sulfonic acid can be used. Investigations showed that with this type of catalysis high
conversion rates are possible. On the other hand longer reaction times are required than for alkaline
catalysts. Furthermore, the concentration of water has to be less than 0.5%. However, from the
economic side longer reaction times should be avoided so therefore it is hard to argue if acid catalyzed
transesterification for ethyl ester production will be an option for technical implementation.

Evaluating literature data of the past years showed that numerous articles are published reporting
investigations of enzyme based transesterification. Different kinds of enzymes from varying sources
are able to transesterify fats and oils into biodiesel with high yields and even high quality. Probably
most of such enzymes are able to show similar transesterification behavior when used for fatty acid
ethyl ester production. Basically, several authors reported such evaluations but compared to FAME
only few data is available. However, all enzyme type transesterification reactions with methanol as
well as ethanol are currently at experimental state. Due to the high prices of the enzymes from the

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commercial point of view such technologies will not be used for large scale biodiesel production in the
near future. Probably this might be changing if enzymes are available at reasonable prices but as
already mentioned, currently enzymes suitable for biodiesel production (in fact the cheapest ones) are
10 times more expensive than classical alkaline catalysts.
Transesterification Conditions Transesterification Conditions Transesterification Conditions Transesterification Conditions
Conditions of transesterification of fats and oils with ethanol generally are comparable to classical
biodiesel production processes. Transesterification can be performed with batch type processes as well
as semi-continuous or continuously. Therefore, from plant design only few modifications would be
necessary to switch from methyl ester to ethyl ester production. Differences to methyl ester production
are typically caused chemically. Increasing the temperature up to 70C during transesterification
would result in higher ester yields and faster reaction time
3
. At such temperatures evaporation of
ethanol has to be suppressed. Higher pressure and intensive agitation are required. Other authors
reported similar behavior even lower temperatures
12
. Catalyst amount is recommended slightly higher
compared to methyl ester production otherwise the ester yields would be to low. Kinetics of ethyl ester
production overall are comparable or even slightly better compared to methyl ester production due to
better ethanol solubility in the oil
13
. Thus, reaction time, catalyst amount and reaction temperature are
the most influencing factors on the velocity of the reaction and have to be therefore optimized for
production. One main problem which has often been discussed is the different phase separation
behavior during ethyl ester production. Main reason for this is the far better solubility of ethanol in the
ethyl ester phase than compared to methanol. Furthermore, saponification of free fatty acids has to be
avoided. Saponification during ethanolysis has found to be more critical than compared to
methanolysis
14
. Also increasing reaction temperature could have an influence on saponification
reactions
12
. Generally, phase separation of glycerol formed during process possibly needs
modifications compared to classical biodiesel process. A possible way for separation of water soluble
substances would be a neutralization step by addition of inorganic acids like HCl. Other acids reported
(acetic acid, H
2
SO
4
, H
3
PO
4
) will form emulsions which can be separated only by addition of 20%
NaCl solution
3,4,15
. Another option for better glycerol separation would be the addition of purified
glycerol phase to the reaction mixture
16
. Furthermore, the use of ion exchange resigns in order to get
better phase separation behavior has also been discussed
6,8
.
Alcohol Alcohol Alcohol Alcohol - -- - Requirements Requirements Requirements Requirements
Many authors reported on the negative influence of water on transesterification
2,10,13-15,17-19
. In fact
water content is a limiting factor of vegetable oils as well but such water content of the feedstock can
be lowered by appropriate oil pre-treatment. Different is the situation in the context of alcohol water
content whereas different ethanol qualities are available. The use of technical or industrial grade
ethanol with water contents up to 5% or even higher would be from commercial side the best
opportunity because such alcohols would be available in large amounts and also very cheap. However,
the use of such ethanol has to be strictly avoided. Most of the transesterification technologies suitable
for ethyl ester production need high purified ethanol with water contents < 0.1%.

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Glycerol Quality Glycerol Quality Glycerol Quality Glycerol Quality
From the evaluated data, no information about changes in glycerol quality from FAEE production
compared to that of FAME production is reported. However, it should be kept in mind that, due to the
better solubility of ethanol in fatty acid ethyl esters and the resulting almost mentioned problems
during phase separation problem might occur from technical side. This means that probably higher by-
product amounts could be found in the glycerol layer and therefore the technical glycerol conditioning
and purification steps would need modifications. Furthermore it should be kept in mind that ethanol
removal during the different processing and purification steps would be more energy consuming due
to the higher boiling point of ethanol compared to methanol.
Retrofitting FAME into FAEE Plants Retrofitting FAME into FAEE Plants Retrofitting FAME into FAEE Plants Retrofitting FAME into FAEE Plants
Because of FAEE production is from the technical approach comparable to FAME production,
existing biodiesel plants should have the technical requirements to produce also FAEE without major
retrofitting problems. However, some technical aspects will need to be modified for processing.
Especially possible problems with phase separation of ethyl esters from glycerol will induce perhaps
an additional processing step (e.g. centrifugation or input of glycerol or acids for better phase
separation). Furthermore, in order to guarantee high conversion rates compared to minimum losses of
chemicals used for transesterification, invests have to be made for equipment used for ethanol
purification coming from the process. It has been mentioned that an excess of ethanol (with high
purity) is necessary for high conversion of the oils. During process this ethanol excess will be, beyond
others contaminated with process water. For reuse of the alcohol the ethanol has to be recycled and
purified which would require additional equipment and therefore additional investment costs. For
retrofitting, this equipment might represent the major part of the additional invests. As far as
experiences with ethyl ester production in industrial scale are still outstanding additional problems
might occur but cannot be evaluated generally. In fact most technologies for ethyl ester production are
based on classical biodiesel processing used for FAME. Especially batch type processing of ethyl
esters has been extensively investigated. For this reason only biodiesel plants with batch type or even
semi-continuous processing would be able to process ethyl esters. The most obvious and important
barrier for ethyl ester production is the commercial aspect which will be more detailed evaluated in
chapter 3.4 and 3.5. Higher prices for ethanol compared to methanol and additional energy input for
processing and ethanol recovery discourage FAME producers to switch to FAEE production.
Additionally, still missing quality standards for FAEE will have negative influences on customers and
engine manufacturers.
G.3 G.3 G.3 G.3 FAME versus FAEE Quality Parameters FAME versus FAEE Quality Parameters FAME versus FAEE Quality Parameters FAME versus FAEE Quality Parameters
Fatty acid ethyl esters have very similar chemically behavior compared to the corresponding methyl
esters. Although in both cases, process technology, used feedstocks, alcohol, and catalysts are similar
the resulting esters would have some differences concerning quality parameters according EN 14214.
Such differences can be classified either into changes of values resulting or induced by the ethyl ester
group and differences of analytical determination methods. Parameters affected directly by the use of
ethanol for production are:

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Viscosity: which might be significantly higher than compared to methyl esters. Basically most
vegetable oil ethyl esters would have viscosities below or nearby the currant EN 14214
specification limit but some of them (e.g. castor oil ethyl esters) would be far above the limit. In
fact, such higher viscosities would be one of the most critical argumentation points especially
for car manufacturers and engine producers in order to successfully introduce such a fuel.
Density: only slight or even negligible increases will be expected but within currant
specification limits.
Flash Point: higher than compared to methyl esters but in fact depending on process technology
for ethanol removal.
Distillation Characteristics: would differ from methyl esters due to the higher boiling points of
ethyl esters. For European specifications not important but included in other National standards
(e.g. U.S.).
Carbon Residue: again expected to be slightly higher but should be definitely within the given
limits.
Oxidation Stability: not many data and experience available but first reports showed comparable
or even slightly higher oxidation stabilities of ethyl esters.
Low Temperature Behavior: similar situation than mentioned on oxidation stability. Not many
data available but the fatty acid ethyl esters should have better low temperature behavior
(CFPP/PP/CP). However, the differences will be in best case only some C.

Additional influences or changes of the mentioned parameters will be strongly dependent on the
technology used for production.

On the contrary even some of the analytical methods of EN 14124 have to be adopted for ethyl ester
application. Most of the currant methods can be used without further modifications but especially the
ester specific methods have to be re-evaluated or even new designed. Concrete actions have to be set
on: ester content method (prEN 14103), linolenic acid ester content (EN 14103), polyunsaturated fatty
acid esters content (currently no existing method), methanol (ethanol) content (EN 14110), mono-, di-,
and triglyceride content (EN 14105), and iodine value if calculated on unsaturated fatty acid ester
content.
G.4 G.4 G.4 G.4 Engine Applications and Experience Engine Applications and Experience Engine Applications and Experience Engine Applications and Experience
Focusing on FAEE as fuel application, besides production technology and quality standards, the
engine behavior of such a fuel is an important criterion for a successful market introduction.
Compared to FAME where lots of studies, reports, and data on engine and driving performance as well
as on exhaust emission behavior are available, only few data on ethyl esters exists. Especially data
which give a direct comparison between behavior of ethyl esters versus methyl esters and diesel fuel
are very rare. The reason is that there has not been such an insistent need on ethyl esters so far.
Furthermore, due to missing large scale production plants for ethyl esters, big fleet programs can not
be realized. Therefore, most of the existing data is limited to short term engine tests or long term tests
with only few vehicles. In fact, most of the investigations have been carried out in USA where
different investigations have been undertaken mainly by the University of Idaho. These initiatives
included, besides research on production technology, also the corresponding evaluation of the engine

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behavior of fatty acid ethyl esters. One project tested a biodiesel fuel prepared from ethanol and waste
French-fry oil
22
. This so called HySEE (hydrogenated soybean oil ethyl ester) fuel was screened in an
300h engine durability test. At the end of the test the engines were dissembled and inspected for
evaluation of the effect of the fuel on engine components. Coking of the pintle injector, pre-
combustion chamber and piston ring grooves were evaluated by inspection. Specific conclusions of
this study were:
The average HySEE injector coking index was 3.07 and 1.00 for D2. Visually, all injector
coking was low especially compared with older tests that included raw vegetable oils.
Opacity was decreased by as much as 71% compared to D2
At rated load, engine power produced by HySEE decreased by 4.8% compared to D2
Peak torque for HySEE at 1700 RPM was reduced by 6% compared to D2 while at 1300 RPM it
was reduced only by 3.2%, demonstrating a flatter torque curve characteristic of biodiesel.
The average fuel consumption (g/s) on a mass basis was 7% higher than that of D2. The
differences in fuel consumption and power reflect the differences in heat of combustion and
density between the two fuels.
Thermal efficiencies for HySEE and D2 were not significantly different.
Emissions tests showed a 54% decrease in HC, 46% decrease in CO, 14.7% decrease in NO
x
,
0.57% increase in CO
2
, and a 14% increase in PM when HySEE was compared to D2. The HC,
CO, and NO
x
differences were statistically significant.

Similar results were obtained in an earlier project of the University of Idaho
23
dealing with the
production and testing of ethyl and methyl esters. Methyl and ethyl esters of four renewable fuels
(canola, rapeseed, soybean oil, and beef tallow) were processed, characterized and performance tested.
Main conclusions of this 150 hours performance tests were:
The esters all have higher levels of injector coking than diesel fuel. Ethyl esters had higher
levels than did the methyl esters. Injector coking was more related to appear molecular weight
and viscosity than to total glycerol. Visually all injector caking was low especially compared
with older tests that include vegetable oils.
Smoke density, as determined by an opacity meter, decreased an average of 75% for the
biodiesel fuels compared to D2. Canola ethyl esters and methyl esters produced the most smoke
of the biodiesel fuels and tallow and soybean methyl esters the least smoke.
At rated load, engine power produced by the biodiesel fuels decreased an average of 4.9%
compared to D2.
Peak torque for biodiesel at 1700 RPM was reduced 5% on the average compared to D2 while at
1300 RPM it was reduced only 3%, demonstrating the flatter torque curve characteristics of
biodiesel.
The average biodiesel fuel consumption (g/s) on a mass basis was 7% higher than that of D2. On
a volume basis the consumption would be 6.7% higher than that of D2.
Average thermal efficiencies for biodiesel fuel in the mapping test was insignificant by
difference when compared to D2.


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Parallel to the above mentioned project an vehicle test with an 1994 Dodge 2500 pickup fuelled with
ethyl esters of rapeseed oil was carried out
24
. A total distance of 14.069 km has been covered and
engine performance and emission behavior have been monitored. Specific conclusions of this test
were:
Emission tests with this vehicle showed a reduction in HC (55.6%), CO (50.6%) and NO
x

(11.8%) and an increase in CO
2
(1.1%) and PM (10.3%). The results for PM were not
significantly different from diesel. The other results were significantly different (P<0.05).
The dynamometer test at 2500 rpm showed 1.8% less power, and 8.9% less fuel economy, and
31.8% less opacity when operated on biodiesel in comparison to diesel control fuel.
Vehicle performance was extremely good and no problems were noted during this test.

The results of these three reports indicate that ethyl esters of vegetable oils lead to comparable results
known of FAME behavior. It should be noted that the mentioned investigations have been performed
with biodiesel produced in lab or even pilot scale and that due to missing specifications especially for
ethyl esters at that time the quality of the tested fuels (given in the reports) would not fit currant EN
14214 specification limits and therefore the results obtained of the engine tests might be influenced by
this varying quality.

However, several additional engine and performance tests have been carried out since that (see also
1.3.2.) but they are mainly small and had demonstration character (e.g. Truck in the Park Biodiesel
Demonstration with Yellowstone National Park, 1999; Experiments with Biodiesel from Yellow
Mustard, university of Idaho, 2003). But in general they led to comparable results (performance as
well as emission characteristics) with earlier projects. The problem is, however, that comprehensive
investigations on ethyl esters are still outstanding. The mentioned results indicate only that the engine
performance is obviously comparable to results obtained for FAME so far. Furthermore, reports with
ethyl ester experiences from Brazil are still missing. Basically, most of the experience should be
available from there, but it has turned out that on this topic no authentic material could be found.
G.5 G.5 G.5 G.5 Summary Summary Summary Summary
Evaluating the covered material on technical bottlenecks and barriers of ethyl ester production the
following conclusions can be drawn:

The technical implementation of ethyl ester production generally will be based on existing technology
of FAME production. In detail, technology based on alkaline or acid transesterification of vegetable
oils and fats will be most promising even for large scale implementation. However, process conditions
will have to be modified concerning catalyst and alcohol ratio, reaction temperature and reaction time.
Still open is the question how to handle possible problems expectable on phase separation when
processing in large scale.

Retrofitting existing FAME plants for FAEE production should be possible within tolerable
additionally invests. It should be noted that, due to the fact of still missing large scale running FAEE
processing plants world-wide, this argumentation is based on a scenario using classical
transesterification processing.

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Glycerol quality coming from FAEE production is expected of being comparable to such out of
FAME production.

Ethanol for transesterification must be purified or purchased in qualities higher than 99% purity.

The quality of FAEE will differ in some parameters compared to FAME when taking EN 14214 as
reference specification. Some parameters might be outside the given limits. Of course this will be
dependant on feedstock and technology used for production. Furthermore, no all of the existing
analytical methods for FAME quality determination will be suitable for FAEE analysis. However,
standardization for FAEE is still open.

Practical engine experiences with FAEE showed no notable differences compared to FAME. Emission
characteristics and performance have been found to be very similar. A statement of engine
manufacturers on possible use of FAEE is of course still missing, also because of lack of experience
and missing legal frameworks.
G.6 G.6 G.6 G.6 References References References References
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Hydroxide in Ethyl Alcohol. J. Am. Oil Chem. Ind. Japan, 36, (1933), 230 -231.
[2] H.J. Wright, J.B. Segur, H.V. Clark, et al.: Report on Ester Interchange. Oil and Soap, (1944), 145
148.
[3] R.O. Feuge, A.T. Gros: Modification of Vegetable Oils, VII, Alkali Catalyzed Interesterification of
Peanut Oil with Ethanol. J. Am. Oil Chem. Soc., 26, (1949), 97 -103.
[4] D.K. Chowdhury, B.K. Mukherji: Ethanolysis of Vegetable Oils Using Sodium Hydroxide as
Catalyst, I, Effect of Ethanol and Catalyst Concentration and Soap Formation. J. Indian Chem. Soc.,
31, (1954), 116 -124.
[5] P.F. Kusy: Transesterification of Vegetable Oils for Fuels. Proceedings of the International
Conference on Plant and Vegetable Oils as Fuels. American Society of Agricultural Engineers, (1982),
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[6] C.B. Johnson: Tallow, Rapeseed oil and their Esters as Diesel Fuel Extenders preparation of
Tallow and Rapeseed Oil Esters, A preliminary report, Department of Scientific and Industrial
research, Palmerston North, New Zealand, (1981).
[7] M.J. Nye, T.W. Williamson, S. Deshpande, et al.: Conversion of Used frying Oil to Diesel Fuel by
Transesterification: Preliminary Tests. J. Am. Oil Chem. Soc., 60, (1983) 1598 1601.
[8] R. Stern, G. Hellion, P. Gateau, et al.: Fatty Acid Esters Used as Substitute Gas Oil Fuels,
Preparation with Water Containing Ethanol, and Composition of the Esters. Fr. Demande, FR
2.577.569 (Cl. C11C3/10), (1985).

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[9] H.A. Aksoy, I. Kahraman, F. Karaosmanoglu, et al.: Evaluation of Turkish Sulphur Olive Oil as an
Alternative Diesel Fuel. J. Am. Oil Chem. Soc., 65, (1988), 936 938.
[10] R.A. Korus, D.S. Hoffmann, N. Bam, et al.: Transesterification Process to Manufacture Ethyl
Esters of Rape Oil. First Biomass Conference of the Americas (Final Program), (1993), Energy,
Environment, Agriculture and Industry, 815 -826.
[11] S. zgl, S. Trkay: In Situ Esterification of Rice Bran Oil with Methanol and Ethanol. J. Am.
Oil Chem. Soc., 70, (1993), 145 -147.
[12] D.K. Chowdhury, B.K. Mukherji: Ethanolysis of Vegetable Oils Using Sodium Hydroxide as
Catalyst, II, Effect of temperature and Moisture. J.Indian Chem. Soc. 31 (1954), 125 128.
[13] E.H. Gauglitz, L.W. Lehman: The Preparation of Alkyl Esters from Highly Unsaturated
triglycerides. K.J. Am. Oil Chem. Soc., 40, (1963), 197 198.
[14] R.L. Glass: Alcoholysis, Saponification and the Preparation of Fatty Acid Methyl Esters. Lipids,
6, (1963), 919 925.
[15] B. Freedman, E.H. Pryde, T.L. mounts: Variables Affecting the Yields of Fatty Esters from
Transesterified Vegetable Oils. J. Am. Oil Chem. Soc., 61, (1984), 1638 1643.
[16] R.R. Szpiz, F.H. Jablonka, D.A. Pereira, et al.: Processo da Transesterificacao de Oleos Vegetais.
Braz. Pedido, PI 8300, (Cl. C 11 C 3/04), (1984), 429.
[17] W.W. Christie: Preparation of Fatty Acid Methyl Esters. INFORM, 3, (1992), 1031 -1034.
[18] S. Romano: Vegetable Oils A new Alternative. Proceedings of the International Conference on
Plant and Vegetable Oils as Fuels, American Society of Agricultural Engineers, (1982), 106 116.
[19] A.W. Schwab, M.O. Bagby, B. Freedmann: Preparation and properties of Diesel Fuel from
Vegetable Oils. Fuel, 66, (1987), 1372 1378.
[20] D. Nimcevic, R. Puntigam, M. Wrgetter, et al.: Preparation of Rapeseed Oil Esters of Lower
Aliphatic Alcohols. J. Am. Oil Chem. Soc., 77, (2000), 275 280.
[21] M. Canakci, J. Van Gerpen: Biodiesel Production via Acid Catalysis. Trans ASAE, 42, (1999),
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[23] Production and Testing of Ethyl and Methyl Esters.
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Case Study. Biomass and Bioenergy, 10, (1996), 331-336.


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Annex H Economi c Issues Rel ated to FAEE
(Graz Uni versi ty)
The subsequently presented economic calculation of ethyl ester production should give an idea on
costs which might be arising for producers and investors interested in this kind of alternative fuel
production. In fact, the given scenarios are representing only rough calculations, influenced by many
different parameters which cannot be included as exact values but only as assessments based on
already existing experience and technology. So therefore, different ancillary conditions had to be set in
order to enable and guarantee a comprehensive cost calculation:
Technology: As already mentioned, experience with large scale ethyl ester production is
currently not available. Only pilot-scale and small scale production plants have been operated so
far. Therefore the scenario for the calculation of production costs is based on available practical
experience and on most promising technology suitable for ethyl ester production even in large
scale. This means in detail that such kind of production plant will be running on classical
biodiesel process including two step batch transesterification of the oil, typically washing and
purification steps for the produced biodiesel, glycerol processing and fertilizer production as by-
products. Classical alkaline transesterification using KOH as catalyst is used.
Alcohol: the Ethanol used for transesterification must be of high purity. Anhydrous alcohol is
therefore selected for the calculation.
Additional invests for ethyl ester production: Within the cost calculation, especially this part is
very difficult to evaluate due to missing experience and references. Additional costs for energy
(ethanol recovery etc.) are estimated being 5%. More invests for the additional technology and
equipment necessary for the biodiesel plant are set on 25%. These invests include mainly the
ethanol recycling path. An excess of ethanol is necessary for the production of the ester. For
ethanol reuse, the alcohol has to be purified again to guarantee anhydrous quality.
Alcohol price scenarios: Different scenarios are included in the calculation. A comparison of
different ethanol prices world-wide is kept as well as differences of methanol prices for a direct
comparison. Furthermore, due to increasing methanol prices during the last months a critical
value for methanol has been calculated. This price indicates equal costs for biodiesel production
of FAEE chain as well as FAME.

Based on these conditions a cost calculation on the production of FAEE compared to FAME has been
performed. The corresponding data are given in Table 1.


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Production Cost Calculation FAME FAME FAEE FAEE FAEE
/to /to /to /to /to
case 1) case 2) case 3) case 4) case 5)
average Methanol price high Methanol price Europe Brazil US

Feedstock 620.0 85% 620.0 591.9 591.9 591.9
Operating Materials 44.0 6% 70.8 153.7 87.4 99.6
Utilities (Power, Steam,...) 22.0 3% 22.0 23.1 23.1 23.1
Capital Costs 30.0 4% 30.0 37.5 37.5 37.5
Fixed Costs, G&A 14.0 2% 14.0 14.0 14.0 14.0

Total costs 730.0 756.8 820.2 753.9 766.1
100% 104% 112% 103% 105%

Tab. 1.: Production Costs Calculation of FAME versus FAEE

The assumptions for the different scenarios (case 1-5) are given in Table 2. The ethanol prices are
mean values of different world-market prices during the last couple of months. Detailed information
and discussion of alcohol price developments will be given below.

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Assumption Case 1
Feedstock Input 1000 kg / to FAME
Feedstock Price 0.62 / kg
Methanol Price 250 / to FAME
Methanol Consumption 107 kg/ to FAME

Assumption Case 2
Methanol Price 500 / to FAME

Assumption Case 3
Feedstock Input 954.7 kg / to FAME
Feedstock Price 0.62 EUR / kg
Ethanol Price 700 / m Europe
Density ethanol 0.79 to / m
Ethanol Consumption 154 kg / to FAEE
Additional Invests 25%
Additional Costs
(Energy) 5%

Assumption Case 4
Ethanol Price 360 / m Brazil (= 450 $/m
3
)

Assumption Case 5
Ethanol Price 423 / m US (=2$/gal)

Scenario Calculated on Target Value
Critical Methanol Price @ Ethanol 700/m
3
for Identical
Production Costs 1090 / to

Tab. 2.: Data for Costs Simulation

The results indicated that if methanol prices increase faster than for ethanol in the upcoming years,
FAEE production from the economic point of view can be an alternative compared to FAME
especially in countries with large ethanol production. Especially for producers nearby large ethanol
production facilities very cheap ethanol prices can be bargained. So therefore countries like Brazil and
USA would have good premises for FAEE production. It should be mentioned that for costs
calculation the higher yields for FAEE (approx. 4.75%) compared to FAME are already included.
Different is the situation in Europe. High ethanol prices make it not attractive for biodiesel producers
to switch from FAME to FAEE also from the economic point of view. Furthermore ethanol taxation is
not clearly defined if the alcohol would be used for biodiesel production. Moreover, it is possibly not
the target to be dependent on feedstock imports from other countries into the EU and therefore legal

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frameworks and incentives for ethanol producers in Europe would be necessary. This discussion is
comparable to the current situation on vegetable oil imports for biodiesel production. However, the
described scenarios should indicate only the economic situation for FAEE production. If producers are
willing to invest in this field of alternative fuel production the technological problems have to be
solved and quality assurance systems have to be implemented too.
Besides all the mentioned influences on production costs, the alcohol price development will have the
highest impact on FAEE production. An economically reasonable scenario however, would require
low ethanol prices. The question is, if such scenarios are conceivable. In fact, several trends on alcohol
prices during the last years (and especially during the last months) lead to the assumption that in the
upcoming years ethanol and methanol prices will further converge. This situation is currently
observable by the increasing prices for methanol world-wide. Table 3 gives an example on historical
price development for methanol.


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Methanex non-Discounted
Reference Price
Methanex European Posted
Contract Price
Methanex Asien Posted
Contract Price
Date $/gal $/MT /MT $/MT
May 01 0.770 256
Jun 01 0.670 223
Jul 01 0.570 190
Aug 01 0.510 170
Sep 01 0.420 140
Oct 01 0.370 123
Nov 01 0.400 133
Dec 01 0.400 133
Jan 02 0.375 125 125
Feb 02 0.360 120 125
Mar 02 0.375 125 125
Apr 02 0.420 140 145
May 02 0.500 166 165
Jun 02 0.560 186 185
Jul 02 0.620 206 208
Aug 02 0.620 206 208
Sep 02 0.620 206 208 202
Oct 02 0.620 206 208 202
Nov 02 0.620 206 208 202
Dec 02 0.620 206 208 202
Jan 03 0.690 229 228 230
Feb 03 0.790 263 228 252
Mar 03 0.820 273 245 270
Apr 03 0.820 273 260 275
May 03 0.820 273 260 275
Jun 03 0.820 273 240 275
Jul 03 0.775 258 225 260
Aug 03 0.720 239 225 250
Sep 03 0.700 233 210 241
Oct 03 0.680 226 190 230
Nov 03 0.680 226 190 230
Dec 03 0.680 226 190 230
Jan 04 0.750 249 200 250
Feb 04 0.750 249 200 250
Mar 04 0.750 249 200 250
Apr 04 0.750 249 200 250
May 04 0.750 249 200 250
Jun 04 0.810 269 200 260
Jul 04 0.840 279 230 272
Aug 04 0.840 279 230 272
Sep 04 0.840 279 230 272
Oct 04 0.840 279 230 272
Nov 04 0.900 299 230 272
Dec 04 0.950 316 230 292
Jan 05 0.950 316 230 302
Feb 05 0.950 316 230 302
Mar 05 0.950 316 230 302
Apr 05 0.950 316 230 302
May 05 0.950 316 230 302
Jun 05 0.950 316 230 290
Jul 05 0.900 299 220 280
Aug 05 0.900 299 220 270
Sep 05 0.900 299 220 260
Oct 05 0.960 319 235 280
Nov 05 0.960 319 235 280
Dec 05 1.020 339 235 295
Jan 06 1.020 339 268 320
Feb 06 1.070 356 268 330
Mar 06 1.070 356 268 330
Apr 06 1.070 356 285 330
May 06 1.030 343 285 310
Jun 06 1.030 343 285 310
Jul 06 1.000 333 250 305

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Aug 06 1.030 343 250 310
Sep 06 1.330 442 250 420
Oct 06 1.800 599 400 550

Tab. 3: Methanol Price Development
( Source: http://www.methanex.com)

The dramatic increase of methanol prices by Oct. 2006 would lead to FAME production costs almost
equal to the scenario calculated for FAEE in Brazil. It will be interesting to observe the methanol price
development in the upcoming months. Unquestionable, increasing methanol prices can have a strong
impact for investors if FAME or FAEE should be produced. On the other hand ethanol prices are also
fluctuating. This can be demonstrated very impressive by two graphs, describing ethanol price changes
during the last years (Figure 1,2).

Fig.1.: Ethanol Price Development 10 Years


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Fig.2.: Ethanol Price Development 18 Months

Especially the dramatic price fluctuation during mid 2006 would make FAEE production at that time
very unattractive. However, the reasons for this price fluctuation could not be evaluated. From the
historic price development for ethanol a trend to slightly increasing world-marked prices in the
upcoming years would be expectable. Of course all this perspectives are strongly dependent and
influenced on ethanol production and consumption world-wide. Forecasts based on market simulations
for the upcoming decade underline this evaluation as given in Table 4-7.

Tab.4.: Ethanol Trade Forecast
Source: http://www.fapri.org

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Tab.5.: U.S. Ethanol Production and Consumption Forecast

Tab.6.: Brazilian Ethanol Production and Consumption Forecast

Tab.7.: EU-15 Ethanol Production and Consumption Forecast

Based on these forecasts, ethanol prices should be more or less constant in the upcoming years. This
would indicate that as already mentioned, those countries which represents the global players in
ethanol production would be the first choice for implementation of FAEE production from the
commercial point of view. The European situation is much more difficult to evaluate. In fact, ethanol
production will be increased in future but nevertheless imports from other countries will be necessary.
It can be suggested that from economic aspects the successful introduction of FAEE production in
Europe will be strongly dependent on incentives for ethanol producers, fuel taxation, quality assurance
(standardization) and technological aspects.


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Annex I Laboratory tests and l i terature survey
(Iterg)
I.1 I.1 I.1 I.1 Description of the project Description of the project Description of the project Description of the project technical objectives technical objectives technical objectives technical objectives
The BIOSCOPES project comprises 2 main objectives:

The first objective is to work on the process of production of ethyl esters in order to identify
technical barriers that still have to be overcome and to improve the process so that actual industrial
FAME based equipment could be use to produce them. Three different processes must be compared at
laboratory scale (homogeneous catalyst, heterogeneous catalyst and enzymatic catalyst) using catalyst
presently available on the market. These works must be done at ITERG, LACCO and LBB (as sub
contractors).

The second objective of the works is to analyse the different kinds of ethyl esters that must be
produced and to analyse them regarding improvements needed for the biodiesel standard EN 14214.
Moreover, the co products (mainly glycerol phase) must also be analysed.

An other objective is to carry out a theoretical analysis of the technical bottlenecks and solutions
thanks to a literature survey. This literature survey, begun by the Institute of Chemistry of the
University of Graz, must be completed by Iterg.
I.2 I.2 I.2 I.2 Summary o Summary o Summary o Summary of Work performed f Work performed f Work performed f Work performed
The results are divided into 4 parts. The first one concerns the literature survey. The three other parts
concern the practical analysis of technical bottlenecks. They correspond to the three different catalyses
(homogeneous, heterogeneous, enzymatic).
Literature Literature Literature Literature
A first bibliography was achieved at Iterg using the books, papers and patents available at our
Consultancy & Transfer department. 44 references were selected. The Institute of Chemistry of the
University of Graz transferred its literature survey to Iterg. 11 references were identical. Therefore, 33
references were added to the literature survey of University of Graz.
I.3 I.3 I.3 I.3 Homogeneous catalyse Homogeneous catalyse Homogeneous catalyse Homogeneous catalyse
A process for the production of the ethyl ester from rapeseed oil for use as a biodiesel fuel was
studied. The essential part of the process is the transesterification of rapeseed oil with ethanol, in the
presence of an homogeneous catalyst.

Several parameters were tested for the production of FAEE. It includes:

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temperature
the type of catalyst
reaction time
the quality of EtOH
the addition of a co-solvent
the ratio EtOH/oil

Treatments were also studied. Several samples of ethyl esters were analysed to obtain yields of
reactions and compositions of the different products.
Methods Methods Methods Methods
M a t e r i a l s M a t e r i a l s M a t e r i a l s M a t e r i a l s
The rapeseed oil used for the experiments was provided by Novance. It is a refined rapeseed oil. Its
fatty acid composition and content were determined by gas chromatography at Iterg. Reagent grade
absolute ethanol from VWR was used. Bio-ethanol and dehydrated bio-ethanol were also provided by
Bio-thanol Nord Picardie company. Potassium hydroxide diluted in ethanol at 0.5N was purchased
from Merck KgaA. Aldrich Chemical Company provided the purified, dry sodium methoxide powder.
E x p e r i m e n t a l S e t u p a n d P r o c E x p e r i m e n t a l S e t u p a n d P r o c E x p e r i m e n t a l S e t u p a n d P r o c E x p e r i m e n t a l S e t u p a n d P r o c e d u r e e d u r e e d u r e e d u r e
Four operations were studied in the experimental work which was performed. These are
transesterification, phase separation, removal of unreacted ethanol and washing. After the reaction was
complete, the reaction products separated into two layers ; the ester product formed the upper layer
and the by-product glycerin formed the lower layer. The residual catalyst and unreacted excess alcohol
were distributed between the two phases. After separation of the phases, alcohol was removed then the
catalyst was washed from the ester with water. Analytical methods are explained below (see chapter
analysis).
T r a n s e s t e r i f i c a t i o n T r a n s e s t e r i f i c a t i o n T r a n s e s t e r i f i c a t i o n T r a n s e s t e r i f i c a t i o n
The transesterification experiments were performed in glass reactors of 250mL, 500mL and 1L using
between 100g and 500g of rapeseed oil. Catalysts were 1% or 0.5% by weight of the oil of potassium
hydroxide or sodium methoxide. The sodium methoxide was added as a solid catalyst and the
potassium hydroxide was diluted in ethanol at 0.5N. Oil and ethanol were added first. Stirring was
maintained at 200 rpm until the programmed temperature was reached in the reaction mixture. Then
stirring was set at 600 rpm and catalyst was then added. Samples of approximately 20 mL of the
reaction mixture were pipetted out during reaction, before and / or during treatments. The more
interesting samples were analysed to determine their compositions and the degree of completion of the
reaction. A co-solvent was sometimes added : it was added either before reaction or just before the end
of reaction (i.e. before treatments). The ratio of co-solvent was equal to 10%w/w of oil.

Operating conditions are detailed below for the 12 experiments that were carried out during the first
semester.

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Tabl e I-1. Operati ng condi t i ons f or t ri al s EE01 t o EE12

Trial catalyst % EtOH ratio T Cosolvent
EE01 MeONa 1 absolute 7.5 80C -
EE02 MeONa 1 absolute 6 80C -
EE03 MeONa 1 absolute 7.5 80C 10% - before
EE04 MeONa 1 absolute 7.5 80C 10% - after
EE05 MeONa 1 absolute 6 80C 10% - after
EE06 MeONa 1 absolute 6 80C 10% - before
EE07 MeONa 1 5% water 6 80C 10% - after
EE10 KOH 1 absolute 6 23C -
EE11 MeONa 0.5 absolute 4.8 23C -
EE12 KOH 1 absolute 6 80C -

P h a s e s e p a r a t i o n P h a s e s e p a r a t i o n P h a s e s e p a r a t i o n P h a s e s e p a r a t i o n
At the end of reaction, the reaction mixture was allowed to stand overnight in a funnel while phase
separations occurred. The ester phase was then decanted from the equilibrium mixture.
R e m o v a l o f e t h a n R e m o v a l o f e t h a n R e m o v a l o f e t h a n R e m o v a l o f e t h a n o l o l o l o l
Unreacted ethanol was removed using a rotavapor. During this operation, temperature was set at
approximately 80C and vacuum near 50 mbars.
W a s h i n g W a s h i n g W a s h i n g W a s h i n g
Residual catalyst, remaining glycerol and few side products were washed from the ester with hot water
(70C). The ester phase was placed in a funnel. Water was carefully poured into the top of the funnel.
During the washing, some of the ester can form an emulsion with the water. Therefore, centrifugation
was sometimes required for the water phase containing catalyst and emulsified ester to settle. If
emulsified ester did not settle after 24h and/or several centrifugations, it was considered as lost in the
water phase.
A n a l y s e s A n a l y s e s A n a l y s e s A n a l y s e s
The composition and content of the ester was quantitatively determined by Gas Chromatography
(GC). Free and total glycerol, monoglyceride, diglyceride and triglyceride contents were quantitatively
determined according to NF EN 14105. Ester content was determined according to NF EN 14103.
These analyses are quite time consuming, that is why analyses were not all made according the
standard EN NF and an internal method was used to determine the completion of the reaction.

Completion of reaction was qualitatively followed by GC using a Fisons with an injector on-column, a
column DB1 HT and a detector FID. The temperature programme was a heating from 100C to 370C
at 10C/minute and a plateau at 370C during 3 minutes. The gas flow is 0.8 bar of hydrogen. This
internal method was also used to estimate qualitatively ester content in samples. In that case, weight
percentages are grams of ester per 100 grams of fatty matter because light products (ethanol, co-

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solvent, glycerol, etc) are not taken into account contrary to quantitative methods (NF EN 14103 for
example) where results are expressed in grams per 100 grams of sample.
Results and discussion Results and discussion Results and discussion Results and discussion
Results are shown below:
Tabl e I-1. Gl ycerol mono-, di -, t ri gl ycer i des cont ent s - quant i t at i ve resul t s.

* these samples contain around 10% of dodecane ; a : before treatments ; ld : after washing &
removal of ethanol.

Tabl e I-2. Est er cont ent - quant i t at i ve r esul t s
Sample name
EE02
A
EE02
B
EE05a A*
EE05a
B*
EE05ld A*
EE05ld
B*
EE6a
A*
EE6a
B*
EE06 ld A* EE06 ld B*
Ester content
(g/100g)
96,7 97,2 78,2 78,4 89,7 89,6 79,2 79,0 89,8 90,1
EN 14214 : specifications for pure FAME (without co-solvent) > 96,5%

* these samples contains around 10% of dodecane ; a : before treatments ; ld : after washing &
removal of ethanol
O p t i m u m C o n d i t i o n s f o r E t h y l E s t e r P r e p a r a t i o n O p t i m u m C o n d i t i o n s f o r E t h y l E s t e r P r e p a r a t i o n O p t i m u m C o n d i t i o n s f o r E t h y l E s t e r P r e p a r a t i o n O p t i m u m C o n d i t i o n s f o r E t h y l E s t e r P r e p a r a t i o n
NB : ester contents were qualitatively estimated for each trial but only the useful qualitative results are
quoted below.
R e a c t i o n R e a c t i o n R e a c t i o n R e a c t i o n
Temperature had no detectable effect on the ultimate conversion to ester. However, higher
temperatures decrease the time required to reach maximum conversion. For example, at 80C,

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completion of reaction was achieved in less than 1 hour with sodium methoxide; whereas at 23C, 3
hours were necessary. At industrial scale, the cost of energy for heating must be compared to the
amount of time saved by using higher temperatures. At lab-scale, a high temperature (80C) was
preferred to carry out more experiments in less time.

Moreover, it is important to have an homogeneous mixture to reach high conversion rates. As high
temperatures favours the miscibility of reactants, heating can improve the transesterification.

The presence of water in the reaction mixture dramatically reduces the conversion of oil to ester. For
example, trial EE07 uses the same operating conditions compared to trial EE05 except for ethanol,
which is a 95% ethanol that contains 5% of water. The ester content is only of 26% for EE07 whereas
EE05 contains more than 98% of ethyl esters (qualitative results see chapter Analysis for more
details). When ethanol contains water, soaps are created.

Three different catalysts were tested :
sodium methoxide (powder)
potassium hydroxide (diluted in ethanol)
sodium carbonate (powder)

Best conversion rates and fastest kinetics were obtained with sodium methoxide. In less than 1 hour,
the ester content reaches at least 96% (for example, 97% for trial EE02). Sodium carbonates required
higher ratio of ethanol (molar ratio ethanol/oil = 12) and very long reaction times (8 hours). Ester
content was equal to 78% after 8h. Potassium hydroxide diluted in ethanol implies quite slower
kinetics and after 5h at 80C only half of the triglycerides had reacted. When sodium methoxide is
used the glycerol phase is darker (orange instead of yellow).

The use of a co-solvent had no influence on transesterification when catalyst is sodium methoxide.

Sodium methoxide catalyst required at least 50% excess alcohol (i.e. molar ratio oil/alcohol equal to
4.5) to achieve high conversion rate (96% for EE08 using 50% excess ethanol). 20% excess alcohol
slightly reduces the conversion rate (92% for EE09 instead of 96% for EE08).
P h a s e S e p a r a t i o n P h a s e S e p a r a t i o n P h a s e S e p a r a t i o n P h a s e S e p a r a t i o n
The type of catalyst used during the transesterification has an important effect on the phase separation.
Phase separation was not complete in the case of potassium hydroxide and centrifugation was
necessary to remove the glycerol phase from the ester phase and obtain a clear ester phase. When
sodium methoxide was used, separation was good and fast; sodium methoxide was judged to give
better results than potassium hydroxide diluted in ethanol.

The more ethanol is used, the easier the phase separation is. For example, when an excess alcohol of
20% is used (trial EE09), glycerol phase settle very slowly.

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The impact of variables other than catalyst and excess alcohol on phase separation was considered
minor relative to their impact on transesterification.
W a s h i n g W a s h i n g W a s h i n g W a s h i n g
The washing step for FAME and FAEE processes are quite similar and the same problems are
encountered.

The importance of washing is the removal of residual catalyst, soaps and glycerol from the ester. The
effluent wash water was monitored for pH and washing continued until pH of the effluent was the
same as pH of the entering wash water. During the washing of the ester phase, water must be added
slowly. A strong agitation of the ester with water form an emulsion which can not be broken. The
more soaps and monoglycerides the ester phase contains, the more emulsified ester phase can be
created.

FAEE phase contains more than 1%w/w of glycerol. (see Table 2) after reaction : nevertheless,
washings can remove this remaining glycerol. It might be necessary to perform more washings (1 or 2)
compared to FAME process but it can not be checked at small scale.
G l y c e r o l G l y c e r o l G l y c e r o l G l y c e r o l
Glycerol phase represents between 9% and 18%w/w of the products obtained during ethanolysis. This
value depends on the ratio of ethanol and on the ratio of co-solvent used (co-solvent is in the ester
phase), classical values are near 10%. Glycerol phase is orange brown when an homogeneous catalyst
is used. It contains near 30% of ethanol. Soaps and remaining catalyst are partially soluble in the
glycerine layer. Therefore, treatment of the glycerol phase consists in removing ethanol (this ethanol
can be reused), neutralising soaps and catalyst with acid (HCl diluted in water for example), distilling
pure glycerol and recovering fatty acids.

To sum up, purification of glycerol in FAEE process is quite similar with FAME process for
homogeneous catalyse.
C o m p a r i s o n b e t w e e n F A M E a n d F A E E p r o c e s s e s C o m p a r i s o n b e t w e e n F A M E a n d F A E E p r o c e s s e s C o m p a r i s o n b e t w e e n F A M E a n d F A E E p r o c e s s e s C o m p a r i s o n b e t w e e n F A M E a n d F A E E p r o c e s s e s
The use of ethanol instead of methanol implies either bigger reactors or smaller amounts of alcohol.
This is mainly due to the molecular weight of the alcohols : Molecular weight of methanol is equal
to32.04g/mol and molecular weight of Ethanol is equal to 46.07g/mol. Classical molar ratios
alcohol/oil for FAME production with homogeneous catalyse are around 6.

Therefore, for FAEE synthesis with homogeneous catalyse :
Using a ratio alcohol/oil of 6 implies a volume of reactor increased of 9%.
Using the same volume of reactor implies a ratio alcohol/oil of 4.2.
Using a ratio alcohol/oil of 4.8 leads to satisfying results (Iterg results at lab scale see EE08)
and only implies a volume of reactor increased of 2.9% (the same reactor can probably be used).


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FAEE can be produced in FAME reactors according to the results obtained in this study. Of course,
these results should be validated at pilot and industrial scales.
I.4 I.4 I.4 I.4 Heterogeneous catalyse Heterogeneous catalyse Heterogeneous catalyse Heterogeneous catalyse
absolute ethanol from VWR was used.
E x p e r i m e n t a l S e t u p a n d P r o c e d u r e E x p e r i m e n t a l S e t u p a n d P r o c e d u r e E x p e r i m e n t a l S e t u p a n d P r o c e d u r e E x p e r i m e n t a l S e t u p a n d P r o c e d u r e
The main operation that was studied in the experimental work was the transesterification. After the
reaction was complete, the catalyst was filtered and unreacted alcohol was removed. Reaction
products were separated into two layers ; the ester product formed the upper layer and the by-product
glycerin formed the lower layer. No washing were done during treatments.
The transesterification experiments were performed under pressure in stainless reactor using 50g of
rapeseed oil. The catalyst was a zinc oxide used in patent EP1505048. Oil, ethanol and catalyst were
added in the reactor. Products were heated under a vigorous stirring. Samples of approximately 4 mL
of the reaction mixture were pipetted out during reaction and / or during treatments. The samples were
analysed to determine their compositions and the degree of completion of the reaction. A co-solvent
was added before reaction in trials AT5 and TA5. The ratio of co-solvent was equal to 30%w/w of the
mixture for AT5 (i.e. 43 g = 85% w/w of oil) and 9%w/w of the mixture for TA5 (i.e. 10 g = 20% w/w
of oil). Two different ratios of co-solvent were tested to see if co-solvent has an influence on
treatments and on the quality of ester phase.

Operating conditions are detailed in Table 4 for the 11 experiments that were carried out. NB :
pressure was near 32 bars for all trials.

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Tabl e I-3. Operati ng condi t i ons f or het er ogeneous cat al yse
Catalyst Alcohol
Trial
Oil
(g) Type Weight Type Ratio
TC
Co-solvent
(g)

AT 4 50 Zinc oxide 4.1 Abs. ethanol 12 185C 0
TA 1 50 Zinc oxide 4.0 Abs. ethanol 18 200C 0
TA 6 50 new catalyst
(LACCO know-
how)
4.8 Abs. ethanol 18 230C 0
TA 8 50 Zinc oxide 4.9 Methanol 26 230C 0

Abs. Ethanol = absolute ethanol
R e m o v a l o f c a t a l y s t a n d e t h a n o l R e m o v a l o f c a t a l y s t a n d e t h a n o l R e m o v a l o f c a t a l y s t a n d e t h a n o l R e m o v a l o f c a t a l y s t a n d e t h a n o l
At the end of reaction, catalyst was filtered. Unreacted ethanol was removed using a rotavapor.
P h a s e s e p a r a t i o n P h a s e s e p a r a t i o n P h a s e s e p a r a t i o n P h a s e s e p a r a t i o n
At the end of reaction, the reaction mixture was allowed to stand overnight in a funnel while phase
separations occurred. The ester phase was then decanted from the equilibrium mixture.
W a s h i n g s W a s h i n g s W a s h i n g s W a s h i n g s
It was decided that the reaction mixture should not be washed to better understand the influence of the
different parameters during the process. Anyway, it is possible to carry out a washing step as described
in chapter 2.2 on homogeneous catalyse. NB : as stated for homogeneous catalyse, washings could
remove some glycerol and monoglyceride. Compared to homogeneous catalyse, washing should be
easier because reaction mixture contains no soaps. Washings could greatly increase the quality of
esters that contains only some remaining monoglycerides and/or glycerol.
The composition and content of several samples were determined by Gas Chromatography (GC) at
LACCO using an LACCO method. Free and total glycerol, monoglyceride, diglyceride and
triglyceride contents in the ester phase were determined according to NF EN 14105 at ITERG. Ester
content in the ester phase was determined according to NF EN 14103 at ITERG.
Results are shown below :


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Tabl e I-4. Gl ycerol mono-, di -, t ri gl ycer i des cont ent s - quant i t at i ve resul t s (It er g)

* : this sample contains around 45% of dodecane

Tabl e I-5. Est er cont ent - quant i t at i ve r esul t s (It er g)

* : this sample contains around 45% of dodecane

Tabl e I-6. Est er , mono-, di -, t r i gl ycer i des cont ent s - quant i t at i ve r esul t s (LACCO)


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NB : In addition to Itergs analytical results, ester contents were estimated by LACCO for each trial.
Only the useful results of LACCO are quoted in the text below.

The addition of a great quantity of co-solvent logically reduces kinetics. The ester content of trial AT5
decreased to 41%w/w of reactants (i.e. 18.3%w/w of the reactants plus co-solvent) instead of 65%w/w
of reactants (trial AT4). Free glycerol content in the ester phase is only divided by two when 45% of
the sample contains a co-solvent. Therefore, the use of a co-solvent only dilutes the sample but do not
drive the residual glycerol from the ester phase. Trial TA 5 confirms that the use of a co-solvent before
reaction reduces kinetics because ester content is only equal to 74% instead of 93% when no co-
solvent is used (trial TA 7).

High temperatures favour high conversions of the triglycerides. A temperature of 230C enables to
reach a high ester content (near 97% for trial TA3 LACCO result). A conversion rate above 90% can
be reached in 7h at 230C (trial TA3 LACCO result), whereas 24h are necessary at 210C (trial TA2
LACCO result).

The highest ester content (100% - TA6) was obtained with a new catalyst after 7h of reaction. This
new catalyst is presently in development at LACCO and is part of the know-how of LACCO
(confidential). It enables to use a temperature of 230C and a ratio alcohol/oil of 18.
Glycerol phase is orange. Ethanol is removed before separation of the glycerol and ester phases,
therefore glycerol phase contains no solvent. Purification of glycerol can be a simple distillation of the
glycerol. In this case, neutralisation step is not necessary because heterogeneous catalyse produces no
soaps contrary to homogeneous catalyse.
C o m p a r i s o n b e t w e e n F A M E a n d F A E E p r o c e s s e s C o m p a r i s o n b e t w e e n F A M E a n d F A E E p r o c e s s e s C o m p a r i s o n b e t w e e n F A M E a n d F A E E p r o c e s s e s C o m p a r i s o n b e t w e e n F A M E a n d F A E E p r o c e s s e s
The use of ethanol instead of methanol implies either bigger reactors or smaller amounts of alcohol
(see homogeneous catalyse). Classical molar ratios alcohol/oil for FAME production with
heterogeneous catalyse are around 26. TA8 (trial with methanol, ratio alcohol/oil = 26) and TA7 (trial
with ethanol, ratio alcohol/oil = 18) give quite similar results (see Table 7).

Therefore, for FAEE synthesis with heterogeneous catalyse :
Using a ratio alcohol/oil of 26 implies a volume of reactor increased of 44%. The reactor must
be changed.
Using a the same volume of reactor implies a ratio alcohol/oil of 18. A ratio ethanol/oil of 18
leads to satisfying results with zinc oxide or the catalyst developed by Lacco in previous works
(confidential results of pre-existing know-how). FAEE can be produced in FAME reactors. Of
course, these results should be validated at pilot and industrial scales.


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I.5 I.5 I.5 I.5 Enzymatic cat Enzymatic cat Enzymatic cat Enzymatic catalyse alyse alyse alyse
absolute ethanol from VWR was used.
E x p e r i m e n t a l S e t u p a n d P r o c e d u r e E x p e r i m e n t a l S e t u p a n d P r o c e d u r e E x p e r i m e n t a l S e t u p a n d P r o c e d u r e E x p e r i m e n t a l S e t u p a n d P r o c e d u r e
The main operation that was studied in the experimental work was the transesterification. After the
reaction was complete, the reaction mixture is centrifuged several times to separate the esters, the
glycerol and the enzyme.
The transesterification experiments were performed in glass conical tubes using between 10 and 100
mL of reactants. The catalysts were 3 different commercial immobilised lipases called A, B and C.
The concentration of the enzymes were equal to 20 g/L. Oil, ethanol, enzyme and a magnetic stirrer
were added in the conical tubes. Products were heated under a vigorous stirring. Reaction time was
dependant of the conversion rate.

Operating conditions are detailed below for the 7 experiments that were carried out during the first
semester.
Tabl e I-7. Operati ng condi t i ons f or enzymat i c cat al yse

P h a s e s e p a r a t i o n a n d r e m o v a l o f e t h a n o l P h a s e s e p a r a t i o n a n d r e m o v a l o f e t h a n o l P h a s e s e p a r a t i o n a n d r e m o v a l o f e t h a n o l P h a s e s e p a r a t i o n a n d r e m o v a l o f e t h a n o l
After completion of the reaction, the reaction mixture was centrifuged a first time and ester phase was
partially removed from the rest of the mixture. Some ethanol was then added to the mixture and a
second centrifugation was carried out to get the enzyme back. Ethanol was removed and a third
centrifugation separated the glycerol phase from the remaining ester phase. No washing were done
during treatments.

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W a s h i n g s W a s h i n g s W a s h i n g s W a s h i n g s
It was decided that the reaction mixture should not be washed to better understand the influence of the
different parameters during the process. Anyway, it is possible to carry out a washing step as described
in chapter 2.2 on homogeneous catalyse. NB : as stated for homogeneous catalyse, washings could
remove some glycerol and monoglyceride. Compared to homogeneous catalyse, washing should be
easier because reaction mixture contains no soaps.
Kinetics were followed qualitatively at LBB using High Performance Liquid Chromatography
(HPLC). Free and total glycerol, monoglyceride, diglyceride and triglyceride contents in the ester
phase were determined according to NF EN 14105 at ITERG. Ester content in the ester phase was
determined according to NF EN 14103 at ITERG.

Glycerol phase was analysed by GC at Iterg. The apparatus is a GC 8000 with an injector on column, a
column ZB5 HT and a FID detector. The operating conditions were a heating of the column between
50C and 370C at 10C/min. Results obtained were qualitative.
Results are shown below :
Tabl e I-8. Gl ycerol mono-, di -, t ri gl ycer i des cont ent s - quant i t at i ve resul t s.

Tabl e I-9. Est er cont ent - quant i t at i ve r esul t s.

A : first analysis ; B : second analysis, centri. = centrifugation
The lipase that leads to the highest conversion rate was identified (it was lipase B). It was shown that
ethanol must not contain water because lipase B is then saturated with water and the effect of catalyse

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is therefore greatly reduced. The best temperature was determined (40C). The ratio ethanol/oil (4, 3
or 3 plus 1 during reaction) was studied. Ester content showed that ester phases obtained after the first
centrifugation has a higher ester content than the one obtained after the third centrifugation. The best
results were obtained with a ratio of ethanol/oil of 3 plus 1 added during the reaction : average ester
content of ester phase is equal to 94%.
Glycerol phase is bright yellow. Ethanol is removed before separation of the glycerol and ester phases,
therefore glycerol phase contains no solvent. Purification of glycerol can be a simple distillation of the
glycerol. In this case, neutralisation step is not necessary because enzymatic catalyse produces no
soaps contrary to homogeneous catalyse. Glycerol layer was qualitatively analysed by GC and it was
shown that it is pure (no mono, di or triglycerides were identified).
C o m p a r i s o n b e t w e e C o m p a r i s o n b e t w e e C o m p a r i s o n b e t w e e C o m p a r i s o n b e t w e e n F A M E a n d F A E E p r o c e s s e s n F A M E a n d F A E E p r o c e s s e s n F A M E a n d F A E E p r o c e s s e s n F A M E a n d F A E E p r o c e s s e s
The use of ethanol instead of methanol implies either bigger reactors or smaller amounts of alcohol.
Classical molar ratios alcohol/oil for FAME production with enzymatic catalyse are near 4.

It is not possible to reduce the amount of alcohol under 3 (equimolarity) otherwise reaction can not be
complete. Therefore, to produce the same quantities of esters, reactors must be changed if ethanol is
used instead of methanol.
I.6 I.6 I.6 I.6 General comments and conclusion General comments and conclusion General comments and conclusion General comments and conclusion
Here are some general comments on the three catalyses tested in this study.

Concerning homogeneous catalyse, ester content is higher than 97% after washings. Partial glyceride
contents of the ester phase are low and respect the specifications (according to EN 14 214) for FAME.
The disadvantages of homogeneous catalyse is the fact that :
catalyst can not be reused,
soaps are created and must be removed thanks to several water washings,
glycerol phase is brown and contains soaps and partial glycerides.
FAEE can be produced in FAME reactors according to the results obtained in this study. Of course,
these results should be validated at pilot and industrial scales.

The advantages of heterogeneous catalyse is the fact that glycerol phase is purer (no soaps) and
catalyst can be reused. High yields (around 97%) were obtained after the optimisation of the
temperature, the ratio alcohol/oil and the reaction time. If FAME equipment is used to produce FAEE,
then ratio alcohol/oil must be reduced to 18 (instead of 26 for FAME), it implies that temperature must
raised to maintain a high ester content. The process must be evaluated from an economical point of
view to validate the cost of FAEE.

Enzymatic catalyse implies lower ester content (94%). Glycerol phase is very pure (no partial
glyceride in it) but its obtaining requires 3 centrifugations (lab scale process) and some additional
ethanol to recycle enzymes.

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To sum up, if the three process had to be compared, the homogeneous catalyse would be the one
giving the best results at the moment. From a technical point of view, heterogeneous catalyse is a very
promising process because it produces less by-products than homogeneous catalyse. New catalysts
developed by Lacco indicate that it is possible to obtain very pure products with high yields. So
heterogeneous catalyse might be the future process for FAEE production. Enzymatic catalyse still
needs some development to obtain purer esters and higher yields.

It should be kept in mind that all results obtained during this study must be validated at industrial scale
before forming any definite opinion. Moreover, this technical study does not take into account
economical aspects: a process with high yields and pure final products might not be economically
viable.

Fatty Acid Ethyl Esters - Biodiesel

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