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Biomass and Bioenergy 25 (2003) 85 – 99

Development of emulsions from biomass pyrolysis liquid and

diesel and their use in engines—Part 1: emulsion production
D. Chiaramontia;∗ , M. Boninia , E. Fratinia , G. Tondib , K. Gartnerc , A.V. Bridgwaterd ,
H.P. Grimme , I. Soldainif , A. Websterg , P. Baglionia;∗
a Department of Chemistry and CSGI (Consorzio Sistemi a Grande Interfase), University of Florence,
via della Lastruccia 3, I-50019 Florence, Italy
b Energetics Department “S. Stecco”, Faculty of Mechanical Engineering, University of Florence,

Via S. Marta 3, I-50139 Florence, Italy

c Institute f,
ur Elektrische Energietechnik (IEE), Universit,at Gh-Kassel, Energietechnik, Fb 16,
Rationelle Energiewandlung, D-34109 Kassel, Germany
d Aston University, Bio-Energy Research Group, Aston Triangle, Birmingham B4 7ET, UK
e WIP, Sylvensteinstr. 2, D81369 M, unchen, Germany
f Pasquali Macchine Agricole, Via Nuova 30, I-50041 Calenzano, Italy
g ORMROD Diesels, Unit 4, Peel Industrial Estate, West Pimbo, Skelmersdale, Lancashire WN8 9PT, UK

Received 18 March 2002; received in revised form 28 October 2002; accepted 28 October 2002

Abstract

The current method of utilising biomass derived fast liquid (bio-crude oil or bio-oil) in a diesel engine requires three fuels
and a complex start-up and shut down procedure. For more rapid and successful commercialisation of this renewable liquid
fuel, a more convenient and cheaper method of utilisation is needed that provides a single fuel that is stable and readily
ignites in a compression engine. This paper describes the production of emulsions from biomass fast pyrolysis liquid and
diesel fuel for utilisation in diesel engines. The objective is to allow unmodi;ed diesel engines to run on fast pyrolysis liquid
derived from biomass without the cost and complexity of a dual fuel system. The immediate application is in stationary
engines for power generation, but there are longer term opportunities for use as a transport fuel. This paper describes the
production of the emulsions that have been tested in di<erent diesel engines (tests in engines is reported in a separate paper).
? 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Biomass pyrolysis; Biomass power production; Emulsion; Diesel engine; Bio-crude oil

1. Introduction condensable gases, acetic acid, acetone and methanol

Pyrolysis is the thermochemical process that
converts biomass into liquid, charcoal and non-
∗ Corresponding authors. Tel.: +39-055-457-3033; fax: +39-
055-457-3032.
E-mail addresses: chiaramonti@apple.csgi.uni;.it
(D. Chiaramonti), piero.baglioni@uni;.it (P. Baglioni).
by heating the biomass to about 750 K in absence of
air. The process can be adjusted to favor charcoal,
pyrolytic oil, gas or methanol production with a fuel
to feed eBciency up to 95%. Pyrolysis can be used
for the production of bio-oil by various processes (e.g.
Dash pyrolysis) [1–5].
Bio-crude oil (BCO) (pyrolysis oil) use for power
and heat production represents a main goal in the

0961-9534/03/$ - see front matter ? 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 6 1 - 9 5 3 4 ( 0 2 ) 0 0 1 8 3 - 6
86 D. Chiaramonti et al. / Biomass and Bioenergy 25 (2003) 85 – 99
biomass sector. The concept of using biomass-based
fuels, speci;cally vegetable oils as diesel fuel
alternatives, is particularly interesting and it is not
new. Rudolf Diesel himself demonstrated that his
engine could run on vegetable oil fuels. Since then a
number of vegetable oils have been tested as diesel
fuel alternatives [6–10]. These fuels are non-toxic,
renewable sources of energy, which do not contribute
to the net global CO2 buildup.
A large number of studies on biomass derived oils
as biofuels have been performed [10–13]. However,
direct use of pyrolysis oils (BCOs) requires signi;cant
adaptations of technology to fuel characteristics, and
it has not yet been fully proven at demonstration scale
[8,10,14].
BCOs have already been used in modi;ed diesel
engines, in which a dedicated fuel feeding system has
been designed, constructed and installed in parallel to
the diesel feeding line: in addition, the operation of
the engine becomes more sophisticated (use of clean-
ing fuels, as methanol, in a particular sequence dur-
ing start-up and shut-down), and a pilot diesel fuel
injection is necessary. This approach requires a sig-
ni;cant adaptation of the engine and, consequently,
capital and O&M costs per kW installed are higher
than standard diesel engines [15,16]. This fact repre-
sents a considerable barrier to the use of BCO in diesel
engines.
Measurements of the combustion performance of
biofuel oils, blends with diesel fuels and emulsions
with water have been reported [12].
The development and use of BCO/diesel oil emul-
sions represent a relatively short-term approach to
the exploitation of the signi;cant biomass resources
potentially available by pyrolysis. The upgrading of
the fuel itself by means of the production of stable
emulsions allows the use of low-cost large-scale mass
production diesel engines with only minor modi;ca-
tions, thus reducing signi;cantly the investment cost
in comparison to dual fuel engines. The fuel pro-
duction process aims therefore at producing low-cost
and stable emulsions, compatible with the existing
diesel technology (only minor modi;cations to the
engine) [17].
This approach to fuel upgrading is investigated by
various research groups. In particular, CANMET has
developed a method for microemulsion production
from pyrolysis oil and diesel oil: stable emulsions
have been produced in the range of 5 – 40% have been
produced and tested.
In the present work, background knowledge on
emulsi;cation processes has been used to understand
the forces that play a fundamental role in the pro-
duction of pyrolysis oil/diesel oil emulsions and to
formulate stable systems [18]. Initially, a large num-
ber of tests at laboratory level have been realized to
select the most appropriate combination of additives.
Once de;ned the surfactants mixture to be used,
the emulsi;cation process has been adjusted and re-
alized at demonstration level in a semi-automatic
plant [17].
2. Theory
2.1. Introduction to the production of emulsions
Though emulsions are ubiquitous in everyday life,
the study of these systems has been often carried on
in empirical ways [19]. Dispersions of two or more
not miscible Duids are produced for many applica-
tions. Examples are abundant either between natu-
ral products (such as milk) and industrial products
[20,21]. Systems obtained from homogenization of
two or more not miscible Duids are indicated as emul-
sions, miniemulsions or microemulsions (or swollen
micelles) depending on the size of the particles
dispersed in the continuous phase [22,23]. These
systems are produced using one or several additives
(surfactants and co-surfactants) that are able to lower
the surface energy of the interface of the produced
droplets [24].
Emulsions are obtained from a dispersion of two
non-miscible Duids. The dispersion produces a con-
tinuous phase and a ;nely dispersed droplets phase.
Most of the properties of the emulsion systems (sta-
bility, viscosity, etc.) depend on the droplets size
and size distribution that usually cover a rather wide
interval, i.e. from 300 to 400 nm to about 10 m.
A commonly used classi;cation of emulsions is
based on the polarity of the dispersant phase compared
to that of the dispersed one. In almost all the appli-
cations, water is one of the Duids, while the other is
characterized by a lower dielectric constant. In general
this second Duid is indicated as oil. Therefore emul-
sions are generally indicated as dispersions of water
 D. Chiaramonti et al. / Biomass and Bioenergy 25 (2003) 85 – 99
Fig. 1. Most important mechanisms of emulsion breaking: (a) stable emulsion; (b) creaming; (c) Ostwald ripening; (d) Docculation;
(e) coalescence; (f) breaking.
droplets in oil (water-in-oil emulsions, W/O) or oil
droplets in water (oil-in-water emulsions, O/W).
2.2. Stability of emulsions
The formation and stability of droplets depends on
two competitive factors:
(i) the migration of the surfactant at the droplets
interface (stabilizing process),
(ii) the droplets coalescence (destabilization
process).
The phase characterized by the highest coalescence
rate will become the continuous phase.
Emulsions formation and stability are also a<ected
by the sequence and the methodology used to mix
together the emulsion components. For example, we
can either dissolve the emulsi;er in the oil and in the
water phase or dissolve the emulsi;er in one Duid and
add it to the other one, etc. Moreover, the mean droplet
diameter depends on the intensity and on the amount
of the introduced energy for the particular preparation
technique.
87
Stability of emulsions can be described by the
Derajaguin, Landau, Vervey and Overbeek (DLVO)
theory and its implementations that take into account
di<erent kind of interactions, as Van der Waals in-
teractions, electrostatic interactions, steric, hydration,
etc. [18,25–28].
The main mechanisms of emulsion breaking are
shown in Fig. 1.
The destabilization of an emulsion goes through
several consecutive and parallel steps before the ;nal
stage of separated layers is reached. At ;rsts, droplets
move due to di<usion (or stirring), and if the repul-
sion potential is too weak, they become aggregated to
each other: in practice, Docculation has taken place.
The single droplets are now replaced by twins (or
multiples) separated by a thin ;lm. The thickness of
the thin ;lm is reduced due to the Van der Waals at-
traction, and when a critical value of its dimension is
reached the ;lm bursts and the two droplets unite to
a single droplet. Coalescence has occurred. In parallel
with these phenomena, the droplets rise through the
medium (creaming) or sink to the bottom (sedimen-
tation) due to di<erences in density of the dispersed
and continuous phase. The ;nal result is a highly
88 D. Chiaramonti et al. / Biomass and Bioenergy 25 (2003) 85 – 99
concentrated emulsion at the top or bottom of the con-
tainer, and the increased number of droplets per vol-
ume increases the Docculation rate in a most decisive
manner. The Docculation and coalescence process lead
to larger and larger droplets until, ;nally, a phase sep-
aration has occurred.
Since emulsions are not thermodynamically stable,
it is obvious that the control of the stability of the
emulsions is limited to the kinetic control of the sepa-
ration of the constituents (oil and water). After some
time, emulsions destabilize as a result of the aging
e<ect, and the total area of the system decreases. The
most common method to verify the stability of emul-
sions is simply by testing the formation of separate
phases at room temperature, by heating the samples
or by centrifuging. More re;ned methods consist in
the analysis of the particle size or of the viscosity as
a function of time [18].
Coalescence is by de;nition slow in stable emul-
sions and measurement of the ageing rate is accel-
erated by use of centrifugation at between 1000 and
25; 000 g.
In addition, in the case of pyrolysis oils, one of the
signi;cant problems in their utilization is their claimed
instability, which manifests as changes in viscosity. A
measure of stability or instability is a valuable indi-
cator of one of the key properties of pyrolysis liquids
and a viscosity index is proposed to provide such a
measure. The viscosity index is de;ned in the equa-
tion below and provides a measure of viscosity change
over a given time period:
(t2 − t1 )
VI = ; is exactly the case of the BCO/diesel oil system.
t1
where VI is the viscosity index, t1 the viscosity at
time t1 (i.e. before storage) and t2 the viscosity at
time t2 (i.e. after 24 h storage at 80◦ C).
The lower the number, the more stable the liquid.
A perfectly stable liquid has a viscosity index of 0.00.
This approach has also been applied to evaluate the
stability properties of the emulsions.
2.3. BCO=diesel emulsions
As reported above, the process for obtaining a stable
emulsion may be very diBcult and time consuming:
in the case of BCO and diesel (Fig. 2), approximately
Fig. 2. BCO/diesel oil mixture (left) and emulsion (right).
one hundred di<erent surfactants, and a consistent
number of mixtures of them, have been tested. The
reason for that mainly relies on the composition of the
BCO itself. In fact, BCO is made of a mixture of sev-
eral organic products: from short chain products, as
aldehyde or carboxylic acid, to polymers.
The interactions that are responsible for the stability
of an emulsion are Van der Waals, electrostatic and
steric interactions. Clearly, if the phases are single
products it is rather simple to evaluate the kind of
molecular interaction and to understand the class of
surfactants that should be used to obtain the emulsion.
If instead the molecular composition of one phase is
complex, it becomes very diBcult to ;gure out the
additive to be used for the emulsi;cation process. This
The methodology to be used is the following: (1) an
e<ective solvent for the BCO has to be identi;ed. This
allows a surfactant to be used even if it is not soluble
in the BCO: it is suBcient that the surfactant is soluble
in the same solvent, (ii) the additive for the emulsion
formation is tested. As the additive class showing the
better results in terms of stability is determined, as
many surfactants as possible belonging to the additive
class must be tested, (iii) a small number of surfactants
can therefore be chosen, and the emulsion properties
optimized. A mixture of di<erent additives can also
be adopted.
As the surfactants to be used for emulsion prepara-
tion are ;nally de;ned, the process for the production
of the ;nal emulsion has to be optimized.
 D. Chiaramonti et al. / Biomass and Bioenergy 25 (2003) 85 – 99
Three kinds of emulsions can be prepared in respect
to the BCO/diesel oil ratio:
• water-in-oil emulsions (W/O) are obtained if up to
∼ 45% w/w BCO is added to the diesel oil phase,
• oil-in-water emulsions (O/W) are obtained if up to
∼ 45% w/w of diesel oil is added in BCO,
• bicontinuous emulsions are obtained when the per-
centage by weight of the two phases is close to 50%.
In the ;rst case, BCO’s droplets dispersed in diesel
oil (continuous medium) form the emulsion. In the
second case Diesel oil’s droplets dispersed in BCO
(continuous medium) form the emulsion. Description
of the third case is more complex: in fact, from a the-
oretical point of view, both oil and water phase are
continuous (no droplets) and form a so-called bicon-
tinuous emulsion.
The choice of the emulsifying agent, which changes
the interfacial properties (namely interaction potential
between droplets) of the system avoiding (or delay-
ing) the emulsion’s breaking, is a procedure driven by
several empirical rules. These rules are built on the
primary condition for an emulsi;er to be eBcient in a
two phase, two-liquid emulsion. It has to be localized
at the oil/water interface to a maximal extent. This
criterion is exempli;ed in the hydrophilic lipophilic
balance (HLB) number.
It is important to emphasize that the HLB number
for a certain molecule denotes the balance between its
hydrophilic/lipophilic properties only; the number per
se does not give any information about the stabilizing
eBcacy of the emulsi;er. The HLB number means
that the emulsi;er is optimal in a water-oil system in
which the properties of the oil match the surfactant.
Hence, each water-oil combination is characterized
by an HLB number. The de;nition of this number is
rather complicated and depends on the family of the
surfactant. A more detailed treatment of this subject
is given in Ref. [18].
More practically, emulsi;ers characterized by HLB
number:
• from 4 to ∼ 8, stabilize W/O emulsions,
• from 8 to ∼ 10, stabilize bicontinuous emulsions,
• from 10 to ∼ 18, stabilize O/W emulsions.
The phase inversion temperature (PIT) or HLB tem-
perature concept relates the emulsi;er selection to
89
the temperature at which an emulsion stabilized by a
non-ionic emulsi;er of the polyethylene glycol type
changed from oil-in-water to water-in-oil with rising
temperature.
A large number (approximately one hundred) of
surfactants were tested, including both of commer-
cial blends and chemically pure composition. Among
them, cationic, anionic, zwitterionic and non-ionic sta-
bilizers. Moreover, for each of these classes of addi-
tives, polymeric and non-polymeric surfactants were
also tested. Additives with sulfur or nitrogen in their
composition have been neglected, in order to avoid an
increase in the NOx and SOx gaseous emissions dur-
ing the emulsion combustion. A list of the most sig-
ni;cant tested surfactants is given in Table 1.
The water-in-oil emulsions have been prepared
by adding the surfactant to diesel oil and thereafter
adding the bio-oil to the resulting mixture. Bicon-
tinuous emulsions have been formulated by adding
the surfactant to diesel oil, and to BCO then mixing
together the resulting mixtures. Oil-in-water emul-
sions have been formulated by adding to the bio-oil
the surfactant and thereafter adding to the resulting
mixture the diesel oil during emulsi;cation.
The emulsi;cation process has been carried out by
using a homogenization unit. The temperature dur-
ing mixing has been preferably maintained between
60 –65◦ C and the emulsi;cation process has been con-
tinued until a homogeneous single phase has been ob-
tained. During the emulsi;er choice phase, emulsions
have been prepared by using a discontinuous process
on a little amount of mixture (from 20 to 500 g). Once
identi;ed the emulsi;er, a continuous process has been
employed to produce a greater amount of material (up
to 10 kg). In this con;guration the tank was a heating
case to have the desired temperature in the continuous
homogenization unit.
It is important to underline that emulsions can be
prepared also at room temperature: however, in this
case the emulsions stability decreases (∼ 20 days).
Nevertheless, the destabilization of the emulsions,
prepared at both high and room temperature, is a
non-irreversible process: mixing (by a stirrer) is
suBcient to obtain again a homogenous system.
The phase diagram of the system BCO \ diesel oil \
emulsi;er has been investigated in order to identify
the best w/w ratio in terms of homogeneity, stability,
engine performance, and operational costs.
90 D. Chiaramonti et al. / Biomass and Bioenergy 25 (2003) 85 – 99

Table 1
List of the most signi;cant tested surfactants. Emulsions’ stability (Stab) is given in terms of days before observing a complete phase
separation. These preliminary tests were performed at room temperature and without using the homogenization unit (stirring was performed
with a magnetic stirrer)

Surfactant Producer Stab Surfactant Producer Stab

Ampholak 7TX Akzo-Nobel 0 Hypermer B261(E) Uniqema 5

Ampholak 7TY Akzo-Nobel 0 Hypermer E-476 Uniqema 5
Amphoteen BTH-35 Berol-Nobel 1 Igepal CO-630 Aldrich 1
Armotan ML Akzo-Nobel 1 Igepal CO-720 Aldrich 1
Armotan MO Akzo-Nobel 1 Igepal CO-850 Aldrich 1
Armotan MRD Akzo-Nobel 1 Igepal CO-880 Aldrich 1
Armotan MS Akzo-Nobel 1 Igepal CO-890 Aldrich 1
Armoteric LB Akzo-Nobel 0 Igepal CO-990 Aldrich 1
Atlas G5000 Uniqema 7 Igepal CO-520 Aldrich 1
Atlox 4912 Uniqema 7 Kelzan Kelco 0
Atlox 4913 Uniqema 7 Kelzan D Kelco 0
Atlox 4914 Uniqema 7 Kelzan M Kelco 0
Atsurf 3969 Uniqema 3 Kelzan S Kelco 0
Bevaloid 6903 Rhodia 2 Marasperse N-22 Reed Lignin Inc. 0
Bretax AM CTP 0 Morwet D-425 PC Petrochemicals Comp. 1
Bretax S CTP 0 Morwet EFW PC Petrochemicals Comp. 1
BrijJ 58 Aldrich 1 OMA-4 Akzo-Nobel 0
BrijJ76 Aldrich 1 PEMULEN BF Goodrich 0
BrijJ92V Aldrich 1 Q-Broxin Boroid International 0
BrijJ96V Aldrich 1 Reax 888 Westvaco 0
Carbopol Ultrez 10 BF Goodrich 0 Reodal NA Dalton 1
Carbopol BF Goodrich 0 Reodal NA 40 Dalton 1
Carbowax 400 Carlo Erba 0 Reodal TF Dalton 1
Chimipal PE/403 Cesalpina 0 Rhodoline DP226/35 Rhodia 0
CTAB Fluka 0 Rolfor EP/526 Cesalpina 0
Dapral GE202 Akzo-Nobel 2 Rolfor HT/11 Cesalpina 0
Darvan n.1 R.T. Vanderbilt Co. 0 SCS 4682 Uniqema 2
Darvan n.2 R.T. Vanderbilt Co. 0 SCS 4683 Uniqema 2
Daxad 19 Grace 0 SCS 4684 Uniqema 2
Daxad 23 Grace 0 SCS 4712 Uniqema 2
Daxad Duoride Grace 0 Span 30 Fluka 1
SDS Fluka 0 Span 40 Fluka 1
Dowfax 2A1 Dow 1 Span 60 Fluka 1
Dowfax 3B2 Dow 1 Span 65 Fluka 1
Duomeen TDO Akzo-Nobel 1 Span 80 Fluka 1
Ethomeen C/12 Akzo-Nobel 1 Span 85V Fluka 1
Ethomeen C/25 Akzo-Nobel 1 Syn-Fac 8337 MilliKen Chemicals 0
Hypermer 1070 Uniqema 5 Synperonic PE/F127 Uniqema 2
Hypermer A-60 Uniqema 4

Fig. 3 shows the phase diagram of the analyzed
system. The most interesting region is the one left to
the dashed line (any concentration of BCO and diesel
oil, emulsi;er ¡ 5% by weight). The circles corre-
spond to the 25% (W/O), 50% (bicontinuous) and
75% (O/W) of BCO by weight. These three regions
have been studied more intensively.
2.4. The emulsiBcation system
Further than the use of an emulsifying agent, the
system used to emulsify BCO and diesel is based
on repeated cut of the Duid columns Dowing in
pre-de;ned channels, at the end of which some blades
cut the Duid threads, thus producing the emulsion. The
 D. Chiaramonti et al. / Biomass and Bioenergy 25 (2003) 85 – 99 91

Diesel oil

W/O Emulsions

O/W Emulsions Bicontinuous

Emulsions

BCO Emulsifier

Fig. 3. Phase diagram for the BCO \ diesel oil \ emulsi;er ternary system.

Fig. 4. Front view of the stator head (left) and front view of rotor head.

emulsi;er head works like a centrifugal pump, the
Duid is sucked from the center, cut and expelled
to the side. The system is constituted by a rotating
head with a series of radial channels in which, due
to the centrifugal force, the liquid is Dowing through
a central hole (Fig. 4). On the outer side, a ;xed
grooved skirt wrapping up the rotating head is present.
The liquid streams are therefore subject to a series
of cuts.
Initially the BCO/diesel oil emulsion was produced
using a laboratory scale emulsi;cation system. This
setup is perfectly similar to the 50 l h−1 emulsi;er
plant described later with exception for the production
capacity (5 l h−1 ) and for pipes, valves and pumps.
Emulsions produced with this system have been used
to perform the surfactants’ screening and to obtain the
;nal emulsion formulation.
In order to produce a suBcient amount of emulsion
for tests (approximately 1:5 t) a 50 l h−1 emulsi-
;er plant was designed and constructed. This plant,
therefore, di<erently from the laboratory scale emul-
si;cation system, includes other components, as
pipes, valves, pumps and tanks that are not strictly
necessary for the production of small quantities of
emulsion. However, the large scale emulsi;cation
system has been assembled in order to obtain the same
92 D. Chiaramonti et al. / Biomass and Bioenergy 25 (2003) 85 – 99

Fig. 5. Layout of the emulsi;cation system by PMA.

operating conditions used in the laboratory. It is • 1 storage tank (200 l) to store the produced emul-
composed by the following main elements: sion,
• 1 electrical control board.
• 1 emulsi;cation tool driven by a 1100 W variable Proper materials for storage, ;tting, sealing etc. have
speed electrical motor, been chosen to resist the corrosive characteristics of
• 3 pumps for BCO, diesel oil and emulsion, BCO.
• 1 water heated tank (1000 ml) for additive (in The main data of the 50 l h−1 emulsi;cation system
which the additive is melted), are the following:
• 1 water heated, process tank (46 l) containing the
• max power: 7:5 kW,
emulsion during the process,
• max capacity: 35 l per batch,
• 2 water heated tanks (25 l) in which diesel oil and
• 50 l h−1 for 30 min batch,
BCO are heated to the process temperature,
• max operating temperature: 80◦ C,
• 2 cooling tanks (30 l) for the produced emulsion,
• max Dow: 24 l min−1 .
that are also used as pre-heating tanks,
• 2 storage tanks (200 l) containing diesel oil and A layout of the emulsi;cation system is reported in
BCO, Fig. 5.
 D. Chiaramonti et al. / Biomass and Bioenergy 25 (2003) 85 – 99
3. Experimental: making emulsions
3.1. Characterization of BCO
Four di<erent types of BCO from various feedstock
and reactor technologies have been selected and or-
dered: (1) ENEL1: pyrolytic oil produced from Cana-
dian oak, produced by ENEL in the transported bed re-
actor by Ensyn in Bastardo (Italy), (2) ENEL2: BCO
from beech wood, produced by ENEL in the same
plant as ENEL1, (3) Dyna1001: BCO from California
pine produced by Dynamotive in the bubbling Duid
bed reactor (Vancouver, Canada); (4) BTG: BCO
from pine wood, produced by BTG (Twente, NL)
in the rotating cone reactor, Netherland. Details on
pyrolysis technologies are given in literature [4].
Table 2 shows the characteristics of the four BCOs
as measured during the research work. BTG oil has
been analyzed only in part due to time constraints.
A brief description of the methods used for the
physico-chemical parameter determination is reported
below.
Density. The density of the samples has been
determined by pycnometers and/or volumetric Dasks
(Klasse A) (di<erent accuracy is due to the viscous
nature of the Canadian oak derived BCO that did not
allow an accurate volume measurement).
Elemental analysis. Elemental analysis has been
performed with the aid of a CHN Analyzer (Carlo
Erba Elemental Analyzer, mod. 1106) according to
the instrument standard procedures.
Viscosity. The viscosity has been determined
by a rotational viscometer Physica USD 200 Paar
Physica on thermostated samples (25◦ C; 35◦ C,
and 45◦ C). In the case of the Canadian oak BCO
it has been used a plate-cone measuring system
(plate=TEK 150P; cone=MK21=89), while on beech
and pine derived BCO it has been used a double gap
measuring system (stator = TEZ180; rotor = Z1DIN).
The plate-cone measuring system needed only 0.5
–1:5 cm3 of sample, whereas double gap measuring
system needed 22:5 cm3 .
Alkali contents. The determination of Na, K, Ca
content has been carried out by atomic absorption
spectroscopy on a solution from ash residues. The
solution has been obtained by nitric-perchloric acid
digestion (about 80◦ C) on residual ash matter. Dis-
tilled water has been added to reach a ;nal volume of
93
25 cm3 in a volumetric Dask. A nitric-perchloric acid
solution (without ash) has been used as reference. The
instrument was a Perkin Elmer Analyst 100 assembled
with air-acetylene Dame.
Ash weight. The ash content has been measured
by weight di<erence with the starting sample after
keeping the sample at 600◦ C for 2 h. Final temper-
ature has been reached in ;ve steps with stops at
100◦ C; 200◦ C; 300◦ C, and 400◦ C to avoid leak of
sample. For this measure, about 2 g of BCO have been
used and the weight of an empty porcelain capsule has
been the tare.
Water weight. The water content has been per-
formed following two di<erent methods, which
provided similar results. The ;rst method employed
is the Karl–Fischer determination. The coulometer
employed has been an Accoumet titration system
(model E-94000) assembled with standard Karl–
Fischer platinum electrodes. The samples of BCO
has been diluted 1:10 by volume with Karl–Fischer
solvent methanol. The titration has been performed
with Karl–Fischer reagent. Solvent and reagent have
been purchased by Fluka.
The second method employed is the drying of
known amount of BCO (about 1 g). The determina-
tion of water content has been performed by weight
di<erence with respect to the starting sample after
leaving the amount of BCO in a drier containing a
dehydration substance (in reported case it has been
used phosphoric anhydride, P2 O5 ). The BCO con-
tainer was a Petri dish in order to have surface area as
wide as possible and therefore the maximum drying
speed rate. The measure has been stopped when the
equilibrium weight of the sample was reached (in our
case less than a week). An important consideration
is that by this second method it has been possible to
check the surface cross-linking process induced by
drying.
Higher heat value (HHV). The HHV of the BCO
samples has been determined according to DIN51900
(see also ISO 1928-1976 for solid fuels).
The HHV allows comparing the energy output from
burning any kind of fuel. This value is measured ex-
perimentally in a calorimeter. There are two kinds of
calorimetric systems based on an isotherm or an adi-
abatic process. In this case an adiabatic system was
used. This means that there is no exchange between
calorimetric bomb and environment.
94 D. Chiaramonti et al. / Biomass and Bioenergy 25 (2003) 85 – 99

Table 2
Measured physico-chemical properties of BCO

Physico-chemical properties ENEL1 ENEL2 Dyna1001 BTG

Canadian oak Beech wood California pine Pine wood
Viscosity (cPoise) at 25◦ C 701 9.8 46.2 21.3
Viscosity (cPoise) at 35◦ C 361 6.7 27.1 14.7
Viscosity (cPoise) at 45◦ C 150 4.1 14.1 9.2

Elemental analysis (% w/w)

H 5.79 5.94 6.31 6.18
C 44.06 34.96 43.52 44.08
O 48.68 58.70 50.07 49.64
N 0.08 0.11 0.07 0.09
S ¡ 0:01 ¡ 0:01 ¡ 0:01 ¡ 0:01

Alkali/BCO (ppm)
Na 103 179 6 168
K 339 694 8 725
Ca 1096 1561 123 1498
Ash weight (% w/w) 1.38 0.28 0.03 0.29

Alkali/ash (mg g−1 ):

Na 7.5 64 20.5 163.7
K 24.6 248 26.9 29.8
Ca 79.4 558 410 624.3

Water weight (% w/w) 22.1[23.1]a 43.6[45.1] 30.5[31.1] 34.4

Density at 20◦ C (g cm−3 ): 1.230 1.165 1.175 1.189
pH 3.2 3.0 2.6 2.9
LHV (kJ kg−1 ) 16942 14577 16779 16090
HHV (kJ kg−1 ) 18205 15873 18155 17460
a Numbers in square brackets indicate water content values measured adopting the Karl–Fisher method

The measure gives the temperature inside of the
calorimetric bomb before, during and at the end of the
fuel burning. On the basis of this information (weight
of the BCO sample, temperature di<erences and chem-
ical reactions during the burning) it is possible to cal-
culate the higher heat value. This process has to be
repeated at least two times to obtain one value, until
two measures di<er no more than 146:4 kJ kg−1 .
Lower heating value (LHV). The lower heating
value is calculated with elemental analysis data by
subtracting the contribution of the water content from
the HHV:
LHV = HHV − (5:84 × F);
where F = water content (%), LHV and HHV in
kcal kg−1 .
3.2. Main diDerences between oak, beech and pine
derived BCO
The beech and pine derived BCO show low viscos-
ity, correlated the larger amount of water, whereas oak
derived BCO shows very high viscosity, in agreement
with high solid noxious fraction relieved in the Duid.
The values obtained for the density are similar and in
all cases higher than water.
Elemental analysis data show that pine and oak
derived BCO are similar, whereas some di<erences,
especially for the carbon and oxygen content, can be
noted with respect to the beech derived BCO.
The alkali content values indicated that a larger con-
centration for these elements corresponds to a greater
presence of water: in fact the BCO with a great amount
 D. Chiaramonti et al. / Biomass and Bioenergy 25 (2003) 85 – 99 95

of water and a low amount of ash has greater values
of Na, K, Ca in comparison with the BCO with a low
amount of water and a greater amount of ash. An ex-
ception is represented by the California pine derived
BCO, probably due to the di<erent technology used,
type of biomass and its pre-treatment. It can be noticed
that in all cases a considerable amount of calcium was
measured.
Furthermore, the higher value of ash in the oak
derived BCO is due to inert and/or ;reproof materi-
als content in the bio-oil. The California pine derived
BCO presents a very low ash content in comparison
with the other two BCOs.
Regarding the heating values, the oak and pine de-
rived BCOs are characterized by a greater value in
comparison with the BCO utilizing beech wood as
feedstock, due to the higher content of carbon and hy-
drogen; anyway the measured values are conform with
those ones reported in literature.
Finally, it is important to remark that the BCO is an
unstable product; it tends to separate in a two phases
Duid, where the upper phase has higher water content
than lower phase. This phenomenon is time dependent
and it can imply a low replicability of the tests.
4. Results of emulsion production
4.1. Characterization of emulsions
Three di<erent emulsions were prepared:
(1) 25% BCO, 74% diesel oil, 1% additive (w/w),
(2) 50% BCO, 49% diesel oil, 1% additive (w/w),
(3) 75% BCO, 24% diesel oil, 1% additive (w/w).
As additive, we used a mixture of polymeric sur-
factants and short chain additives. More information

Table 3
Physico-chemical properties of ENEL2\diesel oil emulsions

Physico-chemical properties 25% ENEL2 50% ENEL2 75% ENEL2

Beech wood Beech wood Beech wood

Viscosity (cStoke) at 25◦ C 9.43 28.3 n.a.

Density at 20◦ C (g cm−3 ): 0.921 1.003 1.084

Elemental analysis (% w/w)

H 12.11 10.09 8.83
C 71.59 56.64 44.98
O 16.13 33.05 45.88
N 0.04 0.07 0.09
S ¡ 0:01 ¡ 0:01 ¡ 0:01

Alkali/emulsion (ppm)
Na 45 91 134
K 174 347 520
Ca 390 781 1171
Ash weight (% w/w) 0.07 0.14 0.21

Alkali/ash (mg g−1 )

Na 64.3 65.0 63.8
K 248.6 247.9 247.6
Ca 557.1 557.9 557.6

Water weight (% w/w) 10.7 [11.1] 21.6 [22.0] 32.4 [32.9]

pH 3.2 3.1 3.0
LHV (kJ kg−1 ) 35.716 27.142 19.260
HHV (kJ kg−1 ) 38.357 29.342 21.186
96 D. Chiaramonti et al. / Biomass and Bioenergy 25 (2003) 85 – 99

Table 4
Physico-chemical properties of Dyna1001\diesel oil emulsions

Physico-chemical properties 25% Dyna1001 50% Dyna1001 75% Dyan1001

California Pine California Pine California Pine
Viscosity (cStoke) at 25◦ C 9.79 25.41 n.a.
Density at 20◦ C (g cm−3 ) 0.923 1.008 1.094

Elemental analysis (% w/w)

H 12.27 10.50 8.98
C 74.63 61.82 51.03
O 13.04 27.6 39.88
N 0.03 0.05 0.07
S ¡ 0:01 ¡ 0:01 ¡ 0:01

Alkali/emulsion (ppm)
Na 2 4 6
K 3 5 8
Ca 41.1 83.2 125.1
Ash weight (% w/w) 0.01 0.02 0.03

Alkali/ash (mg/g)
Na 20.1 20.3 20.4
K 26.0 26.4 26.7
Ca 411 415 417

Water weight (% w/w) 7.3 [ 7.7] 14.9 [15.3] 22.5 [23.1]

PH 3.0 2.9 2.8
LHV (kJ/kg) 35.815 28.354 21.560
HHV (kJ/kg) 38.491 30.645 23.518

about the used additives is given in [29]. The
physico-chemical properties of the emulsions are
strictly related to the properties of the fuels (diesel
oil and BCO). Emulsions prepared from Califor-
nia pine seems the most interesting. Tables 3 and 4
report these properties as measured by CSGI. More-
over, CSGI provided Aston University with some
samples of emulsion for a more detailed analysis of
the viscosity index. The following six samples were
provided:
(1) 25% ENEL2: 25% bio-oil, 75% diesel, ¡ 1%
emulsifying agent,
(2) 50% ENEL2: 50% bio-oil, 50% diesel, ¡ 1%
emulsifying agent,
(3) 75% ENEL2: 75% bio-oil, 25% diesel, ¡ 1%
emulsifying agent,
(4) 25% Dyna1001: 25% bio-oil, 75% diesel, ¡ 1%
emulsifying agent,
(5) 50% Dyna1001: 50% bio-oil, 50% diesel, ¡ 1%
emulsifying agent,
(6) 75% Dyna1001: 75% bio-oil, 25% diesel, ¡ 1%
emulsifying agent.
A Metrohm 758 KFD Titrino, was used for quanti-
tative determination of water in pyrolysis liquids. A
small sample of raw pyrolysis liquid was weighted:
the liquid was then injected through a septum into the
meter. The Titrino determines water content by volu-
metric titration (Tables 3 and 4).
With respect to the viscosity index, it has already
been said that the lower is the number, the more sta-
ble is the liquid. A perfectly stable liquid has a vis-
cosity index of 0.00. The samples analyzed by Aston
University were stable and opaque with no evidence
of phase separation. The stability measurements sug-
gested a higher level of stability than conventional
bio-oils, which is promising. It was observed that the
 D. Chiaramonti et al. / Biomass and Bioenergy 25 (2003) 85 – 99 97

Table 5
Viscosity measurements: results summary

Sample Water Initial Final Viscosity index

content (wt%) viscosity (cS) viscosity (cS) at 80◦ C
Bio-emulsions
25% ENEL2 10.2 9.43 11.59 0.23
50% ENEL2 20.3 28.30 29.20 0.03
75% ENEL2 30.4 3172 ¿ 4000 n.a.
25% BCO1001 7.9 9.79 10.62 0.09
50% BCO1001 15.8 25.41 31.63 0.24
75% BCO1001 23.7 1807.8 ¿ 4000 n.a.

Bio-oils
Aston Duid bed 22.6 1.56
Aston ablative 16.4 0.44
NREL hot vapor 17.2 0.97
;ltered
Ensyn liquid 15.6 0.94
Average of triplicates, Average of duplicates. Average of duplicates. There was no appreciable
¡ 0:2 standard deviation. change in weight (i.e. no
loss of volatiles) during
the test.

75% bio-oil content emulsions had very high viscos-
ity, which make them diBcult to use in most applica-
tions. A summary of these measurements is shown in
Table 5.
5. Conclusions
The research work on emulsions demonstrated
that:
• The emulsions are more stable than the pure BCO:
further than from experimental evidence, this fact
was also con;rmed by the measurement of the
viscosity index.
• Higher the emulsi;er content, higher the
viscosity and stability of emulsions. The optimal
range to have an acceptable viscosity is between
0.5% and 2%. Emulsi;er up to 4% has been
added, in this case an additive (like n-octanol)
must be employed to reduce the viscosity of the
emulsion.
• Higher the BCO content, higher the viscosity of the
emulsion.
• The stability versus time at high temperature (ap-
proximately 70◦ C) of the produced emulsions was
about 3 days.
• The use of fresh bio-oil, i.e. pyrolysis oil immedi-
ately after its production, is recommended, since the
use of aged oils makes the emulsi;cation process
more diBcult and reduces the quality of the emul-
sions in terms of droplet size and stability. In fact,
chemical reactions occurring in BCO (in particular,
polymerization) lead to the formation of solid prod-
ucts. Therefore, in order to obtain a stable emulsion,
it is necessary to micronize these products, making
the necessary emulsi;cation time longer than in the
case of fresh bio-oil.
The possibility of producing stable emulsions in a
very wide range (5/95 to 75/25 o/w emulsions) has
been demonstrated. It is therefore possible to consider
pyrolysis oil emulsi;cation as a possible and rela-
tively short-term approach to the wide use of these oils
reducing the investment in technologies. Nevertheless,
since the quality of the BCO has a great impact on the
selection of the emulsifying agent as well as on the
emulsi;cation process, a general purpose approach is
98 D. Chiaramonti et al. / Biomass and Bioenergy 25 (2003) 85 – 99
not possible. The feedstock and the pyrolysis process
must be precisely de;ned in order to allow the exact
identi;cation of the most appropriate emulsi;cation
technique.
Acknowledgements
Authors wish to acknowledge the persons who
collaborated to this research project: Riccardo Ricceri,
Giuseppe Sarti and Paolo Favuzza (CSGI, Univer-
sity of Florence), Pier Francesco Niccolini, Graziano
Crocetti and Lino Pasquali (Pasquali Macchine Agri-
cole), JVurgen Schmid, Rainer Grischke and Catarina
von Schwerin (IEE, Kassel University), John Leech,
Liz Peacock and Dereck Ormrod (Ormrod Diesels),
Francesco Martelli (Energetics Department “Sergio
Stecco”, University of Florence), and ETA for the
support provided during the experimental campaign.
The authors would also like to acknowledge
Giuliano Grassi (General Secretary of the European
Biomass Industry Association, EUBIA) for his pre-
cious recommendations and advices.
Particular thanks to Dynamotive Technologies Ltd.
(Canada), ENEL (Italy) and BTG (Netherland) for
the provision of oil during the research project.
The research was funded in part by the European
Commission in the framework of the Non Nuclear
Energy Programme JOULE III. A special acknowl-
edgement to the EC oBcers Mario Frias and Michail
Papadoyannakis, for their useful support and collabo-
ration during the project implementation.
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