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Emulsions find a wide range of application in industry and daily life. In the pharmaceutical industry lipophilic active ingredi-
ents are often formulated in the disperse phase of oil-in-water emulsions. Milk, butter, and margarine are examples of emul-
sions in daily life. In the metal processing industry emulsions are used in the form of coolants. Emulsions can be produced
with different systems. In the following, the process of high-pressure homogenization is briefly compared to other common
mechanical emulsification systems. To facilitate the selection of an emulsification system, the influence of the most important
parameters of the emulsion formulation on the resulting mean droplet diameter in the most prevalent continuous emulsifica-
tion systems is outlined. Subsequently, the most common high-pressure homogenization systems are discussed in detail. On
the basis of data from the literature and own experimental results the described high-pressure homogenization systems will
be compared regarding their attainable mean droplet diameter. It shows that homogenizers with a relatively simple geometry
like the patented ªcombined orifice valveº (Kombi-Blende) attain the smallest mean droplet diameters. The advantage of
the ªcombined orifice valveº compared to other high-pressure homogenization systems is not more efficient droplet disrup-
tion but rather more efficient droplet stabilization against coalescence immediately after the droplet breakup. The greatest
research potential concerning the development of new high-pressure homogenization systems is still to be seen in improve-
ments of droplet stabilization, i.e., the reduction of coalescence.
Chem. Eng. Technol. 2004, 27, No. 4 DOI: 10.1002/ceat.200406111 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 361
Review
362 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.de Chem. Eng. Technol. 2004, 27, No. 4
Review
mainly applied in laboratories where mean droplet diame- similar to an orifice, so that there are the same conditions
ters of approximately 0.4 lm can be obtained. Thereby the present as in the simple orifice. In Tab. 1 values and/or
product stress is very high. The production of oil-in-water ranges for the exponent b of the correlation function
emulsions by means of ultrasonic systems is presented in de- x C gbd are indicated. For C no ranges can be indicated, it
tail by Bechtel [10] and Behrend and Schubert [11]. rather has to be defined by experiments for each emulsifica-
Apart from the mechanical characteristics of an emulsifi- tion system and emulsion formulation.
cation process also the characteristics of the product have to The influence of the viscosity of the continuous phase gk
be considered when selecting an emulsification process. In and the disperse phase fraction j is similarly small in all spe-
Tab. 1 the most important product parameters that have an cified emulsification systems. What holds for the correlation
effect on the emulsification process are listed with respect to functions of the viscosity of the continuous phase gk
the industrially relevant continuous emulsification processes. (x C gbk ) also holds for the disperse phase fraction j
The indicated values refer to own results and data from the (x C ejb ). The constant C must also be determined
literature [7,12±14,32]. The viscosity ratio k = gd/gk has only experimentally, since it depends on many factors of the for-
an influence on emulsifying in colloid mills with smooth mulation of the emulsion. Rotor-stator systems are mainly
rotor and stator surfaces. In the Couette flow within those suitable for the production of emulsions with higher viscos-
systems drops can be disrupted only in the range of the mini- ities, while high-pressure systems attain better results in the
mum of the critical laminar Weber number, which is in production of emulsions with low viscosities. An optimal vis-
viscosity-ratios of 0.1 < k < 1 [4]. In all other specified emul- cosity range of emulsion for rotor-stator-systems is 20 to
sification systems the drops of the disperse phase are dis- 5000 mPa´s and for high-pressure systems it is 1 to 200 mPa s
rupted mainly in turbulent flow, in which the viscosity ratio as indicated by Mollet and Grubenmann [14].
does not have an influence on droplet disruption. The interfacial adsorption velocity of the surfactant deter-
An influence of the viscosity of the disperse phase gd is to mines to a large degree the stabilization of the newly bro-
be registered in all specified emulsification processes. With ken-up droplets against coalescence. Depending on the resi-
rising viscosity of the disperse phase the dispersion result is dence time t of the drops in the dispersion unit surfactants
reduced. Due to increasing viscosity of the disperse phase a with different interfacial adsorption velocities can be used.
drop creation is made more difficult. With rising oil viscosity Slow surfactants, such as salted egg yolk, can effectively only
the drops behave more and more like rigid spheres. In ori- be used in dispersion systems with high residence times, like
fices, jet dispergators and ªcombined orifice valvesº (Kom- in colloid mills. Except for the ªcombined orifice valveº only
bi-Blende) this influence is somewhat smaller than in the surfactants with high interfacial adsorption velocities can be
other high-pressure systems. Stang [32] attributes this to the used successfully in high-pressure systems. Here, the resi-
laminar extension flow available in orifices and jet disperga- dence times lie within the range of few milliseconds. The
tors, which are here considerably responsible for droplet dis- new interfaces must be occupied in this short time, before
ruption. The ªcombined orifice valveº is, concerning the part the emulsion leaves the dispersion unit and arrives in zones
which is responsible for droplet disruption, geometrically of laminar flow. Here, the coalescence is clearly higher for
not sufficiently stabilized drop-
lets, compared to the turbulent
Table 1. Product influence on the emulsifying result for industrially relevant continuous emulsifying systems: k = flow in the dispersion unit. The
viscosity ratio, gd = viscosity of the disperse phase, gk = viscosity of the continuous phase, ge = viscosity of the ªCombined orifice valveº pro-
emulsion, x = mean droplet diameter, C = constant (to be determined by experiments), b = exponent of the
correlation function, j = fraction of the disperse phase, t = retention time. vides clearly higher residence
times in turbulent flow than the
other high-pressure systems, so
that also surfactants with medium
interfacial adsorption velocities
lead to good dispersion results.
From the different influences
of each product parameter of
each emulsion formulation on
the dispersion result during the
emulsification with different pro-
cesses it becomes clear that for
the selection of an emulsification
process the formulation of the
emulsion must always be consid-
ered.
In order to compare different
emulsification processes from an
Chem. Eng. Technol. 2004, 27, No. 4 http://www.cet-journal.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 363
Review
industrial point of view, it seems to be best to look at the thus turbulent flown through rotor-stator systems and high-
mean droplet diameter as a function of the product through- pressure dispersion systems. With the high-pressure disper-
put. This attempt fails, however, because of the very high sion systems smaller droplet diameters can be obtained with
number of manufacturers and equipment available. In addi- similar energy densities than with the rotor-stator systems.
tion, no detailed data are available for the newer processes, High-pressure dispersion systems are important due to the
like membrane and ultrasonic emulsification processes. For demands of the industry for emulsions with small droplet di-
these reasons the presentation of the droplet size as a func- ameters and the only possibility to create these when also a
tion of the energy density is selected. Fig. 3 depicts the high product throughput is desired. These systems are dis-
extended diagram adapted from Schubert [15]. It shows the cussed in detail in the following.
attainable mean droplet diameter x as a function of the ener-
gy density EV for different continuous emulsification pro-
cesses. The newly developed ªcombined orifice valveº 3 High-Pressure Dispersion Systems
(Kombi-Blende) is added. It can be recognized that depend-
ing upon the assigned process different energy densities are High-pressure homogenizers generally consist of a high-
needed to obtain certain mean droplet diameters. With mi- pressure pump, mostly in the form of a one- to three-piston
croporous membranes very small droplet diameters (0.3 lm) plunger pump which can be electrically or pneumatically ac-
can be obtained with the lowest energy input. Much higher tuated, and the actual high-pressure dispersion unit. High-
energy input is needed to make medium-size drop diameters pressure dispersion units are subdivided into radial diffusers,
of 0.4 lm with the ultrasonic systems. However, the achiev- counterjet dispergators and axially flown-through nozzle-ag-
able product throughput is small in both processes, so that gregates.
they are only interesting for laboratory use. Emulsification
systems that enable higher product throughputs, as they are
required by industry, need high energy densities to produce 3.1 Radial Diffusers
finely dispersed emulsions. The rotor-stator systems which
create a laminar flow can only be used in a limited range, as The radial diffuser, often referred to as homogenizing
for droplet disruption the viscosity ratio of the continuous to valve, is the most common high-pressure dispersion unit in
the disperse phase must be approximately equal to one [15], industry. The most frequently used types of radial diffusers
which is rarely the case with industrial products. Relevant are schematically shown in Fig. 4A). A standard radial diffu-
emulsification processes for the industrial production are ser consists of a valve face, which causes a deflection of 90
of the direction of the flow, and an
axially mobile valve seat, which
makes a variation of the slit width
possible as well as with constant flow
rate, a variation of the homogenizing
pressure [16].
Phipps [17] has determined by ex-
perimental works the march of
pressure in a flat valve as shown in
Fig. 5. The fluid flows into the valve
with the given homogenization
pressure. In its inlet bore ªaº the
fluid is very strongly accelerated, so
that the static pressure drops very
much. When the vapor pressure of
the fluid is reached, vapor bubbles
(cavitation blisters) develop and the
single-phase flow turns into a two-
phase liquid/vapor flow ªbº. The
subsonic flow turns into a superso-
nic flow and in the further march of
the flow it comes to a compression
shock, in which the pressure sud-
denly rises to a higher level, so that
Figure 3. Mean droplet diameter as a function of energy density for different emulsifying techniques the vapor bubbles collapse and the
adapted from Schubert [15]: viscosity of the continuous phase gk = 30 mPa s, viscosity of the disperse phase
3
gd = 60 mPa s, densities of the phases rk = rd = 1003 kg/m , interfacial tension between the disperse and the flow becomes slower ªcº again. Fi-
continuous phase c = 10 mN/m, r = rotor diameter, s = width of slit. nally, the pressure in the valve out-
364 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.de Chem. Eng. Technol. 2004, 27, No. 4
Review
Cd0:165
B
c0:365 g0:495
d
x (1)
p0:6
H
g0:025
k
0:235
d
Chem. Eng. Technol. 2004, 27, No. 4 http://www.cet-journal.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 365
Review
pergators with two and four orifices as well as a single ori- open jet. She made her findings using an acrylic glass nozzle
fice. The single-orifice setup produces the smallest mean setup and monitored the process. Her finding is therefore in
droplet diameters. Therefore, he reasoned that the laminar contradiction to Stang's conclusions.
extension flow at the inlet of the orifice bore is responsible The ªcombined orifice valveº (Kombi-Blende) is another
for droplet disruption. The scale-up for higher product nozzle-aggregate patented by F. Hoffmann-La Roche AG
throughputs is easy to realize in the jet dispergator by a [42]. The ªcombined orifice valveº shown in Fig. 4C) consists
higher number of orifice bores. The orifice bores have to be of three consecutively arranged orifices of which the first
arranged in pairs opposite to each other. and third one have a smaller thickness and a smaller bore di-
In the so-called interaction chamber of the microfluidizer ameter than the second one so that a so-called turbulence
the premix flow is divided into at least two fractions. These chamber is created. The first orifice (inlet orifice) has a
fractions are directed so that they collide with each other. smaller bore diameter than the third orifice. Furthermore,
The collision of the jets is supposed to be used as an addi- the inlet and outlet bores are arranged eccentrically to each
tional disruption mechanism. As in the case of the jet disper- other. With the ªcombined orifice valveº smaller mean
gator Stang [32,33] is not considering the collision of the droplet diameters can be produced than with simple orifices.
droplets as the most important disruption mechanism. He This can be attributed to a reduction of droplet coalescence
holds a combination of the influence of the laminar exten- by the turbulence chamber [43].
sion flow at the inlet of the interaction chamber and the tur-
bulent flow in the interaction chamber responsible for drop-
let disruption. This hypothesis is supported by the studies of 4 Comparison of Different High-Pressure
the collisions of drops as droplet disrupting mechanism by Homogenization Systems
Kiefer and Treiber [34]. Studies of McCrae [35], Strawbridge
et al. [36], and Robin et al. [37] show that emulsions gener- The emulsification results of the different dispersing units
ated with a microfluidizer lead to smaller mean droplet di- can be compared using the required energy densities EV for
ameters than emulsions generated with radial diffusers. drop disruption. The energy density in high-pressure homo-
In the nanojet also jets of premix collide. However, the at- genizers corresponds to the pressure drop Dp over the dis-
tainable mean droplet diameter is larger compared to those persing unit:
obtained in the jet-dispergator [38]. A new development is
the microjet-reactor dispergator [39] from Synthesechemie EV ~ Dp (2)
GmbH that has a flow pattern similar to the nanojet. In the
system two to three jets of raw emulsion with up to 4000 bar Fig. 6 shows the mean droplet diameter x depicted as a
admission pressure collide in a chamber filled with gas. The function of energy density EV for different high-pressure dis-
gas flow, which is entering the microjet-reactor vertically to persing systems. The oil-in-water emulsions produced by the
the raw emulsion jets, transports the emulsion out of the re- use of the emulsifier LEO-10 have a fraction of disperse
actor. Shear forces in the turbulent flow and cavitation are phase of 30 wt.-% vegetable oil. It can be seen that the emul-
the disrupting mechanisms. The erosion of the dispersing sions made with the radial diffusers (flat-valve and cutting-
unit is mostly prevented, therefore, the tool life is relevantly edge valve) lead to the largest mean droplet diameters.
increased because of the collision of the emulsion jets in a Much smaller droplets can be produced with the dispersing
gas filled chamber. The low risk of blockage in the dispersing systems working with the counterjet principle (jet disperga-
unit is another advantage of the system since the product is tor, microfluidizer, and nanojet). The best dispersing results
discharged by the gas stream. are obtained by the nozzle aggregates (orifice and ªcom-
bined orifice valveº). It is astonishing that the simplest con-
struction of a dispersing unit, the orifice, enables better dis-
3.3 Nozzle Aggregate persing results than the much more complex counterjet
dispergators. The finest emulsions could be produced with
Like the counterjet dispergators the nozzle-aggregates the ªcombined orifice valveº. As already mentioned, the
also contain no movable parts so that they can be in use at reason is not a more efficient droplet breakup, but rather
very high pressures. Contrary to the counterjet dispergators, the decrease of the coalescence following droplet breakup.
the nozzle-aggregates have an axial flow direction. The ori-
fice with a sharp-edged inlet and outlet is shown in Fig. 4C).
It is the simplest type of a nozzle-aggregate. According to 5 Summary and Perspective
Stang [32] droplet disruption mainly occurs in the extension
flow before entering the nozzle bore. The studies of Kolb The comparison of the best-known emulsification pro-
[40,41], by a high-speed video system on the disruption of cesses shows that the industrial production ± that means at
single drops in orifices show, however, that the droplet is high product throughput ± of emulsions with high-pressure
breaking up behind the nozzle bore after the flow conditions systems and rotor/stator systems is the only alternative to
change from laminar to turbulent flow in the core of the produce emulsions in a continuous way. For the choice of an
366 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.de Chem. Eng. Technol. 2004, 27, No. 4
Review
emulsification process the formulation of the produced try leads to an improvement of the dispersion result espe-
emulsion has always to be taken into consideration. The pro- cially in case of a decrease in coalescence [44].
duction of finely dispersed emulsions with a mean droplet A reduction of the energy input at the same quality of dis-
diameter of x < 1 lm requires high-pressure emulsification persion is a further main focus in research especially with re-
systems. spect to the efficiency of the dispersing systems. Less energy
It can be imagined by the presentation of the different input means less erosion of the dispersion units and thus
high-pressure systems how great the interest of industry is in longer tool life which again reduces in a relevant way the
this technology. The large number of quoted literature here production costs of the emulsions.
is just a small selection of the research done in the field. Received: June 18, 2003 [B 6111]
Consecutively new, improved and optimized high-pressure
systems are entering the market. Step by step they will bring
down the mean drop size towards the ªmagic borderº of
100 nm in mean drop size.
Symbols used
Particularly the comparison of the different high-pressure
b [±] exponent of correlation function
systems according to the attainable dispersing result in the
C [±] constant
last section of this presentation shows that in the develop-
d [mm] diameter
ment of new dispersing units the reduction of coalescence is
EV [J/m3] energy density
in future more important than the improvement of an in-
Dp [Pa] pressure drop
crease of droplet breakup. In Fig. 6 it can be seen that the
r [m] rotor diameter
simple orifice generates such an efficient droplet breakup
s [m] width of slit
that it attains better dispersing results than a radial diffuser
t [s] retention time
or a counterjet diffuser. Smaller droplet diameters can only
x [m] mean droplet diameter
be produced with the ªcombined orifice valveº (Kombi-
c [N´m±1] interfacial tension
Blende), however, not because of a stronger droplet breakup
g [Pa´s] dynamic viscosity
compared to the simple orifice but rather with a better stabi-
k [±] viscosity ratio gd/gk
lization of the disrupted droplets.
r [kg´m±3] density
It is certainly possible to reduce the coalescence of the dis-
f [±] fraction of disperse phase
rupted droplets, e.g., by an increased amount of surfactant
or by a choice of a faster adsorbing surfactant. But often the
product formulation does not allow this. The guidance of the
flow must be skillfully designed in a system to lead to a re- Subscripts
duction of the coalescence frequency until the surfaces of
the droplets are completely covered by the surfactant mole- B orifice
cules so that the droplets are protected against coalescence. d disperse phase
Research at the example of the ªcombined orifice valveº e emulsion
(Kombi-Blende) shows that the optimization of the geome- k continuous phase
Chem. Eng. Technol. 2004, 27, No. 4 http://www.cet-journal.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 367
Review
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368 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.de Chem. Eng. Technol. 2004, 27, No. 4