MATEC Web of Conferences 333, 11009 (2021) https://doi.org/10.

1051/matecconf/202133311009
APCChE 2019

Evaluation Method of Emulsion Using Chemical Oxygen

Demand
Kaiki AMAGU1, Riho OKAJIMA1, Moe SHIMIZU2, Makoto NISHIMOTO3, Kazuhito NAGAYAMA4, Takashi HATA4,
Yusuke NISHIUCHI4, and Kaori TADA4*
1Advanced Course of Material Engineering, National Institute of Technology (KOSEN), Kochi College, 200-1 Monobe Otsu,
Nankoku-city, Kochi 783-8508, Japan
2Department of Material Science, National Institute of Technology (KOSEN), Wakayama College, 77 Noshima, Nada-cho,

Gobo-city, Wakayama 644-0023, Japan

3Department of Applied Chemistry and Biochemistry, National Institute of Technology (KOSEN), Wakayama College, 77 Noshima,

Nada-cho, Gobo-city, Wakayama 644-0023, Japan

4Department of Social Design Engineering, National Institute of Technology (KOSEN), Kochi College, 200-1 Monobe Otsu,

Nankoku-city, Kochi 783-8508, Japan

Abstract The “gas–liquid two-phases mixed flow” mechanism that fine bubble generation uses
rapidly swirling water, which shear gas and making small bubbles in water. Based on this
mechanism, sending liquid such as oil into the swirling water instead of gas and it able to be
emulsified. At present, evaluation methods for emulsions are using particle size distribution and
dispersion stability. However, the emulsion with bad separation behavior has a problem to catch
only some dispersed oil particles and use them as a whole evaluation. In this study we examined
emulsion evaluated by chemical oxygen demand (COD) to express numerical evaluation
including the oil particles that cannot be dispersed. Using three emulsions of only one oil, an
anionic and a nonionic emulsifier were mixed and added to the oil, an anionic and another kind
of the nonionic emulsifier were mixed and added to the oil. It was confirmed that COD
decreased and type of only one oil was the most evaporate. These results lead to the conclusion
that the performance of the emulsion could be expressed numerically, including the oil particles
which could not be dispersed. We also directly analyzed evaporate components and compared
them with COD results.

1 Introduction However, the emulsion with bad separation behavior has

a problem to catch only some dispersed oil particles and
An emulsion is a mixture of two or more liquids that are use them as a whole evaluation. This can be visualization.
normally immiscible such as oil and water. The emulsion Nevertheless it is difficult to express numerical data. In
which oil dispersed in water called O/W type emulsion. this study we investigated emulsion evaluated by
On the other hand, the emulsion which water dispersed chemical oxygen demand (COD) to express numerical
in oil called W/O type (Kitahara and Furusawa, 1979). evaluation including the oil particles which cannot be
Example of emulsions in the field of food are milk and dispersed. We also directly analyzed evaporate
mayonnaise. Emulsion is used in various fields, such as components and compared them with COD results.
cosmetics, medical products.
Recently, it was confirmed that fine bubbles have a
diameter under 100 µm have properties different from 2 Experimental Method
those of mm or cm sized bubbles. The “gas–liquid two-
2.1 Producing of emulsion using liquid-liquid
phases mixed flow” mechanism that fine bubble
two-phases mixed flow system
generation uses rapidly swirling water that shear gas and
making small bubbles in water. Based on this In this study we examine emulsion were made by the
mechanism, sending liquid such as oil into the swirling liquid–liquid two-phases mixed flow system applying
water instead of gas and it able to be emulsified. This the gas–liquid two-phase mixed flow system, which is
time, the emulsion was made by this mechanism. the mechanism of fine bubble generation. Figure 1
Main evaluation methods for emulsions are using shows the device outline. In the gas–liquid two-phases
particle size distribution and dispersion stability. mixed flow system, the gas is refined by the shear stress

*
Corresponding author: tada@ge.kochi-ct.ac.jp
© The Authors, published by EDP Sciences. This is an open access article distributed under the terms of the Creative Commons Attribution License 4.0
(http://creativecommons.org/licenses/by/4.0/).
MATEC Web of Conferences 333, 11009 (2021) https://doi.org/10.1051/matecconf/202133311009
APCChE 2019

of rapidly swirling liquid. It is possible to send liquid the particle size by the scattered light when light strikes
instead of gas. The dispersed phase is refined by the the particle.
shear stress of the continuous phase and the dispersed Second, transmittance shows transparency. The
phase. And O/W emulsion which oil is dispersed in measuring device used an ultraviolet-visible
water could be made. spectrophotometer V-630 (JASCO Corporation). The
measurement wavelength was 660 nm. 0.5 mL sample
take to the cell and add 3 ml of ion-exchanged water.
Third, dispersion stability index is an indicator of the
stability of the emulsion. In the case of O/W type
F４
emulsion, the oil droplets accelerate to float and
coalescence over time. Since oil density is bigger than
water density. This phenomenon is called creaming
behavior, and its speed is a measure of dispersion
stability (Tasaki, 2014). In order to observe the creaming
behavior, the emulsion was subjected to centrifugal
Figure 1. Liquid to liquid two phases mixed flow system (F1:
separation. The instantaneous change in transmitted light
disperse phase (oil), F2: continuous phase (water),
F3: formed emulsion, F4: generation nozzle) quantity was regarded as the positional change of the
particle group. Thus, the dispersion stability index was
calculated. Device uses LUMi Fuge (L.M.F).
2.2 Producing of emulsion using conventional Fourth, COD indicates the amount of organic matter
machine in the target.
We made a comparison between this technology and
conventional machine. The following shows the 2.4 Producing of Emulsion
conventional machine.
We used homogenizer, rotor stator type mixer and The dispersed phase and the continuous phase are stirred
ultrasonic emulsifying machine. or mixed as they are, one liquid is refined to make
First, homogenizers emulsify oil and water by high emulsion, but when it is left, the droplets coalesce
pressure. At that time, liquid is injected from the valve immediately and separate into the two liquids as before.
gap. This time, the pressure applied to the valve was 300 The third substance added to stabilize the emulsion is
bar to produce emulsion. called emulsifying. It also reduces the energy required to
Second, rotor stator type mixers stir and make refine the liquid and facilitates emulsification.
emulsion. A rotor rotating at high speed with a conical As a concrete experimental operation, the dispersed
mixer cuts the liquid by stirring it. The rotor speed was phases used was of three types: sample (1) only one oil,
300 rpm for 5 minutes. sample (2) an anionic and a nonionic emulsifier were
Third, ultrasonic emulsifying machines apply mixed and added to the oil, sample (3) an anionic and
ultrasonic waves to oil and water. The relatively low another kind of the nonionic emulsifier were mixed and
frequency ultrasonic emulsification of several tens of added to the oil. The continuous phase was ion-
kHz vibrates the unstable contact interface such as water exchanged water, and the above three dispersed phases
and oil, and formed droplets. They are divided by the were emulsified at 1 vol.%. Also, the oil used was
generated cavitation. On the other hand, high frequency volatile. However, rotor stator type mixers are structural
ultrasonic waves of MHz or more, the size of the problems and cannot make oil only. Samples were
generated cavitation is in the submicron range. Therefore measured every three days for nine days and stored at 60
it is considered to be effective for further refinement of ˚C.
the emulsion droplets that have already been formed
(Atobe, 2012). Based on this, it was pre-emulsification 3. Results and discussion
for 5 minutes with low-frequency ultrasonic wave (45
kHz). After that similarly performed for 5 minutes with
high frequency (1.6 MHz). 3.1 Temporal change of dispersed phase by
COD
2.3 Evaluation of emulsion As a result of particle size distribution for nine days, the
emulsion in sample (1) was polydispersed. On the other
We evaluated made emulsion. The following shows the hand, the emulsions in samples (2) and (3) were
evaluation method. monodispersion and a particle size is about 50 nm. In
Evaluation methods of emulsion are particle size other words, the particle size of the emulsion in sample
distribution, transmittance and dispersion stability index (1) is more than larger the emulsion in sample (2) or (3).
and chemical oxygen demand (COD). And stability is also same as particle size.
First, particle size distribution shows the size and Passed time was taken on the horizontal axis, and the
number of particles. The measuring device used SALD transmittance (Figure 2), particle size distribution
7100 nano (Shimadzu Corporation). This device uses a (Figure 3), and the dispersion stability index (Figure 4)
laser diffraction and scattering equation. They measure are plotted on the vertical axis. It can be confirmed that
the transmittance (Figure 2) and dispersion stability

2
MATEC Web of Conferences 333, 11009 (2021) https://doi.org/10.1051/matecconf/202133311009
APCChE 2019

(Figure 4) are higher with time. As to particle size Next, it was confirmed that the change in oil amount
distribution (Figure 3), it was found that the mode calculated from COD over time (Figure 5). As to the
diameter of the emulsions in sample (2) and (3) emulsion in sample (1), the oil was completely vaporized.
remained stable without change. However the mode And the emulsions in sample (2) and (3) were
diameter of the emulsion in sample (1) was not stable. evaporated about 1000 mg L—1.
Thus, the emulsion tends to be stabilized with time. In Figure 3, because an emulsion of about 10 µm is
observed in sample (1), it is considered that remarkable
creaming and vaporized from the upper layer occurred
due to the relatively large particle size. It is supported by
the results of increased transmittance and decreased
COD value according to a decrease in emulsion
concentration.
From this result, it was found that amount of the oil
dispersed phase was calculated from COD, and the
behavior of the dispersed phase could be confirmed.
○: Sample (1) Emulsion performance is relative to COD results.
□: Sample (2)
△: Sample (3)

○: Sample (1)
□: Sample (2)
△: Sample (3)
Figure 2. Transmittance (this technology)

○: Sample (1)
□: Sample (2)
△: Sample (3)

Figure 5. The amount of oil calculated from COD (this

technology)

3.2 Emulsion tend of this technology and

conventional machines

Similar to this technology, it was confirmed that the

Figure 3. Particle size distribution (mode, this technology) particle diameter was smaller and the transmittance and
dispersion stability were higher on conventional
○: Sample (1)
machines for 9 days. For example, the emulsion made by
□: Sample (2) homogenizer, we show the particle size distribution
△: Sample (3) (Figure 6) and a result of COD (Figure 7).

○: Sample (1)
□: Sample (2)
△: Sample (3)

Figure 4. Dispersion stability index (this technology)

Figure 6. Particle size distribution (mode, Homogenizer)

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MATEC Web of Conferences 333, 11009 (2021) https://doi.org/10.1051/matecconf/202133311009
APCChE 2019

performance by liquid-liquid two-phases mixed flow

system over time.
Measurements other than COD consider that the
slight remaining fine particle were captured and reflected
in the results on the emulsion in sample (1). It appears
stability, over time. Therefore we should not overlook
that decreasing oil. The emulsion such as sample (1) is
that large oil particles are evaporated rapidly and only
small fine particles remain. In comparison with the
emulsion such as sample (1), the emulsion such as
○: Sample (1) sample (2) or (3) is that oil evaporates slowly because
□: Sample (2)
the particles are small.
△: Sample (3)

4. Conclusion
In this study, we measured and evaluated particle size
Figure 7. The amount of oil calculated from COD distribution, transmittance and dispersion stability of
(Homogenizer) O/W type emulsions made by liquid-liquid two-phases
mixed flow system. And temporal changes of emulsions
were evaluated by COD. As time passed, the particle
size was smaller. Besides, the transmittance and
dispersion stability are higher. In other words, the
emulsions tend to be stability from these results.
However the amount of oil calculated from COD
decreased, the emulsion became thinner due to creaming
behavior and evaporated oil. Dispersion oil and amount
of evaporated oil are associated with oil type and the
combination of emulsifiers.
In addition, we evaluated the emulsion which made
by conventional machines with same composition as this
○: Sample (1)
□: Sample (2) technology. As a result, it was found that the particle size
was smaller and the transmittance and the dispersion
stability were higher with time, but the oil dispersion
amount was lower than COD, even the conventional
machine, same as this technology. The emulations by
conventional machines are also about the same
Figure 8. The amount of oil calculated from COD performance.
(Rotor stator type mixer) From these results, the evaluation method using COD
can conform the concentration of the dispersed phase
remaining in solution. The evaluation of COD values is
○: Sample (1) effective in systems without impurities. COD is
□: Sample (2)
important when evaluating the emulsion.
△: Sample (3)

Acknowledgments

This work was supported by Kochi Prefecture industry-

academia-government collaboration commercialization support
project.

References
Kitahara, A. and K. Furusawa; Chemistry of Dispersion and
Emulsification Systems, p. 54, Engineering Books Co Ltd.,
Tokyo, Japan (1979)
Figure 9. The amount of oil calculated from COD Atobe, M.; “Preparation of Surfactant-free Nanoemulsion
(Ultrasonic emulsifying machines) Using Tandem Acoustic Emulsification and Its Application”,
Oleoscience, 12(6), 233–239 (2012)
In addition, a result of COD of other machines show
Tasaki, H.; Characterization of Emulsion and Development of
Figure 8 and Figure 9. New Product, Utilization for Quality Control, pp. 128, 139, 152,
As a result, the emulsion performance by Technical Information Institute Co. Ltd., Tokyo, Japan (2014)
conventional machines is same as the emulsion