Water-Fuel Emulsions for

Energy Application

M. Misra,* S. Chen,' and P. Grlmest

The combustion of petroleum products produces emissions which contain oxides of nitrogen
(NOx), hydrocarbons (HC),and particulate matter (PM) which have adverse health and envi-
ronmental efiects. In recent years there has been increasing interest in the use of water-fie1 emul-
sions as a substitutefor conventionalfuels. Emuls$edfuels are emulsions of water infuel, which
are typically made of 10 to 20 percent of water mired with certain additives andfuel. Studies
have shown that the emulsifed diesel can significantly reduce the emissions of NO, PM and car-
bon monoxide and increase the fuel efficiency. In order to produce a stable diesel emulsion, the
development of an effective surfactant additive is critical. The stability of diesel emulsions is
influenced by many factors, including size distribution of the droplets, the viscosity of the contin-
uous phase, the physical properties of the interfacial film, and temperature. This paper describes
a method to produce emulsified diesel and combustion results obtainedfrom various tests. It has
beenfound that the diesel emulsion made with this additive package was stable during the test,
and the emissions were lower in NO, CO, and PM compared to the baseline diesel.

INTRODUCTION
Diesel engines are widely used in transportation, mining, and power plants. Compared
to gasoline engines, diesel engines have the advantages of high thermal efficiency, high
power-to-weight ratio and good fuel economy [Pischinger, 19981. The current soaring
fuel prices make the diesel engines even more attractive. While diesel engines have the
obvious advantage in fuel economy over gasoline engines, there are concerns associated
with their emissions. The principal pollutants generated from diesel engines include par-
ticulate matter (PM),nitrogen oxides (NO,), carbon monoxide (CO) and hydrocarbons.

* Metallurgical & Materials Engineering, University o f Nevada, Reno, Nevada

t Clean Fuels Technology, 210 Gentry Way, Reno, Nevada
330 ( APPLIED SEPARATIONGENERGY RESOURCE RECOVERY

Generally, the diesel engine produces lower levels of carbon monoxide and hydrocar-
bons, but higher levels of particulate matter and nitrogen oxides compared to the con-
ventional gasoline engine [NRC, 19821. In certain situations, such as the case in the state
of California, this problem prevents the wide application of diesel engines.
Diesel exhaust contains more than 400 different components, including vapors and
fine particles. Exposure to this mixture may result in cancer, exacerbation of asthma,
and other health problems. For the same load and engine conditions, diesel engines gen-
erate more particles than gasoline engines. As a result, diesel engines account for an esti-
mated 26 percent of the total hazardous particulate pollution from fuel combustion
sources in our air, and 66 percent of the particulate pollution from on-road sources. Die-
sel engines also produce nearly 20 percent of the total nitrogen oxides in outdoor air and
26 percent of the total NO, from on-road sources, which is a major contributor to ozone
production and smog. The production of photochemical smog via NO, and HC reactions
with solar ultraviolet radiation might irritate the throat, trachea, lung and eyes [Lin and
Wang, 20031.
The aim of the development of diesel fuel emulsions is to provide an environmen-
tally friendly substitute for traditional diesel fuels, which can be used in diesel engines
for reduction of emissions. Typically diesel emulsions are mixtures of diesel with 10 to
20% of water and several percent of various types of surfactant additives which help to
stabilize the emulsion. Compared to conventional diesel fuel, diesel emulsions have been
reported to simultaneously reduce emissions of nitrogen oxides, carbon monoxide and
particulate matter, without the need for any mechanical modifications [Ryan, et al.
19811.
One of the combustion characteristics of diesel emulsions is the so-called secondary
atomization caused by the vigorous evaporation of the interior liquid. For diesel-fueled
engines the flame temperature is relatively high during combustion (as high as 2200 OF).
Under such conditions free radicals of oxygen and nitrogen are formed and chemically
combined as nitrogen oxides. Use of diesel emulsion can greatly reduce the production
of NO,. When the diesel emulsion enters the combustion chamber, it is atomized into 75
to 100 pm size droplets. The emulsified water droplets within each drop of oil flash into
steam, exploding it into numerous smaller droplets. This phenomenon can increase the
combustible surface area per volume of fuel oil by as much as 100 times, which leads to
more complete combustion. Furthermore, due to the existence of water in diesel emul-
sion, the combustion temperature is lowered. As a result, nitrous oxides generation is
reduced. Another benefit of diesel emulsion is the lower particulate emissions due to the
evaporation of added water and the simultaneous reduction of the temperature. The
water addition may increase OH radicals which are very effective in the oxidation of soot
precursors. The soot formation in the gas phase would be reduced as a result of the oxi-
dation of soot by increased OH radicals [Kadota and Yamasaki, 20021.
The number of vehicles using diesel emulsions is in steady increase as an immediate
solution for the reduction of polluting air emulsions, especially in Europe. It is reported
that around 450 city buses in the UK, 1,000 in France, and 8,500 in Italy use emulsified
diesel fuels. Diesel emulsions can also be used in marine engines, locomotives, power
generation equipment and construction equipment, as well as in industrial boilers and
mining equipment. A test was conducted in London where a proportion of 13% water
was used in the fuel. It was found to achieve a NO, reduction of 13% and PMlO reduc-
tion of 25% where there was no particulate trap fitted [Sadler, 20031.
 WATER-FUEL EMULSIONS FOR ENERGY APPLICATION 1 331

By definition, emulsion is a heterogeneous system consisting of one or more liquids

dispersed in an immiscible liquid in the form of droplets. Usually the diameter of the
droplets is larger than 0.1 pm. Traditionally emulsions are categorized into two groups:
water-in-oil (W/O) and oil-in-water ( O N ) . The W/O emulsion is prepared using either
a mechanical, chemical, or electric homogenizing machine to stir water into micrometer
droplets scattered evenly in the oil layer. A number of devices can be used to produce
emulsions. These devices include rotor-stators, colloid mills, high-pressure homogeniz-
ers, and ultrasonic systems. However, without any additives, emulsions may quickly sep-
arate into two phases due to coalesce. To keep emulsions stable, it is necessary to add
surfactants (emulsifiers) to emulsion [Becher, 20011.
One frequently used method for selection of emulsifiers is known as the hydrophile-
lipofile balance (HLB) method. It is based on the theory that emulsifying agents contains
oil-soluble and water-soluble moieties [Lisant, 19741. This dual nature of the surfactant
molecule tends to limit its solubility in both phases and causes it to concentrate at the
interface. The balance between these groups will determine whether a specific surfac-
tant would be soluble in either water or oil and the type of emulsion it would stabilize. In
general, low HLB (3-6) emulsifiers favor the formation of W/O emulsions, while higher
HLB (8-18) emulsifiers favor the formation of O N emulsions.
Thermodynamically the emulsions are unstable [Becher, 19831. This instability
arises from the large interfacial area, and therefore large surface energy, associated with
finely dispersed systems. Consequently, in order to reduce the total interfacial area, col-
loidal particles tend to either flocculate or to accumulate at an interface. The mechanism
of colloidal instability involves three types of phenomena: creaming, Brownian floccula-
tion, and sedimentation flocculation.
To produce stable diesel emulsions, the selection of appropriate additives (emulsifi-
ers) is critical. The purpose of applying emulsifiers is to reduce the surface tension forces
and to promote the affinity force between water and oil phases. It should also provide
long enough shelf life for transportation and appropriate storage time.
Although a lot of research has been carried out for the development of diesel emul-
sions, there are only a few products currently in small-scale use. The main problems with
diesel emulsion production include high cost, instability, and complex systems. There-
fore new methods which can provide economic, stable, and low-polluting emulsified die-
sel should be developed.
In this paper, a new emulsifier package was used for the preparation of diesel emul-
sions. The physical properties of the emulsion were evaluated. Its stability was also stud-
ied. For evaluation of the performance of this emulsion in engines an emission test was
also conducted.

EXPERIMENTAL PROCEDURE
There are four constituents in the additive used in the study: a carboxylic acid with long
saturated carbon chains, an alkali, a stabilizer, and deionized water. The purpose of the
addition of the stabilizer is to sustain an appropriate stability for the W/O emulsion. The
additive is an amber colored fluid. Appropriate stirring is required before using it for
emulsified diesel production.
In the bench scale experiment, diesel emulsion was prepared with a homogenizer.
First the additive was added to diesel and the content was thoroughly mixed with the
homongenizer at midrange rpm. After that deionized water was added and the mixture
332 / APPLIED SEPARATIONS-ENERGY RESOURCE RECOVERY

TABLE 1 Engine speciticatlons

Englne parameter Speciflcatlon
Engine type Diesel, 4cycle
Model 6067MK6E
Configuration L-6
Displacement 12.7 L (778 CID)
Aspiration Turbocharged
Rated power 430 HP at 2100 rprn
Peak Torque 1550 Ibft at 1200 rpm
Idle speed 600 rpm
Governed idle speed 2225 rpm
Combustion system Dl, TC, ECM, CAC, EGR*
Engine family VH603WAF

* Dl: Direct injection

TC: Turbocharger
ECM: Electronic control module
CAC: Cooled air charge
EGR: Exhaust gas recirculation

was sheared by the homogenizer at midrange rpm. The volume percentage of the addi-
tive, water, and diesel were approximately 2%, 16% and 82 %, respectively.
Characterization of the product was performed by using a DT-1200 electroacoustic
spectrometer (Dispersion Technology Inc.) for measurement of droplet size distribution.
Incubation of the prepared diesel emulsions was carried out in order to measure the
degree of phase separation of the water phase from the oil phase. The freshly prepared
emulsion was placed in a 100 ml cylinder and set at room temperature. The separation
heights were recorded daily.
Emissions generation, collection, and analysis were performed according to the
applicable standards in the Code of Federal Regulations. A 2003 Detroit diesel engine
was selected for the testing of the emulsified diesel. The specifications of the engine are
described in Table 1.

RESULTS AND DISCUSSION

Droplet Size Analysis

The size distribution, or particle size distribution (PSD) of water droplets in the medium
(diesel) provides critical information which can be used in the prediction of emulsion
stability, and in the explanation of combustion performance. It can provide a measure-
ment for quality control purposes as well.
Under the conditions of flocculation and creaming, the droplet sizes tend to become
larger. It was reported that the stability to flocculation increases exponentially with
increasing droplet size. The smaller droplets flocculate quickly to form relatively stable
larger floc [Becher, 19881. If the emulsion is stable, changes in PSD would occur slowly.
From this point of view, it is possible to evaluate the emulsion stability by measurement
of the change of PSD with time.
 WATER-FUEL EMULSIONS FOR ENERGY APPLICATION ( 333

+ Day30
-e- D a y 1
* Day7
+ D a y 1s
+Day20

Diameter [urn]

FIGURE 1 Measurement of PSD of dlesel emulsion

TABLE 2 Mean droplet slze of emulsified diesel

Mean droplet size (pm)
Sample ID Day 1 Day 6 Day 15 Day 20 Day 30
Emulsified Diesel 1.05 1.47 1.69 1.83 2.04

Figure 1shows the PSD measurement results of the diesel emulsion at various time
intervals. In the beginning, a large part of the droplets fell into submicron range, with a
narrow distribution in particle sizes. After that the distribution covered a wider range.
During the first three weeks the median sizes changed very slowly. The mean droplet
sizes measured by electroacoustic spectrometer during a period of one month are shown
in Table 2. The initial mean droplet size was 1.05 pm. The mean size gradually increased
during the period. After 30 days the mean size was 2.04 pm. Although the mean size
increased, the pace was slow, meaning that the diesel emulsion made with this additive
was relatively stable. These results indicated that this additive package is effective in sta-
bilizing the W/O diesel emulsion.

Stablllty Test Results

The stability of diesel emulsion at room temperature is shown in Figure 2. It can be seen
that the percentage of oil phase separation was 8% after a month's incubation. In the
beginning the oil phase separation was more repressed, then the emulsion appeared to
undergo a flocculation period. However, after three weeks, the emulsion seemed to be
334 1 APPLIED SEPARATIONGENERGY RESOURCE RECOVERY

Week 1 Week 2 Week 3 Week 4

-

FIGURE 2 Stablllty of emulslfled diesel at room temperature

TABLE 3 Analysis of fuel properties

Property Base Fuel Diesel Emulsion
API Gravity 32.4 28.3
Sulfur, wt% 0.049 0.038
Cetane Number 43.2 40.3
Cetane Index 44.1 34.6
Aromatics, vol % 37.9 34.0
Olefins, vol % 1.2 2.8
Saturates, vol % 60.9 47.2

stabilized. The percentage of oil separation on the 7th day, 14th day, and 21st day was
measured to be 2%, 4.5%, and 6%, respectively. These results demonstrated a stable die-
sel emulsion with a good shelf life.

Emission Test
For the purpose of comparison, a baseline fuel was obtained and tested, together with
the emulsified diesel. Both fuels were analyzed for their properties. Table 3 presents the
measured fuel properties.
The average emission results obtained from the test of PM and NO, using the emulsi-
fied diesel fuel were compared to the average emission results using the reference diesel
fuel. The comparison is presented in Table 4. The emulsified fuel reduced PM emissions
by 35% and NO, emissions by 14% compared to the reference baseline fuel. The only
emission component which did not meet the requirement of the regulation is particulates.
This phenomenon may have been due to the high aromatic and sulfur content of the base
 WATER-NEL EMULSIONS FOR ENERGY APPLICATION ( 335

TABLE 4 Summary of composite regulated emlsslons

Emisslons Results, glbhphr
Test THC CO NO, Particulate
2003 Standard 1.3 15.5 4.0 0.10
Baseline Fuel
Test 1 Composite 0.10 0.8 2.7 0.17
Test 2 Composite 0.11 0.8 2.8 0.16
Test 3 Composite 0.11 0.7 2.8 0.17
Average of Three Composites 0.11 0.8 2.8 0.17
Emulsified Diesel Fuel
Test 1 Composite 0.11 0.6 2.5 0.11
Test 2 Composite 0.14 0.7 2.4 0.10
Test 3 Composite 0.13 0.8 2.3 0.10
Average of Three Composites 0.13 0.7 2.4 0.11

fuel. It can be expected that an emulsion based on a diesel with a lower sulfur content
may yield reduced PM emissions.
Average hydrocarbon emissions increased from 0.11 for the reference fuel to
0.13 g/hp-hr for the emulsified fuel. However, hydrocarbon emissions for the emulsified
fuel remained well below the limit specified.
Carbon monoxide emissions were 12% lower with the emulsified fuel than with the
reference fuel. Carbon dioxide emissions were not significantly different with the emul-
sified fuel.
Speciation of the volatile hydrocarbon compounds with carbon numbers from C, to
C, and andehydes, ketones, and two ethers (MTBE and ETBE) was also performed.
More than 200 compounds were checked for their presence in the dilute exhaust. In gen-
eral, all compounds found in the exhaust with the emulsified diesel fuel were also found
in the exhaust with the baseline diesel fuel. While no additional compounds were found
with the emulsified diesel fuel, thirteen compounds were detected in the exhaust of
baseline diesel fuel that were not detected with the emulsified diesel fuel.

CONCLUSIONS
A new emulsifier based on long chain carboxylic acids and alkali has been developed for
the production of emulsified diesel oil. An emulsified diesel was prepared by using a
homogenizer. This diesel emulsion is of the W/O type which contains approximately
16% of water and 2% of additive. The stability test conducted with the emulsified diesel
fuel made with this emulsifier showed that a stable diesel emulsion can be achieved by
using the new additive. Particle size analysis also confirmed that this fuel emulsion pre-
sented a droplet size distribution that is relatively stable.
To determine the exhaust characteristics of the emulsified diesel fuel, an emission
test was conducted on a heavy-duty diesel engine. It has been found from the test results
that the emulsified diesel fuel produced results lower than the 2003 emission standards
except for particulate matter. The increase in particulate matter above the standard may
have been due to the high aromatic and sulfur content of the base fuel. Compared to the
baseline diesel fuel, the emulsified diesel produced about 12% less CO emissions, about
336 1 APPLIED SEPARATIONS--ENERGY RESOURCE RECOVERY

1 4 % less NO,, and about 35% less particulate emissions. The speciation of the hydrocar-
bons showed that no additional compounds, which could be attributed to the use of
emulsified diesel fuel, were found in the exhaust at the detection limits for the analytical
procedures.

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