TECHNICAL FIELD
[0001] The present invention relates to the use of a composition containing ferrocene and
lecithin as a fuel additive to improve combustion promotion.
DESCRIPTION OF THE RELATED ART
[0002] Conventionally, ferrocene and derivative(s) thereof are used as an additive for various
liquid fuels. For instance, ferrocene, derivative(s) thereof and a improvement combustion
method of a liquid hydrocarbon in the presence of a fuel additive composition consisting
of an aromatic solvent, an aliphatic solvent and/or a petroleum solvent which are
liquid organic carriers capable of dissolving the ferrocene and derivative(s) thereof
are described in
JP02-132 188A. Moreover, a method of conditioning of diesel engines is described in
US Patent 4389220 specification. In accordance with the method, a deposit containing carbon in the
combustion chamber is removed, and the fuel consumption per distance traveled is reduced
by about 5%, by adding 20-30ppm of ferrocene to the fuel.
[0003] In addition, a method of reducing carbonaceous deposition on the engine and ancillary
equipment thereof is proposed in
JP Patent 3599337 specification. In accordance with the method, 1-100ppm of ferrocene and derivative(s)
thereof, as additives for fuel oil consisting of a heavy residual oil for an internal
combustion, are added to a fuel directly, without blending other additives.
[0004] However, ferrocene and ferrocene derivative(s) used for these inventions have a drawback
of very low solubility in an aromatic solvent, an aliphatic solvent and a petroleum
solvent.
In general, ferrocene is in the solid state. In order to dissolve solid ferrocene,
in particular, a large quantity of agitation power and long time, which depend on
the size of the solid, are needed. Even if the amount of addition is small, solid
ferrocene doesn't dissolve easily either. The trouble occurs in the internal combustion
engine when solid
ferrocene isn't dissolved beforehand before it adds to the fuel. Therefore, under
the present situation, the solid ferrocene is added to a fuel after it is dissolved
in a solvent in a solution tank with an agitator.
DISCLOSURE OF INVENTION
[0005] The present invention is made in view of the aforementioned problems of the conventional
technology and has an object to provide a fuel additive containing ferrocene, which
can easily and stably be dissolved in a fuel and improves the combustion.
[0006] As a result of repeating assiduous studies for achieving the above-mentioned object,
the present inventors found the object to be accomplished by using ferrocene in combination
with lecithin.
[0007] That is, the composition according to the present invention is characterized by containing
ferrocene and lecithin which is used as fuel additive for improving combustion.
[0008] The solid fuel additive composition used according to the present invention for
improving the combustion is characterized by containing 80 to 99 % by mass of ferrocene
and 1 to 20 % by mass of lecithin. The particulate fuel additivecomposition used according
to the present invention is characterized by containing 78 to 99 % by mass of ferrocene
0.9 to 20 % by mass of lecithin and 0.1 to 2 % by mass of water.
[0009] In addition, the liquid fuel additive composition used according to the present invention
for improving the combustion is characterized by containing mineral oil containing
ferrocene and lecithin dissolved therein, and having the ferrocene content of 2 to
5 % by mass and the lecithin content of 5 to 50 % by mass.
[0010] Furthermore, the fuel additive composition used according to the present for improving
the combustion invention is characterized by being used by being added into a fuel
so as to make the concentration of the ferrocene and the lecithin in ranges of 1 to
50 ppm, and 0.01 to 500 ppm, respectively.
BEST MODE OF CARRYING OUT THE INVENTION
[0011] Hereafter, the composition used as a fuel additive according to this invention for
improving the combustion will be explained in detail. In this specification, "%" means
"mass percentage" unless otherwise specified.
[0012] As mentioned above, the composition used as a fuel additive according to this invention
for improving the combustion contains ferrocene and lecithin. These fuel additives
can be in the solid state, especially in the particle state, and in the liquid state.
(1) Ferrocene
[0013] Formally, ferrocene is called bis(cyclopentadienyl)iron, and is also called dicyclopentadienyl
iron.
[0015] In the present invention, ferrocene may be a solid such as a fine powder, a coarse
particle, a pellet and the like, and may be a liquid. The form of ferrocene can be
suitably chosen depending on the form of a fuel additive of the present invention.
It is explained in detail later.
[0016] A fuel additive used in the present invention can have a combustion promotion effect,
a soot reduction effect, a NOx reduction effect and the like, by containing ferrocene.
In particular, in a diesel engine that is an internal combustion engine, a cleaning
effect of the combustion promotion that controls the formation of deposit on a valve,
a piston ring, and a combustion chamber is observed. Since the deposit reduces engine
output and increases attrition of parts by adhering, controlling formation of the
deposit achieves stable driving of a diesel engine. In addition, several percent reduction
of fuel consumption can be realized by preventing superfluous air at the time of combustion,
by the reforming combustion such as combustion promotion, soot reduction, NOx reduction
and the like.
(2) Lecithin
[0017] Lecithin is an animal and plant phospholipid of which the principal ingredients are
a glycerophospholipid and a sphingophospholipid. It is obtained by the purification
process of various kinds of vegetable oil such as soybean oil, rapeseed oil, rice-bran
oil, palm oil, sunflower oil, cocoanut oil, cottonseed oil, corn oil, peanut oil,
linseed oil, safflower oil, olive oil and the like. Usually, a vegetable oil is included
1 to 50%. Depending on the contained amount of the vegetable oil and the ratio between
saturation acid and unsaturated acid in the vegetable oil, lecithin exists in the
liquid form or in the solid form at normal temperature. Moreover, in recent years,
a powder lecithin is manufactured from a liquid lecithin by carrying out oil extraction
and vacuum drying.
[0018] In the present invention, lecithin may be a liquid, and may be a solid such as a
fine powder and the like. The form of lecithin can be suitably chosen depending on
the form of a fuel additive of the present invention. It is explained in detail later.
(3) A form of a fuel additive
[0019] A fuel additive used in the present invention can be in the solid state, in the particle
state, and in the liquid state.
(i) Solid fuel additive
[0020] A solid fuel additive used in the present invention preferably contains 80 to 99%
of ferrocene and 1 to 20% of lecithin. If the content of the lecithin is less than
1%, the ferrocene may not dissolve in the fuel easily. If the content of the lecithin
is 20%, the ferrocene solubility enhancement effect may be obtained completely.
[0021] The form of ferrocene is not especially limited as long as it is solid at normal
temperature, mention may be made, for example, of a solid form such as a fine powder,
a coarse particle, a pellet and the like. In addition, lecithin is preferably in the
powder form at normal temperature, more preferably a fine powder of 1 mm or less in
particle diameter. It is because the mixture with Ferrocene may be made more uniform.
(ii) Particulate fuel additive
[0022] A particulate fuel additive used in the present invention is one aspect of the above-mentioned
solid fuel additive, and is granulated from fine powder ferrocene compound into the
shape of a coarse particle. As for the particle diameter, it is preferable to be 0.5
mm to 15 mm, more preferably 1 mm to 10 mm. When the particle diameter is less than
0.5 mm, the handling workability may be inferior due to powder dust. When the particle
diameter is more than 15 mm, the solubility may decrease due to decreased deflocculability.
A particulate fuel additive preferably contains 78 to 99% of ferrocene, 0.9 to 20%
of lecithin and 0.1 to 2 % of water. If the content of the lecithin is less than 0.9%,
the ferrocenes may not dissolve in the fuel easily. If the content of the lecithin
is 20%, the ferrocene solubility enhancement effect may be obtained completely.
Ferrocene are preferably in the powder form at normal temperature, more preferably
a fine powder of 2 mm or less in particle diameter. In addition, lecithin is also
preferably in the powder form at normal temperature, more preferably a fine powder
of 1 mm or less in particle diameter. It is for the convenience of granulation process.
A powder lecithin used in this invention has high hygroscopicity, and obtains suitable
tackiness for a granulation by mixed with small amount of water. However, when the
content of the water is less than 0.1%, the sufficient tackiness may not be obtained,
and when the content of the water is more than 2%, the above-mentioned powder ferrocene
and the above-mentioned powder lecithin may be agglomerated due to high water content.
(iii) Liquid fuel additive
[0023] A liquid fuel additive of the present invention contains mineral oil containing ferrocene
and lecithin dissolved therein, and preferably the content of the ferrocene is 2 to
5 % and the content of the lecithin is 5 to 50 %. If the content of the lecithin is
less than 5%, the ferrocenes may not dissolve in the mineral oil easily. If the content
of the lecithin is 50%, the effect of enhancing solubility of ferrocenes in mineral
oil may be obtained completely.
The ferrocene may be a solid such as a fine powder, a coarse particle, a pellet and
the like, or may be a liquid, preferably a liquid or a fine powder from the viewpoint
of shape that dissolves easily in mineral oil. And similarly, the lecithin may also
be a liquid, or a solid such as a fine powder and the like, preferably a liquid or
a fine powder, because of the shape thereof that dissolves easily in mineral oil.
As used herein, the term "mineral oil" includes hydrocarbon fuel oil , gas oil, kerosene
and the like. For example, for use in grade C heavy oil used as a fuel of large-scale
diesel engines for marine vessels, grade A heavy oil, grade B heavy oil, gas oil,
kerosene and the like can be preferably used, and grade A heavy oil can be more preferably
used.
(4) Action and effect of lecithin
[0024] Lecithin in the present invention mainly provides the effect as follows.
i) Enhancement of solubility in fuel of ferrocenes
ii) Dispersing action of sludge in fuel oil
iii) Binder action at the time of granulation to prepare a particulate fuel additive
iv) Deflocculation action in a particulate fuel additive
v) Enhancement of solubility in mineral oil of ferrocenes, in a liquid fuel additive
Each above-mentioned effect is described below.
i) Enhancement of solubility in fuel of ferrocene
[0025] Ferrocene have a drawback of low solubility in various fuels, as mentioned above.
As used herein, the term "fuel" includes fuels used as a fuel for diesel engines,
oil incinerators, boiler devices and the like, such as grade A heavy oil, light oil
such as kerosene, gas oil and the like, heavy oil, heavy residue oil, lubricating
oil, waste oil and mixed oil thereof, and also fuel emulsion thereof, and solid fuel
such as coal and the like, but are not limited thereto, as long as the fuel is not
in gaseous form.
[0026] For instance, in case of single ferrocene, a solubility in petroleum solvents such
as aromatic solvent other than benzene, toluene and xylene, aliphatic solvent and
the like is very low. Thus, in such a solvent as above mentioned, single ferrocene
is soluble only up to 3% in concentration at 20 degree C. In addition, ferrocene concentration
in solvent for prolonged stability is preferably 2.5% or less. The same goes for when
ferrocene is dissolved in fuel such as heavy oil and the like. However, by adding
the prescribed amount of lecithin, it is possible for ferrocene to be dissolved up
to 5% in concentration, and the stability of the solution is good in a broad temperature
region.
The relation between the additive amount of lecithin and the maximum solubility of
ferrocene in grade A heavy oil is shown in Table 1.
[0028] Thus, since ferrocene is easily dissolved in a fuel of various combustion facilities
or in a fuel additive itself by adding lecithin that has a solubility enhancement
effect, and a stable solution can be obtained, it becomes possible to spray ferrocenes
in the uniform particle form on a combustion engine. As a result, the action and effect
of ferrocenes can be exerted more than enough.
[0029] Lecithin has an oleophilic portion and a hydrophilic portion, and is known to act
as a surfactant agent. However, in the present invention, it is considered that lecithin
enhances the solubility due to the action of an oleophilic portion. That is, it is
considered as follows. When ferrocene and lecithin are dissolved in a fuel, one part
of oleophilic portions of the lecithin promptly adsorb to the surface of the ferrocene,
and another oleophilic portions of the lecithin enhance lipophilic property on the
surface of the ferrocene, therefore, lecithin contribute to the solubility enhancement
of ferrocene in a fuel.
These actions are not seen in any other surfactant agents such as nonionic surfactant
and the like, and are peculiar to lecithin.
ii) Dispersing action of sludge in fuel oil.
[0030] This action differs from the above mentioned solubility enhancement action of ferrocene.
Lecithin itself acts as a fuel additive, and contributes to long-term stable operation
of the combustion facility including a diesel engine.
[0031] Sludge is an insoluble matter, which exists in a fuel oil, especially in a heavy
oil, and causes clogging of a strainer and incomplete combustion since it is easy
to precipitate. A generation of the sludge arises from change into a hydrocarbon polymer
having few hydrogen atoms by oxidation, polymerization and condensation of hydrocarbon
that remains in a oil residue in a tank, because of heat-treatment, catalytic cracking,
pyrolysis and the like during a purification process of crude oil.
[0032] The above-mentioned change takes place in order of hydrocarbon, malthene, asphaltene,
carbine, carboid and carbon. These polymers initially exist in a heavy oil as a macromolecular
colloid. It is considered that the colloid has a hydrocarbon such as carbine, carboid
and the like as a core with an extremely high C/H ratio, surrounded by some asphaltenes,
and covered sequentially with hydrocarbon polymer with a low C/H ratio.
[0033] An asphaltic substance that exists in a heavy oil as such a colloidal particle will
not be precipitated and cause the problem of clogging of a strainer, incomplete combustion
and the like, as long as it is floating dispersedly as stable colloid. However, this
colloidal particle has polarity and adsorptivity property. Therefore, if equilibrium
condition is disrupted by heating, adding an oil of a different kind, prolonged storage
and the like, the colloidal particles agglutinate together one after another, and
get into an aggregate of big particles (micelle colloid), and form sludge by precipitating.
[0034] Specifically, when a light component is added to a heavy oil containing the above-mentioned
colloidal particle, hydrocarbon polymers and malthene of the colloid surface layer
is dissolved. However, since asphaltene, carboid and the like are unsaturation and
have polarity, the colloidal particles agglutinate each other, the huge asphaltene
particles are separated, and sludge is formed. In addition, when heat is applied,
a colloid surface layer is dissolved and also particle motion is increased because
viscosity is reduced by a rise in heat. And sludge is formed by binding and association,
since opportunities for collision of the asphaltenes are augmented.
[0035] Lecithin infiltrates and absorbs to binding portion and/or association of sludge
such as carbon, asphaltene and the like, and has a mincing action of sludge by dispersion
force by acting as a surfactant agent. Lecithin also has the effect of preventing
separation and precipitation of sludge, by preventing mixing of different-type fuels,
association of the colloidal particles by heating and the like, by this action.
iii) Binder action at the time of granulation to prepare a particulate fuel additive.
[0036] As mentioned above, when a particulate fuel additive is granulated, lecithin obtains
suitable tackiness for a granulation by mixed with small amount of water, and bears
a role of a binder.
iv) Deflocculation action in a particulate fuel additive.
[0037] Lecithin contained in particulate fuel additives has deflocculation action to make
particles easy to crush when the additive is fed into a fuel. In addition, the crushed
additive comes to dissolve very easily by solubility enhancement effect of lecithin.
v) Enhancement of solubility in mineral oil of ferrocene, in a liquid fuel additive
[0038] Ferrocene has a very low solubility in mineral oil, and are soluble only up to about
2.5% in concentration. However, by adding the prescribed amount of lecithin, it is
possible for ferrocene to be dissolved up to 5% in concentration, and the stability
of the solution is good in a broad temperature region.
(5) Concentration in a fuel of ferrocene and lecithin.
[0039] It is preferred that the fuel additive according to the present invention for various
fuels used for diesel engines, oil incinerators, boiler devices and the like, which
are used in a marine vessels, power generating facilities and the like, is added into
the fuels so as to make the concentration of ferrocene and lecithin in ranges of 1
to 50 ppm, and 0.01 to 500 ppm, respectively.
More specifically, as for usual concentration of ferrocene, it is preferred that the
fuel additive is added sequentially into the fuels in order that the fuels in oil
incinerators and boiler devices have ferrocene concentration of 1-10 ppm and the fuels
in diesel engine have ferrocene concentration of 10-50 ppm.
However, in order to greatly improve objective combustion promotion, soot reduction,
NOx reduction and the like, several fold to dozens of the continuous additive amount
can be temporarily added while a short time, based on the condition of a combustion
engine.
[0040] The above-mentioned lecithin has advantageous concentration to dissolve easily and
stably ferrocene in a fuel oil and in fuel additive itself, and to disperse sludge
further, in a heavy fuel oil especially.
[0041] In this manner, by dissolving ferrocene easily and stably with desirable concentration
of lecithin, the action and effect of ferrocene can be exerted more than enough and
it can contribute to long-term stabile operation of combustion facilities.
EXAMPLES
[0042] Hereinafter, this invention is further explained in detail on basis of examples and
comparative example, but this invention is not limited to these examples.
Evaluation of various characteristics was carried out in the following way.
[Evaluation of a solubility test of ferrocene]
Solid fuel additive (Example 1 - 4 and Comparative example 1)
[0043] Ferrocene was added to 200 g of grade A heavy oil (sulfur content = 0.09%, viscosity
=2.8cst (50 degree C)) as a fuel oil, stirring at 20 degree C and 60 rpm, and the
rate of solution until ferrocene concentration reaches 3% was evaluated by measuring
the number of seconds. Then, ferrocene was added further in order to produce the stable
solution of maximum concentration, and stability after still standing for one week
at room temperature was evaluated. The results are shown in Table 2.
Liquid fuel additive (Example 5 - 7 and Comparative example 2)
[0044] While stirring at 20 degree C and 60 rpm, the fuel additives were prepared by compositions
shown in Table 3, and the rate of solution until ferrocene is completely dissolved
in grade A heavy oil was evaluated by measuring the number of seconds. Stability of
the obtained solution after still standing for one week at room temperature was evaluated.
The test was done on a 200 g scale. The results are shown in Table 3.
[0045]
[Table 2]
|
|
Example |
Comparative Example |
|
|
1 |
2 |
3 |
4 |
1 |
additive composition [%] |
Ferrocene |
80 |
98 |
94.5 |
79 |
100 |
Lecithin (Solid) |
20 |
2 |
5 |
20 |
--- |
Water |
--- |
--- |
0.5 |
1 |
--- |
Total |
100 |
100 |
100 |
100 |
100 |
solubility rate |
180 |
370 |
290 |
175 |
660 |
dissolved concentration |
4.8 |
3.5 |
4.1 |
4.9 |
3.0 |
stability test |
very good |
good |
very good |
good |
no good |
Lecithin (Solid) means a powdered lecithin in the solid state, lecithin (liquid) means
a lecithin in the liquid state. Stability test:
"very good" mesns complete dissolution,
"good" mesns almost dissolution,
"passed" mesns a little insoluble matter was observed,
"no good" mesns too much insoluble matter was observed. |
[0046]
[Table 3]
|
|
Example |
Comparative Example |
|
|
5 |
6 |
7 |
2 |
additive composition [%] |
Ferrocene |
3.5 |
5.0 |
4.0 |
2.5 |
Lecithin (Liquid) |
5 |
20 |
50 |
--- |
Water |
--- |
--- |
--- |
--- |
Grade A Heavy Oil |
92 |
75 |
46 |
97.5 |
Total |
100 |
100 |
100 |
100 |
solubility rate |
180 |
370 |
290 |
580 |
dissolved concentration |
4.8 |
3.5 |
4.1 |
2.5 |
stability test |
very good |
good |
good |
passed |
Lecithin(Solid) means a powdered lecithin in the solid state, lecithin (liquid) means
a lecithin in the liquid state. Stability test:
"very good" mesns complete dissolution,
"good" mesns almost dissolution,
"passed" mesns a little insoluble matter was observed,
"no good" mesns too much insoluble matter was observed. |
Results
[0047] The rate of solution of solid fuel additives of the present invention (Example 1
4) until ferrocene concentration reaches 3% is very fast as compared with comparative
example 1. The concentration of a stable solution of comparative example 1 is 3% but
with many insoluble matters, while the concentration of a stable solution of example
1-4 is allowed to be 3.5 to 5.0%. In addition, the evaluations of stability after
storing for one week of Example 1 - 4 are "very good" or "good". Thus, it was confirmed
that a solid fuel additive of this invention was very excellent in all aspects of
solution rate of ferrocene, dissolved concentration and stability evaluation.
[0048] At the time of preparation of fuel additive, the rate of solution of liquid fuel
additives of the present invention (Example 5 - 7) until ferrocene is completely dissolved
in grade A heavy oil is very fast as compared with comparative example 2. In addition,
the evaluations of stability after storing for one week are "very good" or "good".
Thus, it was confirmed that a liquid fuel additive of this invention was very excellent
in all aspects of solution rate of ferrocene, dissolved concentration and stability
evaluation.
[Dispersing effect of sludge]
[0049] Sludge dispersion tests of examples and comparative examples described in Table 2
and Table 3 were done.
[0050] The tests were applied to The Japanese Shipowners' Association method.
Operating procedure
[0051]
- (1) Into a test tube, 0.1g of grade C heavy oil was taken, and 20 ml of normal heptane
was added to this test tube. In addition, 0.02m1 (1/1000) of fuel additive of Examples
1-7 or comparative examples 1-2 was added.
- (2) The test tube was sealed and strongly shaken 20 times or more until thoroughly
mixed.
- (3) The test tube was settled at room temperature and the dispersion state of every
elapsed time was evaluated by the following standard.
Evaluation standard
[0052]
A ... Complete dispersion and no precipitation
B ...Dispersion and precipitation
It is referred to as B1, B2 and B3 in order of increasing amount of precipitation.
C ...No dispersion and precipitated almost
The results are shown in Table 4.
[0053]
[Table 4]
|
soon after mixed |
8 hours after |
24 hours after |
48 hours after |
|
1 |
A |
A |
A |
A∼B1 |
Example |
2 |
A |
A∼B1 |
B1∼B2 |
B2 |
|
3 |
A |
A |
A∼B1 |
B1 |
4 |
A |
A |
A |
A∼B1 |
5 |
A |
A |
A∼B1 |
B1 |
6 |
A |
A |
A |
A∼B1 |
7 |
A |
A |
A |
A∼B1 |
Comparative Example |
1 |
A |
C |
C |
C |
2 |
A |
C |
C |
C |
Additive-free |
A |
C |
C |
C |
Properties of Grade C heavy oil applied to the evaluation
Density(15°C):0. 955
Viscosity(50°C) : 358cst
Sulfer content (%): 3. 07
Carbon Residue content(%): 11. 6
Asphaltene(%) : 6. 94 |
Results
[0054] A solid fuel additive of this invention (Examples 1-4) and a liquid fuel additive
of this invention (Examples 5-7) have a very excellent effect of sludge dispersion
as compared with comparative example 1, 2 and additive-free. Comparative examples
1 and 2, which do not contain lecithin, had no effect at all and were the same as
additive-free grade C heavy oil. An effect of lecithin was the result of being proportional
to an additive amount in general.
[Measurement of combustion rate]
[0055] When 10 mg of fuel oil (grade C heavy oil, the same oil as used for effect evaluation
of the above-mentioned sludge dispersion), to which was added liquid fuel additive
(examples 5-7) of this invention or liquid fuel additive of the comparative example
2, was heated to 500 degree C with a rate of temperature rise of 100 degree C/min.)
and combusted(m1 represents mass of an end point of carbon residue generation), and
kept at 500 degree C by using Differential thermal analysis system TG/DTA6300 (made
by Seiko Instruments Inc.), TG (thermogravimetric analysis) carbon residue combustion
rate constant was computed from the mass reduction curve of generated carbon residue
(m2 represents mass of 95% burned point). The quantity of airflow was 100ml/min. Following
formula (I) was used for the calculating method. * 1, *2
A: constant
T: temperature
m1: mass of an end point of carbon residue generation
m2: mass of 95% burned point
tau: (m2-m1) time
*1 Shibayama et al., the Japan Society of Mechanical Engineers collected papers, 34 (260),
769 (1968)
*2 Hou et al., the Japan Society of Mechanical Engineers collected papers, 54 (507) 3301
(1988)
[0056] The test results are shown in Table 5.
[0057]
[Table 5]
|
additive amount |
TG carbon residue combustion rate constant |
relative rate constant |
|
5 |
500 ppm |
16.21 |
1.030 |
Example |
6 |
500 ppm |
16.26 |
1.033 |
|
7 |
500 ppm |
16.51 |
1.048 |
5 |
1000 ppm |
19.20 |
1.220 |
6 |
1000 ppm |
19.76 |
1.255 |
7 |
1000 ppm |
19.55 |
1.242 |
|
|
|
|
Comparative Example |
2 |
1000 ppm |
15.74 |
1 |
2 |
2000 ppm |
18.27 |
1.161 |
|
|
|
|
|
|
|
|
relative rate constant = relative constant that assumed "1,000ppm of comparison example
2" to be 1 |
Results
[0058] As compared with 1000ppm addition of comparative example 2, as for 1000ppm addition
of liquid fuel additive of this invention (examples 5-7), high TG carbon residue combustion
rate constant (relative velocity constant) was obtained. Since the content of ferrocene
was high level, it was a foregone conclusion. However, also as for 500ppm addition
of Examples 5-7, TG carbon residue combustion rate constant (relative velocity constant)
was higher than that of 1000ppm addition of the comparative example 2. In addition,
as for 1000ppm addition of Examples 5-7, TG carbon residue combustion rate constant
(relative velocity constant) was higher than that of 2000ppm addition of the comparative
example 2.
[0059] This can be imagined to be a synergistic effect between solubility enhancement and
sludge dispersion of lecithin on ferrocene. As for the comparative example 2 that
does not contain lecithin, it is considered that solubility is insufficient also in
fuel oil because ferrocene is unstable in liquid additive. Additionally, it is considered
that the effect was inferior to example 5-7 since there is not a sludge decentralization
effect either when a relative content of ferrocenes was the same.
[A system examination by a diesel engine]
[0060] The system examination of a cargo boat with a diesel engine of the following specification
was done, by using solid fuel additive of this invention (example 3) and solid fuel
additive of comparative example 1.
[0061] The system examination was done, namely, in a solution tank with an agitator, 9.0Kg
of solid fuel additive was dissolved in 360 liters of grade A heavy oil, and was added
of 1/1000 into the fuel (grade C heavy oil) line from this solution tank with injection
pump. (The additive amount of fuel additive was 25ppm.)
[0062] A solid fuel additive of Example 3 or comparative example 1 was added by the above-mentioned
method over four months alternately per one month (30 days) (one month x 2 times for
each solid fuel additive). Then, a fuel consumption and condition of dirt of a heat
exchanger by visual observation was compared. Next, water-wash was performed and dirt
removal performance was compared.
Specification of a cargo boat
[0063]
Gross tonnage: 160,000 t
Deadweight tonnage: 300,500 t
Continuous maximum power: 21,300 kW x 74 rpm
Number of cylinders: ten pieces
Revolutions of a turbosupercharger: 10,000 rpm
Fuel consumption: 90,000 L/day (additive-free)
Test results are shown in Table 6.
[0064]
[Table 6]
|
Example 3 |
Comparative Example 1 |
fuel consumption |
first |
2.597 KL |
2,660 KL |
second |
2,566 KL |
2,647 KL |
dirt of a heat exchange mechanism |
first |
Very little deposit adhered to the surface, |
A deposit almost adhered to the entire surface thinly. |
second |
same as above |
same as above |
removability of dirt of a heat exchange mechanism by flushing with water |
first |
removed by easy rinsing with water |
A lot of time of washing with water was needed until removed. |
second |
same as above |
same as above |
General Properties of a fuel oil (Grade C heavy oil)
Density(15°C) : 0. 984
Viscosity(50°C) :401 cst
Sulfer content(%);3. 61
Carbon Residue contient(%) : 13. 4
Asphaltene(%):8, 98 |
[0065] Since it was an examination with real ship, fuel consumption was influenced by a
wind, flow of tide, difference of output and the like, however, since the results
of two examinations became comparable, the evaluation can be judged to be credible.
As for a solid fuel additive of this invention (Example 3), although the additive
amount of ferrocene itself was more slightly fewer than comparative example 1, the
results showed that the fuel consumption was also less. This means that the combustion
efficiency was improved synthetically synergistically, because lecithin enhances solubility
of ferrocene and a stabilized fuel atomization was realized by dispersion effect of
sludge of lecithin itself. In addition, since the combustion promotion effect was
enhanced, dirt of a heat exchanger was cleaner than comparative example 1. And an
advantage such as the dirt was removed by easy rinsing with water was observed.
In the same way, when fuel additive of Example 3 was dissolved in a solution tank,
it was dissolved by prompt breakup and dispersion thoroughly in about 10 minutes just
after the addition and it was confirmed that neither a precipitation nor a float at
all were seen in the solution tank during the procedure. On the other hand, as for
a fuel additive of comparative example 1, a float was partially seen in about 30 minutes
after stirring and, as for the inside of a solution tank, a precipitate and a float
of ferrocene insoluble were seen also during the procedure.
INDUSTRIAL APPLICABILITY
[0066] According to this invention, by using ferrocene together with lecithin, the fuel
additive in which the ferrocene contained can be dissolved easily and stably can be
provided.