Field of the Invention
[0001] This invention relates to water-in-oil emulsion fuel oil and a production method
and system thereof, and more particularly, to a production method and system for producing
an additive solution for emulsifying fuel oil with water, and emulsified fuel oil
(water-in-oil emulsion fuel oil) using the same.
Background of the Invention
[0002] In a final stage of oil refining process, heavy oil is produced which is generally
divided into three different classes, i.e., heavy oil type A, heavy oil type B and
heavy oil type C in accordance with their viscosity. Since heavy oil generates high
calory (more than 10,000Kcal/Kg) and is relatively inexpensive and easy to handle,
it is estimated that the commercial consumption of heavy oil accounts for nearly 70%-80%
of all oil products which are used in a typical country such as Japan for facilities
in various industries including large scale heating facilities and large vessels.
[0003] When heavy oil, in particular high viscosity heavy oil such as heavy oil B and heavy
oil C, is burnt, a large volume of pollutants, such as, sulphur oxide, nitrogen oxide,
carbon monoxide, soot and dust is generated. If no effective antipollution countermeasure
is taken, these pollutants can contaminate the environment and pose a serious threat
to the ecological system.
[0004] Accordingly, the Japanese government has promulgated various standards regarding
the maximum permissible discharge levels of toxic pollutants for facilities which
burn heavy oil. The government imposes on the industries strict preventive measures
to keep the discharge level below the standard level. As a result, the industries
in which heavy oil is used as a fuel generally tend to make substantially large investments
to equip heavy oil burning facilities with highly complex and expensive antipollution
devices and facilities.
[0005] However, these antipollution devices and facilities tend to become more complex and
expensive, particularly when lower grade oil, such as heavy oil C, is used. Major
electric companies, for example, use heavy oil C because heavy oil C is relatively
inexpensive as compared with heavy oil A and B, although heavy oil C generates more
pollutants. In order to comply with the government antipollution standard and regulation,
the electric companies have to make substantial investments in antipollution facilities
or, alternatively, mix heavy oil C with heavy oil A or heavy oil B in order to reduce
emission of pollutants, resulting in a substantial increase in cost. Furthermore,
a perfect combustion of heavy oil B and heavy oil C is relatively difficult unless
they are sprayed into substantially small particles.
[0006] It is appreciated that, when heavy oil is used for the operation of, for example
a boiler, heavy oil is sprayed by a jet injector to form a jet stream of very fine
particles in order to achieve a satisfactory combustion. However, the jet stream itself
tends to disrupt the combustion of the particles of heavy oil. This will lower the
thermal efficiency of the boiler. In order to improve the thermal efficiency, the
air/oil ratio may be adjusted. However, such an adjustment of air/oil ratio tends
to enlarge the size of oil particles, and results in imperfect combustion of heavy
oil and thus higher emission of pollutants.
[0007] Waste oil may be burnt for treatment. In facilities where waste oil is generated
as a result of routine operations, such as, waste machine oil at a garage or a factory,
waste machine oil may be separated into a reusable part, a non-reusable part, water,
etc. In accordance with the Japanese government antipollution regulations, the non-reusable
oil must be completely burnt in an incinerator while controlling the emission of pollutants
below the strict discharge levels set by the government.
[0008] Water may be separated by using a waste oil purification separator tank or by natural
separation of water from oil during storage. While the separated water generally does
not appear to contain any waste oil, the water has offensive smell because it is contaminated
with the waste oil. Therefore, the separated water must be thoroughly filtered and
purified to completely remove oil content therefrom before being discharged. If this
separated water is discharged into a river or a lake without a proper filtration or
a purification treatment, the river or the lake will be contaminated. To filter and
purify the separated water, a water filtration and purification facility is required,
in addition to the waste oil treatment facilities.
Summary of the Invention
[0009] Therefore, it is an object of the present invention to provide a production system
for producing an additive for emulsifying a fuel oil with water, and emulsified fuel
oil using the same which is capable of reducing the emission of pollutants in the
combustion of heavy oil and waste oil.
[0010] It is another object of the present invention to provide a production system and
method with a relatively simple structure and process as well as low cost for producing
a fuel oil product with low emission of pollutants.
[0011] It is a further object of the present invention to provide a production system and
method for producing a heavy oil product with a higher combustion efficiency and a
lower emission of pollutants.
[0012] It is a further object of the present invention to provide a production system and
method for producing a heavy oil product with a higher combustion efficiency to substantially
reduce overall consumption of heavy oil in heating facilities and the like.
[0013] It is still a further object of the present invention to provide a production system
and method for producing an emulsified oil (water-in-oil fuel oil) product in which
disperse phases of water are substantially uniformly distributed in a dispersion medium
of oil.
[0014] The above noted objects and advantages are achieved in accordance with the production
system and method of the present invention which produces a water-in-oil emulsion
fuel in which each of the fuel particles has a core made of water encapsulated by
the dispersion medium of heavy oil.
[0015] The production system of the present invention for producing a water-in-oil emulsion
fuel includes an additive solution tank for producing an emulsifying additive solution
by mixing NaOH and CaCl
2 and water and storing the additive solution therein, a water tank for producing mixed
water by mixing the emulsifying additive solution from the additive solution tank
with water and storing the mixed water therein, a mixing tank for mixing heavy oil
and the mixed water from the water tank having the water and emulsifying additive
solution so that the water substantially uniformly distributed and suspended in the
dispersion medium of the heavy oil to produce the water-in-oil emulsion fuel, and
a storage tank for storing the water-in-oil emulsion fuel therein to provides the
emulsion fuel to a burning facility.
[0016] Consequently, it is recognized that the particles comprise cores of water encapsulated
in heavy oil, i.e., water-in-oil capsularized emulsion particle fuel. When the particles
burn, the capsule portion of oil first evaporates and burns while the heat of the
burning capsule portion of oil heats up the core of water. Before the capsule portion
completely evaporates, the water at the core explosively evaporates and ruptures the
shell of oil which sprays the oil content into much smaller particles. As a result,
a complete combustion is achieved.
[0017] Thus, the water-in-oil fuel of the present invention substantially improves the thermal
efficiency of a boiler and other burning facilities and reduces the generation of
pollutants and expenses for maintaining the facilities. Because of the substantial
reduction of the pollutants, cleaner and safer environment can be achieved. Further,
because of the high thermal efficiency of the boiler and other burning facilities,
substantial reduction of oil consumption can be achieved.
Brief Description of the Invention
[0018] Figure 1 is a microscopic photograph (170 times magnified) of a water-in-heavy oil
emulsion which is obtained by the use of an emulsifying additive solution in accordance
with one embodiment of the present invention.
[0019] Figure 2 is a microscopic photograph (250 times magnified) of a water-in-oil emulsion
which is obtained by the use of an emulsifying additive solution in accordance with
one embodiment of the present invention.
[0020] Figure 3 is a microscopic photograph (170 times magnified) of an oil-in-water emulsion
which is obtained by the use of a conventional emulsifying additive.
[0021] Figure 4 schematically shows a layout of one embodiment of an emulsified fuel storage
and supply system which supplies an emulsion fuel to a boiler facility.
[0022] Figure 5 is a schematic diagram showing an example of production system for producing
a water-in-oil emulsion fuel in accordance with the present invention.
Detailed Description of the Preferred Embodiments
[0023] In the embodiments of the present invention, an emulsifying additive solution is
first produced to emulsify oil with water to form an water-in-oil emulsion. As described
below in greater detail, the water-in-oil emulsion is essentially formed by disperse
phases of water which are generally uniformly distributed and suspended in a dispersion
medium of oil. In other words, particles of water are generally uniformly distributed
and suspended in the body of oil in the water-in-oil emulsion.
[0024] In the water-in-oil emulsion, it is observed that each of the water particles is
enclosed or encapsulated in oil, and that the water particles are separated from each
other by oil. A variety of different types of oil have been examined. It has been
recognized that an emulsifying additive in accordance with embodiments of the present
invention effectively emulsifies, for example, a heavy oil (e.g. heavy oil A, B and
C), motor oil which is used for lubrication of automobile engines, edible oil and
other machine oil.
[0025] In accordance with one embodiment of the present invention, caustic soda (NaOH),
calcium chloride (CaCl
2) and water are mixed together to form an emulsifying additive solution. It is noted
that caustic soda (NaOH) and calcium chloride (CaCl
2) may be premixed prior to mixing with water, or all of the three may be mixed together
at once. In one embodiment, substantially the same amount of caustic soda (NaOH) and
calcium chloride (CaCl
2) are mixed with water.
[0026] A variety of mixing ratios between caustic soda (NaOH) and calcium chloride (CaCl
2) and water have been examined to verify the effectiveness of the emulsifying additive
solution. Caustic soda (NaOH) and calcium chloride (CaCl
2) and water are mixed together in a weight ratio ranging between about 10:10:100 and
about 50:50:100 (e.g., 10Kg:10Kg:100Kg and 50Kg:50Kg:100Kg) to form an emulsifying
additive solution. These mixing ratios have been found to provide effective emulsifying
additive solutions.
[0027] In preferred embodiments, caustic soda (NaOH) and calcium chloride (CaCl
2) and water are mixed together in a weight ratio ranging between about 15:15:100 and
about 35:35:100 (e.g., 15Kg:15Kg:100Kg and 35Kg:35Kg:100Kg). It is recognized that
these mixing ratios provide optimum emulsifying additive solutions in view of both
the economy and efficiency. In a preferred embodiment, about 20Kg of caustic soda
(NaOH), about 20Kg of calcium chloride (CaCl
2) and 100 liter of water are thoroughly mixed at room temperature to form an emulsifying
additive solution (Additive No. 1).
[0028] Further, a mixture of about 30Kg of caustic soda (NaOH), about 30Kg of calcium chloride
(CaCl
2) and 100 liter of water, and a mixture of about 25Kg of caustic soda (NaOH) and about
25Kg of calcium chloride (CaCl
2) and 100 liter of water each provides substantially the same result in the emulsification
of a heavy oil with water as obtained by the mixing ratio of about 20Kg of caustic
soda (NaOH), about 20Kg of calcium chloride (CaCl
2) and 100 liter of water.
[0029] An emulsifying additive solution in accordance with an embodiment of the present
invention is thoroughly mixed with oil and water to form a water-in-oil emulsion in
which disperse phases of water are substantially uniformly distributed and suspended
in a dispersion medium of oil. An emulsifying additive solution can be mixed with
water and oil in a wide range of mixing ratios for effective emulsification of oil
and water. According to tests carried out by the inventor, the emulsifying additive
solution Additive No. 1 noted above efficiently emulsifies a mixture of oil and water
having a mixing ratio ranging between about 95:5 and about 30:70 (e.g., 95Kg:5Kg and
30Kg:70Kg).
[0030] In another test, heavy oil type C and water are mixed in a mixing ratio ranging between
about 70:30 and about 75:25 (e.g., 70Kg:30Kg and 75Kg:25Kg) for an optimum combustion
efficiency. In these tests, the emulsifying additive solution Additive No. 1 and mixture
of water and oil were mixed in a mixing ratio ranging from about 0.002:1 to about
0.003:1 (e.g., 0.2-0.3Kg of emulsifying additive solution: 100Kg of mixture of water
and oil). These mixing ratios resulted in good emulsification of water and oil.
[0031] In a further embodiment, the emulsifying additive solution Additive No. 1 and the
mixture of water and oil was mixed in a mixing ratio at about 0.001:1 (e.g., 0.1Kg:100Kg).
This mixing ratio generally resulted in good but minimum emulsification efficiency.
In another embodiment, the emulsifying additive solution Additive No. 1 and the mixture
of water and oil was mixed in a mixing ratio at about 0.01:1 (e.g., 1Kg:100Kg).
[0032] The above noted mixing ratio of about 0.01: 1 shows a best efficiency in reaching
an optimum level of emulsification. It is also observed that the efficiency in emulsification
does not substantially change if the amount of the emulsifying additive solution is
increased further than this mixing ratio with respect to the amount of the mixture
of water and oil. Thus, preferred embodiments have a mixing ratio between the emulsifying
additive solution Additive No. 1 and the mixture of water and oil at least 0.01:1.
[0033] In one embodiment, heavy oil type C, water and Additive No. 1 in a weight ratio of
about 50:50:0.3 (e.g., 50g:50g:0.3g) were thoroughly and vigorously mixed until the
mixture becomes an emulsion. The emulsion was stored at room temperature (about 25
degree Centigrade) for 7 days. Photographs of Figure 1 and Figure 2 were taken 7 days
after the emulsion was made. As shown in the photographs of Figures 1 and 2, particles
of water (white dots) are generally uniformly distributed and suspended in the heavy
oil C (water-in-oil emulsion).
[0034] In a test to verify the magnitude of separation between water content and oil content,
a specimen (100ml) of the emulsion was heated to 60 degree Centigrade and subjected
to a centrifugal separator for 20 minutes at a relative centrifugal force of 600,
it was observed that substantially no separation of water content from the oil content
occurred. It was further observed that, even after 40 days, the emulsion was stable,
and the water content and oil content did not separate from each other.
[0035] In another embodiment, heavy oil C, water and Additive No.1 in a weight ratio of
about 30:70:0.3 were thoroughly and vigorously mixed until the mixture becomes an
emulsion. It was also observed that substantially no separation of water content from
the oil content occurred. The emulsion at this mixing ratio has a volume resistivity
of about 4.1 x 10
9. It is observed that the volume resistivity does not change for a long time. This
also shows that the water-in-oil emulsion fuel made in accordance with embodiments
of the present invention is very stable and therefore can be stored for a long time.
As a result, the water-in-oil emulsion fuel made in accordance with embodiments of
the present invention can be used immediately after storage of the emulsion fuel for
a substantial period of time without an extra mixing operation for re-emulsification.
[0036] In contrast, when heavy oil type C, water and a conventional emulsifying agent (a
surface active agent) in a weight ratio of about 50:50:2.5 (e.g., 50g:50g:2.5g) are
mixed until the mixture becomes an emulsion, particles of heavy oil type C (circular
dots in various sizes) are suspended in water (oil-in-water emulsion), as shown in
a photograph of Fig. 3. It is observed that the oil-in-water emulsion made by the
typical conventional emulsifying agent is not stable. The oil content and the water
content of the oil-in-water emulsion generally start separating from each other in
several days after the emulsion is formed.
[0037] In the above embodiments of the present invention, caustic soda (NaOH) and calcium
chloride (CaCl
2) and water are first mixed to form an emulsifying additive solution, and the emulsifying
additive solution is added to oil and water only when an emulsion of the oil and water
is to be made. Caustic soda (NaOH) and calcium chloride (CaCl
2) may be directly added in water and oil when the water and oil are mixed. However,
it is observed that if caustic soda (NaOH) and calcium chloride (CaCl
2) are directly added in water and oil when an emulsion is made, a substantially larger
amount of both caustic soda (NaOH) and calcium chloride (CaCl
2) is required as compared with the amount of the emulsifying additive solution which
is required to achieve a similar result of emulsification.
[0038] Figure 4 schematically shows a layout of one embodiment of an emulsified fuel storage
and supply system which supplies an emulsion fuel to a boiler facility. A storage
tank 10 stores a fuel oil, such as for example, heavy oil B, C or a mixture thereof.
The fuel oil stored in the storage tank 10 is pumped out by an oil pump 12 and conveyed
to a mixer 14. At the mixer 14, the fuel oil is mixed with water supplied through
a water supply line 16 and an emulsifying additive solution supplied through an emulsifying
additive solution supply line 18.
[0039] The mixture of the fuel oil, water and emulsifying additive solution are thoroughly
mixed until the mixture becomes an emulsion. The emulsion may be conveyed to an emulsion
fuel storage tank 20 for storage or directly conveyed to a burner 22 for the operation
of a boiler 24. Since the emulsion fuel made in accordance with embodiments of the
present invention is stable, and the fuel oil content in the emulsion fuel does not
separate from the water content, the emulsion fuel can be stored in the fuel storage
tank 20 for a relatively long time.
[0040] Figure 5 is a schematic diagram showing an example of production system for producing
a water-in-oil emulsion fuel in accordance with the present invention. A solution
storage tank 31 stores an emulsifying additive solution made of, for example, caustic
soda (NaOH) and calcium chloride (CaCl
2) and water with a weight ratio ranging, for example, between about 15:15:100 and
about 35:35:100 (e.g., 15Kg:15Kg:100Kg and 35Kg:35Kg:100Kg). The solution storage
tank 31 is provided with a motor 32 to rotate mixing blades 33 and 34 in the tank
for occasionally mixing the additive solution. A level gauge 67 is provided to monitor
the surface level of the additive solution in the solution tank 31. When the surface
level is lower than the predetermined level, the level gauge 67 sends a signal to
a control panel (not shown) so that new additive solution is produced in the solution
tank 31.
[0041] The additive solution is supplied to a water tank 37 through a pump 35 and an adjustment
tank 36 to be mixed with water. The adjustment tank 36 is to adjust the volume of
additive solution to be supplied to the water tank. The water is supplied to the water
tank 37 through a water supply pipe 38. The water tank 37 includes a motor 43 to rotate
mixing blades 44 and 45 to effectively mix the additive solution with the water. The
emulsifying additive solution and the water are mixed in a mixing ratio, for example,
about 0.003:1, i.e., 0.3Kg of the emulsifying additive solution with respect to 100Kg
of the water.
[0042] A level gauge 68 is provided to monitor the surface level of the water mixed with
the emulsifying additive solution in the water tank 37. When the surface level in
the water tank 37 is lower than the predetermined level, the level gauge 68 sends
a signal to the control panel to fill the water and the additive solution in the tank
37 to produce the mixture thereof. Preferably, the water tank 37 is provided with
a steam pipe 39 to warm the water in the tank. Other means such as an electric heater
may also be used to heat the water.
[0043] The warmed water mixed with the emulsifying additive solution is supplied to a mixing
tank 51 through a pump 40 and pipe 46. A fuel oil, such as heavy oil B, heavy oil
C or a mixture thereof is supplied from a storage (not shown) to the mixing tank 51
through an oil pipe 53. The mixing tank 51 includes a motor 55 connected to mixing
blades 56 and 57 which rotate within the mixing tank, a level gauge 59 to monitor
the liquid level in the mixing tank, and a steam pipe 52 for heating the liquid in
the tank. The steam pipe 52 is useful to lower the viscosity of the liquid in the
tank 51 particularly in a cold season.
[0044] At the mixing tank 51, the fuel oil is mixed with water which includes the emulsifying
additive solution made in the water tank 37 and supplied through the water supply
pipe 46. The mixing ratio of the heavy oil type C and water is ranging between about
70:30 and about 75:25 (e.g., 70Kg:30Kg and 75Kg:25Kg) for an optimum combustion efficiency.
However, as noted above, a wide range of the mixing ratio between the heavy oil and
the water is possible such as ranging from about 95:5 to about 30:70. The level gauge
59 monitors the surface level of the water-in-oil fuel in the mixing tank 51. When
the surface level is lower than the predetermined level, the level gauge 59 sends
a signal to the control panel (not shown) to fill the water with the additive solution
and the heavy oil in the mixing tank 51 to produce additional water-in-oil fuel oil
therein.
[0045] The water-in-oil fuel produced through the foregoing system and process is supplied
to a fuel storage tank 61 through a pump 58 and a pipe 60. In the water-in-oil fuel
of the present invention, particles of water are generally uniformly distributed and
suspended in the heavy oil C. Since the water-in-oil fuel is stable and the water
content and oil content will not separate from each other after several weeks, the
storage tank 61 may store a large volume of fuel enough to be used for a relatively
long time. Preferably, a steam pipe 63 is provided to heat the fuel in the storage
tank 61 so as to prevent the fuel from increasing viscosity because of low temperature
and the like.
[0046] The water-in-oil fuel stored in the storage tank 61 is introduced to a burner of
a large scale heating facility (not shown) through a fuel pump 65 and a fuel pipe
69. A level gauge 66 may preferably be provided to monitor the surface level of the
fuel oil in the storage tank 61 to introduce the new fuel oil from the mixing tank
51 when the surface level decreases to a specified level.
[0047] The water-in-oil emulsion fuel of the present invention is produced as described
in the foregoing. Conventionally, a complete combustion of heavy oil type B and type
C is relatively difficult unless they are sprayed into particles of substantially
small diameter. Minute particles of heavy oil type C, for example, may completely
evaporate and achieves a complete combustion. In contrast, when the size of particles
of heavy oil type C is relatively large, the central portion of each particle does
not completely evaporate even though the surface portion achieves a complete evaporation.
Rather, the heat at the surface portion tends to solidify the central portion of the
particle. This will cause a higher emission of pollutants.
[0048] In the present invention, however, an emulsifying additive solution provides a water-in-oil
emulsion fuel in which disperse phases of water are distributed in a dispersion medium
of oil. When the water-in-oil emulsion fuel is sprayed into minute particles, for
example in the operation of a boiler, such particles have cores of water. In other
words, in the water-in-oil emulsion fuel of the present invention, cores of water
are encapsulated in the heavy oil (encapsulated emulsion oil particles).
[0049] Therefore, when the particles burn, the capsule portion of oil first evaporates and
burns while the heat of the burning capsule portion of oil heats up the core of water.
Before the capsule portion completely evaporates, the water at the core explosively
evaporates and ruptures the shell of oil, which sprays the oil content into much smaller
particles. As a result, a complete combustion is achieved. Moreover, in the operation
of a boiler facility, the use of a water-in-oil emulsion fuel oil (water and heavy
oil B or C) reduces air requirement for a complete combustion, improves the thermal
efficiency of the boiler facility and reduces the generation and deposit of carbon
and ash on the boiler interior walls. The water-in-oil emulsion fuel oil of the present
invention also contributes to substantially reduce the oil consumption in such burning
facilities because of the improvement in the thermal efficiency.
[0050] The presently disclosed embodiments are to be considered in all respects as illustrative
and not restrictive. The scope of the invention being indicated by the appended claims,
rather than the foregoing description, and all changes which come within the meaning
and range of equivalency of the claims are, therefore, intended to be embraced therein.
1. A system for producing a water-in-oil emulsion fuel, comprising:
an additive solution tank for producing an emulsifying additive solution by mixing
NaOH and CaCl2 and water and storing the additive solution therein;
a mixing tank for mixing heavy oil, water and said emulsifying additive solution from
said additive solution tank so that said water substantially uniformly distributed
and suspended in the dispersion medium of said heavy oil to produce said water-in-oil
emulsion fuel; and
a storage tank for storing said water-in-oil emulsion fuel therein to provides said
emulsion fuel to a burning facility.
2. A system for producing a water-in-oil emulsion fuel as defined in claim 1, wherein
said mixing tank is comprised of a first mixing tank for producing mixed water by
mixing said emulsifying additive solution from said additive solution tank with water
and storing said mixed water therein, and a second mixing tank for mixing heavy oil
and said mixed water from said first mixing tank having said water and emulsifying
additive solution to produce said water-in-oil emulsion fuel.
3. A system for producing a water-in-oil emulsion fuel as defined in claim 1, wherein
said NaOH; CaCl2 and water are mixed in a weight ratio ranging from about 10:10:100 to about 50:50:100.
4. A system for producing a water-in-oil emulsion fuel as defined in claim 1, wherein
said NaOH; CaCl2 and water are mixed in a weight ratio ranging from about 15:15:100 to about 35:35:100.
5. A system for producing a water-in-oil emulsion fuel as defined in claim 1, wherein
said heavy oil includes heavy oil type A, heavy oil type B and heavy oil type C.
6. A system for producing a water-in-oil emulsion fuel as defined in claim 1, wherein
said water and said heavy oil are mixed in said mixing tank in a weight ratio from
about 95:5 to about 30:70.
7. A system for producing a water-in-oil emulsion fuel as defined in claim 1, wherein
said water and said heavy oil are mixed in said mixing tank in a weight ratio from
about 70:30 to about 75:25.
8. A system for producing a water-in-oil emulsion fuel as defined in claim 1, wherein
said water-in-oil emulsion fuel oil in said storage tank has a mixing ratio between
a sum of said water and heavy oil and said emulsifying additive solution from about
1:0.01 to about 1:0.001 in a weight ratio.
9. A method of making a water-in-oil emulsion fuel, comprising the following steps of:
mixing NaOH; CaCl2 and water to form an emulsifying additive solution in a weight ratio ranging from
about 10:10:100 to about 50:50:100;
adding said emulsifying additive solution to a mixture of heavy oil and water wherein
said mixture contains heavy oil and water in a weight ratio from about 95:5 to about
30:70; and
mixing said emulsifying additive solution and said mixture of heavy oil and water
wherein said mixture of heavy oil and water and said emulsifying additive are mixed
in a weight ratio from about 1:0.01 to about 1:0.001.
10. A method of making a water-in-oil emulsion fuel as defined in Claim 9, further comprising
a step of heating the mixture of said heavy oil, said water and said emulsifying additive
solution to maintain a low degree of viscosity of said mixture.