TWI427141B - Milky fuel and its manufacturing method - Google Patents

Description

Milky fuel and method of manufacturing same

The present invention relates to a milky fuel such as diesel oil, kerosene, animal and vegetable oil, or the like which does not contain residual oil, and water, and a method for producing the same.

In addition to the amount of fuel used, the amount of fuel used can be reduced by adding water to the fossil fuel, and the amount of coal ash and nitrogen oxides can be reduced, and some of them have been put into practical use in various countries around the world. Stage.

However, since the affinity between water and oil is low, it is necessary to use an emulsifier in order to stabilize the emulsified state of the emulsion fuel. In addition, refined oils such as diesel oil and kerosene having more refined hydrocarbons have lower affinity with water. Therefore, the higher the fine system, the emulsification of the oil requires a large amount of emulsifier, for example, in a diesel or kerosene-based emulsion fuel, 5 to 20% by weight of an emulsifier is used.

Emulsifiers are generally quite expensive compared to fuels, and the large use of emulsifiers reduces the cost-effectiveness of emulsification, making it a hindrance to the expansion of the use of diesel and kerosene-based emulsion fuels.

Lubrizol 10002 (manufactured by Lubrizol Co., Ltd.) is known as the most excellent emulsifier in terms of the amount of demand and stability. The lubrizol 10002 can impart emulsifying stability to the diesel and kerosene-based emulsification in an amount of only 3% by weight, and is the most widely used emulsifier in the range known to the inventors. However, even when lubrizol 10002 is used, it is impossible to maintain the emulsified state. The emulsified layer will be separated into a layer with a large amount of moisture and a small layer after a certain period of emulsification, and it must be lighted every few days to several weeks. Stir.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-023726

As described above, it has been practical to stabilize the emulsified state with a 3% by weight emulsifier to a practical degree of diesel or kerosene-based emulsion fuel.

However, the price of the emulsifier is very high, such as 5 to 10 times that of diesel or kerosene. Therefore, even if it is 3% by weight, the influence on the cost of the emulsion fuel is not small.

Therefore, in order to expand the use of the emulsion fuel such as diesel or kerosene, it is necessary to greatly reduce the amount of the emulsifier used.

The present invention has been made in view of the above circumstances, and is intended to achieve the object of any one or more of the following.

That is, the object of the present invention is to provide a milky fuel having a good emulsified state and a method for producing the same.

Another object of the present invention is to provide a low cost emulsion fuel and a method of manufacturing the same.

Still another object of the present invention is to provide an emulsion fuel which reduces the amount of emulsifier used and a method of producing the same.

Still another object of the present invention is to provide a separated emulsion fuel which can prevent or at least suppress an emulsion layer having a large moisture content, and a method for producing the same.

The present invention relates to a milk-like fuel comprising: an oil containing no residual oil, a heavy oil or a mixture thereof and water, and containing the above-mentioned oil containing no residual oil, the above-mentioned A heavy oil and the total content of the above water 0.001~ 3 wt% of C heavy oil (Patent No. 1 of the patent application); or a milky fuel comprising: a milky fuel containing no residual oil and water, characterized in that it contains the above oil containing no residual oil C heavy oil with a total content of the above water of 0.001 to 3% by weight (application patent item 2).

The present invention is based on the addition of a small amount of C heavy oil to an emulsion fuel containing oil containing no residual oil, A heavy oil or a mixture thereof and water (hereinafter, for the sake of simplicity, simply referred to as "water/oil emulsion fuel") The discovery that the emulsified state can be stabilized.

In the present invention, it is not clear what mechanism is used to achieve the above effects.

However, in the present invention, compared with any kind of emulsifier (surfactant), a very significant emulsion stabilization effect can be achieved only by adding a small amount of C heavy oil, so it is presumed to be different from the emulsifier or interfacial activity. The mechanism of the agent is at work.

When the water/oil emulsion fuel in which the emulsified state is not completely stabilized, the emulsified state changes or deteriorates in various forms depending on the type and content of the oil and the emulsifier. For example, when the emulsion layer is destroyed and separated into two layers of the water layer and the oil layer, if the emulsion layer remains a certain amount and the water layer or the oil layer or both of them are separated by the emulsion layer, the emulsion layer is separated into a layer having a large moisture content and a small amount. The situation of the layer.

Among these, as the quality of the fuel, it is particularly important to suppress the separation of the aqueous layer or the emulsified layer having a large water content, which may cause ignition failure or engine stop. On the other hand, if only the oil layer is separated, the amount of oil to be separated is not less than a certain value, and it is considered that there is a case where there is no serious adverse effect on the quality of the fuel product.

In the water/oil emulsification, the C heavy oil is added, and for various types of oils containing no residual oil and A heavy oil, there is an effect of suppressing the change or deterioration of the emulsified state of many of the above-described aspects, but according to the study of the present inventors It has been confirmed that the effect of suppressing the separation of the aqueous layer or the separation of the emulsified layer having a large moisture content is high.

The present invention achieves the excellent emulsion stabilization effect as described above, and further, the C heavy oil used in the present invention can be said to provide a low price because it is less expensive than the oil containing no residual oil and A heavy oil. And high quality water/oil emulsion fuels.

The content of the C heavy oil in the present invention is 0.001 to 3% by weight based on the total content of the oil containing no residual oil, A heavy oil and water.

In the present invention, the effect of remarkably stabilizing the emulsified state can be exhibited by the addition of a very small amount of C heavy oil, and even if it is excessively added to a certain extent, it is not particularly fatal.

However, when the amount of C heavy oil added is increased, the amount of oil separated from the oil layer is increased. Further, when the amount of C heavy oil added is increased, the combustion characteristics of the oil containing no residual oil may be changed, or the specification may be differentiated. Will change. Furthermore, depending on the situation, only the upper limit value is set, and when the range of the lower limit value is not set, it may be considered that the invention is not clear.

The content range (0.001 to 3% by weight) of the C heavy oil of the present invention is determined in consideration of the above, and the upper limit and the lower limit are not critical. The preferred lower limit of the content of the C heavy oil of the present invention is 0.01% by weight, and the lower limit is preferably 0.05% by weight. The preferred upper limit of the content of the C heavy oil of the present invention is 2% by weight, the upper limit is preferably 1% by weight, and the upper limit is preferably 0.6% by weight.

The term "oil" as used in this case refers to a flammable substance which can be separated from water by plants, minerals and the like. In this case, "crude oil" means unrefined petroleum. The "residual oil" in this case is the residual oil of distilled crude oil, including atmospheric distillation residue and vacuum distillation residual oil.

In this case, the "C heavy oil" is a residual oil or a residual oil as a main component, at 50. An oil product having a moving viscosity of 50 cSt (mm ² /s) or more and a specific gravity of 0.87 or more. The "C heavy oil" in this case contains oil that satisfies the three regulations of JIS K 2205 1991.

The "oil without oil" in this case means an oil that does not substantially contain residual oil. The residual oil content of the "residual oil-free oil" in the present invention is, for example, 0.1% by weight or less, or 0.01% by weight or less, or 0.001% by weight or less. The "residual oil-free oil" in this case contains petroleum oil such as diesel oil, kerosene or gasoline which is refined by removing crude oil from the crude oil, or does not contain crude oil as a raw material, so it is substantially free from the beginning. Oil and animal oil, non-petroleum oil such as biodiesel fuel. According to the emulsion stabilizing effect of the present invention, it has been experimentally confirmed that the oil containing no residual oil is particularly remarkable.

In the present case, "A heavy oil" means the oil of the first type of specification of JIS K 2205 1991. The correct composition of the A heavy oil was not known to the inventors at the time of the application, and the applicant is not sure whether the "A heavy oil" is included in the "oil without oil". In summary, however, in the emulsion stabilizing effect according to the present invention, it has been confirmed experimentally that A heavy oil is also exhibited.

The "water" in this case includes tap water, distilled water, purified water, ion-exchanged water, alkaline water, acidic water, pure water, ultrapure water, and the like.

In the "milk fuel", the W/O in which the water droplets are dispersed in the continuous layer of the oil and the O/W type in which the oil droplets are dispersed in the continuous layer of the water, etc., the "emulsification" in the present case includes all types of emulsions including the above. fuel. According to the state or period of storage of the "milk fuel", some of the emulsified state is eliminated, or the water layer is separated from the oil layer. However, even if it has a separate water layer and oil layer, it contains 0.001 to 3% by weight of C heavy oil and contains residual emulsified state as long as it contains oil containing no residual oil, heavy oil or a mixture thereof and water. The invention "milk fuel".

The weight ratio of the total content of the oil-free oil and the heavy oil of the emulsion fuel of the present invention to the water content is preferably 95:5 to 60:40, more preferably 90:10 to 70:30. It is especially good at 95:15~75:25.

The emulsion fuel of the present invention may contain other components in addition to the oil containing no residual oil, A heavy oil, water, and C heavy oil. It may contain an emulsifier, a surfactant, a dispersant, a rust preventive, an antioxidant, an antifoaming agent, a fragrance, a coloring material, etc., and may contain a certain purpose, and may contain impurities or unavoidable components. Intent to contain.

In the present invention, it is preferred to further contain an emulsifier (claim 4).

According to the invention, a milky fuel having a more stable and emulsified state can be obtained.

Generally, an "an emulsifier" is known as an anionic emulsifier, a cationic emulsifier, a nonionic emulsifier, and a zwitterionic emulsifier. The "emulsifier" in the present invention includes all of these. Emulsifiers, also known as surfactants, can be given any name. The emulsifier of the present invention can be used particularly preferably, and a nonionic surfactant can be mentioned.

In the present invention, an emulsifier having an HLB value of 2 to 15 as determined by the following formula (1) is preferably used.

HLB=(ΣInorganic value/ΣOrganic value)×10 (1)

The HLB value shown in the above formula (1) is calculated by Oda's HLB method, which is widely known to the practitioner (Oda Era, "Synthesis and Application of Surfactant", 槇书局 (1964)) . Here, the above-mentioned "inorganic value" and "organic value" of each substituent in the reactive nonionic surfactant are based on the value of the organic concept map promoted by Fujita as shown in Table 1 below. Good Health: "Organic Concept Map - Foundation and Application -", San Gong Publishing (1985), Guibo 2: Oil Chemistry 36 (12), 961 (1987)), HLB calculated by Oda by the above formula (1) value.

In the present invention, by containing C heavy oil, the emulsion stabilization effect can be greatly increased for a wide variety of emulsifiers and various oils containing no residual oil and A heavy oil. Therefore, in the present invention, the necessary content of the emulsifier required for the emulsification of the water/residual oil-free oil can be greatly reduced. In order to reduce the cost of the emulsion fuel, the content of the emulsifier is preferably as small as possible, so that the preferred content of the emulsifier of the present invention is less than 3% by weight based on the total content of the oil containing no residual oil, A heavy oil and water. Further, it is preferably less than 2% by weight, particularly preferably less than 1% by weight, and most preferably less than 0.5% by weight.

The present invention relates to a method for producing a milk-like fuel, which comprises producing an oil containing no residual oil, a heavy oil or a mixture thereof, and water, and containing the above-mentioned oil containing no residual oil and the total content of the above-mentioned A heavy oil and the above water 0.001~ a milky fuel of 3% by weight of C heavy oil, characterized in that the pressurizing means is pressurized by a pressurizing means having a pressurized liquid and a flow path through which the liquid pressurized by the pressurizing means passes The liquid is emulsified by the above-mentioned light oil, water and C heavy oil in a high-pressure stirring device which is stirred while passing through the above-mentioned flow path (Patent No. 7 of the patent application).

According to the invention, the emulsified state of the emulsion fuel can be made more stable by stirring using a high-pressure stirring device.

The "high-pressure stirring device" in the present invention is a pressurizing means having a pressurized liquid, and a flow path through which the liquid pressurized by the pressurizing means passes, and the liquid pressurized by the pressurizing means passes through the flow path. Stirred stirring device. The pressurization by the pressurizing means of the present invention is preferably 20 MPa or more, more preferably 30 MPa or more, further preferably 50 MPa or more, and particularly preferably 80 MPa or more. The flow rate of the liquid pressurized by the pressurizing means of the present invention in the flow path is preferably 30 m/sec or more, more preferably 50 m/sec or more, and particularly preferably 100 m/sec or more.

The "high-pressure stirring device" of the present invention comprises a nano high-pressure homogenizer device and a homogenizer device as defined below.

The cross-sectional area S of the flow path of the "Nano High Pressure Homogenizer" is 1 mm ² or less, and the aspect ratio R (the value obtained by dividing the flow path sectional area S by the flow path length L) is 10 mm ^-1 or more. The nano high-pressure homogenizing device agitates the liquid by the cavitation effect and shear force generated when the liquid passes through the flow path, and/or refines and/or highly disperses the particles (droplets) in the liquid. The flow path of the nano high-pressure homogenizer can be linear or curved, bent or branched.

The cross-sectional area S of the flow path and the aspect ratio R are preferably S≦1 mm ² and R≧10 mm ^{-1 , more} preferably S≦0.5 mm ² and R≧50 mm ⁻¹ , and S≦0.1 mm ² , R≧. 100mm ^{-1 is} especially good. The flow path length L is preferably 2 mm or more, and particularly preferably 3 mm or more.

Furthermore, the cross-sectional area S of the flow path does not have to be uniform across the entire length. In this case, the average cross-sectional area (the integrated value of the cross-sectional area in the longitudinal direction is divided by the L quotient) is compared with AS, and the aspect ratio R is = L / AS, preferably AS ≦ 1 mm ² , R ≧ 10 mm ^{-1 , more} preferably AS ≦ 0.5 mm ² , R ≧ 50 mm ^{-1 , and particularly} preferably AS ≦ 0.1 mm ² and R ≧ 100 mm ^-1 . The flow path can be bent, bent or branched.

Fig. 1(A) is an explanatory view showing the configuration of an exemplary nano high-pressure homogenizing device 1.

The nano high-pressure homogenizing device 1 has a metal outer casing 2; a generator 3 that maintains a stirring effect; the retainer 4 held by left and right squeezing pressures by a lock screw or the like; and a coupler 5 connected to an external pipe; 6; and the inflow path 7 and the outflow path 8 connecting the holding mass 4 and the couplers 5, 6.

The coupler 5 on the inlet side of the above-described nano high-pressure homogenizing device 1 has a pipe 10 connected to a container 9 for storing a liquid to be treated (a liquid containing oil containing no residual oil, water, and C heavy oil, etc.), and is supplied with a high-pressure pump 11 The pressed liquid is sent to the nano high-pressure homogenizing device 1, and the piping 12 is connected to the outlet-side coupler 6, and the liquid stirred by the generator 3 is stored in the container 13. Further, the container 9 is agitator 14 which is required to have a mixed state of the liquid to be treated.

Fig. 1(B) is an explanatory view showing a generator 3a of a simple configuration using the nano high-pressure homogenizing device 1.

In the generator 3a, a linear flow path (thin tube) 30a having a flow path sectional area Sa and a flow path length La is formed in the vicinity of the center. The cross-sectional shape of the flow path 30a may be any of a circular shape, an elliptical shape, a polygonal shape, or the like.

The nano high-pressure homogenizing device 1 having such a linear flow path 30a can be subjected to a cavitation effect generated between a liquid and a flow path wall, and a shear force generated by a flow velocity difference between the distances of the flow path walls, and the like. The liquid passing through the flow path 30a is stirred and/or the particles (droplets) in the liquid are refined and/or highly dispersed.

The "homogeneizer apparatus" speeds up the liquid by dispersing the liquid of the dispersed particles through the flow path, and stirs the liquid by moving the liquid at high speed and/or against the wall surface, and/or the particles in the liquid (liquid Dropping device for miniaturization and/or high dispersion.

Fig. 2(A) is an explanatory view showing the configuration of the exemplified homogenizer device 20 (manufactured by Yoshida Machinery Co., Ltd.), and Fig. 2(B) is an enlarged view showing the structure around the valve 24.

As shown in the figure, the homogenizer device 20 includes: a homogenizing valve 21 of the main body; and a high pressure pump 22, which is a liquid to be treated (including oil containing no residual oil, water, and liquid of C heavy oil, etc.) The supply valve 21 is boosted.

The homogenizing valve 21 has a valve seat 23 formed with a pipe 23a for receiving a liquid supply from the high pressure pump 22, and a valve 24 abutting against the valve seat 23 at a position of the opening 23b of the plug pipe 23a; The opening 23b and the collision ring 25 of the valve 24; the screw 26, the spring 27, and the plunger 28 that urge the valve 24 to the valve seat 23.

In the homogenizer device 20, a small gap (flow path) is formed between the valve seat 23 and the valve 24 by the liquid pressure of the pipe 23a and the urging force applied to the valve 24 by the lock screw of the screw 26. . The liquid from the opening 23b, after hitting the valve 24, is diffused to the outside in the radial direction at the high-speed jet 29, and hits the wall 25b in the collision ring 25.

In the homogenizer apparatus 20, the liquid collides with the valve 24 and the collision ring 25, the liquid is stirred when passing through the minute gap 29, and/or the particles (droplets) in the liquid are refined and/or highly dispersed. The treated liquid is discharged from the discharge port 25a formed in the collision ring 25.

The stirring conditions (the conditions for miniaturization and/or high dispersion) of the homogenizer device 20 can be adjusted by the pressure of the high pressure pump 22 and the lock condition of the screw 27.

The present invention relates to a method for producing a milk-like fuel, which comprises producing an oil containing no residual oil, a heavy oil or a mixture thereof, and water, and containing the above-mentioned oil containing no residual oil and 0.001 of the total content of the above-mentioned A heavy oil and the above water. ~3 wt% of C heavy oil emulsion fuel, characterized by comprising: a first step of mixing oil containing no residual oil, A heavy oil or a mixture thereof and C heavy oil; adding water stirring to the above mixed liquid in the first step The second step (application patent scope item 8).

According to the invention, by mixing (dissolving) the C heavy oil with the oil containing no residual oil and emulsifying with water, the deviation of the C heavy oil component can be reduced, and a more stable emulsified state can be obtained. Further, in the emulsion fuel containing an emulsifier, it is preferred to mix the oil containing no residual oil, the C heavy oil and the emulsifier in the first step.

Fig. 3 is an explanatory view showing the configuration of the collision type generator 3b installed in the nano high-pressure homogenizing device 1 in the following experiment.

As shown in FIG. 3(A), the generator 3b includes a first flow path element 34, two second flow path elements 35 and 36, and a third flow path element 37.

The first to third flow path members 34 to 37 are formed of sintered diamond-made substrates S1 to S4 having a substantially square shape in plan view, and metal ring members R1 to R4 integrally embedded on the outer periphery thereof.

The substrate S1 of the first flow path element 34 has two through holes 34a and 34b having a predetermined radius r1 at a predetermined distance D1 from each other, and the substrates S2 and S3 of the second flow path elements 35 and 36 have a wide size. The long holes 35a and 36a having the same length as r1 and having the same length D2 and D1; and the substrate S4 of the third flow path member 37 having a radius r2 of about 3 times r1 at a position at the same distance from D1. The holes 37a and 37b are formed in the metal ring members R1 to R4 of the first to third flow path members 34 to 36 at four equal intervals in the circumferential direction.

Fig. 3(B) shows a generator 3b formed by combining the first to third flow path elements 34 to 37 in a cross-sectional view. As shown in the figure, the through holes 34a and 34b communicate with the both ends of the long hole 35a, and the long hole 35a and the long hole 36a communicate with each other at the intersection position, so that both ends of the long hole 36a communicate with the through holes 37a and 37b, respectively. The first to third flow path elements 34 to 37 are stacked in a state in which the insertion tips inserted into the insertion hole insertion holes P are positioned to each other.

In the generator 3b, four flow paths (thin tubes) 30b are formed, that is, (1) a flow path 30b that enters through the through holes 34a and passes through the long holes 35a and 36a, and is separated from the through holes 37a; (2) The flow path 30b which enters through the through hole 34, passes through the long holes 35a and 36a, the path which is separated by the through hole 37b, (3) enters through the through hole 34b, and flows through the long hole 35a and 36a, and is separated from the through hole 37a. The path 30b, (4) enters through the through hole 34b, and passes through the long hole 35a and 36a, and the flow path 30b which is separated from the through hole 37b.

In the generator 3b, when the liquid passes through the through holes 34a, 34b, 37a, 37b and the long holes 35a, 36a, the particles in the liquid are refined by the same cavitation effect and shear force as the generator 3a. Or highly decentralized. Further, when the liquid of the through holes 34a and 34b collides with the surface of the flow path member 36, or the impact force when the liquid collides with each other at the position where the long holes 35a and 36a intersect each other, the particles in the liquid can be made fine and/or high. Decentralized.

The flow path sectional area Sb and the flow path length Lb of the flow path 30b of the generator 3b may be thicker than the first to third flow path elements 34 to 37, and the diameters r1 and r2 of the through holes 34a, 34b, 37a, 37b. The width W and the lengths D1 and D2 of the long holes 35a and 36a are set. In the following experiments, in any one of the four first flow path 30b, each flow path cross-sectional area Sb of 0.0113 ~ 0.0136mm ² (inner diameter 0.12 ~ 0.13mmψ), the flow path length Lb of 3.8mm, an aspect ratio R = 27.9 ~33.6mm ^-1 generator 3b.

Example

The following materials and machines were used in the following experiments.

<Use materials>

1. Oil without residual oil

‧ Diesel: Synergy Diesel from Dongfang General Petroleum Co., Ltd.

‧ Kerosene: ENEOS kerosene made by New Japan Petroleum Co., Ltd.

‧ Vegetable oil: Nissin oilio Co., Ltd. made salad oil

‧ Biodiesel fuel: Synthetic products from refined palm oil made by Fuji Oil Co., Ltd.

2. A heavy oil

‧ F0A01 (low sulfur A heavy oil) made by Dongfang General Petroleum Co., Ltd.

3. Water

‧ purified water produced by Wako Pure Chemical Industries Co., Ltd.

4. C heavy oil

‧ C heavy oil 1: C heavy oil (3.0LP) RV (M) made by Nippon Oil Co., Ltd.

‧ C heavy oil 2: Singapore Taiping Shipping Company made marine fuel oil MF0380cSt

5. Emulsifier

‧ Glycerol monooleate (made by Japan SURFACTANT Industrial Co., Ltd.)

‧ FE18103E (made by MIYOSHI Oil Co., Ltd.)

‧ FE18105E (made by MIYOSHI Oil Co., Ltd.)

‧ FE18108E (made by MIYOSHI Oil Co., Ltd.)

‧ M-CDE (manufactured by MIYOSHI Oil Co., Ltd. / alkyl alkanolamine)

‧ POE (20) GIIS (made by Japan EMULSION Co., Ltd. / POE (20) glyceryl stearate)

‧ POE (5) HCTIS (made by Japan EMULSION Co., Ltd. / POE (5) hydrogenated castor oil triisostearate)

‧ PCAISAPOE (30) HC (made by Nippon Emulsifier Co., Ltd. / PCA isostearic acid POE (30) hydrogenated castor oil)

‧ POE (30) HCTIS (made by Nippon Emulsifier Co., Ltd. / POE (30) hydrogenated castor oil triisostearate)

‧ POE (40) HCTIS (made by Nippon Emulsifier Co., Ltd. / POE (40) hydrogenated castor oil isostearate)

‧ Lubrizol 10002 (made by Lubrizol, USA)

<Use machine>

‧ Pipe Mixer: VTX-3500 made by LMS Co., Ltd.

‧ CLAIR MIX: CLM-0.8S manufactured by M-TECHNIQUE Co., Ltd. (Rotor: R4/SCREEN: S2.0-24)

‧ High-pressure stirring device: Nano high-pressure homogenizing device 1 (Nanomizer mark II, NM2-L200 made by Yoshida Machinery Co., Ltd., using generator 3b of Fig. 3)

‧ Laser microscope: LASERTEC Co., Ltd. OPTELICS H1200

‧ Particle distribution meter: Dynamic scattering particle distribution meter NanoS made by MALVERN, UK

[Experiment 1: Verification of the effect of C heavy oil addition]

Experiment 1 for verifying the effect of adding C heavy oil was carried out using three kinds of hetero-double-type nonionic surfactants (Surfactant) as an emulsifier. In Experiment 1, diesel oil was used as the oil containing no residual oil, and C heavy oil 1 was used as the C heavy oil. Oil without residual oil: The ratio of water (volume ratio) is 85:15.

<Experimental procedure>

‧ Procedure 1

255 mL of diesel oil was weighed in a 1000 mL beaker, and three kinds of emulsifiers (0.9 g each) and C heavy oil (0 g or 0.3 g) were added and dissolved in a glass rod. Further, a mixed liquid of the samples 1 to 6 was prepared by adding 45 mL of water to the solution. The addition amount of the C heavy oil in the samples 1 to 6, the type of the emulsifier, and the addition amount are shown in Table 2.

Further, the total weight of 255 mL of diesel oil and 45 mL of water was 257.16 g, so the content of C heavy oil in Samples 4 to 6 was 0.117% by weight (= 0.3 ÷ 257.16 × 100) of the total content of diesel oil and water.

‧ Procedure 2

The CLAIR MIX obtained in the procedure 1 was pre-stirred at 4500 rpm for 10 minutes, and then each of the samples was stirred/emulsified by repeatedly treating the pressure of the high-pressure pump 11 at a pressure of 100 MPa five times using a high-pressure stirring device.

‧ Procedure 3

Each of the emulsified samples was taken to a 50 mL graduated cylinder, and an appearance photograph was taken after being stored in an incubator at 25 ° C for 7 days.

<Experimental results>

A photograph of the appearance of the sample after 7 days from the emulsification is shown in Fig. 4. In Fig. 4, an indicator line indicating the oil layer (O), the water layer (W), the emulsion layer (E) and the boundary of each layer in each sample is attached next to each photograph. Further, when the emulsified layer (E) is separated into two layers, the emulsified layer having a small moisture content is represented by E1, and the emulsified layer having a large water content is represented by E2.

As is apparent from Fig. 4, the emulsion layer E of the sample 1 completely disappeared and separated into the oil layer O and the water layer W. Only a small amount of the emulsion layer E remained in the samples 2 and 3, and most of them were separated into the oil layer O and the water layer W.

In this case, the samples 4 to 6 of the C heavy oil were added, and the emulsified layer (E1+E2) at the time of emulsification for 7 days was remarkably increased with respect to the samples 1 to 3, and it was confirmed that the emulsified state was added by adding the C heavy oil. The effect of stabilization.

However, in the samples 4 to 6, since the water layer W was separated by the emulsification for 7 days, it was preferable to further stabilize the emulsified state.

[Experiment 2: Verification of the effects of emulsifiers and C heavy oil types]

In order to verify the effect of adding more emulsifiers to the C heavy oil, including the presence or absence of an emulsifier, Experiment 2 was conducted. In Experiment 2, in order to improve the diversity of the emulsifier to be evaluated, seven emulsifiers having greatly different organic and inorganic values were used. An organic concept diagram of various emulsifiers used in Experiment 2 plotted as organic values and inorganic values is shown in FIG. The FE18105E and FE18108E used in Experiment 1 are also shown in FIG.

Further, in Experiment 2, diesel oil was used as the oil containing no residual oil, and two types of C heavy oil 1 and C heavy oil 2 were used as the C heavy oil. Oil without residual oil: The ratio of water (volume ratio) is 80:20.

<Experimental procedure>

‧Program 1

Take 1000 mL of diesel oil in a 1000 mL beaker, and add a certain amount of emulsifier and C heavy oil respectively. Dissolved by mixing with a glass rod. Further, 17 samples of the samples shown in Table 3 were prepared by adding 40 mL of water to the solution. Table 3 shows the types of C heavy oil, emulsifier, and addition amount of each sample.

Further, since the total weight of the diesel oil 160 mL and the water 40 mL is 173.12 g, the C heavy oil content of the samples 7B to 14B and 14C to which the C heavy oil is added is 0.116% by weight of the total content of the diesel oil and the water (= 0.2 ÷ 173.12 × 100). ).

‧Program 2

Each sample of Procedure 1 was stirred/emulsified. The conditions of stirring/emulsification were about 1 minute with respect to the samples 7A and 7B, and about the other samples (samples 8A, 8B to 14A, 14B, and 14C) by CLAIR MIX, 10000 rpm × 5 minutes.

‧ Procedure 3

Each sample of the appropriate amount of procedure 2 was taken in a centrifuge tube, and the change in the emulsified state was observed by standing at room temperature. Observation was carried out by taking a sample in which the same emulsifier was added, and taking a photograph of the appearance when the emulsified state of the sample in the same group was different.

<Experimental results>

A photograph of the appearance of each sample of Experiment 2 is shown in Fig. 6. Fig. 6 also shows the interval on the organic concept map of the emulsifier added to each sample and the elapsed time from emulsification to photographing. Further, with respect to a sample in which an emulsified layer which is separated into a large amount of moisture and a small emulsified layer can be observed, an arrow is attached to the boundary thereof.

As apparent from Fig. 6, the following is known.

(1) Without an emulsifier (samples 7A, 7B), separation into an aqueous layer and an oil layer occurred immediately after emulsification. However, when Sample 7B of C heavy oil was added, although there was only a slight difference between the water layer and the oil layer, there was a residual emulsion layer. Therefore, it can be said that the stabilizing effect of the emulsified state can be produced by adding the C heavy oil even when no emulsifier is added.

(2) The results regarding the addition of the emulsifier sample are as follows.

‧ Glycerol monooleate

No C heavy oil (sample 8A): oil layer separation in the upper part

Add C heavy oil (sample 8B): no separation

‧ FE18103E

No C heavy oil (sample 9A): separated into an oil layer in the upper part, the moisture content of the emulsion layer is lower

Add C heavy oil (sample 9B): no separation

‧ POE(20)GIIS

No C heavy oil (sample 10A): oil layer separation in the upper part

Add C heavy oil (sample 10B): no separation

‧ POE(5)HCTIS

No C heavy oil (sample 11A): separated into oil layer on the upper part, water layer on the lower part

Add C heavy oil (sample 11B): no separation

‧ PCAISAPOE (30) HC

No C heavy oil (sample 12A): oil layer separation in the upper part

Add C heavy oil (sample 12B): no separation

‧ POE (40) HCTIS

No C heavy oil (sample 13A): oil layer separation in the upper part

Add C heavy oil (sample 13B): no separation

‧ POE(30)HCTIS

No C heavy oil (Sample 14A): Separated into an oil layer at the top, with a high moisture content in the lower part

Add C heavy oil (sample 14B): oil layer separated in the upper part

All of the additives studied were confirmed as described above, and the addition of C heavy oil added stabilized the emulsified state. In the emulsifier studied in Experiment 2, since the HLB value obtained by the following formula (1) is widely distributed in the range of 2 to 15, the emulsifier in which the HLB value is in this range can be said to be added by the C heavy oil. The stabilization effect of the remarkable emulsified state is high.

HLB = (Σ inorganic value / Σ organic value) × 10 (1)

Further, from the above results, it can be said that the addition of the C heavy oil has an effect of suppressing the separation of the oil layer, the separation of the water layer, and the separation of the emulsion layer having a large water content.

(3) From the comparison of the samples 14B and 14C, it was found that the difference between the types of the C heavy oil added (the C heavy oil 1 and the C heavy oil 2) was not observed.

[Experiment 3: Verification of the influence of the type of oil]

Experiment 3 was performed to verify the effect of the addition of C heavy oil on various oil types. The oil of the research object of Experiment 3 is the oil containing no residual oil (kerosene, vegetable oil, biodiesel diesel fuel) and A heavy oil.

In Experiment 3, C heavy oil 1 was used as the C heavy oil, and POE (30) HCTIS was used as the emulsifier to prepare eight kinds of samples 15A, 15B to 18A, and 18B in which 160 mL of oil and 40 mL of water were added with C heavy oil and an emulsifier. The types of oil used in each sample, the amount of C heavy oil and the amount of emulsifier added are shown in Table 4. Table 4 also shows the content ratio of C heavy oil of each sample (weight ratio of C heavy oil content to total content of oil and water).

The modulation and observation methods of each sample were the same as in Experiment 2.

<Experimental results>

A photograph of the appearance of each sample of Experiment 3 is shown in FIG. In Fig. 7, as in Fig. 6, the sample was stirred/emulsified to the elapsed time of the photographing, and a sample in which an emulsified layer having a large moisture content and a small amount of the emulsified layer were observed was attached, and an arrow was attached to the boundary.

Regarding the kerosene, vegetable oil, and biodiesel fuel (samples 15 to 17) containing no residual oil, the samples 15A to 17A in which no C heavy oil was added were separated into an oil layer and an emulsion layer having a large water content. On the other hand, in the samples 15B and 17B to which the C heavy oil was added, although the separated oil layer was observed, all of the samples 15B to 17B did not have an emulsified layer having a large separation moisture content. Therefore, regarding any of kerosene, vegetable oil, and biodiesel fuel, it can be said that the addition of C heavy oil has an effect of stabilizing the emulsified state. Further, the addition of the C heavy oil tends to suppress the separation of the emulsified layer having a large water content, and the effect of suppressing the separation of the oil layer tends to be high.

Regarding the A heavy oil (samples 18A, 18B), although oil layer separation occurred, the separation of the emulsion layer which did not produce a large amount of water was caused by stirring/emulsification for 4 days, and no emulsification due to the presence or absence of the addition of the C heavy oil was observed. The difference in stability.

[Experiment 4: Confirmation of the effect of C heavy oil addition on A heavy oil]

In Experiment 4, since the effect of the addition of the C heavy oil on the emulsion stability of the A heavy oil was not confirmed, the experiment 4 was carried out for reconfirmation.

In Experiment 4, 255 mL of A heavy oil was added, and two kinds of emulsifiers (POE (30) HCTIS, M-CDE) and C heavy oil were added and stirred. 45 mL of water was added thereto, and CLAIR MIX was pre-stirred at 4500 rpm for 10 minutes. The high-pressure stirring device (high-pressure pump 11 was repeatedly treated at a pressure of 100 MPa for 5 times) was stirred/emulsified to prepare three kinds of samples 19A to 19C having different amounts of C heavy oil added. The addition amount and content rate of the C heavy oil in the samples 19A to 19C (the weight ratio of the C heavy oil content to the total content of the oil and water) and the amount of the emulsifier added are shown in Table 5.

The prepared samples 19A to 19C were taken to a glass bottle (50 mL), and the upper layer of Fig. 8 shows a photograph of the appearance of each sample taken from the side when it was allowed to stand at room temperature for 7 days. No separation was observed in this state, and the difference between the samples could not be confirmed. However, when the bottom of the vial was observed, a small amount of separated water was generated. Therefore, the glass of each sample was left to stand at a temperature of about 30 degrees for several minutes to concentrate the separated water in one place, and an appearance photograph taken from the bottom of the glass bottle in this state is shown in the middle layer of FIG. The lower layer of Fig. 8 is a schematic view of a photograph of the middle layer, with hatched portions indicating the separation of water.

As is apparent from Fig. 8, in the samples 19A to 19C, only a slight amount of separated water was generated from the emulsification for 7 days, and the amount thereof was the order of the sample 19A>the sample 19B>the sample 19C, and it was confirmed that the higher the content of the C heavy oil, the smaller the separated water. Therefore, it can be said that the A heavy oil can also stabilize the emulsified state by adding the C heavy oil.

[Experiment 5: Effect of stirring/emulsification conditions]

Experiment 5 was carried out in order to confirm the effect of adding C heavy oil at the time of stirring/emulsification using a high-pressure stirring device. In Experiment 5, diesel, C heavy oil 1 and POE (30) HCTIS were used as the oil containing no residual oil, C heavy oil and emulsifier, and the oil containing no residual oil: the ratio of water (volume ratio) was 85:15.

<Experimental procedure>

Procedure 1

255 mL of diesel oil was weighed in a 1000 mL beaker, and an emulsifier (0 g or 0.9 g) and a C heavy oil (0.3 g) were added and dissolved in a glass rod.

‧ Procedure 2

To the solution obtained in the procedure 1, 45 mL of water was added, and pre-stirring was carried out at CLAIR MIX 4500 rpm × 10 minutes.

‧ Procedure 3

The stirring/emulsification was further treated by the high pressure stirring device by the liquid obtained in the procedure 2. The stirring conditions were repeated five times with a pressure of the high pressure pump 11 of 100 MPa.

‧ Procedure 4

The sample of 0 g of the emulsifier was 20 A, and the sample of 0.9 g of the emulsifier was 20 B, and observation/photographing was performed in the same manner as in Experiment 2.

<Experimental results>

A photograph of the appearance of the samples 20A and 20B in Experiment 5 is shown in Fig. 9 . For comparison, the photographs of the appearance of the samples 14A, 14B taken in Experiment 2 are also shown. In the same manner as in Fig. 9 and Fig. 6, the sample was stirred/emulsified to the elapsed time of the photographing, and a sample in which an emulsified layer having a large moisture content and a small amount of the emulsified layer were observed was attached, and an arrow was attached to the boundary.

In comparison with the samples 20A and 20B, in the case of using a high-pressure stirring device, it was confirmed that the emulsified state by the addition of the C heavy oil was stabilized (the separation of the emulsified layer having a large moisture content was not produced).

Further, from the comparison of the samples 14A and 20A or the comparison of the samples 14B and 20B, it is understood that when the high-pressure stirring device is used for stirring/emulsification, the separation of the oil layer can be alleviated when the CLAIR MIX is used only. Therefore, it can be said that the agitation stability can be further improved by stirring/emulsification by a high-pressure stirring device.

[Experiment 6: Verification of the effect of C heavy oil content on emulsified state]

Experiment 6 was conducted to verify the effect of changing the amount of C heavy oil added on the emulsion stability. In Experiment 6, five kinds of samples in which the amount of C heavy oil added were different were produced. The composition other than the C heavy oil is the same as the sample 20B. The preparation method of the sample was the same as that of Experiment 5. The photos were all taken after 4 days from stirring/emulsification. The content of C heavy oil in each sample is shown in Fig. 10 .

<Experimental results>

A photograph of the appearance of each sample of Experiment 6 is shown in FIG. In Fig. 10, a sample in which an emulsion layer separated into a large amount of moisture and a small emulsion layer were observed was attached with an arrow at its boundary.

From the results of Fig. 10, the following is known.

In the absence of added C heavy oil (content = 0% by weight), the separation of the emulsified layer with a large moisture content occurred 4 days after emulsification, but the content of C heavy oil was in the range of 0.05-0.6% by weight, and no moisture content was observed. Separation of the emulsion layer. As the C heavy oil content increases, the amount of oil separated from the oil layer tends to increase, but other than this, the stability of the emulsified state in the range of 0.05 to 0.6% by weight does not greatly differ. . In this way, the stabilizing effect of the emulsified state of the C heavy oil was observed in a very small amount (0.058% by weight), and it was confirmed that the effect was not significantly changed even if the content was changed to 10 times.

[Experiment 7]

In order to compare the water/diesel latex of the emulsifier lubrizol 10002 manufactured by LUBRIZOL Co., Ltd., and the emulsified state of the water/diesel latex to which C heavy oil (C heavy oil 1) was added, Experiment 7 was carried out.

‧ Procedure 1

255 mL of diesel oil was added according to Table 6 by adding C heavy oil/emulsifier. Table 6 shows the types of emulsifiers in each sample; the amount of C heavy oil and emulsifier added; and the content rate.

‧ Procedure 2

Further, 45 m of water was added to each sample of the procedure 1, and the mixture was pre-stirred under conditions of CLAIR MIX 4500 rpm × 10 minutes, and then the high-pressure pump 11 was repeatedly treated with a pressure of 100 MPa for 5 times using a high-pressure stirring device to stir/emulsifie each sample.

‧ Procedure 3

Each sample prepared in the procedure 2 was collected in a 50 mL measuring cylinder and a sample bottle, and stored in an incubator at 25 °C.

‧ Procedure 4

The sample of the graduated cylinder was photographed by emulsification for 1 day, 7 days, and 14 days. Regarding the sample of the sample bottle, the particle size measurement (average particle diameter of the droplets) was carried out using a particle distribution meter after 20 hours and 14 days from the emulsification.

<Experimental results>

The photograph of the appearance of each sample which was emulsified for 1 day, 7 days, and 14 days is shown in Fig. 11 . One day after the emulsification, only the samples LI and L2 were observed to have a separation layer at the lower portion, and 7 days after the emulsification, a separation layer was observed in the lower portion and the upper portion in the samples L1 to L3 and the sample 21, and 14 days after the emulsification, A separation layer was observed in the lower part and the upper part in all the samples. An emulsified layer in which all the separation layers have different moisture contents (the water content of the lower one becomes more). In Figure 11, an arrow is added to the boundary between the separation layers.

The thickness (height) of the upper separation layer after 7 days of emulsification and 14 days later was measured, and the results plotted for the concentration of the emulsifier are shown in Fig. 12. In addition, in this concentration, the addition amount (g) of the emulsifier is W, and the total volume (mL) of the oil and water containing no residual oil is V, and the value calculated by W ÷ V × 100.

The thickness of the upper and lower separation layers is considered to indicate the degree of progress of the collapse of the emulsified state. Therefore, the stability of the emulsified state can be evaluated to the same extent by the same thickness of the lower separation layer after the same time. From the viewpoint of the evaluation of Fig. 12 from this viewpoint, the emulsified state of the sample 21 was evaluated to have the same degree of stability as the water/diesel latex having a concentration of lubrizol 10002 of 1.35 to 2.65% (content of 1.57 to 3.09 wt%).

In addition, the separation of the emulsion layer which emphasizes a large amount of moisture has a great influence on the quality and characteristics of the fuel, and the thickness of the lower layer of the lower layer is regarded as the standard of the emulsion quality of the emulsion fuel, and the emulsification quality of the sample 21 can be evaluated as It has the same degree of emulsification quality as the water/diesel latex of lubrizol 10002 at a concentration of 2.5 to 2.65% (content of 2.92 to 3.09 wt%).

The results of plotting the particle size measurement values after emulsification for 20 hours and 14 days from the emulsifier concentration are shown in Fig. 13. The definition of the emulsifier concentration is the same as described above. In the collapse process of the emulsified state, it can be considered that the droplets in the latex are combined with each other to gradually form larger droplets. Therefore, the average particle diameter of the droplets is the same at the same time from the emulsification, and the stability of the emulsified state can be evaluated to the same extent. From the viewpoint of the evaluation of Fig. 13, the emulsified state of the sample 21 was evaluated to have the same degree of stability as the water/diesel latex having a concentration of lubrizol 10002 of 1.4 to 1.45% (content of 1.63 to 1.69 wt%).

Taking the results of Figs. 12 and 13, the sample 21 has the same degree of emulsion stability as the water/diesel latex having a lubrizol 10002 content of 1.57 to 3.09 wt%, or water/diesel having a lubrizol 10002 content of 2.92 to 3.09 wt%. The same degree of emulsification quality of latex.

As described above, lubrizol 10002 is a range known to the inventors to obtain a practically emulsifiable stability emulsifier with a minimum amount of emulsifier, and 3.0% by weight of lubrizol 10002 water/diesel emulsion fuel has Very extensive use of performance. Therefore, in Experiment 7, it can be said that by adding C heavy oil, a small amount (0.35% by weight) of emulsifier can be used to achieve the same or at least a degree of emulsification with the current water/diesel latex having a practical performance. Stability, emulsification quality.

1. . . Nano high pressure homogenizer

2. . . Metal case

3. . . Generator

4. . . Maintain quality

5, 6. . . Coupler

7. . . Inflow

8. . . Outflow path

9. . . container

10. . . Piping

11. . . High pressure pump

12. . . Piping

13. . . container

14. . . Mixer

3a. . . Generator

30a. . . Straight flow path (thin tube)

Sa. . . Flow path sectional area

La. . . Long flow path

20. . . Homogenizer

twenty one. . . Homogenizing valve

twenty two. . . High pressure pump

twenty three. . . Seat

23a. . . Plugging pipe

23b. . . Opening

twenty four. . . valve

25. . . Collision ring

25a. . . Discharge

25b. . . Middle wall

26. . . Screw

27. . . Screw

28. . . Plunger

29. . . Clearance (flow path)

34. . . First flow path component

35, 36. . . Second flow path component

37. . . Third flow path component

S1~S4. . . Substrate

R1~R4. . . Metal ring member

34a, 34b. . . Through hole

35a, 36a. . . Long hole

37a, 37b. . . Through hole

P. . . Inserting hole

1(A) and 1(B) are explanatory views showing the configuration of a nano high-pressure homogenizing apparatus.

2(A) and 2(B) are explanatory views showing the configuration of the homogenizer apparatus.

3(A) and 3(B) are explanatory views showing the structure of a generator for a nano high pressure homogenizing apparatus for experiments.

Figure 4 is a photograph of the appearance of each sample.

Fig. 5 is a view showing an organic concept in which each emulsifier is plotted as an organic value and an inorganic value.

Figure 6 is a photograph of the appearance of each sample.

Figure 7 is a photograph of the appearance of each sample.

Figure 8 is a photograph of the appearance of each sample.

Figure 9 is a photograph of the appearance of each sample.

Figure 10 is a photograph of the appearance of each sample.

Figure 11 is a photograph of the appearance of each sample.

Fig. 12 is a characteristic diagram showing the relationship between the concentration of the emulsifier and the thickness of the upper and lower separation layers.

Fig. 13 is a characteristic diagram showing the relationship between the concentration of the emulsifier and the diameter of the water droplets.

1. . . Nano high pressure homogenizer

2. . . Metal case

3. . . Generator

4. . . Maintain quality

5, 6. . . Coupler

7. . . Inflow

8. . . Outflow path

9. . . container

10. . . Piping

11. . . High pressure pump

12. . . Piping

13. . . container

14. . . Mixer

3a. . . Generator

30a. . . Straight flow path (thin tube)

Sa. . . Flow path sectional area

La. . . Long flow path

Claims (8)

A milky fuel comprising: an oil containing no residual oil, a heavy oil or a mixture thereof and water, and containing 0.001 to 3% by weight of the total content of the oil containing no residual oil, the above-mentioned A heavy oil and the above water C heavy oil. The emulsion fuel according to claim 1, which comprises: an oil containing no residual oil, and a milky fuel of water, wherein the oil containing no residual oil and the total content of the water is 0.001~ 3 wt% of C heavy oil. The emulsion fuel according to claim 1, wherein the weight ratio of the total oil content of the residual oil-free oil and the A heavy oil to the water content is 95:5-60:40. The emulsion fuel according to any one of claims 1 to 3, wherein the oil containing no residual oil is diesel oil, kerosene, gasoline, animal and vegetable oil, biodiesel fuel or a mixture thereof. The emulsion fuel according to any one of claims 1 to 3, further comprising an emulsifier. The emulsion fuel according to claim 5, wherein the HLB value obtained by the following formula (1) is 2 to 15 with respect to the above emulsifier: HLB = (Σ inorganic value / Σ organic value) × 10 ( 1). A method for producing a milk-like fuel, comprising: an oil containing no residual oil, a heavy oil or a mixture thereof, and water, and containing the above-mentioned oil containing no residual oil and 0.001 to 3% by weight of the total content of the above-mentioned A heavy oil and the above water The emulsion fuel of C heavy oil is characterized by: a high-pressure stirring device that agitates the liquid pressurized by the pressurizing means while passing through the flow path by using a pressurizing means having a pressurized liquid and a flow path through which the liquid pressurized by the pressurizing means passes. Emulsify the above light oil, water and C heavy oil. A method for producing a milk-like fuel, comprising: an oil containing no residual oil, a heavy oil or a mixture thereof, and water, and containing the above-mentioned oil containing no residual oil and 0.001 to 3% by weight of the total content of the above-mentioned A heavy oil and the above water The method for the emulsion fuel of C heavy oil, comprising: a first step of mixing an oil containing no residual oil, a heavy oil of A or a mixture thereof with C heavy oil; and adding a water stirring to the mixed liquid of the first step 2 steps.