Emulsification dispersants, a method for emulsification and dispersion using the emulsification dispersants, emulsions, and emulsion fuels

Abstract

An emulsifying dispersant includes, as the main component, vesicles formed from an amphiphilic substance capable of self-assembly or an emulsifying dispersant comprising single particles of a biopolymer as the main component. The particles made from amphiphilic substances capable of self-assembly are used. The amphiphilic substances are selected from among polyoxyethylene-hydrogenated castor oil derivatives wherein the average number of added ethylene oxide molecule is 5 to 15, dialkyldimethyl-ammonium halides wherein the chain length of the alkyl or alkenyl is 8 to 22, and phospholipids or phospholipid derivatives. According to the invention a three-phase structure composed of an aqueous phase, an emulsifying dispersant phase and an oil phase is formed on the surface of an emulsion to give an emulsion (such as emulsion fuel) excellent in thermal stability and long-term stability.

Claims

1. An emulsification dispersant comprising: a biopolymer disintegrated into single globular particles, wherein, when the biopolymer is disintegrated into the single globular particles, an average particle size of the single globular particles in the emulsification dispersant is at most 800 nm.

2. The emulsification dispersant according to claim 1, wherein, when the biopolymer is disintegrated into the single globular particles, the average particle size of the single globular particles in the emulsification dispersant is at least 50 nm.

3. The emulsification dispersant according to claim 1, wherein, when the biopolymer is disintegrated into the single globular particles, the average particle size of the single globular particles in the emulsification dispersant is at least 200 nm.

4. The emulsification dispersant according to claim 1, wherein, when the biopolymer is disintegrated into the single globular particles, a concentration of the single globular particles in the emulsification dispersant is at most 20 wt %.

5. The emulsification dispersant according to claim 4, wherein, when the biopolymer is disintegrated into the single globular particles, the concentration of the single globular particles in the emulsification dispersant is at least 0.04 wt %.

6. The emulsification dispersant according to claim 4, wherein, when the biopolymer is disintegrated into the single globular particles, the concentration of the single globular particles in the emulsification dispersant is at least 5 wt %.

7. The emulsification dispersant according to claim 1, wherein the biopolymer is from the group consisting of a polysaccharide, a phospholipid, a polyester, and a chitosan.

8. The emulsification dispersant according to claim 7, wherein the biopolymer is a microbially produced biopolymer.

9. The emulsification dispersant according to claim 7, wherein the polysaccharide is a microbially produced polysaccharide.

10. The emulsification dispersant according to claim 7, wherein the polysaccharide is a naturally-derived polysaccharide.

11. An emulsion formed by mixing an oil component with the emulsification dispersant according to claim 1.

12. The emulsion according to claim 11, wherein, when the emulsion is formed, a weight ratio of the oil component and the emulsification dispersant is 1 to 1000.

13. The emulsion according to claim 11, wherein, when the emulsion is formed, a weight ratio of the oil component and the emulsification dispersant is 50 to 2000.

14. The emulsion according to claim 11, wherein, when the emulsion is formed, an average particle size of the single globular particles in the emulsion is at most 500 nm.

15. The emulsion according to claim 14, wherein, when the emulsion is formed, the average particle size of the single globular particles in the emulsion is at least 5 nm.

16. The emulsion according to claim 14, wherein, when the emulsion is formed, the average particle size of the single globular particles in the emulsion is at least 8 nm.

17. The emulsion according to claim 11, wherein, when the emulsion is formed, water below a designated temperature is added to a mixture of the oil component and the emulsification dispersant.

18. The emulsion according to claim 17, wherein the designated temperature is 60° C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIGS. 1A and 1B illustrate an emulsification mechanism, of which FIG. 1A is a diagram illustrating an adsorption mechanism of a monomolecular film of a conventional surfactant, and FIG. 1B is a diagram illustrating an adherence mechanism of nanoparticles.

(2) FIG. 2A is a diagram illustrating phenomena caused by a thermal collision with surfactant molecules of conventional adsorption type, and FIG. 2B is a diagram illustrating phenomena caused by a thermal collision with vesicles of emulsifier phase adherence type.

(3) FIG. 3 is a TEM photograph of DMPC-C14TAB emulsifier particles (Xs=0.5, equimolar mixture).

(4) FIG. 4 is a distribution of scattering strength and TEM photographs of DMPC-C14TAB emulsifier particles with an average particle size of 390.0 nm (A) and 2097.8 nm (B).

(5) FIG. 5 is a figure showing observation results of an XRD peak of an emulsification by adding oil into 0.5 wt % of DMCP-C14TAB liquid crystals mixed with water.

(6) FIG. 6 is a block diagram describing a manufacturing method for an emulsification dispersant.

(7) FIG. 7 illustrates patterns of differences in the emulsified states according to the oil content.

(8) FIG. 8 is a block diagram that illustrates a manufacturing method for an emulsion fuel.

(9) FIG. 9A is a photograph showing a state of an emulsion that has been left for two days after conditioning a light oil and a heavy oil A using a conventional surfactant,

(10) FIG. 9B is a photograph showing a state of an emulsion that has been left for thirty days after conditioning a light oil and a heavy oil A using the three-phase emulsification method.

(11) FIG. 10 is a photograph showing the emulsification state of Table 2.

(12) FIG. 11 is a photograph showing the emulsification state of Table 5.

(13) FIG. 12 is a photograph that showing the emulsification state of Table 6.

(14) FIG. 13 shows the results of viscosity conditioning conducted with kerosene, light oil, heavy oil A, and liquid paraffin.

(15) FIG. 14 shows the results of an experiment in which changes in concentration of each exhaust gas component is measured while shifting from the combustion of a light oil to the combustion of a light oil emulsion.

(16) FIG. 15 shows the results of an experiment in which changes in concentration of each exhaust gas component is measured while shifting from the combustion of a heavy oil A to the combustion of a heavy oil A emulsion.

BEST MODE FOR CARRYING OUT THE INVENTION

(17) Hereinafter, the ideal embodiments of the present invention are explained.

(18) FIG. 1 conceptually illustrates an emulsification method with a conventional surfactant and the three-phase emulsification method adopted herein.

(19) In an emulsification method using a conventional surfactant, as shown in FIG. 1A, in the same molecule, the surfactant has both hydrophilic and lipophilic groups, which are different in their nature. As for a hydrophilic emulsifier, the lipophilic groups of the surfactant are dissolved into the oil, while the hydrophilic groups are aligned outside the oil particle, thus the oil particle is likely to have affinity to water and mixed homogeneously in the aqueous medium to produce an O/W type emulsion. Whereas, for a lipophilic surfactant, the hydrophilic groups of the surfactant are oriented toward the water particles, while the lipophilic groups are aligned outside of the water particle, thus the water particle is likely to have affinity to the oil and mixed homogeneously in the oil medium to produce a W/O type emulsions.

(20) However, with such conventional emulsification method, the surfactant is adsorbed on the oil surface, forming an emulsified monomolecular film, and it is inconvenient that surface properties change depending on the type of the surfactant. Moreover, as shown in FIG. 2A, due to the coalescence caused by thermal collisions of the oil drops, the size of the oil drops gradually become larger, and finally, a separation of the oil and the surfactant aqueous solution takes place. In order to prevent this, it is necessary to form microemulsions for which a large amount of a surfactant must be used, and therefore is inconvenient.

(21) In the present invention, as shown in FIG. 1B, nanoparticles of an emulsifier phase attach to the oil or water particles, creating a three-phase structure consisting of aqueous phase—emulsification dispersant phase—oil phase, without lowering the surface energy and without any mutual solubility at interface, unlike conventional surfactants, and long term stability of an emulsion can be achieved by preventing the coalescence caused by thermal collisions as shown in FIG. 2B. Furthermore, based on such a mechanism, the method adopts a new emulsification method (three-phase emulsification method) that allows for the formation of emulsions using only a small amount of emulsification dispersant.

(22) As for the emulsification dispersant, in order to realize such three-phase emulsification, an emulsification dispersant mainly comprised of vesicles that are formed from amphiphilic substances capable of forming vesicles spontaneously and that adhere onto the surface of an oil based material, or an emulsification dispersant mainly comprised of a biopolymer disintegrated into single particles have both been considered.

(23) The preferred average particle size of the vesicles formed from an amphiphilic substance is between 8 nm and 500 nm. A particle size smaller than 8 nm reduces the suction action attributed to the Van der Waals force, thereby impeding the vesicles from adhering onto the surface of the oil drops; however, if the particle size is larger than 500 nm, stable emulsions will not be maintained. In FIG. 3, a TEM photograph is shown representing a particle size of 8 nm. Moreover, if the particle size is larger than 500 nm when the emulsion is being formed, needle-shaped particles will be generated, and therefore, stable emulsions will not be maintained. In FIG. 4, distributions of scattering strength and TEM photographs of an average particle size of 390.0 nm (smaller than 500 nm: (A) in the figure) and of an average particle size of 2097.8 nm (larger than 500 nm: (B) in the figure) are shown.

(24) In order to maintain the particle size of the vesicles within this range while an emulsion is formed, a range of 200 nm to 800 nm when the dispersant is being conditioned within a concentration range of 5 to 20 wt % in the dispersion is acceptable for conditioning of the dispersant. This is due to the fact that vesicles are processed into fine particles during the emulsion formation process. By observing the XRD peak in FIG. 5, it is confirmed that the vesicles have not been destroyed in this process. In the figure, X.sub.H represents the mol fraction of the oil phase to the emulsifier.

(25) For the amphiphilic substances forming such vesicles, it is preferable to adopt polyoxyethylene-hydrogenated caster oil derivatives represented by the following general formula (Formula 4), or dialkylammonium derivatives represented by the general formula (Formula 5), including halides of trialkylammonium derivatives, tetraalkylammonium derivatives, dialkenylammonium derivatives, trialkenylammonium derivatives, or tetraalkeylammonium derivatives.

(26) ##STR00003##
R.sub.1, R.sub.2: Alkyl or alkenyl group of C.sub.8-C.sub.22
R.sub.3, R.sub.4: H or alkyl group of C.sub.1-C.sub.4
X: F, Cl, Br or I

(27) As for the polyoxyethylene-hydrogenated caster oil derivatives, derivatives with an average number of 5 to 15 added ethylene oxide molecules (E) may be used. An example wherein the average number of added ethylene oxide molecules has been changed from 5 to 20 is shown in Table 1. The range between 5 and 15 is stable; however, at 20, an emulsion formation is possible for a few days, but the stability cannot be maintained. In order to enhance the adhering strength, the vesicles to be obtained may be ionized. In forming such ionized vesicles as ionic surfactants, for the cationization, the use of alkyl or alkenyltrimethylammonium salt (with a carbon chain length of 2 to 22), preferably hexadecyltrimethylammonium bromide (hereinafter called CTAB), wherein the carbon chain length is 16, for the anionization, alkylsulphate (CnSO.sub.4.sup.−M.sup.+ with a carbon chain length of 8 to 22, M: alkali metals, alkaline earth, ammonium salt, etc.) is recommended. As for the method of ionization, for example, mix HCO-10 and CTAB with an ethanol solvent, remove the ethanol to form a mixture of HCO10 and CTAB, and then, add distilled water into the mixture so that HCO-10 becomes 10 wt %, and stir to incubate in a temperature-controlled container. In the mixed vesicles of HCO-10 and CTAB, if the CTAB mol fraction (Xs) is Xs≤0.1, coherent cationic properties of the mixed vesicles cannot be maintained, while if it is 0.33≤Xs, stable mixed vesicles cannot be obtained, and thus, a range of 0.1≤Xs≤0.33 is preferred for the cationization.

(28) TABLE-US-00001 TABLE 1 An example of heavy oil A emulsification with HCO-5. No. 1 2 3 4 5 HCO-5 2 2 2 2 2 Water 78 58 38 18 8 Heavy oil A 20 40 60 80 90 Emulsification stability ∘ ∘ Δ Δ Δ (After 1 day) Emulsification stability ∘ Δ Δ Δ Δ (After 7 days) Emulsified state W/O type emulsion An example of heavy oil A emulsification with HCO-15. No. 1 2 3 4 5 HCO-5 2 2 2 2 2 Water 78 58 38 18 8 Heavy oil A 20 40 60 80 90 Emulsification stability ∘ ∘ ∘ ∘ ∘ (After 1 day) Emulsification stability ∘ ∘ ∘ Δ Δ (After 7 days) Emulsified state O/W type emulsion W/O type emulsion An example of heavy oil A emulsification with HCO-20. No. 1 2 3 4 5 HCO-5 2 2 2 2 2 Water 78 58 38 18 8 Heavy oil A 20 40 60 80 90 Emulsification stability Δ Δ x x x (After 1 day) Emulsification stability x x x x x (After 7 days) Emulsified state O/W type emulsion W/O type emulsion ∘: No phase separation, Δ: Separated due to difference in specific gravity (coacervation), x: Separated Figures are shown in weight %

(29) Furthermore, as for the amphiphilic substance that forms the vesicles, phospholipids or phospholipids derivatives, etc. may be used. For the phospholipids, among structures represented by the following general formula (Formula 6), DLPC with a carbon chain length of 12 (1, 2-Dilauroyl-sn-glycero-3-phospho-rac-1-choline), DMPC with a carbon chain length of 14 (1, 2-Dimyristoyl-sn-glycero-3-phospho-rac-1-choline) and DPPC with a carbon chain length of 16 (1, 2-Dialmitoyl-sn-glycero-3-phospho-rac-1-choline) may be used.

(30) ##STR00004##

(31) Additionally, among structures represented by the following general formula (Formula 7), DLPG with a carbon chain length of 12 (1, 2-Dilauroyl-sn-glycero-3-phospho-rac-1-glycerol) Na salt or NH.sub.4 salt, DMPG with a carbon chain length of 14 (1, 2-Dimyristoyl-sn-glycero-3-phospho-rac-1-glycerol) Na salt or NH.sub.4 salt, or DPPG (1, 2-Dipalmitoyl-sn-glycero-3-phospho-rac-1-glycerol) Na salt or NH.sub.4 salt may also be used.

(32) ##STR00005##

(33) Furthermore, egg yolk lecithin or soybean lecithin may be used as phospholipids. Moreover, for the emulsification and dispersion of an oil component using an emulsification dispersant comprising said vesicles, it is recommended to have the oil component emulsified and said emulsification dispersant mixed with said oil component by a weight ratio of 4 to 200.

(34) On the other hand, for biopolymers, provided for example are microbially produced biopolymers comprising as structure elements some sugars among the monosaccharides, such as ribose, xylose, rhamnose, fructose, glucose, mannose, glucuronic acid, and gluconic acid, etc. As for microorganisms that produce polysaccharides with these particular structures, alcaligenes, xanthomonas, arthrobacter, bacillus, hansenula, and brunaria are known, and any polysaccharide or mixture of such may be used. Gelatin or blockcopolymers may also be used in place of a biopolymer.

(35) When emulsifying and dispersing an oil component using an emulsification dispersant comprising as the main component a biopolymer disintegrated into single particles, it is recommended that the oil component is emulsified and said emulsification dispersant mixed with said oil component by a weight ratio of 50 to 2000.

(36) A method of producing the emulsification dispersant described above requires a process for dispersing an amphiphilic substance capable of self-assembly into vesicles (vesiclization), or a process for disintegrating into single particles (step I). This requires various ingenuities depending on the material used, however, as shown in FIG. 6, a process of water-dispersing or water-swelling the amphiphilic substance (step I-1), a process of thermally adjusting the temperature to approx. 80° C. (step I-2), a process of adding a denaturant such as urea to destroy the hydrogen bond (step I-3), a process of conditioning the pH to below 5 (step I-4), any of such processes, or a combination of which may achieve disintegration into single particles, or vesiclization. Particularly with caster oil derivatives, disintegration is achievable by adding the caster oil derivative dropwise into water below 60° C. while stirring.

(37) After a process for conditioning the designated concentration by addition into water below the designated temperature (below 60° C.) (step II), and a process for stirring to process the particles into fine particles (step III), an emulsification dispersant is produced. As for the stirring, stirring at a high speed (up to 16000 rpm, in lab.) is preferred; however, when using a stirring device, stirring at up to approximately 1,200 rpm will allow for processing in fewer minutes. In addition, it is preferable to perform the process of adding into the water and the process of processing the particles into fine particles at the same time. Biopolymers, etc. require a complicated process, since the network structures must be destroyed in order to disintegrate into single particles; however, these processes are individually described for each embodiment (embodiment 6, embodiment 8, embodiment 9, and embodiment 10).

(38) Hereinafter, several embodiments of emulsification dispersants comprising as the main component vesicles formed from amphiphilic substances, and embodiments of emulsification dispersants comprising as a main component of biopolymers disintegrated into single particles are described.

Embodiment 1

An Embodiment Wherein Vesicles from Hydrogenated Caster Oil are Used as an Emulsification Dispersant

(39) As the vesicles from hydrogenated caster oil, among polyoxyethylene-hydrogenated caster oil derivatives, a derivative with an average number of 10 added ethylene oxide (EO) molecules (E) (from hereon HCO-10; molecular weight 1380 g/mol) is used.

(40) It is known that the HCO-10 is hardly soluble in water and forms vesicles by assembling themselves in water (Ref “Regarding a Formation of Vesicles of Non-ionic Surfactant Related to Poly(oxyethylene) Hydrogenated Caster Oil” Journal of Japan Oil Chemist's Society, vol. 41, No. 12, P. 1191-1196, (1992), “Thermal Properties of Poly(oxyethylene) Hydrogenated Caster Oil Vesicle Dispersant Solution” Japan Oil Chemist's Society, vol. 41, No. 12, P 1197-1202, (1992)), as shown in Table 2, although the average particle size depends on the concentration; however, at the stage of aqueous dispersion the particle size is 200 nm to 800 nm. Considering the stability of the dispersion, the size was set in the range of 5 to 20 wt %.

(41) TABLE-US-00002 TABLE 2 Average particle size at various concentration of HCO-10. Average Second most Concentration particle Most distributed distributed (wt %) size/nm particle size/nm particle size/nm 1 243.17 88.43 3 321.13 205.63 6 440.8 449.67 136.47 7 443.33 160.7 8 473.33 136.1 9 513.3 92.73 256.2 10 760.5 37.7 313.8 15 775 64.73 415.3 20 735.57 41.5 192.8

(42) For the purpose of investigating an equivalent or better emulsification capability compared to conventional surfactants using such emulsification dispersant, a system of heavy oil A and water was used wherein the concentration of HCO-10 to water was set at 10 wt %, for which regular tap water was used for the water, and where the emulsification was conducted in room temperature by stirring for approximately five minutes at 8000 rpm using a homomixer. The emulsified state was examined by changing the weight ratio of the heavy oil A. The proportion of each composition of the hydrogenated caster oil (HCO-10)-water-heavy oil A, and the result of the emulsified state of the emulsions are shown in Table 3.

(43) TABLE-US-00003 TABLE 3 Example (1) of emulsification with HCO-10. No. 1 2 3 4 5 6 7 8 9 10 HCO-10 9 8 7 6 5 4 3 2 1 0.5 Water 81 72 63 54 45 36 27 18 9 4.5 Heavy oil A 10 20 30 40 50 60 70 80 90 95 Emulsification ◯ ◯ ◯ ◯ ◯ Δ Δ X X X stability (1 month/room temperature) Emulsified (1) (2) (3) state Figures are shown in weight %. ◯: No phase separation, Δ: Separated due to difference in specific gravity (coacervation), X: Separated (1): O/W type emulsion, (2): W/O type emulsion, (3): W/O microemulsion and separated aqueous phase

(44) As shown by these results, with a small amount of HCO-10, it was possible to emulsify up to 70 wt % of the heavy oil A. As shown in FIG. 7, in which the pattern changes of the emulsified states are shown after changing the proportion of the heavy oil A and the water, by increasing the proportion of the heavy oil A to water, from a diluted O/W type emulsion state (a) to a thick O/W type emulsion state, and after passing a transient state (c), then reaching a deposit W/O type emulsion state (d), when the proportion of the heavy oil A is exceeded, the reverse micro-emulsion state of (e) and a separate aqueous phase was formed. Said No. 1 to No. 5 are states of either (a) or (b), No. 6 and No. 7 are states of (d), and No. 8 through No. 10 correspond to states of (e). In addition, a characteristic of the invention was that in No. 6 and 7, apparently partial coacervation (creaming) was observed, which was redispersed by stirring moderately. However unlike the creaming state obtained by the conventional surfactant, a coalescence of oil drops was not observed, even after having been left to sit for an extended period of time.

Embodiment 2

(45) For the purpose of examining the emulsified state of HCO-10 in a system of various types of oil agents, such as liquid paraffin and water, the concentration of the HCO-10, the emulsification dispersant of the water, and the concentration of the entire system were fixed as 10 wt % and 7 wt %, respectively, for which regular tap water was used for the water, and the emulsified state per each oil agent was examined after stirring for approximately five minutes by a normal stirrer at room temperature, thereby obtaining the results shown in Table 4.

(46) TABLE-US-00004 TABLE 4 Emulsification example (2) with HCO-10 Emulsification stability (1 month/ Emulsified Oil type HCO-10 Water room temperature) state Liquid paraffin 7 63 ◯ O/W type Olive oil 7 63 ◯ O/W type Silicone (2 cSt) 7 63 ◯ O/W type Silicone (5 cSt) 7 63 ◯ O/W type Silicone (100 cSt) 7 63 ◯ O/W type Isopropyl 7 63 ◯ O/W type myristate Hexadecane 7 63 ◯ O/W type Limonene 7 63 ◯ O/W type Tocopherol 7 63 ◯ O/W type (Vitamin E) Figures are shown in wt %. Oil content is 30 wt %.

(47) As seen from these result, a favorable emulsified state was obtained regardless of the type of oil agent. Moreover, since this emulsified state did not change even after having been left to incubate at room temperature for one month, excellent emulsions were obtained.

Embodiment 3

An Embodiment Wherein Distearyldimethylammoniumchloride is Used as the Emulsification Dispersant

(48) Next, an embodiment wherein distearyldimethylammoniumchloride is used as an emulsification dispersant is described. The emulsified state of liquid paraffin using this emulsification dispersant was examined, and the results are shown in Table 5. With approximately 0.5 wt % or over, a favorable state was obtained. Furthermore, even with silicone oil, a favorable state was obtained as shown in Table 6.

(49) TABLE-US-00005 TABLE 5 No. 1 2 3 Emulsifier 0.5 2.5 5 Water 49.5 47.5 45 Liquid paraffin 50 50 50 Emulsified state O/W type O/W type O/W type Emulsification stability Δ ◯ ◯ (1 month/room temperature) Figures are shown in wt %. ◯: No phase separation, Δ: Separated due to difference in specific gravity (coacervation), X: Separated

(50) TABLE-US-00006 TABLE 6 Emulsifier 3.1 Water 59 Silicone oil (2cs) 37.9 Emulsified state O/W type Emulsification stability ◯ (1 month/room temperature) Figures are shown in wt %. ◯: No phase separation

Embodiment 4

An Embodiment Wherein Phospholipids are Used as the Emulsification Dispersant

(51) Next, an embodiment wherein phospholipids are used as the emulsification dispersant is described.

(52) The emulsified state when using said phospholipids (DMPC, DMPG, DPPC) was examined by changing the type of oil agents as shown in Table 7. With each oil agent, the oil composition was set within a range of 0.1 to 35 wt %, and regular tap water was used for the water, where a normal stirrer was used for the five minutes stirring at a room temperature. Furthermore, the concentration of the phospholipids was set in a range of 0.005 to 0.5 wt %.

(53) TABLE-US-00007 TABLE 7 Emulsification Stability (1 month/room Emulsified Oil type Phospholipids Water temperature) state Liquid paraffin 0.005-0.5 64.5-99 ◯ O/W type Olive oil 0.005-0.5 64.5-99 ◯ O/W type Silicone (2 cSt) 0.005-0.5 64.5-99 ◯ O/W type Silicone (5 cSt) 0.005-0.5 64.5-99 ◯ O/W type Silicone (100 cSt) 0.005-0.5 64.5-99 ◯ O/W type Octan 0.005-0.5 64.5-99 ◯ O/W type Decane 0.005-0.5 64.5-99 ◯ O/W type Dodecane 0.005-0.5 64.5-99 ◯ O/W type Tetradecane 0.005-0.5 64.5-99 ◯ O/W type Hexadecane 0.005-0.5 64.5-99 ◯ O/W type Octadecane 0.005-0.5 64.5-99 ◯ O/W type Benzene 0.005-0.5 64.5-99 ◯ O/W type Nonylbenzene 0.005-0.5 64.5-99 ◯ O/W type Limonene 0.005-0.5 64.5-99 ◯ O/W type Tocopherol 0.005-0.5 64.5-99 ◯ O/W type (Vitamin E) Figures are shown in wt %. Oil content is 0.1-35 wt %.

(54) From these results, in emulsifications using phospholipids (DMPC, DMPG, and DPPC), favorable emulsified states were also obtained with a small amount of phospholipids, regardless of the type of oil agent. Moreover, the obtained emulsions had excellent thermal and long term stability with no changes in the emulsified state after having been left to incubate at room temperature for one month.

Embodiment 5

(55) In addition, egg yolk lecithin was used as a phospholipid, and the emulsified state was examined for egg yolk lecithin and silicone oil, and egg yolk lecithin and hexadecane. The results are shown in Table 8. In the Table, the case of (1) is an embodiment wherein the egg yolk lecithin had been hydrogenated, and (2) is an embodiment wherein the egg yolk lecithin had not been hydrogenated. Also in these case, emulsions with excellent thermal and long term stability were obtained.

(56) TABLE-US-00008 TABLE 8 Emulsification stability Phospho- Amount (1 month/room Emulsified Oil type lipids of oil Water temperature) state Silicone (1) 0.3 33.8 65.9 ◯ O/W type (2 cSt) Hexadecane (2) 0.9 33 66.1 ◯ O/W type Figures are shown in wt %.

Embodiment 6

An Embodiment Wherein a Biopolymer Disintegrated into Single Particles is Used as the Emulsification Dispersant

(57) Next, an embodiment in shown in which the emulsification dispersant comprises as a main component a biopolymer disintegrated into single particles

(58) For the biopolymer, among the microbially produced biopolymers described previously, a polysaccharide produced by alcaligenes was used. The polysaccharide forms a network structure when dispersed in water and becomes a viscous liquid; therefore, the network structure must be disintegrated into single particles. Then, the biopolymer aqueous solution, wherein the powder of the biopolymer was dispersed into a certain amount of water, was left all the day so as to make it swell, and then thermally adjusted for thirty minutes at 80° C., into which urea was added to destroy the hydrogen bonds of the biopolymer so as to disintegrate into single particles. It was possible to disintegrate a biopolymer of up to 0.1 wt % into single particles using an urea aqueous solution of 4 mol/dm.sup.3.

(59) In order to examine whether an aqueous dispersion of a biopolymer disintegrated into single particles has the same emulsification capability with oil agents as conventional surfactants, a liquid paraffin that is one of the hydrocarbon oils was used to examine the emulsification capability according to the dispersion concentration of the biopolymer as shown in Table 9, whereby it was possible to emulsify up to 70 wt % (water 30 wt %) for the concentration of liquid paraffin with aqueous dispersions of 0.05 wt % biopolymer. Moreover, the state of the emulsion did not show any changes elapsed after preparation and was extremely stable. In addition, when the biopolymer was set to be 0.04 wt % and the liquid paraffin to be 30 wt %, the temperature for the emulsification changed within a range of 25° C. to 75° C.; the formed emulsions were stable at any temperature.

(60) TABLE-US-00009 TABLE 9 Biopolymer Amount of liquid paraffin (wt %) (wt %) 10 30 50 60 70 80 0.01 X X X X X X 0.05 ◯ ◯ ◯ ◯ ◯ X 0.09 ◯ ◯ ◯ ◯ X X

(61) Furthermore, while the concentration of liquid paraffin as an oil agent was set to be 30 wt %, the biopolymer concentration was changed in order to examine the emulsification capability of the biopolymer, and emulsification from 0.04 wt % was found to be possible.

Embodiment 7

(62) Next, when the concentration of the biopolymer was set to be 0.04 wt % and the concentration of the oil agent to be 30 wt %, various kind of oils was changed to examine the effect on the emulsified state of the emulsion. The results are shown in Table 10. The oil agents used here were hexadecane, silicone, isopropylmyristate, squalane, olive oil, jojoba oil, cetostearyl alcohol, oleyl alcohol, and oleic acid. Though emulsion of oleic acid showed separation after several days, emulsion of the other oil agents was stable.

(63) TABLE-US-00010 TABLE 10 Emulsification stability Bio- (1 months/room Emulsified Oil type polymer Water temperature) state Hexadecane 0.04 69.96 ◯ O/W type Silicone 0.04 69.96 ◯ O/W type Isopropylmyristate 0.04 69.96 ◯ O/W type Squalane 0.04 69.96 ◯ O/W type Olive oil 0.04 69.96 ◯ O/W type Jojoba oil 0.04 69.96 ◯ O/W type Cetostearyl alcohol 0.04 69.96 ◯ O/W type Oleyl alcohol 0.04 69.96 ◯ O/W type Oleic acid 0.005-0.5 64.5-99 X O/W type The figures are shown in wt %. Oil content is 30 wt %.

(64) From the above results, it has become apparent that a biopolymer has excellent emulsification capability, and even in low concentrations of 0.04 wt % the emulsion was stable, which is considered to be due to the single particles of the biopolymer adhering around the oil droplets creating an emulsification dispersant phase, and forming three-phase emulsion of aqueous phase—emulsification dispersant phase—oil phase.

Embodiment 8

(65) The following example is a case in which naturally-derived starch is used as a biopolymer.

(66) Potato starch, glutinous-rice powder, and tapioca powder (cassava potato powder) were used as the typical example of starch, and liquid paraffin and hexadecane were used as oil.

(67) When conditioning the emulsifier, in order to disintegrate these starch into single particles, these starch were dispersed in water and heated to 90° C. with stirring, and then cooled down to room temperature so as to obtain a favorable dispersion, and from this operation a sugar polymer dispersion was obtained for use as the emulsifier.

(68) Moreover, when conditioning the emulsions at room temperature after the operation of disintegration into single particles, the emulsions were conditioned by the addition of an oil phase with stirring as appropriate for the starch aqueous dispersion. The results are shown in Table 11 through Table 13.

(69) TABLE-US-00011 TABLE 11 Example (1) for emulsified state using starch. No. 1 2 3 4 5 6 7 8 9 10 11 Potato starch 0.18 0.16 0.14 0.12 0.1 0.08 0.07 0.06 0.05 0.04 0.02 Water 89.82 79.84 69.86 59.88 49.9 39.92 34.93 29.94 24.95 19.96 9.98 Liquid paraffin 10 20 30 40 50 60 65 70 75 80 90 Emulsification stability Δ Δ Δ Δ Δ Δ ◯ ◯ ◯ ∇ X (1 month/room temperature) Figures are shown in wt % ◯: No phase separation, Δ: Separated due to the difference in specific gravity with the O/W type emulsion (coacervation), ∇: Separated due to the difference in specific gravity with the W/O type emulsion (coacervation), X: Separation of the W/O type emulsion and water

(70) TABLE-US-00012 TABLE 12 Example (2) for emulsified state using starch. No. 1 2 3 4 5 6 7 8 9 Glutinous rice powder 0.18 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 starch Water 89.82 79.84 69.86 59.88 49.9 39.92 29.94 19.96 9.98 Liquid paraffin 10 20 30 40 50 60 70 80 90 Emulsification stability Δ Δ Δ Δ ∇ ∇ ∇ X X (1 month/room temperature) Figures are shown in wt % Δ: Separated due to the difference in specific gravity with the O/W type emulsion (coacervation), ∇: Separated due to the difference in specific gravity with the W/O type emulsion (coacervation), X: Separation of the W/O type emulsion and water

(71) TABLE-US-00013 TABLE 13 Example (3) for emulsified state according to different types of starch. Emulsifier Emulsified Starch type amount Water state Potato starch powder 0.1 49.9 ◯ Glutinous rice powder 0.1 49.9 ◯ Tapioca powder (cassava potato) 0.5 49.5 ◯ Figures are shown in wt % Oil: soybean oil 50 wt %

Embodiment 9

The Following Case is an Example of an Embodiment Wherein Chitosan is Used as the Biopolymer

(72) Liquid paraffin was used as the oil.

(73) When conditioning the emulsifier, the chitosan was dispersed in water and acidified to below pH 5 in order to disintegrate chitosan into single particles. This operation apparently led to be transparent and chitosan was disintegrated into single particles, and a favorable dispersion was ultimately obtained. When forming the emulsion by at various pHs, pH adjustment was performed after disintegrating into single particles. Moreover, when forming the emulsions, after the operation of disintegration into single particles, the emulsions were formed by adding an oil phase with stirring suitable for the chitosan dispersion. The results are shown in Table 14. Additionally, the results obtained after adjusting the pH to 4, 7, and 10 are shown in Table 15.

(74) TABLE-US-00014 TABLE 14 Emulsified state using chitosan. No. 1 2 3 4 5 6 7 8 9 10 11 Chitosan 0.45 0.4 0.35 0.3 0.25 0.2 0.175 0.15 0.125 0.1 0.05 Water 89.55 79.6 69.65 59.7 49.75 39.8 34.83 29.85 24.88 19.9 9.95 Liquid paraffin 10 20 30 40 50 60 65 70 75 80 90 Emulsification stability Δ Δ Δ Δ Δ Δ ◯ ◯ ◯ Δ X (1 month/room temperature) Figures are shown in wt % ◯: No phase separation, Δ: Separated due to the difference in specific gravity with the O/W type emulsion (coacervation), ∇: Separated due to the difference in specific gravity with the W/O type emulsion (coacervation), X: Separation of the W/O type emulsion and water

(75) TABLE-US-00015 TABLE 15 Effect of pH on emulsification using chitosan No. 1 2 3 pH 4 7 10 Emulsified state Δ Δ ◯ ◯: No phase separation, Δ: Separated due to the difference in specific gravity with O/W type emulsion (coacervation)

Embodiment 10

The Following Case is an Embodiment Wherein Kelp Powder, a Naturally-Derived Polysaccharide is Used as the Biopolymer

(76) Fucoidan contained in kelp powder was used as a sugar polymer component.

(77) When conditioning the emulsifier, kelp powder was dispersed in water and acidified to below pH 5 in order to disintegrate fucoidan into single particles.

(78) Furthermore, when forming the emulsions after disintegrating into single particles, the emulsions were formed by adding an oil phase with stirring suitable for the kelp powder dispersion.

(79) The results are shown in Table 16.

(80) TABLE-US-00016 TABLE 16 Emulsified state using kelp powder. No. 1 2 3 4 5 6 7 8 9 Kelp powder 0.45 0.4 0.35 0.3 0.25 0.2 0.15 0.1 0.05 Water 89.55 79.6 69.65 59.7 49.75 39.8 29.85 19.9 9.95 Liquid paraffin 10 20 30 40 50 60 70 80 90 Emulsification stability (1 Δ Δ Δ Δ Δ Δ ∇ ∇ X month/room temperature) Figures are shown in wt % Δ: Separated due to the difference in specific gravity with the O/W type emulsion (coacervation), ∇: Separated due to the difference in specific gravity with the W/O type emulsion (coacervation), X: Separation of the W/O type emulsion and water

(81) When an emulsification method (three-phase emulsification method) in which an emulsification dispersant comprising vesicles formed from an amphiphilic substance or a biopolymer disintegrated into single particles is used as the main component is compared to an emulsification method using a conventional surfactant, the following common characteristics were acknowledged.

(82) First, in the conventional emulsification method, a surfactant was adsorbed onto interface of oil and water, and performed emulsion by lowering the interfacial energy of the oil/water. Secondly, the three-phase emulsification method is characterized in that an emulsification dispersant phase is constructed as a result of adherence of nanoparticles onto the interface of oil and water due to van der Waals force, thus permitting an emulsification without changing the interfacial energy regardless of the required HLB value of an oil based agent to be emulsified.

(83) As a result, in an emulsification using conventional surfactant, coalescence were induced due to the thermal collision of oil droplets; on the other hand, in case of the three-phase emulsification, since the nanoparticles in the emulsifier phase adhered onto the surface of the oil droplets, even if they collided, coalescence were less likely to occur, then thermal stability was sustained for long period of time.

(84) Furthermore, in the emulsification using conventional surfactants, the selection of an appropriate surfactant is required in accordance with the properties of the oil droplets; on the other hand, in the three-phase emulsification method, once the nanoparticles are selected, the same emulsifier may be used regardless of the type of oil droplets, thus also allowing for coexistence and mixture of emulsions with different types of oil agents.

(85) Moreover, in the conventional emulsification method, because the oil droplets form microemulsions, a large amount of the surfactant was required, while in the three-phase emulsification method, emulsification was possible using only a low concentration of emulsification dispersant.

(86) Additionally, in the three-phase emulsions described above, 1) a stable formation of large oil drops shaped like salmon roe is possible, 2) as for the creaming state being dependent on the difference in specific gravity, the emulsified state showed no difference even when the separated phase was removed, and 3) it was possible to form emulsions even with the addition of additives into the aqueous phase or into the oil phase of the three-phase emulsification.

(87) Hereinafter, an embodiment wherein the emulsification dispersant realizing the three-phase emulsification described above is applied to emulsion fuels is described. The emulsion fuels in the present invention contain said emulsification dispersant as the essential component in the fuels: water-added oils; e.g. light oil, heavy oil (heavy oil A, heavy oil C), high viscosity heavy oil, kerosene, or gasoline, etc.

(88) Herein, the preferred average particle size of the vesicles formed from an amphiphilic substance is 8 nm to 500 nm. A particle size smaller than 8 nm reduces the attractive force attributed to the van der Waals force, and then the vesicles may not adhere onto the surface of the oil, whereas, if the particle size is larger than 500 nm, stable emulsions cannot be maintained as previously described.

(89) In order to maintain the particle size of the vesicles within this range while an emulsion is being formed, a range of 200 nm to 800 nm is acceptable for conditioning of the dispersant. Such particles size for emulsifier was due to a reason because the vesicles are processed into fine particles during the emulsion formation process.

(90) For the amphiphilic substance forming such vesicles, polyoxylene-hydrogenated caster oil derivatives represented by the general formula (Formula 4) are to be used.

(91) For hydrogenated caster oil derivatives, derivatives with an average number of 5 to 15 added ethylene oxide molecules (E) may be used. Furthermore, in order to enhance the thermal stability of said vesicles depending on the purpose, other ionic surfactants, amphoteric surfactants or other nonionic surfactants may be used together with said emulsification dispersant.

(92) Moreover, for the method of producing emulsion fuels described above, particularly with high viscosity heavy oil, temperature control is crucial. That is, for emulsion fuels in which high viscosity oils such as heavy oil, etc. are used, processes are required for conditioning the fluidization (step IV), and for adjusting the temperature in order to reduce the temperature of the fluidity-conditioned high viscosity oil to the designated temperature (below 60° C.) (step V).

(93) As shown in FIG. 8, a process for conditioning the fluidization (step IV) is achievable by: a process for thermally adjusting the temperature to approximately 80° C. so as to permit fluidization of the crude oil (step IV-1), followed by a process for adding a required amount of oil of which the viscosity is to be conditioned (step IV-2), and a process for homogenization by stirring (step IV-3). The viscosity during homogenization is controllable depending on the amount of oil to be added. Moreover, the temperature to be reached during the temperature adjustment in step IV-1 does not necessarily have to be 80° C., provided it is mixable with the oil; however when using high viscosity oils such as heavy oils, etc., the temperature must be reduced down to approximately 60° C. or below when mixing with the emulsification dispersant. Therefore, when using high viscosity oils, after the process of fluidity-conditioning, a process for temperature adjustment (step V) is required to reduce the temperature of the fluidity-conditioned crude oil to the designated temperature (below 60° C.). The processes in step IV and step V may be omitted depending on the crude oil used.

(94) Subsequently, the emulsion fuel is generated after a process of adding the crude oil to be fluidized into the emulsification dispersant liquid (step VI) and a process of stirring for process the particles into fine particles (step VII). That is, the gradual addition of a small amount of fluidity-conditioned heavy oil or light oil, etc., into water and an emulsification dispersant for the emulsion fuel composition, after having been stirred, results in creation of the emulsion fuel. A high speed of stirring (up to 16000 rpm, in lab.) is preferred; however, any stirring speed is acceptable as long as an increase in temperature is not observed. It is also preferable to perform the process of adding into the water and the process of processing the particles into fine particles at the same time.

Embodiment 11

(95) Hereinafter, an embodiment is described wherein emulsion fuels are formed, along with the emulsification of water and light oil or heavy oil A, using an emulsification dispersant comprising as the main component vesicles formed from an amphiphilic substance.

(96) An attempt was made to emulsify a commercially produced light oil, and a heavy oil A using regular tap water. For the emulsification dispersant, among polyoxyethylene-hydrogenated caster oil derivatives forming hydrophilic nanoparticles, a dispersion was used wherein a derivative with an average number of 10 added ethylene oxide (EO) molecules (from hereon HCO-10; molecular weight 1380 g/mol) was dispersed with water. As previously described, HCO-10 is known to be hardly soluble in water and forms vesicles by assembling themselves in water, as shown in Table 2, and although the average particle size depends on the concentration, at the stage of aqueous dispersion, the size is 200 nm to 800 nm. Considering the stability of the dispersion, the concentration was set within a range of 5 to 20 wt %. No surfactant was used.

(97) As for the emulsifying machine, a conventional homogenizer was used, and as for the combustion, a combustion device with a burner designated for kerosene was used, and the five components (NO, CO, SO.sub.2, CO.sub.2, and O.sub.2) of combustion exhaust gases were monitored automatically.

(98) A fuel was added to the HCO-10 aqueous dispersion and stirred for ten minutes by the homogenizer at 16000 rpm to prepare the emulsion. The composition of the emulsion in a weight ratio is HCO-10 at 5 wt %, oil phase at 50 wt %, and water at 45 wt %.

(99) In FIGS. 9A and 9B, after forming the emulsions of light oil and heavy oil A using a conventional surfactant and the emulsions of light oil and heavy oil A using the three-phase emulsification method of the present invention, the results are shown for the state of the emulsion using the surfactant two days later, and for the state of the emulsion using the three-phase emulsification method thirty days later (the state remained the same after two months). As seen from the figure, the emulsion using the conventional surfactant showed a complete phase separation, whereas the emulsion using the three-phase emulsification method remained extremely stable over time, even without the use of additives other than the HCO-10 emulsification dispersant.

(100) Furthermore, after changing the weight ratio of HCO-10, oil phases (heavy oil A, light oil) and water, and stirring to regulate the emulsions, the states of one week after and one month after were observed in room temperature.

(101) Examples of emulsification with heavy oil A is shown in Table 17 through Table 19. Furthermore, the photographs representing the emulsified states in Table 18 are shown in FIG. 10. In the short term, emulsions were formed with the HCO-10 at 0.5 wt % and the oil phase at 95 wt %; however, when the oil phase exceeded 80 wt %, changes in the time dependence were observed.

(102) TABLE-US-00017 TABLE 17 Examples (1) of Heavy oil A emulsification using 10 wt % HCO-10 aqueous dispersion No. 1 2 3 4 5 6 7 8 9 10 HCO-10 9 8 7 6 5 4 3 2 1 0.5 Water 81 72 63 54 45 36 27 18 9 4.5 Heavy oil A 10 20 30 40 50 60 70 80 90 95 Emulsification stability (7 ◯ ◯ ◯ ◯ ◯ ◯ Δ Δ Δ Δ days/room temperature) Emulsification stability ◯ ◯ ◯ ◯ ◯ ◯ Δ X X X (1 month/room temperature) Emulsified state (1) (2) (3) Figures are shown in wt %. ◯: No phase separation, Δ: Separated due to the difference in specific gravity (coacervation), X: Separated (1): O/W type emulsion, (2): W/O type emulsion, (3): W/O microemulsion

(103) TABLE-US-00018 TABLE 18 Examples (2) of heavy oil A emulsification using 15 wt % HCO-10 aqueous dispersion No. 1 2 3 4 5 6 7 8 9 10 11 HCO-10 14.3 13.5 12 10.5 9 7.5 6 4.5 3 1.5 0.75 Water 80.8 76.5 68 59.5 51 42.5 34 25.5 17 8.5 4.25 Heavy Oil A 5 10 20 30 40 50 60 70 80 90 95 Emulsification stability (7 ◯ ◯ ◯ ◯ ◯ ◯ ◯ Δ Δ Δ Δ days/room temperature) Emulsification stability ◯ ◯ ◯ ◯ ◯ ◯ ◯ Δ X X X (1 month/room temperature) Emulsified state (1) (2) (3) Figures are shown in wt %. ◯: No phase separation, Δ: Separated due to the difference in specific gravity (coacervation), X: Separated (1): O/W type emulsion, (2): W/O type emulsion, (3): W/O microemulsion

(104) TABLE-US-00019 TABLE 19 Examples (3) of Heavy oil A emulsification at various concentrations of HCO-10 HCO-10 Heavy Emulsified state Concentration Water oil A After 1 day After 20 days 0.1 39.9 60 ◯ Δ 0.2 39.8 60 ◯ Δ 0.4 39.6 60 ◯ Δ 0.6 39.4 60 ◯ ◯ 0.8 39.2 60 ◯ ◯ 1 39 60 ◯ ◯ 2 38 60 ◯ ◯ 4 36 60 ◯ ◯ 6 34 60 ◯ ◯ 10 30 60 ◯ ◯ Figures are shown in wt %. ◯: No phase separation, Δ: Separated due to the difference in specific gravity (coacervation)

(105) As seen from the above results, a composition comprised of HCO-10 at 0.1-14.25 wt %, heavy oil A at 5-95 wt % and the corresponding proportion of water, and preferably a composition comprised of HCO-10 at 5-14.25 wt %, heavy oil A at 5-60 wt % and the corresponding proportion of water are recommended.

(106) Emulsification examples with light oil are shown in Table 20 through Table 23. In addition, photographs representing the emulsified states of Table 22 are shown in FIG. 11, and photographs representing the emulsified states of Table 23 are shown in FIG. 12. In these case, with the oil phase exceeds 80 wt %, a stable emulsion could not be formed. However, no changes were observed over time.

(107) TABLE-US-00020 TABLE 20 Example (1) of light oil emulsification with 10 wt % HCO-10 aqueous dispersion No. 1 2 3 4 5 6 7 8 9 10 HCO-10 9 8 7 6 5 4 3 2 1 0.5 Water 81 72 63 54 45 36 27 18 9 4.5 Light oil 10 20 30 40 50 60 70 80 90 95 Emulsification ◯ ◯ ◯ ◯ ◯ ◯ Δ X X X stability (7 days/room temperature) Emulsification ◯ ◯ ◯ ◯ ◯ ◯ Δ X X X stability (90 days/room temperature) Emulsified (1) (2) (3) state Figures are shown in wt %. ◯: No phase separation, Δ: Separated due to the difference in specific gravity (coacervation), X: Separated (1): O/W type emulsion, (2): W/O type emulsion, (3): W/O micro emulsion and separated aqueous phase

(108) TABLE-US-00021 TABLE 21 Example (2) of light oil emulsification with 10 wt % HCO-10 aqueous dispersion No. 1 2 3 4 5 6 7 8 9 HCO-10 4.5 4 3.5 3 2.5 2 1.5 1 0.5 Water 85.5 76 66.5 57 47.5 38 28.5 19 9.5 Light oil 10 20 30 40 50 60 70 80 90 Emulsification ◯ ◯ ◯ ◯ ◯ ◯ X X X stability (7 days/room temperature) Emulsification ◯ ◯ ◯ ◯ ◯ ◯ X X X stability (90 days/room temperature) Emulsified state (1) (3) Figures are shown in wt %. ◯: No phase separation, Δ: Separated due to the difference in specific gravity (coacervation), X: Separated (1): O/W type emulsion, (3): W/O micro emulsion and separated aqueous phase

(109) TABLE-US-00022 TABLE 22 Example (5) of light oil emulsification with 10 wt % HCO-10 aqueous dispersion No. 1 2 3 4 5 6 7 8 9 10 11 HCO-10 0.95 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.05 Water 94.1 89.1 79.2 69.3 59.4 45.5 39.4 29.7 19.8 9.9 4.95 Light oil 5 10 20 30 40 50 60 70 80 90 95 Emulsification stability ◯ ◯ ◯ Δ Δ Δ Δ X X X X (7 days/room temperature) Emulsification stability ◯ ◯ ◯ Δ Δ Δ Δ X X X X (90 days/room temperature) Emulsified state (1) (2) (3) Figures are shown in wt %. ◯: No phase separation, Δ: Separated due to the difference in specific gravity (coacervation), X: Separated (1): O/W type emulsion, (2): W/O type emulsion, (3): W/O micro emulsion and separated aqueous phase

(110) TABLE-US-00023 TABLE 23 Example (4) of light oil emulsification at various concentrations of HCO-10. HCO-10 Concentration Water Light oil Emulsified state 0.5 49.5 50 Δ 1 49 50 Δ 2.5 47.5 50 ◯ 5 45 50 ◯ 10 40 50 ◯ Figures are shown in wt %. ◯: No phase separation, Δ: Separated due to the difference in specific gravity (coacervation)

(111) As shown by the above results, a composition consisting of HCO-10 at 0.4-10.0 wt %, light oil at 5-95 wt % and the corresponding proportion of water, and preferably a composition consisting of HCO-10 at 0.8-10.0 wt %, light oil at 5-60 wt %, and the corresponding proportion of water are recommended.

(112) In the examples so far, cases were shown using light oil and heavy oil A; furthermore, in the examples of emulsification with gasoline, kerosene, and heavy oil C, as shown in Table 24, stable emulsified states have also been observed using a small amount of emulsification dispersant.

(113) TABLE-US-00024 TABLE 24 Examples of the emulsified state according to different oils. Emulsified Oil type HCO-10 Water state Gasoline 5 45 ◯ kerosene 5 45 ◯ Heavy oil C 5 45 ◯ Figures are in wt %. Oil content is 50 wt %.

(114) An emulsification with high viscosity heavy oil has to go through a viscosity-conditioning process. As for the viscosity-conditioning agent to be used therein, light oil, low viscosity oil obtained as a distillate from the oil refining process, or heavy oil A is preferred; however, as long as homogeneously mixable with high viscosity heavy oil, oil type need not be particularly limited.

(115) In Table 25 and in FIG. 13, the results of the viscosity conditioning using petroleum, light oil, Heavy oil A, and liquid paraffin are shown.

(116) TABLE-US-00025 TABLE 25 Viscosity of each type of conditioned heavy oil kerosene 10 20 30 40 50 60 70 80 90 Residue oil 90 80 70 60 50 40 30 20 10 Viscosity (mPs) — 33383 2250 341 122 76 65 61 61 Viscosity of heavy oil conditioned with light oil Light oil 10 20 30 40 50 60 70 80 90 Residue oil 90 80 70 60 50 40 30 20 10 Viscosity (mPs) — 98980 7005 922 230 112 71 61 61 Viscosity of heavy oil conditioned with heavy oil A Heavy oil A 10 20 30 40 50 60 70 80 90 Residue oil 90 80 70 60 50 40 30 20 10 Viscosity (mPs) — 16900 6536 1794 317 147 92 75 66 Viscosity of heavy oil conditioned with liquid paraffin Liquid paraffin 10 20 30 40 50 60 70 80 90 Residue oil 90 80 70 60 50 40 30 20 10 Viscosity (mPs) — — — 95064 19788 10384 1461 849 339 —: immeasurable (20° C., B-type viscometer, Rotor No. 3 is used) Viscosity of heavy oil conditioned with kerosene

(117) In FIG. 13, up to approx. 30,000 mPs does not cause a handling problem in the next process. As for an emulsification example in which 40 wt % of liquid paraffin was used as the viscosity-conditioning agent, although the emulsification itself was possible, subsequent handling was difficult due to unfavorable fluidity.

(118) Furthermore, results of the emulsifications of a conditioned heavy oil using heavy oil A added at 30 wt % as a viscosity conditioning agent and 10 wt % HCO-10 aqueous dispersion are shown in Table 26 and Table 27.

(119) TABLE-US-00026 TABLE 26 An emulsification example of conditioned heavy oil (Heavy oil A 30 wt %) with 10 wt % HCO-10 dispersion No. 1 2 3 4 5 6 7 8 9 10 HCO-10 9 8 7 6 5 4 3 2 1 0.5 Water 81 72 63 54 45 36 27 18 9 4.5 Conditioned heavy oil 10 20 30 40 50 60 70 80 90 95 Emulsification stability ◯ ◯ ◯ ◯ ◯ ◯ ◯ Δ X X (1 month/room temperature) Figures are shown in wt % ◯: No phase separation, Δ: Separated due to the difference in specific gravity (coacervation), X: Separated

(120) TABLE-US-00027 TABLE 27 An emulsification example of conditioned heavy oil with various concentration of HCO-10. Conditioned Emulsified HCO-10Concentration Water heavy oil state 0.5 49.5 50 ◯ 1 49 50 ◯ 2.5 47.5 50 ◯ 5 45 50 ◯ 0.3 29.7 70 ◯ 1.5 28.5 70 ◯ 3 27 70 ◯ Figures are shown in wt %. ◯: No phase separation, Δ: Separated due to the difference in specific gravity (coacervation) Viscosity conditioning agent: heavy oil A, Heavy oil A/high viscosity heavy oil wt ratio = 3/7

(121) In addition, examples of emulsification experiments wherein petroleum, light oil, and liquid paraffin were used as viscosity-conditioning agents are shown in Table 28, Table 29, and Table 30.

(122) TABLE-US-00028 TABLE 28 Emulsification example (1) of each type of conditioned heavy oil with 10 wt % HCO-10 dispersion. Oil type Heavy Liquid kerosene/ Light oil/ oil A/ paraffin/ heavy oil heavy oil heavy oil heavy oil Viscosity conditioning 30/70 30/70 30/70 40/60 agent/ Heavy oil Conditioned heavy oil 50 50 50 50 Water 45 45 45 45 HCO-10  5  5  5  5 Emulsification stability ◯ ◯ ◯ Δ (1 month/room temperature) Figures are shown in wt %. ◯: No phase separation (good fluidity) Δ: No phase separation (fluidity defect)

(123) TABLE-US-00029 TABLE 29 Emulsification example (2) of each type of conditioned heavy oil with 10 wt % HCO-10 dispersion. Oil type Heavy Liquid kerosene/ Light oil/ oil A/ paraffin/ heavy oil heavy oil heavy oil heavy oil Viscosity conditioning 30/70 30/70 30/70 40/60 agent/ Heavy oil Conditioned heavy oil 70 70 70 70 Water 27 27 27 27 HCO-10  3  3  3  3 Emulsification stability ◯ ◯ ◯ Δ (1 month/room temperature) Figures are shown in wt %. ◯: No phase separation (good fluidity) Δ: No phase separation (fluidity defect)

(124) TABLE-US-00030 TABLE 30 Emulsification example (3) of each type of conditioned heavy oil with 10 wt % HCO-10 dispersion. Oil type kerosene/ Light oil/ Heavy oil A/ heavy oil heavy oil heavy oil Viscosity conditioning agent/ 50/50 50/50 50/50 Heavy oil Conditioned heavy oil 70 70 70 Water 27 27 27 HCO-10  3  3  3 Emulsification stability ◯ ◯ ◯ (1 month/room temperature) Figures are shown in wt %. ◯: No phase separation (good fluidity) Δ: No phase separation (fluidity defect)

(125) As shown by the above results, a composition consisting of HCO-10 at 0.3-9 wt %, conditioned heavy oil at 80-10 wt % and the corresponding proportion of water, and preferably a composition consisting of HCO-10 at 0.3-9 wt %, conditioned heavy oil at 70-30 wt+% and the corresponding proportion of water are recommended.

(126) Combustion experiments using a light oil emulsion and a heavy oil A emulsion were individually conducted. Using a combustion device specifically designated for kerosene, without modifying the burner, the emulsion fuels were completely burnt without extinguishing.

(127) The results of the measurement of exhaust gases from the light oil combustion are shown in FIG. 14, and the results of the measurement of exhaust gases from the heavy oil A combustion are shown in FIG. 15.

(128) As shown by FIG. 14, when the fuel was changed from light oil to emulsion, the NOx concentration in the exhaust gases was significantly reduced, and became approximately 1/10 of the regular concentration for normal fuel once the combustion was stabilized. Furthermore, although the CO concentration was previously increased, a tendency toward reduction was observed along with the SO.sub.2 concentration. On the contrary, the oxygen concentration in the exhaust gases increased, and the CO.sub.2 concentration also increased even taking account that considering that the fuel component was 50 wt %. Therefore, the combustion is deemed to be more complete than a fuel solely comprised of light oil. The combustion temperature of the light oil and the emulsion was approx. 1150° C. and 950° C., respectively, a decrease of approximately 200° C.

(129) In addition, as clearly shown by FIG. 15, when the fuel change occurred from heavy oil A to emulsion, the NOx concentration in the exhaust gas was significantly reduced, and became approximately ⅙ of the regular concentration of normal fuel once the combustion was stabilized. Although the CO concentration was previously increased, a tendency toward reduction was observed along with the SO.sub.2 concentration. On the contrary, the oxygen concentration in the exhaust gases increased, and the CO.sub.2 concentration also increased even taking account that considering that the fuel component was 50 wt %. Therefore, the combustion is deemed to be more complete than a fuel solely comprised of heavy oil A. The combustion temperature of the Heavy oil A and the emulsion was approx. 1050° C. and 900° C., respectively, a decrease of approximately 150° C.

(130) Hence, by using the emulsion fuels described above, it is expected that air pollution can be significantly decreased, and thus reducing the adverse effects on the environment.

INDUSTRIAL APPLICATION

(131) The invention is applicable to functional oil-based agents such as cosmetics, medical products, food products, agrichemicals, fuel emulsions, soil conditioners, etc, or applicable to emulsified preparations in which granule particles have been emulsified and dispersed, and also applicable to uses involving dispersions, etc.