JP7063703B2 - Emulsion stabilization method and emulsion and emulsion fuel using it - Google Patents

Description

The present invention relates to a method for stabilizing a water-in-oil (W / O) emulsion in which water is dispersed in animal and vegetable oil, and an emulsion.

Fats and oils such as animal and vegetable oils are renewable biomass and have better biodegradability than petroleum products prepared from fossil fuels. Attention is gathering. Fatty acids, glycerol, higher alcohols, which are decomposition products of fats and oils, and their derivatives are used as basic chemicals for fats and oils in various final products such as cosmetics, pharmaceuticals, surfactants, plasticizers, lubricants, paints, fuels, and inks. However, the fat itself is also widely used as a processed fat or oil alone or as an emulsion (emulsion) (Non-Patent Document 1).

Non-Patent Document 2 describes the state of an emulsion (emulsion), its measurement method, the basics of stabilization, and the emulsification technique. An emulsion is one in which one of the liquid phases that do not dissolve in each other, such as water and oil, is dispersed in the other as fine droplets, and the phase dispersed as particles (droplets) is called the "dispersed phase". The outer medium is called the "continuous phase", and the system in which oil droplets are dispersed in water is Oil-in-Water (O / W), and the system in which water droplets are dispersed in oil is Water-in-Oi1 (W / O). It is called a mold emulsion.

In order to form an emulsion, it is necessary to apply mechanical energy to the mass of the dispersed phase to form fine particles.However, since the emulsion usually has a high energy state and is thermodynamically unstable, it is a surfactant. Therefore, it is necessary to reduce the interfacial energy and add energy by an external force.

As an emulsion consisting only of water and oil without using a surfactant, for example, in Patent Document 1, an emulsion is prepared from water and camellia oil by an emulsion manufacturing apparatus using the surface of a wetted portion in contact with the emulsion liquid as an insulating material. Method, Patent Document 2 describes a method of producing an emulsion fuel by a device that pressurizes water and fuel oil using a high-pressure pump and mixes water and fuel oil using an ejector. The former emulsion is an O / W emulsion, and its stabilizing mechanism is that the oil droplets are repelled by each other by charging the surface of the oil droplets to stabilize the dispersion. For the latter emulsion, a W / O emulsion is prepared by applying external force energy by an apparatus.

However, in an emulsion consisting only of water and oil without using a surfactant, even if the dispersed phase is once dispersed in a continuous phase, the dispersed state cannot be stabilized for a long period of time. Even if it is stabilized once, it is not suitable for practical use because it tends to lose its stability depending on the storage tank and usage environment.

Various methods using a third substance without using a surfactant have also been studied. Non-Patent Document 3 introduces a pickering emulsion, which is an emulsion stabilized by solid particles adsorbed on an oil-water interface. Further, Patent Document 3 discloses a three-phase emulsification method in which nanoparticles of an amphipathic compound existing as an independent phase in an oil / amphipathic compound / aqueous system are emulsified by adhering to the oil by van der Waals force. Has been done.

However, since the interfacial tension is not lowered by these methods, although stabilization can be achieved by optimization, there are problems in quality stability, reproducibility, and cost because there are restrictions on the interfacial adsorption of particles and the method of preparing an emulsion.

On the other hand, in the emulsification method using a surfactant, the basic principle of the emulsification / dispersion method is to adsorb the surfactant at the interface between oil and water and reduce the interface energy. Since W / O emulsions easily develop oily components on the skin and have high emollient properties, water-in-oil (W / O) emulsions using these technologies can be used in cosmetics, pharmaceuticals, foods, fuels, etc. It is widely used for inks and the like (Patent Documents 4 to 8).

Water-in-oil (W / O) emulsions using fossil fuels and animal and vegetable oils have been used as fuels for emulsion fuels using various emulsifiers (Patent Documents 9 to 12). Animal and vegetable oil is a renewable raw material, and is attracting attention as a main fuel oil for internal combustion engines as an alternative to heavy oil and light oil due to problems such as global warming and depletion of fossil fuels. Although direct fuel conversion has been studied for a long time, animal and vegetable oils have high viscosity, high boiling point and low _{evaporability} , so they have low NOx, but their spray characteristics deteriorate and nozzles in the engine It was difficult to continue using it due to problems such as the accumulation of carbon-like substances on the tip of the chip and the formation of sticks on the piston ring, which caused serious problems (Non-Patent Documents 4 and 5). In order to solve these problems, the above emulsion fuel and further nanoemulsion fuel (Non-Patent Document 6) have been developed. However, in general, since the animal and vegetable oil has a certain degree of polarity, the emulsifier dissolves in the animal and vegetable oil and does not efficiently adsorb to the oil-water interface, so it is necessary to add a large amount of emulsifier to keep the emulsification stable. There was a problem. Therefore, the present inventors have developed a formulation that improves high-temperature stability by blending a polymer such as a carboxymethyl cellulose salt with water (Patent Document 13).

Japanese Unexamined Patent Publication No. 2013-000704 Japanese Unexamined Patent Publication No. 2009-203233 Japanese Unexamined Patent Publication No. 2006-241424 International Publication No. 1999/025310 Japanese Unexamined Patent Publication No. 2005-126369 Japanese Unexamined Patent Publication No. 2005-151834 Japanese Unexamined Patent Publication No. 2012-184366 Japanese Unexamined Patent Publication No. 2007-308617 Japanese Unexamined Patent Publication No. 6-346071 Japanese Patent Application Laid-Open No. 2003-201485 Japanese Unexamined Patent Publication No. 2009-280761 Japanese Patent Application Laid-Open No. 2015-214616 Japanese Unexamined Patent Publication No. 2016-121250 Japanese Unexamined Patent Publication No. 2012-016668 Japanese Unexamined Patent Publication No. 8-192001

Basics and applications of fats and oils, edited by Japan Oil Chemists' Society (2005) Color material, 77 (10) 462-469 (2004) Dictionary of Modern Interfacial Colloidal Science p186-187 Cosmetics 1-Pickering Emulsion (2010) Use of palm oil and palm kernel oil Low Carbon Flower Buildup, Low Smoke, and Efficient Diesel Operation with Vegetable Oils by Conversion to Mono-Esters and Blending with Diesel Oil or Alcohols 1984, SAE Paper, No.841161, Murayama, T. et al New Energy Venture Technological Innovation Business New Energy Venture Technological Innovation Business (Biomass) Development of Practical Biomass Fuel by Degaming and Emulsifying Palm Crude Oil (2010-2011 Results Report) J. Soc. Cosmet. Chem. Jpn. 44 (4) 1269-277 (2010) Langmir, 7 (7), 1370-1377 (1991)

However, emulsions are generally thermodynamically unstable and require more emulsifiers to maintain high temperature and long-term stability, resulting in emulsifier-derived skin irritation, stinks, off-flavors and thickening. Depending on the application, the effect on the effect is a problem. In particular, it is known that there are far fewer methods for stabilizing W / O emulsions as compared with O / W emulsions, and the stability further decreases as the amount of water added increases.

Non-Patent Document 1 describes a D-phase emulsification method, a liquid crystal emulsification method, a phase inversion temperature emulsification method, and a method of adding a higher alcohol as an emulsification aid as a method for stabilizing an O / W emulsion. It is known that the method of adding a higher alcohol as an emulsifying aid improves the stability by thickening the system and turning it into a liquid crystal state. There is no description of improvement.

Non-Patent Document 7 describes the improvement of the stability of the system by using a higher fatty acid in a specific preparation, but it is a method for stabilizing an O / W emulsion, and the effect on the W / O emulsion is Not mentioned.

Non-Patent Document 8 describes that various alcohols and stearic acids are used as stabilizers for W / O emulsions, but styrene-divinylbenzene oils are used, and the description in animal and vegetable oils is described. not.

Further, Patent Document 14 relates to a water-in-oil (W / O) type emulsion obtained by a three-phase emulsification method using a petroleum-based hydrocarbon solvent as an oil phase and a reverse vesicle as an emulsifier, for the purpose of reducing viscosity. However, it is said that a long-chain fatty acid having 12 or more carbon atoms or a salt thereof can be contained, but there is no suggestion about the expression of the stability improving effect.

Patent Document 15 states that the combined effect of fatty acids is useful for assisting emulsification and imparting excellent emulsion stability with a small amount of emulsifier, but with an organopolysiloxane composition composed of silicone oil and fine powder silica. In Example 3 which is for a W / O emulsion type defoaming agent composition with water and uses a fatty acid and an emulsifier, the total amount used is as large as 25% (20 parts out of 80 parts).

Among fuel oils, vegetable oils and animal oils may have a high melting point or a high viscosity at room temperature in emulsion fuel applications. When using such fuel oils, the viscosity should be such that the load is not applied to transportation or the engine. Therefore, it is necessary to store the emulsion fuel at a high temperature.

However, since the separation of emulsion fuel is promoted as the amount of emulsifier added is small and the temperature is high, a stable emulsion fuel that has a particularly small amount of emulsifier added and suppresses separation even at 60 ° C or higher and maintains a uniform emulsion state for a long time It is important to manufacture. Further, even if the same kind of animal and vegetable oils are used, there is a problem that the stability of the emulsion fuel varies.

The present invention has been made in view of the above circumstances, and water is dispersed in animal and vegetable oils that can stably maintain an emulsified state at high temperature and for a long period of time even if the amount of emulsifier used is reduced. It is an object of the present invention to provide a method for stabilizing a water-in-oil (W / O) emulsion and an emulsion fuel using the water-in-oil (W / O) emulsion.

In order to solve the above problems, the method for stabilizing the emulsion of the present invention comprises at least one oil selected from (A) vegetable oil and animal oil, (B) water, (C) polyhydric alcohol hydroxy fatty acid ester or At least one emulsifier selected from the derivative, (D) fatty acid is contained as an optional component, and the acid value of the oil (A) and the fatty acid (D) is 0.3 to 100 mgKOH / g in the oil. It is characterized by preparing an aqueous (W / O) emulsion.

The method for stabilizing an emulsion of the present invention is at least one selected from (A) at least one oil selected from vegetable oils and animal oils, (B) water, (C) polyhydric alcohol hydroxy fatty acid esters or derivatives thereof. It is characterized by containing an emulsifier and (D) fatty acid as an optional component, and preparing a water-in-oil (W / O) emulsion so that the acid value of the emulsion is 0.4 to 100 mgKOH / g.

The water-in-oil (W / O) emulsion of the present invention is selected from at least one oil selected from (A) vegetable oil and animal oil, (B) water, (C) polyhydric alcohol hydroxy fatty acid ester or a derivative thereof. It is characterized in that it contains at least one emulsifier, (D) fatty acid as an optional component, and the acid value of (A) oil and (D) fatty acid as a whole is 0.3 to 100 mgKOH / g.

The water-in-oil (W / O) emulsion of the present invention is selected from at least one oil selected from (A) vegetable oil and animal oil, (B) water, (C) polyhydric alcohol hydroxy fatty acid ester or a derivative thereof. It is characterized by containing at least one emulsifier, (D) fatty acid as an optional component, and an acid value of 0.4 to 100 mgKOH / g of the emulsion.

The emulsion fuel of the present invention is characterized by using the emulsion.

According to the present invention, even if the amount of the emulsifier used is reduced, the emulsified state can be stably maintained at high temperature and for a long period of time.

It is a micrograph of an emulsion. It is a photograph of the phase separation state (60 ° C.) of an emulsion. It is a photograph of the phase separation state (80 ° C.) of an emulsion.

Hereinafter, the present invention will be described in detail.

The oil (A) used for the emulsion in the present invention is at least one selected from vegetable oils and animal oils.

Vegetable oils include jatrofa oil, rapeseed oil, soybean oil, rice bran oil, castor oil, cottonseed oil, corn oil, sunflower oil, palm oil and its fractionated oils (palm olein oil, palm double olein oil, palm stea, which is a high melting point fraction). Oil, etc.) and the like. Examples of animal oils include beef tallow, lard, sheep tallow, chicken fat, fish oil and the like. These may be crude oil refined, modified or degummed. Further, refined animal and vegetable oils may be hydrogenated, transesterified, or fractionated and crystallized. In addition, waste animal and vegetable oils such as waste cooking oil may be used for these from the viewpoint of reducing wastewater treatment costs and recycling resources.

The water (B) used in the emulsion of the present invention is not particularly limited, such as purified water, ultrapure water, RO water, ion-exchanged water, tap water, and well water, but neutral water may be used, for example. Desirably, when acidic or alkaline water is used, it can be purified by neutralization, ion exchange or the like.

The emulsifier (C) used in the emulsion in the present invention is at least one selected from polyhydric alcohol hydroxy fatty acid esters or derivatives thereof.

The polyhydric alcohol hydroxy fatty acid ester is a compound having a structure in which a trihydric or higher aliphatic polyhydric alcohol and a hydroxy fatty acid are ester-bonded.

Examples of the derivative of the polyhydric alcohol hydroxy fatty acid ester include an alkylene oxide adduct of the polyhydric alcohol hydroxy fatty acid ester or a fatty acid ester thereof.

The alkylene oxide adduct of the polyhydric alcohol hydroxy fatty acid ester is a compound having a structure in which the alkylene oxide is added to the polyhydric alcohol hydroxy fatty acid ester.

The fatty acid ester of the alkylene oxide adduct of the polyhydric alcohol hydroxy fatty acid ester is a compound having a structure in which the polyhydric alcohol hydroxy fatty acid ester alkylene oxide adduct and the fatty acid are ester-bonded.

Examples of the trihydric or higher aliphatic polyhydric alcohol in the polyhydric hydroxy fatty acid ester include glycerin, polyglycerin, sorbitol, pentaerythritol, sucrose and the like. Among these, glycerin and polyglycerin are preferable.

Examples of the hydroxy fatty acid in the polyhydric alcohol hydroxy fatty acid ester include 2-hydroxylauric acid (C12), 2-hydroxymyristic acid (C14), 2-hydroxypalmitic acid (C16), and 3-hydroxypalmitic acid (C16). 8-Hydroxypalmitic acid (C16), 2-hydroxystearic acid (C18), 3-hydroxystearic acid (C18), 12-hydroxystearic acid (C18), 17-hydroxystearic acid (C18), 18-hydroxystearic acid (C18), ricinolic acid (C18: 1), α-oxylinolenic acid (C18: 3), 3,11-dihydroxymyristic acid, 3,12-dihydroxymyristic acid, Treo-9, 10-dihydroxystearic acid (C18) ), Elytro-9, 10-dihydroxystearic acid (C18), 2,15,16-trihydroxypalmitic acid (C16), sesame oil fatty acid, hardened pine oil fatty acid, dihydroxylated rapeseed oil fatty acid and the like, and these hydroxy fatty acids. Condensed hydroxy fatty acids, which are dehydration condensates of the above alone or different kinds. Among these, ricinoleic acid, 12-hydroxystearic acid, 9,10-dihydroxystearic acid, condensed ricinoleic acid, condensed hydroxystearic acid, condensed dihydroxystearic acid, and condensed castor oil fatty acid are preferable. These may be used alone or in combination of two or more.

Examples of the alkylene oxide in the alkylene oxide adduct of the polyhydric alcohol hydroxy fatty acid ester include ethylene oxide, propylene oxide, butylene oxide and the like. Among these, it is preferable to use ethylene oxide alone.

The fatty acid in the fatty acid ester of the alkylene oxide adduct of the polyhydric alcohol hydroxy fatty acid ester is not particularly limited, and examples thereof include saturated, unsaturated and branched fatty acids contained in fats and oils. Examples of the saturated fatty acid include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, lignoceric acid and the like. Examples of unsaturated fatty acids include myristoleic acid, palmitoleic acid, oleic acid, erucic acid, erucic acid, linoleic acid, eikosazienoic acid, docosadienoic acid, linolenic acid, erucic acid, docosahexaenoic acid, and arachidonic acid. .. Examples of the branched fatty acid include 2-ethylhexanoic acid, isononanoic acid, dimethyloctanoic acid, isomyristic acid, isoparmitic acid, isostearic acid and the like. These may be used alone or in combination of two or more.

As the polyhydric alcohol hydroxy fatty acid ester of the emulsifier (C) used in the emulsion of the present invention, a polyglycerin condensed hydroxy fatty acid ester is preferable. Examples of the polyglycerin condensed hydroxy fatty acid ester include polyglycerin condensed lysynoleic acid ester, polyglycerin condensed hydroxystearic acid ester, polyglycerin condensed dihydroxystearic acid ester and the like.

Examples of the polyglycerin-condensed ricinol acid ester include diglycerin-condensed ricinol acid ester, tetraglycerin-condensed ricinol acid ester, pentaglycerin-condensed ricinol acid ester, hexaglycerin-condensed lysinol acid ester, octaglycerin-condensed ricinol acid ester, and decaglycerin-condensed ricinol acid ester. Examples thereof include acid esters. Among these, diglycerin-condensed ricinoleic acid ester, tetraglycerin-condensed ricinoleic acid ester, pentaglycerin-condensed ricinoleic acid ester, and hexaglycerin-condensed ricinoleic acid ester are preferable.

Examples of the polyglycerin condensed hydroxystearic acid ester include diglycerin condensed hydroxystearic acid ester, tetraglycerin condensed hydroxystearic acid ester, pentaglycerin condensed hydroxystearic acid ester, hexaglycerin condensed hydroxystearic acid ester, and octaglycerin condensed hydroxystearic acid. Examples thereof include esters and decaglycerin condensed hydroxystearic acid esters. Among these, diglycerin condensed hydroxystearic acid ester, tetraglycerin condensed hydroxystearic acid ester, pentaglycerin condensed hydroxystearic acid ester, and hexaglycerin condensed hydroxystearic acid ester are preferable.

Examples of the polyglycerin condensed dihydroxystearic acid ester include diglycerin condensed dihydroxystearic acid ester, tetraglycerin condensed dihydroxystearic acid ester, pentaglycerin condensed dihydroxystearic acid ester, hexaglycerin condensed dihydroxystearic acid ester, and octaglycerin condensed dihydroxystearic acid. Examples thereof include esters and decaglycerin condensed dihydroxystearic acid esters. Among these, diglycerin condensed hydroxystearic acid ester, tetraglycerin condensed hydroxystearic acid ester, and pentaglycerin condensed hydroxystearic acid ester are preferable.

As the alkylene oxide adduct of the polyhydric alcohol hydroxy fatty acid ester of the emulsifier (C) used in the emulsion of the present invention or the fatty acid ester thereof, the alkylene oxide adduct of the glycerin hydroxy fatty acid ester or the fatty acid ester thereof is preferable.

As the alkylene oxide adduct of glycerin hydroxy fatty acid ester or its fatty acid ester, for example, polyoxyalkylene gourd oil containing glycerin trilysinol acid ester polyoxyalkylene adduct as a main component and glycerin trihydroxystearic acid polyoxyalkylene adduct are mainly used. Polyoxyalkylene hardened bean oil which is a component, polyoxyalkylene dihydroxylated rapeseed oil which is mainly composed of glycerin tridihydroxystearic acid polyoxyalkylene adduct, polyoxyalkylene bean oil which is a fatty acid ester of glycerin tolyricinol acid ester. Examples include fatty acid ester, polyoxyalkylene cured castor oil fatty acid ester which is a glycerin trihydroxystearic acid polyoxyalkylene adduct fatty acid ester, glycerin tridihydroxystearic acid polyoxyalkylene adduct fatty acid ester, and polyoxyalkylene dihydroxylated rapeseed oil fatty acid ester. Be done.

Examples of the polyoxyalkylene castor oil include polyoxyethylene (4) castor oil, polyoxyethylene (7.5) castor oil, polyoxyethylene (10) castor oil, polyoxyethylene (20) castor oil, and polyoxyethylene (25) castor oil. , Polyoxyethylene (30) castor oil, polyoxyethylene (50) castor oil and the like.

Examples of the polyoxyalkylene hardened castor oil include polyoxyethylene (5) hardened castor oil, polyoxyethylene (10) hardened castor oil, polyoxyethylene (15) hardened castor oil, polyoxyethylene (20) hardened castor oil, and polyoxyethylene ( 25) Hardened castor oil, polyoxyethylene (30) hardened castor oil, polyoxyethylene (40) hardened castor oil, polyoxyethylene (50) hardened castor oil, polyoxyethylene (60) hardened castor oil, polyoxyethylene (80) hardened castor oil, Examples thereof include polyoxyethylene (100) hardened castor oil.

Examples of the polyoxyalkylene castor oil fatty acid ester include polyoxyethylene (4) castor oil triisostearate, polyoxyethylene (7.5) castor oil triisostearate, polyoxyethylene (10) castor oil triisostearate, and poly. Oxyethylene (20) Castor oil triisostearate, Polyoxyethylene (25) Castor oil triisostearate, Polyoxyethylene (30) Castor oil triisostearate, Polyoxyethylene (50) Castor oil triisostearate, Polyoxyethylene (4) Castor oil diisostearate, polyoxyethylene (7.5) Castor oil diisostearate, polyoxyethylene (10) Castor oil diisostearate, polyoxyethylene (20) Castor oil diisostearate, polyoxyethylene (25) Castor oil diisostearate, polyoxyethylene (30) Castor oil diisostearate, polyoxyethylene (50) Castor oil diisostearate, polyoxyethylene (4) Castor oil trioleate, polyoxyethylene (7.5) Castor oil trioleate, polyoxyethylene (10) castor oil trioleate, polyoxyethylene (20) castor oil trioleate, polyoxyethylene (25) castor oil trioleate, polyoxyethylene (30) castor oil trioleate, polyoxyethylene (50) castor oil trioleate, polyoxy Ethylene (4) castor oil dioleate, polyoxyethylene (7.5) castor oil dioleate, polyoxyethylene (10) castor oil dioleate, polyoxyethylene (20) castor oil dioleate, polyoxyethylene (25) castor oil dioleate, polyoxyethylene (30) ) Castor oil dioleate, polyoxyethylene (50) castor oil dioleate and the like.

Examples of the polyoxyalkylene hardened bean oil fatty acid ester include polyoxyethylene (5) hardened bean oil triisostearate, polyoxyethylene (10) hardened bean oil triisostearate, and polyoxyethylene (15) hardened bean oil triisostearate. , Polyoxyethylene (20) Hardened Stearic Acid Triisostearate, Polyoxyethylene (25) Hardened Stearic Acid Triisostearate, Polyoxyethylene (30) Hardened Stearic Acid Triisostearate, Polyoxyethylene (40) Hardened Stearic Acid Triiso Stearate, Polyoxyethylene (50) Hardened Stearic Acid Triisostearate, Polyoxyethylene (60) Hardened Stearic Acid Triisostearate, Polyoxyethylene (80) Hardened Stearic Acid Triisostearate, Polyoxyethylene (100) Hardened Stearic Acid Triisostearate, polyoxyethylene (5) hardened sardine oil diisostearate, polyoxyethylene (10) hardened sardine oil diisostearate, polyoxyethylene (15) hardened sardine oil diisostearate, polyoxyethylene (20) Hardened sardine oil diisostearate, polyoxyethylene (25) hardened sardine oil diisostearate, polyoxyethylene (30) hardened sardine oil diisostearate, polyoxyethylene (40) hardened sardine oil diisostearate, polyoxyethylene ( 50) Hardened sardine oil diisostearate, polyoxyethylene (60) hardened sardine oil diisostearate, polyoxyethylene (80) hardened sardine oil diisostearate, polyoxyethylene (100) hardened sardine oil diisostearate, polyoxy Ethylene (5) Hardened Stearic Acid Trioleate, Polyoxyethylene (10) Hardened Stearic Acid Tritrioleate, Polyoxyethylene (15) Hardened Stearic Acid Tritrioleate, Polyoxyethylene (20) Hardened Stearic Acid Tritrioleate, Polyoxyethylene (25) Hardened Stearic Acid Tritrioleate, Polyoxyethylene (30) Hardened Stearic Acid Tritrioleate, Polyoxyethylene (40) Hardened Stearic Acid Tritrioleate, Polyoxyethylene (50) Hardened Stearic Acid Tritrioleate, Polyoxyethylene (60) Hardened Stearic Acid Trioleate, Polyoxyethylene (80) Hardened Stearic Acid Trioleate, Polyoxyethylene (100) Hardened Stearic Acid Trioleate, Polyoxyethire (5) Hardened castor oil diolate, Polyoxyethylene (10) Hardened castor oil trioleate, Polyoxyethylene (15) Hardened castor oil diolate, Polyoxyethylene (20) Hardened castor oil diolate, Polyoxyethylene (25) Hardened castor oil diisooleate, Polyoxy Ethylene (30) Hardened Castor Oil Dioreate, Polyoxyethylene (40) Hardened Castor Oil Dioreate, Polyoxyethylene (50) Hardened Castor Oil Dioreate, Polyoxyethylene (60) Hardened Castor Oil Dioreate, Polyoxyethylene (80) Hardened Castor Oil Dioreate, Polyoxy Examples thereof include ethylene (100) hardened castor oil dioleate.

Examples of the polyoxyalkylene dihydroxylated canola oil include polyoxyethylene (5) dihydroxylated canola oil, polyoxyethylene (10) dihydroxylated canola oil, polyoxyethylene (15) dihydroxylated canola oil, and polyoxyethylene (20). ) Dihydroxylated canola oil, polyoxyethylene (25) dihydroxylated canola oil, polyoxyethylene (30) dihydroxylated canola oil, polyoxyethylene (50) dihydroxylated canola oil and the like.

Examples of the polyoxyalkylene dihydroxylated rapeseed oil fatty acid ester include polyoxyethylene (5) dihydroxylated rapeseed oil tetraisostearate, polyoxyethylene (10) dihydroxylated rapeseed oil tetraisostearate, and polyoxyethylene (15). Dihydroxylated rapeseed oil tetraisostearate, polyoxyethylene (20) dihydroxylated rapeseed oil tetraisostearate, polyoxyethylene (25) dihydroxylated rapeseed oil tetraisostearate, polyoxyethylene (30) dihydroxylated rapeseed oil tetra Isostearate, polyoxyethylene (50) dihydroxylated rapeseed oil tetraisostearate, polyoxyethylene (5) dihydroxylated rapeseed oil triisostearate, polyoxyethylene (10) dihydroxylated rapeseed oil triisostearate, poly Oxyethylene (15) dihydroxylated rapeseed oil triisostearate, polyoxyethylene (20) dihydroxylated rapeseed oil triisostearate, polyoxyethylene (25) dihydroxylated rapeseed oil triisostearate, polyoxyethylene (30) Dihydroxylated Rapeseed Oil Triisostearate, Polyoxyethylene (50) Dihydroxylated Rapeseed Oil Triisostearate, Polyoxyethylene (5) Dihydroxylated Rapeseed Oil Tetraoleate, Polyoxyethylene (10) Dihydroxylated Rapeseed Oil Tetraole Ate, polyoxyethylene (15) dihydroxylated rapeseed oil tetraoleate, polyoxyethylene (20) dihydroxylated rapeseed oil tetraoleate, polyoxyethylene (25) dihydroxylated rapeseed oil tetraoleate, polyoxyethylene (30) Dihydroxylated rapeseed oil tetraoleate, polyoxyethylene (50) dihydroxylated rapeseed oil tetraoleate, polyoxyethylene (5) dihydroxylated rapeseed oil trioleate, polyoxyethylene (10) dihydroxylated rapeseed oil trioleate, polyoxyethylene ( 15) Dihydroxylated rapeseed oil trioleate, polyoxyethylene (20) dihydroxylated rapeseed oil trioleate, polyoxyethylene (25) dihydroxylated rapeseed oil trioleate, polyoxyethylene (30) dihydroxylated rapeseed oil trioleate, polyoxyethylene (50) Examples thereof include dihydroxylated rapeseed oil trioleate.

As the emulsifier (C) used for the emulsion in the present invention, a polyglycerin condensed hydroxy fatty acid ester, an ethylene oxide adduct of a glycerin hydroxy fatty acid ester or a fatty acid ester thereof is particularly preferable, and for example, a polyglycerin condensed lysinol acid ester or poly. Examples thereof include oxyethylene bean oil or a fatty acid ester thereof, polyoxyethylene hydrogenated bean oil or a fatty acid ester thereof, polyoxyethylene dihydroxylated rapeseed oil or a fatty acid ester thereof.

The emulsifier (C) used in the emulsion in the present invention may contain an organic carboxylic acid derived from unreacted raw materials, impurities, by-products and the like, and an acid component derived from the residue of an acidic catalyst.

A nonionic surfactant other than the above may be used in combination as the emulsifier, and the nonionic surfactant other than the above is not particularly limited, and examples thereof include polyglycerin fatty acid ester.

In the present invention, the fatty acid (D) as an optional component contained in the emulsion is not particularly limited as long as it is a fatty acid, but a fatty acid having 8 to 24 carbon atoms is preferable from the viewpoint of emulsification stability, and a fatty acid having 12 to 18 carbon atoms is preferable. Fatty acids are more preferred.

Examples of fatty acids include saturated fatty acids, unsaturated fatty acids, branched fatty acids, and hydroxy fatty acids. The fatty acid may be a fatty acid contained in fats and oils.

Examples of the saturated fatty acid include, but are not limited to, caprylic acid (C8, melting point 16.7 ° C.), capric acid (C10, melting point 31 ° C.), lauric acid (C12, melting point 44-46 ° C.), myristic acid (C14, Melting point 54.4 ° C), palmitic acid (C16, melting point 62.9 ° C), stearic acid (C18, melting point 69.6 ° C), behenic acid (C22, melting point 79.9 ° C), lignoceric acid (C24, melting point 84) .2 ° C) and the like. Among them, palmitic acid and stearic acid are preferable from the viewpoint of stability.

The unsaturated fatty acid is, for example, caproleic acid (C10: 1), lindelic acid (C12: 1), myristoleic acid (C14: 1), palmitreic acid (C16: 1), sapienoic acid (C16: 1), but not particularly limited. C16: 1), oleic acid (C18: 1), elaidic acid (C18: 1), buxenic acid (C18: 1), gadrain acid (C20: 1), eicosenoic acid (C20: 1), erucic acid (C22 :) 1), nervonic acid (C24: 1), linoleic acid (C18: 2), eikosazienoic acid (C20: 2), docosadienoic acid (C22: 2), linolenic acid (C18: 3), pinolenic acid (C18: 3) , Eleostearic acid (C18: 3), Meadic acid (C20: 3), Dihomo-γ-linolenic acid (C20: 3), Eikosatrienic acid (C20: 3) and the like. Among them, oleic acid, which is liquid at room temperature (25 ° C.), is preferable from the viewpoint of stability and handling.

In addition, branched fatty acids can also be used. The branched fatty acid is not particularly limited, and is, for example, 2-ethylhexanoic acid (C8), isononanoic acid (C9), dimethyloctanoic acid (C10), isomyristic acid (C14), isoparmitic acid (C16), isostearic acid ( C18) and the like can be mentioned. Among them, isostearic acid which is liquid at room temperature (25 ° C.) is preferable from the viewpoint of stability and handling.

Further, the hydroxy fatty acid is not particularly limited, for example, 2-hydroxylauric acid (C12), 2-hydroxymyristic acid (C14), 2-hydroxypalmitic acid (C16), 3-hydroxypalmitic acid (C16), 8. -Hydroxypalmitic acid (C16), 2-hydroxystearic acid (C18), 3-hydroxystearic acid (C18), 12-hydroxystearic acid (C18), 17-hydroxystearic acid (C18), 18-hydroxystearic acid ( C18), ricinolic acid (C18: 1), α-oxylinolenic acid (C18: 3), 3,11-dihydroxymyristic acid, 3,12-dihydroxymyristic acid, Treo-9, 10-dihydroxystearic acid (C18) , Elytro-9, 10-dihydroxystearic acid (C18), 2,15,16-trihydroxypalmitic acid (C16) and the like.

The fatty acid may be used alone or in combination of two or more. Inexpensive distilled distilled fatty acid produced in the step of deodorizing fats and oils, which is advantageous in terms of cost, may be used.

In one aspect of the present invention, the emulsion is adjusted so that the total acid value of the oil (A) and the fatty acid (D) is 0.3 to 100 mgKOH / g. The acid components contained in animal and vegetable oils include free fatty acids and phospholipids, and the total acid value of these and the fatty acid (D) is adjusted within this range. When the acid value is 0.3 mgKOH / g or more, emulsification is stable and a stable emulsion state can be maintained even at a high temperature of 60 ° C. or higher. Considering this point, the acid value is preferably 0.5 mgKOH / g or more. When the acid value is 50 mgKOH / g or less, it is preferable from the viewpoint of corrosion resistance to metals.

In the present invention, the emulsion contains a fatty acid (D) as an optional component in order to keep the acid value within the above range and improve the stability. That is, the emulsion stability is improved by adding the fatty acid (D) when the acid value of the oil (A) alone is not within the above range. Of course, when the acid value of the oil (A) alone is within the above range, the fatty acid (D) may not be added. It is preferable to add the fatty acid (D) in order to further improve the stability. It is preferable to add the fatty acid (D) in an amount of 0.1 to 8% by mass with respect to the total amount of the oil (A) and the water (B) from the viewpoint of emulsion stability. Since the fatty acid salt does not affect the acid value of the oil, the effect of the present invention cannot be obtained.

In another aspect of the invention, the emulsion is adjusted to have an acid value of 0.4-100 mgKOH / g. From the same point of view as the acid value of the oil (A) and the fatty acid (D) as a whole, it is preferable to adjust the acid value of the emulsion to 0.4 to 50 mgKOH / g, preferably 0.4 to 50 mgKOH / g. It is more preferable to adjust the amount to 30 mgKOH / g.

In the present invention, the content of the emulsifier (C) in the emulsion is affected by the type of oil (A) and the mixing ratio with water (B). For example, when the ratio of water (B) increases, the emulsifier (C) also increases. However, from the viewpoint of emulsification stability, it is preferably 0.05% by mass or more and less than 5% by mass with respect to the total amount of the oil (A) and the water (B). When the content of the emulsifier (C) is 0.05% by mass or more, emulsification is stable, and a stable emulsion state can be maintained even at a high temperature of 60 ° C. or higher. Considering this point, the content of the emulsifier (C) is more preferably 0.1% by mass or more, and further preferably 0.3% by mass or more. When the content of the emulsifier (C) is less than 5% by mass, the balance between cost and emulsification stability is good. Considering this point, the content of the emulsifier (C) is preferably 2.5% by mass or less, more preferably 1% by mass or less.

In the present invention, the emulsion has a volume ratio of oil (A) to water (B) in the range of 40:60 to 95: 5, which is preferable from the viewpoint of stability.

The emulsion of the present invention can also be cooled after emulsification and stored and used in a solid state.

The use of the emulsion in the present invention is not particularly limited, and examples thereof include cosmetics, pharmaceuticals, foods, fuels, inks, paints, and adhesives.

In the present invention, other additives can be added to the emulsion as long as the effects of the present invention are not impaired. Examples of such other additives include colorants, pigments, pharmaceutical ingredients, food additives, thickeners, rust inhibitors, corrosion inhibitors, combustion temperature lowering agents, cleaning dispersants, various surfactants, and the like. Be done.

The method for emulsifying oil (A), water (B), emulsifier (C), fatty acid (D) and the like is not particularly limited. For example, a method of heating and mixing an emulsifier (C) and a fatty acid (D) in an oil (A) to uniformly dissolve them, and then gradually adding heated water to emulsify the oil (A) with the emulsifier (C). Examples thereof include a method in which the fatty acid (D) is heated and mixed to uniformly dissolve the fatty acid (D), and then water is mixed and added in a batch. At this time, it is desirable that the temperature of the oil (A) and the water (B) in which the emulsifier (C) and the fatty acid (D) are dissolved is equal to or higher than the melting point of the oil (A).

The emulsification mixer is not particularly limited. For example, a stirring mixer having a propeller blade, a paddle blade, a turbine blade, an anchor blade, a ribbon blade, etc., an ultrasonic homogenizer, a high-speed stirring / disperser using a stirring homogenizer, a high-speed rotary shear type agitator, a high-pressure injection emulsification / disperser, etc. Be done. Further, these devices may be combined and emulsified through a pre-emulsification step, or may be efficiently emulsified by circulating.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
1. 1. Preparation of emulsion In the examples and comparative examples, the following raw materials were used for the emulsion.
(Animal and vegetable oil (A))
・ Degumming Jatropha oil Acid value 15mg KOH / g
Crude jatropha oil with degumming treatment ・ Refined jatropha oil Acid value 0.2mgKOH / g
Purified by decolorizing and deodorizing crude jatropha oil ・ Degumming palm oil Acid value 14mg KOH / g
Crude palm oil with degumming treatment ・ Refined palm oil (RBDPO: Refined Breached Deodorized Palm Oil) Acid value 0.1 mgKOH / g (immediately after acquisition) 0.2 mgKOH / g, 1 mgKOH / g (60 ° C, 1 month storage) Product), 1.4 mgKOH / g (stored at room temperature for 1 year), 7.6 mgKOH / g (stored at 60 ° C for 6 months), 9.7 mgKOH / g (stored at 60 ° C for 1 year)
Refined palm oil that has been degummed, decolorized, deodorized, etc. ・ Refined palm olein oil Acid value 0.2 mgKOH / g
Low melting point component obtained by separation of refined palm oil ・ Refined palm double olein oil Acid value 0.2 mgKOH / g
Obtained by two-step fractionation of refined palm oil ・ Refined palm stearin oil (RBDPS: Refined Breached Deodorized Palm Stearin) Acid value 1 mgKOH / g
Melting point component (water (B)) obtained by separation of refined palm oil
-Ion-exchanged water (emulsifier (C))
-Emulsifier (C1) Acid value 22 mgKOH / g
Polyoxyethylene (30) Hardened castor oil Triisostearate / emulsifier (C2) Acid value 0.9 mgKOH / g
Polyoxyethylene (40) Hardened castor oil / emulsifier (C3) Acid value 1.2 mgKOH / g
Polyoxyethylene (60) Hardened castor oil / emulsifier (C4) Acid value 1.4 mgKOH / g
Tetraglycerin condensed ricinoleic acid ester / emulsifier (C5) Acid value 0.5 mgKOH / g
Hexaglycerin condensed ricinoleic acid ester / emulsifier (C6) Acid value 1.1 mgKOH / g
Decaglycerin stearate / emulsifier (C7) Acid value 6.7 mgKOH / g
Polyoxyethylene (30) Castor oil trioleate / emulsifier (C8) Acid value 10.5 mgKOH / g
Polyoxyethylene (30) Dihydroxylated rapeseed oil Tetraisostearate / emulsifier (C9) Acid value 0.4 mgKOH / g
Polyoxyethylene (6) Nonylphenol ether / emulsifier (C10) Acid value 3.1 mgKOH / g
Polyoxyethylene (5) nonylphenol ether (fatty acid (D)) fatty acids (D1 to D6) were manufactured by Miyoshi Oil & Fat Co., Ltd. The fatty acid (D7) is described in Sime Drby Austral Sdn. Bhd. Made of. The fatty acid (D8) used was manufactured by Oleon. As the fatty acid salt (E), a reagent manufactured by Wako Pure Chemical Industries, Ltd. was used.
・ Fatty acid (D1)
Palmitic acid 98 Melting point 61.9 ° C Acid value 219 mgKOH / g
・ Fatty acid (D2)
Stearic acid 98 Melting point 68.6 ° C Acid value 197 mg KOH / g
・ Fatty acid (D3)
Myristic acid 98 Melting point 53.9 ° C Acid value 246 mgKOH / g
・ Fatty acid (D4)
Lauric acid 98 Melting point 43.5 ° C Acid value 280 mgKOH / g
・ Fatty acid (D5)
Stearic acid 55 Melting point 56.5 ° C Acid value 207 mg KOH / g
(1% myristic acid, 43% palmitic acid, 55% stearic acid, 1% icosanoic acid)
・ Fatty acid (D6)
PM-400C Cloud point 4.2 ° C Acid value 197.8 mgKOH / g
(4% palmitic acid, 1% stearic acid, 1% palmitoleic acid, 68% oleic acid, 23% linoleic acid, 1% linolenic acid)
・ Fatty acid (D7)
PFAD Melting point 45.2 ° C Acid value 195.7 mg KOH / g
(Palm Fatty Acid Distlated; Palm Distilled Fatty Acid)
・ Fatty acid (D8)
RADIACID0907 (isostearic acid) Cloud point 4.7 ° C Acid value 192.8 mgKOH / g

The melting point, acid value, and cloud point of fatty acids were measured by the following methods.
[Melting point]
The melting point was measured according to "3.2.2.2-2013 melting point (rising melting point)" of the standard oil and fat analysis method (Japan Oil Chemicals Society).
[Acid value (neutralization value)]
The acid value was measured according to "3.3.1-2013" of the standard oil and fat analysis method (Japan Oil Chemicals Society).
[Cloud point]
The cloud point was measured according to "2.2.7-2013 cloud point" of the standard oil and fat analysis method (Japan Oil Chemicals Society).
(Fatty acid salt (E))
Potassium laurate (higher alcohol (F))
Cetyl alcohol

2. 2. Emulsification method The emulsifier (C) and, if necessary, the fatty acid (D) were weighed in a 500 mL tall beaker, and the animal and vegetable oil (A) was added in a predetermined amount and uniformly dissolved at 60 ° C. or 80 ° C. Add ion-exchanged water (B) heated to 60 or 80 ° C while stirring at 60 or 80 ° C. at a rotation speed of 10000 rpm using a stirring homogenizer (Homomixer MARKII 2.5 type manufactured by Primix Corporation), and add ion-exchanged water (B) at high speed for 10 minutes. It was stirred and pre-emulsified. The total volume of animal and vegetable oil (A) and water (B) was set to 200 mL. The emulsified solution was further emulsified using a tabletop ultrafine granulation tester (NM2-L100, manufactured by Yoshida Kikai Kogyo Co., Ltd.) by high-pressure, high-shear stirring while keeping the temperature at 60 or 80 ° C. under the conditions of 100 MPa and 5 Pass.

3. 3. Microscopic observation For Examples 3, 4, 6, 13, 22, 24, 33 and Comparative Examples 2, 4 and 6, optical microscope observation (manufactured by Carl Zeiss, Axio Imager. A2m) immediately after emulsification was performed. The magnification was 1600 times. The slide used for microscopic observation was taken out and used immediately before observation after being well warmed in a constant temperature bath at 50 ° C. The results are shown in FIG.

As a result, in Examples 3, 4, 6, 13, 22, 24, 33, very fine particles were observed immediately after emulsification, and it was found that the emulsified state was good. On the other hand, in Comparative Examples 2, 4 and 6, it is considered that fairly coarse particles were observed immediately after emulsification, and the large particles were united to form an aqueous layer and separated. In particular, Comparative Example 6 shows that even the palmitic acid used in Example 2 and the cetyl alcohol having the same alkyl chain length had no effect on the emulsion stability. In other words, it is considered that the stabilization of these particles is due to the contribution of the added fatty acid, which orients the W / O emulsified particles together with the emulsifier, strengthening the interface film, and having a synergistic effect of improving thermal stability. Will be.

4. Stability evaluation The obtained emulsions of Examples 1 to 36 and Comparative Examples 1 to 6 were evaluated for stability immediately after emulsification (amount of separated water, separation rate of upper and lower layers).

The obtained emulsion was transferred to a graduated cylinder with a stopper with a 50 mL scale and allowed to stand in an incubator at 60 ° C. or 80 ° C. to determine the amount of separated water and the separation rate of the upper and lower layers after 6 hours, 1 day or 7 days. I measured it. Stability was evaluated according to the following criteria based on the amount of separated water and the separation rate of the upper and lower phases.

The phase separation ratio is the volume ratio of each of the completely separated oil phase volume (O), emulsion phase (E), and emulsion lower layer (CE) that has become creamy and moist, and O / (O + E + CE) is the upper phase. The separation rate and CE / (O + E + CE) were taken as the lower phase separation rate and converted into a percentage (%).

Stability was evaluated according to the following criteria based on the amount of separated water and the separation rate of the upper and lower phases. The results are shown in Tables 1 to 5. FIG. 2 shows a representative photograph of the separated water of the emulsion and the phase separation state.
Evaluation criteria (separated water volume)
◎: No separation-fine water droplets ○: Water droplets-less than 0.2 mL △: 0.2 mL or more and less than 0.5 mL ×: 0.5 mL or more
Evaluation criteria (upper and lower phase separation rate)
⊚: less than 3% 〇: 3% or more and less than 10% △: 10% or more and less than 20% ×: 20% or more

As a result, in Examples 1 to 36, which are emulsions of the present invention, the amount of separated water is clearly smaller than that after 6 hours and 1 day at 60 ° C. of Comparative Examples 1 to 6, and the separation rate of the upper and lower layers is also low. In Examples 5, 13 and 14, a stable emulsion was maintained even after 6 hours and 1 day even at a higher temperature of 80 ° C. Further, in Example 22, even if the emulsion was stored at 60 ° C. for one week, the amount of separated water was not present, the separation rate of the upper layer and the lower layer was very low, and a stable emulsion was maintained. From FIG. 2, Examples 3, 4, 6, 7, 22, and 24 form a good emulsion phase (E), whereas Comparative Examples 1, 2, 4, and 5 clearly have an aqueous layer separation. It has progressed. In particular, Example 22 was found to be a high-quality emulsion capable of stabilizing W / O emulsification at a high temperature for a long time despite a high water content of 60%. Further, from FIG. 3, which showed the stability of the appearance at 80 ° C., Examples 5, 13 and 14 formed a good emulsion. On the other hand, it was confirmed that Comparative Example 3 in which the fatty acid salt (potassium laurate) was used instead of the fatty acid became a creamy O / W emulsion at the time of pre-emulsification and did not become the desired W / O emulsion.

As described above, the method for stabilizing an emulsion of the present invention contains the fatty acid (D), so that even if the amount of the emulsifier used is small, the emulsion is monodisperse, the phase separation rate of the upper layer and the lower layer of the emulsified layer is low, and water. A stable emulsion state could be maintained at high temperature with almost no separation, and it was confirmed that this is a method for obtaining a high-quality emulsion.

The emulsions of Examples 4 to 7, 10 to 15, 17, 18, 21, 27 to 36 using 160 mL of refined palm oil (RBDPO) having different acid values and 40 mL of water as animal and vegetable oils, and refined palm oil (RBDPO). In Examples 22 to 25 in which the ratio of water and water was changed, it was confirmed that the emulsification was stabilized by adjusting the total acid value of the refined palm oil (RBDPO) and the fatty acid (D) to 0.5 to 43 mgKOH / g. rice field.

The emulsions of Examples 4 to 7, 10 to 15, 17, 18, 21, 27 to 36, and refined palm oil (RBDPO) using 160 mL of refined palm oil (RBDPO) having different acid values and 40 mL of water as animal and vegetable oils. In Examples 22 to 25 in which the ratio of water and water was changed, it was confirmed that the emulsification was stabilized when the acid value of the emulsion was adjusted to 0.4 to 24.2 mgKOH / g.

It was confirmed that the emulsion was stable even when the emulsifier (C1, polyoxyethylene (30) cured castor oil triisostearate) and the emulsifier (C6, decaglycerin stearate) in the present invention were used in combination as in Example 15. rice field.

5. Combustion evaluation (NO _x reduction rate, smoke concentration reduction rate)
A combustion test was conducted using a "small diesel generator manufactured by Yanmar Construction Machinery: model: YDG350VA-5E", and the NO _x concentration and smoke concentration in the exhaust gas were measured. The NO _x concentration was measured using testo350-MARITIME manufactured by Testo, and the smoke concentration was measured using DSM-10N manufactured by Banzai. The pump inlet temperature was about 60 ° C. For the combustion test, the emulsions of Examples 1, 3, 5, 13, 14, 19, 20, and 22 after 6 hours stored at 60 ° C. were used, and the amount of NO _x generated and smoke were measured as exhaust gas measurement after 5 hours of operation. The concentration was measured and evaluated by the reduction rate when only the fuel oil was burned as 100%. In general, the amount of NO _x generated and the smoke concentration tend to decrease as the ratio of water increases. The results are shown in Tables 1 to 5.

As a result, the NO _x reduction rate of Example 1 was 59%, and the smoke concentration reduction rate was 70%. In addition, the NO _x reduction rate of Example 3 was 60%, and the smoke concentration reduction rate was 62%. The NO _x reduction rate of Example 5 was 54%, and the smoke concentration reduction rate was 57%. The NO _x reduction rate of Example 13 was 61%, and the smoke concentration reduction rate was 71%. The NO _x reduction rate of Example 14 was 51%, and the smoke concentration reduction rate was 66%. The NO _x reduction rate of Example 19 was 52%, and the smoke concentration reduction rate was 58%. The NO _x reduction rate of Example 20 was 57%, and the smoke concentration reduction rate was 63%. The NO _x reduction rate of Example 22 was 87%, and the smoke concentration reduction rate was 70%.

As described above, the emulsion of the present invention suppresses the generation of NO _x and smoke environmental pollutants even when stored at high temperature, and enables stable combustion. The more water there was, the higher the rate of decrease in NO _x . On the other hand, since the emulsion of Comparative Example 2 after 6 hours of storage at 60 ° C. showed a large amount of water separation, the emulsified layer excluding the water separation layer was used in the same manner as in Example 1. As a result, the NO _x reduction rate of Comparative Example 2 was as low as 29%, and the smoke concentration reduction rate was as low as 38%.

In addition, the emulsions of the other comparative examples after 6 hours of storage at 60 ° C. clearly had poor emulsion stability and water separation was observed, so that stable combustion could not be maintained and the NO _x reduction rate was reduced. And the smoke concentration reduction rate is assumed to be clearly lower than that of the emulsion fuel of the example, and there is a risk of causing serious damage such as carbon-like substance depositing on the tip of the nozzle tip in the engine and the stick of the piston ring. The test was not conducted because it was judged that there was some.

As described above, it was confirmed that the emulsion of the present invention is useful as an emulsion fuel.

Claims (15)

Contains at least one oil selected from (A) vegetable oils and animal oils, (B) water, (C) at least one emulsifier selected from polyhydric alcohol hydroxy fatty acid esters or derivatives thereof, and (D) fatty acid as an optional component. Let me
The content of the emulsifier (C) is 2.5% by mass or less with respect to the total amount of the oil (A) and the water (B).
A method for stabilizing an emulsion, which prepares a water-in-oil (W / O) emulsion so that the acid value of the oil (A) and the fatty acid (D) as a whole is 0.3 to 100 mgKOH / g. Contains at least one oil selected from (A) vegetable oils and animal oils, (B) water, (C) at least one emulsifier selected from polyhydric alcohol hydroxy fatty acid esters or derivatives thereof, and (D) fatty acid as an optional component. Let me
The content of the emulsifier (C) is 2.5% by mass or less with respect to the total amount of the oil (A) and the water (B).
A method for stabilizing an emulsion, which prepares a water-in-oil (W / O) emulsion so that the acid value of the emulsion is 0.4 to 100 mgKOH / g. The method for stabilizing an emulsion according to claim 1 or 2, wherein the fatty acid (D) is added when preparing a water-in-oil (W / O) emulsion. The method for stabilizing an emulsion according to claim 3, wherein the fatty acid (D) is added in an amount of 0.1 to 8% by mass with respect to the total amount of the oil (A) and the water (B). The method for stabilizing an emulsion according to any one of claims 1 to 4, wherein the fatty acid (D) is a fatty acid having 8 to 24 carbon atoms. The method for stabilizing an emulsion according to any one of claims 1 to 5, wherein the volume ratio of the oil (A) to the water (B) is 40:60 to 95: 5. The stable emulsion according to any one of claims 1 to 6, wherein the emulsifier (C) contains at least one selected from a polyglycerin condensed hydroxy fatty acid ester, an ethylene oxide adduct of a glycerin hydroxy fatty acid ester, or a fatty acid ester thereof. How to make it. Contains at least one oil selected from (A) vegetable oils and animal oils, (B) water, (C) at least one emulsifier selected from polyhydric alcohol hydroxy fatty acid esters or derivatives thereof, and (D) fatty acid as an optional component. death,
The content of the emulsifier (C) is 2.5% by mass or less with respect to the total amount of the oil (A) and the water (B).
A water-in-oil (W / O) emulsion having an acid value of (A) oil and (D) fatty acid as a whole of 0.3 to 100 mgKOH / g. Contains at least one oil selected from (A) vegetable oils and animal oils, (B) water, (C) at least one emulsifier selected from polyhydric alcohol hydroxy fatty acid esters or derivatives thereof, and (D) fatty acid as an optional component. death,
The content of the emulsifier (C) is 2.5% by mass or less with respect to the total amount of the oil (A) and the water (B).
A water-in-oil (W / O) emulsion having an acid value of 0.4 to 100 mgKOH / g. The water-in-oil (W / O) emulsion according to claim 8, wherein the total acid value of the oil (A) and the fatty acid (D) is 0.5 to 50 mgKOH / g. The emulsion according to any one of claims 8 to 10, wherein the content of the fatty acid (D) is 0.1 to 8% by mass with respect to the total amount of the oil (A) and the water (B). The emulsion according to any one of claims 8 to 11, wherein the fatty acid (D) is a fatty acid having 8 to 24 carbon atoms. The emulsion according to any one of claims 8 to 12, wherein the volume ratio of the oil (A) to the water (B) is 40:60 to 95: 5. The emulsion according to any one of claims 8 to 13, wherein the emulsifier (C) contains at least one selected from a polyglycerin condensed hydroxy fatty acid ester, an ethylene oxide adduct of a glycerin hydroxy fatty acid ester, or a fatty acid ester thereof. An emulsion fuel using the emulsion according to any one of claims 8 to 14.

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