JP2019188294A - Method for stabilizing emulsified product, and emulsified product and emulsion fuel using the same - Google Patents

Abstract

To provide: a method for stabilizing a water-in-oil (W/O) type emulsified product in which water is dispersed in animal/vegetable oil, that enables a stable maintenance of the emulsion state at high-temperature and for long term even if the use amount of emulsifier is reduced; and a water-in-oil (W/O) type emulsified product and an emulsion fuel using the same.SOLUTION: The method for stabilizing emulsified product of the present invention comprises containing (A) at least one oil selected from vegetable oil and animal oil, (B) water, (C) at least one emulsifier selected from a polyhydric alcohol hydroxy fatty acid ester or a derivative thereof, and (D) fatty acid as an optional component, and is characterized in that a water-in-oil (W/O) type emulsified product is prepared so that the acid value of oil (A) and fatty acid (D) in the total is 0.3 to 100 mgKOH/g.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for stabilizing a water-in-oil (W / O) emulsion obtained by dispersing water in animal and vegetable oils, and the emulsion.

  Fats and oils such as animal and vegetable oils are renewable biomass and have better biodegradability than petroleum products prepared from fossil raw materials, so they are renewed from the viewpoints of petroleum resource depletion, global environmental conservation, safety, and nature orientation. Attention has been gathered. Fatty acids, glycerol, higher alcohols and their derivatives, which are decomposition products of fats and oils, are used as fat and oil basic chemicals in various end products such as cosmetics, pharmaceuticals, surfactants, plasticizers, lubricants, paints, fuels, and inks. However, fats and oils themselves are widely used alone or as emulsions (emulsions) (Non-patent Document 1).

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

  In order to produce an emulsion, it is necessary to add mechanical energy to the mass of the dispersed phase to make fine particles. Usually, an emulsion has a high energy state and is thermodynamically unstable. Therefore, it is necessary to reduce the interfacial energy and to add energy by external force.

  As an emulsion composed only of water and oil that does not use a surfactant, for example, in Patent Document 1, an emulsion is produced from water and straw oil using an emulsion production apparatus in which the surface of the wetted part in contact with the emulsion liquid is an insulating material. The method, Patent Document 2, describes a method of producing emulsion fuel by an apparatus 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 as a stabilization mechanism, the oil droplets repel each other by being charged on the surface of the oil droplets, and the dispersion is stabilized. In the latter emulsion, an external force energy is applied by an apparatus to prepare a W / O emulsion.

  However, an emulsion consisting only of water and oil that does not use a surfactant cannot stabilize the dispersed state for a long period of time even once the dispersed phase is dispersed in the continuous phase. Once stabilized, stability is easily lost depending on the storage tank and usage environment, which is not suitable for practical use.

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

  However, since these methods do not lower the interfacial tension, stabilization can be achieved by optimizing, but there is a problem in quality stability, reproducibility, and cost because there are limitations on the interfacial adsorption of particles and the emulsion preparation method.

  On the other hand, in the emulsification method using a surfactant, the basis of the emulsification / dispersion method is that the surfactant is adsorbed on the interface between oil and water and the interfacial energy is reduced. Since W / O emulsions are easy to spread oily components on the skin and have high emollient properties, water-in-oil (W / O) emulsions using these technologies are used in cosmetics, pharmaceuticals, foods, fuels, It is used in a wide variety of inks (Patent Documents 4 to 8).

In water-in-oil (W / O) emulsions using fossil fuels and animal and vegetable oils, efforts have been made to emulsion fuels using various emulsifiers as fuel applications (Patent Documents 9 to 12). Animal and vegetable oils are renewable raw materials, and are attracting attention as fuel oils for internal combustion engines that replace heavy oil and light oil because of problems such as global warming and fossil fuel depletion. While regarding direct fuel reduction have been made to consider a long, animal and vegetable oils, for high viscosity, a high boiling point and low volatility, while a low NO _x, spray characteristics deteriorated and the nozzle in the engine There are problems such as the accumulation of carbonaceous material at the tip of the tip and the occurrence of serious obstacles such as the sticking of the piston ring, and it has been difficult to use continuously (Non-Patent Documents 4 and 5). In order to solve these problems, the above-mentioned emulsion fuel, and further nanoemulsion fuel (Non-Patent Document 6) have been developed. However, in general, in animal and vegetable oils, there is a certain degree of polarity, so the emulsifier dissolves in the animal and vegetable oil and does not adsorb efficiently at the oil-water interface. Therefore, a large amount of emulsifier needs to be added 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 carboxymethyl cellulose salt with water (Patent Document 13).

JP 2013-000704 A JP 2009-203323 A JP 2006-241424 A International Publication No. 1999/025310 JP 2005-126369 A Japanese Patent Laid-Open No. 2005-151834 JP 2012-184366 A JP 2007-308617 A JP-A-6-346071 JP 2003-201485 A JP 2009-280761 A JP-A-2015-214616 JP, 2006-121250, A JP 2012-016668 A JP-A-8-192001

Basics and Application of Oils and Fats Japan Oil Chemists' Society (2005) Color material, 77 (10) 462-469 (2004) Dictionary of Modern Interfacial Colloid 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 Technology Innovation Business New Energy Venture Technology Innovation Business (Biomass) Development of Practical Biomass Fuel by Degumming and Emulsifying Palm Crude Oil (Fiscal 2010–2011 Results Report) J. et al. Soc. Cosmet. Chem. Jpn. 44 (4) 1269-277 (2010) Langmuir, 7 (7), 1370-1377 (1991).

  However, emulsions are generally thermodynamically unstable, and more emulsifiers are necessary to maintain high temperature and long-term stability. Depending on the application, the effect on the effect is a problem. In particular, it is known that the method for stabilizing a W / O emulsion is much less than that for an O / W emulsion, 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 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 higher alcohol is added as an emulsification aid, and the stability of the system is improved by increasing the viscosity of the system and becoming a liquid crystal state. There is no mention of improvement.

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

  Non-Patent Document 8 describes the use of various alcohols and stearic acid as stabilizers for W / O emulsions, but uses oils of styrene-divinylbenzene, and the description in animal and vegetable oils is as follows. Absent.

  Patent Document 14 relates to a water-in-oil (W / O) emulsion obtained by a three-phase emulsification method in which an oil phase is a petroleum hydrocarbon solvent and an inverse vesicle is used as an emulsifier. As a long-chain fatty acid having 12 or more carbon atoms or a salt thereof can be contained, there is no suggestion about expression of the stability improvement effect.

  Patent Document 15 states that the combined use effect of fatty acid is useful for assisting emulsification and imparting excellent emulsion stability with a small amount of emulsifier, and an organopolysiloxane composition comprising silicone oil and finely divided silica; In Example 3 using a fatty acid and an emulsifier as well as a W / O emulsion antifoam composition with water, the total amount used is 25% (20 parts in 80 parts), which is still a large amount.

  In emulsion fuel applications, among vegetable oils, vegetable oils and animal oils may have a high melting point or a high viscosity at room temperature. When using such fuel oils, the viscosity should not be applied to transportation or engines. 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 lower and the temperature is higher, the amount of emulsifier added is particularly low, and a stable emulsion fuel that keeps a uniform emulsion state for a long time while suppressing separation even at 60 ° C or higher. It is important to manufacture. Further, even when the same kind of animal and vegetable oil is used, there is a problem that the stability of the emulsion fuel varies.

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

  In order to solve the above-described problems, the emulsion stabilization method of the present invention comprises (A) at least one oil selected from vegetable oils and animal oils, (B) water, (C) polyhydric alcohol hydroxy fatty acid esters or At least one emulsifier selected from the derivatives, (D) fatty acid as an optional component, and the oil (A) and the fatty acid (D) as a whole have an acid value of 0.3 to 100 mg KOH / g in the oil. It is characterized by preparing a water-type (W / O) emulsion.

  The method for stabilizing an emulsion of the present invention comprises (A) at least one oil selected from vegetable oils and animal oils, (B) water, (C) polyhydric alcohol hydroxy fatty acid esters or derivatives thereof. An emulsifier and (D) fatty acid as an optional component are contained, and a water-in-oil (W / O) emulsion is prepared 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 (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 contains at least one emulsifier and (D) fatty acid as an optional component, and has an acid value of 0.3 to 100 mgKOH / g in the whole of (A) oil and (D) fatty acid.

  The water-in-oil (W / O) emulsion of the present invention is 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 contains at least one emulsifier, (D) fatty acid as an optional component, and the emulsion has an acid value of 0.4 to 100 mgKOH / g.

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

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

It is a microscope picture of an emulsion. It is a photograph of the phase separation status (60 ° C) of the emulsion. It is a photograph of the phase separation status (80 ° C.) of the emulsion.

  The present invention is described in detail below.

  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 jatropha oil, rapeseed oil, soybean oil, rice bran oil, castor oil, cottonseed oil, corn oil, sunflower oil, palm oil and fractionated oil (palm olein oil, palm double olein oil, palm stearin which is a high melting point fraction) Oil, etc.). Animal oils include beef tallow, pork tallow, sheep tallow, chicken tallow, fish oil and the like. These may be those obtained by refining, reforming, or degumming crude oil. Moreover, the refined animal and vegetable oils may be hydrogenated, transesterified, and fractionally crystallized. Moreover, you may use waste animal and vegetable oils, such as a waste edible oil, from the viewpoint of reduction of wastewater treatment cost and resource recycling.

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

  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.

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

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

  Examples of the trihydric or higher aliphatic polyhydric alcohol in the polyhydric alcohol hydroxy fatty acid ester include glycerin, polyglycerin, sorbitol, pentaerythritol, and sucrose. Among these, glycerol and polyglycerol 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), 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), ricinoleic acid (C18: 1), α-oxylinolenic acid (C18: 3), 3,11-dihydroxymyristic acid, 3,12-dihydroxymyristic acid, threo-9, 10-dihydroxystearic acid (C18) ), Erythro-9 Examples include 10-dihydroxystearic acid (C18), 2,15,16-trihydroxypalmitic acid (C16), castor oil fatty acid, hydrogenated castor oil fatty acid, dihydroxylated rapeseed oil fatty acid, and the like. The condensed hydroxy fatty acid which is a condensate is mentioned. 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 a 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, and lignoceric acid. Examples of the unsaturated fatty acid include myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, erucic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, erucic acid, docosahexaenoic acid, arachidonic acid and the like. . Examples of the branched fatty acid include 2-ethylhexanoic acid, isononanoic acid, dimethyloctanoic acid, isomyristic acid, isopalmitic acid, and isostearic acid. 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, polyglycerin condensed hydroxy fatty acid ester is preferable. Examples of the polyglycerol condensed hydroxy fatty acid ester include polyglycerol condensed ricinoleic acid ester, polyglycerol condensed hydroxy stearic acid ester, polyglycerol condensed dihydroxy stearic acid ester, and the like.

  Examples of the polyglycerin condensed ricinoleic acid ester include diglycerin condensed ricinoleic acid ester, tetraglycerin condensed ricinoleic acid ester, pentaglycerin condensed ricinoleic acid ester, hexaglycerin condensed ricinoleic acid ester, octaglycerin condensed ricinoleic acid ester, decaglycerin condensed ricinoleic acid ester. Acid ester etc. are mentioned. 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 polyglycerol condensed hydroxy stearate include, for example, diglycerol condensed hydroxy stearate, tetraglycerin condensed hydroxy stearate, pentaglycerin condensed hydroxy stearate, hexaglycerin condensed hydroxy stearate, octaglycerin condensed hydroxy stearate Examples 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 polyglycerol condensed dihydroxy stearic acid ester include diglycerin condensed dihydroxy stearic acid ester, tetraglycerin condensed dihydroxy stearic acid ester, pentaglycerin condensed dihydroxy stearic acid ester, hexaglycerin condensed dihydroxy stearic acid ester, and octaglycerin condensed dihydroxy stearic 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.

  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 is preferably an alkylene oxide adduct of glycerin hydroxy fatty acid ester or a fatty acid ester thereof.

  Examples of alkylene oxide adducts of glycerin hydroxy fatty acid esters or fatty acid esters thereof include polyoxyalkylene castor oil mainly composed of glycerin triricinoleate polyoxyalkylene adducts and polyoxyalkylene adducts of glycerin trihydroxystearate. Polyoxyalkylene hardened castor oil, polyoxyalkylene castor oil glycerin tridihydroxystearate polyoxyalkylene adduct, polyoxyalkylene dihydroxylated rapeseed oil, glycerin triricinoleate polyoxyalkylene adduct fatty acid ester polyoxyalkylene castor oil Fatty acid ester, polyoxyalkylene hard glycerin trihydroxystearate polyoxyalkylene adduct fatty acid ester Castor oil fatty acid esters, glycerin tri-dihydroxy stearic acid polyoxyalkylene adduct fatty acid esters, polyoxyalkylene hydroxylated rapeseed oil fatty acid esters.

  Examples of 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 hydrogenated castor oil include polyoxyethylene (5) hydrogenated castor oil, polyoxyethylene (10) hydrogenated castor oil, polyoxyethylene (15) hydrogenated castor oil, polyoxyethylene (20) hydrogenated castor oil, 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 include polyoxyethylene (100) hydrogenated 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, 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 , Polyoxyethylene (4) castor oil dioleate, polyoxyethylene (7.5) castor oil dioleate, polyoxyethylene (10) castor oil dioleate, polyoxy Ethylene (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 castor oil fatty acid ester include polyoxyethylene (5) hardened castor oil triisostearate, polyoxyethylene (10) hardened castor oil triisostearate, polyoxyethylene (15) hardened castor oil triisostearate , Polyoxyethylene (20) hardened castor oil triisostearate, polyoxyethylene (25) hardened castor oil triisostearate, polyoxyethylene (30) hardened castor oil triisostearate, polyoxyethylene (40) hardened castor oil triisostearate Stearate, polyoxyethylene (50) hydrogenated castor oil triisostearate, polyoxyethylene (60) hydrogenated castor oil triisostearate, polyoxyethylene (80) hydrogenated castor oil triisostearate, poly Xylethylene (100) hydrogenated castor oil triisostearate, polyoxyethylene (5) hydrogenated castor oil diisostearate, polyoxyethylene (10) hydrogenated castor oil diisostearate, polyoxyethylene (15) hydrogenated castor oil diisostearate, Polyoxyethylene (20) hardened castor oil diisostearate, polyoxyethylene (25) hardened castor oil diisostearate, polyoxyethylene (30) hardened castor oil diisostearate, polyoxyethylene (40) hardened castor oil diisostearate Rate, polyoxyethylene (50) hardened castor oil diisostearate, polyoxyethylene (60) hardened castor oil diisostearate, polyoxyethylene (80) hardened castor oil diisostearate, polyoxyethylene (100) hard Castor oil diisostearate, polyoxyethylene (5) hardened castor oil trioleate, polyoxyethylene (10) hardened castor oil tritrioleate, polyoxyethylene (15) hardened castor oil tritrioleate, polyoxyethylene (20) hardened castor oil tritriole Polyoxyethylene (25) hardened castor oil tritrioleate, polyoxyethylene (30) hardened castor oil tritrioleate, polyoxyethylene (40) hardened castor oil tritrioleate, polyoxyethylene (50) hardened castor oil tritrioleate, Polyoxyethylene (60) hydrogenated castor oil trioleate, polyoxyethylene (80) hydrogenated castor oil trioleate, polyoxyethylene (100) hydrogenated castor oil trioleate, polyoxyethylene (5) hardened castor oil dioleate, polyoxyethylene (10) hardened castor oil trioleate, polyoxyethylene (15) hardened castor oil dioleate, polyoxyethylene (20) hardened castor oil dioleate, polyoxyethylene (25) hardened castor oil diisooleate, polyoxy Ethylene (30) hardened castor oil dioleate, polyoxyethylene (40) hardened castor oil dioleate, polyoxyethylene (50) hardened castor oil dioleate, polyoxyethylene (60) hardened castor oil dioleate, polyoxyethylene (80) hardened castor oil dioleate, polyoxy And ethylene (100) hardened castor oil dioleate.

  Examples of the polyoxyalkylene dihydroxylated rapeseed oil include polyoxyethylene (5) dihydroxylated rapeseed oil, polyoxyethylene (10) dihydroxylated rapeseed oil, polyoxyethylene (15) dihydroxylated rapeseed oil, polyoxyethylene (20 ) Dihydroxy rapeseed oil, polyoxyethylene (25) dihydroxy rapeseed oil, polyoxyethylene (30) dihydroxy rapeseed oil, polyoxyethylene (50) dihydroxy rapeseed 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, 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 (1 ) Dihydroxylated rapeseed oil triisostearate, polyoxyethylene (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, poly Oxyethylene (10) dihydroxylated rapeseed oil tetraoleate, polyoxyethylene (15) dihydroxylated rapeseed oil tetraoleate, polyoxyethylene (20) dihydroxylated rapeseed oil tetraoleate, polio Siethylene (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, Examples include polyoxyethylene (30) dihydroxylated rapeseed oil trioleate, polyoxyethylene (50) dihydroxylated rapeseed oil trioleate, and the like.

  As the emulsifier (C) used in the emulsion in the present invention, polyglycerin condensed hydroxy fatty acid ester, ethylene oxide adduct of glycerin hydroxy fatty acid ester or fatty acid ester thereof is particularly preferable. For example, polyglycerin condensed ricinoleic acid ester, Examples thereof include oxyethylene castor oil or fatty acid ester thereof, polyoxyethylene hydrogenated castor oil or fatty acid ester thereof, polyoxyethylene dihydroxylated rapeseed oil or fatty acid ester thereof, and the like.

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

  Nonionic surfactants other than those described above may be used in combination as emulsifiers, and examples of nonionic surfactants other than those described above include, but are not limited to, polyglycerin fatty acid esters and the like.

  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 emulsion stability, and 12 to 18 carbon atoms. The fatty acid is 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 saturated fatty acids 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 these, palmitic acid and stearic acid are preferable from the viewpoint of stability.

  Examples of unsaturated fatty acids include, but are not limited to, caproleic acid (C10: 1), Linderic acid (C12: 1), myristoleic acid (C14: 1), palmitoleic acid (C16: 1), and sapienoic acid ( C16: 1), oleic acid (C18: 1), elaidic acid (C18: 1), vaccenic acid (C18: 1), gadoleic acid (C20: 1), eicosenoic acid (C20: 1), erucic acid (C22: 1), nervonic acid (C24: 1), linoleic acid (C18: 2), eicosadienoic acid (C20: 2), docosadienoic acid (C22: 2), linolenic acid (C18: 3), pinolenic acid (C18: 3) Eleostearic acid (C18: 3), mead acid (C20: 3), dihomo-γ-linolenic acid (C20: 3), eicosatrienoic acid (C20: 3) and the like. . Among them, oleic acid which is liquid at room temperature (25 ° C.) is preferable in terms of stability and handling.

  In addition, branched fatty acids can also be used. Although it does not specifically limit as branched fatty acid, For example, 2-ethylhexanoic acid (C8), isononanoic acid (C9), dimethyloctanoic acid (C10), isomyristic acid (C14), isopalmitic acid (C16), isostearic acid ( C18). Among these, liquid isostearic acid is preferred at room temperature (25 ° C.) from the viewpoint of stability and handling.

  Furthermore, examples of the hydroxy fatty acid include, but are not limited to, 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), ricinoleic acid (C18: 1), α-oxylinolenic acid (C18: 3), 3,11-dihydroxymyristic acid, 3,12-dihydroxymyristic acid, threo-9, 10-dihydroxystearic acid (C18) Erythro-9,10-dihydroxy Stearate (C18), 2,15,16- trihydroxy palmitic acid (C16) and the like.

  The said fatty acid may be used individually by 1 type, and may be used in combination of 2 or more type. Inexpensive distilled distillate fatty acid produced in the oil and fat deodorization process, which is advantageous in terms of cost, may be used.

  1 aspect of this invention WHEREIN: An emulsion is adjusted so that the acid value in the whole of oil (A) and a fatty acid (D) may be 0.3-100 mgKOH / g. Acid components contained in animal and vegetable oils include free fatty acids, phospholipids, etc., and the total acid value of these and fatty acids (D) is adjusted within this range. When the acid value is 0.3 mg KOH / g or more, emulsification is stable, and a stable emulsion state can be maintained even at a high temperature of 60 ° C. or more. Considering this point, the acid value is preferably 0.5 mgKOH / g or more. An acid value of 50 mgKOH / g or less 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 improve the stability with the acid value within the above range. That is, when the acid value of the oil (A) alone is not within the above range, the emulsion stability is improved by adding the fatty acid (D). Of course, the fatty acid (D) may not be added when the acid value of the oil (A) alone is within the above range. In order to further improve the stability, it is preferable to add the fatty acid (D). It is preferable from the viewpoint of emulsion stability that 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 water (B). In addition, 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 embodiment of the present invention, the emulsion is adjusted so that the acid value is 0.4 to 100 mgKOH / g. From the same point as the acid value in the whole of the oil (A) and the fatty acid (D), it is preferable to adjust the acid value of the emulsion to 0.4 to 50 mgKOH / g. It is more preferable to adjust so that it may become 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. Although mix | blended, from a viewpoint of emulsion stability, 0.05 mass% or more and less than 5 mass% are preferable with respect to the total amount of oil (A) and water (B). Emulsification is stable when the content of the emulsifier (C) is 0.05% by mass or more, 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. If content of an emulsifier (C) is less than 5 mass%, the balance of a cost surface and emulsification stability is good. Considering this point, the content of the emulsifier (C) is preferably 2.5% by mass or less, and more preferably 1% by mass or less.

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

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

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

  In the present invention, other additives can be blended in the emulsion within a range not impairing the effects of the present invention. Examples of such other additives include colorants, pigments, pharmaceutical ingredients, food additives, thickeners, rust inhibitors, corrosion inhibitors, combustion temperature lowering agents, detergent dispersants, various surfactants, and the like. It is done.

  The method for emulsifying oil (A), water (B), emulsifier (C), fatty acid (D) and the like is not particularly limited. For example, the emulsifier (C) and the fatty acid (D) are heated and mixed in the oil (A) and uniformly dissolved, and then heated water is gradually added to emulsify the oil (A). There is a method in which the fatty acid (D) is heated and mixed and dissolved uniformly, and then the water is mixed and added. At this time, the oil (A) and water (B) in which the emulsifier (C) and the fatty acid (D) are dissolved are preferably at a temperature equal to or higher than the melting point of the oil (A).

  The emulsifying 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, an ultrasonic homogenizer, a high-speed stirring disperser using a stirring homogenizer, a high-speed rotary shearing stirrer, a high-pressure jet emulsion disperser, etc. It is done. Moreover, you may emulsify efficiently by combining these apparatuses and emulsifying through a preliminary emulsification process, or making it circulate.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
1. Preparation of Emulsions In Examples and Comparative Examples, the following materials were used for the emulsions.
(Animal and vegetable oil (A))
・ Degummed Jatropha oil Acid value 15mgKOH / g
Crude jatropha oil with degumming treatment ・ Purified jatropha oil Acid value 0.2mgKOH / g
Crude jatropha oil with decolorization, deodorization treatment, etc. refined ・ Degummed palm oil Acid value 14mgKOH / g
Crude palm oil with degumming treatment-Refined palm oil (RBDPO) Acid value 0.1 mg KOH / g (immediately after acquisition) 0.2 mg KOH / g, 1 mg KOH / g (stored at 60 ° C. for 1 month) 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)
Crude palm oil refined by degumming, decolorization, deodorization, etc. ・ Purified palm olein oil Acid value 0.2mgKOH / g
Low melting point component / purified palm double olein oil obtained by fractionation of refined palm oil Acid value 0.2 mgKOH / g
What was obtained by two-stage fractionation of refined palm oil, refined palm stearin oil (RBDPS) Acid value 1mgKOH / g
High melting point component (water (B)) obtained by fractionation of refined palm oil
・ Ion exchange water (emulsifier (C))
・ Emulsifier (C1) Acid value 22mgKOH / g
Polyoxyethylene (30) hydrogenated castor oil triisostearate / emulsifier (C2) Acid value 0.9 mgKOH / g
Polyoxyethylene (40) hydrogenated castor oil and emulsifier (C3) Acid value 1.2 mgKOH / g
Polyoxyethylene (60) hydrogenated castor oil and emulsifier (C4) Acid value 1.4mgKOH / 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 10.5mgKOH / 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
The polyoxyethylene (5) nonylphenol ether (fatty acid (D)) fatty acid (D1-D6) used the product made by Miyoshi oil and fat company. Fatty acid (D7) was obtained from Sim Drby Australian Sdn. Bhd. Made from Fatty acid (D8) manufactured by Oleon was used. 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 219mgKOH / g
・ Fatty acid (D2)
Stearic acid 98 Melting point 68.6 ° C Acid value 197mgKOH / g
・ Fatty acid (D3)
Myristic acid 98 Melting point 53.9 ° C Acid value 246mgKOH / g
・ Fatty acid (D4)
Lauric acid 98 Melting point 43.5 ° C Acid value 280mgKOH / g
・ Fatty acid (D5)
Stearic acid 55 Melting point 56.5 ° C Acid value 207mgKOH / g
(Myristic acid 1%, palmitic acid 43%, stearic acid 55%, eicosanoic acid 1%)
・ Fatty acid (D6)
PM-400C Cloud point 4.2 ° C Acid value 197.8mgKOH / 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 195.7mgKOH / g
(Palm Fatty Acid Distilled; Palm Distilled Fatty Acid)
・ Fatty acid (D8)
RADICID 0907 (isostearic acid) Cloud point 4.7 ° C. Acid value 192.8 mg KOH / g

The melting point, acid value, and cloud point of the fatty acid were measured by the following methods.
[Melting point]
Melting | fusing point was measured according to "3.2.2.2-2013 melting | fusing point (rising melting | fusing point)" of the reference | standard fats and oils analysis method (Japan Oil Chemical Society).
[Acid value (neutralization value)]
The acid value was measured according to “3.3.1-2013” of the standard fat analysis method (Japan Oil Chemists' Society).
[Cloud point]
The cloud point was measured according to “2.2.7-2013 cloud point” of the standard fat analysis method (Japan Oil Chemists' Society).
(Fatty acid salt (E))
Potassium laurate (higher alcohol (F))
Cetyl alcohol

2. Emulsification method When necessary, the emulsifier (C) and the fatty acid (D) were weighed in a 500 mL tall beaker, and a predetermined amount of animal and vegetable oil (A) was added and uniformly dissolved at 60 ° C or 80 ° C. Add ion-exchanged water (B) heated to 60 or 80 ° C. while stirring at a rotation speed of 60 or 80 ° C. and 10000 rpm using a stirring homogenizer (homomicer MARK II2.5 type manufactured by PRIMIX Co., Ltd.) for 10 minutes at high speed. Stirred and pre-emulsified. The total volume of animal and vegetable oil (A) and water (B) was 200 mL. The emulsified liquid was further emulsified by high-pressure high-shear stirring while maintaining the temperature at 60 or 80 ° C. under the conditions of 100 MPa and 5 Pass using a tabletop ultrafine atomization tester (NM2-L100, manufactured by Yoshida Kikai Kogyo Co., Ltd.).

3. Microscopic Observation Examples 3, 4, 6, 13, 22, 24, 33 and Comparative Examples 2, 4, 6 were subjected to optical microscopic observation immediately after emulsification (Axio Imager. A2m, manufactured by Carl Zeiss). The magnification was observed at 1600 times. In addition, the preparation used for microscopic observation was taken out immediately before observation after warming well in a 50 degreeC thermostat. The results are shown in FIG.

  As a result, in Examples 3, 4, 6, 13, 22, 24, and 33, very fine particles were observed immediately after emulsification, indicating that the emulsion was in a good emulsified state. 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 joined together to form an aqueous layer and separated. In particular, Comparative Example 6 shows that even cetyl alcohol having the same alkyl chain length as palmitic acid used in Example 2 had no effect on the emulsion stability. In other words, the stabilization of the particles is attributed to the synergistic effect that the added fatty acid contributes to orient the W / O emulsified particles with the emulsifier together with the emulsifier, strengthening the interface film and improving the thermal stability. It is done.

4). Stability evaluation About each obtained emulsion of Examples 1-36 and Comparative Examples 1-6, stability evaluation (amount of separated water, upper layer lower layer phase separation rate) immediately after emulsification was performed.

  Transfer the obtained emulsion to a stoppered measuring cylinder with a 50 mL scale and leave it in a 60 ° C. or 80 ° C. incubator. After 6 hours, 1 day or 7 days later, the amount of separated water and the upper / lower phase separation rate are calculated. Measured. Stability was evaluated from the amount of separated water and the upper layer lower layer phase separation rate according to the following criteria.

  The phase separation rate is the volume ratio of the completely separated oil phase (O), the emulsion phase (E), and the volume ratio of the lower layer of emulsion (CE) creamed and increased in water, O / (O + E + CE) as the upper layer phase. The separation rate, CE / (O + E + CE) was defined as the lower layer phase separation rate and converted to a percentage (%).

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

  As a result, Examples 1-36 which are the emulsions of this invention clearly have a small amount of separated water and a lower upper layer / lower layer phase separation rate compared to Comparative Examples 1-6 after 6 hours at 60 ° C. and 1 day later. In Examples 5, 13, and 14, a stable emulsion was maintained after 6 hours and 1 day even at a higher temperature of 80 ° C. Further, in Example 22, even when stored at 60 ° C. for 1 week, there was no amount of separated water, the upper layer / lower layer separation rate 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), while Comparative Examples 1, 2, 4, and 5 clearly have an aqueous layer separation. Progressed. In particular, Example 22 was found to be a high-quality emulsion that can stabilize the W / O emulsification at a high temperature for a long time, despite the high water content of 60%. Further, from FIGS. 3A and 3B showing the stability of the appearance at 80 ° C., Examples 5, 13, and 14 formed good emulsions. On the other hand, it was confirmed that Comparative Example 3 using a fatty acid salt (potassium laurate) instead of a fatty acid became a creamy O / W emulsion at the time of preliminary emulsification and did not become a target W / O emulsion.

  As described above, the method for stabilizing an emulsion of the present invention includes a fatty acid (D), and even if the amount of the emulsifier used is small, it is monodispersed and the phase separation rate of the upper and lower layers of the emulsion layer is low. It was confirmed that this was a method capable of maintaining a stable emulsion state at a high temperature with almost no separation, and obtaining a high-quality emulsion.

  Emulsions of Examples 4-7, 10-15, 17, 18, 21, 27-36 and refined palm oil (RBDPO) using 160 mL of purified palm oil (RBDPO) and 40 mL of water having different acid values 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 stable when the total acid value of refined palm oil (RBDPO) and fatty acid (D) was adjusted to 0.5 to 43 mg KOH / g. It was.

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

  As in Example 15, it was confirmed that the emulsified product was stable when the emulsifier (C1, polyoxyethylene (30) hydrogenated castor oil triisostearate) and the emulsifier (C6, decaglycerin stearate) were used in combination. It was.

5. Combustion evaluation (NO _x reduction rate, smoke concentration reduction rate)
"Yanmar construction equipment made small diesel generator: Model: YDG350VA-5E" perform combustion test was used to determine the concentration of NO _x in the exhaust gas, the smoke density. Measurement of the NO _x concentration, using a Testo made testo350-MARITIME, respect to the smoke concentration, was used Banzai Co. DSM-10 N. The pump inlet temperature was about 60 ° C. In 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 NO _x generation amount and smoke were measured as exhaust gas measurement after 5 hours of operation. The concentration was measured and evaluated by the rate of decrease when the fuel oil alone was burned as 100%. In general NO _x generation amount and the smoke density tends to be decreased as the ratio of water is increased. The results are shown in Tables 1-5.

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%. In Example 5, the NO _x reduction rate was 54%, and the smoke concentration reduction rate was 57%. In Example 13, the NO _x reduction rate was 61%, and the smoke concentration reduction rate was 71%. In Example 14, the NO _x reduction rate was 51%, and the smoke concentration reduction rate was 66%. In Example 19, the NO _x reduction rate was 52%, and the smoke concentration reduction rate was 58%. In Example 20, the NO _x reduction rate was 57%, and the smoke concentration reduction rate was 63%. In Example 22, the NO _x reduction rate was 87%, and the smoke concentration reduction rate was 70%.

Thus, the emulsion of the present invention suppresses the generation of NO _x and smoke environmental pollutants even when stored at high temperatures, and enables stable combustion. As the water is large, the reduction rate of NO _x was higher. On the other hand, the emulsion of Comparative Example 2 after 6 hours stored at 60 ° C. was observed in the same manner as in Example 1 by using the emulsified layer excluding the water separation layer because many water separations were observed. As a result, the NO _x reduction rate in Comparative Example 2 was as low as 29% and the smoke concentration reduction rate was 38%.

In addition, the emulsions of other comparative examples after 6 hours stored at 60 ° C. clearly have poor emulsion stability and water separation was observed, so that stable combustion could not be maintained, and NO _x reduction rate It is assumed that the rate of decrease in smoke concentration will be significantly lower than that of the emulsion fuel in the embodiment, and carbonaceous material may accumulate at the tip of the nozzle tip in the engine and cause serious damage such as piston ring sticks. The test was not carried out because it was judged that there was also.

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

Claims (15)

  (A) at least one oil selected from vegetable oils and animal oils, (B) water, (C) at least one emulsifier selected from polyhydric alcohol hydroxy fatty acid esters or derivatives thereof, containing (D) fatty acid as an optional component And a water-in-oil (W / O) emulsion is prepared so that the acid value of the oil (A) and the fatty acid (D) as a whole is 0.3 to 100 mgKOH / g.   (A) at least one oil selected from vegetable oils and animal oils, (B) water, (C) at least one emulsifier selected from polyhydric alcohol hydroxy fatty acid esters or derivatives thereof, containing (D) fatty acid as an optional component The emulsion is stabilized by preparing a water-in-oil (W / O) emulsion so that the acid value of the emulsion is 0.4 to 100 mg KOH / g.   The method for stabilizing an emulsion according to claim 1 or 2, wherein the fatty acid (D) is added when preparing the water-in-oil (W / O) emulsion.   The stabilization method of the emulsion of Claim 3 which adds a fatty acid (D) in the quantity used as 0.1-8 mass% with respect to the total amount of oil (A) and 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 volume ratio of oil (A) to water (B) is 40:60 to 95: 5;
Emulsification as described in any one of Claims 1-5 whose content of an emulsifier (C) is 0.05 mass% or more and less than 5 mass% with respect to the total amount of oil (A) and water (B). Stabilization method.   The emulsifier (C) contains at least one selected from polyglycerin condensed hydroxy fatty acid esters, ethylene oxide adducts of glycerin hydroxy fatty acid esters or fatty acid esters thereof, and the stability of the emulsion according to any one of claims 1 to 6. Method.   (A) at least one oil selected from vegetable oils and animal oils, (B) water, (C) at least one emulsifier selected from polyhydric alcohol hydroxy fatty acid esters or derivatives thereof, containing (D) fatty acid as an optional component And (A) oil and (D) water-in-oil (W / O) emulsion having an acid value of 0.3 to 100 mg KOH / g in the whole fatty acid.   (A) at least one oil selected from vegetable oils and animal oils, (B) water, (C) at least one emulsifier selected from polyhydric alcohol hydroxy fatty acid esters or derivatives thereof, containing (D) fatty acid as an optional component A water-in-oil (W / O) emulsion having an acid value of 0.4 to 100 mg KOH / g.   The water-in-oil (W / O) emulsion according to claim 8, wherein the acid value of the whole 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 relative to the total amount of the oil (A) and 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 volume ratio of oil (A) to water (B) is 40:60 to 95: 5;
The emulsification according to any one of claims 8 to 12, wherein the content of the emulsifier (C) is 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). object.   The emulsifier according to any one of claims 8 to 13, wherein the emulsifier (C) comprises at least one selected from polyglycerin condensed hydroxy fatty acid ester, ethylene oxide adduct of glycerin hydroxy fatty acid ester or fatty acid ester thereof.   The emulsion fuel using the emulsion as described in any one of Claims 8-14.