JP2016180075A - Emulsifier for water emulsion fuel and water emulsion fuel containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an emulsifier for a water emulsion fuel for obtaining a water emulsion fuel having sufficient emulsion stability and low viscosity.SOLUTION: There is provided an emulsifier for an emulsion fuel which contains (a) a fatty acid alkanolamide having 10 to 22 carbon atoms, (b) an alkanolamine and (c) a fatty acid having 10 to 22 carbon atoms, wherein when the total amount of the emulsifier is 100 wt.%, the content of (a) is 50 to 80 wt.%, the content of (b) is 5 to 40 wt.%, the content of (c) is 1 to 30 wt.% and the molar ratio (b)/(c) between (b) and (c) is 1<[(b)/(c)]<20.SELECTED DRAWING: None

Description

  The present invention relates to an emulsifier for water emulsion fuel for emulsifying and dispersing fuel oil (especially fuel oil that is liquid at normal temperature such as light oil, heavy oil, kerosene, mineral oil, etc.) and water with low viscosity. It relates to the water emulsion fuel used.

  In recent years, W / O type water emulsion fuel in which water is dispersed in oil or O / in which oil is dispersed in water due to reduction of nitrogen oxides (NOx) in combustion exhaust gas and increasing interest in the global environment. W-type water emulsion fuel has attracted attention, and efforts to put it into practical use are being actively pursued. Also, since 2016, tertiary regulations on nitrogen oxide (NOx) emissions from ships engaged in international voyages will be implemented by the International Maritime Organization (IMO), and NOx emissions from marine diesel engines are specified. In the regulated sea area, 80% reduction from the primary regulation value is required. By combining with other technologies such as EGR (Disposal Recirculation) system and SCR (Selective Catalyst Reduction) system, the 80% reduction required by tertiary regulations can be reduced more efficiently than EGR and SCR alone. Water emulsion fuel is gaining more and more attention.

Among water emulsion fuels, many W / O type emulsions have been proposed because they are excellent in combustibility and ignitability, and have been put to practical use in some applications. For example, in Patent Document 1, an emulsifier containing four kinds of compounding ingredients, ethoxylated alkylphenol, fatty acid amide, naphtha and oleic acid, is disclosed in Patent Document 2 in which oleic acid, fatty acid diethanolamide, ethanol, 2-aminoethanol, cyclohexylamine Patent Document 3 proposes a solubilizer containing a total of 10 types of fatty acid compounds, such as glycerin palm nut fatty acid ester, as an additive containing 6 types of blending components called ammonia.
Furthermore, in Patent Document 4, a solubilizer containing five kinds of blending components, fatty acid alkanolamide and alkanol, fatty acid, amine, ammonia, is disclosed in Patent Document 5, palm fatty acid diethanolamide, vegetable oleic acid, ethanolamine, In Patent Document 6, an additive containing four kinds of compounding components called cyclohexylamine is a) ether type nonionic surfactant, b) ester type nonionic surfactant, c) alkylene glycol, d) mononitro compound, e ) Additives containing five kinds of blending components called aromatic monocarboxylic acid amine salts have been proposed.

JP2005-530862 JP2008-255208 JP2011-063633 JP2011-245470 JP2012-021105 JP2012-126759

However, the emulsifiers shown in these patent documents consist of relatively many components and are said to be able to maintain an emulsified state for a long time, but maintain stability by increasing the viscosity of water emulsion fuel. For this reason, when used as a fuel, there is a risk of clogging in the fuel supply nozzle or the liquid feed pump unless the temperature is raised to a very high temperature. If the viscosity is high, the particle size of the water emulsion fuel ejected from the fuel supply nozzle will increase, and the amount of consumption will increase accordingly. I am troubled.
An object of this invention is to provide the emulsifier for obtaining the water emulsion fuel which has sufficient emulsification stability and is low-viscosity in view of the said problem.

  As a result of intensive studies on the above problems, water emulsion fuels using emulsifiers containing fatty acid alkanolamides, alkanolamines, and fatty acids in specific ratios have sufficient emulsion stability and a relatively low viscosity. I found out. These can be easily prepared by simply stirring and mixing at room temperature in the same container. That is, this invention relates to the emulsifier for water emulsion fuels and water emulsion fuel of the following items 1-7.

Item 1. (A) An emulsifier for emulsion fuel containing a fatty acid alkanolamide having 10 to 22 carbon atoms, (b) alkanolamine, and (c) a fatty acid having 10 to 22 carbon atoms, and the total amount of the emulsifier is 100 wt% (A) is 50 to 80 wt%, (b) is 5 to 40 wt%, (c) is 1 to 30 wt%, and (b) / (c) molar ratio (b) / (c) Is an emulsifier for water emulsion fuels, wherein 1 <[(b) / (c)] <20.
Item 2. Item 2. The emulsifier for water emulsion fuel according to Item 1, wherein the fatty acid alkanolamide is fatty acid diethanolamide.
Item 3. Item 3. The emulsifier for water emulsion fuel according to Item 1 or 2, wherein the alkanolamine is a secondary amine or a tertiary amine.
Item 4. Item 4. The emulsifier for water emulsion fuel according to any one of Items 1 to 3, further comprising a surfactant.
Item 5. Item 5. A water emulsion fuel comprising the emulsifier according to any one of Items 1 to 4, water and fuel oil.
Item 6. Item 6. The water emulsion fuel according to Item 5, wherein the total amount of the water emulsion fuel is 100 wt%, and the emulsifier is 0.1 to 10 wt%.
Item 7. Item 7. The water emulsion fuel according to Item 5 or 6, wherein water is 5 to 40 wt% when the total amount of water emulsion fuel is 100 wt%.

  The emulsifier of the present invention is excellent in the emulsification stability of fuel oil and water. Moreover, since the water emulsion fuel manufactured using the emulsifier of this invention has a comparatively low viscosity, the spray state from a nozzle is good and favorable combustion is obtained.

<emulsifier>
The emulsifier for water emulsion fuel of the present invention comprises (a) a fatty acid alkanolamide, (b) an alkanolamine, and (c) a fatty acid.

  (A) The fatty acid alkanolamide may be either a fatty acid monoalkanolamide or a fatty acid dialkanolamide, but fatty acid diethanolamide is preferably used. The fatty acid constituting the amide is preferably a saturated fatty acid having 10 to 22 carbon atoms or an unsaturated fatty acid having 10 to 22 carbon atoms. The fatty acid can be a straight chain fatty acid or a branched chain fatty acid. Examples of the saturated fatty acid include capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, and behenic acid. Examples of the unsaturated fatty acid include myristoleic acid, palmitoleic acid, sapienoic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid and the like. The fatty acid may be selected from vegetable fatty acids containing 50% or more of saturated fatty acid or unsaturated fatty acid as a main component, such as coconut oil (coconut oil), palm kernel oil, palm oil, olive oil, cocoa butter and the like. Good.

  The fatty acid alkanolamide is obtained by amidation of the fatty acid with an alkanolamine such as monoalkanolamine or dialkanolamine.

  Examples of the alkanolamine used for amidation include monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine, aminoethylethanolamine and the like.

  Specific examples of fatty acid alkanolamides include oleic acid monoethanolamide, oleic acid monoisopropanolamide, oleic acid aminoethylethanolamide, oleic acid diethanolamide, oleic acid diisopropanolamide, stearic acid diethanolamide, lauric acid diethanolamide, laurin Examples include acid monoethanolamide, lauric acid diethanolamide, lauric acid monoisopropanolamide, lauric acid diisopropanolamide, lauric acid aminoethylethanolamide, stearic acid diethanolamide, coconut oil fatty acid monoethanolamide, coconut oil fatty acid diethanolamide, etc. be able to.

  As the fatty acid alkanolamide, a commercially available product may be used, or it may be produced by an amidation reaction between a known fatty acid and an alkanolamine.

  As the fatty acid alkanolamide, it is preferable to use a fatty acid alkanolamide derived from a fatty acid close to the carbon number of the main component of the oil used as the fuel oil. For example, when light oil is used as the fuel oil, oleic acid diethanolamide or lauric acid diethanolamide may be selected.

  One type of fatty acid alkanolamide may be used alone, or two or more types may be used in combination.

  The ratio of the fatty acid alkanolamide is usually 50 to 80 wt% when the total amount of the emulsifier is 100 wt%, and is preferably 55 to 70 wt% from the viewpoint of emulsion stability.

  (B) The alkanolamine may be any of primary amine, secondary amine, and tertiary amine. As the alkanolamine, any of monoalkanolamine, dialkanolamine, and trialkanolamine may be used. The primary amine is monoethanolamine, monoisopropanolamine, etc. The secondary amine is diethanolamine, diisopropanolamine, etc. The tertiary amine is triethanolamine, triisopropanolamine, monoisopropanoldiethanolamine, diisopropanolethanolamine, cyclohexylamine Etc. can be illustrated. Among these, secondary amines or tertiary amines are preferably used from the viewpoint of emulsion stability and compatibility with fuel oil. Specifically, diethanolamine and triethanolamine are preferably used.

  One alkanolamine may be used alone, or two or more alkanolamines may be mixed and used.

  The proportion of the alkanolamine is usually 5 to 40 wt%, preferably 8 to 35 wt%, when the total amount of the emulsifier is 100 wt%.

  (C) The fatty acid may be either a saturated fatty acid or an unsaturated fatty acid as long as it has 10 to 22 carbon atoms, and may be a linear fatty acid or a branched chain fatty acid. The fatty acid illustrated as a fatty acid which comprises the above-mentioned (a) fatty-acid alkanolamide can be used. Fatty acids having the same number of carbon atoms as the fatty acid of the fatty acid alkanolamide used and fatty acids close to the carbon number of the main component of the oil used as fuel oil are preferably used. For example, when light oil is used as the fuel oil, oleic acid or lauric acid may be selected.

  One fatty acid may be used alone, or two or more fatty acids may be mixed and used.

  The ratio of the fatty acid is usually 1 to 30 wt%, preferably 3 to 20 wt% when the total amount of the emulsifier is 100 wt%.

In the emulsifier of the present invention, the alkanolamine and the fatty acid may form a salt (fatty acid alkanolamine salt). In this case, part of the alkanolamine and fatty acid in the emulsifier may be added as a fatty acid alkanolamine salt, or the alkanolamine and the fatty acid are added separately, and part of them forms a salt during the emulsifier manufacturing process. You may make it do.
In the emulsifier of the present invention, since alkanolamine is added in excess of the fatty acid, the emulsifier always contains free alkanolamine.

  The molar ratio (b) / (c) between (b) and (c) is preferably 1 <[(b) / (c)] <20, and 1 <[(b) / (c)] More preferably, it is <10. By setting the amine within this range, a water emulsion fuel having excellent emulsification stability and low viscosity can be obtained.

  The emulsifier of the present invention may contain a surfactant and a rust preventive agent in addition to the above (a) to (c).

  As the surfactant, any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant may be used.

  Examples of the anionic surfactant include alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl benzyl dimethyl ammonium salt and the like. Specific examples include dodecyltrimethylammonium chloride, octyldodecyldimethylammonium chloride, didecyldimethylammonium chloride, and decylisononyldimethylammonium chloride.

  Examples of the cationic surfactant include fatty acid salts, alkyl sulfates, alkyl polyoxyethylene sulfates, alkylbenzene sulfonates, alkyl phosphates, and sulfosuccinates. Specific examples include sodium linoleate, sodium oleate, sodium dodecyl sulfonate, sodium polyoxyethylene lauryl ether sulfate, sodium dodecyl benzene sulfonate, sodium polyoxyethylene alkyl ether phosphate, sodium ethylhexyl sulfosuccinate, and the like. be able to.

  Examples of nonionic surfactants include polyhydric alcohol fatty acid esters, polyoxyalkylene alkylene glycols, polyoxyalkylene alkyl ethers, higher fatty acid alkylene oxide adducts, and the like. Specifically, sorbitan monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan distearate, sorbitan tristearate, sorbitan trisoleate, (poly) glycerin monooleate, (poly) Glycerin monostearate, polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene lauryl ether, polyoxyethylene polyoxypropylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene polyoxypropylene oleyl ether, poly Oxyethylene laurate, polyoxyethylene polyoxypropylene laurate, polyoxyethylene Oleic acid esters, polyoxyethylene polyoxypropylene stearic acid esters and the like.

  Examples of amphoteric surfactants include alkyl dimethylamine oxide and alkyl carboxybetaine. Specific examples include dodecyldimethylamine oxide, lauryldimethylamine oxide, dodecyldimethylcarboxybetaine, dodecyldimethylamidopropylcarboxybetaine, and the like.

  The addition amount of the surfactant is usually 0.1 wt% to 30 wt% when the total amount of the emulsifier is 100 wt%.

  Although it does not specifically limit as a rust preventive agent, For example, aliphatic amines, such as an ethylamine, diethylamine, a triethylamine, a butylamine, a dibutylamine, a tributylamine, an octylamine, a dodecylamine, an oleylamine, can be mentioned.

<Water emulsion fuel>
The water emulsion fuel is a liquid that contains fuel oil, water, and the above-mentioned emulsifier, and is obtained by uniformly emulsifying and dispersing fuel oil and water. The fuel oil that can be used for the water emulsion fuel of the present invention is a fuel oil that is liquid at room temperature, such as heavy oil (A heavy oil, B heavy oil, C heavy oil), light oil, kerosene, mineral oil, waste oil and the like.

  The amount of the emulsifier of the present invention added to the fuel oil may be appropriately selected according to the type of fuel oil, the amount of water, etc., but when the total amount of water emulsion fuel is 100 wt%, it is usually 0.1 to 10. It is 0 wt%, and 1.0 to 5.0 wt% is preferable.

  The water emulsion fuel of the present invention may be either an oil-in-water dispersion (O / W) type or a water-in-oil dispersion (W / O) type, but the W / O type is more preferable from the viewpoint of combustion efficiency.

  In the case of producing a W / O type water emulsion fuel, the fuel oil and the emulsifier are first stirred and mixed, and then water is added little by little and mixed and stirred. On the other hand, when producing an O / W type water emulsion fuel, water and an emulsifier are first stirred and mixed, and then fuel oil is added little by little and mixed and stirred. Specifically, the W / O type water emulsion fuel is produced by adding a predetermined amount of an emulsifier to the fuel oil, and then stirring the mixture at a low speed (for example, 500 to 2000 rpm) to lightly disperse the emulsifier in the fuel oil. The rotational speed is increased to a high speed (for example, 2500 to 5000 rpm), and the emulsifier is completely dispersed in the fuel oil. Subsequently, water is added little by little, and the mixture is stirred and mixed at a higher speed (for example, 6000 to 8000 rpm) to prepare a W / O type water emulsion fuel. As an apparatus used for stirring and mixing, an ordinary mixer or stirring machine having a stirring blade such as a screw type can be used.

  The viscosity of the water emulsion fuel is about the same as or lower than that of the fuel oil alone, and is preferably 1000 mPa · s or less at 25 ° C.

  The proportion of water contained in the water emulsion fuel can vary depending on the type of fuel oil and the amount of emulsifier added, but from the viewpoint of emulsion stability and viscosity, when the total amount of water emulsion fuel is 100 wt%, It is 5-40 wt%, Preferably it is 15-30 wt%. Moreover, the ratio of fuel oil is 60-95 wt% normally, Preferably it is 70-85 wt%.

  The water emulsion fuel of the present invention can be used for any application as long as it is a target that uses fuel such as automobiles, ships, generators, boilers and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to the content shown in these Examples.

Examples 1-7, Comparative Examples 1-7
Fatty acid alkanolamides, alkanolamines and fatty acids were mixed in the compounds and proportions shown in Table 1 to produce emulsifiers.

(Emulsion stability test)
Take the emulsifier and light oil or heavy oil in a 300 ml tall beaker and stir at 1000 rpm for 3 minutes using a homomixer (TK KHOMO MIXER made by Tokushu Kika), and then stir at 2500 rpm for 3 minutes. Completely dispersed. Subsequently, weighed tap water was added little by little, and further mixed and stirred at 7000 rpm for 3 to 5 minutes to prepare a water emulsion fuel. The ratios of emulsifier, fuel oil and water are shown in Table 1. The total amount of fuel oil and water was 200 g.
100 ml of the adjusted water emulsion fuel was sampled in a 100 ml sample bottle and allowed to stand in a 30 ° C. incubator for 7 days to evaluate the emulsion stability. The emulsification stability was evaluated by the emulsification rate (%) calculated by the following (Formula 1).
Formula 1: Emulsification rate (%) = (full length of emulsified phase / full length of water emulsion fuel) × 100

(viscosity)
The viscosity was measured at 25 ° C. using a B-type viscometer (BMII manufactured by Tokimec) equipped with an attached rotor (No. 1). The rotational speed of the rotor is 60 rpm when the viscosity is ~ 100 mPa · s, 30 rpm when ~ 200 mPa · s, 12 rpm when ~ 500 mPa · s, 6 rpm when ~ 1000 mPa · s, and ~ 2000 mPa · s 3 rpm. The viscosity of the light oil at 25 ° C. was 3 mPa · s.

Claims (7)

  (A) An emulsifier for emulsion fuel containing a fatty acid alkanolamide having 10 to 22 carbon atoms in fatty acid, (b) alkanolamine, and (c) a fatty acid having 10 to 22 carbon atoms, and the total amount of the emulsifier is 100 wt%. (A) is 50 to 80 wt%, (b) is 5 to 40 wt%, (c) is 1 to 30 wt%, and (b) / (c) molar ratio (b) / (c) Is an emulsifier for water emulsion fuels, wherein 1 <[(b) / (c)] <20.   The emulsifier for water emulsion fuel according to claim 1, wherein the fatty acid alkanolamide is fatty acid diethanolamide. The emulsifier for water emulsion fuel according to claim 1 or 2, wherein the alkanolamine is a secondary amine or a tertiary amine. Furthermore, the emulsifier for water emulsion fuels as described in any one of Claims 1-3 containing surfactant. The water emulsion fuel containing the emulsifier as described in any one of Claims 1-4, water, and fuel oil.   The water emulsion fuel according to claim 5, wherein the emulsifier is 0.1 to 10 wt% when the total amount of the water emulsion fuel is 100 wt%.   The water emulsion fuel according to claim 5 or 6, wherein water is 5 to 40 wt% when the total amount of water emulsion fuel is 100 wt%.