JP4687861B2 - Oil / water emulsion fuel composition - Google Patents

Description

  The present invention relates to fuel oil and water W / O type water / water emulsion fuel that are used as low pollution fuel with improved combustion characteristics and handling of light oil, kerosene, heavy oil, animal and vegetable oils, etc., and particularly stable at low addition amount. The present invention relates to the provision of an emulsifier composition capable of supplying a fresh W / O type oil / water emulsion fuel.

  Fuel oil such as light oil, kerosene, heavy oil, animal and vegetable oil is used in large boilers used for diesel engines, turbine engines, power generation, large ships, steam generation in large-scale factories, and the like. However, when these fuel oils are burned alone, CO and NOx, which are incomplete combustion products, are generated, and in the case of fuel gas, gasoline, etc., smoke is generated. As a countermeasure, a method of installing a removal device to remove incompletely combusted materials has been proposed, but costs such as installation costs, equipment costs, maintenance costs, management costs, etc., and incompletely combusted materials, etc. There are many technical challenges such as removal and incomplete combustion that contaminates the equipment and lowers thermal efficiency. On the other hand, an oil / water emulsion fuel composed of fuel oil and water has been proposed for the purpose of reducing the occurrence of incompletely combusted substances.

  This oil / water emulsion fuel has been studied in recent years, but if the ratio of fuel oil to water is not kept constant as an emulsified liquid, the combustibility will decrease, and if the emulsion liquid is not stable, the emulsified liquid will be emulsified. Problems arise in the case of combustion devices that temporarily store liquids. Further, when the emulsification performance is poor and a large amount of addition is required, there is an economical problem. Under such circumstances, several emulsifiers for oil / water emulsion fuels have been proposed, and there are disclosures of the technologies of Patent Document 1 and Patent Document 2 using a nonionic surfactant as an emulsifier, and hydrocarbyl substitution. Patent Document 3, Patent Document 4, and Patent Document 5 which use a hydrolyzate of acid or acid anhydride are disclosed. In any case, there was room for improvement in emulsion stability and the amount added.

JP 53-44327 A (page 3) JP-A-10-53778 (pages 1-2 and 13) Special table 2002-525385 (pages 2-7, 61-63) Publication 63-502254 (pages 1-4, 20) US Pat. No. 6,419,714 (pages 26-32)

  An agent that reduces the amount of emulsifier (surfactant) used and has excellent emulsification stability when water is dispersed in light oil, kerosene, heavy oil, animal and vegetable oils, etc. to obtain a W / O oil / water emulsion fuel. Offer. Another object of the present invention is to provide a W / O type oil / water emulsion fuel having good stability using the emulsifier of the present invention.

（但し式中、Ｒ ³ は炭素数８〜２２のアルキル基又はアルケニル基を、Ｒ ⁴ は炭素数２〜３のアルキレン基を、ｃは１〜２０の整数を示す。）で表される化合物から選ばれる一種または二種以上の化合物を含み、さらに、一般式（Ｂ１）、

（但し式中、Ｒ ¹ 及びＲ ² は水素原子もしくは炭素数７〜２１の飽和または不飽和脂肪酸残基を示すが、Ｒ ¹ 、Ｒ ² がともに水素原子であることはない。またａ及びｂは１以上の整数であり、ａ＋ｂは２〜４０の整数を表す。）で表される化合物、及び
一般式（Ｂ３）、

（但し式中、Ｒ ⁵ は炭素数７〜２１の飽和または不飽和脂肪酸残基を、Ｒ ⁶ は炭素数２〜３のアルキレン基を、ｄは１〜５０の整数を、Ｒ ⁷ は水素原子又は炭素数７〜２１の飽和ま
たは不飽和脂肪酸残基を表す。）
で表される化合物の群から選ばれる一種または二種以上の化合物を含むものであることを特徴とするＷ／Ｏ型油・水エマルション燃料組成物に関する。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a certain ratio of a specific polybutenyl succinate and a specific nonionic surfactant is used in the production of a W / O type oil / water emulsion fuel. It has been found that the emulsifier blended in (1) exhibits excellent emulsifiability and has reached the present invention.
That is, the present invention provides an emulsifier for obtaining a W / O type oil / water emulsion fuel containing 95 to 50 parts by weight of fuel oil and 5 to 50 parts by weight of water (provided that the total amount of fuel oil and water is 100 parts by weight). , polybutenyl succinate (a) and nonionic surfactant (B) and (a) :( B) = 20~ 60 % by weight: a composition containing in a proportion of 40 to 80 wt%, and the fuel A W / O type oil / water emulsion fuel composition characterized by using 0.03 to 5.0 parts by weight based on the total amount of water , wherein the nonionic surfactant (B) has the general formula (B2)

(Wherein R ³ represents an alkyl group or alkenyl group having 8 to 22 carbon atoms, R ⁴ represents an alkylene group having 2 to 3 carbon atoms, and c represents an integer of 1 to 20). 1 type or 2 types or more compounds chosen from, Furthermore, General formula (B1),

(In the formula , R ¹ and R ² represent a hydrogen atom or a saturated or unsaturated fatty acid residue having 7 to 21 carbon atoms, but R ¹ and R ² are not both hydrogen atoms. A and b) Is an integer of 1 or more, and a + b represents an integer of 2 to 40), and
Formula (B3),

(In the formula , R ⁵ represents a saturated or unsaturated fatty acid residue having 7 to 21 carbon atoms, R ⁶ represents an alkylene group having 2 to 3 carbon atoms, d represents an integer of 1 to 50, and R ⁷ represents a hydrogen atom. Or saturated with 7 to 21 carbon atoms
Or represents an unsaturated fatty acid residue. )
It is related with the W / O type oil and water emulsion fuel composition characterized by including the compound of 1 type, or 2 or more types chosen from the group of the compound represented by these.

  The polybutenyl succinate (A) has an average molecular weight of 300 to 3000, and the polybutenyl group in the compound is mainly composed of isobutenyl and partially or completely neutralized with ammonia or an organic amine. A W / O type oil / water emulsion fuel composition which is a salt.

  The compound represented by the general formula (B1) is obtained by reacting boric acid with glycerin to obtain glycerol borate, adding ethylene oxide, and further esterifying with fatty acid to obtain polyoxyethylene glycerol borate A W / O type oil / water emulsion fuel composition which is a fatty acid ester.

  The emulsifier composition of the present invention exhibits significantly better performance than the case where each is used alone due to the synergistic effect of combining polybutenyl succinate and nonionic surfactant at a specific blending ratio. is there. In particular, the emulsion stability of the W / O type oil / water emulsion fuel is excellent, and the amount of the emulsifier added is also superior. It is possible to provide an excellent W / O type oil / water emulsion fuel that is expected to contribute to environmental problems such as CO, NOx, and soot of imperfect combustion products.

The present invention will be described in detail below.
In the present invention, polybutenyl succinate (A) is hydrolyzed by reacting maleic anhydride with polybutene or liquid polybutene having an average molecular weight of 300 to 3000 by a known production method, and partially or completely neutralized with alkalis. However, in terms of quality and performance, polybutenyl succinate having an average molecular weight of 800 to 2000 is preferable, and one that can be partially or completely neutralized with ammonia or an organic amine is preferable. Polybutene or liquid polybutene is a copolymer in which normal butenes are partially reacted mainly with isobutene, but may be polyisobutene obtained by stereoregularly polymerizing only isobutene.

  Examples of alkalis for obtaining polybutenyl succinate (A) include monovalent alkali metals such as caustic soda and caustic potash, ammonia, or alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, morpholine and cyclohexyl. Although organic amines, such as an amine, can be mention | raise | lifted, an alkanolamine is preferable at the point of an effect.

  The nonionic surfactant represented by the general formula (B1) according to the present invention is known to react boric acid with glycerin to obtain glycerol borate, add ethylene oxide, and further esterify with fatty acid. The polyoxyethylene glycerol borate fatty acid ester obtained by the manufacturing method is represented.

R ¹ and R ² represent a hydrogen atom or a saturated or unsaturated fatty acid residue having 7 to 21 carbon atoms, and examples of the fatty acid include cabric acid, lauric acid, myristic acid, oleic acid, linoleic acid, palmitic acid, and tall. Examples include oil fatty acid, erucic acid, castor oil fatty acid and the like. R ¹ and R ² may be the same or a mixture, and may be either a branched chain or a straight chain, but oleic acid or linoleic acid is preferred from the viewpoint of effects.

  Glycerol borate is preferably added with ethylene oxide as an integer of 1 or more, and the total of a + b in the general formula (B1) is preferably in the range of 2 to 40 mol, but if it exceeds 40 mol, the emulsifiability deteriorates. . More preferably, it is the range of 25-35 mol from the point of emulsification.

  The polyoxyalkylene monoalkyl ether or polyoxyalkylene monoalkenyl ether, which is an alkylene oxide addition-type nonionic surfactant represented by the general formula (B2) according to the present invention, is obtained by converting alkylene oxide to a higher alcohol by a known production method. Obtained by addition reaction.

The higher alcohol for obtaining the polyoxyalkylene monoalkyl ether or polyoxyalkylene monoalkenyl ether of the present invention is a linear or branched higher alcohol having R ³ of 8 to 22 carbon atoms, and examples thereof include decyl alcohol and lauryl alcohol. , Cetyl alcohol, stearyl alcohol, oleyl alcohol, secondary tridecyl alcohol, secondary tetradecyl alcohol and the like alone or in combination.

The alkylene oxide for the higher alcohol is ethylene oxide or propylene oxide in which R ⁴ has 2 or 3 carbon atoms, and may be either single, composite, block, or random addition. The added mole number of alkylene oxide (c in the general formula (B2)) is 1 to 20 moles, but if it exceeds 20 moles, the emulsifiability deteriorates rapidly. More preferably, it is 3-10 mol from the point of emulsification. Among these alkylene oxide addition type nonionic surfactants, the most preferable one is that 3 to 8 mol of alkylene oxide is added to a higher alcohol having 16 to 18 carbon atoms.

  The polyalkylene glycol fatty acid ester type nonionic surfactant represented by the general formula (B3) according to the present invention can be obtained by a known production method such as reaction of polyalkylene glycol and fatty acid.

As for the fatty acid for obtaining the polyalkylene glycol fatty acid ester type nonionic surfactant, R ⁵ and R ⁷ are octyl acid, capric acid, coconut oil fatty acid, lauric acid, myristic acid, stearic acid, behenic acid, oleic acid, Residues such as linoleic acid, tall oil fatty acid, erucic acid, castor oil fatty acid and the like can be mentioned. R ⁵ . The fatty acids having R ⁷ may be the same or a mixture, and may be either a branched chain or a straight chain, but oleic acid and linoleic acid are most preferable from the viewpoint of effects.

The alkylene oxide for obtaining the polyalkylene glycol fatty acid ester type nonionic surfactant is ethylene oxide or propylene oxide in which R ⁶ has 2 or 3 carbon atoms, and may be any of single, composite, block, or random addition. . The added mole number of alkylene oxide (d in the general formula (B3)) is in the range of 1 to 50 moles, and if it exceeds 50 moles, the emulsifiability deteriorates rapidly. It is particularly preferable to use polyethylene glycol having a molecular weight of 200 (5 mol) to 2000 (46 mol) as a raw material in terms of effect and economy.

  The emulsifier composition used in the present invention is a blend of two or more types, but the blending ratio is 20 to 90% by weight of polybutenyl succinate (A) and 80 of nonionic surfactant (B). It is a ratio of -10 wt%. More preferably, a mixture in which (A) is 40 to 60% by weight and (B) is 40 to 60% by weight exhibits the most appropriate synergistic effect.

  The addition amount of the emulsifier composition of the present invention is 0.03 to 5.0% by weight with respect to the total weight of the fuel oil and water, but the preferred use amount is 0.1 to 0.5% by weight in view of the effect. Range. If the addition is less than 0.03% by weight, the stability of the emulsion is lowered due to insufficient emulsifier, and the desired effect of the present invention is not exhibited. On the other hand, if the addition exceeds 5.0%, the emulsifiability is not improved any more and the economy is improved. It is not preferable in terms of quality.

  The emulsification method of the oil / water emulsion is preferably that water is added to the fuel oil in which the emulsifier is dissolved, and then stirred at a normal temperature, but if a commonly used emulsifier such as a homomixer or dispamil is used, a finer and more stable emulsion Is obtained.

  Thus, by using the specific polybutenyl succinate (A) and nonionic surfactant (B) according to the present invention at a specific blending ratio, the excellent emulsification performance of the present invention is exhibited. The reason for the excellent performance is not yet clear, but when forming an emulsion, the fuel oil has a relatively large molecule and a moderately branched polybutene group and relatively molecules. Small nonionic surfactants are effectively arranged on the surface of the emulsified droplets, while water is considered to be a combined effect in which the hydrophilicity of polybutenyl succinic acid salt acts effectively . The use of the polybutenyl succinic acid salt and the nonionic surfactant according to the present invention alone is ineffective, and if the blending ratio is deviated, the performance is significantly lowered.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to a following example, unless the meaning is exceeded.

Production Example of Polybutenyl Succinate (A) <Production Method of Polybutenyl Succinate (A)>
A reaction vessel was charged with 1000 g (1.0 mol) of Nisseki polybutene (manufactured by Nippon Oil Co., Ltd., average molecular weight 1000) and 118 g (1.2 mol) of maleic anhydride. Mix and dissolve for minutes. Subsequently, the temperature is raised to 230 to 240 ° C., and after the reaction for 6 hours, the mixture is cooled to 90 ° C. Next, 22 g (1.2 mol) of water was added, and the mixture was stirred at 100 ° C. for 3 hours for hydrolysis, then cooled to 40 ° C., and 71 g (1.2 mol) of monoethanolamine was gradually added. ) Of polybutenyl (average molecular weight 1000) monoethanolamine salt of succinic acid was obtained.
Compounds A-2 and A-3 in Table 1 were synthesized in the same manner as Compound A-1.

Production Example of Nonionic Surfactant (B) <Method for Producing Polyoxyethylene Glycol Borate Fatty Acid Ester-Type Surfactant of the Present Invention (B1)>
A reaction vessel was charged with 62 g (1.0 mol) of boric acid and 184 g (2.0 mol) of glycerin, reacted at 230 ° C. for 4 hours, cooled to 120 ° C., 1 g of BF ₃ ethyl ether was added as a catalyst, and 1322 g of ethylene oxide. (30 mol: equivalent to the total amount of a + b in the general formula (B1)) was reacted for 3 hours.
Next, 282 g (1.0 mol) of oleic acid was added, the temperature was raised to 230 ° C., and esterification was carried out for 6 hours to obtain 1800 g of polyoxyethylene glycol borate monooleate of the present invention (B1-1).
Compounds B1-2 and B1-3 in Table 1 were synthesized in the same manner as Compound B1-1.

<Method for Producing Ethylene Oxide Addition Type Surfactant of the Present Invention (B2)>
To the reaction vessel, 270 g (1.0 mol) of oleyl alcohol was added with 0.5 g of caustic potash as a catalyst, and 264 g (6.0 mol) of ethylene oxide was sequentially introduced at 170 to 180 ° C. over 3 hours to react. , 530 g of an oleyl alcohol ethylene oxide 6 mol adduct of the present invention (B2-1) was obtained.
Compounds B2-2 and B2-3 in Table 1 were synthesized in the same manner as Compound B2-1.

<Method for producing polyethylene glycol fatty acid ester type surfactant of the present invention (B3)>
The reaction vessel was charged with 400 g (1.0 mol) of polyethylene glycol (molecular weight 400) and 560 g (2.0 mol) of oleic acid, 2 g of caustic potash was added as a catalyst, and the reaction was carried out at 210 to 220 ° C. for 4 hours. The present invention (B3-1) 900 g of polyethylene glycol (MW400) dioleic acid ester was obtained.
Compounds (B3-2) and (B3-3) in Table 1 were synthesized in the same manner as for compound (B3-1).

Compound Example <Production Method of Mixture 1>
A mixing vessel was charged with 50 parts by weight of polybutenyl (average molecular weight 1000) monoethanolamine salt of succinic acid (Compound A-1) and 50 parts by weight of oleyl alcohol ethylene oxide 6 mol adduct (Compound B2-1) at 30 to 40 ° C. Mixing for 30 minutes gave Mixture 1.
Moreover , the mixture 2, the reference example mixtures 1-3 and the comparative mixtures 1-5 were obtained by the same method. Table 2 summarizes the blend compositions of Mixtures 1-2, Reference Example Mixtures 1-3 , and Comparative Mixtures 1-5.

<Emulsion stability test method and test result of mixture>
Based on the emulsifier composition prepared in Table 2, a W / O type oil / water emulsion composed of fuel oil, water and an emulsifier composition was prepared, and the stability of the emulsion was evaluated.
<Preparation of emulsion>
1200 g of light oil and 0.45 g of the emulsifier composition (mixture 1 in Table 2) were added and mixed in a 2 L emulsification container. The mixture of the light oil and the emulsifier composition was adjusted to 20 ° C., and 300 g of water at 20 ° C. was gradually added. . Thereafter, T.W. K. The mixture was stirred at 7000 rpm and 20 to 25 ° C. for 5 minutes with a homomixer (manufactured by Tokushu Kika Co., Ltd.) to obtain Example mixture 1 as an oil / water emulsion fuel in Table 3.
In addition, the other emulsifier compositions described in Table 2 (mixture 2, reference example mixtures 1 to 3, comparative mixture 1 to 5) were used, respectively, and Example mixture 2 which was an oil / water emulsion fuel in the same manner , reference Example mixtures 1 to 3 and comparative mixtures 1 to 5 were obtained, respectively . Table 3 summarizes the preparations of Examples Mixes 1 and 2, Reference Mixtures 1 to 3 , and Comparative Mixtures 1 to 5 that are oil / water emulsion fuels .

<Emulsion stability evaluation method>
Emulsion stability test branch cylinders with a capacity of 250 ml (samples can be taken from the top and bottom with cylinders according to JIS-K-2208) The emulsion prepared above is transferred until it reaches the marked line in the cylinder. I took it. Six cylinders are prepared for one emulsion. Three of the six were tested as accelerated tests in a 40 ° C. thermostat (temperature error ± 1 ° C.), and the remaining three were placed in a 20 ° C. thermostatic chamber (temperature error ± 1 ° C.). After the lapse of the specified number of days, emulsions were collected in the order of 50 ml from the upper part of the cylinder and 50 ml from the lower part, and each was measured for moisture according to the Karl Fischer method (JIS-K-0067). The measured value was an average of three points, and the difference in moisture between the upper and lower portions of each emulsion was shown as the emulsification stability (%).
Emulsification stability (%) = Lower moisture (%)-Upper moisture (%)
Therefore, in this test, when the emulsion concentration is constant, the moisture content is 0% without any difference. The closer to 0%, the better the emulsion stability (%).

Using the emulsifier composition shown in the formulation as shown in Table 2, W / O type oil / water emulsion fuel based on the formulation in Table 3 was prepared. An emulsification stability test was carried out for each sample of Example Mixes 1-2, Reference Example Mixtures 1-3, and Comparative Mixtures 1-5, which are W / O type oil / water emulsion fuels shown in Table 3, and the test results Are summarized in Table 4.

Example mixture Nos. Of the emulsion stability test results in Table 4 1-2 are the results of using the emulsifier composition of the examples of the present invention. 1 to 5 are the results of evaluation with emulsifier compositions other than the present invention. The numerical value indicating the emulsification stability (%) of the W / O type oil / water emulsion fuel is the difference in moisture (%) of 5% or less after 3 days in a 20 ° C. incubator, and the constant temperature of 40 ° C. The criterion was to satisfy the two requirements of a difference in moisture (%) of 10% or less after 30 days in a container.

  The mixtures of the examples all had good emulsion stability. On the other hand, in the comparative mixture 1 which is a mixture of polybutenyl succinic acid and a nonionic surfactant which is not in the form of salt, the comparative mixture 4 which is a polybutenyl succinate alone, and the comparative mixture 5 which is out of the mixing ratio, the emulsion stability. Was inferior.

  In the case of obtaining an oil / water emulsion fuel by dispersing water in light oil, kerosene, heavy oil, animal or vegetable oil, etc., the use of the emulsifier according to the present invention reduces the amount used and is excellent in emulsion stability. O-type oil / water emulsion fuel can be provided, and generation of incompletely combusted products can be suppressed.

Claims (3)

In obtaining a W / O type oil / water emulsion fuel containing 95 to 50 parts by weight of fuel oil and 5 to 50 parts by weight of water (provided that the total amount of fuel oil and water is 100 parts by weight), polybutenyl is used as an emulsifier. A composition in which succinate (A) and nonionic surfactant (B) are blended in a ratio of (A) :( B) = 20-60 wt%: 40-80 wt% A W / O type oil / water emulsion fuel composition characterized by using 0.03-5.0 parts by weight based on the amount, wherein the nonionic surfactant (B) is represented by the general formula (B2)

(Wherein R ³ represents an alkyl group or alkenyl group having 8 to 22 carbon atoms, R ⁴ represents an alkylene group having 2 to 3 carbon atoms, and c represents an integer of 1 to 20). 1 type or 2 types or more compounds chosen from, Furthermore, General formula (B1),

(In the formula, R ¹ and R ² represent a hydrogen atom or a saturated or unsaturated fatty acid residue having 7 to 21 carbon atoms, but R ¹ and R ² are not both hydrogen atoms. A and b) a is an integer of 1 or more, a + b is an integer of 2 to 40.) the compound represented by, and <br/> general formula (B3),

(In the formula, R ⁵ represents a saturated or unsaturated fatty acid residue having 7 to 21 carbon atoms, R ⁶ represents an alkylene group having 2 to 3 carbon atoms, d represents an integer of 1 to 50, and R ⁷ represents a hydrogen atom. Or a saturated or unsaturated fatty acid residue having 7 to 21 carbon atoms.)
A W / O type oil / water emulsion fuel composition comprising one or more compounds selected from the group of compounds represented by formula (1). The polybutenyl succinate (A) has an average molecular weight of 300 to 3000, the polybutenyl group in the compound is mainly composed of isobutene, and is partially or completely neutralized with ammonia or an organic amine. The W / O type oil / water emulsion fuel composition according to claim 1, which is a salt. The compound represented by the general formula (B1) is obtained by reacting boric acid with glycerin to obtain glycerol borate, adding ethylene oxide, and further esterifying with fatty acid to obtain polyoxyethylene glycerol borate The W / O type oil / water emulsion fuel composition according to claim 1, which is a fatty acid ester.