WO2007094171A1

WO2007094171A1 - Fuel oil composition

Info

Publication number: WO2007094171A1
Application number: PCT/JP2007/051581
Authority: WO
Inventors: Yuki Sugiura; Masato Namiki
Original assignee: Adeka Corporation
Priority date: 2006-02-14
Filing date: 2007-01-31
Publication date: 2007-08-23
Also published as: JP2007217450A

Abstract

Disclosed is a fuel oil composition which contains no metal, has a good lubricating property, and has a small unwashed existent gum content. The fuel oil composition comprises a fuel oil and a compound represented by the general formula (1): (1) wherein R represents a hydrocarbon group having 6 to 20 carbon atoms.

Description

Fuel oil composition

Technical field

TECHNICAL FIELD [0001] The present invention relates to a fuel oil composition having good lubricity and a small amount of unwashed actual gum.

[0002] Most automobiles, ships, airplanes, etc. use internal combustion engines such as gasoline engines and diesel engines, and fuel oils such as gasoline, light oil, heavy oil, and kerosene are used as power sources for driving these internal combustion engines. Is used. In recent years, it has been pointed out that exhaust gas from which internal combustion engine power is discharged is one of the causes of air pollution, and various regulations including voluntary regulations have been implemented.

[0003] The exhaust gas contains many substances that are considered to have an adverse effect on the environment, such as carbon dioxide, nitrogen oxides, and sulfur oxides. Some of these substances are removed by, for example, automobile exhaust catalysts and are not released into the environment. However, since all the substances cannot be removed and the absolute amount of exhaust gas is enormous, it was a major challenge to reduce the exhaust gas itself.

[0004] In order to reduce exhaust gas, for example, it is known to add a friction reducing agent such as organic molybdenum to the lubricating oil. By reducing the frictional resistance of the operating part of the internal combustion engine, energy loss is reduced, fuel consumption is reduced, and exhaust gas is reduced. Similarly, a friction reducing agent was added to the fuel oil in order to bring out the same effect.

[0005] As a friction reducer for such fuel oil, for example, Patent Document 1 discloses (a) a fuel containing a product obtained by transesterification of a tridaricide-type fat or its alkylene oxide adduct and an alcohol. An oil additive composition (Claim 1) is disclosed. Patent Document 2 also discloses that a major amount of hydrocarbon having a boiling point in the boiling range of gasoline oil, and an additive composition for fuel comprising an amount for reducing fuel consumption comprising the following components (a) and (b): A fuel composition comprising: (a) at least one amine selected from the group consisting of (1) and (2) below Compound: (1) Fuel-soluble aliphatic hydrocarbon-substituted amine having at least one basic nitrogen atom, the number-average molecular weight of the hydrocarbon group being in the range of 700 to 3,000, and (2 ) A poly (oxyalkylene) amine having at least one basic nitrogen atom, wherein the oxyalkylene unit is soluble in a hydrocarbon having a boiling point in the boiling range of gasoline oil. And (b) an ester of a carboxylic acid and a polyhydric alcohol, the carboxylic acid having 1 to 4 carboxylic acid groups and 8 to 50 carbon atoms. And an ester wherein the polyhydric alcohol has 2 to 50 carbon atoms and 2 to 6 hydroxy groups (Claim 1) is disclosed. Further, Patent Document 3 discloses a fuel oil composition (Claim 1) characterized in that an alkaline earth metal salt having a thermal decomposition start temperature of 220 ° C or higher is added to the fuel oil. A fuel oil addition characterized by containing a molybdenum amine salt obtained by reacting a compound containing a hexavalent molybdenum atom with an amine represented by the following general formula (1) or (2) Agent

[Chemical 1]

(In the formula, R ¹ represents an alkyl group or a alkenyl group having 4 or more carbon atoms, and R ² and R ³ represent a hydrogen atom or a hydrocarbon group.)

[Chemical 2]

{Wherein R ⁴ represents a hydrocarbon group, a represents a number of 0 or 1, R ⁵ and R ⁶ each independently represent a hydrogen atom, a hydrocarbon group, (AO) H (A is a hydrocarbon Group, side chain is ether Represents a hydrocarbon group substituted with a group, or a hydrocarbon group whose side chain is substituted with an ester group, and b represents a number of 1 or more) or represented by the following general formula (3) Represents a group. However, when a is 0, at least one of R ^{5 and} R ⁶ is a group represented by — (AO) H or a group represented by the general formula (3).

(In the formula, R ⁷ represents an alkylene group, X represents a hydrogen atom, a hydrocarbon group, or an alkyl group having 2 to 4 carbon atoms, and c represents a number of 1 to 5.)}

Is disclosed.

[0007] Patent Document 1: Japanese Patent Laid-Open No. 7-26276

Patent Document 2: Japanese Patent Laid-Open No. 11 310783 Patent Claim

Patent Document 3: Japanese Patent Application Laid-Open No. 2002-302686 Claims

Patent Document 4: Japanese Patent Application Laid-Open No. 2003-27073 Claims

Disclosure of the invention

Problems to be solved by the invention

[0008] However, an ester-based additive that is also composed of a compound having an ester bond as disclosed in Patent Documents 1 and 2 is a residue called unwashed real gum when added to a fuel such as gasoline. There may be many things. Unwashed real gum is a vaporized residue derived from fuel additives, and if there is too much unwashed real gum, it may cause clogging of filters and valves. Furthermore, a compound having an ester bond may wear the metal chemically due to fatty acids generated by deterioration. In addition, metal additives such as those disclosed in Patent Documents 3 and 4 can be converted into metal oxides by combustion, poisoning exhaust gas catalysts, or being released outdoors and adversely affecting the environment. is there.

[0009] Therefore, the object of the present invention is to contain a metal, have good lubricity, and have an unwashed actual gum content. Less is to provide a fuel oil composition.

Means for solving the problem

[0010] Thus, as a result of intensive studies, the present inventors have found a fuel oil composition that does not contain metal and has a small amount of unwashed actual gum, and has reached the present invention.

That is, the present invention provides a fuel oil having the following general formula (1)

[Chemical 4]

(Wherein R is a hydrocarbon group having 6 to 20 carbon atoms)

The fuel oil composition characterized by containing the compound represented by these. The invention's effect

The effect of the present invention is to provide a fuel oil composition that does not contain metal, has good lubricity, and has a small amount of unwashed actual gum.

BEST MODE FOR CARRYING OUT THE INVENTION

The fuel oil composition of the present invention is characterized by containing a compound represented by the following general formula (1):

[Chemical 5]

[0013] In the general formula (1), R represents a hydrocarbon group having 620 carbon atoms, such as a hexyl group, a secondary hexyl group, a heptyl group, a secondary heptyl group, an octyl group, 2 -Ethylhexyl group, secondary octyl group, nonyl group, secondary nonyl group, decyl group, secondary decyl group, undecyl group, secondary undecyl group, dodecyl group, secondary dodecyl group, tridecyl group, isotridecyl group, Secondary tridecyl group, tetradecyl group, secondary tetradecyl group, hexadecyl group, secondary hexadecyl group, stearyl group, eicosyl group and other alkyl groups; hexyl group, heptul group, otaenyl group, nonenyl group, decenyl group Group, undecenyl group, dodecenyl group, tetradecyl group, oleyl group, etc .; fullyl group, tolyl group, xylyl group, xenyl group, mesityl group, benzyl group, fernell group, styryl group , Cinnamyl group, benzhydryl group, trityl group, ethylphenol group, propylphenol group, butylphenol group, pentylphenol group, hexylphenol group, heptylphenol group, octylphenol group, nor- Aryl groups such as rufur group, decyl group, undecyl group, dodecyl group, etc .; methyl cyclopentyl group, methyl cyclohexyl group And cycloalkyl groups such as a methyl group, a methylcyclohexyl group, a cyclopentyl group, a cyclohexenyl group, a cycloheptyl group, a methylcyclopentyl group, a methylcyclohexyl group, and a methylcycloheptyl group.

[0014] Among these hydrocarbon groups, the generation amount of unwashed actual gum is small, and therefore, the effect of lowering the friction coefficient preferred by alkyl groups and cycloalkyl groups without double bonds is high. Of the alkyl groups that are more preferred, alkyl groups are more preferred. The carbon number of R is preferably 8-18, more preferably 10-16, and even more preferably 12-16. If the carbon number of R is less than 6, the effect of lowering the friction coefficient is inferior, and if the carbon number of R exceeds 20, the unwashed real gum may be generated in large quantities or may be precipitated just by blending. Preferred for being.

[0015] Here, the unwashed actual gum will be described in detail. The fuel oil composition may cause problems such as clogging of fuel filters and valves due to the formation of gum-like substances due to acid and sour deterioration. Therefore, in order to regulate the amount of gum generated from the fuel oil composition, the amount of unwashed actual gum is stipulated by JIS as 20 mgZl00ml or less, and a large amount of compounds (additives) that easily generate unwashed actual gum is formulated I can't do it. When the fuel oil composition is produced, when the additive is added to the fuel oil, the additive amount is often determined in accordance with the unwashed actual gum amount. As described above, most of the substances causing unwashed real gum are additives added to fuel oil, and compounds having bonds such as ester bonds, amide bonds, and unsaturated bonds, and compounds having a large molecular weight are not yet available. It is known that it is easy to generate a real gum In particular, a compound having an ester bond or an amide bond generates a large amount of unwashed real gum. In addition, when R in the general formula (1) is a hydrocarbon group having a double bond, the amount of unwashed real gum of the compound represented by the general formula (1) may increase. The compound represented by the formula (1) may not be preferable as an additive. Also, a compound having a large molecular weight such that R has more than 20 carbon atoms is not preferred.

[0016] The compound represented by the general formula (1) can be produced using any of the existing synthesis methods. For example, a method of dehydrating an alcohol represented by ROH and glycerin, ROH A method of hydrolyzing the resulting epoxy compound by reacting with epoxychlorohydrin, reacting ROH with aryl chloride, acidifying the resulting aryl ether to make an epoxy compound, and then adding water. Examples thereof include a method of decomposing, a method of reacting ROH and glycidol, a method of reacting ROH and 1 chloro-2,3-propanediol, and the like.

[0017] The fuel oil that can be used in the fuel oil composition of the present invention may be any liquid fuel oil that can be used as fuel in an internal combustion engine. For example, gasoline, light oil, heavy oil, kerosene, jet fuel, fatty acid Examples include biofuels such as methyl ester. Among these, gasoline used as a fuel for automobiles or gasoline that prefers light oil is more preferable.

[0018] In addition, in recent years, gasoline and light oil used as fuel oil may reduce the sulfur content to 50 mass ppm or less from the viewpoint of environmental load, but elemental sulfur is used as an anti-wear agent. Therefore, there is a problem that the use of low-sulfur fuel promotes wear inside the engine. When the compound represented by the general formula (1) is added to such a low sulfur content fuel oil, it is possible to prevent internal wear of the engine. Therefore, the low sulfur content fuel oil is used as the fuel oil of the fuel oil composition of the present invention. The use is expected to have a great effect from the viewpoint of improving the wear resistance.

[0019] The compound represented by the general formula (1) is preferably contained in an amount of 0.001 to 0.5% by mass based on the entire fuel oil composition of the present invention. More preferred is 0.001 to 0.1% by mass. If the amount of added calories to the fuel oil of the compound represented by the general formula (1) is less than 0.001% by mass, the added amount may be too small to produce the effect. If the added amount exceeds 1% by mass, it is preferable because the unwashed actual gum may cause sludge and the inside of the engine may become dirty.

[0020] The fuel oil composition of the present invention may contain other additives as long as the effects of the present invention are not impaired. Other additives include, for example, anti-knock agents such as tetraethyl lead, tetramethyl lead, and biscyclopentane diphenol iron; octane number improvers such as methyl tertiary butyl ether and methyl tertiary mill ether; nitric acid Cetane improvers such as heptyl, octyl nitrate and cyclohexyl nitrate; 2-Ethinolehexyl boronate, butyl diisobutyl boronate and other surface ignition preventives; tricresyl phosphate, trimethinorephosphate, tris (chloroethyl) phosphate, polybutene, polypropylene, etc. N, N, -diisopropyl-p-phenylenediamine, N, N, dioctyl-p-phenylenediamine, 2,6 ditertiarybutylphenol, 2,6 ditertiarybutyl-4-methylphenol, 2 , 4 Antioxidants such as dimethyl-6 tersialib tyrphenol; ethylenediamine, N, N, monodisalicylidene-1, 2-diaminopropane, N, N 'disalicylidene 2-cyclohexanediamine, N, N'-disalicylidene ethylenedi Metal deactivators such as amine, N, N, monobis (dimethylsalicylidene) ethylenediamine, N, N, -bis (dimethylsalicylidene) ethylenetetrimine, salicylaldoxime; phosphate amide, aminoalkane , Alkylamine phosphates, polyetheramines, polybutenylamines and other detergents; anti-icing agents; corrosion prevention Agents; microorganism bactericides; antistatic agents; fluidity improvers; dyes and the like can be added as appropriate. These other additives can be used alone or in combination of two or more.

[0021] Here, when an anti-knock agent is added, the addition amount is in the range of 0.01 to 0.5 mass%, preferably 0.01 to 0.2 mass%, with respect to the entire fuel oil composition. Is within. Further, when the octane number improver is added, the amount added is within a range of 0.01 to 0.5% by mass, preferably 0.01 to 0.2% by mass with respect to the entire fuel oil composition. is there. Further, when a cetane number improver is added, the amount added is in the range of 0.01 to 0.5% by mass, preferably 0.01 to 0.2% by mass with respect to the whole fuel oil composition. It is. Also, when adding a surface ignition inhibitor The amount of the additive is 0.0001-0.005 mass%, preferably 0.0001-0.003 mass%, based on the entire fuel oil composition. Further, when the deposit improver is added, the amount of the added soot is 0.0001-0.005% by mass, preferably in the range of 0.0001-0.003% by mass with respect to the whole fuel oil composition. It is. In addition, when an antioxidant is added, the amount of the additive is within the range of 0.001 to 0.05% by mass, preferably 0.001 to 0.02% by mass with respect to the entire fuel oil composition. is there. Further, when adding the metal deactivator, the amount of addition ί Also, 0.1 for the entire fuel oil yarn且成product 0001-0. 005 mass ^_0/0, preferably ί or 0. 0001-0. 003 It is in the range of mass%. Further, when the detergent is added, the addition amount is 0.01 to 0.5% by mass, preferably 0.01 to 0.2% by mass, based on the entire fuel oil composition. Further, when an anti-icing agent is added, the amount added is in the range of 0.01-0.6% by mass, preferably 0.01-0.4% by mass, based on the entire fuel oil composition. Moreover, when adding a corrosion inhibitor, the addition amount is 0.001 to 0.05 mass% with respect to the whole fuel oil composition, Preferably it exists in the range of 0.001 to 0.02 mass%. Further, when the microbial disinfectant is added, the amount added is in the range of 0.0001 to 0.005% by mass, preferably 0.0001 to 0.003% by mass with respect to the entire fuel oil composition. When the antistatic agent is added, the amount added is in the range of 0.001 to 0.05 mass%, preferably 0.001 to 0.02 mass%, based on the entire fuel oil composition. Further, when a fluidity improver is added, the amount added is in the range of 0.01 to 0.5% by mass, preferably 0.01 to 0.2% by mass, based on the entire fuel oil composition. . Further, when adding the dye, the addition amount is 0.1 for the entire fuel oil composition from 0,001 to 0.005 mass ^_0/0, preferably <it is 0.0001 to 0. The range of 003 wt% It is. However, when adding these additives, it is preferable to avoid the use of metal-containing additives as much as possible.

[0022] The fuel oil composition of the present invention is suitably used as a fuel oil composition for various internal combustion engines using biofuels such as gasoline, light oil, heavy oil, kerosene, jet fuel, and fatty acid methyl ester as fuel oil. can do.

Example

Hereinafter, the present invention will be specifically described with reference to examples. In the following examples and the like, “%” and “ppm” are mass standards unless otherwise specified. Example

The following additives were blended with commercially available regular gasoline or white gasoline according to the formulations shown in Tables 1 and 2, and the test was conducted.

(A--1:) Monolauryl glyceryl ether

(A--2 :) Monomyristyl darericyl ether

(A--3 :) Monopalmityldariceryl ether

(A- -4:) Monostearyl glyceryl ether

(A--5:> mono-2-ethylhexylglyceryl

(A--6 :) Monooleyl glyceryl ether

(B-1) Monolauryl glyceryl ester

(B-2) Monooleyl glyceryl ester

(B-3) Monooleic acid diethanolamide

(B- ■ 4) Monobutyl darericyl ether

(B- ■ 5) Monodocosylglyceryl ether

The lubricity of the fuel oil was measured using the HFRR test (PCS Instruments) and the friction coefficient and wear scar diameter.

The fuel oil used in the test was commercially available regular gasoline with an octane number of 90 and a sulfur content of lOppm.

Testing machine: HFRR testing machine (manufactured by PCS Instruments)

Test temperature: 30 ° C

Load: 400g

Stroke frequency: 20Hz

Stroke length: _lmm Sample: 2ml

Under the above conditions, the above additives were added to gasoline at the rate shown in Table 1, and the friction coefficient and wear scar diameter were measured. [0025] <Unwashed actual gum amount test>

The above additives were adjusted according to the formulation shown in Table 1, and the amount of unwashed actual gum was measured using the method defined in JISK2261. That is, sample oil (in which the above additives are dissolved in 50 ml of white gasoline so as to have the addition amount shown in Table 1) is placed in a 100 ml beaker, and this beaker is placed in an evaporation bath at 155 ° C ± 5 ° C. Put in. Subsequently, hot air of 160 to 165 ° C. is jetted for 30 minutes here with an air jet device to evaporate the sample. The sample was left in a desiccator for 2 hours or more, and the residue was weighed. The results are shown in Table 1. The reason for using white gasoline is that the amount of unwashed actual gum is 0, and it is easy to compare the amount of unwashed actual gum from the additive.

[0026] [Table 1]

table 1

[0027] <Friction and abrasion test 2>

The above additives were added to the above white gasoline so that the amount of unwashed actual gum was 3 mgZ 100 ml, and the test was performed using the same tester and test method as in <Friction and abrasion test 1>.

[0028] [Table 2] Table 2

From Table 1, the regular gasoline with the addition of ester and amide additives, which is a comparative example, has a friction coefficient almost the same as that of the product of the present invention, but tends to wear metal, and unwashed real gum. The amount! Therefore, it can be seen that the white gasoline added with the ester and amide additives of the comparative example shows a larger value than the white gasoline using the ether additive of the example as an additive.

In addition, when these additives are actually added to fuel oil, they are often added at a constant unwashed gum content. From Table 2, it was confirmed that when the amount of unwashed actual gum was kept constant, the difference in lubricity appeared remarkably, and the additives A-2 and A-3 showed the best results.

Claims

Claims [1] In fuel oil, the following general formula (1)

[Chemical 1]

(In the formula, R is a hydrocarbon group having 6 to 20 carbon atoms)

The fuel oil composition characterized by including the compound represented by these.

[2] The fuel oil composition according to claim 1, wherein R is a linear alkyl group having 8 to 18 carbon atoms.

[3] The content of the compound represented by the general formula (1) is 0.001 to the entire fuel oil composition.

The fuel oil composition according to claim 1 or 2, which is in the range of -1 mass%.

[4] The fuel oil composition according to any one of claims 1 to 3, wherein the fuel oil is gasoline or light oil.

[5] The fuel oil composition according to any one of claims 1 to 4, wherein the sulfur content of the fuel oil is 50 ppm by mass or less.

[6] Furthermore, anti-knock agents, octane number improvers, cetane number improvers, surface ignition inhibitors, deposit improvers, antioxidants, metal deactivators, detergents, anti-icing agents, corrosion inhibitors, fine The biocide, the antistatic agent, the fluidity improver and the group power consisting of a dye strength, comprising one or two or more other additives selected as claimed in any one of claims 1 to 5. Fuel oil composition.