JPH11228978A - Gas oil additive and gas oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a gas oil additive which can reduce the abrasion loss at a metal contact surface in a low-sulfur diesel gas oil improved in low-temp. storage stability by using a fatty acid ester of a polyhydric alcohol as the additive. SOLUTION: A compd. of formula I is used. In the formula, Ra is a polyhydric alcohol residue formed by removing hydroxyl groups from a 2-to 20-hydric alcohol provided a compd. of formula II is excluded; and R<1> to R<n> are each H or RCO- (wherein R is 6-22C alkyl, 6-22C alkenyl, 6-22C alkadienyl, or 6-22C alkatrienyl) provided at least one of them is II and at least one of them is RCO-. The compd. of formula I can be used as a mixture with a compd. of formula III in a wt. ratio of former compd. to the latter of (5/95)-(10/0). The additive is added in an amt. of 0.001-0.1 pt.wt. to 100 pts.wt. gas oil.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas oil additive and a gas oil composition capable of reducing abrasion at a metal contact surface in a low sulfur content gas oil.

[0002]

2. Description of the Related Art Diesel oil has supported the people's lives as fuel for diesel vehicles such as transportation trucks and buses. The demand for gas oil is increasing year by year and is expected to grow further in the future. On the other hand, diesel vehicles using light oil as fuel are required to reduce nitrogen oxides (NO _x ) and particulate matter (particulates (PM)) in exhaust gas. NO _x is one of the causative substances of photochemical smog,
PM is an air pollutant composed of soot (black smoke), unburned substances, sulfate ions, and the like.

In accordance with the report of the Central Pollution Countermeasures Council on December 22, 1989, "Environmental Measures to Reduce Future Vehicle Emissions," the Environment Agency has stepped up emission gas regulations for diesel vehicles. . New PM in short-term regulations
It is regulated added, the long-term regulation, as compared to the short-term regulation, up to 46% in NO _x, seeking to reduce up to 64% in PM.

[0004] The Central Pollution Control Council has determined that the sulfur content of diesel oil should be reduced to 0.2% by weight before the adoption of an exhaust gas recirculation system (EGR) for diesel trucks and buses in conjunction with the tightening of regulations on diesel vehicles. With the goal of
In the long term, it is necessary to systematically reduce the amount by 0.05% by weight before a post-processing device such as a trap oxidizer is put to practical use. "

[0005] As described in this report, the reduction of the sulfur content of diesel oil is carried out for the purpose of preserving the atmospheric environment. However, the aim is not to directly improve the exhaust gas, but rather to reduce diesel emissions. Required for the introduction of car exhaust purification systems. EGR returns a portion of the exhaust gas back to the engine and lowers the combustion temperature to reduce N
This is a system for reducing O _x . However, the EGR has a problem in that sulfur oxides generated by the combustion of sulfur compounds in light oil react with water to form sulfuric acid, which causes corrosion and wear of various parts of the engine such as a pistol ring and a cylinder liner. For this reason, when EGR is put to practical use in diesel vehicles, it is required to reduce the sulfur content of light oil.

Means for reducing PM include an exhaust gas aftertreatment device (trap oxidizer and oxidation catalyst). When a catalyst is used, low sulfur gas oil is required. Gas oil sulfur reduction is being promoted in two stages.
The IS standard was revised to reduce the sulfur content from 0.5% by weight to 0.2% by weight or less.

[0007] The low sulfur this time, in response to long-term regulations,
The sulfur content is set to 0.05% by weight or less. Current,
The sulfur content of light oil is regulated by the "JIS Standards" in the Air Pollution Control Law and the Act on Ensuring the Quality of Volatile Oil and the Like (Crystal Quality Assurance Act). In line with these revisions, diesel oil shipped from refineries in Japan will have a sulfur content of 0.0% from July this year.
Since October 1, gas oil supplied from petroleum manufacturers has a sulfur content of 0.05% by weight or less.

[0008] Reduction of the sulfur content of gas oil has been promoted in Europe and the United States, and in October 1993 in the United States and 19 in Europe.
Since October 1996, the sulfur content in light oil has been reduced to 0.05% by weight or less. In Sweden, ultra-low sulfur, low aromatic gas oil was introduced to the market in 1991 under tax incentives. This gas oil is extremely refined with a sulfur content of 10 ppm by weight or less, and is a very light gas oil having a viscosity and a distillation property equivalent to kerosene. However, the use of this Swedish gas oil reported abnormal wear of the fuel injection pump, and it was pointed out that lubrication performance was reduced as a problem associated with the reduction of sulfur in the gas oil.

As fuel injection pumps used for diesel vehicles, there are a row type pump used for large vehicles such as large trucks and buses, and a distribution type pump used for small and medium vehicles such as small trucks and passenger cars. Among them, the line type pump lubricates the inside with lubricating oil, and is not affected by the decrease in lubricity of light oil. On the other hand, distributing pumps use internal fuel for fuel lubrication, which may cause malfunctions due to reduced lubrication of light oil.In the worst case, the injection pumps are subject to wear and seizure of sliding parts. May break down and the engine may become inoperable.

[0010] In order to solve the above-mentioned problems relating to low sulfur, WO 94/17160 discloses a light oil composition to which an ester of a carboxylic acid having 2 to 50 carbon atoms and an alcohol is added. Examples thereof include glycerin monooleate and diisodecyl adipate, and attempts have been made to improve the lubricity of light oil. Further, Japanese Patent Application Laid-Open Nos. 9-13052 and 9-1
No. 69986 discloses glycerin monooleate, monomethyl oleate of trimethylolpropane alkylene oxide adduct, and the like.

Among the compounds disclosed in these patents, glycerin monooleate is an interesting compound as an additive that exhibits a large effect with a small amount of addition, but the melting point of glycerin monooleate is higher than room temperature. In particular, when the compound is allowed to stand in the winter without keeping it warm, it solidifies and cannot be easily added to light oil. Therefore, a mixture with glycerin dioleate or glycerin trioleate to lower the melting point, or a glycerin ester to which a large amount of linoleic acid or linolenic acid having two or more unsaturated double bonds in a fatty acid residue is added. In addition had to use. The glycerin ester produced in this way has been able to maintain fluidity even at a relatively low temperature, but storage stability at 0 ° C. or less cannot be easily improved, and some glycerin monooleate esters have There remains a problem that a phenomenon of precipitation is observed.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a gas oil additive and a gas oil composition capable of reducing the amount of wear at the metal contact surface in a low sulfur diesel gas oil having improved storage stability at low temperatures. To provide.

[0013]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies, and as a result, a fatty acid ester of polyhydric alcohol has become a compound capable of reducing the amount of abrasion on a good metal contact surface. Moreover, the low-temperature fluidity is improved, and that the fatty acid ester obtained by mixing the fatty acid glycerin ester and the fatty acid ester of the polyhydric alcohol at a specific ratio has the same effect, and by blending these compounds with light oil, The present inventors have found that an excellent diesel light oil composition capable of reducing the amount of wear can be obtained, and completed the present invention.

That is, the present invention provides the following general formula (I)
A light oil additive comprising a compound represented by the formula:

[0015]

Embedded image [In the formula, Ra is an alcohol residue obtained by removing a hydroxyl group from a polyhydric alcohol having 2 to 20 valences, and R ^{1 to} R ⁿ are a hydrogen atom or an RCO-group (R is a straight chain having 6 to 22 carbon atoms or A branched-chain alkyl group, a straight-chain or branched-chain alkenyl group having 6 to 22 carbon atoms, a straight-chain or branched-chain alkadienyl group having 6 to 22 carbon atoms, or 6 to 22 carbon atoms
Wherein at least one of R ^{1 to} R ⁿ is a hydrogen atom, and at least one of R ^{1 to} R ⁿ is an RCO— group. However, as Ra

Embedded image Excluding groups]

The present invention further relates to a compound represented by the following general formula (II), wherein the compound represented by the general formula (I) / the compound represented by the general formula (II) = 5/95 -10
The present invention relates to the above light oil additive, which is contained at a ratio of 0/0 (weight ratio).

[0017]

Embedded image [Wherein, R ¹ , R ² and R ³ represent a hydrogen atom or RCO-
A group (R is a linear or branched alkyl group having 6 to 22 carbon atoms, a linear or branched alkenyl group having 6 to 22 carbon atoms, a linear or branched alkadienyl group having 6 to 22 carbon atoms, or represents a linear or branched alkatrienyl group) having 6 to 22 carbon atoms, R ^1,
At least one of R ² and R ³ is a hydrogen atom,
And at least one of R ¹ , R ² and R ³ is RCO
-Is a group]

The present invention also provides a straight-chain or branched-chain alkyl group having 6 to 22 carbon atoms, a straight-chain or branched-chain alkenyl group having 6 to 22 carbon atoms, and a straight-chain or branched chain having 6 to 22 carbon atoms. The total number of moles of polyhydric alcohol and glycerin is relative to 1 mole of fatty acids having at least one selected from a chain alkadienyl group and a linear or branched alkatrienyl group having 6 to 22 carbon atoms. The present invention relates to the above gas oil additive, characterized in that it contains a compound obtained by esterification or transesterification using 0.5 to 10 mol.

The present invention also relates to the compounds represented by the general formulas (I) and (II)
R ^{1 to} R ⁿ (R ³ ) in which the ratio of RCO— groups is
Fatty acids 30 having one unsaturated bond in terms of fatty acids
６０60% by weight, fatty acid having two unsaturated bonds 20〜6
0% by weight, 0.1 to 20 fatty acids having three unsaturated bonds
% By weight and 0.1 to 20% by weight of a saturated fatty acid.

Further, the present invention provides the above light oil additive,
The present invention relates to a light oil composition comprising 0.001 to 0.1 part by weight based on 100 parts by weight of light oil.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The compound used in the present invention is a fatty acid ester of a polyhydric alcohol having one or more hydroxyl groups represented by the above general formula (I) in the molecule, or a compound represented by the general formula (II) And mixtures with monoglycerides and diglycerides. The mixing ratio of the compound represented by the general formula (I) and the compound represented by the general formula (II) is such that the compound represented by the general formula (I) / the compound represented by the general formula (II) = 5 / 95-100 / 0 (weight ratio), preferably 10
/ 90 to 100/0 is good. If the mixing ratio of the compound represented by the general formula (I) is less than 5% by weight, the pour point or low-temperature stability of the compound represented by the general formula (II) can hardly be improved.

A linear or branched alkyl group having 6 to 22 carbon atoms in the general formulas (I) and (II),
Specific examples of the alkenyl group, alkadienyl group, and alkatrienyl group include the following.

Examples of the linear alkyl group include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and nonadecyl. Group, eicosanyl group, hen eicosanyl group, docosan group and the like.

Examples of the branched alkyl group include a 1-methylnonyl group, a 1-propylheptyl group, a 3,7-dimethyloctyl group, a 2,4,6-trimethylheptyl group, a 4-cyclohexylbutyl group, a butylcyclohexyl group, ,
3,5,5-tetramethylcyclohexyl group, 1-methyldecyl group, 2-methyldecyl group, 2-ethylnonyl group, 1-methylundecyl group, 2-methylundecyl group, 2-ethyldecyl group, 1- (2 ′ -Methylpropyl) -3,5-dimethylhexyl group, 2,4,6,8-
Tetramethylnonyl group, 2-methyldodecyl group, 2-ethylundecyl group, 1-3'-methylbutyl) -6-methylheptyl group, 1- (1'-methylbutyl) -4-methylheptyl group, 1-methyl Tridecyl group, 2-methyltridecyl group, 2-ethyldodecyl group, 2- (3'-methylbutyl) -7-methyloctyl group, 2- (1'-methylbutyl) -5-methyloctyl group, 1- to Xylnonyl group, 2-methyltetradecyl group, 2-ethyltridecyl group, 1-methylpentadecyl group, 1- (1 ′,
3 ', 3'-trimethylbutyl) -4,6,6-trimethylheptyl group, 1- (3'-methylhexyl) -6
Methylnonyl group, 8-methylheptadecyl group, 2-heptylundecyl group, 2- (1 ', 3', 3'-trimethylbutyl) -5,7,7-trimethyloctyl group, 2-
(3'-methylhexyl) -7-methyldecyl group, 2-
Methyloctadecyl group, 2,3-dimethylheptadecyl group, 3-methylnonadecyl group, 2,2-dimethyloctadecyl group, 2,3-dimethyloctadecyl group, 2-butyl-2-heptylnonyl group, 2-methyleicosanyl And a 20-methylheneicosanyl group.

Examples of the linear alkenyl group, alkadienyl group and alkatrienyl group include 2-decenyl group, 9-decenyl group, 9-undecenyl group, 10-undecenyl group,
2-dodecenyl group, 3-dodecenyl group, 2-tridecenyl group, 4-tetradecenyl group, 9-tetradecenyl group,
9-pentadecenyl group, 9-hexadecenyl group, 9-heptadecenyl group, 9-octadecenyl group, 9,12-octadecadienyl group, 9,12,15-octadecatrienyl group, 9-nonadecenyl group, 11 -Eicosenyl group, 13-docosenyl group and the like.

A branched alkenyl group, an alkadienyl group,
Examples of the alkatrienyl group include a 3-methyl-2-nonenyl group, a 2,4-dimethyl-2-decenyl group, a 2-methyl-9-octadecenyl group, and a 2,2-dimethyl-11-eicosenyl group. .

The general formulas (I) and (I) used in the present invention
The carbon number of the straight-chain or branched-chain alkyl group, alkenyl group, alkadienyl group and alkatrienyl group in I) is from 6 to 22. 22 are preferred. In terms of anti-wear performance, straight-chain alkyl groups,
Straight-chain alkenyl, straight-chain alkadienyl and straight-chain alkatrienyl are preferred. More preferably, a straight-chain alkenyl group, a straight-chain alkadienyl group, and a straight-chain alkatrienyl group are preferable.

As described above, the general formulas (I) and (I
As the RCO-group in R ^{1 to} R ⁿ (R ³ ) in I), a saturated fatty acid residue may be mixed. Its content is at most 20% by weight, preferably at most 15% by weight, more preferably at most 10% by weight, based on the total amount of fatty acid residues.
It is as follows.

A preferred composition which satisfies the solubility in gas oil and better abrasion resistance is a mixture of a linear alkyl group, a linear alkenyl group, a linear alkadienyl group and a linear alkatrienyl group. Has the general formula (I)
And the ratio of RCO-groups in R ^{1 to} R ⁿ (R ³ ) in (II) is, in terms of fatty acids, 30 to 60% by weight of a fatty acid having one unsaturated bond with respect to the total amount, 20 to 60% by weight of a fatty acid having two bonds, 0.1 to 20% by weight of a fatty acid having three unsaturated bonds, and 0.1% by weight of a saturated fatty acid.
1 to 20% by weight, and the carbon number of the fatty acid having one unsaturated bond is 14,1% by weight.
One or more carbon atoms selected from 6 and 18, the fatty acid having two unsaturated bonds has 18 carbon atoms, the fatty acid having three unsaturated bonds has 18 carbon atoms, and the saturated fatty acid has 14 carbon atoms. , 16 and 18 are preferably at least one carbon number.

The fatty acids used as a raw material of the compounds represented by the general formulas (I) and (II) in the present invention may be either carboxylic acids or fatty acid esters such as alkyl esters having 1 to 12 carbon atoms. .

The polyhydric alcohol used as a raw material of the compound represented by the general formula (I) in the present invention is preferably an alcohol having 2 to 20 in terms of the valency of the alcohol, more preferably 2 to 10 valent, and still more preferably. Is preferably a divalent to tetravalent alcohol. The carbon number is 2 to 60, preferably 2 to 30
It is better to have

Specifically, dihydric alcohols such as neopentyl glycol, ethylene glycol, propanediol, butanediol and 1,6-hexanediol, trimethylolpropane, trimethylolethane,
Examples include trihydric alcohols such as 2,4-butanetriol, 1,2,6-hexanetriol and 1,1,1-hexanetriol, and tetrahydric or higher alcohols such as diglycerin, polyglycerin and pentaerythritol. Among these, trimethylolpropane and pentaerythritol are preferred.

Further, in the present invention, saccharides can also be used as the polyhydric alcohol.

The saccharides usable in the present invention include:
Monosaccharide having 5 to 7 carbon atoms, disaccharide composed of hexose, sugar alcohol having 4 to 6 carbon atoms, ether compound of monosaccharide having 5 to 7 carbon atoms and monohydric alcohol, and disaccharide composed of hexose and monovalent One or more sugars selected from ether compounds with alcohols can be mentioned.

The monosaccharide having 5 carbon atoms includes arabinose, ribose, xylose, lyxose, xylulose, ribulose, 2-deoxyribose and the like. The monosaccharide having 6 carbon atoms includes glucose, galactose, fructose, and the like. Mannose, sorbose, talose, 2-deoxyglucose, 6-deoxygalactose, 6-deoxymannose, 2-deoxygalactose, etc., and as monosaccharides having 7 carbon atoms, alloheptulose, sedoheptulose, mannoheptulose, glucoheptuz Loin and the like.

Examples of the disaccharide composed of hexose include maltose, sucrose, sophorose and the like.

Examples of the sugar alcohol having 4 to 6 carbon atoms include erythritol, ribitol, xylitol, allitol, sorbitol, mannitol, galactitol and the like.

As an ether compound of a monosaccharide having 5 to 7 carbon atoms or a disaccharide comprising hexose and a monohydric alcohol, those having 1 to 12 carbon atoms, particularly 1 to 6 carbon atoms, are preferable. If it is such alcohol,
The carbon chain may be linear, branched, saturated, unsaturated, unsubstituted, or substituted, but is preferably methyl alcohol, ethyl alcohol, propyl alcohol,
Butyl alcohol. In this case, the position of the ether bond between the saccharide and the monohydric alcohol is not particularly limited, and may be any position. Specific examples include glycosides such as methyl glucoside, ethyl glucoside, propyl glucoside, methyl fructoside, methyl mannoside, methyl maltoside, and methyl lactoside, and sugars such as 6-O-methyl glucose and 6-O-methyl fructose. Ethers. As the alkyl glucosides, those having an alkyl group as an aglycone in the hemiacetal (anomeric) hydroxyl group of the above saccharide are used, and the configuration of the hemiacetal (anomeric) hydroxyl group after alkyl substitution is α or β alone. And those in which α and β are mixed in an arbitrary ratio can be used.

Among these saccharides, glucose, fructose, galactose, mannose, maltose, sucrose, sorbitol, mannitol, methyl glucoside, ethyl glucoside, propyl glucoside, butyl glucoside, methyl fructoside, methyl polyglucoside (maltoside, isomaltside) Are preferably used, and particularly, mannitol, sorbitol and glucose are preferably used.

In the present invention, one or more saccharides selected from monosaccharides having no substituent and having 5 to 7 carbon atoms, disaccharides composed of hexose, and sugar alcohols having 4 to 6 carbon atoms are used. One or more ether compounds of the above saccharides and monohydric alcohols can be used in combination, whereby a mixture of a fatty acid ester and a sugar ether fatty acid ester can be produced at a ratio corresponding to the combined use ratio and with good production efficiency. Can be synthesized at once.

The polyhydric alcohol fatty acid ester, fatty acid monoglyceride and fatty acid diglyceride used in the present invention may be commercially available products or may be produced by the following method.

In general, a polyhydric alcohol or a mixture of glycerin and a polyhydric alcohol and the above fatty acids are produced by esterification or transesterification.

The mode and form of the reaction between the fatty acid and the polyhydric alcohol (a mixture of the polyhydric alcohol and glycerin) are not particularly limited. For example, a batch type or a continuous type may be used. When a mixture of a fatty acid polyhydric alcohol ester and a fatty acid glyceride is obtained, the polyhydric alcohol and glycerin may be mixed at the same time and then esterified with a fatty acid, or may be separately esterified. , May be mixed.

The amount of the reactant used is preferably 0.5 to 10 mol of polyhydric alcohol (polyhydric alcohol and glycerin) per mol of fatty acid. If the polyhydric alcohol exceeds 10 moles with respect to 1 mole of the fatty acid, the unreacted polyhydric alcohol (polyhydric alcohol and glycerin) increases, which is not suitable. Conversely, if the amount is less than 0.5 mol, a large amount of the di-form or more is contained, and the abrasion reduction performance is inferior. More preferably, the polyhydric alcohol (polyhydric alcohol and glycerin) is 0.6 to 2 mol, more preferably 0.7 to 0.7 mol per 1 mol of the fatty acid.
1.7 moles.

The method of charging the fatty acid and the polyhydric alcohol (polyhydric alcohol and glycerin) includes a method of charging all at the start of the reaction and a method of charging sequentially, and is not particularly limited.

The above reaction may be carried out in the presence of a solvent. As for the solvent, an inert solvent for the reaction, for example, an aromatic compound such as benzene, toluene and xylene, and a saturated hydrocarbon can be used, depending on the reaction temperature.

To promote the reaction, acid catalysts such as sulfuric acid and p-toluenesulfonic acid, metal catalysts such as tin oxide, tetraphenoxytitanium and zinc oxide, alkali metals such as sodium hydroxide and potassium hydroxide, and alkaline earths A metal-like catalyst can also be used. The amount of the catalyst used depends on the reaction mode, but is used, for example, in an amount of about 0.01 to 10% by weight based on the fatty acid.

The reaction temperature varies depending on the reaction mode, the amount of the catalyst and the type of the reactants, but is usually 100 to 300 ° C., preferably 150 to 250 ° C.

The reaction pressure is not particularly limited, and may be normal pressure reaction or reduced pressure reaction.

The reaction time varies depending on the type of the reactants, the amount of the catalyst and the type of the catalyst, but is usually about 1 to 10 hours.

After completion of the reaction, the method for obtaining the resulting polyhydric alcohol ester or the polyhydric alcohol ester and glyceride is not particularly limited. For example, when a catalyst is used, a polyhydric alcohol ester, or a polyhydric alcohol ester and glyceride can be obtained by filtering, removing the catalyst, and distilling the filtrate. When the filtrate is difficult to pass through when filtering the catalyst, a filter aid can be used. During or after the esterification reaction, when performing a step of removing water and / or the solvent from the reaction mixture, the water and / or the solvent is distilled and collected. Thereafter, if necessary, the solid matter may be removed by filtration or centrifugation.

In the polyhydric alcohol ester, or the polyhydric alcohol ester and glyceride thus produced, the composition of the mono-form and the di-form is more than that of the mono-form and the di-form from the viewpoint of the abrasion reduction performance and the low-temperature solubility in gas oil. Is preferably from 0.15 to 0.80, more preferably from 0.25 to 0.60.

Compounds and triglycerides in which all of the hydroxyl groups of the coexisting polyhydric alcohol are esterified with fatty acids have poor metal-adsorbing ability and poor abrasion-preventing properties, and therefore the total amount of fatty acid esters, polyhydric alcohols and glycerin 40% by weight or less, more preferably 2%
It is preferably at most 0% by weight, particularly preferably at most 15% by weight. Unreacted polyhydric alcohols and glycerin have no anti-wear effect on their own, but rather impair the anti-wear effect of fatty acid esters, and have low solubility in light oil. %
It is preferably at most 2.5% by weight, particularly preferably at most 1% by weight.

The amount of the gas oil additive of the present invention to be added to gas oil is not particularly limited, but is used at least in an amount sufficient to suppress abrasion while the gas oil is in contact with the metal surface. Specifically, 0.00 parts by weight of light oil
It is preferable to use 1 to 0.1 part by weight. When the amount is less than 0.001 part by weight, the effect of suppressing wear is inferior. On the other hand, when the amount is more than 0.1 part by weight, the effect of suppressing wear is leveled off, which is economically disadvantageous.

In the present invention, a low-sulfur gas oil having a sulfur content of 0.2% by weight or less is particularly preferably used as the gas oil to be used. As the low-sulfur gas oil used in the present invention, a gas oil fraction obtained by atmospheric distillation of crude oil is subjected to hydrodesulfurization by, for example, hydrodesulfurization at a high reaction temperature,
Hydrodesulfurization at a high hydrogen partial pressure, a method using a hydrodesulfurization catalyst having high activity, and the like, may be mentioned. However, the sulfur content measured by the radiation excitation method described in JISK2541 is 0.2%. The method of desulfurization is not particularly limited as long as it is not more than weight%.

The light oil additive and light oil composition of the present invention may contain various other additives. These include antioxidants, conductivity improvers, metal deactivators, deicing additives, cetane improvers, combustion improvers (including smoke suppressants), surfactants / dispersants, intake system cleaners, Includes corrosion inhibitors, demulsifiers, top cylinder lubricants, dyes, and the like.

[0057]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the following examples.

Examples 1 to 13 and Comparative Examples 1 to 4 Into a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, and a dehydrating tube equipped with a condenser, the fatty acid compositions A to D shown in Table 1 were used. Unsaturated double bond-containing linear fatty acid 1
07 g (0.382 mol) of polyhydric alcohol, or polyhydric alcohol and glycerin were weighed in the amounts shown in Tables 2 to 6, 0.11 g of zinc oxide was added as a catalyst, and the ester was reacted at 220 ° C. for 5 hours in a nitrogen stream. The reaction was carried out. After cooling the reaction product, filtration was performed to obtain an esterified product. In addition, for the system to which glycerin was added, the filtrate was thin-film distilled (13
0 ° C./0.2 torr) and unreacted glycerin 1.3
g was removed to obtain an esterified product. Tables 2 to 6 also show the weight ratio of the esterified product to the mono-form and the di-form or more, and the analysis method was GPC (column: TSKgel G1000H _XL ,
7.8 mm × 30 cm, manufactured by Tosoh Corporation, mobile phase: TH
F (1.0 ml / min), column temperature: 40 ° C., detection: RI). Further, as a result of analysis by GPC, the content of the compound in which all the hydroxyl groups were esterified with a fatty acid was 30% by weight or less in Examples 1 to 13.

The esterified product thus synthesized was used in an amount of 0.01
3 g, light oil 100 containing 10 ppm by weight of sulfur
g. The performance of the gas oil was evaluated by performing HFRR measurement shown below. In addition, as the properties of the esterified product, the pour point and the appearance after storage at 0 ° C. for 1 week (○: transparent, no precipitate, x: presence of precipitate) were measured. The results are shown in Tables 2 to 6.

(Measurement of HFRR) The International Organization for Standardization (IS
In TC22 / SC7 / WG6, which is the working of O), a lubricating property evaluation test method for light oil was examined, and as a simple test method having a high correlation with the durability test result of the actual pump, H
FRR (High Frequency Recipr
ocating Rig) test was selected. In the HFRR test, a test steel ball and a test disk are rubbed in a sample light oil at a high frequency, and the lubricity of the light oil is evaluated based on a wear scar diameter (an average value in the X direction and the Y direction) of the test steel ball. In Japan, the Petroleum Institute of Japan has established a committee specializing in the test method for light oil lubricity, and is engaged in petroleum manufacturers, automobile manufacturers, additive manufacturers,
Parts manufacturers jointly studied the technical problems of the HFRR test, and at the end of March 1997, the Japan Petroleum Institute Law (JPI-
5S-50-97) was enacted. Therefore, according to the Japan Petroleum Institute standard JPI-5S-50-97, the wear scar diameter (WS
D) was measured.

[0061]

[Table 1] Fatty acid distribution (% by weight) C ₁₄ F ₀ ^* C ₁₆ F ₀ C ₁₈ F ₀ C ₁₈ F ₁ C ₁₈ F ₂ C ₁₈ F ₃ Fatty acid A 0 4 3 40 33 20 Fatty acid B 1 4 2 45 40 8 Fatty acid C 0 0 2 50 45 3 Fatty acid D 0 1 1 35 55 8 * The number to the right of C indicates the number of carbon atoms, and the number to the right of F indicates the number of unsaturated bonds.

[0062]

Table 1 Example 1 Example 2 Example 3 Example 4 Type and amount of fatty acid (g) A: 107 B: 107 A: 107 A: 107 Pentaerythritol (g) 57.2 0 46.8 78.0 Amount of trimethylolpropane ( g) 0 56.4 0 0 Polyhydric alcohol / fatty acid (molar ratio) 1.10 1.10 0.90 1.50 Mono- / di-form or more (weight ratio) 0.39 0.39 0.33 0.51 Pour point (° C) -42.5 -27.5 -45.0 -37.5 Store at 0 ° C 7 Days ○ ○ ○ ○ HFRR measurement result WSD (mm) 405 415 425 385

[0063]

Table 3 Example 5 Example 6 Example 7 Example 8 Type and amount of fatty acid (g) A: 107 A: 107 A: 107 A: 107 Glycerin amount (G) (g) 27.1 22.2 19.7 34.8 Pentaerythritol Amount (P) (g) 17.2 0 12.4 5.8 Amount of trimethylolpropane (T) (g) 0 13.9 0 0 Polyhydric alcohol ^* / fatty acid (molar ratio) 1.10 0.90 0.80 1.10 ((P) + (T)) / ( (P) + (T) + (G)) (weight ratio) 0.39 0.39 0.39 0.14 Mono / Di-form or higher (weight ratio) 0.38 0.33 0.28 0.39 Pour point (° C) -32.5 -30.0 -37.5 -20.00 Store at 0 ° C 7 days ○ ○ ○ ○ HFRR measurement result WSD (mm) 400 425 430 415 * Includes glycerin (same for Tables 4 to 6).

[0064]

Table 9 Example 9 Example 10 Example 11 Example 12 Type and amount of fatty acid (g) B: 107 C: 107 D: 107 A: 107 Glycerin amount (G) (g) 27.1 27.1 27.1 37.0 Pentaerythritol Amount (P) (g) 17.2 17.2 17.2 23.5 Amount of trimethylolpropane (T) (g) 0 0 0 Polyhydric alcohol / fatty acid (molar ratio) 1.10 1.10 1.10 1.50 ((P) + (T)) / (( (P) + (T) + (G)) (weight ratio) 0.39 0.39 0.39 0.39 Mono / Di-form or higher (weight ratio) 0.37 0.37 0.39 0.50 Pour point (℃) -30.0 -40.0 -42.5 -27.5 Store at 0 ℃ 7 Days ○ ○ ○ ○ HFRR measurement result WSD (mm) 410 415 410 385

[0065]

[Table 5]

[0066]

[Table 6] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Type and amount of fatty acid (g) A: 107 B: 107 C: 107 D: 107 Glycerin amount (G) (g) 38.7 38.7 38.7 38.7 Pentaerythritol Amount (P) (g) 0 0 0 0 Trimethylolpropane amount (T) (g) 0 0 0 0 Polyhydric alcohol / fatty acid (molar ratio) 1.10 1.10 1.10 1.10 ((P) + (T)) / (( (P) + (T) + (G)) (weight ratio) 0.000 or more mono- / di-form (weight ratio) 0.41 0.42 0.42 0.42 Pour point (° C) -2.5 -2.5 -17.5 -17.5 Store at 0 ° C 7 Days × × × × HFRR measurement result WSD (mm) 435 440 430 430

As described above, the light oil additive of the present invention has good low-temperature stability, and the light oil additive satisfying the measured value of HFRR by adding 130% by weight of the light oil additive of the present invention to light oil. A composition is obtained.

Examples 14 to 17 70 g of the fatty acid glycerin ester shown in Comparative Example 1
SO-10 (sorbitan monooleate) and SO-15 as sorbitan fatty acid esters manufactured by Nikko Chemicals Co., Ltd.
(Sorbitan sesquiolate fatty acid ester), SR-10 (Sorbitan monositol oil fatty acid ester), and SR-15 (Sorbitan sesquitol oil fatty acid ester) were added to each sample. 0.013 g of the thus obtained mixture was taken and dissolved in 100 g of light oil containing 10 ppm by weight of sulfur. HF which described the performance of this gas oil
It was evaluated by performing RR measurement. In addition, as the properties of the esterified product, the pour point and the appearance after storage at 0 ° C. for 1 week (○: transparent, no precipitate, x: presence of precipitate) were measured. Table 7 also shows the results.

[0069]

Table 14 Example 14 Example 15 Example 16 Example 17 Fatty acid glycerin ester (g) 70 70 70 70 SO-10 (g) 300 0 00 SO-15 (g) 0 30 0 0 SR-10 ( g) 0 0 30 0 SR-15 (g) 0 0 0 30 Pour point (° C) −30.0 −27.5 −32.5 −30.0 7 days storage at 0 ° C ○ ○ ○ ○ HFRR measurement result WSD (mm) 395 405 385 395

As described above, the light oil additive of the present invention has good low-temperature stability, and the light oil additive satisfying the measured value of HFRR by adding 130% by weight of the light oil additive of the present invention to light oil. A composition is obtained.

Continuation of front page (72) Inventor Takeo Inagaki 1-7-3 Honjo, Sumida-ku, Tokyo Lion Corporation

Claims (5)

[Claims] 1. A gas oil additive comprising a compound represented by the following general formula (I). Embedded image [In the formula, Ra is an alcohol residue obtained by removing a hydroxyl group from a polyhydric alcohol having 2 to 20 valences, and R ^{1 to} R ⁿ are a hydrogen atom or an RCO-group (R is a straight chain having 6 to 22 carbon atoms or A branched-chain alkyl group, a straight-chain or branched-chain alkenyl group having 6 to 22 carbon atoms, a straight-chain or branched-chain alkadienyl group having 6 to 22 carbon atoms, or 6 to 22 carbon atoms
Wherein at least one of R ^{1 to} R ⁿ is a hydrogen atom, and at least one of R ^{1 to} R ⁿ is an RCO— group. However, as Ra: Excluding groups] 2. The compound represented by the following general formula (II) is further converted into a compound represented by the following general formula (I) / a compound represented by the following general formula (I)
The gas oil additive according to claim 1, wherein the compound represented by I) is contained in a ratio of 5/95 to 100/0 (weight ratio). Embedded image [Wherein, R ¹ , R ² and R ³ represent a hydrogen atom or RCO-
A group (R is a linear or branched alkyl group having 6 to 22 carbon atoms, a linear or branched alkenyl group having 6 to 22 carbon atoms, a linear or branched alkadienyl group having 6 to 22 carbon atoms, or represents a linear or branched alkatrienyl group) having 6 to 22 carbon atoms, R ^1,
At least one of R ² and R ³ is a hydrogen atom,
And at least one of R ¹ , R ² and R ³ is RCO
-Is a group] 3. A linear or branched alkyl group having 6 to 22 carbon atoms, a linear or branched alkenyl group having 6 to 22 carbon atoms, a linear or branched alkadienyl group having 6 to 22 carbon atoms, And the total number of moles of the polyhydric alcohol and glycerin is 0.5 to 1 mole of the fatty acid having one or more kinds selected from linear or branched alkatrienyl groups having 6 to 22 carbon atoms. 10
3. The gas oil additive according to claim 2, wherein the gas oil additive contains a compound obtained by esterification or transesterification in a molar amount. 4. R ^{1 to} R ⁿ in the general formulas (I) and (II)
The ratio of the RCO- group in (R ³ ) is, in terms of fatty acid, 30 to 60% by weight of a fatty acid having one unsaturated bond,
The fatty acid having two unsaturated bonds is 20 to 60% by weight, the fatty acid having three unsaturated bonds is 0.1 to 20% by weight, and the saturated fatty acid is 0.1 to 20% by weight. The light oil additive according to any one of Items 1 to 3. 5. The gas oil additive according to claim 1, wherein the gas oil additive is contained in an amount of 0.001 to 0.
A light oil composition comprising 1 part by weight.