WO2016181799A1

WO2016181799A1 - High octane gasoline composition

Info

Publication number: WO2016181799A1
Application number: PCT/JP2016/062857
Authority: WO
Inventors: 鈴木崇将; 高瀬一郎
Original assignee: 株式会社ダイセル
Priority date: 2015-05-12
Filing date: 2016-04-22
Publication date: 2016-11-17
Also published as: JP2018127503A; TW201704460A

Abstract

A high octane gasoline composition is provided which can be prepared at low cost and which is environmentally friendly. This gasoline composition contains a gasoline base material and at least one item selected from the group consisting of ketones of 3-10 carbon atoms and aldehydes of 3-10 carbon atoms, and is characterized by either the content of the ketones of 3-10 carbon atoms being greater than or equal to 0.1 wt% with respect to the total amount of the composition (100 wt%), or the content of the aldehydes of 3-10 carbon atoms being greater than or equal to 0.5 wt% with respect to the total amount of the composition (100 wt%).

Description

High octane gasoline composition

The present invention relates to a gasoline composition having a high octane number. This application claims the priority of Japanese Patent Application No. 2015-097582 for which it applied to Japan on May 12, 2015, and uses the content here.

Due to the recent increase in energy problems and environmental problems, there is a demand for the creation of fuels with good fuel consumption characteristics and low emissions. For example, for the purpose of improving fuel economy characteristics of regular gasoline and the like, a method of adding a specific additive to form a gasoline composition is known. Examples of the additive include aromatic hydrocarbons, oxygenated compounds, amines , Branched paraffins and olefins are widely known. For example, a high-octane fuel having a research octane number (hereinafter sometimes referred to as RON) of about 100 can be prepared by adding these additives to regular gasoline.

As specific examples of additives, ethyl tertiary butyl ether (see Patent Document 1), ethanol (see Patent Document 2), amine compounds and carboxylic acids (see Patent Document 3) are known.

JP 2004-285205 A JP 2004-238575 A JP 2005-132973 A

However, conventional additives are expensive, and depending on the type of additive used, exhaust gas (for example, carbon monoxide, SOx, NOx, etc.) that adversely affects the environment may be generated. Further, since it is difficult to say that the fuel efficiency characteristics of a gasoline composition containing the additive are sufficient, creation of a more useful gasoline composition is required.

The present invention has been made in view of the above prior art, and an object thereof is to obtain a high-octane gasoline composition that can be prepared at low cost and is environmentally friendly.

The present inventor has found that a gasoline composition having a low octane number and a high octane number can be obtained by blending a specific component with a gasoline base material. Moreover, it discovered that the gasoline composition of a high octane number could be easily prepared at low cost by oxidizing a gasoline base material on specific conditions.

In the present invention, a gasoline composition comprising at least one selected from the group consisting of a ketone having 3 to 10 carbon atoms and an aldehyde having 3 to 10 carbon atoms, and a gasoline base material,
The content of the ketone having 3 to 10 carbon atoms is 0.1% by weight or more based on the total amount of the composition (100% by weight), or
A gasoline composition in which the content of aldehydes having 3 to 10 carbon atoms is 0.5% by weight or more based on the total amount of the composition (100% by weight) is provided.

In the gasoline composition, acetone, 2-heptanone, 3-heptanone, 4-heptanone, 2,3-heptanedione, and 2,4,4-trimethyl-3 are used as the ketone having 3 to 10 carbon atoms. -Containing at least one selected from the group consisting of pentanone, or selected from the group consisting of heptanal, 2,2-dimethyl-1-propanal, and benzaldehyde as the aldehyde having 3 to 10 carbon atoms. Preferably, at least one of them is included.

The above gasoline composition preferably further contains an alcohol having 3 to 10 carbon atoms.

In the gasoline composition, the alcohol having 3 to 10 carbon atoms includes 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1,2-heptanediol, 1,7-heptanediol, , 2-dimethyl-1-propanol, 2,4,4-trimethyl-2-pentanol, and at least one selected from the group consisting of benzyl alcohol.

The gasoline composition preferably further contains a carboxylic acid having 3 to 10 carbon atoms.

In the gasoline composition, the carboxylic acid having 3 to 10 carbon atoms is at least one selected from the group consisting of 2,2-dimethyl-1-propanoic acid, heptanoic acid, heptanedioic acid, and benzoic acid. Preferably including one.

In the gasoline composition, the research octane number in the spray ignition test is preferably 89 or more.

More specifically, the present invention relates to the following.
[1] A gasoline composition comprising at least one selected from the group consisting of a ketone having 3 to 10 carbon atoms and an aldehyde having 3 to 10 carbon atoms, and a gasoline base material,
The content of the ketone having 3 to 10 carbon atoms is 0.1% by weight or more based on the total amount of the composition (100% by weight), or
A gasoline composition in which the content of aldehydes having 3 to 10 carbon atoms is 0.5% by weight or more based on the total amount of the composition (100% by weight).
[2] The gasoline composition according to [1], comprising a ketone having 3 to 10 carbon atoms, an aldehyde having 3 to 10 carbon atoms, and a gasoline base material.
[3] The ketone having 3 to 10 carbon atoms is selected from the group consisting of acetone, 2-heptanone, 3-heptanone, 4-heptanone, 2,3-heptanedione, and 2,4,4-trimethyl-3-pentanone. The gasoline composition according to [1] or [2], comprising at least one of the above.
[4] The gasoline composition according to any one of [1] to [3], wherein the content of the ketone having 3 to 10 carbon atoms is 0.1% by weight or more based on the total amount of the composition (100% by weight). .
[5] The aldehyde having 3 to 10 carbon atoms includes at least one selected from the group consisting of heptanal, 2,2-dimethyl-1-propanal, and benzaldehyde. The gasoline composition described.
[6] The gasoline composition according to any one of [1] to [5], wherein the content of the aldehyde having 3 to 10 carbon atoms is 0.5% by weight or more based on the total amount of the composition (100% by weight). .
[7] The gasoline composition according to any one of [1] to [6], further comprising an alcohol having 3 to 10 carbon atoms.
[8] The gasoline according to any one of [1] to [7], comprising a ketone having 3 to 10 carbon atoms, an aldehyde having 3 to 10 carbon atoms, an alcohol having 3 to 10 carbon atoms, and a gasoline base material. Composition.
[9] As alcohol having 3 to 10 carbon atoms, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1,2-heptanediol, 1,7-heptanediol, 2,2-dimethyl-1- The gasoline composition according to [7] or [8], comprising at least one selected from the group consisting of propanol, 2,4,4-trimethyl-2-pentanol, and benzyl alcohol.
[10] The gasoline composition according to any one of [7] to [9], wherein the content of the alcohol having 3 to 10 carbon atoms is 1% by weight or more based on the total amount of the composition (100% by weight).
[11] The gasoline composition according to any one of [1] to [10], further comprising a carboxylic acid having 3 to 10 carbon atoms.
[12] A ketone having 3 to 10 carbon atoms, an aldehyde having 3 to 10 carbon atoms, an alcohol having 3 to 10 carbon atoms, a carboxylic acid having 3 to 10 carbon atoms, and a gasoline base material. [11] The gasoline composition according to any one of [11].
[13] The carboxylic acid having 3 to 10 carbon atoms includes at least one selected from the group consisting of 2,2-dimethyl-1-propanoic acid, heptanoic acid, heptanedioic acid, and benzoic acid [11] or [12] The gasoline composition according to [12].
[14] The gasoline composition according to any one of [11] to [13], wherein the content of the carboxylic acid having 3 to 10 carbon atoms is 0.1% by weight or more with respect to the total amount of the composition (100% by weight). object.
[15] The gasoline composition according to any one of [1] to [14], wherein the content of the gasoline base is 20 to 99% by weight relative to the total amount of the composition (100% by weight).
[16] The content (total amount) of alcohol having 3 to 10 carbon atoms, ketone having 3 to 10 carbon atoms, and aldehyde having 3 to 10 carbon atoms is 1% by weight or more based on the total amount of the composition (100% by weight) The gasoline composition according to any one of [1] to [15].
[17] The gasoline composition according to any one of [1] to [16], further including other oxygen-containing hydrocarbons.
[18] Other oxygen-containing hydrocarbons include at least one selected from the group consisting of alcohols having 11 or more carbon atoms, aldehydes having 11 or more carbon atoms, carboxylic acids having 11 or more carbon atoms, and ethers. The gasoline composition described in 1.
[19] The gasoline composition according to [17] or [18], wherein the content of other oxygen-containing hydrocarbons is 20% by weight or less based on the total amount of the composition (100% by weight).
[20] The gasoline composition according to any one of [1] to [19], which has a research octane number of 89 or more in a spray ignition test.
[21] The gasoline composition according to any one of [1] to [20], obtained by oxidizing a gasoline base material. [22] Obtained by oxidizing a gasoline base in the presence of oxygen and ozone, or obtained by oxidizing a gasoline base in the presence of oxygen and an imide compound having a cyclic imide skeleton [21] The gasoline composition described in 1.

The gasoline composition of the present invention can be prepared at low cost, and a gasoline composition with high fuel consumption characteristics (high octane number) can be obtained. Further, when the obtained gasoline composition is used as fuel, it is environmentally friendly because it does not emit SOx and NOx, and the CO content in the exhaust gas is small. Furthermore, the gasoline composition of the present invention can also be obtained by oxidizing a gasoline base material under specific conditions. In this case, the gasoline composition can be prepared easily and at low cost. Furthermore, since the gasoline composition of the present invention can be prepared in the vehicle by providing the oxidation reaction device in the vehicle, a tank for storing the additive in the engine room is not required.

FIG. 3 is a correlation diagram between the research octane number of reaction solutions and the conversion rate of raw materials in Examples 1 to 5. FIG. 3 is a correlation diagram between the research octane number of reaction liquids in Examples 1 to 5 and the content of alcohol components in gasoline compositions. FIG. 5 is a correlation diagram between the research octane number of reaction solutions in Examples 1 to 5 and the content of ketone components in gasoline compositions. FIG. 3 is a correlation diagram between the research octane number of reaction liquids in Examples 1 to 5 and the oxygen content in gasoline compositions.

<Gasoline composition>
The gasoline composition of the present invention comprises at least one selected from the group consisting of a specific amount of a ketone having 3 to 10 carbon atoms and an aldehyde having 3 to 10 carbon atoms, and a gasoline base material as essential components. And Further, as a component other than the above, an alcohol having 3 to 10 carbon atoms or a carboxylic acid having 3 to 10 carbon atoms may further be included.

The gasoline composition of the present invention particularly includes at least one selected from the group consisting of ketones having 3 to 10 carbon atoms and aldehydes having 3 to 10 carbon atoms as components other than the gasoline base. Although not limited, it is preferable that a ketone having 3 to 10 carbon atoms and an aldehyde having 3 to 10 carbon atoms are included from the viewpoint of fuel efficiency characteristics of the obtained gasoline composition. Further, it preferably further contains a ketone having 3 to 10 carbon atoms, an aldehyde having 3 to 10 carbon atoms, and an alcohol having 3 to 10 carbon atoms, and includes a ketone having 3 to 10 carbon atoms, an aldehyde having 3 to 10 carbon atoms, carbon Most preferably, it contains an alcohol having 3 to 10 carbon atoms and a carboxylic acid having 3 to 10 carbon atoms.

[Gasoline substrate]
The gasoline base used in the present invention is usually a petroleum fraction obtained by subjecting crude oil to various refining treatments. For example, light naphtha or heavy naphtha obtained by atmospheric distillation of crude oil, the light naphtha Desulfurized light naphtha and desulfurized heavy naphtha obtained by desulfurizing and heavy naphtha, cracked gasoline obtained by catalytic cracking and hydrocracking, light cracked gasoline obtained by distilling the cracked gasoline and heavy By adding lower olefins to hydrocarbons such as cracked gasoline, fractions obtained by removing benzene in reformed gasoline obtained by catalytic reforming (debenzene reformed gasoline), polymerized gasoline obtained by olefin polymerization, and isobutane Obtained alkylate, isomerate (isomerized gasoline) obtained by isomerization of linear lower paraffinic hydrocarbon, de-N-paraffin oil, Beauty like fractions and aromatic hydrocarbons of these specific ranges and the like. As the gasoline base material in the gasoline composition of the present invention, these various gasoline base materials may be used alone. However, in order to satisfy various performances, a gasoline base material obtained by combining a plurality of gasoline base materials is usually used.

The components of the gasoline base material are not particularly limited, and examples thereof include hydrocarbons having 3 to 10 carbon atoms. More specifically, as components contained in the gasoline base, for example, a linear or branched aliphatic hydrocarbon having 3 to 10 carbon atoms, an alicyclic hydrocarbon having 3 to 10 carbon atoms, and a carbon number Examples thereof include 6 to 10 aromatic hydrocarbons.

Examples of the linear or branched aliphatic hydrocarbon having 3 to 10 carbon atoms include linear alkanes having 3 to 10 carbon atoms such as propane, butane, pentane, hexane, heptane, octane, nonane and decane; 2-methylpropane, 2-methylbutane, 2,2-dimethylpropane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2-methylhexane, 3-methylhexane, 3,4-dimethylhexane, C3-C10 branched alkanes such as 3-methyloctane and 2,4,4-trimethylpentane; propylene, isobutylene, 1-pentene, 1-hexene, 2-hexene, 1-heptene, 1-octene, C3-C10 linear or branched alkene such as 1-decene, 1-dodecene, 1-tetradecene, 1,4-hexadiene Properly it is like alkadiene.

Examples of the alicyclic hydrocarbon having 3 to 10 carbon atoms include cycloalkanes having 3 to 10 carbon atoms such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, etc .; cyclopropene, cyclobutene Cycloalkene having 3 to 10 carbon atoms such as cyclopentene, cyclooctene, cyclohexene, cycloheptene, cyclododecaene; cycloalkenyl having 3 to 10 carbon atoms such as cyclopentadiene, 1,3-cyclohexadiene, 1,5-cyclooctadiene, etc. Examples include alkadienes.

Examples of the aromatic hydrocarbon having 6 to 10 carbon atoms include benzene, toluene, o-xylene, m-xylene, p-xylene, naphthalene and the like.

[Ketones with 3 to 10 carbon atoms]
The ketone in the gasoline composition of the present invention is not particularly limited as long as it has 3 to 10 carbon atoms. However, the number of carbonyl groups in the ketone molecule is preferably 1 to 6, and more preferably 1 to 3 It is.

Examples of the ketone include a linear ketone having 3 to 10 carbon atoms, a branched ketone having 3 to 10 carbon atoms, an alicyclic ketone having 3 to 10 carbon atoms, and an aromatic ketone having 7 to 10 carbon atoms. It is done. The gasoline composition of the present invention may contain one of these ketones alone or two or more.

The linear ketone having 3 to 10 carbon atoms is not particularly limited as long as at least one carbon atom of the linear hydrocarbon is substituted with a carbonyl group. For example, acetone, methyl ethyl ketone, 2-pentanone, C3-C10 straight chain having one carbonyl group such as 2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, nonan-2-one and positional isomers of the carbonyl group Ketones: C3-C10 linear ketones having two carbonyl groups such as 2,5-hexanedione, 2,3-heptanedione and acetylacetone. The branched chain ketone having 3 to 10 carbon atoms is not particularly limited as long as it is a ketone in which at least one carbon atom of the branched chain hydrocarbon is substituted with a carbonyl group, but 2,2-dimethyl-1-propanone, Examples include 2,4,4-trimethyl-3-pentanone and the positional isomer of the carbonyl group. The alicyclic ketone having 3 to 10 carbon atoms is not particularly limited as long as at least one carbon atom of the alicyclic hydrocarbon is substituted with a carbonyl group. For example, cyclobutanone, cyclopentanone, cyclohexanone, Examples include cycloheptanone, cyclooctanone, and positional isomers of the carbonyl group.

From the viewpoint of improving fuel efficiency, the gasoline composition of the present invention is a ketone having 3 to 10 carbon atoms such as acetone, 2-heptanone, 3-heptanone, 4-heptanone, 2,3-heptanedione, and 2, Preferably, it contains at least one selected from the group consisting of 4,4-trimethyl-3-pentanone, and is selected from the group consisting of acetone, 2-heptanone, and 2,4,4-trimethyl-3-pentanone More preferably, it contains at least one, and more preferably contains at least 2-heptanone. That is, from the viewpoint of improving fuel efficiency, at least one selected from the group consisting of a linear ketone having 3 to 10 carbon atoms and a branched ketone having 3 to 10 carbon atoms is used as the ketone having 3 to 10 carbon atoms. And more preferably at least a linear ketone having 3 to 10 carbon atoms.

[Aldehyde having 3 to 10 carbon atoms]
The aldehyde in the gasoline composition of the present invention is not particularly limited as long as it is an aldehyde having 3 to 10 carbon atoms. For example, a linear aldehyde having 3 to 10 carbon atoms, a branched aldehyde having 3 to 10 carbon atoms, and a carbon number 7-10 aromatic aldehydes are mentioned. The gasoline composition of the present invention may contain one of these aldehydes alone or may contain two or more.

The straight-chain aldehyde having 3 to 10 carbon atoms is not particularly limited as long as the terminal carbon atom of the straight-chain hydrocarbon is substituted with a carbonyl group. For example, butanal, pentanal, hexanal, heptanal, octanal And nonanal. The branched aldehyde having 3 to 10 carbon atoms is not particularly limited as long as it is an aldehyde in which the terminal carbon atom of the branched hydrocarbon is substituted with a carbonyl group. For example, 2,2-dimethyl-1-propanal (Pivalaldehyde), 2,4,4-trimethyl-2-pentanal and the like. The aromatic aldehyde is not particularly limited as long as it is an aldehyde in which the carbon atom at the terminal of the hydrocarbon having an aromatic hydrocarbon group is substituted with a carbonyl group, and examples thereof include benzaldehyde.

From the viewpoint of improving fuel efficiency, the gasoline composition of the present invention is at least one selected from the group consisting of heptanal, 2,2-dimethyl-1-propanal, and benzaldehyde as the aldehyde having 3 to 10 carbon atoms. It is preferable to include one, and it is more preferable to include at least benzaldehyde. In other words, from the viewpoint of improving fuel efficiency, as an aldehyde having 3 to 10 carbon atoms, a linear aldehyde having 3 to 10 carbon atoms, a branched aldehyde having 3 to 10 carbon atoms, and an aromatic aldehyde having 7 to 10 carbon atoms. It is preferable to include at least one selected from the group consisting of, and more preferable to include at least an aromatic aldehyde having 7 to 10 carbon atoms.

[C3-C10 alcohol]
The alcohol in the gasoline composition of the present invention is not particularly limited as long as it is an alcohol having 3 to 10 carbon atoms, but the number of hydroxyl groups in the alcohol molecule is preferably 1 to 6, and more preferably 1 to 3 It is a piece.

Examples of the alcohol having 3 to 10 carbon atoms include linear or branched alcohols having 3 to 10 carbon atoms, alicyclic alcohols having 3 to 10 carbon atoms, and aromatic alcohols having 6 to 10 carbon atoms. . The gasoline composition of the present invention may contain one of these alcohols alone or two or more.

The linear alcohol having 3 to 10 carbon atoms is not particularly limited as long as it is an alcohol in which at least one hydrogen atom of the linear hydrocarbon is substituted with a hydroxyl group. For example, 1-propanol, 1-butanol, 1 -Pentanol, 1-hexanol, 1-heptanol, 1-octanol and the positional isomers of its hydroxyl group (eg 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol) , 2-heptanol, 3-heptanol, 4-heptanol, 2-octanol, 3-octanol), etc., a straight-chain alcohol having 3 to 10 carbon atoms such as 1,2-propanediol, 1,3- Propanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, , 5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol and hydroxyl groups thereof And a straight-chain alcohol having 3 to 10 carbon atoms having two hydroxyl groups, such as The branched chain alcohol having 3 to 10 carbon atoms is not particularly limited as long as it is an alcohol in which at least one hydrogen atom of the branched chain hydrocarbon is substituted with a hydroxyl group. For example, isobutyl alcohol, 2,2-dimethyl-1 -Propanol, 2,4,4-trimethyl-2-pentanol and positional isomers of the hydroxyl group thereof (for example, tertiary butyl alcohol, 2-ethylhexanol) and the like. The alicyclic alcohol having 3 to 10 carbon atoms is not particularly limited as long as it is an alcohol in which at least one hydrogen atom of the alicyclic hydrocarbon is substituted with a hydroxyl group. For example, cyclopropanol, cyclobutanol, cyclopentanol , Cyclohexanol, cycloheptanol, cyclooctanol and the positional isomers of the hydroxyl group thereof. The aromatic alcohol having 6 to 10 carbon atoms is not particularly limited as long as it is an alcohol in which at least one hydrogen atom of the aromatic hydrocarbon is substituted with a hydroxyl group. For example, it relates to phenol, benzyl alcohol, salicyl alcohol and the hydroxyl group thereof. And positional isomers.

From the viewpoint of improving fuel efficiency, the gasoline composition of the present invention has 1 to heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1,2-heptanediol, alcohol having 3 to 10 carbon atoms, , 7-heptanediol, 2,2-dimethyl-1-propanol, 2,4,4-trimethyl-2-pentanol, and benzyl alcohol. At least one selected from the group consisting of heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 2,2-dimethyl-1-propanol, 2,4,4-trimethyl-2-pentanol, and benzyl alcohol More preferably, 2,2-dimethyl-1-propanol, 2,4,4-trimethyl 2-pentanol, and more preferably contains at least one selected from the group consisting of benzyl alcohol, and most preferably contains at least benzyl alcohol. That is, from the viewpoint of improving fuel efficiency, the alcohol having 3 to 10 carbon atoms is a linear alcohol having 3 to 10 carbon atoms, a branched alcohol having 3 to 10 carbon atoms, and an aromatic alcohol having 6 to 10 carbon atoms. Preferably, it contains at least one selected from the group consisting of, and contains at least one selected from the group consisting of branched alcohols having 3 to 10 carbon atoms and aromatic alcohols having 6 to 10 carbon atoms. Is more preferable, and it is more preferable to include at least an aromatic alcohol having 6 to 10 carbon atoms.

[Carboxylic acid having 3 to 10 carbon atoms]
The carboxylic acid in the gasoline composition of the present invention is not particularly limited as long as it is a carboxylic acid having 3 to 10 carbon atoms. For example, a linear carboxylic acid having 3 to 10 carbon atoms or a branched chain carboxylic acid having 3 to 10 carbon atoms. Examples thereof include acids and aromatic carboxylic acids having 7 to 10 carbon atoms. The gasoline composition of the present invention may contain one of these carboxylic acids alone or may contain two or more.

The linear carboxylic acid having 3 to 10 carbon atoms is not particularly limited as long as it is a carboxylic acid in which the terminal carbon atom of the linear hydrocarbon is substituted with a carboxyl group. For example, butanoic acid, pentanoic acid, hexane Examples thereof include linear monocarboxylic acids having 3 to 10 carbon atoms such as acid, heptanoic acid and octanoic acid, and linear dicarboxylic acids having 3 to 10 carbon atoms such as heptanedioic acid. The branched carboxylic acid having 3 to 10 carbon atoms is not particularly limited as long as it is a carboxylic acid in which the terminal carbon atom of the branched hydrocarbon is substituted with a carboxyl group. For example, 2,2-dimethyl-1- Examples include propanoic acid (pivalic acid) and isooctanoic acid. The aromatic carboxylic acid is not particularly limited as long as it is a carboxylic acid in which the carbon atom at the terminal of the hydrocarbon having an aromatic hydrocarbon group is substituted with a carboxyl group, and examples thereof include benzoic acid and phthalic acid.

From the viewpoint of improving fuel efficiency, the gasoline composition of the present invention comprises 2,2-dimethyl-1-propanoic acid, heptanoic acid, heptanedioic acid, and benzoic acid as a carboxylic acid having 3 to 10 carbon atoms. It is preferable to include at least one selected from the group, and it is more preferable to include at least benzoic acid. That is, the carboxylic acid having 3 to 10 carbon atoms is at least selected from the group consisting of branched carboxylic acids having 3 to 10 carbon atoms and aromatic carboxylic acids having 7 to 10 carbon atoms from the viewpoint of improving fuel efficiency. 1 is preferable, and at least an aromatic carboxylic acid having 7 to 10 carbon atoms is more preferable.

[Other oxygen-containing hydrocarbons]
In the gasoline composition of the present invention, an oxygen-containing hydrocarbon other than an alcohol having 3 to 10 carbon atoms, a ketone having 3 to 10 carbon atoms, an aldehyde having 3 to 10 carbon atoms, and a carboxylic acid having 3 to 10 carbon atoms (hereinafter, (Referred to as “other oxygenated hydrocarbons”). In the present invention, “oxygen-containing hydrocarbon” refers to a compound obtained by oxidizing a hydrocarbon (for example, alcohol, ketone, aldehyde, carboxylic acid, etc.). Examples of other oxygen-containing hydrocarbons include alcohols having 11 or more carbon atoms, aldehydes having 11 or more carbon atoms, carboxylic acids having 11 or more carbon atoms, and ethers.

In the gasoline composition of the present invention, an alcohol having 3 to 10 carbon atoms, a ketone having 3 to 10 carbon atoms, an aldehyde having 3 to 10 carbon atoms, a carboxylic acid having 3 to 10 carbon atoms, and other oxygen-containing hydrocarbons (hereinafter referred to as “carbonic acid”) "Alcohol having 3 to 10 carbon atoms") may be obtained by oxidizing the gasoline base (or the hydrocarbon in the gasoline base). In this case, it is preferable that it is a thing obtained by making a gasoline base material (or hydrocarbon in a gasoline base material) react on the specific oxidation conditions mentioned later. Since the alcohol having 3 to 10 carbon atoms is obtained by oxidizing a gasoline base material, when a gasoline composition is used as a fuel, it does not emit SOx and NOx, and contains CO in exhaust gas. Since the amount is small, there is no adverse effect on the environment, and the fuel efficiency of the gasoline composition tends to be improved. Furthermore, when the alcohol having 3 to 10 carbon atoms is obtained by reacting hydrocarbons in a gasoline base material under specific oxidation conditions, the fuel consumption characteristics of the gasoline composition tend to be further improved.

Further, the other oxygen-containing hydrocarbons may be obtained by oxidizing the hydrocarbons in the gasoline base material. In this case, it is preferable that the hydrocarbon is obtained by reacting hydrocarbons in the gasoline base material under specific oxidation conditions described later.

[Additive]
The gasoline composition of the present invention may further contain various additives as necessary. Such additives include metal deactivators such as Schiff compounds and thioamide compounds, lubricity improvers such as fatty acids and fatty acid esters, surface ignition inhibitors such as organophosphorus compounds, succinimides, polyalkylamines , Detergents such as polyetheramines, anti-icing agents, alkali metals and alkaline earth metal salts of organic acids, sulfuric acid esters of higher alcohols, anionic surfactants, cationic surfactants, double-sided surfactants, etc. Known anti-static agents, rust inhibitors such as alkenyl succinic acid esters, identification agents such as kilyzanine and coumarin, odorants such as natural essential oils and synthetic fragrances, and coloring agents such as azo dyes. The gasoline composition of the present invention may contain one of these additives alone or two or more.

[Content of components in gasoline composition]
In the gasoline composition of the present invention, the content (total amount) of the alcohol having 3 to 10 carbon atoms, the ketone having 3 to 10 carbon atoms, and the aldehyde having 3 to 10 carbon atoms is not particularly limited. 100% by weight) is preferably 1% by weight or more (for example, 1 to 80% by weight), more preferably 5 to 60% by weight, and most preferably 10 to 50% by weight. By setting it as the said structure, there exists a tendency for the research octane number of a gasoline composition to improve.

When the gasoline composition of the present invention contains a ketone having 3 to 10 carbon atoms, the content thereof is not particularly limited. For example, it is 0.1% by weight or more (for example, 0.1% by weight relative to the total amount of the composition (100% by weight)). 1 to 50% by weight), more preferably 0.1 to 20% by weight, and most preferably 0.5 to 15% by weight. By setting it as the said structure, there exists a tendency for the fuel consumption characteristic of a gasoline composition to improve.

When the gasoline composition of the present invention contains an aldehyde having 3 to 10 carbon atoms, the content thereof is not particularly limited, but for example, 0.5% by weight or more (for example, 0.8% or more) with respect to the total amount of the composition (100% by weight). 5 to 30% by weight), more preferably 1 to 20% by weight, and most preferably 1 to 10% by weight. By setting it as the said structure, there exists a tendency for the fuel consumption characteristic of a gasoline composition to improve.

When the gasoline composition of the present invention contains an alcohol having 3 to 10 carbon atoms, the content thereof is not particularly limited. For example, it is 1% by weight or more (for example, 1 to 80% by weight) with respect to the total amount of the composition (100% by weight). %), More preferably 1 to 50% by weight, and most preferably 1 to 30% by weight. By setting it as the said structure, there exists a tendency for the fuel consumption characteristic of a gasoline composition to improve.

When the gasoline composition of the present invention contains a carboxylic acid having 3 to 10 carbon atoms, the content is not particularly limited. For example, it is 0.1% by weight or more (for example, 0% with respect to the total amount of the composition (100% by weight)). 0.1 to 30% by weight), more preferably 1 to 25% by weight, and most preferably 2 to 20% by weight. By setting it as the said structure, there exists a tendency for the fuel consumption characteristic of a gasoline composition to improve.

In the gasoline composition of the present invention, the content of the gasoline base is preferably 20 to 99% by weight, more preferably 40 to 95% by weight, most preferably the total amount (100% by weight) of the composition. 50 to 90% by weight. By setting it as the said structure, there exists a tendency for the fuel consumption characteristic of a gasoline composition to improve.

In the gasoline composition of the present invention, when “other oxygenated hydrocarbons” are contained, the content thereof is not particularly limited. For example, it is 20% by weight or less (for example, 0.00%) with respect to the total amount of the composition (100% by weight). 01 to 20% by weight), preferably 10% by weight or less (0.1 to 10% by weight), and most preferably 5% by weight or less (1 to 5% by weight). By setting it as the said structure, there exists a tendency for the fuel consumption characteristic of a gasoline composition to improve.

The research octane number of the gasoline composition of the present invention is preferably 89 or more, more preferably 94 or more, still more preferably 98 or more, and most preferably 104 or more. By setting it as the said structure, there exists a tendency for the fuel consumption characteristic of a gasoline composition to improve. In the present invention, the research octane number is calculated by a spray ignition test.

The content (content) of the oxygen-containing hydrocarbon in the gasoline composition of the present invention is not particularly limited. For example, it is 1% by weight or more (for example, 1 to 80% by weight) with respect to the total amount of the composition (100% by weight). It is preferably 5 to 60% by weight, most preferably 10 to 50% by weight. By setting it as the said structure, there exists a tendency for RON of a gasoline composition to improve.

The oxygen content of the gasoline composition of the present invention is not particularly limited. For example, it is preferably 0.1% by weight or more (0.1 to 20% by weight) with respect to the total amount of the composition (100% by weight), More preferably, it is 0.5 to 10% by weight, and further preferably 1 to 10% by weight. By setting it as the said structure, there exists a tendency for the fuel consumption characteristic of a gasoline composition to improve. The “oxygen content” of the gasoline composition means the weight ratio of oxygen atoms (total amount) of components (for example, oxygen-containing hydrocarbons) contained in the gasoline composition to the gasoline composition (total amount).

<Method for producing gasoline composition>
The gasoline composition of the present invention has a gasoline base, at least one selected from the group consisting of a specific amount of a ketone having 3 to 10 carbon atoms, and an aldehyde having 3 to 10 carbon atoms, and optionally 3 carbon atoms. It can be prepared by mixing ˜10 alcohol, carboxylic acid having 3 to 10 carbon atoms, and other oxygen-containing hydrocarbons. Moreover, it is good also as a gasoline composition by oxidizing a gasoline base material (or hydrocarbon in a gasoline base material). In addition, when preparing the gasoline composition of this invention by oxidizing a gasoline base material, it is good also as a gasoline composition of this invention by oxidizing a gasoline base material in presence of oxygen. Furthermore, it is good also as a gasoline composition of this invention by mixing a gasoline base material and the oxidized gasoline base material.

Hereinafter, a method for preparing (manufacturing) a gasoline composition by oxidizing a gasoline base material (or a hydrocarbon in the gasoline base material) will be described. In addition, as a method for preparing (manufacturing) a gasoline composition, a method of oxidizing a gasoline base material in the presence of oxygen can be mentioned. More specifically, a method of oxidizing a gasoline base material in the presence of oxygen and ozone, and a method of oxidizing a gasoline base material in the presence of oxygen and an imide compound having a cyclic imide skeleton may be mentioned.

In the present invention, hydrocarbons in a gasoline base material may be oxidized in the presence of oxygen and ozone or in the circulation of oxygen gas and ozone gas to obtain the gasoline composition of the present invention. By using oxygen as an oxidizing agent together with ozone, it is possible to promote the extraction of hydrogen from the hydrocarbons in the gasoline base material, and to activate the radical reaction. Therefore, the oxidation reaction can be promoted even under mild conditions (reaction pressure: normal pressure, reaction temperature: about room temperature to 200 ° C., preferably 50 to 150 ° C., particularly preferably 60 to 120 ° C.). When the reaction is performed under the flow of oxygen gas and ozone gas, the amount of ozone gas in the ozone gas-containing oxygen gas is, for example, about 0.1 to 10% by volume of oxygen gas from the viewpoint of reactivity and economy.

It is preferable to use molecular oxygen as oxygen. As molecular oxygen, pure oxygen may be used, and oxygen diluted with an inert gas such as nitrogen, helium, argon, carbon dioxide, or air at normal pressure or pressure (1 to 100 atm) is used. May be.

The above-mentioned ozone has an action as a radical generator. It is preferable to use ozone gas as ozone. Further, the ozone gas may be supplied intermittently or continuously as long as the reaction proceeds smoothly.

A radical generator is a compound that generates radicals under mild reaction conditions (for example, heating, light irradiation, etc.). In the present invention, as a radical generator other than ozone, an imide compound having a cyclic imide skeleton described later and other radical generators may be used.

In the present invention, the gasoline base material may be oxidized by oxidizing a gasoline base material in the presence of oxygen (oxygen gas) and an imide compound having a cyclic imide skeleton. In addition, it is preferable to use molecular oxygen as oxygen (oxygen gas). As molecular oxygen, pure oxygen may be used, and oxygen diluted with an inert gas such as nitrogen, helium, argon, carbon dioxide, or air at normal pressure or pressure (1 to 100 atm) is used. May be. This reaction proceeds even under mild conditions (reaction pressure: normal pressure, reaction temperature: for example, room temperature to 200 ° C., preferably 50 to 150 ° C., particularly preferably 60 to 120 ° C.).

[Imide compound having a cyclic imide skeleton]
As the imide compound having a cyclic imide skeleton, imide compounds having various known cyclic imide skeletons can be used as an oxidation catalyst. Examples of the imide compound having a cyclic imide skeleton include a cyclic imide skeleton represented by the following formula (I).

In the formula (I), the bond between the nitrogen atom and X is a single bond or a double bond. The imide compound may have a plurality of cyclic imide skeletons represented by the formula (I) in the molecule. In the imide compound, when X is an —OR group and R is a protecting group for a hydroxyl group, a portion of the cyclic imide skeleton excluding R (N-oxy cyclic imide skeleton) It may be bonded via.

Examples of the protecting group for the hydroxyl group represented by R include an alkyl group (eg, a C _1-4 alkyl group such as methyl and t-butyl group), an alkenyl group (eg, an allyl group), a cycloalkyl group, and the like. (Eg, cyclohexyl group), aryl group (eg, 2,4-dinitrophenyl group), aralkyl group (eg, benzyl, 2,6-dichlorobenzyl, 3-bromobenzyl, 2-nitrobenzyl, triphenylmethyl) A substituted methyl group (for example, methoxymethyl, methylthiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl, 2,2,2-trichloroethoxymethyl, bis (2-chloroethoxy) methyl, 2- (trimethylsilyl) ethoxymethyl group, etc.), substituted ethyl groups (for example, 1-ethoxyethyl, 1-methyl-1-methoxyethyl, 1-isopropoxyethyl, 2,2,2-trichloroethyl, 2-methoxyethyl group, etc.), tetrahydropyranyl group, tetrahydrofuranyl group, 1-hydroxyalkyl group etc. (for example, A group capable of forming an acetal or hemiacetal with a hydroxyl group of 1-hydroxyethyl, 1-hydroxyhexyl, 1-hydroxydecyl, 1-hydroxyhexadecyl, 1-hydroxy-1-phenylmethyl group, etc .; an acyl group (for example, Aliphatic saturated or not such as C _1-20 aliphatic acyl group such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, lauroyl, myristoyl, palmitoyl, stearoyl group, etc. Saturated reed Group: acetoacetyl group; alicyclic acyl group such as cycloalkanecarbonyl group such as cyclopentanecarbonyl, cyclohexanecarbonyl group; aromatic acyl group such as benzoyl, naphthoyl group, etc .; sulfonyl group (methanesulfonyl, ethanesulfonyl, trifluoro) Lomethanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, naphthalenesulfonyl group, etc.), alkoxycarbonyl groups (eg, C _1-4 alkoxy-carbonyl groups such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl groups, etc.), aralkyloxycarbonyl Groups (eg, benzyloxycarbonyl group, p-methoxybenzyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl groups (eg, carbamoyl, methylcarbamoyl, phenylcarbamoyl groups, etc.) A group obtained by removing an OH group from an inorganic acid (for example, sulfuric acid, nitric acid, phosphoric acid, boric acid, etc.), a dialkylphosphinothioyl group (for example, a dimethylphosphinothioyl group), a diarylphosphinothioyl group ( Examples thereof include a diphenylphosphinothioyl group) and a substituted silyl group (for example, trimethylsilyl, t-butyldimethylsilyl, tribenzylsilyl, triphenylsilyl group, etc.).

In the case where X is an —OR group, R in the case where a plurality of cyclic imide skeletons excluding R (N-oxy cyclic imide skeleton) are bonded via R is, for example, oxalyl, malonyl Polycarboxylic acid acyl groups such as succinyl, glutaryl, adipoyl, phthaloyl, isophthaloyl, terephthaloyl groups; carbonyl groups; polyvalent hydrocarbon groups such as methylene, ethylidene, isopropylidene, cyclopentylidene, cyclohexylidene, benzylidene groups ( In particular, a group that forms an acetal with two hydroxyl groups).

Preferred R includes, for example, a hydrogen atom; a group capable of forming an acetal or hemiacetal with a hydroxyl group; an OH group removed from an acid such as carboxylic acid, sulfonic acid, carbonic acid, carbamic acid, sulfuric acid, phosphoric acid, boric acid, etc. Hydrolyzable protecting groups that can be removed by hydrolysis of groups (acyl group, sulfonyl group, alkoxycarbonyl group, carbamoyl group, etc.) and the like are included.

In the formula (I), n represents 0 or 1. That is, Formula (I) represents a 5-membered cyclic imide skeleton when n is 0, and represents a 6-membered cyclic imide skeleton when n is 1.

A typical example of the imide compound is an imide compound represented by the following formula (1). In the formula (1), n represents 0 or 1. X represents an oxygen atom or an —OR group (R represents a hydrogen atom or a hydroxyl protecting group). R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, A substituted oxycarbonyl group, an acyl group or an acyloxy group is shown. At least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be bonded to each other to form a double bond, and form a ring with the carbon atoms constituting the cyclic imide skeleton. May be. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , or R ⁶ , or at least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are bonded together. In addition, one or two or more cyclic imide groups represented by the following formula (1) may be bonded to the ring formed together with the carbon atoms constituting the double bond or the cyclic imide skeleton.

The halogen atoms in the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ of the imide compound represented by the formula (1) include iodine, bromine, chlorine, and fluorine atoms. Alkyl groups include, for example, about 1 to 30 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, decyl, dodecyl, tetradecyl, hexadecyl groups, etc. 1-20) linear or branched alkyl groups are included.

Examples of the aryl group include phenyl and naphthyl groups, and examples of the cycloalkyl group include cyclopentyl and cyclohexyl groups. Examples of the alkoxy group include about 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, t-butoxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, tetradecyloxy, and octadecyloxy groups (particularly, carbon The alkoxy group of the formula 1 to 20) is included.

Examples of the substituted oxycarbonyl group include C _1-30 alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl, hexyloxycarbonyl, decyloxycarbonyl, hexadecyloxycarbonyl groups ( In particular, C _1-20 alkoxy-carbonyl groups); cycloalkyloxycarbonyl groups such as cyclopentyloxycarbonyl and cyclohexyloxycarbonyl groups (particularly 3 to 20-membered cycloalkyloxycarbonyl groups); phenyloxycarbonyl, naphthyloxycarbonyl groups and the like aryloxycarbonyl group (especially, C _6-20 aryloxy - carbonyl group); aralkyloxycarbonyl group such as benzyloxycarbonyl group (particularly, C _7-21 aralkyloxy - carbonyl group).

Acyl groups include, for example, C _1-30 aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl, hexanoyl, octanoyl, decanoyl, lauroyl, myristoyl, palmitoyl, stearoyl groups (especially C ₁ Aliphatic saturated or unsaturated acyl groups such as _-20 aliphatic acyl groups; acetoacetyl groups; alicyclic acyl groups such as cycloalkanecarbonyl groups such as cyclopentanecarbonyl and cyclohexanecarbonyl groups; aromatics such as benzoyl and naphthoyl groups Group acyl group and the like.

Acyloxy groups include, for example, formyloxy, acetyloxy, propionyloxy, butyryloxy, isobutyryloxy, valeryloxy, pivaloyloxy, hexanoyloxy, octanoyloxy, decanoyloxy, lauroyloxy, myristoyloxy, palmitoyloxy, stearoyloxy An aliphatic saturated or unsaturated acyloxy group such as a C _1-30 aliphatic acyloxy group (particularly a C _1-20 aliphatic acyloxy group); an acetoacetyloxy group; a cyclopentanecarbonyloxy group, a cyclohexanecarbonyloxy group, etc. Examples include alicyclic acyloxy groups such as cycloalkanecarbonyloxy group; aromatic acyloxy groups such as benzoyloxy and naphthoyloxy groups.

Examples of the ring that may be formed together with the carbon atoms constituting the cyclic imide skeleton by bonding at least two of the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ to each other, for example, A 5- to 12-membered ring (particularly preferably a 6- to 10-membered ring). The ring includes a hydrocarbon ring, a heterocyclic ring, and a condensed heterocyclic ring. Specific examples of such a ring include a non-aromatic alicyclic ring (a cycloalkane ring which may have a substituent such as a cyclohexane ring, a cyclohexane which may have a substituent such as a cyclohexene ring). Alkene ring, etc.), non-aromatic bridged ring (eg, bridged hydrocarbon ring optionally having substituent such as 5-norbornene ring), aromatic ring optionally having substituent ( (Including a condensed ring) (benzene ring, naphthalene ring, etc.). Examples of the substituent that the ring may have include, for example, an alkyl group, a haloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, a substituted oxycarbonyl group, an acyl group, an acyloxy group, a nitro group, a cyano group, and an amino group. And halogen atoms.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , or R ⁶ , or at least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are bonded together. In addition, one or two or more cyclic imide groups represented by the above formula (1) may be bonded to the ring formed together with the carbon atoms constituting the double bond or the cyclic imide skeleton, for example, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , or R ⁶ is an alkyl group having 2 or more carbon atoms, the two adjacent carbon atoms constituting the alkyl group are included to form the cyclic imide group. It may be. When at least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are bonded to each other to form a double bond, the cyclic imide group is formed including the double bond. You may do it. Furthermore, at least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form the cyclic imide group together with the carbon atoms constituting the cyclic imide skeleton. .

Preferred imide compounds include compounds represented by the following formula. In the formula, R ¹¹ to R ¹⁶ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, a substituted oxycarbonyl group, an acyl group, or an acyloxy group. Indicates a group. R ¹⁷ to R ²⁶ are the same or different and each represents a hydrogen atom, an alkyl group, a haloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, a substituted oxycarbonyl group, an acyl group, an acyloxy group, a nitro group, a cyano group, an amino group, Or a halogen atom is shown. R ¹⁷ to R ²⁶ are groups in which adjacent groups are bonded to each other to form a 5-membered or 6-membered member represented by the formula (1c), (1d), (1e), (1f), (1h), or (1i) The cyclic imide skeleton may be formed. A represents a methylene group or an oxygen atom. X is the same as above.

In the substituents R ¹¹ to R ^16, the halogen atom, alkyl group, aryl group, cycloalkyl group, hydroxyl group, alkoxy group, carboxyl group, substituted oxycarbonyl group, acyl group, and acyloxy group are the same as those in R ¹ to R ⁶ . Examples corresponding to the corresponding groups are exemplified.

Examples of the alkyl group in the substituents R ¹⁷ to R ²⁶ include the same alkyl groups as those exemplified above (preferably an alkyl group having about 1 to 6 carbon atoms, particularly preferably a lower alkyl group having 1 to 4 carbon atoms). Examples of the haloalkyl group include a haloalkyl group having about 1 to 4 carbon atoms such as a trifluoromethyl group, and the alkoxy group is the same alkoxy group as described above (particularly a lower alkoxy group having about 1 to 4 carbon atoms). Examples of the oxycarbonyl group include the same substituted oxycarbonyl groups as described above (alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.). Examples of the acyl group include the same acyl groups as described above (aliphatic saturated or unsaturated acyl group, acetoacetyl group, alicyclic acyl group, aromatic acyl group, etc.), and the acyloxy group is the same as described above. Examples include acyloxy groups (aliphatic saturated or unsaturated acyloxy groups, acetoacetyloxy groups, alicyclic acyloxy groups, aromatic acyloxy groups, etc.). Examples of the halogen atom include fluorine, chlorine and bromine atoms. The substituents R ¹⁷ to R ²⁶ are particularly preferably a hydrogen atom, a lower alkyl group having about 1 to 4 carbon atoms, a carboxyl group, a substituted oxycarbonyl group, a nitro group, or a halogen atom.

Moreover, since oxygen as an oxidizing agent is used in the presence of ozone or an imide compound having a cyclic imide skeleton, the gasoline base material as a reaction substrate can be oxidized with a very excellent oxidizing power. Therefore, the solubility parameter [SP value; the temperature at which the evaporation energy of the oxygen atom (—O—) constituting the ester bond is 3350 J / mol and the molar volume is 3.8 cm ³ / mol by the Fedors method of the imide compound (25 ° C. )] Exceeds, for example, 26 [(MPa) ^1/2 ] (preferably exceeds 26 [(MPa) ^1/2 ] and 40 [(MPa) ^1/2 ] or less). Even if it exists, reaction can be advanced rapidly in the absence of a solvent, and an oxide can be obtained efficiently. In addition, SP value is a method described in the literature [RFFedors, Polym. Eng. Sci., 14 (2), 147 (1974); EAGrulke, Polymer Handbook, VII / 675; Yuji Harasaki, Coating Technology, 3, 129 (1987) Reference].

Representative examples of compounds having a 5-membered cyclic imide skeleton among preferable imide compounds include N-hydroxysuccinimide, N-hydroxy-α-methylsuccinimide, N-hydroxy-α, α-dimethylsuccinimide. N-hydroxy-α, β-dimethylsuccinimide, N-hydroxy-α, α, β, β-tetramethylsuccinimide, N-hydroxymaleimide, N-hydroxyhexahydrophthalimide, N, N ′ -Dihydroxycyclohexanetetracarboxylic acid diimide, N-hydroxyphthalimide, N-hydroxytetrabromophthalimide, N-hydroxytetrachlorophthalimide, N-hydroxyheptimide, N-hydroxyheimic acid imide, N-hydroxytrimellitic acid imide, N, N'-dihydroxy Romellitic acid diimide, N, N'-dihydroxynaphthalenetetracarboxylic acid diimide, α, β-diacetoxy-N-hydroxysuccinimide, N-hydroxy-α, β-bis (propionyloxy) succinimide, N-hydroxy- α, β-bis (valeryloxy) succinimide, N-hydroxy-α, β-bis (lauroyloxy) succinimide, α, β-bis (benzoyloxy) -N-hydroxysuccinimide, N-hydroxy- 4-methoxycarbonylphthalimide, 4-ethoxycarbonyl-N-hydroxyphthalimide, N-hydroxy-4-pentyloxycarbonylphthalimide, 4-dodecyloxy-N-hydroxycarbonylphthalimide, N-hydroxy-4-phenoxycarbonylphthalimide, N- Hydro Si-4,5-bis (methoxycarbonyl) phthalimide, 4,5-bis (ethoxycarbonyl) -N-hydroxyphthalimide, N-hydroxy-4,5-bis (pentyloxycarbonyl) phthalimide, 4,5-bis ( Dodecyloxycarbonyl) -N-hydroxyphthalimide, N-hydroxy-4,5-bis (phenoxycarbonyl) phthalimide and the like, wherein X is an —OR group and R is a hydrogen atom; Corresponding compounds wherein R is an acyl group such as acetyl, propionyl, benzoyl, etc .; formulas such as N-methoxymethyloxyphthalimide, N- (2-methoxyethoxymethyloxy) phthalimide, N-tetrahydropyranyloxyphthalimide X in (1) is an —OR group and R is hydroxy A compound which is a group capable of forming an acetal or hemiacetal with a group; N in formula (1) such as N-methanesulfonyloxyphthalimide, N- (p-toluenesulfonyloxy) phthalimide and the like, and R is a sulfonyl group A compound in which N in formula (1) is an —OR group and R is a group obtained by removing an OH group from an inorganic acid, such as a sulfate ester, nitrate ester, phosphate ester or borate ester of N-hydroxyphthalimide Etc.

Typical examples of compounds having a 6-membered cyclic imide skeleton among preferred imide compounds include N-hydroxyglutarimide, N-hydroxy-α, α-dimethylglutarimide, N-hydroxy-β, β-dimethylglutarimide. N-hydroxy-1,8-decalin dicarboxylic acid imide, N, N′-dihydroxy-1,8; 4,5-decalin tetracarboxylic acid diimide, N-hydroxy-1,8-naphthalenedicarboxylic acid imide (N— Hydroxynaphthalimide), N, N′-dihydroxy-1,8; compounds such as 4,5-naphthalenetetracarboxylic acid diimide wherein X is an —OR group and R is a hydrogen atom; Wherein R is an acyl group such as an acetyl group, a propionyl group or a benzoyl group; N-methoxymethyl X in formula (1) such as oxy-1,8-naphthalenedicarboxylic acid imide, N, N′-bis (methoxymethyloxy) -1,8; 4,5-naphthalenetetracarboxylic acid diimide and the like is an —OR group; A compound wherein R is a group capable of forming an acetal or hemiacetal with a hydroxyl group; N-methanesulfonyloxy-1,8-naphthalenedicarboxylic imide, N, N′-bis (methanesulfonyloxy) -1,8; 4 N-hydroxy-1,8-naphthalenedicarboxylic acid imide or N, N′-dihydroxy-, a compound in which X in the formula (1) is an —OR group and R is a sulfonyl group, such as 1,5-naphthalenetetracarboxylic acid diimide; 1,8; 4,5-naphthalene tetracarboxylic acid diimide sulfate, nitrate, phosphate or borate, etc. Compound X in the formula (1) is a group and R in -OR groups obtained by dividing the OH group of an inorganic acid and the like.

Among the imide compounds, a compound in which X is an —OR group and R is a hydrogen atom (N-hydroxyimide compound) is a conventional imidization reaction, for example, reacting a corresponding acid anhydride with hydroxylamine, It can be produced by a method of imidizing via ring opening and ring closing of an acid anhydride group. Of the imide compounds, a compound in which X is an —OR group and R is a hydroxyl protecting group is introduced into a compound in which the corresponding R is a hydrogen atom (N-hydroxyimide compound). It can manufacture by introduce | transducing a desired protecting group using reaction. For example, N-acetoxyphthalimide can be produced by reacting N-hydroxyphthalimide with acetic anhydride or reacting acetyl halide in the presence of a base.

Particularly preferred imide compounds are N-hydroxyimide compounds derived from aliphatic polyvalent carboxylic anhydrides or aromatic polycarboxylic anhydrides (for example, N-hydroxysuccinimide (SP value: 33.5 [( MPa) ^1/2 ]), N-hydroxyphthalimide (SP value: 33.4 [(MPa) ^1/2 ]), N, N′-dihydroxypyromellitic diimide, N-hydroxyglutarimide, N-hydroxy- 1,8-naphthalenedicarboxylic acid imide, N, N′-dihydroxy-1,8; 4,5-naphthalenetetracarboxylic acid diimide), and the like, by introducing a protecting group into the hydroxyl group of the N-hydroxyimide compound The resulting compound is included.

An imide compound having a cyclic imide skeleton can be used singly or in combination of two or more. The imide compound may be produced in the reaction system. In the present invention, for example, the trade name “N-hydroxyphthalimide” (manufactured by Wako Pure Chemical Industries, Ltd.), the trade name “N-hydroxysuccinimide” ”(Manufactured by Wako Pure Chemical Industries, Ltd.) and the like can be suitably used.

The amount of the imide compound having a cyclic imide skeleton is, for example, 0.0001 to 20 parts by weight, preferably 0.001 to 10 parts by weight, particularly preferably 0.001 to 100 parts by weight of the gasoline base material as a reaction substrate. 01 to 5 parts by weight. By using an imide compound having a cyclic imide skeleton within the above range, the oxidation reaction can proceed at an excellent reaction rate.

[Other radical generators]
In the present invention, when a gasoline composition is prepared by oxidizing a gasoline base material, as a radical generator other than imide compounds having ozone and a cyclic imide skeleton (referred to as other radical generators), known and commonly used radical generation An agent may be used, for example, a nitroxy radical generator or an azo radical generator may be used.

Examples of the nitroxy radical generator include 2,2,6,6-tetramethylpiperidine-1-oxyl, 9-azabicyclo [3.3.1] nonane-N-oxyl, 2-azaadamantane-N—. Specific examples include oxyl, 1-methyl-2-azaadamantane-N-oxyl, 1,3-dimethyl-2-azaadamantane-N-oxyl and the like.

Examples of the azo radical generator include

dimethyl

2,2′-azobis (2-methylpropionate), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile, 2,2 ′. -Azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyano Valeric acid), 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 1,1′-azobis (Cyclohexane-1-carbonitrile), 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis (methyl isobutyrate), 2,2′-azobis (ethyl isobutyrate), etc. Azo compounds Rukoto can.

[Cocatalyst]
In the present invention, when preparing a gasoline composition by oxidizing a gasoline base material, a metal compound may be used as a promoter.

The metal compound includes a metal compound containing at least one metal element selected from cobalt, manganese, zirconium, and molybdenum, that is, at least one selected from a cobalt compound, a manganese compound, a zirconium compound, and a molybdenum compound. It is preferable to use it.

Examples of the metal compound include the metal element simple substance, a hydroxide of the metal element, an oxide (including a complex oxide), a halide (fluoride, chloride, bromide, iodide), an oxo acid salt (for example, Inorganic compounds such as nitrates, sulfates, phosphates, borates, carbonates, etc., salts of isopolyacids, salts of heteropolyacids; organic acid salts (eg acetates, propionates, cyanates, naphthenic acids) Salts, stearates, etc.), complexes and the like.

Examples of the ligand constituting the complex include OH (hydroxo), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), acyl (acetyl, propionyl, etc.), alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, etc.), acetylacetonato , Cyclopentadienyl, halogen atoms (chlorine, bromine, etc.), CO, CN, oxygen atoms, H ₂ O (aquo), phosphines (triarylphosphine such as triphenylphosphine), phosphorus compounds, NH ₃ (ammine) , NO, NO ₂ (nitro), NO ₃ (nitrato), nitrogen-containing compounds such as ethylenediamine, diethylenetriamine, pyridine, phenanthroline, and the like.

Taking a cobalt compound as an example of a metal compound, inorganic compounds such as cobalt hydroxide, cobalt oxide, cobalt chloride, cobalt bromide, cobalt nitrate, cobalt sulfate, and cobalt phosphate; cobalt acetate, cobalt naphthenate, cobalt stearate, etc. Organic acid salts of: divalent or trivalent cobalt compounds such as complexes of cobalt acetylacetonate and the like. Examples of other metal element compounds include compounds corresponding to the cobalt compounds. In addition, it is preferable to use at least a cobalt compound from the point which is especially excellent in the reaction promotion effect, and it is preferable to use it combining a cobalt compound and a manganese compound especially. The metal compound may be added all at the time of preparation, or may be added continuously or intermittently in the reaction system.

In the present invention, when a gasoline composition is prepared by oxidizing a gasoline base material, the oxidation reaction can be performed by a conventional method such as a batch system, a semi-batch system, or a continuous system. From the viewpoint of improving the rate, it is preferably a continuous type.

Hereinafter, specific examples of the present invention will be described with reference to examples and comparative examples. However, the present invention is not limited to these.

(Spray ignition test)
When the hydrocarbon component contained in regular gasoline is oxidized and oxygenated hydrocarbons such as alcohol and ketone are produced, the boiling point of the oxidation reaction liquid becomes significantly higher than the boiling point of regular gasoline. For this reason, the research octane number of the oxidation reaction liquid was estimated by a spray ignition test capable of measuring high boiling point fuel.
After the combustion chamber is heated to 500 ° C. by a heater attached to the outer wall, 20 g of a measurement sample is charged into a fuel reservoir and compressed 400 times with an air cylinder. A measurement sample is injected from the combustion reservoir through a nozzle inserted into the combustion chamber into the combustion chamber at a high pressure for 10 milliseconds. The research octane number was studied by evaluating the ignition delay time and the heat generation behavior.

(Example 1)
As a gasoline surrogate fuel equivalent to regular gasoline with a research octane number of 90, in a 100 mL SUS316 pressure-resistant reactor (made by pressure-resistant glass industry, TVS-1 type) equipped with a gas ventilation line and an insertion rod 70 ml of a mixed solution of toluene, 63% by weight of 2,4,4-trimethylpentane, and 17% by weight of n-heptane (hereinafter referred to as raw material) was added. After immersing the reactor in an oil bath to a liquid temperature of 95 ° C., air containing ozone gas generated using an ozone generator (Wintech Co., Ltd.) (oxygen concentration: 20.7% by volume, ozone gas) The raw material was oxidized by bubbling and supplying (content: 0.3% by volume). This reaction solution was subjected to component analysis by gas chromatography (column: 007-FFAP). When the raw material conversion reached 10%, the supply of ozone gas was stopped and the reactor was cooled to room temperature. The results of component analysis are listed in Table 1. Thereafter, the research octane number was measured by subjecting the obtained reaction liquid (gasoline composition) to a spray ignition test. The results are shown in Table 1. The “conversion rate of the raw material” was calculated by [the disappearance amount of the raw material in the reaction liquid (mole)] / [the raw material before the reaction (mole)].

Furthermore, from the results of component analysis, the oxygen-containing hydrocarbon content, the alcohol content, the ketone content, the aldehyde content, the carboxylic acid content, and the gasoline composition (reaction liquid) The oxygen content was calculated and listed in Table 1. Here, “oxygen-containing hydrocarbon” refers to an oxide (compound) derived from a raw material. In addition, the content ratio of each component by component analysis and the oxygen content rate described the value which rounded off one decimal place.

(Examples 2 to 5)
The same operation as in Example 1 was performed to prepare gasoline compositions having a raw material conversion of 20%, 30%, 40%, and 50%. Table 1 shows the measured values of the content ratio, the oxygen content rate, and the research octane number of the components contained in the gasoline composition.

(Comparative Example 1)
The research octane number was measured by subjecting the raw material to a spray ignition test. Table 1 shows the content ratio of the components contained in the raw materials and the oxygen content ratio together with the results.

Fig. 1 shows the correlation between the conversion rate of raw materials and the research octane number of gasoline compositions. Furthermore, the correlation diagrams of the alcohol component content, the ketone component content, and the oxygen content of the gasoline composition with the research octane number of the gasoline composition are shown in FIGS.

From Table 1, it became clear that the research octane number of the gasoline composition was improved as the content of oxygen-containing hydrocarbons increased. Further, FIG. 1 shows that when the oxygen-containing hydrocarbon content reaches 27%, a gasoline composition equivalent to high octane fuel (RON = 100) is obtained. Furthermore, it can be understood from FIGS. 2 to 4 that the Lisa-thiooctane number increases as the oxygen content of the gasoline composition increases. Further, it has been found that when the content of the ketone component increases in the range of about 0 to 1.5% by weight, the research octane number of the gasoline composition increases efficiently.

(Comparative Example 2, Examples 6 to 11)
As gasoline surrogate fuel, gasoline compositions 1 to 7 (corresponding to Comparative Example 2 and Examples 6 to 11) containing the components shown in Table 2 were prepared. Further, the research octane numbers of gasoline compositions 1 to 7 were measured based on the spray ignition test method.

As is clear from Comparative Example 2 and Examples 6 to 11 (research octane numbers of gasoline compositions 1 to 7), the carbon number of 3 to 10 such as heptanol, 2-heptanol, 2,2-dimethyl-1-propanol, etc. A gasoline composition by adding an alcohol, acetone, 2-heptanone, etc., a ketone having 3-10 carbon atoms, an aldehyde having 3-10 carbon atoms, such as benzaldehyde, and a carboxylic acid having 3-10 carbon atoms, such as benzoic acid, etc. It became clear that the research octane number improved.

Example 12
A 100 mL SUS316 pressure-resistant reactor (TVS-1 type, manufactured by Pressure Glass Industrial Co., Ltd.) equipped with a gas vent line and an insertion tube was charged with 1.9 g (12 mmol) of N-hydroxyphthalimide, cobalt (II) stearate 1 0.5 g (2 mmol) and 70 ml of raw material were added. After the reactor was attached to an oil bath and the liquid temperature was adjusted to 95 ° C., the raw material was oxidized by bubbling air. This reaction solution was analyzed in the same manner as in Example 1. When the raw material conversion reached 10%, the air supply was stopped and the reactor was cooled to room temperature. The research octane number was measured in the same manner as in Example 1, and the content ratio of the components contained in the obtained gasoline composition (the content of oxygen-containing hydrocarbons, the content of alcohol components, the content of ketone components, the content of aldehyde components) Table 3 shows the measured values of the content rate, the content rate of the carboxylic acid component), the oxygen content rate, and the research octane number.

(Example 13)
By performing the same operation as in Example 12, a gasoline composition having a raw material conversion of 20% was prepared, and the content ratio of components contained in the gasoline composition (the content of oxygen-containing hydrocarbons, the content of alcohol components) Table 3 shows the measured values of the rate, the content of the ketone component, the content of the aldehyde component, the content of the carboxylic acid component), the oxygen content, and the research octane number.

Claims

A gasoline composition comprising at least one selected from the group consisting of a ketone having 3 to 10 carbon atoms and an aldehyde having 3 to 10 carbon atoms, and a gasoline base material,
The content of the ketone having 3 to 10 carbon atoms is 0.1% by weight or more based on the total amount of the composition (100% by weight), or
A gasoline composition in which the content of aldehydes having 3 to 10 carbon atoms is 0.5% by weight or more based on the total amount of the composition (100% by weight).
The ketone having 3 to 10 carbon atoms is at least selected from the group consisting of acetone, 2-heptanone, 3-heptanone, 4-heptanone, 2,3-heptanedione, and 2,4,4-trimethyl-3-pentanone. Contains one or
The gasoline composition according to claim 1, comprising at least one selected from the group consisting of heptanal, 2,2-dimethyl-1-propanal, and benzaldehyde as the aldehyde having 3 to 10 carbon atoms.
The gasoline composition according to claim 1 or 2, further comprising an alcohol having 3 to 10 carbon atoms.
Examples of the alcohol having 3 to 10 carbon atoms include 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1,2-heptanediol, 1,7-heptanediol, 2,2-dimethyl-1-propanol, 2 The gasoline composition according to claim 3, comprising at least one selected from the group consisting of 1,4,4-trimethyl-2-pentanol, and benzyl alcohol.
The gasoline composition according to any one of claims 1 to 4, further comprising a carboxylic acid having 3 to 10 carbon atoms.
The gasoline according to claim 5, wherein the carboxylic acid having 3 to 10 carbon atoms includes at least one selected from the group consisting of 2,2-dimethyl-1-propanoic acid, heptanoic acid, heptanedioic acid, and benzoic acid. Composition.
The gasoline composition according to any one of claims 1 to 6, which has a research octane number of 89 or more in a spray ignition test.