JP5432521B2 - Gasoline composition - Google Patents

Description

  The present invention relates to a gasoline composition excellent in environmental performance and driving performance.

Since global warming due to fossil fuel-derived greenhouse gases has been a major social problem, gasoline that has less impact on global warming than conventional petroleum-derived gasoline has been proposed and marketed.
For this type of gasoline, the concept of carbon neutral, that is, carbon in plants is fixed from atmospheric carbon dioxide in the past, so plant-derived fuels increase the carbon dioxide concentration in the atmosphere. Based on the idea that this would not be the case, so-called biogasoline has been intensively developed to reduce the impact on global warming due to fuel consumption by mixing plant-derived base materials with conventional petroleum-derived gasoline. It was.
However, for such biogasoline, various problems in driving performance have been reported. For example, ethyl alcohol (ethanol), which is a typical biogasoline base material, increases the vapor pressure when mixed with conventional petroleum-derived gasoline, and is not suitable for use at high temperatures. There are also concerns about engine failures (for example, Patent Documents 1 and 2). On the other hand, ethyl-tert-butyl ether (ETBE), which is a biogasoline base material already introduced in Japan, is less concerned, but reduces oxidation stability when mixed with conventional petroleum-derived gasoline. There is a concern that organic acids such as formic acid and acetic acid are generated in gasoline during long-term storage, which may corrode metal parts of storage facilities and automobiles (for example, Patent Document 3).
Therefore, there is a demand for biogasoline that contributes to mitigating global warming and has an operation performance equivalent to or higher than that of conventional petroleum-derived gasoline.

JP 2004-238576 A Japanese Patent Laid-Open No. 61-037896 JP 2007-270038 A

  The present invention is an environmentally friendly gasoline that contributes to mitigating global warming by reducing carbon dioxide emissions, and provides a gasoline composition that is excellent in lubricity such as oxidation stability and wear resistance. It is what.

  As a result of intensive studies on the relationship between the biogasoline base material and various driving performances in the environment-friendly biogasoline, the present inventors have found that the object can be achieved by blending isobutyl alcohol as the base material. . The present invention has been completed based on such findings.

That is, the present invention
[1] A gasoline composition containing 2 to 30% by volume of isobutyl alcohol and satisfying the following (1) to (7):
(1) Research method octane number is 96 or more (2) Sulfur content is 10 mass ppm or less (3) Aromatic content is 10-45 vol%
(4) Benzene content is 1.0 volume% or less (5) Olefin content is 5-40 volume%
(6) Reed vapor pressure (RVP) is 55 to 90 kPa
(7) 50% distillation temperature is 70 to 115 ° C, 70% distillation temperature is 100 to 140 ° C, 90% distillation temperature is 130 to 175 ° C

[2] In the method specified in JPI-5S-98, the wear scar diameter after 10 minutes at a temperature of 25 ° C. is 430 μm or less, and the wear scar diameter after 75 minutes is 800 μm or less. 1], the gasoline composition according to
[3] The gasoline composition according to [1] or [2], wherein the oxidation stability according to JIS K-2287 is 2000 minutes or more.

[ 4 ] The gasoline composition according to any one of [1] to [ 3 ], wherein the isobutyl alcohol is biomass-derived isobutyl alcohol .
[ 5 ] When producing a gasoline composition satisfying the following (1) to (7), a gasoline composition in which isobutyl alcohol is added to the base gasoline so as to contain 2 to 30% by volume based on the gasoline composition. how to improve the oxidative stability of a product, and (1) RON of 96 or higher (2) a sulfur content of less than 10 mass ppm (3) an aromatic content of 10 to 45 volume%
(4) Benzene content is 1.0 volume% or less (5) Olefin content is 5 to 40 volume% or less (6) Reed vapor pressure (RVP) is 55 to 90 kPa
(7) 50% distillation temperature is 70 to 115 ° C, 70% distillation temperature is 100 to 140 ° C, 90% distillation temperature is 130 to 175 ° C
[6] The method according to [5] above, further improving the lubricity of the gasoline composition,
About.

  According to the present invention, by blending biomass-derived isobutyl alcohol, it has excellent environmental performance of reducing carbon dioxide emissions, and is a disadvantage of biogasoline blended with ethanol and ETBE, which are conventional biogasoline substrates. A gasoline composition that overcomes a certain lead vapor pressure (RVP) increase and oxidative stability decrease, has good oxidative stability even after long-term storage, and has excellent lubricating properties such as wear resistance. can do. In addition, the present invention can provide a gasoline composition with significantly reduced antioxidant.

[Isobutyl alcohol]
The gasoline composition of the present invention contains 2 to 30% by volume of isobutyl alcohol. If the content of isobutyl alcohol in the gasoline composition of the present invention is 2% by volume or more, the effect of improving the abrasion resistance and oxidation stability of gasoline can be obtained. Further, if the content of isobutyl alcohol is 30% by volume or less, it is possible to maintain good driving performance without difficulty in controlling the air-fuel ratio of the engine.
From the above points, the content of isobutyl alcohol is preferably 3% by volume or more, more preferably 5% by volume or more, and the upper limit is preferably 20% by volume, more preferably 15% by volume. Therefore, the content of isobutyl alcohol in the gasoline composition is preferably 3 to 20% by volume, and more preferably 5 to 15% by volume.

  The method for producing isobutyl alcohol used in the present invention is not particularly limited, and isobutyl alcohol obtained by any known method can be used. For example, as a method for producing isobutyl alcohol, a known method of hydrogenating isobutyraldehyde after oxo synthesis of propylene can be mentioned. In addition, isobutyl alcohol obtained by fermenting biomass such as sugar cane and corn is preferable in terms of mitigating global warming from the concept of carbon neutral.

[Gasoline composition]
The gasoline composition of the present invention contains 2 to 30% by volume of the above isobutyl alcohol and satisfies the following properties or compositions.
(1) Research method octane number is 96 or more (2) Sulfur content is 10 mass ppm or less (3) Aromatic content is 10-45 vol%
(4) Benzene content is 1.0 volume% or less (5) Olefin content is 5-40 volume%
(6) Reed vapor pressure (RVP) is 55 to 90 kPa
(7) 50% distillation temperature is 70 to 115 ° C, 70% distillation temperature is 100 to 140 ° C, 90% distillation temperature is 130 to 175 ° C

  The gasoline composition of the present invention has a research octane number (RON) of 96 or more. If the RON is 96 or more, the driving performance is good, for example, knocking does not occur in the premium specification car. On the other hand, the upper limit of RON is not particularly limited in terms of performance, but is usually about 105. From the above points, the RON of the gasoline composition of the present invention is preferably 97 or more, more preferably 98 or more, and still more preferably 99 or more. The research octane number (RON) is a value measured by JIS K 2280 “Petroleum products—fuel oil—octane number and cetane number test method and cetane index calculation method”.

  The gasoline composition of the present invention has a sulfur content of 10 mass ppm or less. If the sulfur content is 10 mass ppm or less, the exhaust gas catalyst is excellent in durability and preferable. From the above points, the sulfur content is preferably 5 mass ppm or less, more preferably 3 mass ppm or less. The sulfur content is a value measured according to JIS K 2541-2 “Crude oil and petroleum products—sulfur content test method”.

The gasoline composition of the present invention has an aromatic content of 10 to 45% by volume. If the aromatic content is 45% by volume or less, an increase in total hydrocarbons and carbon monoxide in the exhaust gas can be suppressed, and there is little risk that the spark plug will cause smoldering. On the other hand, if the aromatic content is 10% by volume or more, RON can be maintained high and the driving performance is good. Moreover, it is preferable without deteriorating fuel consumption.
From the above points, the aromatic content in the gasoline composition of the present invention is preferably 40% by volume or less, and more preferably 35% by volume or less. Moreover, it is preferably 15% by volume or more, and more preferably 20% by volume or more. The aromatic content is a value measured by an all component test method using a gas chromatograph in JIS K 2536-2 “Petroleum product component test method”.

  The gasoline composition of the present invention has a benzene content of 1.0% by volume or less, preferably 0.5% by volume or less. If the benzene content is 1.0% by volume or less, the benzene content in the exhaust gas is reduced, and environmental pollution is not a problem, which is preferable. In addition, there is little risk that gasoline itself will adversely affect the human body. In addition, benzene content is the value measured by the all component test method by the gas chromatograph of JISK2536-2 "Petroleum product-component test method".

In the gasoline composition of the present invention, the olefin content is 5 to 40% by volume. Since the olefin content and isobutyl alcohol have a synergistic effect on improving the wear resistance, if the olefin content is 5% by volume or more, the improvement in wear resistance due to the inclusion of isobutyl alcohol becomes more remarkable. preferable. Further, if the olefin content is 5% by volume or more, there is no fear of misfire in a lean combustion state, and it is possible to ensure the driving performance of a direct injection engine vehicle or the like, which is preferable. Furthermore, if the olefin content is 40% by volume or less, nitrogen oxides in the exhaust gas will not increase, and gasoline evaporated in the atmosphere will not generate ozone. Furthermore, there is little risk that the oxidation stability of gasoline itself will deteriorate. From the above points, the olefin content is preferably 5 to 30% by volume.
In addition, an olefin content is the value measured by the all-component test method by the gas chromatograph of JISK2536-2 "Petroleum product-component test method".

  The gasoline composition of the present invention has a Reid vapor pressure (RVP) of 55 to 90 kPa, and preferably 55 to 75 kPa. When the RVP is 55 kPa or more, sufficient low temperature startability is obtained, and when the RVP is 90 kPa or less, hydrocarbons in the exhaust gas do not increase, and the operation performance is deteriorated due to the vapor lock phenomenon. Less preferred. In addition, the lead vapor pressure (RVP) is a value measured in accordance with JIS K-2258.

The gasoline composition of the present invention has the following distillation properties, and is preferably a value shown in parentheses from the viewpoint of driving performance such as acceleration.
50% distillation temperature (T50): 70 to 115 ° C (75 to 110 ° C)
70% distillation temperature (T70): 100-140 ° C (100-130 ° C)
90% distillation temperature (T90): 130-175 ° C (130-150 ° C)
If T50, T70, and T90 are within the above ranges, it is preferable that driving performance such as acceleration performance is kept good and fuel consumption is not deteriorated. The above T50, T70 and T90 are values obtained from the distillation properties measured based on JIS K 2254 “Petroleum product-distillation test method”.

  The gasoline composition of the present invention preferably contains substantially no ethyl alcohol from the viewpoint of suppressing an increase in vapor pressure. Here, “substantially ... not contained” means that ethyl alcohol can be contained as long as the effects of the present invention are exhibited.

  The gasoline composition of the present invention preferably has an oxidation stability measured by JIS K 2287 “Gasoline oxidation stability test method (induction period method)” of 2000 minutes or more. If the oxidation stability is 2000 minutes or more, it is preferable to have excellent oxidation stability because there is no fear of generating gum during storage. From the above points, the oxidation stability is more preferably 2100 minutes or more, and further preferably 2200 minutes or more.

  The abrasion-resistant gasoline composition of the present invention can further contain an antioxidant. Preferred antioxidants in the present invention include phenolic antioxidants, amine antioxidants, and aminophenol antioxidants. If such an antioxidant is contained, the oxidation stability can be improved while maintaining the wear resistance. Specific examples of such phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6-tert-butylphenol, and 2,6-di-tert-butylphenol. 4,4'-bis (2,6-di-tert-butylphenol), 4,4'-bis (2-methyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-) tert-butylphenol) and the like.

Specific examples of amine-based antioxidants include phenylenediamines such as N, N′-disecondarybutyl-p-phenylenediamine and N, N′-diisopropyl-p-phenylenediamine, and aminophenol-based oxidation. Examples of the inhibitor include tert-alkylamino such as 2,6-di-tert-α-dimethylamino-p-cresol and 2,6-di-tert-butyl-4 (N, N′-dimethylaminomethylphenol). Phenol etc. are mentioned.
Among these, 2,6-di-tert-butylphenol and N, N′-disecondarybutyl-p-phenylenediamine are preferable in terms of the above effects.

  Such antioxidant may be used individually by 1 type, and may be used in combination of 2 or more type. The content of this antioxidant is usually 1 to 100 ppm by mass. However, isobutyl alcohol alone has an antioxidant effect on gasoline, so in the present invention, the use of the expensive antioxidant is remarkably reduced. Since the effect that it can do is acquired, 1-20 mass ppm is preferable, and it is more preferable that it is especially 1-10 mass ppm.

  The gasoline composition of the present invention is excellent in lubricity such as wear resistance, specifically, in accordance with “light oil-lubricity test method” defined in JPI-5S-98, at a test temperature of 25 ° C. In the lubricity test conducted, the lubrication state is good. The lubricity test method based on JPI-5S-98 “light oil-lubricity test method” referred to in the present invention is substantially the method specified in JPI-5S-98, and the test temperature is set to 60 ° C. to 25 ° C. In addition, it is a method for measuring the friction and wear state of a lubricity test for gasoline and the like.

  In this case, the test temperature is set to 25 ° C. in consideration of ignition of gasoline as a sample. The measurement of the lubrication state in the initial stage of the lubricity test means not only the measurement of the wear scar diameter when the test time defined by JPI-5S-98 is 75 minutes, but also the wear when the test time is 10 minutes. It measures the diameter and coefficient of friction.

In the gasoline composition of the present invention, the wear scar diameter after the test time of 10 minutes in the lubricity test is preferably 430 μm or less, more preferably 410 μm or less, and 400 μm or less. Further preferred. This gasoline having a wear scar diameter of 430 μm or less is preferable in that it has good wear resistance and effectively suppresses wear of the sliding portion of the fuel pump.
In the gasoline composition of the present invention, in the lubricity test method, the wear scar diameter when the test time is 75 minutes is preferably 800 μm or less, and more preferably 790 μm or less. It can be confirmed that the wear resistance is good if the wear scar diameter is 750 μm or less when the test time is 75 minutes.

  The gasoline composition of the present invention is not particularly limited in its production method. For example, the above-mentioned properties are obtained by blending the base gasoline with isobutyl alcohol in an amount of 2 to 30% by volume based on the gasoline composition. A gasoline composition satisfying the compositions (1) to (7) can be produced.

  Although the said base gasoline includes conventionally well-known gasoline, each property, such as a sulfur content and a research octane number (RON), satisfy | fills the requirements of (1)-(7) which the gasoline composition of the said invention has. Preferably there is. Base gasoline can be prepared by blending various gasoline bases singly or in combination. Examples of such gasoline base materials include light naphtha obtained by atmospheric distillation of crude oil, desulfurized light naphtha, cracked gasoline obtained by catalytic cracking or hydrocracking, and reforming obtained by catalytic reforming. Distillate from which benzene is removed from gasoline (debenzene reformed gasoline), polymerized gasoline obtained by olefin polymerization, alkylate obtained by adding lower olefin to hydrocarbon such as isobutane, linear lower paraffinic carbonization Examples thereof include isomerates (isomerized gasoline) obtained by isomerization of hydrogen, de-n-paraffin oil, and a specific range of fractions and aromatic hydrocarbons.

Suitable methods for preparing base gasoline include those containing desulfurized light naphtha, cracked gasoline, debenzene-modified gasoline, alkylate, and isomerized gasoline and butane. In this case, it is particularly preferable to blend light cracked gasoline, and the blending amount is, for example, preferably 10 to 90% by volume and more preferably 20 to 80% by volume based on the base gasoline. As a result, a base gasoline having the above-described preferred properties and composition can be obtained.
The contents of isobutyl alcohol used in the preparation of the gasoline composition of the present invention and the antioxidant used as necessary and the preferred blending amounts thereof are as described above.

  Various additives can be appropriately blended in the gasoline composition of the present invention 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 such as polyhydric alcohols and ethers, organic acid alkali metal and alkaline earth metal salts, auxiliary alcohols such as higher alcohol sulfates, anionic surfactants, cationic interfaces Activators, antistatic agents such as double-sided surfactants, rust inhibitors such as esters of alkenyl succinic acid, identifiers such as kilyzanine and coumarin, odorants such as natural essential oils and synthetic fragrances, colorants such as azo dyes, etc. Well-known gasoline additives can be mentioned, and one or more of these additives can be added. Further, the additive amount of these additives may be appropriately selected depending on the situation, but it is usually preferable that the total amount of additives is 0.1% by mass or less based on the gasoline composition.

In the present invention, when producing a gasoline composition satisfying the following (1) to (7), the base gasoline is blended with isobutyl alcohol in an amount of 2 to 30% by volume based on the gasoline composition. A method for improving the lubricity and / or oxidation stability of a gasoline composition is provided.
(1) Research method octane number is 96 or more (2) Sulfur content is 10 mass ppm or less (3) Aromatic content is 10-45 vol%
(4) Benzene content is 1.0 volume% or less (5) Olefin content is 5-40 volume%
(6) Reed vapor pressure (RVP) is 55 to 90 kPa
(7) 50% distillation temperature is 70 to 115 ° C, 70% distillation temperature is 100 to 140 ° C, 90% distillation temperature is 130 to 175 ° C
Base gasoline, isobutyl alcohol, gasoline composition, and each property and composition are as described above. The effect of improving lubricity and / or oxidation stability is also as described above.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The properties, composition and performance of the gasoline base and gasoline composition were determined according to the following method.

[Composition, properties and performance]
(1) Research octane number (RON)
It was measured according to JIS K 2280.
(2) Density The density was measured according to JIS K 2249.
(3) Distillation property Measured according to JIS K 2254.

(4) Aromatic content and saturated hydrocarbon content Measured according to Petroleum Institute Standard JPI-5S-49-97.
(5) Benzene content, olefin content Measured according to JIS K 2536-2.
(6) Sulfur content Measured according to JIS K 2541-2.
(7) Reed vapor pressure (RVP)
Measurement was performed in accordance with JIS K 2258.

(8) Lubricity In the method prescribed in the Japan Petroleum Institute Standard JPI-5S-98, the test temperature is set to 60 ° C. and the wear scar diameter is measured when the test time is 75 minutes and the test time is 10 minutes. The wear scar diameter was also measured.
(9) Oxidation stability Measured according to JIS K 2287 “Gasoline oxidation stability test method (induction period method)”.

Examples 1-6 and Comparative Examples 1-6
Table 2 shows properties, compositions, and performances of gasoline compositions prepared by blending gasoline base materials, isobutyl alcohol, and the like at the ratios shown in Table 2 using the gasoline base materials shown in Table 1 and the following compounds. In Tables 1 and 2, ALK is alkylate, FG is cracked gasoline, LFG is light cracked gasoline, PGPZ is debenzene-modified gasoline, BB is butene fraction, i-BuOH is isobutyl alcohol, EtOH is ethyl alcohol, ETBE Represents ethyl-tert-butyl ether. As the antioxidant, commercially available AO-613 (Maruwa Bussan Co., Ltd.) was used.

  As is clear from Table 2, the gasoline compositions of the examples have a low Reid vapor pressure, good lubricity, and excellent oxidation stability. In contrast to the examples, the comparative example in which isobutyl alcohol is not blended is inferior in lubricity, and even if ethyl alcohol is blended therewith, there is no effect of improving the lubricity as shown in Comparative Examples 2 and 5, and ethyl It can be seen that the reed vapor pressure increases with the blending of alcohol. Similarly, as can be seen from Comparative Examples 3 and 6 in which ethyl-tert-butyl ether was blended, it can be seen that ethyl-tert-butyl ether has no effect of improving lubricity and oxidation stability.

  According to the present invention, it is possible to obtain a gasoline composition that is excellent in environmental performance of reducing carbon dioxide emissions, has good oxidation stability even after long-term storage, and has excellent wear resistance. Since it can do, the gasoline composition of this invention can be used conveniently as a fuel oil for gasoline engines.

Claims (6)

A gasoline composition containing 2 to 30% by volume of isobutyl alcohol and satisfying the following (1) to (7).
(1) Research method octane number is 96 or more (2) Sulfur content is 10 mass ppm or less (3) Aromatic content is 10-45 vol%
(4) Benzene content is 1.0 volume% or less (5) Olefin content is 5-40 volume%
(6) Reed vapor pressure (RVP) is 55 to 90 kPa
(7) 50% distillation temperature is 70 to 115 ° C, 70% distillation temperature is 100 to 140 ° C, 90% distillation temperature is 130 to 175 ° C   In the method prescribed in JPI-5S-98, the wear scar diameter after 10 minutes when the temperature is 25 ° C is 430 µm or less, and the wear scar diameter after 75 minutes is 800 µm or less. Gasoline composition.   The gasoline composition according to claim 1 or 2, wherein the oxidation stability according to JIS K-2287 is 2000 minutes or more. The gasoline composition according to any one of claims 1 to 3 , wherein the isobutyl alcohol is biomass-derived isobutyl alcohol. In preparing the gasoline composition meets the following (1) to (7), isobutyl alcohol based gasoline is formulated to contain 2-30% by volume based on the gasoline composition, the oxidation of gasoline composition A way to improve stability .
(1) Research method octane number is 96 or more (2) Sulfur content is 10 mass ppm or less (3) Aromatic content is 10-45 vol%
(4) Benzene content is 1.0 volume% or less (5) Olefin content is 5-40 volume%
(6) Reed vapor pressure (RVP) is 55 to 90 kPa
(7) 50% distillation temperature is 70 to 115 ° C, 70% distillation temperature is 100 to 140 ° C, 90% distillation temperature is 130 to 175 ° C 6. The method of claim 5, further improving the lubricity of the gasoline composition.