JP5432519B2 - 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 of 93 or more and less than 96 (2) Sulfur content is 10 mass ppm or less (3) Aromatic content is 10 to 35% by volume
(4) benzene content is 1.0 volume% or less (5) olefin content is 20 volume% or less (6) Reed vapor pressure (RVP) is 55 to 90 kPa
(7) 50% distillation temperature is 75-100 ° C, 70% distillation temperature is 100-120 ° C, 90% distillation temperature is 140-165 ° 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. ] Gasoline composition of description,
[3] The gasoline composition according to the above [1] or [2], wherein the oxidation stability according to JIS K-2287 is 1000 minutes or more.
[4] The gasoline composition according to any one of [1] to [3], containing 1 to 20 ppm by mass of an antioxidant,

[ 5 ] The gasoline composition according to any one of [1] to [ 4 ], wherein the isobutyl alcohol is biomass-derived isobutyl alcohol .
[ 6 ] When producing a gasoline composition satisfying the following (1) to (7), a gasoline composition is added so that isobutyl alcohol is contained in the base gasoline in an amount of 2 to 30% by volume based on the gasoline composition. to improve the oxidative stability of an object method, and (1) less than research octane number of 93 or more 96 (2) sulfur content of less than 10 mass ppm (3) an aromatic content of 10 to 35 volume%
(4) benzene content is 1.0 volume% or less (5) olefin content is 20 volume% or less (6) Reed vapor pressure (RVP) is 55 to 90 kPa
(7) 50% distillation temperature is 75-100 ° C, 70% distillation temperature is 100-120 ° C, 90% distillation temperature is 140-165 ° C.
[7] The method according to [6], 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, according to the present invention, it is possible to provide a gasoline composition that is significantly reduced in antioxidants and excellent in economic efficiency.

[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 of 93 or more and less than 96 (2) Sulfur content is 10 mass ppm or less (3) Aromatic content is 10 to 35% by volume
(4) benzene content is 1.0 volume% or less (5) olefin content is 20 volume% or less (6) Reed vapor pressure (RVP) is 55 to 90 kPa
(7) 50% distillation temperature is 75-100 ° C, 70% distillation temperature is 100-120 ° C, 90% distillation temperature is 140-165 ° C.

  The gasoline composition of the present invention has a research octane number (RON) of 93 or more and less than 96. If the RON is within this range, it can be used as it is without any risk of a reduction in driving performance, such as knocking, with respect to a gasoline model with RON95. From the above points, the RON of the gasoline composition of the present invention is preferably 95 or less. 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 6 ppm by mass or less, more preferably 5 ppm by mass or less, and further preferably 3 ppm by mass 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 35% by volume. If the aromatic content is 35% by volume or less, an increase in the total hydrocarbons and carbon monoxide in the exhaust gas can be suppressed, and the spark plug is less likely to 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 26% by volume or less, more preferably 24% by volume or less, and preferably 15% 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 0.6% by volume or less, and more 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 20% by volume or less, preferably 18% by volume or less. If the olefin content is 20% by volume or less, nitrogen oxides in the exhaust gas are reduced, and, for example, gasoline that has evaporated in the atmosphere is less likely to generate ozone. Furthermore, the oxidation stability of the fuel oil itself is good. 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): 75-100 ° C (80-95 ° C)
70% distillation temperature (T70): 100-120 ° C (100-116 ° C)
90% distillation temperature (T90): 140-165 ° C (140-150 ° 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 1000 minutes or more. If the oxidation stability is 1000 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 1200 minutes or more, and further preferably 1500 minutes or more.

  The 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. 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 also excellent in lubricity such as abrasion resistance. Specifically, the gasoline composition conforms to “light oil-lubricity test method” defined in JPI-5S-98, and the test temperature is 25 ° C. In the lubricity test conducted in, 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 in the lubricity test after 10 minutes of the test time is preferably 430 μm or less, more preferably 420 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 when the wear scar diameter at the test time of 75 minutes is 800 μm or less.

  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 blended with desulfurized light naphtha, cracked gasoline, debenzene-modified gasoline, and those blended with alkylate, isomerized gasoline and butane. In this case, it is particularly preferable to blend cracked gasoline, and the blending amount is preferably, for example, 10 to 90% by volume, 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 of 93 or more and less than 96 (2) Sulfur content is 10 mass ppm or less (3) Aromatic content is 10 to 35% by volume
(4) benzene content is 1.0 volume% or less (5) olefin content is 20 volume% or less (6) Reed vapor pressure (RVP) is 55 to 90 kPa
(7) 50% distillation temperature is 75-100 ° C, 70% distillation temperature is 100-120 ° C, 90% distillation temperature is 140-165 ° 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.

[Properties, composition 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.
(8) Oxidation stability Measured according to JIS K 2287 “Gasoline oxidation stability test method (induction period method)”.

Examples 1-6 and Comparative Examples 1-7
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, FG is cracked gasoline, LFG is light cracked gasoline, PGPZ is debenzene-modified gasoline, DLN is desulfurized light naphtha, ALK is alkylate, BB is a butene fraction, i-BuOH is isobutyl alcohol, EtOH represents ethyl alcohol, and ETBE represents ethyl-tert-butyl ether. As the antioxidant, commercially available AO-613 (Maruwa Bussan Co., Ltd.) was used. Was used.

  As is clear from Table 2, the gasoline compositions of Examples 1 to 6 have low Reed vapor pressure, good lubricity, and excellent oxidation stability. Further, in contrast to the examples, comparative examples in which no isobutyl alcohol is blended are inferior in lubricity, and in comparative examples 2 and 6 in which ethyl alcohol is blended with this, the Reid vapor pressure is increased and the lubricity is also inferior. I understand. Moreover, from the comparison between Comparative Examples 3 and 7, it can be seen that when ethyl tert-butyl ether is blended with gasoline, the lubricity and oxidation stability are deteriorated, so that the antioxidant cannot be reduced.

  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 (7)

A gasoline composition containing 2 to 30% by volume of isobutyl alcohol and satisfying the following (1) to (7).
(1) Research method octane number of 93 or more and less than 96 (2) Sulfur content is 10 mass ppm or less (3) Aromatic content is 10 to 35% by volume
(4) benzene content is 1.0 volume% or less (5) olefin content is 20 volume% or less (6) Reed vapor pressure (RVP) is 55 to 90 kPa
(7) 50% distillation temperature is 75-100 ° C, 70% distillation temperature is 100-120 ° C, 90% distillation temperature is 140-165 ° 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 1000 minutes or more.   The gasoline composition in any one of Claims 1-3 which contains 1-20 mass ppm of antioxidants. The gasoline composition according to any one of claims 1 to 4 , 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 of 93 or more and less than 96 (2) Sulfur content is 10 mass ppm or less (3) Aromatic content is 10 to 35% by volume
(4) benzene content is 1.0 volume% or less (5) olefin content is 20 volume% or less (6) Reed vapor pressure (RVP) is 55 to 90 kPa
(7) 50% distillation temperature is 75-100 ° C, 70% distillation temperature is 100-120 ° C, 90% distillation temperature is 140-165 ° C. The method of claim 6 further improving the lubricity of the gasoline composition.