JP4938332B2 - Gasoline composition - Google Patents

Description

  The present invention relates to a gasoline composition, and more particularly to a gasoline composition that suppresses the emission of carbon monoxide and unburned hydrocarbons from a gasoline engine and has good oxidation stability even after long-term storage.

In recent years, regarding environmentally friendly gasoline, it has been studied to add an oxygen-containing compound as a method for reducing carbon monoxide (CO) and unburned hydrocarbon (THC) in exhaust gas, which has been considered important. However, environmentally friendly gasoline is required to reduce carbon dioxide (CO ₂ ) emissions from the viewpoint of preventing global warming. In response to this requirement, the concept of carbon neutral, that is, oxygenated compounds derived from plants is considered not to increase carbon dioxide in the atmosphere in the life cycle, It is preferred as a measure for reducing carbon dioxide. Therefore, for example, gasoline blended with ethanol produced from biomass has attracted attention.
Under such circumstances, the present inventor has found that gasoline blended with ethanol and the like has poor oxidation stability after long-term storage and may cause various problems in practice. That is, such gasoline suppresses the generation of carbon monoxide and unburned hydrocarbons in the exhaust gas, but during long-term storage, organic acids such as formic acid and acetic acid are generated in the gasoline, and storage facilities and automobiles The phenomenon of corroding metal parts occurs. Therefore, by blending ethanol or the like, it is possible to provide a gasoline having excellent oxidation stability after long-term storage while maintaining the function of suppressing the emission of carbon monoxide and unburned hydrocarbons in the exhaust gas. Needed.

  On the other hand, as a method for improving the oxidation stability of gasoline, for example, a method for adjusting the content of a specific olefin compound or the composition of a specific olefin compound is known, but the purpose cannot always be achieved sufficiently. (For example, refer to Patent Documents 1 and 2). Therefore, there is a demand for technological development that further improves oxidation stability.

Japanese Patent Laid-Open No. 10-316980 JP 2006-28402 A

  The present invention has been made under such circumstances, and provides a gasoline composition that suppresses the emission of carbon monoxide and unburned hydrocarbons from a gasoline engine and has good oxidation stability even after long-term storage. It is intended to do.

  The present inventors have found that the object can be achieved by blending ethanol with gasoline having a specific composition and adjusting the content of the aldehyde compound. The present invention has been completed based on such findings.

That is, the present invention
1. 0.5% to 10% by volume of ethanol, 0 to 20% by volume of light cracked gasoline, and reformed gasoline, desulfurized heavy cracked gasoline, and desulfurized light naphtha are blended with the following properties and compositions: A method for producing a gasoline composition , characterized by comprising :
(1) Research octane number of 89-105
(2) Olefin content is 35 vol% or less (3) Aromatic content is 45 vol% or less (4) Benzene content is 1.0 vol% or less (5) Sulfur content is 10 mass ppm or less (6) Aldehyde compound is contained 2. Production of gasoline composition according to 1 above, wherein the amount is 35 mass ppm or less 2. 50% distillation temperature is 100 ° C. or less, 70% distillation temperature is 135 ° C. or less, and 90% distillation temperature is 180 ° C. or less. Way ,
Is to provide.

  The gasoline composition of the present invention is a gasoline composition that suppresses the emission of carbon monoxide and unburned hydrocarbons from a gasoline engine and has good oxidation stability even after long-term storage.

The gasoline composition of the present invention is required to contain 0.5% by volume or more, preferably 1% by volume or more, more preferably 2% by volume or more of ethanol (hereinafter sometimes referred to as “ETOH”). If the content of ETOH is 0.5% by volume or more, an effect of suppressing the emission amount of carbon monoxide and hydrocarbons can be obtained. On the other hand, the upper limit of the ETOH content is 10% by volume or less, preferably 5% by volume or less, more preferably 3% by volume or less. If the content of ETOH is 10% by volume or less, it is possible to maintain good driving performance without difficulty in controlling the air / fuel ratio of the engine.
The content of ETOH is a value measured by an all-component analysis method using a gas chromatograph in JIS K 2536-2 “Petroleum product-component test method”.

The ETOH used in the present invention is not particularly limited, and any ETOH obtained by any production method can be used. For example, what is obtained from a known production method such as a sulfuric acid hydrolysis method may be used. However, carbon dioxide (CO ₂ ) Good for countermeasures.

  The gasoline composition of the present invention has a research octane number (RON) of 89 or more, preferably 90 or more. If the RON is 89 or more, there is no possibility that the driving performance is deteriorated such as knocking. However, in the premium specification, 96 or more is preferable. On the other hand, the upper limit of RON is not particularly limited, but is usually about 105. The octane number of the research method is a value measured by JIS K 2280 “Petroleum products—fuel oil—octane number and cetane number test method and cetane index calculation method”.

  In the gasoline composition of the present invention, the olefin content is 35% by volume or less, preferably 30% by volume or less. If the olefin content is 35% by volume or less, nitrogen oxides in the exhaust gas will not increase, and gasoline evaporated in the atmosphere will not generate ozone. Furthermore, the oxidation stability of gasoline itself is not likely to deteriorate. The olefin content is a value measured by a total component analysis method using a gas chromatograph of JIS K 2536-2 “Petroleum products—component test method”.

  The gasoline composition of the present invention has an aromatic content of 45% by volume or less, preferably 35% by volume or less, more preferably 25% by volume or less. If the aromatic content is 45% by volume or less, there is little fear that THC and CO in the exhaust gas will increase, and there is little fear that the spark plug will smolder, and good operating performance can be maintained. On the other hand, the lower limit of the aromatic content is not particularly limited, but it is preferably 5% by volume or more from the viewpoint of deterioration of fuel consumption and prevention of reduction in driving performance. The aromatic content is a value measured by a total component analysis method using a gas chromatograph of JIS K 2536-2 “Petroleum products—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 benzene is 1.0 volume% or less, benzene content in exhaust gas will decrease and there is no possibility that environmental pollution will become a problem. In addition, there is no 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".

The gasoline composition of the present invention has a sulfur content of 10 mass ppm or less, preferably 5 mass ppm or less, more preferably 3 mass ppm or less. If the sulfur content is 10 mass ppm or less, the durability of the catalyst does not decrease.
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 further requires that the content of the aldehyde compound be 50 mass ppm or less, preferably 35 mass ppm or less. When the content of the aldehyde compound is 50 ppm by mass or less, the oxidation stability of gasoline is not lowered, and good oxidation stability is exhibited even after long-term storage. In addition, content of an aldehyde compound is the value measured by the analytical method of the aldehyde prescribed | regulated to JISK6727 "styrene".

The gasoline composition of the present invention preferably has the following distillation properties. In addition, the inside of () shows a more preferable range.
50% distillation temperature (T50): 100 ° C. or less (80 to 95 ° C.)
70% distillation temperature (T70): 135 ° C. or less (100 to 125 ° C.)
90% distillation temperature (T90): 180 ° C. or lower (130 to 165 ° C.)
If T50, T70, and T90 are in the above ranges, the driving performance such as acceleration is kept good, and the fuel efficiency is not deteriorated. The above T50, T70, and T90 are values obtained from the distillation properties measured based on JIS K 2254 “Petroleum products-distillation test method”.

The gasoline composition of the present invention can be produced by any method. For example, both ETOH can be prepared using the following gasoline base material. Examples of the gasoline base include light naphtha obtained by atmospheric distillation of crude oil, cracked gasoline obtained by catalytic cracking or hydrocracking, light cracked gasoline excluding heavy fraction of cracked gasoline, cracked Desulfurized heavy cracked gasoline obtained by desulfurizing heavy fraction removed from gasoline, fraction obtained by removing benzene from reformed gasoline obtained by catalytic reforming (debenzene reformed gasoline), polymerization of olefins Polymerized gasoline obtained by the above, an alkylate obtained by adding a lower olefin to a hydrocarbon such as isobutane, an isomerized gasoline (isomerate) obtained by isomerization of a linear lower paraffinic hydrocarbon, a de-n-paraffin oil , And these specific ranges of fractions and aromatic hydrocarbons.
Among the above-mentioned base materials, the light cracked gasoline preferably has a blending amount of 35% by volume or less, more preferably 20% by volume or less, based on the composition. If the blending amount of light cracked gasoline is 35% by volume or less, it is possible to easily adjust the content of the aldehyde compound to the target range. Regarding the distillation properties of light cracked gasoline, the end point of distillation is preferably 120 ° C. or less, more preferably 100 ° C. or less, from the viewpoint of securing the anti-knock property and volatility of the gasoline composition.

Preferred examples of the composition of the gasoline composition of the present invention include the following. However, the inside of () shows a preferable range.
(1) Reformed gasoline (debenzene reformed gasoline) 0-70 (10-60) volume%
(2) Cracked gasoline 0-80 (0-60) volume%
(Mixture of light cracked gasoline and desulfurized heavy cracked gasoline)
(3) Light cracked gasoline 0-35 (0-20) volume%
(4) Desulfurized heavy cracked gasoline 0-50 (0-20) volume%
(5) Alkylate 0-60 (0-20) volume%
(6) Desulfurized light naphtha 0-40 (0-20) volume%
(7) Butane, LPG 0-15 (0-10) volume%
(8) ETOH 0.5-10 (0.5-5) volume%

  Various additives can be appropriately blended in the gasoline composition of the present invention as necessary. Examples of such additives include phenolic and amine antioxidants, metal deactivators such as Schiff compounds and thioamide compounds, surface ignition inhibitors such as organic phosphorus compounds, succinimides, and polyalkylamines. , Detergents such as polyetheramines, antifreezing 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 surfactants Agents, 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. 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.

EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not restrict | limited at all by these examples. The properties and performance of the gasoline composition were determined according to the following method.
[Properties of gasoline composition]
・ Research method octane number,
Measurement was performed according to JIS K 2280.
-Sulfur content Measured according to JIS K 2541-2.
Aromatic content, olefin content, benzene These were measured according to JIS K 2536-2.
-Distillation property Measured according to JIS K 2254.
-Density Measured according to JIS K 2249.
-Vapor pressure Measured according to JIS K 2258.

-Oxidation stability Measured according to JIS K2541.
・ Oxidation stability after storage Under conditions specified in JIS K 2287, the sample oil was deteriorated for 16 hours at a temperature of 100 ° C., an atmosphere gas of an oxygen atmosphere, and a pressure of 0.69 MPa. Was quantified.

Examples 1 and 2 and Comparative Examples 1 and 2
A gasoline composition is prepared by mixing a metal base agent shown in Table 1 with a metal deactivator and an antioxidant at a ratio shown in Table 2, and the properties, composition and performance are shown in Table 2. Show. The antioxidant in Table 2 is “Sumilyzer BPA-M1” manufactured by Sumitomo Chemical Co., Ltd., and the metal deactivator is N, N′-disalicylidene-1,2-diaminopropane.
In Table 1, PG represents debenzene-modified gasoline, LFG represents light cracked gasoline, DHFG represents desulfurized heavy cracked gasoline, DLN represents desulfurized light naphtha, and ETOH represents ethanol.
In addition, the compounding quantity of the antioxidant of Example 2 of Table 2 and the comparative example 2 differs from the compounding quantity in the case of Example 1 and the comparative example 1 because the compounding quantity of antioxidant is a composition. It is because it was set as the compounding quantity of the result adjusted individually so that the induction period by JISK2541 may become 960 minutes or more.

  As can be seen from Table 2, since the gasoline compositions of Examples 1 and 2 contain ETOH, which is an oxygen-containing compound, carbon monoxide in the exhaust gas can be reduced, and formic acid after deterioration and The total content of acetic acid is as low as 18 and 12 mass ppm. On the other hand, in Comparative Example 1 in which the blending amount of ETOH exceeds 10% by volume, the total content of formic acid and acetic acid after degradation is as large as 115 mass ppm. In Comparative Example 2 in which the content of the aldehyde compound exceeds 50 ppm by mass, the total amount of formic acid and acetic acid after deterioration is 800 ppm by mass or more, which is extremely large.

  According to the gasoline composition of the present invention, it is possible to obtain a gasoline composition that suppresses the emission of carbon monoxide and unburned hydrocarbons and has good oxidation stability after long-term storage. Moreover, since ethanol produced from biomass can be used as a raw material, it can be effectively used as gasoline that contributes to prevention of global warming.

Claims (2)

By blending 0.5 to 10% by volume of ethanol, 0 to 20% by volume of light cracked gasoline, and reformed gasoline, desulfurized heavy cracked gasoline, and desulfurized light naphtha, the following properties and compositions are obtained. A method for producing a gasoline composition , characterized by being prepared as follows .
(1) Research octane number of 89-105
(2) Olefin content is 35 vol% or less (3) Aromatic content is 45 vol% or less (4) Benzene content is 1.0 vol% or less (5) Sulfur content is 10 mass ppm or less (6) Aldehyde compound is contained The amount is 35 mass ppm or less The method for producing a gasoline composition according to claim 1, wherein the 50% distillation temperature is 100 ° C or lower, the 70% distillation temperature is 135 ° C or lower, and the 90% distillation temperature is 180 ° C or lower.