JPH09302359A - gasoline - Google Patents

Abstract

(57) [PROBLEMS] To provide gasoline with a high octane number, which is excellent in engine output performance, particularly in acceleration response. Further, it is intended to reduce harmful components in the exhaust gas while improving the output performance of the engine, especially the acceleration responsiveness while reducing the blending amount of the aromatic hydrocarbon fraction. A gasoline is characterized by containing 0.5 to 50% by volume of methylcyclopentene.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to gasoline having excellent engine output performance and capable of preventing an increase in harmful components in exhaust gas.

[0002]

2. Description of the Related Art An automobile is required to have less harmful substances contained in exhaust gas and to have good fuel consumption. One way to improve fuel efficiency is to increase the compression ratio of the engine to improve thermal efficiency. However, in an engine with a high compression ratio, knocking easily occurs, so gasoline with a high octane number is required. In order to produce a gasoline with a high octane number, in the past, a method of adding an alkylated lead, which is an anti-knock agent, to gasoline to increase the octane number has been adopted. However, the use of lead alkylated has become a problem starting from the so-called lead pollution problem. In addition, gasoline that does not affect the purification performance of the catalyst purification device that has been installed in automobiles since 1975 has been required. Therefore, high octane gasoline produced by adjusting the components in gasoline has come to be produced and sold. Specifically, in order to improve the octane number of gasoline, the blending amount of the aromatic hydrocarbon fraction, which is a component showing a high octane number, has been increased.

However, in recent years, the influence of the aromatic hydrocarbon component on the human body has become a problem, and it has been required to reduce the blending amount of the aromatic hydrocarbon fraction in gasoline. Therefore, gasoline containing a light aliphatic hydrocarbon-based component having a high octane number and gasoline containing an oxygen-containing organic compound such as methyl-t-butyl ether have come to be marketed.

Also in general gasoline, as in high octane gasoline, the aromatic hydrocarbon component has become a problem, and it has been required to reduce the blending amount of the aromatic hydrocarbon fraction. . For this reason, gasoline containing a light component of an aliphatic hydrocarbon has come to be marketed.

[0005]

However, it is difficult to produce a light aliphatic hydrocarbon raw material having a high octane number in a large amount. In addition, when a light aliphatic hydrocarbon or an oxygen-containing organic compound is contained in gasoline, the calorific value becomes smaller than that in the case where an aromatic hydrocarbon is contained, so that the output of the engine tends to decrease. . In addition, the flame speed in the engine becomes slower, and especially during acceleration, light aliphatic hydrocarbons and oxygen-containing organic compounds are supplied to the engine with priority over heavy components, resulting in acceleration responsiveness. It turned out to be low.

An object of the present invention is to provide gasoline having a high octane number and excellent engine output performance, particularly acceleration responsiveness. Another object of the present invention is to improve the output performance of the engine, especially the acceleration response, while reducing the blending amount of the aromatic hydrocarbon fraction or reducing the harmful components in the exhaust gas.

[0007]

Means for Solving the Problems The gasoline of the present invention as a means for achieving the above object is characterized by containing methylcyclopentene in an amount of 0.5% by volume or more and 50% by volume or less.

As the base material of the gasoline of the present invention, straight-run gasoline obtained by atmospheric distillation of crude oil or soft naphtha, cracked gasoline obtained by catalytic cracking method, hydrocracking method or thermal cracking method, catalytic reforming It is possible to use reformate gasoline obtained by the method or the like, alkylate obtained by adding a lower olefin such as propylene to alkylate a lower hydrocarbon such as isobutane, or an ismate obtained by isomerization of soft naphtha. it can. Furthermore, oxygen-containing compounds such as methyl-t-butyl ether can be included in the base material of gasoline.

At present, the most commonly used gasoline base material is methylcyclopentene at a maximum of 0.1.
It contains only about% by volume. Further, methylcyclopentene was mixed or produced in the process of refining a gasoline base material, and was not particularly recognized as an additive. However, the present inventor found that when methylcyclopentene was added to gasoline in an amount of 0.5% by volume or more and an exhaust gas test and an acceleration performance test of gasoline were performed, both of them exhibited unexpectedly improved properties. Has reached the present invention. That is, it was discovered that by adding methylcyclopentene to gasoline instead of aromatic hydrocarbons, harmful substances from the exhaust gas of the engine can be reduced and the acceleration performance can be improved.

Furthermore, the research method octane number of methylcyclopentene is "Technical Data B".
look, Petroleum Refining En
"Glish Edition Volume I" (A
american Petroleum Insitu
te) is 94 (1-methylcyclopentene, previously ASTM No. 225 (1958)).
The value of 184 is listed in.). When the present inventors added methylcyclopentene (synthesized by the present inventor, about 65% of 1-methylcyclopentene) to ordinary gasoline, they found that the base material had a research octane number of about 110. did. As described above, the inventors have found that it is possible to improve the octane number of gasoline by blending methylcyclopentene into gasoline, and completed the present invention.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In order to obtain the gasoline of the present invention, it is necessary to add and mix methylcyclopentene produced in another step to the above-mentioned gasoline base material which is usually used. Methylcyclopentene is one of the products in the dehydrogenation reaction of methylcyclopentane [Amano et al; Asahi Glass Industrial Technical Report Research Report Vol. Two
5,269 (1974). ]. It can also be produced by isomerizing cyclohexene (Japanese Patent Laid-Open No. 47-0319).
55 publication). It can also be obtained by hydrogenating methylcyclopentadiene. The reaction products of these reactions can be added to the gasoline base material as they are, or methylcyclopentene can be separated and purified from these reaction products and added to the gasoline base material.

In this case, the alkylcyclopentene other than methylcyclopentene, cyclohexene, and alkylcyclohexene (such as methylcyclohexene) may be contained in the gasoline, but those having a high boiling point are very effective in improving the engine output of the gasoline. Does not play.

From the viewpoint of improving octane number and calorific value of gasoline without increasing harmful substances in exhaust gas, and particularly improving acceleration performance thereof, the methylcyclopentene concentration in gasoline is at least 0.5% by volume.
It is necessary to In order to further improve the acceleration performance, it is preferable to contain 2% by volume or more,
It is more preferable to contain 5% by volume or more.

Within the range of 0.5% by volume or more, as the content of methylcyclopentene is increased, the output of gasoline is further improved and the octane number is also improved. However, considering the fractional distillation properties that affect drivability in summer (occurrence of vapor lock phenomenon), the upper limit is about 50% by volume. However, adding a large amount of methylcyclopentene increases the cost of gasoline, so 40% by volume
The following is preferable, and 30% by volume or less is more preferable. However, if there are no problems with drivability and cost in the summer,
It may be added up to about 50% by volume, and under these conditions,
It goes without saying that a high engine output can be obtained by the synergistic effect of improving the octane number and the heat generation amount.

The benzene content of the gasoline of the present invention is preferably 1% by volume or less from the viewpoint of reducing harmful components in exhaust gas. This lower limit is not particularly limited, and may be 0% by volume. Further, the content of aromatic hydrocarbons in the gasoline of the present invention is preferably 40% by volume or less, and more preferably 35% by volume or less in order to reduce harmful substances in exhaust gas. preferable.

[0016]

【Example】

(Synthesis method of methylcyclopentene) Using methylcyclopentane as a reagent, a dehydrogenation reaction is performed by the method of Amano et al., And the obtained product is distilled,
Separation of methylcyclopentene, 93% pure methylcyclopentene (83% of 1-methylcyclopentene)
I got The following experiments were conducted using this methylcyclopentene.

(Experimental Example 1: Measurement of Fire Speed and Engine Output) Using an "ASTM-CFR" gasoline engine, the pressure in the combustion chamber of this engine was detected by a pressure pickup ("8QPC" manufactured by AVL), and the indicated output was obtained. (Engine output) is a combustion analysis device (manufactured by Ono Sokki Co., Ltd., "CB-
466 "). Further, using a spark plug (made by Nippon Denso Co., Ltd.) installed on the side wall of the combustion chamber, a voltage of 24 V is applied to this spark plug, and the ion current generated in this plug due to the arrival of the flame is detected by an oscilloscope, and the spark plug is used. The time (flame speed) from the time of ignition to the detection of ion current was measured. "ASTM-CF
Table 1 shows the specifications of the "R" gasoline engine.

[0018]

[Table 1]

As a sample, 90% by volume of isooctane
Was prepared by adding 10% by volume of methylcyclopentene, benzene, cyclohexene, cyclohexane, and hexane, respectively, and only isooctane was prepared. For each sample, the flame speed and engine output were measured as described above, and the measurement results are shown in Table 2. Table 2
In, “λ” indicates an excess air ratio. The values shown in Table 2 are absolute values for the sample containing only isooctane. For other samples, the following relative values are shown. [(Flame speed or engine power for each sample-flame speed or engine power for isooctane sample) / flame speed or engine power for isooctane sample]

[0020]

[Table 2]

As can be seen from the results shown in Table 2, the sample to which methylcyclopentene was added showed a significant improvement in flame speed and engine output as compared with the sample containing only isooctane or the sample containing cyclohexane and hexane. Moreover, it was found that the flame speed and the engine output showed the same effect as compared with the sample to which benzene which was a heavy additive was added.

(Experimental Example 2: Measurement of toxic substances in exhaust gas) A commercially available passenger car (displacement 1.49 liters) registered in 1993 equipped with an electronic fuel injection control device and a three-way catalyst was used to measure the chassis. The operation was performed on a dynamometer to measure harmful substances in the exhaust gas. When carrying out this measurement, the exhaust gas was subjected to a constant volume sampler (HORIBA, Ltd., “CVS- 910
0S ”), and the amount of benzene was measured by gas chromatography [Hewlett Packard Co., HP5
890 Series II; non-polar capillary column (0.3
2 mmφ, length 60 m, film thickness 1 μm), hydrogen flame ion detector], and the amount of benzene discharged during 11-mode running was calculated.

To each sample prepared in Experimental Example 1, 3% by volume of isopentene was further added in order to increase the vapor pressure.
Each sample was added to prepare each sample for this example, and the above measurement was performed for each sample. The results are shown in Table 3.

[0024]

[Table 3]

For the sample to which benzene was added, an amount of 385 mg was detected in the exhaust gas, but when gasoline containing methylcyclopentene was used, this amount was about 1%.
Only about / 8 benzene was detected, which was not much different from the case where cyclohexane or cyclohexene was used, and the amount of benzene discharged was remarkably reduced when methylcyclopentene was used. As described above, when gasoline containing methylcyclopentene is used, the amount of harmful substances in the exhaust gas can be made relatively small, and particularly when compared with the case where a heavy aromatic additive is used, it can be significantly reduced.

(Experimental Example 3 Test of Acceleration Response Using Base Gasoline) Methylcyclopentene was added to the base gasoline having the properties shown in Table 4 by 5.0% by volume or 20.0% by volume. Inventive Example gasoline samples 3.1 or 3.2 were prepared and tested for accelerated responsiveness. For comparison, the same test was performed on the base gasoline having the properties shown in Table 4 without adding methylcyclopentene.

[0027]

[Table 4]

As is clear from Table 4, the octane number was improved when methylcyclopentene was added, but the octane number of methylcyclopentene was calculated back from this improved value to 110.2. From this, it became clear that the addition of methylcyclopentene to ordinary gasoline can greatly improve the octane number of gasoline.

A commercially available engine having the specifications shown in Table 5 was installed in a constant temperature room, and the engine was operated in the mode shown in FIG. 1 while being controlled by a DC dynamometer. However, in the operation mode graph of FIG. 1, the vertical axis represents throttle opening (%) and the horizontal axis represents time (seconds). The maximum torque (Tmh) after the engine has been sufficiently warmed up and the maximum torque (Tmc) at the cold start (when the engine is cold) are measured, and the ratio T
The acceleration response was evaluated by obtaining r (Tr = Tmc / Tmh). The results are shown in Table 6.

[0030]

[Table 5]

[0031]

[Table 6]

As is clear from this result, it is understood that the acceleration response is rapidly improved by adding methylcyclopentene. In addition, samples 3-1 and 3 in Table 4
From 2, it can be seen that the density increases as the amount of methylcyclopentene added increases, and that it acts as a heavy component.

(Experimental Example 4: Acceleration response test using catalytic reformed gasoline) 10% by volume of methylcyclopentene was added to 90% by volume of catalytically reformed gasoline having the properties shown in Table 7, The gasoline of the example of the present invention was prepared, and the acceleration response was tested for this gasoline. For comparison, the catalytically reformed gasoline having the properties shown in Table 7 was replaced by benzene instead of methylcyclopentene.
The gasoline of each comparative example was prepared by adding 2,4-dimethylpentene and 1-hexene, and the same test was performed for each gasoline.

[0034]

[Table 7]

A commercial engine having the specifications shown in Table 5 was installed at a constant room temperature, and the acceleration response was evaluated in the same manner as in Experimental Example 3. However, the acceleration data was measured 5 times in succession. Table 8 shows the results.

[0036]

[Table 8]

As can be seen from these results, by adding methylcyclopentene to gasoline, as compared with the case of adding benzene or dimethylpentene,
Acceleration response was remarkably improved.

[0038]

EFFECTS OF THE INVENTION The gasoline of the present invention contains methylcyclopentene to improve the octane number without increasing harmful components in the exhaust gas, and further significantly improve the engine output performance, especially the acceleration response. There is a special effect that can be done.

[Brief description of drawings]

FIG. 1 is a graph showing an operation mode of an engine for evaluation of acceleration responsiveness performed in Experimental Examples 3 and 4.

Claims (1)

[Claims] 1. A gasoline containing 0.5 to 50% by volume of methylcyclopentene.