JP6709751B2 - Unleaded gasoline - Google Patents

Description

The present invention relates to unleaded gasoline.

Gasoline is configured by appropriately selecting a plurality of base materials and blending these base materials in appropriate amounts so as to satisfy various fuel standards. The octane number, which is one of the fuel standards, is an important factor from the viewpoint of ensuring drivability. As the base material for adjusting the octane number, base materials such as isomerized gasoline, cracked gasoline, catalytically reformed gasoline, catalytically cracked gasoline and oxygen-containing compounds are generally used.
Among these base materials, the catalytically reformed gasoline is a high octane base material that has a high density and contains abundant aromatic compounds that are high octane constituents. In particular, the heavy catalytic reformed gasoline obtained by fractionating the catalytic reformed gasoline has a high aromatic content.

Heavy catalytic reformed gasoline contains mixed xylenes. Mixed xylene is a fraction containing o-xylene, m-xylene, p-xylene, and ethylbenzene. Mixed xylenes can be obtained from heavy catalytic reforming gasoline by distillation and are used, for example, as a raw material for petrochemical products.

Therefore, mixed xylene for the raw material of petrochemicals is manufactured by demixing xylene treatment for heavy catalytic reformed gasoline, while using the heavy catalytic reformed gasoline obtained by this demixed xylene treatment, gasoline It is desired to develop a base material for

For example, Patent Document 1 relates to a technology for producing a base material used for gasoline and a raw material for petrochemical products by hydrorefining a naphtha fraction and heavy hydrocarbons obtained by atmospheric distillation of crude oil. Disclosed is a method for producing a catalytically reformed gasoline, which is characterized in that a mixed fraction with the obtained refined naphtha fraction is used as a raw material and catalytically reformed. According to this production method, it is possible to increase the production of the catalytically reformed gasoline fraction and also increase the production of aromatic hydrocarbons having 6 to 8 carbon atoms such as benzene, toluene and xylene.

On the other hand, from the viewpoint of environmental protection, the use of an oxygen-containing base material derived from biomass such as ethanol is also being considered for suppressing carbon dioxide emissions. When these oxygen-containing base materials are used as fuel, it is considered that the carbon dioxide emission into the atmosphere is small even if they are burned, because the plant is made by absorbing carbon dioxide from the atmosphere. (For example, see Non-Patent Document 1).

JP, 2008-297471, A

ANTONIO F. LOPEZ and 3 others, Latin American Research, 1990, 20, p. 183-187

However, when mixed xylene is extracted from the heavy catalytic reformed gasoline by dexylene treatment, the content of mixed xylene, which is a component that contributes to a high octane number, decreases, so the octane number of the treated heavy catalytic reformed gasoline is descend. In order to secure the octane number of the final product gasoline by using such a heavy catalytic reformed gasoline having a low octane number as a base material, a means of increasing the compounding amount of the heavy catalytic reformed gasoline as compared with the conventional method is used. Can be considered. However, when the blending amount of the heavy catalytic reformed gasoline is increased, the proportion of the heavy catalytic reformed gasoline in the final product gasoline becomes high and the heavy gasoline becomes heavy. If gasoline becomes heavier, the use of such gasoline can reduce the startability of the vehicle engine and cause smoldering of the spark plug.

Smoldering of a spark plug refers to a phenomenon that causes a so-called misfire, in which a carbonaceous substance generated by incomplete combustion of gasoline is deposited on a glass insulator of a spark plug to increase a leakage current and a spark does not fly. ..
As a result, when the phenomenon of smoldering of the spark plug occurs, the internal combustion engine (engine) cannot be started, or even if the phenomenon is light, the increase of unburned hydrocarbons in the exhaust gas, the acceleration performance, etc. It tends to cause problems such as deterioration.
It is known that smoldering of a spark plug is more likely to occur especially when the aromatic content in gasoline is large.

Therefore, the heavy catalytic reformed gasoline after dexylene treatment is used as a base material, and the desired octane number is obtained without blending at a blending amount higher than that of the conventional one, and the startability of the internal combustion engine, the accelerating ability of the vehicle, and the spark plug. Gasoline with various properties such as smoldering control is desired.

Furthermore, as mentioned above, gasoline containing an oxygen-containing base material such as ethanol is considered to emit little carbon dioxide into the atmosphere even if it is burned. Causes a significant reduction in the distillation properties, and there is a concern that the driving performance of automobiles will be adversely affected.
Therefore, even when blended with an oxygen-containing base material, gasoline having a desired octane number and having performance such as startability of an internal combustion engine, acceleration of a vehicle, suppression of smoldering of a spark plug is also desired. Be done.

The present invention has been made in view of the above situation, the octane number is maintained even if the heavy catalytic reformed gasoline after dexylene treatment is blended as a base material, and the startability of the internal combustion engine, the vehicle It is an object of the present invention to provide unleaded gasoline which is excellent in the acceleration property of the fuel cell and in suppressing the smoldering of the spark plug.

The present inventors have conducted extensive studies to achieve the above-mentioned object, and as a base material to be blended with gasoline, a light catalytic cracking gasoline having a specific composition and properties, and a dexylene treatment having a specific composition and properties. It was found that the above-mentioned problems can be solved by blending the heavy catalytic reforming gasoline obtained by the above in a specific amount, and the present invention has been completed.

That is, means for solving the above problems include the following embodiments.
<1> The light catalytic cracking gasoline base material A shown in (1) below is used in an amount of 5% to 40% by volume based on the total volume of unleaded gasoline, and the heavy catalytic reforming gasoline base material B shown in (2) below is used. Unleaded gasoline which is blended with 10% by volume to 45% by volume with respect to the total volume of unleaded gasoline and which satisfies the following (3) to (14).

(1) Light catalytic cracking gasoline base material A: 10% by volume distillation temperature is 30°C to 45°C, 50% by volume distillation temperature is 35°C to 50°C, 90% by volume distillation temperature is 55°C to 75°C. The end point is 80°C to 100°C, the density at 15°C is 0.650 g/cm ^{3 to} 0.670 g/cm ³ , and the olefin content is 40% by volume to 55% by volume with respect to the total volume of the light catalytic cracking gasoline base material A. A light catalytic cracking gasoline base material having a hydrocarbon content of 7 or more carbon atoms of 10% by volume or less based on the total capacity of the light catalytic cracking gasoline base material A.

(2) Heavy catalytic reforming gasoline base material B: The following base material b1 and the following base material b2 are included, and the mixing ratio (b1:b2) of the base material b1 and the base material b2 is 95: by volume. Heavy catalytic reforming gasoline base stock, ranging from 5 to 5:95.
The base material b1 has a 10% by volume distillation temperature of 95°C to 115°C, a 50% by volume distillation temperature of 100°C to 120°C, a 90% by volume distillation temperature of 105°C to 125°C, and an end point of 110°C to 130°C. The density at 80° C. and 15° C. is 0.840 g/cm ^{3 to} 0.860 g/cm ³ , the aromatic component having 7 carbon atoms is 70% by volume to 85% by volume and 8% carbon number with respect to the total volume of the base material b1. A heavy catalytic reforming gasoline base material having an aromatic content of 10% by volume or less with respect to the total capacity of the base material b1 and an aromatic content of 9 carbon atoms or less with respect to the total capacity of the base material b1. The base material b2 has a 10% by volume distillation temperature of 155 to 165° C., a 50% by volume distillation temperature of 160° C. to 170° C., a 90% by volume distillation temperature of 165° C. to 175° C., and an end point of 175° C. Heavy catalytic reforming with a density at 190° C. and 15° C. of 0.860 g/cm ^{3 to} 0.880 g/cm ³ and an aromatic content of 9 carbon atoms of 90% by volume or more based on the total volume of the base material b2. It is a gasoline base material.

(3) Research octane number is 93 or more and less than 98.
(4) The octane number of the motor method is 81 or more and less than 87.
(5) The density at 15° C. is 0.710 g/cm ^{3 to} 0.783 g/cm ³ .
(6) 50% by volume distillation temperature is 75°C to 110°C.
(7) The 70°C distillate amount is 18% by volume to 45% by volume with respect to the total volume of unleaded gasoline.
(8) Reed vapor pressure is 45 kPa to 93 kPa.
(9) The content of benzene is 1% by volume or less.
(10) The sulfur content is 10 mass ppm or less.
(11) The olefin content is 10% by volume to 30% by volume with respect to the total volume of unleaded gasoline.
(12) The aromatic content is 15% by volume to 45% by volume with respect to the total volume of unleaded gasoline.
(13) The aromatic content having 7 carbon atoms is 26% by volume or less based on the total capacity of the aromatic content in the unleaded gasoline.
(14) The aromatic content having 8 carbon atoms is 5% by volume or less with respect to the total capacity of the aromatic content in the unleaded gasoline.

<2> The unleaded gasoline according to <1>, further containing 1% by volume to 15% by volume of the oxygen-containing base material with respect to the total volume of the unleaded gasoline.

According to the present invention, the octane number is maintained even when the heavy catalytic reformed gasoline after dexylene treatment is blended as a base material, and the startability of the internal combustion engine, the acceleration property of the vehicle, and the smoldering suppression of the spark plug are suppressed. It is possible to provide excellent unleaded gasoline.

Hereinafter, modes for carrying out the present invention will be described in detail.
In addition, in this specification, "-" showing a numerical range represents the range containing the numerical value each described as the upper limit and the lower limit. Moreover, in the numerical range represented by "-", when a unit is described only in the upper limit value, it means that the lower limit value is also in the same unit.
In the present specification, the ratio or amount of each component in gasoline refers to the ratio of the total of the plurality of substances present in gasoline, unless there are plural types of substances corresponding to each component in gasoline. Or, means the amount.
In the present specification, the “aromatic content” of gasoline includes monocyclic or polycyclic aromatic hydrocarbons other than benzene, which may have a hetero atom in the structure.

《Unleaded gasoline》
In the unleaded gasoline of the present invention, at least a light catalytic cracking gasoline base material A (hereinafter also simply referred to as “light catalytic cracking gasoline base material A”) showing the following (1) is 5 volumes with respect to the total capacity of the unleaded gasoline. % To 40% by volume of the heavy catalytic reforming gasoline base material B shown in (2) below (hereinafter also simply referred to as "heavy catalytic reforming gasoline base material B") with respect to the total capacity of unleaded gasoline. And 10% by volume to 45% by volume.

Since the unleaded gasoline of the present invention has the above configuration, the octane number is maintained even when the heavy catalytic reformed gasoline after dexylene treatment is blended as a base material, and the startability of the internal combustion engine and the acceleration of the vehicle are accelerated. Excellent in suppressing smoldering of spark plugs.
Further, the unleaded gasoline of the present invention maintains an octane number even when an oxygen-containing base material is blended, and is excellent in startability of an internal combustion engine, acceleration of a vehicle, and suppression of smoldering of a spark plug. It can be expected to maintain the atmospheric environment while maintaining the practical performance required for driving.

(1) Light catalytic cracking gasoline base material A: 10% by volume distillation temperature is 30°C to 45°C, 50% by volume distillation temperature is 35°C to 50°C, 90% by volume distillation temperature is 55°C to 75°C. The end point is 80°C to 100°C, the density at 15°C is 0.650 g/cm ^{3 to} 0.670 g/cm ³ , and the olefin content is 40% by volume to 55% by volume with respect to the total volume of the light catalytic cracking gasoline base material A. A light catalytic cracking gasoline base material having a hydrocarbon content of 7 or more carbon atoms is 10% by volume or less based on the total capacity of the light catalytic cracking gasoline base material A.

(2) The heavy catalytic reforming gasoline base material B includes the following base material b1 and the following base material b2, and the mixing ratio (b1:b2) of the base material b1 and the base material b2 is 95 by volume. A heavy catalytic reforming gasoline base material in the range of 5:5:95.
The base material b1 has a 10% by volume distillation temperature of 95°C to 115°C, a 50% by volume distillation temperature of 100°C to 120°C, a 90% by volume distillation temperature of 105°C to 125°C, and an end point of 110°C to 130°C. The density at 80° C. and 15° C. is 0.840 g/cm ^{3 to} 0.860 g/cm ³ , the aromatic component having 7 carbon atoms is 70% by volume to 85% by volume and 8% carbon number with respect to the total volume of the base material b1. A heavy catalytic reforming gasoline base material having an aromatic content of 10% by volume or less with respect to the total capacity of the base material b1 and an aromatic content of 9 carbon atoms or less with respect to the total capacity of the base material b1. The base material b2 has a 10% by volume distillation temperature of 155 to 165°C, a 50% by volume distillation temperature of 160°C to 170°C, a 90% by volume distillation temperature of 165°C to 175°C, and an end point of 175 to 190°C. Heavy catalytic reforming gasoline group having a density of 0.860 g/cm ³ to 0.880 g/cm ^{3 at} 15° C. and 15° C. and an aromatic content of 9 carbon atoms of 90% by volume or more based on the total volume of the base material b2. It is a material.

The light catalytic cracking gasoline base material A is a base material composed of light catalytic cracking gasoline distilled from a fluid catalytic cracking apparatus, and the heavy catalytic reforming gasoline base material B is a catalytic reforming apparatus distilled from a catalytic reforming apparatus. It is a base material made of gasoline. The unleaded gasoline of the present invention contains these light catalytic cracking gasoline base material A and heavy catalytic reforming gasoline base material B as essential base materials.
Hereinafter, the unleaded gasoline of the present invention will be described in detail.

The unleaded gasoline of the present invention preferably contains a light catalytic cracking gasoline base material A distilled from a fluid catalytic cracking unit and a heavy catalytic reforming gasoline base material B distilled from a catalytic reforming unit. Hereinafter, each component contained in the unleaded gasoline of the present invention will be described below.

<Light catalytic cracking gasoline base material A>
The light catalytic cracking gasoline base material A is a base material composed of light catalytic cracking gasoline distilled from a fluid catalytic cracking apparatus, and has the specific composition and properties shown in (1) above.

Light catalytic cracking gasoline is a catalytic cracking gasoline obtained by decomposing a petroleum fraction (preferably heavy gas oil or vacuum gas oil) such as kerosene or light oil, atmospheric residual oil with a solid acid catalyst by a fluid catalytic cracking method. What is obtained by distilling is mentioned.

The fluidized catalytic cracking method is a method for producing catalytically cracked gasoline from heavy hydrocarbons, and known publicly known methods can be used. Examples of the fluid catalytic cracking method include UOP method, shell two-step method, flexi cracking method, ultra orthoflow method, Texaco method, Gulf method, ultracat cracking method, RCC method, HOC method and the like.

More specifically, the fluid catalytic cracking method is a process in which a fluid catalyst and a hydrocarbon oil are brought into contact with each other at a high temperature to obtain gasoline, middle distillates and the like. For the fluid catalytic cracking method, for example, the FCC (Fluid Catalytic Cracking) process described on pages 107 to 110 of HYDROCARBON PROCESSING/NOVEMBER 2000 can be referred to.

Light catalytic cracking gasoline uses the above FCC process to convert hydrocarbon oil (hydrocarbon mixture) boiling above the boiling point of gasoline into a solid acid catalyst such as zeolite, silica-alumina, or alumina (so-called solid acid catalyst). May be contacted at high temperature with.

The FCC process on a commercial scale usually involves continuously circulating an FCC catalyst (solid acid catalyst) inside an FCC unit consisting of two vessels, a vertically installed cracking reactor and a catalyst regenerator. , Carry out catalytic decomposition. That is, the hot regenerated catalyst emerging from the catalyst regenerator is mixed with the hydrocarbon oil and directed upward in the cracking reactor. As a result, the solid acid catalyst is deactivated by the carbon (coke) deposited on the catalyst, separated from the decomposition products, further stripped, and then sent to the catalyst regenerator to be regenerated. The regenerated catalyst is supplied to the cracking reactor again and used.
On the other hand, the decomposition products are separated by distillation into one or more heavy fractions such as dry gas, liquefied petroleum gas (LPG), gasoline fraction, light cycle oil (LCO), heavy cycle oil (HCO) and slurry oil. .. Some or all of these decomposition products may be recycled into the cracking reactor to further advance the decomposition reaction.

In the gasoline of the present invention, of the fractions separated from the products cracked by the FCC process, the light gasoline fraction obtained by distilling the gasoline fraction may be used as the light catalytic cracking gasoline.

Examples of heavy hydrocarbons (hereinafter, also referred to as “raw hydrocarbons”) that are raw materials used to obtain the light catalytic cracking gasoline base material A include hydrocarbon mixtures that boil above the boiling point of gasoline.
In the present specification, the hydrocarbon mixture boiling above the boiling point of gasoline means a gas oil fraction obtained by distilling crude oil under atmospheric pressure or vacuum distillation, atmospheric pressure distillation residual oil and vacuum distillation residual oil, and the like, coker gas oil, Solvent deasphalted oil, solvent deasphalted asphalt, tar sand oil, shale oil oil, coal liquefied oil and the like are also included.
Furthermore, the raw material hydrocarbon is a known hydrotreating agent, for example, in the presence of a hydrotreating catalyst such as a Ni—Mo based catalyst, a Co—Mo based catalyst, a Ni—Co—Mo based catalyst, a Ni—W based catalyst, It may be a hydrotreated oil hydrodesulfurized under high temperature and high pressure, and the hydrotreated oil may be used in a FCC process as a raw hydrocarbon oil.

In the FCC apparatus used in the FCC process, the operating conditions of the cracking reactor are a temperature of 400° C. to 600° C., preferably 450° C. to 550° C., and a pressure of atmospheric pressure to 5 kg/cm ³ , preferably atmospheric pressure. a ~3kg / cm ^3, the compounding ratio of the catalyst and the raw material hydrocarbon oil (catalyst / feedstock hydrocarbon oil), by weight, 2 to 20, preferably preferably has 4 to 15.

When the reaction temperature of the cracking reactor is 400° C. or higher, the progress of the cracking reaction of the raw hydrocarbon oil is promoted, and the amount of the cracked product obtained tends to be improved. Further, when the reaction temperature is 600° C. or lower, an appropriate amount of olefin content tends to be obtained, and a desired octane number can be secured.
When the pressure is 5 kg/cm ³ or less, it is possible to suppress the increase in the number of moles due to the decomposition reaction, and it is possible to prevent the progress of the decomposition reaction from decreasing. Further, when the mixing ratio of the catalyst and the feedstock hydrocarbon oil (catalyst/feedstock hydrocarbon oil) is 2 or more, the catalyst concentration in the cracking reactor does not become too low, and the progress of the feedstock oil decomposition is prevented from decreasing. Is possible. Further, when the compounding ratio is 20 or less, the effect of the catalyst can be effectively exhibited.

The distillation properties of the light catalytic cracking gasoline base material A are as follows: 10% by volume distillation temperature (T10) is 30°C to 45°C, 50% by volume distillation temperature (T50) is 35°C to 50°C, 90% by volume distillation temperature. (T90) is 55°C to 75°C, and the end point (EP) is 80°C to 100°C.
When the 10% by volume distillation temperature, 50% by volume distillation temperature, 90% by volume distillation temperature and end point of the light catalytic cracking gasoline base material A are within the above ranges, the octane number of the light catalytic cracking gasoline base material A is kept high. It becomes possible to efficiently produce unleaded gasoline having a high octane number. Furthermore, the unleaded gasoline of the present invention produced using the light catalytic cracking gasoline base material A tends to have excellent driving performance and engine cleanliness.
From the above viewpoint, the light catalytic cracking gasoline base material A preferably has a 10% by volume distillation temperature of 33°C to 44°C, a 50% by volume distillation temperature of 38°C to 50°C, and a 90% by volume distillation temperature of 90% by volume. 58° C. to 73° C., end point is 85° C. to 100° C., more preferably 10% by volume distillation temperature is 35° C. to 43° C., 50% by volume distillation temperature is 40° C. to 50° C., 90% by volume distillation The temperature is 60°C to 70°C, and the end point is 90°C to 100°C.
In addition, the said distillation property means the value measured based on JISK2254(1998).

The research method octane number of the light catalytic cracking gasoline base material A is preferably 92 or more, more preferably 93 or more, and further preferably 94 or more.
When the research octane number is 92 or more, the blending amount of the heavy catalytic reforming gasoline base material B can be suppressed, so that the product gasoline satisfying the standard can be easily prepared.
The research octane number is a value measured according to JIS K 2280-1 (2013).

The density of the light catalytic cracking gasoline base material A at 15° C. is 0.650 g/cm ^{3 to} 0.670 g/cm ³ .
When the density is within the above range, it is possible to suppress the lightening of the unleaded gasoline of the present invention.
From the above viewpoint, the density is preferably ^{0.653g / cm 3 ~0.670g / cm 3} , more preferably at ^{0.655g / cm 3 ~0.670g / cm 3} .
In addition, the said density means the value measured based on JISK2249(2011).

The olefin content of the light catalytic cracking gasoline base material A is 40% by volume to 55% by volume, preferably 40% by volume to 53% by volume, and more preferably 40% by volume, based on the total capacity of the light catalytic cracking gasoline base material A. It is from 50% by volume to 50% by volume.
When the olefin content of the light catalytic cracking gasoline base material A is within the above range, the octane number of the light catalytic cracking gasoline base material A can be maintained at a high level.
The olefin content means the total (volume %) of the olefin content measured by the Japan Petroleum Institute method JPI-5S-33-90 (gas chromatograph method) and contained in the light catalytic cracking gasoline base material A.

The hydrocarbon content having 7 or more carbon atoms in the light catalytic cracking gasoline base material A is 10% by volume or less with respect to the total capacity of the light catalytic cracking gasoline base material A.
When the content of the hydrocarbon component having 7 or more carbon atoms is 10% by volume or less, the octane number tends to be improved. From the above viewpoint, the hydrocarbon content having 7 or more carbon atoms is preferably 9% by volume or less, more preferably 8% by volume or less.

In the light catalytic cracking gasoline base material A, the hydrocarbon content having 5 carbon atoms is preferably 68% by volume or less, more preferably 65% by volume or less, based on the total capacity of the light catalytic cracking gasoline base material A. The lower limit is preferably 63% by volume.
Further, the hydrocarbon content having 6 carbon atoms in the light catalytic cracking gasoline base material A is preferably 45% by volume or less, more preferably 43% by volume or less, based on the total capacity of the light catalytic cracking gasoline base material A. The lower limit is preferably 40% by volume.
From the viewpoint of maintaining the octane number, the light catalytic cracking gasoline base material A has a hydrocarbon content of 5 carbon atoms of 68% by volume or less, a hydrocarbon content of 6 carbon atoms of 45% by volume or less, and a hydrocarbon content of 7 or more carbon atoms. Is particularly preferably 10% by volume or less.
In addition, the content of the hydrocarbon component of each carbon number means a value measured according to the Japan Petroleum Institute method JPI-5S-33-90 (gas chromatograph method).

<Heavy catalytic reforming gasoline base material B>
The heavy catalytic reforming gasoline base material B is a base material composed of heavy catalytic reforming gasoline that is distilled from the catalytic reforming apparatus, and includes a base material b1 and a base material b2 described later, and the above-mentioned ( It has a specific composition and properties shown in 2).
The heavy catalytic reforming gasoline base material B includes a heavy catalytic reforming gasoline base material b1 and a heavy catalytic reforming gasoline base material b2 described later.

The heavy catalytic reformed gasoline is a known catalytic reforming oil obtained from a catalytic reforming apparatus, and is subjected to a known debenzene treatment. It is a distillate that distills when the xylene treatment is performed. Suitable operating conditions of the catalytic reformer will be described later.

The base material b1 is a fraction containing, as a main component, an aromatic component having a carbon number of 7 among the fractions distilled when the dexylene treatment is performed, and the base material b2 is an aromatic component having a carbon number of 9. Is a main component, and a mixture of these base materials b1 and b2 with a predetermined gasoline is a heavy catalytic reforming gasoline base material B.

The fraction having a carbon number 7 aromatic component as a main component constituting the base material b1 and the fraction having a carbon number 9 aromatic component as a main component constituting the base material b2 are, for example, catalytic reforming. The oil is fractionated into a light catalytic reformed oil fraction, a crude benzene fraction and a heavy catalytic reformed oil fraction by a distillation method, and the obtained heavy catalytic reformed oil fraction is further distilled. Alternatively, it can be obtained by fractional distillation into an aromatic fraction having 7 carbon atoms, a xylene fraction and an aromatic fraction having 9 carbon atoms by a method such as an extraction method.

Heavy catalytic reforming gasoline can be produced by catalytic reforming of heavy straight run naphtha (eg, platform forming method, magna forming method, aromatizing method, reniforming method, hood reforming method, ultra forming method, power forming method). Method, etc.) and contact treatment with a catalyst at high temperature and pressure in a steam flow. Various catalysts can be used as the catalyst used in the catalytic reforming reaction, and a platinum/alumina-based catalyst (for example, a platinum content of 0.2% by mass to 0.8% by mass) is preferably used. be able to. The platinum/alumina-based catalyst may further contain rhenium, germanium, tin, iridium and the like.

The catalytic reforming device is not particularly limited and may be a device to which any method such as a fixed bed semi-regeneration type, a cyclic type and a continuous regeneration type is applied.

When the catalytic reformer is a fixed bed semi-regeneration type, the operating conditions of the catalytic reformer are: reaction temperature: 470° C. to 540° C., reaction pressure: 1 MPa to 3.5 MPa, hydrogen oil ratio: 76 NL/L to 3000 NL. / L, LHSV (liquid Hourly space velocity; liquid hourly space ^velocity): is preferably 1h is ^-1 ~4h -1.
When the reaction temperature is 470° C. or higher, the octane number of the obtained catalytically modified oil tends to be improved. When the reaction temperature is 540° C. or lower, there is a tendency that hydrogenolysis progresses to suppress a decrease in liquid yield and also a decrease in catalyst activity due to generation of coke. When the reaction pressure is 1 MPa or more, it becomes possible to suppress the production of coke. When the reaction pressure is 3.5 MPa, it is possible to obtain a catalytically reformed oil having a high octane number without suppressing the dehydrocyclization reaction.

When the catalytic reformer is a continuous regeneration type, the operating conditions of the catalytic reformer are: reaction temperature: 510° C. to 530° C., reaction pressure: 0.35 MPa to 1 MPa, hydrogen oil ratio: 140 NL/L to 530 NL/L. , ^LHSV: is preferably 1h is ^-1 ~4h -1.
When the reaction temperature is 510° C. or higher, it becomes possible to improve the octane number of the obtained catalytically reformed oil. Further, when the reaction temperature is 530° C. or lower, there is a tendency that the hydrogenolysis progresses to suppress the decrease in the liquid yield and the decrease in the catalytic activity due to the formation of coke.
When the reaction pressure is 0.35 MPa or more, it becomes possible to suppress the production of coke. When the reaction pressure is 1 MPa or less, it is possible to obtain a catalytic reforming treated oil having a high octane number without suppressing the dehydrocyclization reaction.

The base materials b1 and b2 included in the heavy catalytic reforming gasoline base material B will be described below.

(Base material b1)
The distillation properties of the base material b1 are as follows: 10% by volume distillation temperature (T10) is 95°C to 115°C, 50% by volume distillation temperature (T50) is 100°C to 120°C, and 90% by volume distillation temperature (T90). 105°C to 125°C, and the end point (EP) is 110°C to 130°C.
When the 10% by volume distillation temperature, the 50% by volume distillation temperature, the 90% by volume distillation temperature, and the end point of the base material b1 are within the above ranges, the operability is maintained and the harmful components in the exhaust gas are removed. It is possible to prevent increase and deterioration of engine cleanliness.
From the above viewpoint, the substrate b1 preferably has a 10% by volume distillation temperature of 85°C to 125°C, a 50% by volume distillation temperature of 90°C to 130°C, and a 90% by volume distillation temperature of 95°C to 135°C. C., more preferably, 10% by volume distillation temperature is 95.degree. C. to 105.degree. C., 50% by volume distillation temperature is 100.degree. C. to 110.degree. C., and 90% by volume distillation temperature is 105.degree.
The above-mentioned distillation properties are values measured according to JIS K 2254 (1998).

The heavy catalytically reformed gasoline base material b1 preferably has a research octane number of 103 or more. When the research method octane number is 103 or more, the blending amount of the heavy catalytic reforming gasoline B described later can be suppressed, and the product gasoline satisfying the standard can be easily adjusted.
From the above viewpoint, the octane number by the research method of the heavy catalytic reforming gasoline base material b1 is preferably 104 or more, more preferably 105 or more.
The research octane number means a value measured according to JIS K 2280-1 (2013).

The density of the heavy catalytic reforming gasoline base material b1 at 15° C. is 0.840 g/cm ^{3 to} 0.860 g/cm ³ . When the density is within the above range, it is possible to prevent the unleaded gasoline of the present invention from being lightened and to prevent changes in distillation properties.
From the above viewpoint, the density is preferably 0.840 g/cm ^{3 to} 0.850 g/cm ³ , and more preferably 0.840 g/cm ^{3 to} 0.845 g/cm ³ .
In addition, this density means the value measured based on JISK2249-4 (2011).

In the base material b1, the aromatic content having 7 carbon atoms is 70% by volume to 85% by volume with respect to the total capacity of the base material b1, the aromatic content having 8 carbon atoms is 10% by volume or less, and The aromatic content having 9 carbon atoms is 5% by volume or less.
When the aromatic content having 7 carbon atoms, the aromatic content having 8 carbon atoms and the aromatic content having 9 carbon atoms in the base material b1 are within the above ranges, deterioration of the smoldering property is prevented while maintaining the driving performance. However, it is possible to prevent an increase in the amount of deposits in the engine and to suppress an increase in harmful components in the exhaust gas.
From the above viewpoint, the aromatic content having 7 carbon atoms is preferably 75% by volume to 85% by volume, more preferably 80% by volume to 85% by volume or less, and has 8 carbon atoms based on the total volume of the base material b1. The aromatic content is preferably 5% by volume or less, more preferably 3% by volume or less, and the aromatic content having 9 carbon atoms is preferably 4% by volume or less, more preferably 3% by volume or less.
In addition, the aromatic content of each carbon number means a value measured according to JIS K 2536-2 (2003).

(Base material b2)
The distillation properties of the base material b2 are as follows: 10% by volume distillation temperature (T10) is 155°C to 165°C, 50% by volume distillation temperature (T50) is 160°C to 170°C, and 90% by volume distillation temperature (T90) is. 165°C to 175°C, and the end point (EP) is 175°C to 190°C.
When the 10% by volume distillation temperature, the 50% by volume distillation temperature, the 90% by volume distillation temperature and the end point are within the above ranges, it is possible to prevent the heavy catalytic reforming gasoline base material B from becoming heavy. Become. Therefore, it is possible to prevent the increase of harmful components in the exhaust gas and the deterioration of the engine cleanliness while maintaining the driving performance such as the startability of the internal combustion engine and the acceleration of the vehicle.
From the above viewpoint, as the distillation property of the base material b2, the 10 vol% distillation temperature is 157° C. to 165° C., the 50 vol% distillation temperature is 160° C. to 168° C., and the 90 vol% distillation temperature is 165° C. to 173° C. ℃, the end point is preferably 180 ℃ ~ 190 ℃, 10 vol% distillation temperature 160 ℃ 165 ℃, 50 vol% distillation temperature 162 ℃ 165 ℃, 90 vol% distillation temperature 165 ℃. It is more preferable that the temperature is ˜170° C. and the end point is 183° C. to 188° C.
The above distillation properties are values measured according to JIS K 2254 (1998).

The density of the base material b2 at 15° C. is 0.860 g/cm ^{3 to} 0.880 g/cm ³ .
When the density of the base material b2 is within the above range, it becomes possible to suppress the unleaded gasoline of the present invention from becoming lighter and from being distorted due to distillation properties.
From the above viewpoint, the density is preferably ^{0.865g / cm 3 ~0.880g / cm 3} , more preferably at ^{0.870g / cm 3 ~0.880g / cm 3} .
In addition, this density means the value measured based on Japan Petroleum Institute method JPI-5S-33-90 (gas chromatograph method).

In the base material b2, the aromatic content having 9 carbon atoms is 90% by volume or more with respect to the total capacity of the base material b2.
When the aromatic content having 9 carbon atoms is within the above range, deterioration of smolderability is prevented, an increase in the amount of deposits in the engine is prevented, and the exhaust gas in the exhaust gas is maintained while maintaining the driving performance. It is possible to suppress an increase in harmful components.
From the above viewpoint, the aromatic content having 9 carbon atoms is preferably 91% by volume or more, more preferably 94% by volume or more.
In addition, the aromatic content of each carbon number means a value measured according to the Japan Petroleum Institute method JPI-5S-33-90 (gas chromatograph method).

<Amount and ratio of gasoline base material>
In the unleaded gasoline of the present invention, the content of the light catalytic cracking gasoline base material A is 5% by volume to 40% by volume, preferably 10% by volume to 40% by volume, and more preferably, the total volume of the unleaded gasoline. It is 13% by volume to 40% by volume.
The content of the heavy catalytic reforming gasoline base material B is 5% by volume to 45% by volume, preferably 20 to 53% by volume, more preferably 23 to 52% by volume, based on the total volume of unleaded gasoline. is there.
The blending ratio (b1:b2) of the base material b1 and the base material b2 in the heavy catalytic reforming gasoline base material B is 95:5 to 5:95 on a volume basis, and preferably 90:10 to 10:. 90, more preferably 80:20 to 10:90.

In the unleaded gasoline of the present invention, the blending amount and blending ratio of the light catalytic cracking gasoline base material A and the heavy catalytic reforming gasoline base material B are within the above ranges, so that the operating performance is maintained and the exhaust gas It is possible to prevent an increase in harmful components and deterioration of engine cleanliness. Further, it becomes possible to prevent deterioration of the oxidation stability of unleaded gasoline.

<Oxygen-containing substrate>
The unleaded gasoline of the present invention may further include an oxygen-containing base material in addition to the light catalytic cracking gasoline base material A and the heavy catalytic reforming gasoline base material B. When the unleaded gasoline of the present invention contains an oxygen-containing base material, the octane number of the unleaded gasoline of the present invention can be further improved.

Examples of the oxygen-containing compound applied as the oxygen-containing base material include alcohols such as methanol and ethanol, and ethers or esters that are derivatives from alcohols.
From the viewpoints of reducing carbon dioxide emissions and environmental protection, the oxygen-containing compound is preferably a biomass-derived alcohol, or an ether or ester that is a derivative of the alcohol.

The oxygen-containing compound is preferably an alcohol having 2 to 5 carbon atoms, an ether having 4 to 8 carbon atoms, or an ester having 4 to 8 carbon atoms, and an alcohol having 2 to 5 carbon atoms or an ester having 4 to 8 carbon atoms. Ether is more preferable, and ether having 4 to 8 carbon atoms is further preferable.

Examples of the alcohol having 2 to 5 carbon atoms include ethanol, propyl alcohol and butyl alcohol.
Further, as ethers and esters which are derivatives from alcohols, ethers having 4 to 8 carbon atoms include ethyl isopropyl ether, ethyl tert-butyl ether (ETBE), ethyl secondary butyl ether (ESBE), diisopropyl ether, and tert-ether. Liamyl ethyl ether (TAEE) may be mentioned.

Examples of the ester having 4 to 8 carbon atoms include ethyl acetate and ethyl propionate.

Of these, ethyl tertiary butyl ether (ETBE) is preferable as the oxygen-containing compound from the viewpoint of reducing carbon dioxide emissions and environmental protection.

When the unleaded gasoline of the present invention contains an oxygen-containing compound, the blending amount of the oxygen-containing compound is preferably 1% by volume to 15% by volume based on the total volume of the unleaded gasoline. When the blending amount of the oxygen-containing compound is within the above range, there is little concern that fuel consumption will be adversely affected by a decrease in calorific value, and reduction of carbon monoxide (CO), total hydrocarbons (THC), etc. in exhaust gas can be achieved. It is possible to plan.
From the above viewpoint, the blending amount of the oxygen-containing compound is preferably 3% by volume to 13% by volume, more preferably 5% by volume to 12% by volume.

The unleaded gasoline of the present invention contains a base material other than the light catalytic cracking gasoline base material A, the heavy catalytic reforming gasoline base material B and the oxygen-containing base material (hereinafter, also referred to as "other base material"). Good. Examples of other base materials include the following components (a) to (d).

(A) Desulfurized light naphtha, which is a light fraction obtained by distilling the desulfurized straight-distilled naphtha obtained by desulfurizing the straight-distilled naphtha obtained by distilling crude oil under atmospheric pressure by distillation ( b) Alkylate (c) obtained by reacting isobutane with a lower olefin (butene, propylene, etc.) as a raw material in the presence of an acid catalyst (sulfuric acid, hydrogen fluoride, aluminum chloride, etc.) (c) Crude oil, crude oil, etc. Obtained by isomerization of a C4 fraction (d) straight-chain lower paraffinic hydrocarbon mainly composed of butane and butene obtained by distillation during pressure distillation, reformed gasoline production or cracked gasoline production Isopentane obtained by precision distillation of isomerate or isomerate

The unleaded gasoline of the present invention may contain a detergent such as polyetheramine, polyalkylamine, polyisobuteneamine, and succinimide.
When the unleaded gasoline of the present invention contains a detergent, the added amount of the detergent is preferably in the range of 50 mass ppm to 1000 mass ppm with respect to the total mass of the unleaded gasoline.
When the added amount of the detergent is 50 mass ppm or more, it becomes possible to prevent the intake valve deposit from increasing. Further, when the added amount is 1000 mass ppm or less, it becomes possible to prevent an increase in the combustion chamber deposit. When the unleaded gasoline of the present invention contains the detergent in the above-mentioned range, the effect of suppressing the formation of the in-engine deposit by the application of the heavy catalytic reforming gasoline B is effectively suppressed. Is possible.
From the above viewpoint, the amount of the detergent added is preferably 100 mass ppm to 500 mass ppm.

The unleaded gasoline of the present invention may further contain various additives as required.
Examples of the additives include phenol-based and amine-based antioxidants, metal deactivators such as thioamide compounds, surface ignition inhibitors such as organophosphorus compounds, antifreeze agents such as polyhydric alcohols and ethers thereof, and organic acids. Alkali metal and alkaline earth metal salts, combustion improvers such as sulfuric acid esters of higher alcohols, anionic surfactants, cationic surfactants, antistatic agents such as amphoteric surfactants, rust preventives such as alkenyl succinic acid esters , And known fuel additives such as colorants such as azo dyes.
The additives may be used alone or in combination of two or more.
The amount of the fuel additive added is arbitrary, and normally, the total amount of the fuel additives added is preferably 0.1% by mass or less based on the total mass of the unleaded gasoline.

The method for producing the unleaded gasoline of the present invention is not particularly limited and can be prepared by a known method. As the method for producing unleaded gasoline of the present invention, for example, the specific light catalytic cracking gasoline is used in an amount of 5% to 40% by volume with respect to the total volume of unleaded gasoline, and the heavy catalytic reformed gasoline C is used in the entire amount of unleaded gasoline. On the other hand, 10% by volume to 45% by volume may be blended so as to satisfy the following (3) to (14).

<Properties of unleaded gasoline>
As described above, the unleaded gasoline of the present invention contains the light catalytic reforming gasoline base material A shown in (1) in an amount of 5% to 40% by volume based on the total volume of unleaded gasoline, and the heavy gasoline shown in (2). The catalytic reforming gasoline base material B is blended with 10% by volume to 45% by volume with respect to the total volume of unleaded gasoline, and satisfies (3) to (14).
The properties of unleaded gasoline will be described below.

(3) Research method octane number (RON)
The unleaded gasoline of the present invention has a research octane number (RON) of 93 or more and less than 98. When the research method octane number is 93 or more, knocking can be suppressed and high driving performance can be maintained.
From the above viewpoint, the research octane number is preferably 94 to 98.
The research method octane number means a value measured according to JIS K 2280-1 (2013).

(4) Motor method octane number (MON)
The unleaded gasoline of the present invention has a motor octane number (MON) of 81 or more and less than 87.
When the octane number by the motor method is 81 or more, it is possible to prevent the antiknock property from deteriorating during high speed running.
From the above viewpoint, the octane number by the motor method is preferably 81.5 or more and less than 87.
The motor method octane number means a value measured according to JIS K 2280-2 (2013).

(5) Density The unleaded gasoline of the present invention has a density at 15° C. of 0.710 g/cm ^{3 to} 0.783 g/cm ³ .
When the density is 0.710 g/cm ³ or more, good fuel economy can be secured. If the density is 0.783 g/cm ³ or less, the high-density aromatic component tends to be reduced, and the amount of the aromatic compound discharged to the atmosphere by the exhaust gas can be reduced.
From the above viewpoint, the density is preferably 0.710 g/cm ^{3 to} 0.770 g/cm ³ .
The density is a value measured according to JIS K 2249-4 (2011).

(6) 50% by volume distillation temperature and (7) 70°C distillation amount The unleaded gasoline of the present invention has a 50% by volume distillation temperature (T50) of 75°C to 110°C.
Further, the unleaded gasoline of the present invention has a 70° C. distillate amount (E70) of 18% by volume to 45% by volume with respect to the total capacity of the unleaded gasoline.
When the 50% by volume distillation temperature and the 70° C. distillation amount are within the above ranges, there is a tendency to prevent problems relating to operating performance such as startability and acceleration.
From the above viewpoint, the 50% by volume distillation temperature is preferably 75°C to 105°C.
From the same viewpoint, the 70° C. distillation amount (E70) is preferably 20% by volume to 45% by volume.
The 50% by volume distillation temperature and 70° C. distillation amount are values measured according to JIS K 2254 (1998).

(8) Reid vapor pressure (RVP)
The unleaded gasoline of the present invention has a Reid Vapor Pressure (RVP) of 45 kPa to 93 kPa.
When the Reid vapor pressure is 45 kPa or more, it is possible to prevent the low temperature startability and the deterioration of the warm air property. Further, if the Reid vapor pressure is 93 kPa or less, the amount of vaporized gas can be reduced.
From the above viewpoint, the Reid vapor pressure is preferably 50 kPa to 90 kPa.
The Reed vapor pressure means a value measured according to JIS K 2258-1 (2009).

(9) Content of benzene In the unleaded gasoline of the present invention, the content of benzene is 1% by volume or less with respect to the total capacity of the unleaded gasoline. When the content of benzene is 1% by volume or less, an increase in the concentration of benzene in the atmosphere tends to be suppressed, and it becomes possible to reduce environmental pollution.
From the above viewpoint, the content of benzene is preferably 0.8% by volume or less.
In addition, the content of benzene means the total (volume %) of the content of benzene in unleaded gasoline measured according to the Japan Petroleum Institute method JPI-5S-33-90 (gas chromatograph method).

(10) Sulfur content In the unleaded gasoline of the present invention, the sulfur content is 10 mass ppm or less based on the total mass of the unleaded gasoline.
When the sulfur content is 10 mass ppm or less, the ability of the exhaust gas purifying catalyst tends to be suppressed from deteriorating, and nitrogen oxides (NOx), carbon monoxide (CO), and total hydrocarbons (THC) in the exhaust gas may be suppressed. It is possible to suppress an increase in concentration.
From the above viewpoint, the sulfur content is preferably 8 mass ppm or less.
The above sulfur content is the total sulfur content in unleaded gasoline (capacity measured according to JIS K 2541-6 (2003) "Crude oil and petroleum products-Sulfur content test method Part 6: UV fluorescence method" %) is meant.

(11) Olefin content In the unleaded gasoline of the present invention, the olefin content is 10% by volume to 30% by volume based on the total volume of the unleaded gasoline.
When the olefin content is 10% by volume to 30% by volume, it becomes possible to prevent deterioration of oxidation stability. From the above viewpoint, the olefin content is preferably 12% by volume to 28% by volume.
The olefin content means the total (volume %) of the olefin content in unleaded gasoline measured according to JPI-5S-33-90 (Gas Chromatograph Method) of Japan Petroleum Institute.

(12) Aromatic content In the unleaded gasoline of the present invention, the aromatic content is 15% by volume to 45% by volume with respect to the total capacity of the unleaded gasoline. When the aromatic content is 45% by volume or less, it becomes possible to prevent the harmful components contained in the exhaust gas from increasing.
From the above viewpoint, the aromatic content is preferably 20 to 45% by volume.
The aromatic content means the total amount (volume %) of the aromatic content in unleaded gasoline measured according to JPI-5S-33-90 (Gas Chromatograph Method) of the Japan Petroleum Institute.

(13) Aromatic component having 7 carbon atoms In the unleaded gasoline of the present invention, the aromatic component having 7 carbon atoms is 26% by volume or less based on the total amount of the aromatic content in the unleaded gasoline. When the aromatic content having 7 carbon atoms is 26% by volume or less, the production of mixed xylene can be increased.
From the above viewpoint, the aromatic content having 7 carbon atoms is preferably 24% by volume.
In addition, this C7 aromatic content is the total of the C7 aromatic content in unleaded gasoline measured according to the Japan Petroleum Institute method JPI-5S-33-90 (gas chromatograph method) (capacity %) is meant.

(14) Aromatic Component Having 8 Carbons In the unleaded gasoline of the present invention, the aromatic content having 8 carbons is 5% by volume or less based on the total amount of the aromatic content in the unleaded gasoline. When the aromatic component having 8 carbon atoms is 5% by volume or less, it is possible to increase the production of mixed xylene.
From the above viewpoint, the aromatic content having 8 carbon atoms is preferably 4% by volume.
In addition, this C8 aromatic content is the total of the C8 aromatic content in unleaded gasoline (capacity measured according to the Japan Petroleum Institute method JPI-5S-33-90 (gas chromatograph method). %) is meant.

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.

(Examples 1 to 12, Comparative Examples 1 to 10)
Heavy catalytic reforming gasoline base materials (b1 and b2), light catalytic cracking gasoline base materials (A1, A2 and C) and other base materials (alkylate, desulfurization catalytic cracking gasoline, desulfurization light) having the properties shown in Table 1 Using naphtha and C4 fraction), unleaded gasoline having the properties shown in Tables 3 and 4 was obtained.

The heavy catalytic reforming gasoline base materials B1 to B5 shown in Tables 3 and 4 are mixed base materials obtained by blending the heavy catalytic reforming gasoline base materials b1 and b2 shown in Table 1 at the compounding ratio shown in Table 2. Yes, it is a heavy catalytic reforming gasoline base material included in the heavy catalytic reforming gasoline base material B described above.
The heavy catalytic reforming gasoline base materials b1 and b2 are base materials included in the base materials b1 and b2 described above, respectively.
The light catalytic cracking gasoline base materials A1 and A2 are both base materials included in the heavy catalytic reforming gasoline base material A described above.
The light catalytic cracking gasoline base material C is a base material outside the range of the light catalytic cracking gasoline base material A described above.

The properties of the heavy catalytic reforming gasoline base material, the light catalytic cracking gasoline base material, the alkylate, the desulfurization catalytic cracking gasoline, the desulfurization light naphtha, the C4 fraction and the unleaded gasoline are based on the above-mentioned test method and measurement method. Was measured.
In addition, "-" in Table 1, Table 3, and Table 4 shows that the corresponding component is not included.

In Table 1, the proportions (volume %) of the olefin content and the aromatic content are based on the total capacity of the gasoline base material.
The proportions (volume %) of the C5 hydrocarbon content, the C6 hydrocarbon content, and the C7 or higher hydrocarbon content are all based on the total capacity of the gasoline base material.
C6 aromatic content, C7 aromatic content, C8 aromatic content, C9 aromatic content, C10 aromatic content, C11 aromatic content, C12 aromatic content, and C13 or higher aromatic content ratio (volume %) is Is based on the total volume of gasoline base material.

The abbreviations in Table 4 are as follows.
・ETBE: Ethyl tertiary butyl ether (oxygen-containing base material)

In Tables 3 and 4, the proportions (volume %) of the olefin content and the aromatic content are based on the total capacity of gasoline.
The benzene content, the C7 aromatic content, the C8 aromatic content, and the proportion (volume %) of the C9 or higher aromatic content are all based on the total volume of the gasoline base material.

[Evaluation]
The following evaluations were carried out using the unleaded gasolines prepared in Examples 1-12 and Comparative Examples 1-10. The results are shown in Tables 5 and 6.

<Startability>
The startability was evaluated by using a vehicle having a displacement of 2 L, a direct injection system (DI), and an automatic transmission (AT) under the conditions of a test temperature of 20° C. and a humidity of 50%.
The vehicle was started, and the time from the start of cranking to the complete explosion (that is, the time until the engine can continue to rotate by itself (starting time)) was measured.
When the starting time is within 2.00 seconds, it is evaluated as excellent in acceleration.

<Acceleration (driving performance)>
The acceleration performance was evaluated using a vehicle having a displacement of 2 L, a direct injection (DI) system, and an automatic transmission (AT) under the conditions of a test temperature of 20° C. and a humidity of 50%.
After starting the engine of the vehicle, idling was performed for 10 seconds, and the time until the vehicle speed reached 40 km/h was measured at an accelerator opening of 50%.
When the acceleration time is within 4.20 seconds, it is evaluated as excellent in acceleration property.

<Smolderability of spark plug>
The smoldering suppression of the spark plug was evaluated by the following method. Using a vehicle with a displacement of 2 L, a multi-point injection (MPI) system, and an automatic transmission (AT), under the test temperature condition of -10°C, an evaluation test of 1 cycle of about 30 minutes is performed, and then the spark plug is tested. The insulation resistance value was measured using an insulation resistance meter (model number: DM-1526, manufactured by Sanwa Electric Instrument Co., Ltd.).
After starting the engine and repeating acceleration/deceleration of 10 km/h to 20 km/h 10 times, the engine is turned off and cooled for 28 minutes.
The fluctuation of the insulation resistance value of the spark plug is an index of the pollution degree of the spark plug.
When the insulation resistance value of the spark plug reaches 100 MΩ or less, it is determined that smoldering of the plug has occurred. The evaluation test was repeatedly performed until it was determined that smoldering of the plug had occurred, and the smoldering property of the plug was evaluated by the number of tests (the number of cycles) until it was determined that smoldering of the plug had occurred.
When the number of cycles is 13 or more, it is judged that it is excellent in suppressing the smoldering of the spark plug.

The unleaded gasolines of Examples 1 to 12 showed good results in both the startability of the internal combustion engine, the vehicle acceleration, and the suppression of smoldering of the spark plug. On the other hand, in the unleaded gasoline of Comparative Examples 1 to 10 in which the composition of the base material or the fuel property does not satisfy even one of the constituents according to the present invention, the startability of the internal combustion engine and the acceleration of the vehicle and the smoldering of the spark plug are suppressed. No satisfactory results were obtained.
Further, the unleaded gasolines of Examples 7 to 12 were excellent in the startability of the internal combustion engine and the acceleration of the vehicle and the suppression of smoldering of the spark plug even when they contained ETBE which is an oxygen-containing compound.

From the above results, it is understood that the unleaded gasoline of the present invention maintains the octane number and is excellent in the startability of the internal combustion engine, the acceleration of the vehicle, and the suppression of smoldering of the spark plug. In addition, the unleaded gasoline of the present invention containing an oxygen-containing base material can contribute to the preservation of the atmospheric environment.

Claims (2)

The light catalytic cracking gasoline base material A shown in (1) below is 5% to 40% by volume with respect to the total volume of unleaded gasoline, and the heavy catalytic reformed gasoline base material B shown in (2) below is of unleaded gasoline. Unleaded gasoline which is blended with 10% by volume to 45% by volume with respect to the total volume and satisfies the following (3) to (14).
(1) Light catalytic cracking gasoline base material A: 10% by volume distillation temperature is 30°C to 45°C, 50% by volume distillation temperature is 35°C to 50°C, 90% by volume distillation temperature is 55°C to 75°C. The end point is 80°C to 100°C, the density at 15°C is 0.650 g/cm ^{3 to} 0.670 g/cm ³ , and the olefin content is 40% by volume to 55% by volume with respect to the total volume of the light catalytic cracking gasoline base material A. A light catalytic cracking gasoline base material having a hydrocarbon content of 7 or more carbon atoms of 10% by volume or less based on the total capacity of the light catalytic cracking gasoline base material A.
(2) Heavy catalytic reforming gasoline base material B: The following base material b1 and the following base material b2 are included, and the mixing ratio (b1:b2) of the base material b1 and the base material b2 is 95: by volume. Heavy catalytic reforming gasoline base stock, ranging from 5 to 5:95.
The base material b1 has a 10% by volume distillation temperature of 95°C to 115°C, a 50% by volume distillation temperature of 100°C to 120°C, a 90% by volume distillation temperature of 105°C to 125°C, and an end point of 110°C to 130°C. The density at 80° C. and 15° C. is 0.840 g/cm ^{3 to} 0.860 g/cm ³ , the aromatic component having 7 carbon atoms is 70% by volume to 85% by volume and 8% carbon number with respect to the total volume of the base material b1. A heavy catalytic reforming gasoline base material having an aromatic content of 10% by volume or less with respect to the total capacity of the base material b1 and an aromatic content of 9 carbon atoms or less with respect to the total capacity of the base material b1. The base material b2 has a 10% by volume distillation temperature of 155 to 165°C, a 50% by volume distillation temperature of 160°C to 170°C, a 90% by volume distillation temperature of 165°C to 175°C, and an end point of 175 to 190°C. ° C., density 0.860 g ^/ cm 3 at 15 ℃ ~0.880g / cm ^3, and heavy catalytic reformate above 90% by volume based on the total volume of the aromatic content base b2 having 9 carbon atoms It is a base material.
(3) Research method octane number is 93 or more and less than 98 (4) Motor method octane number is 81 or more and less than 87 (5) Density at 15° C. is 0.710 g/cm ^{3 to} 0.783 g/cm ³
(6) 50% by volume distillation temperature is 75°C to 110°C
(7) 70°C distillate amount is 18% by volume to 45% by volume based on the total volume of unleaded gasoline.
(8) Reid vapor pressure is 45 kPa to 93 kPa
(9) Benzene content is 1% by volume or less (10) Sulfur content is 10 mass ppm or less (11) Olefin content is 10% by volume to 30% by volume with respect to the total volume of unleaded gasoline.
(12) Aromatic content is 15% by volume to 45% by volume based on the total volume of unleaded gasoline.
(13) The aromatic content having 7 carbon atoms is 26% by volume or less based on the total capacity of the aromatic content in unleaded gasoline. (14) The aromatic content having 8 carbon atoms corresponds to the total capacity of aromatic content in unleaded gasoline. 5% by volume or less The unleaded gasoline according to claim 1, further comprising 1 to 15% by volume of the oxygen-containing base material with respect to the total volume of the unleaded gasoline.