JP4429881B2 - Unleaded high octane gasoline - Google Patents

Description

  The present invention relates to unleaded high-octane gasoline, particularly unleaded high-octane low vapor pressure gasoline, and more specifically, environmentally friendly as an automotive fuel having specific distillation characteristics and specific component composition, and startability and drivability. It also relates to unleaded high octane low vapor pressure gasoline.

In recent years, from the viewpoint of environmental improvement, environmental pollution due to exhaust gas from automobiles has been regarded as a problem, and various efforts have been made to reduce exhaust gas from the fuel surface. On the other hand, reduction of ozone generation, which is a factor of photochemical smog, is strongly desired.
In general, it is said that NOx and HC affect ozone generation. To reduce these, it is considered effective to reduce exhaust gas from automobiles or evaporated gas from fuel. In order to reduce the evaporated gas from the fuel, it is considered important to lower the vapor pressure of the fuel.
Conventionally, gasoline having a low vapor pressure has a hydrocarbon content of 4 carbon atoms, an olefin content, etc. (see, for example, Patent Document 1), or a 10% distillation temperature or carbon number. Those that specify a hydrocarbon content of 4 or less, a hydrocarbon content of 6 or less carbon atoms (for example, see Patent Document 2), or those that specify a distillation amount up to 70 ° C. (for example, Patent Document 3 and Patent Document 4) are known.
Usually, reducing the vapor pressure of fuel has an effect on reducing the evaporated gas from the fuel, but it may adversely affect the startability and drivability of the automobile, and without reducing these performances. There is a demand for a fuel that can reduce evaporative gas.

Japanese Patent Laid-Open No. 11-236580 JP 2000-248287 A Japanese Patent Laid-Open No. 2004-124055 Japanese Patent Laid-Open No. 2004-124056

  An object of the present invention is to provide a lead-free high-octane gasoline having a small amount of evaporated gas from fuel and excellent startability and operability under such circumstances.

As a result of intensive research from the viewpoints described above, the present inventors have found that the object can be achieved by unleaded high octane gasoline having a specific component composition and a specific distillation property, and completed the present invention. It came to do.
That is, the present invention provides the following lead-free high octane gasoline.

(1) Debenzene contact reforming with a research octane number (RON) of 100 or more, a motor method octane number (MON) of 88 or more, a Reid vapor pressure (RVP) of 30 to 38.0 kPa, and a boiling point range of 28 to 210 ° C. 30-60% by volume of gasoline,
Research method octane number (RON) is 93 or more, motor method octane number (MON) is 81 or more, Reed vapor pressure (RVP) is 90 kPa or more, and light catalytic cracking gasoline having a boiling point range of 25 to 110 ° C is 20 to 55% by volume,
An alkylate with a research octane number (RON) of 93 or higher, a motor octane number (MON) of 90 or higher, a Reid vapor pressure (RVP) of 40 kPa or higher, a boiling point range of 30 to 215 ° C., and a C8 fraction of 50 vol% or higher. Containing 0-40% by volume,
Lead-free high-octane gasoline that satisfies the following properties.
1) Reed vapor pressure (RVP) is 45 to 65 kPa
2) 50% distillation temperature (T50) is 80-110 ° C
3) Distillation at 70 ° C (E70) is 18-40% by volume
4) 130 ° C distillate (E130) is 70-90 vol%
5) Aromatic content is 36.2 to 45 vol% or less 6) Olefin content is 30 vol% or less 7) Benzene content is 1 vol% or less 8) Sulfur content is 10 mass ppm or less 9) The density at 15 ° C. is 0.68 to 0.78 g / cm ^3.
10) Gas-liquid ratio (V / L) at 60 ° C. is 25-50
11) Research octane number (RON) of 97-105
12) Motor method octane number (MON) is 85-92

  The lead-free high-octane gasoline of the present invention has little evaporated gas from fuel and is excellent in startability and drivability, and can maintain the atmospheric environment while maintaining practical performance.

Hereinafter, the contents of the present invention will be described in more detail.
The lead vapor pressure (RVP) of the unleaded high octane gasoline of the present invention is 45 to 65 kPa, preferably 48 to 65 kPa. By setting RVP to 65 kPa or less, the amount of evaporating gas can be reduced, and by setting it to 45 kPa or more, it is possible to prevent the low temperature startability and warming performance from being deteriorated. This Reid vapor pressure (RVP) is a value measured according to JIS K 2258.

  The distillation properties of the lead-free high-octane gasoline of the present invention are as follows: (a) 50% distillation temperature (T50) is 80 to 110 ° C, preferably 85 to 110 ° C, (b) 70 ° C distillation amount (E70) Is 18 to 40% by volume, preferably 18 to 35% by volume, and (c) 130 ° C. distillate (E130) is 70 to 90% by volume, preferably 70 to 85% by volume. When T50, E70, and E130 are within the above ranges, it is possible to prevent a problem in starting performance, driving performance, and acceleration performance. These distillation properties are values measured according to JIS K 2254.

  The aromatic content of the lead-free high octane gasoline of the present invention is 45% by volume or less, preferably 10 to 45% by volume. If the aromatic content is within 45% by volume, an increase in harmful components in the exhaust gas can be prevented, which is preferable. The aromatic content is a value measured in accordance with the Petroleum Institute Method JPI-5S-33-90 (gas chromatographic method).

  The olefin content of the unleaded high octane gasoline of the present invention is 30% by volume or less, preferably 5 to 25% by volume. When the olefin content is within 30% by volume, a decrease in oxidation stability can be prevented, which is preferable. The olefin content is a value measured in accordance with the Petroleum Institute Method JPI-5S-33-90 (gas chromatographic method).

  The lead-free high octane gasoline of the present invention has a benzene content of 1% by volume or less, preferably 0.8% by volume or less. If the benzene content is within 1% by volume, an increase in the amount of benzene emissions in the atmosphere can be prevented and environmental pollution can be reduced. The benzene content is a value measured in accordance with the Petroleum Institute method JPI-5S-33-90 (gas chromatographic method).

  The lead content of the lead-free high octane gasoline of the present invention is 10 ppm by mass or less, preferably 8 ppm by mass or less. If the sulfur content is within 10 ppm by mass, it is preferable because the capability of the exhaust gas purification catalyst can be prevented from being lowered and NOx, CO, and THC emissions in the exhaust gas can be reduced. The sulfur content is a value measured according to JIS K 2541.

The density of the unleaded high octane gasoline of the present invention at 15 ° C. is 0.68 to 0.78 g / cm ³ , preferably 0.69 to 0.77 g / cm ³ . When this density is 0.68 g / cm ³ or more, good fuel consumption can be ensured. In addition, by setting the density to 0.78 g / cm ³ or less, it is possible to reduce the high-density aromatic component, and it is possible to reduce the amount of aromatic emissions into the atmosphere by exhaust gas. This density is a value measured in accordance with JIS K 2249.

  The gas-liquid ratio (V / L) at 60 ° C. of the unleaded high octane gasoline of the present invention is 25 to 50, preferably 25 to 45. When this V / L is 25 or more, good startability can be ensured. Further, it is preferable that V / L is 50 or less because there is a possibility that problems in acceleration and drivability can be reduced. The V / L is a value measured according to ASTM D 2533-93a.

  And the octane number of the lead-free high octane gasoline of the present invention is (a) Research method octane number (RON) is 97 to 105, preferably 98 to 103, (b) Motor method octane number (MON) is 85 to 92, preferably Is 86-90. If RON is 97 to 105, high driving performance can be maintained, and if MON is 85 to 92, it is possible to prevent a decrease in anti-knock property at high speeds, which is preferable. Note that RON and MON are values measured in accordance with JIS K 2280.

  The production method of the lead-free high octane gasoline of the present invention is not particularly limited, and can be produced by any method. However, as a base material, a debenzene contact reformed gasoline, a debenzene obtained by fractionating the same It can be suitably produced using light catalytic reforming gasoline, debenzene heavy catalytic reforming gasoline, light catalytic cracking gasoline, alkylate and the like.

The debenzene contact reformed gasoline used in the lead-free high octane gasoline of the present invention is a heavy-running straight naphtha or the like reformed by catalytic reforming (plating, magna forming, aromaizing, reniforming, food reforming). Obtained by contact treatment with a catalyst (for example, an alumina carrier carrying platinum, rhodium and chlorine) under high temperature and pressure in a hydrogen stream by a forming method, ultraforming method, power forming method, etc. The benzene fraction is removed from the reformed gasoline by distillation, and the properties thereof are RON 100 or more, preferably 100 to 107, MON 88 or more, preferably 88 to 95, RVP 30 kPa or more, preferably 30 -50 kPa, and the boiling range is 28-210 ° C, preferably 30-200 ° C.
The content of debenzene contact reformed gasoline in the lead-free high octane gasoline of the present invention is preferably 30 to 60% by volume, more preferably 30 to 50% by volume. If the content of this debenzene-catalyzed reformed gasoline is 30% by volume or more, it is possible to prevent a decrease in RON, and if it is within 60% by volume, the distillation property becomes heavier and the aromatic content can be reduced. preferable.

The debenzene light catalytic reformed gasoline is a light fraction that is obtained by distilling the catalytic reformed gasoline obtained by contact treatment by the above catalytic reforming method into a light fraction, a benzene fraction, and a heavy fraction. The properties thereof are RON 78 or more, preferably 78 to 90, MON 70 or more, preferably 70 to 83, RVP 85 or more, preferably 85 to 105, boiling range 26 to 100 ° C., preferably 28-95 ° C. The debenzene heavy catalytic reformed gasoline, which is a heavy fraction, has a RON of 101 or more, preferably 101 to 110, MON of 89 or more, preferably 89 to 98, and RVP of 3 kPa or more, preferably 3 to 15 kPa. The boiling point range is 90 to 210 ° C, preferably 95 to 205 ° C.
The content of debenzene light catalytic reformed gasoline and debenzene heavy catalytic reformed gasoline in the unleaded high octane gasoline of the present invention is preferably 2 to 15% by volume and 30 to 50% by volume, more preferably 2 to 10% by volume, 35-50% by volume. If the debenzene light catalytic reformed gasoline is 2% by volume or more, it is preferable to prevent the distillation property from becoming heavy, and if it is within 15% by volume, it is preferable to prevent a decrease in density. In addition, if the debenzene heavy catalytic reformed gasoline is 30% by volume or more, it is possible to prevent a decrease in RON, and if it is within 50% by volume, the distillation property becomes heavier and the aromatic content is prevented from increasing. This is preferable.

Furthermore, the light catalytic cracking gasoline used in the lead-free high-octane gasoline of the present invention is conventionally known as a petroleum fraction ranging from kerosene / light oil to atmospheric residual oil, preferably heavy gas oil or vacuum gas oil. Catalytic cracking method, especially fluid catalytic cracking method (UOP method, shell two-stage method, flexi cracking method, ultra ortho flow method, texaco method, gulf method, ultra cat cracking method, ultra ortho flow method, texaco method, gulf method, Contact obtained by desulfurizing catalytic cracking gasoline obtained by cracking with a solid acid catalyst (eg, silica / alumina blended with zeolite) by ultra cat cracking method, RCC method, HOC method, etc. It is a light component obtained by distilling cracked gasoline, and its properties are RON 93 or more, preferably 93 to 97, MON 81 or more, preferably 81 to 85, RVP 90 kP a or more, preferably 90 to 110 kPa, boiling range 25 to 110 ° C, preferably 25 to 100 ° C.
The content of the light catalytic cracking gasoline in the unleaded high octane gasoline of the present invention is preferably 20 to 55% by volume, more preferably 25 to 50% by volume. If the content of the light catalytic cracking gasoline is 20% by volume or more, it is possible to prevent the distillation property from becoming heavy, and if it is within 55% by volume, the olefin content is increased and the oxidation stability is decreased. It is preferable to prevent this.

The alkylate used in the lead-free high-octane gasoline of the present invention is reacted with isobutane and a lower olefin (butene, propylene, etc.) as raw materials in the presence of an acid catalyst (sulfuric acid, hydrogen fluoride, aluminum chloride, etc.). The properties of RON are 93 or more, preferably 94 to 96, MON is 90 or more, preferably 91 to 94, RVP is 40 kPa or more, preferably 40 to 60 kPa, and the boiling point range is 30 to 215. ° C, preferably 30-210 ° C.
The content of alkylate in the lead-free high octane gasoline of the present invention is preferably 0 to 40% by volume, more preferably 5 to 40% by volume. If the alkylate content is within 40% by volume, it is preferable to prevent a decrease in density and fuel consumption.

  The lead-free high-octane gasoline of the present invention may further contain various additives as necessary. Such additives include phenolic and amine antioxidants, metal deactivators such as thioamide compounds, surface ignition inhibitors such as organophosphorus compounds, succinimides, polyalkylamines, polyetheramines. , Detergent dispersants such as polyisobutyleneamine, friction modifiers (FM) such as long chain alkylamines, amides, imides and derivatives thereof, anti-icing agents such as polyhydric alcohols and ethers thereof, alkali metals and alkaline earths of organic acids Metal salts, auxiliary agents such as sulfates of higher alcohols, anionic surfactants, cationic surfactants, antistatic agents such as amphoteric surfactants, rust inhibitors such as alkenyl succinates, and azo dyes Known fuel additives such as colorants can be used. These can be added alone or in combination. The addition amount of these fuel additives is arbitrary, but usually the total addition amount is preferably 0.1% by mass or less.

Furthermore, the lead-free high-octane gasoline of the present invention includes, if necessary, butane and butene obtained by distillation during atmospheric distillation of crude oil, crude oil, etc., during the production of reformed gasoline, or during the production of cracked gasoline. Isomers obtained by isomerization of straight chain lower paraffin hydrocarbons, light naphtha, preferably desulfurized straight naphtha, or isopentane obtained by precision distillation of isomerates, oxygen-containing Compounds such as ethyl tertiary butyl ether (ETBE), tertiary amyl methyl ether (TAME), tertiary amyl ethyl ether (TAEE), ethanol, toluene obtained from aromatic production equipment, and xylene can also be added. . Also, a base material obtained by removing aromatic components having 9 or more carbon atoms and hydrocarbon components having 4 carbon atoms from the light catalytic cracking gasoline, the debenzene catalytic reforming gasoline, the debenzene light catalytic reforming gasoline, etc. by distillation. It is also possible to blend.
When the C4 fraction is blended, the C4 content is less than 4% by volume, preferably less than 3.5% by volume, and if the C4 content is within 4% by volume, the increase in vapor pressure is suppressed, This is preferable because evaporated gas from the fuel is reduced.

  The content of the present invention will be described in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited thereto.

Examples 1 and 2 and Comparative Examples 1 and 2
Each gasoline base material having the properties and composition shown in Table 2 is mixed in the proportions shown in Table 3 to prepare unleaded high octane low vapor pressure gasoline, and various performance evaluation tests described below are conducted with a displacement of 2L, direct injection system (DI), an automatic transmission (AT) vehicle was used under the conditions of a test temperature of 20 ° C. and a humidity of 50%. The method is described below, and the results are shown in Table 3.

(Startability)
The time from cranking start to complete explosion (time until the engine can continue to rotate by itself) was evaluated.
(Acceleration)
The engine was idled for 10 seconds after the engine was started, and the time until the vehicle speed reached 40 km / h with an accelerator opening of 50% was evaluated.
(Demerit score)
Evaluation was performed according to the CRC (Coordinating Research Council) Report No. 483 evaluation method.
The evaluation method was determined by the demerit score given by the degree of the phenomenon that occurred (Σ = demerit score × defect coefficient).
It should be noted that stalls during idling and running were not calculated, and the respective coefficients were added. The smaller the score, the better the performance.

  From the results, the lead-free high-octane gasoline of the present invention has little evaporated gas from the fuel, is excellent in startability and operation performance, and can maintain the atmospheric environment while maintaining practical performance.

Claims (1)

30 debenzene contact reformed gasoline with a research octane number (RON) of 100 or more, a motor octane number (MON) of 88 or more, a Reid vapor pressure (RVP) of 30 to 38.0 kPa, and a boiling point range of 28 to 210 ° C. ~ 60% by volume,
Research method octane number (RON) is 93 or more, motor method octane number (MON) is 81 or more, Reed vapor pressure (RVP) is 90 kPa or more, and light catalytic cracking gasoline having a boiling point range of 25 to 110 ° C is 20 to 55% by volume,
An alkylate with a research octane number (RON) of 93 or higher, a motor octane number (MON) of 90 or higher, a Reid vapor pressure (RVP) of 40 kPa or higher, a boiling point range of 30 to 215 ° C., and a C8 fraction of 50 vol% or higher. Containing 0-40% by volume,
Lead-free high-octane gasoline that satisfies the following properties.
1) Reed vapor pressure (RVP) is 45 to 65 kPa
2) 50% distillation temperature (T50) is 80-110 ° C
3) Distillation at 70 ° C (E70) is 18-40% by volume
4) 130 ° C distillate (E130) is 70-90 vol%
5) Aromatic content is 36.2 to 45 vol% or less 6) Olefin content is 30 vol% or less 7) Benzene content is 1 vol% or less 8) Sulfur content is 10 mass ppm or less 9) The density at 15 ° C. is 0.68 to 0.78 g / cm ^3.
10) Gas-liquid ratio (V / L) at 60 ° C. is 25-50
11) Research octane number (RON) of 97-105
12) Motor method octane number (MON) is 85-92