JP4633411B2 - Gasoline composition - Google Patents

Description

  The present invention relates to a gasoline composition produced from a hydrocarbon such as petroleum, and more particularly to a gasoline composition having an improved octane number and exhibiting excellent fuel efficiency.

The vapor pressure of gasoline in summer has been decided to be regulated to 65 kPa or less since 2005, and the blending of gasoline with light fractions with high vapor pressure, such as butane and isopentane, will be reduced. Since the light fraction has a relatively high octane number, it causes a decrease in the octane number of gasoline and a heavy distillation property.
On the other hand, fuel efficiency regulations for automobiles will be strengthened from 2010, and measures to improve CO2 emissions by raising the octane number of gasoline, especially regular gasoline, as one of the measures to achieve the CO ₂ emission reduction target by ratification of the Kyoto Protocol. Is expected.

However, in order to increase the octane number of regular gasoline, by mixing a large amount of aromatic hydrocarbons with relatively high octane number (hereinafter, also simply referred to as “aromatics”) into the gasoline, this is combined with the effects of the above-mentioned decrease in vapor pressure. Further, since the distillation properties become heavier and the volatility during fuel injection deteriorates, there is a concern that the acceleration performance of the vehicle, the driving force, and the like will decrease. That is, it is desired to develop a gasoline composition that can maintain the acceleration and driving force of a vehicle without increasing the distillation properties even if the vapor pressure is reduced and the octane number is improved.
Then, this invention makes it a subject to provide the gasoline composition which shows the outstanding fuel-consumption performance which raised the octane number, maintaining the acceleration property and driving force of a vehicle.

  The present inventor has come up with the idea that the light octane of fluid catalytic cracking gasoline can be used as a regular gasoline base material, and the octane number of regular gasoline can be increased without using a heavy fraction as a gasoline base material. . The idea is that the acceleration can be maintained by adjusting the carbon number distribution of isoparaffins and olefins of lighter fractions with a relatively high octane number without increasing the mixing amount of the aromatic substrate. And arrived at the present invention.

That is, the gasoline composition according to the present invention has a research octane number of 92 to 96 , a vapor pressure of 65 kPa or less, a 10% distillation temperature of 47 to 48.5 ° C, and a 50% distillation temperature of 90 ° C to 90 ° C. 103 ° C., 70% distillation temperature of 110 ° C. to 134 ° C., 90% distillation temperature of 165 ° C. or less, aromatic content of 30% by volume or less, and the following formulas (1) and ( It satisfies 2).
290 ≦ T = 3 × (50% distillation temperature [° C.]) + 0.3 × (70% distillation temperature [° C.]) + 0.03 × (90% distillation temperature [° C.]) − 0.6 × ( Vapor pressure [kPa]) ≦ 310 (1)
0.610 ≦ A = (IC6 + C6O) /C6≦0.700 (2)
Here, C6 is the content [volume%] of the hydrocarbon having 6 carbon atoms, IC6 is the content [volume%] of the isoparaffin having 6 carbon atoms, and C6O is the content [volume%] of the olefin having 6 carbon atoms. Show.

Gasoline composition of the present invention, the sulfur content is more than 1.5 mass ppm by thiols, and preferably a doctor test is negative, 90% fluidized catalytic cracking gasoline base material of distillation temperature of 0.99 ° C. to 175 ° C. It is preferable to contain 30% by volume or more. Moreover, it is preferable to contain 10-30 volume% of light fluid catalytic cracking gasoline whose 95% distillation temperature is 55.0-80.0 degreeC.

Distillation properties such as 50% distillation temperature as specified in formula (1) and vapor pressure within a predetermined range, and increase the proportion of isoparaffin or olefin occupying 6 carbon atoms as defined in formula (2) Thus, even if the vapor pressure is lowered, the acceleration property and driving force of the vehicle can be maintained without increasing the distillation properties, and the octane number can be improved.
Furthermore, driving performance and fuel efficiency improvement by increasing the octane number are expected to have a significant effect not only on current vehicles with knock sensors but also on regular high-octane vehicles that are expected to be in the future. .

  The gasoline composition according to the present invention has a research octane number (hereinafter, also simply referred to as “RON”) of 91.5 or more, preferably 92 to 96, particularly preferably 93 to 95. The measuring method of the research method octane number is defined in JIS K2202.

  The gasoline composition according to the present invention has a vapor pressure at 37.8 ° C. of 65 kPa or less, preferably 61 to 65 kPa. The vapor pressure in this specification is defined in JIS K 2258.

The gasoline composition according to the present invention has a 10% distillation temperature of 47 ° C or higher, preferably 47.5 to 48.5 ° C, and a 50% distillation temperature of 90 to 103 ° C, preferably 98 to 103 ° C. The 70% distillation temperature is 110 to 134 ° C, preferably 115 to 125 ° C, and the 90% distillation temperature is 165 ° C or lower, preferably 155 to 165 ° C. The distillation temperature is specified in JIS K 2254.
T = 3 × (50% distillation temperature [° C.]) + 0.3 × (70% distillation temperature [° C.])
+ 0.03 × (90% distillation temperature [° C.]) − 0.6 × (vapor pressure [kPa])
≦ 315 (1)
This T is preferably in the range of 290 to 310.

  The aromatic content of the gasoline composition according to the invention is not more than 30% by volume, preferably 20 to 28% by volume, in particular 22 to 27% by volume. The benzene content is preferably 1% by volume or less.

Furthermore, the gasoline composition according to the present invention satisfies the following formula (2) with respect to the content of carbon 6 isoparaffin and olefin.
A = (IC6 + C6O) / (C6) ≧ 0.600 (2)
That is, A is not less than 0.600, preferably 0.610 to 0.700. Here, C6 is the content [capacity%] of hydrocarbons having 6 carbon atoms, IC6 is the content of isoparaffins having 6 carbon atoms, C6O is the content of olefins having 6 carbon atoms, and JIS K 2536 It is specified by the content according to “Test method for all components by gas chromatography”. In addition, isoparaffin means here the thing of the broad sense which is not a linear structure but has a branched side chain. The olefin is a hydrocarbon having at least one unsaturated bond.

  The sulfur content of the gasoline composition according to the present invention is preferably 0.1 to 10 ppm by mass, particularly preferably 0.5 to 5 ppm by mass. Sulfur content by thiols is preferably 1.5 ppm by mass or less, particularly preferably 0.1 to 1.2 ppm by mass, and the ratio of sulfur content by thiols in the sulfur content is 30% or less, especially 10 to 30%. It is preferable that Moreover, it is preferable that a doctor test is negative. Thiols are organic sulfur compounds containing SH groups, chain thiols with SH groups added to chain paraffins, alicyclic thiols with SH groups added to cyclic paraffins, and SH groups added directly to aromatic rings. Containing aromatic thiols.

  The gasoline composition according to the present invention preferably contains 30% by volume or more of a fluid catalytic cracking gasoline base material having a 90% distillation temperature of 150 to 175 ° C. The fluid catalytic cracking gasoline base material preferably has a 90% distillation temperature of 155 to 170 ° C and a 50% distillation temperature of 85 to 97 ° C.

  The process for producing the fluid catalytic cracking gasoline base material does not particularly limit the catalytic cracking apparatus, the operating conditions and the catalyst to be used, and any known production process can be adopted. The catalytic cracking unit uses a catalyst such as amorphous silica alumina, zeolite, etc., in addition to petroleum fractions from light oil to vacuum gas oil, while being obtained from heavy oil indirect desulfurization unit, it can be obtained directly from degassing oil or heavy oil direct desulfurization unit. This is a device that obtains a high octane gasoline base material by catalytically cracking degassed oil, atmospheric residue oil, etc. For example, UOP catalytic cracking method, flexi cracking method, ultra-orthoflow method, fluid catalytic cracking method such as Texaco fluid catalytic cracking method, RCC method, HOC method, etc. Examples include fluid catalytic cracking. Also, 21st JPI Petroleum Refining Conference “Recent Progress in Petroleum Process Technology”, p.113-158 (2002), Sulfur, 268, 35, (2000), “Production of Low Sulfur Gasoline and Diesel Fuels: Tier 2 and Beyond” , Petroleum Refining Technology Seminar, p.4-24 (August 2001), JP-A-6-277519, catalytic cracking catalyst having high desulfurization effect and additive having desulfurization effect are added to catalytic cracking catalyst It can also be used.

  As the feedstock oil for catalytic cracking equipment, atmospheric distillation residue obtained by atmospheric distillation of crude oil, vacuum gas oil that is a distillate fraction obtained by distillation of atmospheric distillation residue under reduced pressure, crude oil at atmospheric pressure Among the distillate oil fractions obtained by distillation, straight distillation gas oil fraction, pyrolysis heavy gas oil fraction obtained by pyrolyzing vacuum distillation residue oil obtained by vacuum distillation of atmospheric distillation residue oil, etc. Is preferably used by hydrorefining so that the sulfur content is 4000 mass ppm or less, particularly 2000 mass ppm or less, and the nitrogen content is 1000 mass ppm or less, particularly 500 mass ppm or less.

  The fluid catalytic cracking gasoline base material is a fraction obtained by fractionating the above-mentioned distillation property fraction from fractions generated from the catalytic cracking apparatus. Preferably, the fluid catalytic cracking gasoline base is formulated into the gasoline composition after being treated to reduce thiols. The method for reducing thiols is not particularly limited, but is a method other than hydrodesulfurization, and it is preferable to selectively reduce thiols. Specifically, thiols are obtained by a method of sweetening thiols in fluid catalytic cracking gasoline by contacting with an alkaline substance or a method of contacting fluid catalytic cracking gasoline with a desulfurization agent having an adsorption or sorption function of sulfur compounds. A preferable method is a method of selectively removing.

  Since fluid catalytic cracking gasoline is a base material that contains more sulfur than other gasoline base materials, as a method of reducing the sulfur content, the use of a low sulfur content as a feedstock for catalytic cracking equipment In addition to adding a catalytic cracking catalyst having a high desulfurizing effect or an additive having a desulfurizing effect to the catalytic cracking apparatus in the catalytic cracking apparatus, there is a method of desulfurizing fluid catalytic cracking gasoline. Fluid catalytic cracking gasoline can be desulfurized by existing methods such as hydrodesulfurization, adsorptive desulfurization, and desorption / removal sulfur, but from the viewpoint of suppressing octane loss, a method of desulfurizing only heavy catalytic cracking gasoline is preferred. As a method. Further, the remaining fluid catalytic cracked gasoline obtained by fractionating heavy catalytic cracked gasoline, that is, light catalytic cracked gasoline has a relatively low sulfur content, does not need to be desulfurized, and has a high octane number. It can be used as a material. The distillation properties of light catalytic cracking gasoline are preferably 5% distillation temperature of 25.0 to 43.0 ° C and 95% distillation temperature of 55.0 to 80.0 ° C.

  Conventionally, in petroleum refining, sweetening has been performed to treat thiols to make the product non-brominated, such as Petrotech 17 (11), 974 (1994) and Kodansha Scientific “Petroleum Refining Process”. The Marlox method described in (1998) is preferably used. In sweetening, since olefins are retained as they are, RON does not decrease. However, desulfurized heavy catalytic cracking gasoline fraction contains a lot of heavy thiols derived from olefins in heavy catalytic cracking gasoline, but such thiols have low reactivity in the conventional Marlox method. There is a possibility that it cannot be fully converted. In that case, it is necessary to select a sweetening process capable of removing heavy thiols. Specific examples include the MERICAT-II process described in NPRA 2000 Annual Meeting AM-00-54.

  Thiols are converted to disulfides by the presence of alkaline substances such as caustic soda and ammonia. At this time, conversion efficiency can be improved by using an additive and a catalyst. In addition, since the extraction type sweetening process allows thiols to react with an alkaline substance and be separated from the oil, the sulfur content in the oil can be reduced.

  As described above, the fluid catalytic cracking gasoline base material includes fluid catalytic cracking gasoline itself, light fluid catalytic cracking gasoline obtained by fractionating fluid catalytic cracking gasoline, heavy fluid catalytic cracking gasoline, and heavy fluid Desulfurized heavy fluid catalytic cracked gasoline obtained by subjecting catalytic cracked gasoline to various desulfurization treatments can be mentioned, and particularly light fluid catalytic cracked gasoline and desulfurized heavy fluid catalytic cracked gasoline can be preferably used. Further, desulfurized fluid catalytic cracking gasoline in which light fluid catalytic cracking gasoline and desulfurized heavy fluid catalytic cracking gasoline are mixed in any proportion in advance is also preferable, and particularly, lightening desulfurization with an increased mixing ratio of light fluid catalytic cracking gasoline. Fluid catalytic cracking gasoline can be preferably used.

  The gasoline composition according to the present invention preferably contains less than 70% by volume, in particular 10 to 50% by volume, more preferably 20 to 40% by volume, of another gasoline base in the fluid catalytic cracking gasoline base. Other gasoline base materials include catalytically modified gasoline base materials, alkylate gasoline base materials, base materials obtained by desulfurizing straight-run naphtha, and methyl t-butyl ether (MTBE), ethyl t-butyl ether (ETBE), t- Oxygenated gasoline base materials such as amyl ethyl ether (TAEE), ethanol, methanol, etc. can be used. Further, as the catalytic reforming gasoline base, a fraction containing 80% by volume or more, particularly 95% by volume or more of toluene is preferably used.

  Preferred blending amounts are 50 to 90% by volume, especially 60 to 80% by volume of fluid catalytic cracked gasoline base, 5 to 35% by volume, especially 7 to 25% by volume of catalytically modified gasoline base, and other bases. Is 0 to 30% by volume, particularly 5 to 20% by volume.

  Furthermore, the gasoline composition of the present invention may contain one or more fuel oil additives known in the art as needed. Although these compounding quantities can be selected suitably, it is preferable to maintain the total compounding quantity of an additive to 0.1 weight% or less normally. Examples of fuel oil additives that can be used in the gasoline of the present invention include phenolic, amine-based antioxidants, Schiff-type compounds, metal deactivators such as thioamide-type compounds, and organic phosphorus-based surfaces. Anti-ignition agent, detergent / dispersant such as succinimide, polyalkylamine, polyetheramine, anti-icing agent such as polyhydric alcohol or its ether, alkali metal salt or alkaline earth metal salt of organic acid, sulfuric acid of higher alcohol Examples include an auxiliary combustor such as an ester, an anionic surfactant, a cationic surfactant, an antistatic agent such as an amphoteric surfactant, and a colorant such as an azo dye.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

  In this example, the distillation properties were measured according to JIS K 2254, and the vapor pressure was measured according to JIS K 2258. The sulfur content was measured by the microcoulometric titration method of JIS K2541. The sulfur compound content (sulfur equivalent) was measured by gas chromatography using a Shimadzu gas chromatograph equipped with an ANTEK sulfur chemiluminescence detector that selectively detects and quantifies sulfur compounds by chemiluminescence. . The hydrocarbon component composition and RON were measured by a gas chromatograph method using a PIONA apparatus manufactured by Hured Packard. The doctor test was measured according to JIS K 2276.

A gasoline base material having the properties and component composition shown in Table 1 was prepared. Each substrate was prepared by the following method.
DS-LG: straight-run gasoline, obtained by hydrodesulfurizing a naphtha fraction of Middle Eastern crude oil, and distilling and separating the lighter fraction.

FCCG: catalytic cracking light fraction obtained by fractionating a catalytic cracking gasoline fraction and having a 5% distillation temperature of 25.0 to 43.0 ° C and a 95% distillation temperature of 55.0 to 80.0 ° C Get a gasoline fraction. Moreover, after reducing sulfur content by hydrodesulfurization of catalytic cracking heavy gasoline fraction, thiol reduction treatment is performed by sweetening treatment, and the above catalytic cracking light gasoline fraction is in a ratio (volume ratio) of 1: 1. Is a mixture of
FCCG (light): The light catalytic cracking gasoline fraction and the two-stage desulfurized heavy catalytic cracking gasoline fraction are mixed in a ratio (volume ratio) of 1: 0.8.
FL: The light catalytic cracking gasoline fraction. That is, a light catalytic cracking gasoline having a 5% distillation temperature of 25.0 to 43.0 ° C and a 95% distillation temperature of 55.0 to 80.0 ° C obtained by fractionating a catalytic cracking gasoline fraction. Distillate.

ALKG: alkylate gasoline, a fraction containing butylene as a main component and a fraction containing isobutane as a main component were reacted with a sulfuric acid catalyst to obtain a hydrocarbon having a high isoparaffin content.

AC7: Light reformed gasoline, heavy naphtha is reacted with a solid catalyst using a moving bed reactor, reformed to a hydrocarbon with high aromatic content, and separated by distillation to have 7 carbon atoms. A fraction containing 95% or more of hydrocarbons was obtained.
AC9: Heavy reformed gasoline, heavy naphtha is reacted with a solid catalyst using a moving bed reactor, reformed to a hydrocarbon with a high aromatic content, and subjected to distillation separation to have a carbon number of 9 A fraction containing 95% or more of the above hydrocarbons was obtained.

The gasoline bases shown in Table 1 were blended at the ratios shown in Table 2 to prepare gasolines of Examples 1 and 2 and Comparative Examples 1 and 2. The properties and characteristics of the prepared gasoline are also shown in Table 2.
The acceleration time is a vehicle speed of 0 km / hr to 10 km / hr when the chassis dynamometer device is used and the accelerator opening is set to 50% by the automatic operation device (ADS7000) of Horiba Seisakusho. Measured by the time to reach.

  T (= 3 × (50% distillation temperature [° C.]) + 0.3 × (70% distillation temperature [° C.]) + 0.03 × (90% distillation temperature [° C.]) − 0.6 × (steam The pressure [kPa])) is 315 or less and A ((IC6 + C6O) / C6) is 0.66 or more, so that the acceleration time in the actual vehicle test is quick, the fuel consumption is improved, and the octane number (RON) is high. A composition can be obtained.

  Even if the vapor pressure of the gasoline composition of the present invention is lowered, the acceleration property and driving force of the vehicle can be maintained without increasing the distillation properties, and the octane number can be improved. Therefore, the gasoline composition of the present invention is expected to improve drivability and fuel efficiency, and is useful as a gasoline that is environmentally friendly and economical, even for vehicles that meet the high-octane number of regular specifications that are expected in the future. It is.

Claims (4)

Vapor pressure is 65kPa or less, 10% distillation temperature is 47 to 48.5 ° C, 50% distillation temperature is 90 ° C to 103 ° C, 70% distillation temperature is 110 ° C to 134 ° C, and 90% distillation. A gasoline composition having a temperature of 165 ° C. or less, an aromatic content of 30% by volume or less, a research octane number of 92 to 96 , and satisfying the following formulas (1) and (2): object.
290 ≦ T = 3 × (50% distillation temperature [° C.]) + 0.3 × (70% distillation temperature [° C.]) + 0.03 × (90% distillation temperature [° C.]) − 0.6 × ( Vapor pressure [kPa]) ≦ 310 (1)
0.610 ≦ A = (IC6 + C6O) /C6≦0.700 (2)
(Where C6 is the content of carbon 6 hydrocarbons [volume%], IC6 is the content of carbon 6 isoparaffins [volume%], and C6O is the content of carbon 6 olefins [volume%]. Is shown respectively.)   The gasoline composition according to claim 1, wherein the sulfur content by thiols is 1.5 ppm by mass or less, and the doctor test is negative.   The gasoline composition according to claim 1 or 2, comprising 30% by volume or more of a fluid catalytic cracking gasoline base material having a 90% distillation temperature of 150 to 175 ° C.   The 95% distillation temperature obtained by distilling and separating fluid catalytic cracking gasoline is 55.0 to 80.0 ° C, and contains 10 to 30% by volume of light fluid catalytic cracking gasoline. Gasoline composition.