JP4855003B2 - Gasoline composition and method for producing the same - Google Patents

Description

  The present invention relates to a gasoline composition with reduced environmental impact and a method for producing the same. In particular, the present invention relates to a gasoline composition that secures sufficient operating characteristics while reducing the impact on the environment by securing a high octane number even when the vapor pressure is limited, and a method for producing the same.

In recent years, environmental load due to automobile fuel and its combustion exhaust gas has become a problem, and there is a demand for automobile fuel that maintains high driving performance and has low environmental impact. In particular, it is required to suppress the volatilization of hydrocarbons from a gasoline composition (hereinafter also simply referred to as gasoline), and a reduction in the vapor pressure of gasoline is required.
On the other hand, CO ₂ discharged as combustion exhaust gas is also required to be reduced in order to prevent global warming. In order to reduce CO ₂ emissions, it is essential to improve the fuel efficiency of gasoline automobiles. To that end, the gasoline octane number is increased and the sulfur content is reduced to improve the compression ratio of the engine and the exhaust gas purification catalyst. It is necessary to reduce the reproduction frequency.

In order to lower the vapor pressure of gasoline, the blending amount of gasoline with a low boiling point base represented by butane is reduced. However, this butane has a high octane number, and if it is reduced, the octane number in the low boiling point region is lowered and the operation performance is lowered.
This invention solves such a problem, and makes it a subject to provide the gasoline composition which can suppress a vapor pressure, and its manufacturing method, without reducing an octane number and driving | operation performance.

  By reducing the blending of hydrocarbons with 4 carbon atoms such as butane and blending hydrocarbons with 5 carbon atoms, especially those containing a large amount of olefins, the octane number and operational performance of the gasoline composition will not decrease. I got the idea that the pressure could be lowered.

In the method for producing gasoline according to the present invention, the content of olefins having 5 carbon atoms is 20% by volume or more, the content of normal paraffins having 4 carbon atoms is 1% by volume or less, and the 10% distillation temperature is 25 ° C. Above, C5 gasoline base material with 90% distillation temperature of 65 ° C or less and sulfur content of 5 mass ppm or less is mixed with 2% by volume or more and other gasoline base materials, and C4 normal paraffin is 2% by volume or less. The ratio (volume ratio) of the olefin having 5 carbon atoms to the hydrocarbon having 4 carbon atoms is 6 or more, the vapor pressure is 60 kPa or less, the 50% distillation temperature is 105 ° C. or less, and the sulfur content is 10 mass ppm or less. is there.
The C5 gasoline base material preferably has a C5 hydrocarbon content of 50% by volume or more and a C4 hydrocarbon content of 2% by volume or less. Moreover, it is preferable that such a C5 gasoline base material is obtained by distilling and separating a product obtained from a fluid catalytic cracking apparatus.

In addition, the gasoline according to the present invention has 1% by volume or less of normal paraffins having 4 carbon atoms, the ratio (volume ratio) of 5 olefins to 4 carbon atoms is 6 or more, the vapor pressure is 60 kPa or less, and 50%. The distillation temperature is 100 ° C. or less and the sulfur content is 10 mass ppm or less.
It is preferable that the hydrocarbon having 4 carbon atoms is 2% by volume or less, the ratio of the olefin having 5 carbon atoms to the hydrocarbon having 4 carbon atoms is 7 or more, and the research octane number is 92 or more. It is preferable that hydrogen is 1 volume% or less, 50% distillation temperature is 99 ° C. or less, research octane number is 98 or more, and sulfur content is 2 mass ppm or less.

  Since the gasoline according to the present invention contains more hydrocarbon components having 5 carbon atoms, especially olefins having 5 carbon atoms, the octane number and the driving performance, particularly in the acceleration performance at low speed, are maintained. It becomes possible to lower the vapor pressure and reduce the sulfur content.

[C5 gasoline base material]
The C5 gasoline base material used in the production method of the present invention is a base material mainly composed of hydrocarbons having 5 carbon atoms, and the content of olefins having 5 carbon atoms (unsaturated hydrocarbon compounds) is 20% by volume or more. is there. Examples of the olefin having 5 carbon atoms include trans-2-pentene, cis-2-pentene, 3-methyl-1-butene, 1-pentene, 2-methyl-1-butene, and 2-methyl-2-butene. A saturated hydrocarbon compound is mentioned. Note that the content of the hydrocarbon having 5 carbon atoms is preferably 50% by volume or more, more preferably 60% by volume or more, and particularly preferably 70% by volume or more.

In this C5 gasoline base material, the normal paraffin (linear saturated hydrocarbon compound) having 4 carbon atoms is normal butane, and its content is 1% by volume or less, preferably 0.3% by volume or less. The C4 hydrocarbon is preferably 2% by volume or less, particularly preferably 1% by volume or less. In addition to the normal butane, examples of the hydrocarbon having 4 carbon atoms include isobutane, 1-butene, isobutene, trans-2-butene, and cis-2-butene.
Here, “iso” is not limited to an isomer having a methyl side chain at the second carbon atom from the end of a straight chain, and is used as a general term for a branched chain hydrocarbon isomer having at least one side chain. .

In the distillation properties of this C5 gasoline base, the 10% distillation temperature is 25 ° C or higher, preferably 27-34 ° C. The 50% distillation temperature is preferably 30 to 40 ° C, and the 90% distillation temperature is 65 ° C or less, preferably 60 ° C or less. Further, the sulfur content is 5 mass ppm or less, preferably 2 mass ppm or less, more preferably 1 mass ppm or less.
This C5 gasoline base material can be obtained by distillation separation from the petroleum refining process and, if necessary, sulfur content removal by extraction, adsorption, sorption and the like. The product of a naphtha pyrolysis apparatus (ethylene cracker) in petrochemistry is also preferably obtained by distillation separation and diene removal. As a method for removing the diene, an extractive distillation method or a hydrogenation method using dimethylformamide (DMF) or acetonitrile is used.

[Combination]
The blending amount of the C5 gasoline base in the whole gasoline is 2% by volume or more, preferably 2 to 50% by volume, particularly 8 to 40% by volume. Other gasoline bases to be blended other than C5 gasoline bases are not particularly limited, but are desulfurized naphtha bases obtained by desulfurizing catalytic cracking gasoline bases, catalytic reformed gasoline bases, alkylate gasoline bases, straight-run naphtha. Known gasoline base materials such as materials and oxygen-containing gasoline base materials can be used. The other gasoline base material preferably has a sulfur content of 20 mass ppm or less, particularly preferably 15 mass ppm or less. In the case of catalytic cracking gasoline base and catalytic reforming gasoline base, it is fine and flexible by using fractions obtained by distillation and separating in appropriate boiling range such as light fraction and heavy fraction, respectively. A gasoline composition can be blended and prepared.

  Examples of the oxygen-containing gasoline base material include methyl t-butyl ether (MTBE), ethyl t-butyl ether (ETBE), t-amyl ethyl ether (TAEE), ethanol, methanol, etc. Among them, from the effect of improving octane number and handling properties Ethanol or ETBE is preferred, and ETBE is more preferred. The blending amount of the oxygen-containing gasoline base is preferably 0 to 20% by volume, and from the effect of improving the octane number, it is 5% by volume or more, further 7% by volume or more, and particularly preferably 10% by volume or more. Moreover, 20 volume% or less is preferable from the surface of a fuel consumption, 17 volume% or less is preferable from a rust prevention property and water-separation property, and 15 volume% or less is more preferable.

  Examples of preferable blending amounts of other gasoline base materials include C5 gasoline base material: 2 to 50% by volume, desulfurized naphtha base material: 0 to 10% by volume, alkylate gasoline base material: 2 to 30% by volume, catalytic cracking Gasoline base material: 2 to 80% by volume, catalytically modified gasoline base material: 10 to 70% by volume, oxygen-containing gasoline base material: 0 to 20% by volume. Particularly preferably, C5 gasoline base: 5-30% by volume, desulfurized naphtha base: 0-3% by volume, alkylate gasoline base: 3-20% by volume, catalytic cracking gasoline base: 2-80% by volume, Catalytic reforming gasoline base: 10-60% by volume, oxygen-containing gasoline base: 5-15% by volume. The blending amount of the carbon number 4 fraction (butane) substrate is preferably 2% by volume or less, and particularly preferably substantially not blended.

[Other additives]
Furthermore, the gasoline of the present invention can be blended with 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.

[Gasoline of the present invention]
In the gasoline composition of the present invention, the content of normal paraffin having 4 carbon atoms is 2% by volume or less, and preferably 1% by volume or less. The content of the olefin having 5 carbon atoms with respect to the hydrocarbon having 4 carbon atoms is 6 or more, particularly 7 or more in terms of volume ratio. Further, the content of the hydrocarbon having 4 carbon atoms is preferably 2% by volume or less, particularly preferably 1% by volume or less. By containing a relatively large amount of olefin having a high octane number and having 5 carbon atoms, the acceleration performance at low speed can be enhanced while the vapor pressure is suppressed to 60 kPa or less.

  The distillation property of the gasoline of the present invention is that the 50% distillation temperature is 105 ° C. or less, preferably 90 to 102 ° C., particularly preferably 95 to 100 ° C. A preferable 10% distillation temperature is 60 to 92 ° C, and a preferable 90% distillation temperature is 100 to 165 ° C.

  The sulfur content of the gasoline of the present invention is 10 ppm by mass or less, preferably 2 ppm by mass or less. The sulfur content in gasoline becomes a sulfur oxide compound in the exhaust gas and poisons the nitrogen oxide removal catalyst. For this reason, fuel is used to form a reducing atmosphere in order to restore the activity of the nitrogen oxide catalyst, which causes a deterioration in fuel consumption. Therefore, the fuel efficiency improves as the sulfur content in gasoline decreases. The octane number of the gasoline of the present invention can be 92 to 102, particularly 92 to 96 or 98 to 102.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

  Gasoline base materials having the properties shown in Table 1 were prepared and blended at the mixing ratio (volume%) shown in the upper part of Table 2 to prepare gasoline compositions as Examples and Comparative Examples. The gasoline base material used was prepared as follows.

C4:
A so-called butane fraction was obtained by distilling and separating the desulfurized liquefied petroleum gas to obtain a fraction containing 95% or more of hydrocarbons having 4 carbon atoms and 73% by volume of normal butane.
DS-LG:
Desulfurized straight-run light naphtha obtained by hydrodesulfurizing a naphtha fraction of Middle Eastern crude oil and distilling the light fraction.
ALKG:
A hydrocarbon having a high isoparaffin content was obtained by reacting a fraction mainly composed of butylene and a fraction mainly composed of isobutane with a sulfuric acid catalyst.

FCCG:
Desulfurized gas oil and desulfurized heavy oil were decomposed with a solid catalyst using a fluidized bed reactor to obtain a hydrocarbon having a high olefin content, that is, fluid catalytic cracking gasoline (FCCG).
FCCGL:
It is a light fraction (FCCGL) obtained by distilling the fluid catalytic cracking gasoline (FCCG) into a light fraction and a heavy fraction.
FCCGLL:
Corresponding to C5 gasoline base material, the light fraction (FCCGL) of the above-mentioned fluid catalytic cracking gasoline (FCCG) is further distilled and separated to form a lighter fraction, mainly composed of hydrocarbons having 5 carbon atoms ( FCCGLL) was obtained.
AC7:
Light reformed gasoline. When obtaining the desulfurized straight-run light naphtha (DS-LG), after desulfurization, the heavy fraction (desulfurized heavy naphtha) is distilled and separated. This desulfurized heavy naphtha was reformed with a solid catalyst using a moving bed reactor to obtain a hydrocarbon with a high aromatic content, that is, reformed gasoline. This was subjected to distillation separation to obtain a fraction (AC7) containing 95% or more of hydrocarbons having 7 carbon atoms.
AC9:
This is a heavy reformed gasoline, and in the distillation separation of the reformed gasoline prepared as described above, a fraction containing 5% or less of hydrocarbons having 11 or more carbon atoms and 90% or more of hydrocarbons having 9 or 10 carbon atoms. Minute (AC9) was obtained.

ETBE:
Ethyl tertiary butyl ether, ethanol and isobutylene were reacted in the presence of an ion exchange resin catalyst (Amberlyst-15), and purified by distillation to obtain ETBE having a purity of 95%.

The properties of the gasoline base materials and the gasoline compositions of Examples and Comparative Examples shown in Tables 1 and 2 were measured by the following method.
Distillation properties: JIS K 2254 "Petroleum products-Distillation test method"
Vapor pressure (RVP): JIS K 2258 "Crude oil and fuel oil-Vapor pressure test method-Reed method"
Octane number (RON): JIS K 2280 “Petroleum products—Fuel oil—Octane number and cetane number test method and cetane index calculation method” research method Octane number test method Sulfur content: JIS K 2541 “Crude oil and petroleum products—Sulfur content test method” Microcoulometric titration oxidation method density: JIS K 2249 "Crude oil and petroleum products-Density test method"
Compositions having 4 and 5 carbon atoms: Gas chromatographic method of JIS K 2536 “Petroleum products-Ingredient testing method”

  In Examples 1 and 2 shown in Table 2, C4 used in Comparative Examples 1 and 2 was not used, and the amount of DS-LG was reduced, and FCCGLL was used instead. In Examples 1 and 2, it can be seen that the ratio of the olefin having 5 carbon atoms to the hydrocarbon having 4 carbon atoms is 6.3 and 9.3, respectively. As a result, the vapor pressure could be reduced without significantly changing the octane number and the 50% distillation temperature.

  Further, comparing Example 3 with Comparative Example 3, in Example 3, FCCGLLL was used instead of DS-LG and FCCGL used in Comparative Example 3. In the examples, it can be seen that the ratio of the olefin having 5 carbon atoms to the hydrocarbon having 4 carbon atoms is 11.8, sufficiently exceeding 7. As a result, the octane number was further improved, and the sulfur content could be reduced without greatly increasing the 50% distillation temperature.

Claims (2)

  The content of olefin having 5 carbon atoms is 20% by volume or more, the content of normal paraffin having 4 carbon atoms is 1% by volume or less, the 10% distillation temperature is 25 ° C. or more, and the 90% distillation temperature is 65%. 2% by volume or more of a C5 gasoline base material having a sulfur content of 5 ppm by mass or less and another gasoline base material are mixed, and the carbon number 4 normal paraffin is 2% by volume or less and the number of carbon atoms is 4 A method for producing a gasoline composition, wherein a ratio (volume ratio) of a olefin having 5 carbon atoms to hydrocarbon is 6 or more, a vapor pressure is 60 kPa or less, a 50% distillation temperature is 105 ° C. or less, and a sulfur content is 10 mass ppm or less.   The gasoline composition according to claim 1, wherein the C5 gasoline base has a hydrocarbon content of 5 or more carbon atoms of 50% by volume or more and a hydrocarbon content of 4 carbon atoms of 2% by volume or less. Method.