JP4866004B2 - Novel gasoline base material and gasoline composition containing the base material - Google Patents

Description

  The present invention relates to a novel gasoline base material and a gasoline composition containing the base material, and more particularly to a novel gasoline base material obtained by using cracked gasoline generated from a catalytic cracking apparatus and a gasoline composition containing the base material. .

According to JIS K 2202, the research method octane number (hereinafter sometimes abbreviated as “RON”) of No. 2 gasoline (so-called regular gasoline) is 89.0 or more, and the RON of No. 1 gasoline (so-called premium gasoline) is 96. It is defined as 0 or more. Therefore, RON of regular gasoline is gasoline in the range of 89 or more and less than 96. On the other hand, RON of regular gasoline in the market is within the range of the above standard, but there are many about 90, and most of newly developed regular gasoline has the same level of RON (for example, Patent Document 1, See Example 2). Under such circumstances, cracked gasoline having a relatively low RON is used as a main base material for regular gasoline.
However, it is necessary to reduce carbon dioxide emissions as a measure against global warming, and there is a demand to increase the RON of regular gasoline higher than before, for example, 93 or more in order to achieve the purpose. In addition, as a measure against exhaust gas, it is necessary to further reduce the sulfur content in gasoline and aromatic components such as benzene in consideration of the SO _x and benzene concentration in the exhaust gas.

However, cracked gasoline, which is the main base material for regular gasoline, has a RON of about 90 to 92 and a high content of sulfur and benzene. Further, when hydrodesulfurization treatment is performed in order to reduce the sulfur content of the cracked gasoline, the olefin content in the cracked gasoline is hydrogenated, resulting in a phenomenon that the octane number further decreases. In addition, the problem of reducing the benzene content cannot be solved.
From such a background, a gasoline base material that satisfies the properties of high octane number, low sulfur, low benzene and the like and can be stably supplied as a main raw material of regular gasoline is required. At the same time, there is a demand for the development of environmentally friendly gasoline that has a relatively high octane number, satisfies low sulfur, low benzene, etc., and solves environmental pollution such as global warming and exhaust gas regulations.

JP 2000-73074 A JP 2001-288383 A

  The present invention has been made under such circumstances, and by utilizing easily cracked catalytic cracked gasoline, a gasoline substrate having a high octane number, a low sulfur and a low benzene is obtained, and such a novel gasoline substrate is obtained. An object of the present invention is to provide an environmentally friendly gasoline composition.

  The present inventors can obtain a target gasoline base material by distilling catalytically cracked gasoline into three fractions and using light and heavy fractions excluding middle fractions, Moreover, it discovered that the composition containing such a gasoline base material could achieve the objective. The present invention has been completed based on such findings.

That is, the present invention
1. A gasoline base material obtained by fractionating cracked gasoline obtained from a catalytic cracker into a light fraction, a middle fraction, and a heavy fraction, and mixing the light fraction and the heavy fraction excluding the middle fraction ,
2. The gasoline base material according to 1, wherein the middle distillate has a boiling range of 90 to 180 ° C.
3 The gasoline base material according to 1 above, wherein the middle distillate has a boiling range of 75 to 180 ° C.
4). The gasoline base material according to any one of 1 to 3, wherein the octane number is 93 or more,
5. The gasoline composition containing the gasoline base material in any one of said 1-4,
6). Exhaust gas index with a research octane number of 89 or more and less than 96, a sulfur content of 10 mass ppm or less, an aromatic content of 45 vol% or less, a benzene content of 1 vol% or less, and the following formula (I) The gasoline composition according to 5 above, wherein (Y) is 2.5 or less,
Y = 1.07BZ + 0.12TO + 0.11EB + 0.05XY + 0.03C 9 + A + 0.005 [100- (BZ + TO + EB + XY + C 9 + A) ]
・ ・ ・ ・ ・ ・ ・ ・ ・ (I)
[In the formula, BZ is benzene content, TO is toluene content, EB is ethylbenzene content, XY is xylene content, C ₉ ⁺ A is aromatic content with 9 or more carbon atoms (all in gasoline composition) % By volume). ]
Is to provide.

  The high octane gasoline base material of the present invention has a high octane number, low sulfur and low benzene, and uses a cracked gasoline that can be stably obtained as a raw material. Therefore, the gasoline composition of the present invention containing this is an environment-friendly gasoline having an increased octane number, low sulfur and low benzene, and capable of suppressing global warming, exhaust gas pollution, and the like.

As described above, the gasoline base material in the present invention is a light fraction obtained by fractionating cracked gasoline obtained from a catalytic cracking apparatus into a light fraction, a middle fraction, and a heavy fraction, and removing the middle fraction. It is a gasoline base material made by mixing heavy fractions.
Here, the cracked gasoline obtained from the catalytic cracking unit is a fluid catalytic cracking unit that processes a fraction distilled from an indirect desulfurization unit, or a heavy oil fluidized catalytic cracking unit that processes a fraction distilled from a heavy oil direct desulfurization unit. Distilled cracked gasoline refers to a mixture of cracked gasoline obtained from the fluid catalytic cracker and heavy oil fluidized catalytic cracker.
The boiling range of this cracked gasoline is usually about 10 to 230 ° C., the octane number is about 88 to 93, the sulfur content is about 0 to 100 ppm by mass, the aromatic content is about 5 to 50% by volume, and the benzene content is about 0. It has properties such as 5-2.5% by volume.

In the gasoline base material of the present invention, a light fraction and a heavy fraction other than the middle fraction of the cracked gasoline are used. That is, it is a gasoline base material composed of a light fraction and a heavy fraction of cracked gasoline. In this case, the boiling range of the middle distillate to be removed may be 70 to 180 ° C., but 90 to 180 ° C. or 75 to 180 ° C. is particularly preferable. If the boiling range of the middle distillate to be removed is 90 to 180 ° C., since many low octane compounds exist in this boiling range, the octane number of the obtained gasoline base can be increased. Moreover, when the boiling range of the middle distillate to be removed is 75 to 180 ° C., the octane number of the obtained gasoline base material is improved, the benzene content and the like can be extremely reduced, and the exhaust gas index described later is reduced. It is an effective base material as a base material.
In addition, the fraction removed as an intermediate fraction does not necessarily need to be a fraction covering the whole boiling range, and may be a fraction of the boiling range. For example, even if it is a middle distillate whose boiling range is 90-160 degreeC or 75-160 degreeC, said effect is acquired.

The gasoline base material obtained as described above preferably has the following properties.
The octane number is 93 or more, more preferably 94 or more, and particularly preferably 95 or more. The sulfur content is 20 ppm by mass or less, more preferably 10 ppm by mass or less, the aromatic content is 45% by volume or less, more preferably 40% by volume or less, and the benzene content is 1.5% by volume or less, more preferably 0.5% by volume. The capacity is less than%. The boiling point range is approximately 20 to 220 ° C.

Next, in the gasoline composition of this invention, it is necessary to contain the said gasoline base material.
Accordingly, it is possible to easily produce an environmentally friendly gasoline that is a regular gasoline having a high octane number and suppresses global warming, exhaust gas pollution, and the like.
The content of the gasoline base material in the gasoline composition of the present invention is not particularly limited, but is preferably 50% by volume or more, more preferably 60 to 100% by volume, particularly preferably 70 to 98% by volume. It is. If the content of the gasoline base material of the present invention is 50% by volume, the octane number can be increased, the sulfur content and the benzene content can be reduced, and the exhaust gas index can be kept low.

  The gasoline composition of the present invention can use a gasoline base other than those described above. For example, light naphtha obtained by atmospheric distillation of crude oil, cracked gasoline obtained by catalytic cracking or hydrocracking, and fractions from which benzene has been removed from reformed gasoline obtained by catalytic reforming (debenzene modified) Quality gasoline), polymerized gasoline obtained by polymerization of olefins, alkylates obtained by adding lower olefins to hydrocarbons such as isobutane, isomerates obtained by isomerization of straight chain lower paraffin hydrocarbons, de-n- Examples include paraffin oil, pyrolysis gasoline obtained by pyrolysis of naphtha, fractions of these, aromatic hydrocarbons such as toluene and xylene, isoparaffins, and oxygen-containing compounds such as alcohol and ether. .

  Moreover, various additives can be appropriately blended in the gasoline composition of the present invention as necessary. Examples of such additives include phenolic and amine antioxidants, metal deactivators such as Schiff compounds and thioamide compounds, surface ignition inhibitors such as organic phosphorus compounds, succinimides, and polyalkylamines. Detergents such as polyetheramines, anti-icing agents such as polyhydric alcohols and ethers, organic acid alkali metal and alkaline earth metal salts, auxiliary alcohols such as higher alcohol sulfates, anionic surfactants, cationic interfaces Activators, antistatic agents such as double-sided surfactants, rust inhibitors such as esters of alkenyl succinic acid, identifiers such as kilyzanine and coumarin, odorants such as natural essential oils and synthetic fragrances, colorants such as azo dyes, etc. Well-known gasoline additives can be mentioned, and one or more of these additives can be added. Further, the additive amount of these additives may be appropriately selected depending on the situation, but it is usually preferable that the total amount of additives is 0.1% by mass or less based on the gasoline composition.

The gasoline composition of the present invention preferably has the following properties.
The RON in the gasoline composition of the present invention is preferably 89 or more, more preferably 90 or more, further 92 or more, and particularly preferably 93 or more. The upper limit value of RON is not particularly limited, but is usually less than about 96 and further 95 or less. If RON is 89 or more, there is no fear of knocking and good driving performance can be secured. Moreover, if RON is 93 or more and less than 96, the effect of reducing a carbon dioxide emission amount can also be anticipated. The research octane number is a value measured according to JIS K 2280.
The gasoline composition of the present invention preferably has a sulfur content of 10 mass ppm or less, more preferably 5 mass ppm or less. If the sulfur content is 10 ppm by mass or less, it is possible to suppress an increase in SOx in the exhaust gas and an increase in CO, hydrocarbon, NOx, etc. in the exhaust gas due to a decrease in the activity of the three-way catalyst. The sulfur content is a value measured according to the microcoulometric titration method of JIS K2541.

  In the gasoline composition of the present invention, the aromatic content is preferably 45% by volume or less, more preferably 40% by volume or less. If the aromatic content is 45% by volume or less, the spark plug does not cause smoldering and good driving performance can be obtained. On the other hand, the lower limit of the aromatic content is not particularly limited, but is preferably 10% by volume or more, and more preferably 15% by volume or more from the viewpoint of preventing a decrease in operating performance. The aromatic content is a value measured by the fluorescent indicator adsorption method of JIS K 2536 “Petroleum product component test method”.

  The gasoline composition of the present invention has a benzene content of 1% by volume or less, more preferably 0.7% by volume or less. If benzene is 1 volume% or less, benzene content in exhaust gas can be suppressed. In addition, benzene content is the value measured by the all-component test method by the gas chromatography of JISK2536 "Petroleum product component test method".

Furthermore, the gasoline composition of the present invention preferably has the following distillation properties. That is, the 50% distillation temperature (T50) is 60 to 100 ° C, further 65 to 90 ° C, the 70% distillation temperature (T70) is 70 to 145 ° C, and further 80 to 135 ° C, 90% distillation temperature ( T90) is from 105 to 165 ° C, and further from 110 to 150 ° C. If it has such a distillation property, driving performance, such as acceleration, is kept favorable.
In addition, said T50, T70, and T90 are the values calculated | required from the distillation property measured based on JISK2254.

  In addition, the high-performance gasoline of the present invention usually preferably has the following properties. That is, the content of MTBE (methyl-tert-butyl ether) is preferably 0.1% by volume or less. If MTBE exceeds 0.1% by volume, environmental problems such as groundwater contamination may occur. The MTBE content is a value measured by JIS K 2536 “Petroleum product component test method”.

The motor octane number (MON) is preferably 79 or more, more preferably 82 or more, and particularly preferably 84 or more. When the MON is 79 or more, there is no risk of knocking at a high speed, and the driving performance can be kept good. On the other hand, the upper limit of MON is not particularly limited, but is usually about 89.
Since the gasoline composition of the present invention has the properties as described above, an exhaust gas index (Y) represented by the following (I) is 2.5 or less, further 2.0 or less, particularly 1.5 or less. Obtainable.

Y = 1.07BZ + 0.12TO + 0.11EB + 0.05XY + 0.03C 9 + A + 0.005 [100- (BZ + TO + EB + XY + C 9 + A) ]
・ ・ ・ ・ ・ ・ ・ ・ ・ (I)
[In the formula, BZ is benzene content, TO is toluene content, EB is ethylbenzene content, XY is xylene content, C ₉ ⁺ A is aromatic content with 9 or more carbon atoms (all in gasoline composition) % By volume). ]
In addition, content of each aromatic content is the value computed from the total composition analysis (based on Petroleum Institute method JPI-5S-90) of the gasoline composition by a gas chromatograph method.

EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not restrict | limited at all by these examples. The properties and performance of the gasoline composition were determined according to the following method.
[Properties of gasoline]
-Research octane number: measured according to JIS K 2280.
Sulfur content: Measured by the microcoulometric titration method of JIS K2541.
Aromatic content: Measured according to JIS K2536.
-Content of aromatic compounds such as benzene and toluene: Measured by JIS K 2536 "Petroleum product component test method" All component test method by gas chromatography.
Distillation property: Measured according to JIS K2541.
[Performance of gasoline]
-Exhaust gas index: It was determined by the general formula (I).

Examples 1 and 2 and Reference Example 1
(I) Example 1
The cracked gasoline having the properties shown below obtained from the catalytic cracker was fractionated to obtain a light fraction, a middle fraction, and a heavy fraction. An intermediate fraction having a boiling range of 90 to 160 ° C. was removed, and a light fraction (LFG) and a heavy fraction (HFG) were mixed to obtain a gasoline substrate 1 (Example 1). The properties are shown in Table 1.
(2) Example 2
Except that the boiling range of the middle distillate is 75 to 160 ° C., a light base (LFG) and a heavy distillate (HFG) are mixed in the same manner as in Example 1 to mix gasoline base 2 (Example 2). ) The properties are shown in Table 1.

Properties and boiling point range of cracked gasoline : 31.0-197.5 ° C
・ RON: 91.6
・ Aromatic content: 37.2% by volume
・ Sulfur content: 7 mass ppm

  For reference, the properties of conventional cracked gasoline (FG) are shown in Table 1 as Reference Example 1.

From Table 1, the gasoline base material 1 of Example 1 and the gasoline base material 2 of Example 2 have RON of 93.5 and 96.2, which is higher than RON of FG (cracked gasoline). Moreover, it turns out that the benzene content of the gasoline base material 2 is 0 volume%, Comprising: The benzene content of FG is lower than 0.7 volume%.
Examples 3 to 6 and Comparative Examples 1 and 2

It is obtained by blending gasoline base materials 1 and 2 of Examples 1 and 2 shown in Table 1, FG of Reference Example 1 and other gasoline base materials 1 (PG) and 2 (DLN) in proportions shown in Table 2. Table 2 shows the properties of the gasoline composition and the exhaust gas index.
The other base material 1 is catalytic reformed gasoline (PG), and the other base material 2 is light naphtha (DLN), both of which are known gasoline base materials.

According to the present invention, it is possible to obtain a gasoline base material from cracked gasoline which has a high octane number, low sulfur and low benzene, and can be obtained stably, and the gasoline composition of the present invention containing the gasoline base material The product has an increased octane number and is useful as an environmentally friendly regular gasoline that can suppress global warming, exhaust gas pollution, and the like.

Claims (6)

The cracked gasoline obtained from the catalytic cracker is fractionated into light fractions, middle fractions, and heavy fractions, and light fractions and heavy fractions excluding the middle fractions having a boiling range of 90 to 180 ° C. minute Ri name were mixed, research octane number gasoline base material Ru der 95 or more. The cracked gasoline obtained from the catalytic cracker is fractionated into a light fraction, a middle fraction, and a heavy fraction, and the light fraction and the heavy fraction excluding the middle fraction having a boiling range of 75 to 180 ° C. A gasoline base material having a benzene content of 1.5% by volume or less and a research octane number of 95 or more. The gasoline composition containing the gasoline base material of Claim 1 or 2 . The gasoline composition according to claim 3, wherein the research octane number is 93 or more. The gasoline composition according to claim 3 or 4, wherein the benzene content is 1% by volume or less. Exhaust gas index with a research octane number of 93 or more and less than 96, a sulfur content of 10 mass ppm or less, an aromatic content of 45 vol% or less, a benzene content of 1 vol% or less, and the following formula (I) (Y) is 2.5 or less, The gasoline composition in any one of Claims 3-5 .
Y = 1.07BZ + 0.12TO + 0.11EB + 0.05XY + 0.03C 9 + A + 0.005 [100- (BZ + TO + EB + XY + C 9 + A) ]
・ ・ ・ ・ ・ ・ ・ ・ ・ (I)
[In the formula, BZ is benzene content, TO is toluene content, EB is ethylbenzene content, XY is xylene content, C ₉ ⁺ A is aromatic content with 9 or more carbon atoms (all in gasoline composition) % By volume). ]