JP2010095566A - Gasoline composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gasoline composition having an enhanced octane number by stably enhancing an octane number of fluidized catalytically cracked gasoline mainly used as a base material of a gasoline composition even after the sulfur content thereof is decreased by a two-stage desulfurization method or the like. <P>SOLUTION: The gasoline composition comprises at least 90 vol% of a gasoline fraction obtained by mixing a base material 1 having a 90% distillation temperature of 80-120°C and a base material 2 having a 10% distillation temperature of 100-130°C and a 90% distillation temperature of 190°C or lower, and has a total sulfur content of at most 10 mass ppm, a research octane number of 90-96, a Reid vapor pressure of at most 55 kPa, an aromatics content of 10-30 vol% and an olefin content of at least 10 vol%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a gasoline composition having a high octane number, and in particular, a gasoline composition characterized in that the octane number is improved by increasing the research octane number of a fluid catalytic cracking gasoline base mainly used as a gasoline base. It is about.

  In an internal combustion engine that compresses and ignites a mixed gas of fuel and air, when the gasoline research octane number (hereinafter referred to as octane number) is high, the thermal efficiency is improved by increasing the compression ratio. I can do it. Here, in order to improve the thermal efficiency by increasing the octane number of regular gasoline, it is effective to increase the octane number of fluid catalytic cracking gasoline as the main base material. However, in order to increase the octane number of fluid catalytic cracking gasoline, for example, even if the reaction conditions of the fluid catalytic cracking apparatus are changed, it has been found that the octane number improving effect is reduced for the following reason.

  That is, a two-stage desulfurization method is used to remove the sulfur content contained in the gasoline while suppressing a decrease in the octane number of fluid catalytic cracking gasoline. In the two-stage desulfurization method, the octane number is relatively low. The high-light fraction is distilled and separated, and only the heavy component containing a large amount of sulfur is hydrodesulfurized and then mixed with the light component again, but the reaction conditions of the fluid catalytic cracking unit are changed to improve the octane number. In this case, the effect of improving the octane number is mainly obtained as a result of a change in the heavy component of fluid catalytic cracking gasoline, for example, aromatization by dehydrogenation, whereas in the two-stage desulfurization method after fluid catalytic cracking, Hydrogen is again added to the heavy component by hydrodesulfurization of the heavy component, and the aromatic component is naphthenized, so that the octane number of the heavy component having the increased octane number decreases again.

  Conventionally, as a method for increasing the octane number of fluid catalytic cracking gasoline, in addition to the method of changing the reaction conditions of the fluid catalytic cracking device described above, a component having a relatively low octane number in the middle boiling point region of the gasoline is distilled and separated. A process is known in which a component having a low and relatively high octane number is mixed with a component having a high boiling point and a high octane number compared to the intermediate boiling point region (Patent Document 1).

However, the octane number in the predetermined boiling range of fluid catalytic cracking gasoline varies depending on the raw materials and reaction conditions of the fluid catalytic cracking device, and the boiling point is relatively low because the octane number of the heavy component is reduced by the above-mentioned two-stage desulfurization. The octane number is not necessarily improved by a process of mixing a component having a high octane number and a component having a high boiling point and a high octane number compared to the middle boiling point region.
JP 2006-182997 A

  Therefore, an object of the present invention is to increase the octane number of the regular gasoline, even after the sulfur content is reduced by the two-stage desulfurization method, etc., for the fluid catalytic cracking gasoline that is the main base material of the gasoline. Another object of the present invention is to provide a gasoline composition having an improved octane number by using such a base material.

  As a result of intensive studies to achieve the above object, the present inventors have found that the heavy component of the fluid catalytic cracking gasoline is heavier than the heavy component of fluid catalytic cracking gasoline by the above-described two-stage desulfurization method. The fraction (hereinafter referred to as the post-fraction) is hydrogenated to lower the octane number, and when the light and heavy components are remixed in the two-stage desulfurization method, the specific olefin component and the specific aromatic It has been found that the octane number improving effect is affected by the size of the component. Furthermore, the present inventors based on these findings, more specifically, by devising the preparation conditions of the above-mentioned fraction of fluid catalytic cracking gasoline while optimizing the reaction conditions of the fluid catalytic cracking apparatus. A base material having a 90% distillation temperature in a specific range obtained by distillation separation of fluid catalytic cracking gasoline and another base material having a 10% distillation temperature and a 90% distillation temperature in a specific range By combining them, it was found that a gasoline composition having a high octane number was stably obtained, and the present invention was completed.

  That is, the gasoline composition according to the present invention includes a base material 1 having a 90% distillation temperature of 80 to 120 ° C, and a base material having a 10% distillation temperature of 100 to 130 ° C and a 90% distillation temperature of 190 ° C or less. The gasoline fraction obtained by mixing 2 with 90% by volume or more, the total sulfur content is 10 mass ppm or less, the research octane number is 90 to 96, the Reid vapor pressure is 55 kPa or less, and the total aromatic content is 10 -30% by volume and olefin content is 10% by volume or more.

  In a preferred example of the gasoline composition of the present invention, the aromatic content having 11 or more carbon atoms is 3.0% by volume or less, and the olefin content having 6 or more carbon atoms is 22.0% by volume or more.

  Further, in another preferred embodiment of the gasoline composition of the present invention, the base material 1 and the base group are more than the research method octane number calculated from the research method octane number of the base material 1 and the base material 2 by the mixing volume ratio. The research octane number measured for the gasoline fraction obtained by mixing the material 2 is higher than 0.1.

  The gasoline composition of the present invention has an effect that the octane number is high, the octane number improving effect after mixing the base material is high, the volatility is good, the vapor pressure is low, and the sulfur content is low.

  The present invention is described in detail below. The gasoline composition of the present invention comprises a base material 1 having a 90% distillation temperature of 80 to 120 ° C, a base material 2 having a 10% distillation temperature of 100 to 130 ° C and a 90% distillation temperature of 190 ° C or less. The gasoline fraction obtained by mixing is contained. Here, the volume ratio (base material 1 / base material 2) between the base material 1 and the base material 2 in the gasoline fraction is not particularly limited, but a range of 60/40 to 40/60 is preferable. .

  The gasoline composition of the present invention has a total sulfur content of 10 ppm by mass or less, preferably 5 ppm by mass or less, more preferably 3 ppm by mass or less, from the viewpoint of preventing deterioration of the automobile catalyst.

  In order to improve fuel efficiency by improving the compression ratio, the higher the octane number of regular gasoline, the better. Therefore, the gasoline composition of the present invention has a research octane number of 90.0 or more, preferably 90.5 or more, more preferably It is 91.0 or more. On the other hand, in general, increasing the octane number increases the amount of aromatic compounds having low volatility and deteriorates the startability of the vehicle when cold, so the gasoline composition of the present invention has an octane number of 96.0 or less, preferably 95 0.0 or less, more preferably 94.0 or less.

  In order to increase the octane number, the gasoline composition of the present invention has an aromatic content of 10% by volume or more, preferably 11% by volume or more, and more preferably 13% by volume or more. On the other hand, if the aromatic content is large, the volatility deteriorates or the exhaust gas properties are easily deteriorated. Therefore, the gasoline composition of the present invention has an aromatic content of 30% by volume or less, preferably 29% by volume. Hereinafter, it is more preferably 28% by volume or less.

  In order to increase the octane number, the gasoline composition of the present invention has an olefin content of 10% by volume or more, preferably 15% by volume or more, and more preferably 20% by volume or more. On the other hand, if a large amount of olefin is contained, the oxidation stability deteriorates and the influence on the atmospheric environment due to evaporation of gasoline vapor increases, so the gasoline composition of the present invention preferably has an olefin content of 40% by volume or less. More preferably, it is 35% by volume or less.

  If the 90% distillation temperature of the base material 1 is too low, the influence on the atmospheric environment due to evaporation of gasoline vapor becomes large. Therefore, the 90% distillation temperature of the base material 1 is 80 ° C. or higher, preferably 85 ° C. or higher. More preferably, it is 90 ° C. or higher. Further, if the 90% distillation temperature of the substrate 1 is too high, the sulfur content becomes high and the exhaust gas purification catalyst is likely to be poisoned. Therefore, the 90% distillation temperature of the substrate 1 is 120 ° C. or less, preferably 115 ° C. or lower, more preferably 110 ° C. or lower.

  Further, if the 10% distillation temperature of the base material 2 is too low, the decrease in octane number due to hydrodesulfurization increases, so the 10% distillation temperature of the base material 2 is 100 ° C. or higher, preferably 105 ° C. or higher. Preferably it is 110 degreeC or more. Further, since the octane number is lowered when the 10% distillation temperature of the substrate 2 is too high, the 10% distillation temperature of the substrate 2 is 130 ° C. or less, preferably 125 ° C. or less, more preferably 123 ° C. or less. .

  Further, if the 90% distillation temperature of the base material 2 is too high, the effect of improving the octane number after the base material mixing is lowered, so the 90% distillation temperature of the base material 2 is 190 ° C. or lower, preferably 188 ° C. or lower, More preferably, it is 185 degrees C or less. In addition, if the 90% distillation temperature of the base material 2 is too low, the influence on the atmospheric environment due to evaporation of gasoline vapor becomes large. Therefore, the 90% distillation temperature of the base material 2 is preferably 125 ° C. or more, Preferably it is 130 degreeC or more.

  In the gasoline composition of the present invention, the content of the gasoline fraction obtained by mixing the base material 1 and the base material 2 is 90% by volume or more, and butane and butylene may be appropriately mixed for adjusting the vapor pressure. The content of the gasoline fraction in which the base material 1 and the base material 2 are mixed in order to increase the research octane number is preferably 95% by volume or more, and more preferably 100% by volume.

  In order to enhance the octane number improving effect after mixing the base material while maintaining good volatility, the gasoline composition of the present invention preferably has an aromatic content of 11 or more carbon atoms, preferably 3.0% by volume or less, more preferably Is not more than 2.0% by volume, particularly preferably not more than 1.0% by volume.

  In addition, since the olefin having 6 or more carbon atoms enhances the effect of improving the octane number after mixing the base material, the gasoline composition of the present invention preferably has an olefin content having 6 or more carbon atoms, more preferably 22.0% by volume or more. Is 22.5% by volume or more, particularly preferably 23.0% by volume or more.

  In addition, from the viewpoint of suppressing the impact on the air environment due to the evaporation of gasoline vapor in vehicles sold on the market, it is preferable that the vapor pressure (37.8 ° C) of gasoline is low, but in general, butane used for vapor pressure adjustment is regular gasoline. Since the octane number is high as compared with the above, in order to mix a large amount of this with regular gasoline, it is particularly preferable that the vapor pressure of fluid catalytic cracking gasoline is low. Therefore, the gasoline composition of the present invention has a lead vapor pressure of 55 kPa or less, preferably 50 kPa or less, more preferably 40 kPa or less, particularly 35 kPa or less.

  In addition, the research method octane number obtained by measuring the gasoline fraction obtained by mixing the base material 1 and the base material 2 rather than the research method octane number calculated from the research method octane number of the base material 1 and the base material 2 by the mixing volume ratio. If it is low, it is necessary to increase the octane number of the base material 1 and the base material 2, and the amount of carbon dioxide emitted during production increases, so this octane number difference (referred to as octane number bonus) is preferably 0.1 or more. More preferably, it is 0.2 or more, particularly preferably 0.3 or more.

  Although not particularly limited, the gasoline composition of the present invention has a 10% distillation temperature of preferably 50 to 80 ° C and a 90% distillation temperature of preferably 120 to 175 ° C.

[Gasoline base material]
The base material 1 and the base material 2 used in the gasoline composition of the present invention are obtained, for example, by distilling and separating fluid catalytic cracking gasoline. The fluid catalytic cracking gasoline uses petroleum fractions from light oil to vacuum gas oil, degasified oil obtained from heavy oil indirect desulfurization equipment, direct desulfurized oil obtained from heavy oil direct desulfurization equipment, and normal pressure residual oil as raw materials. It is a high octane gasoline base material obtained by catalytic cracking with a catalyst such as amorphous silica alumina or zeolite. A known manufacturing process can be arbitrarily adopted as the catalytic cracking apparatus. 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. This fluid catalytic cracking gasoline is a substrate having a relatively high sulfur content. Accordingly, it is preferable to perform fluid catalytic cracking after adjusting the sulfur content of the raw material in advance, or to remove the sulfur content of the obtained fluid catalytic cracked gasoline by operations such as extraction, adsorption and sorption. In addition, when sorbing and removing sulfur from fluid catalytic cracking gasoline, it is effective to remove diene beforehand by extractive distillation or hydrogenation using dimethylformamide (DMF) or acetonitrile. Sulfur content can be reduced.

[Other additives]
Furthermore, in the gasoline composition of the present invention, one or more fuel oil additives known in the technical field can be blended with the above-described base material as necessary. Although these compounding quantities can be selected suitably, it is preferable to maintain the total compounding quantity of an additive to 0.1 mass% or less normally. Examples of fuel oil additives that can be used in the gasoline composition of the present invention include Schiff type compounds, metal deactivators such as thioamide type compounds, surface ignition preventives such as organophosphorus compounds, succinimides, and polyalkylamines. Detergents such as polyetheramines, anti-freezing agents such as polyhydric alcohols or ethers thereof, organic metal alkali metal salts or alkaline earth metal salts, auxiliary alcohols such as higher alcohol sulfates, anionic surfactants And antistatic agents such as cationic surfactants and amphoteric surfactants, and colorants such as azo dyes. When these additives are used, the oxidation stability may deteriorate, so it is preferable to confirm that the oxidation stability does not deteriorate before and after the addition of the additive. Moreover, it is also effective to appropriately add a phenol-based additive such as dibutylhydroxytoluene or an amine-based additive such as diphenylamine as an antioxidant.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

  The gasoline base materials used in preparing the gasoline compositions of Examples and Comparative Examples are as follows. Table 1 shows the properties of each substrate.

  The reaction temperature and catalyst / fuel flow ratio (C / O) of the fluid catalytic cracker are reacted under the reaction conditions that are the basis, and then separated by distillation to obtain LCN which is a light component, and hydrodesulfurizing a heavy component. DH-CN was obtained. In addition, the reaction conditions are set so that the octane number is higher than the above-mentioned standard reaction conditions, and the reaction is followed by distillation separation to obtain LCNx which is a light component, and hydrodesulfurizing a heavy component to obtain DH-CNx. It was.

Moreover, the following each base material was prepared as follows.
DH-CNx 5% cut: 95% by volume light fraction obtained by distilling 5% by volume of DH-CNx heavy fraction.
DH-CNx 10% cut: 90% by volume light fraction obtained by distilling 10% by volume of DH-CNx heavy fraction.
DH-CNx 60% cut: 40% by volume light fraction obtained by distilling 60% by volume of DH-CNx heavy fraction.
DH-CNx 60% heavy: 60% by volume heavy of DH-CNx separated by distillation as described above.

  The gasoline compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were obtained by mixing at the blending amounts shown in Table 2 using the base material shown in Table 1.

  In addition, the property of the gasoline base material shown in Table 1 and Table 2, and the property of the gasoline composition of an Example and a comparative example were measured with the following method.

(1) Density: JIS K 2249 "Crude oil and petroleum products-Density test method"

(2) Octane number (RON): The research method octane number test method of JIS K 2280 "Petroleum products-fuel oil-octane number and cetane number test method and cetane index calculation method" was used.

(3) Vapor pressure (RVP): JIS K 2258 "Crude oil and fuel oil-Vapor pressure test method-Reed method"

(4) Distillation properties: JIS K 2254 "Petroleum products-Distillation test method"

(5) Total sulfur content: The total sulfur content was determined to 2 digits after the decimal point in accordance with the microcoulometric titration method of JIS K2541 “Crude oil and petroleum products—Sulfur content test method”.

(6) Component composition of various hydrocarbon compounds such as aromatic content, olefin content, etc .: Measured by the all component test method according to the gas chromatograph method of JIS K2536.

  From Table 2, it can be seen that the gasoline compositions of Examples 1 to 3 have higher octane numbers than Comparative Examples 1 to 3.

  Moreover, since the content of olefins having 6 or more carbon atoms is higher in Examples 1 to 3 than in Comparative Examples 1 to 3, Examples 1 to 3 have a high effect of improving the octane number after mixing the base materials. I understand.

  Furthermore, since Examples 1-3 have a larger difference (RON bonus) between the calculated value calculated from the octane number of the base material and the octane number obtained by actual measurement than Comparative Examples 2-3, the base material It can be seen that the effect of improving the octane number after mixing is high.

  Moreover, since the content of aromatics having 11 or more carbon atoms is lower in Examples 1 to 3 than in Comparative Examples 1 to 3, it can be seen that Examples 1 to 3 have good volatility.

  Furthermore, since Examples 1-3 have a 90% lower distillation temperature than Comparative Examples 1-3, it can be seen that Examples 1-3 have good volatility.

Claims (3)

  A gasoline fraction obtained by mixing a base material 1 having a 90% distillation temperature of 80 to 120 ° C and a base material 2 having a 10% distillation temperature of 100 to 130 ° C and a 90% distillation temperature of 190 ° C or less. The total sulfur content is 10 mass ppm or less, the research octane number is 90 to 96, the lead vapor pressure is 55 kPa or less, the aromatic content is 10 to 30% by volume, and the olefin content is 10 volumes. A gasoline composition characterized by being at least%.   The gasoline composition according to claim 1, wherein the aromatic content having 11 or more carbon atoms is 3.0% by volume or less, and the olefin content having 6 or more carbon atoms is 22.0% by volume or more.   The research which measured the gasoline fraction obtained by mixing the said base material 1 and the said base material 2 rather than the research method octane number calculated by the mixing volume ratio from the research method octane number of the said base material 1 and the said base material 2 The gasoline composition according to claim 1 or 2, wherein the octane number is 0.1 or more higher.