JP2009227693A - Gasoline composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gasoline composition being excellent in water turbidity prevention performance and being also excellent in environment performance while taking into consideration the importance of an environment problem in the gasoline composition not formulated with an oxygen-containing substrate. <P>SOLUTION: In the gasoline composition, (α) 10-50 vol.% of a catalytic reforming derived gasoline substrate (I) having an aromatic composition of a predetermined ratio and having T10 and T90 of predetermined temperatures or 10-50 vol.% of a catalytic reforming derived gasoline substrate (II) having an aromatic composition of a predetermined ratio in a different range from the catalytic reforming derived gasoline substrate (I) and T10 of a predetermined temperature and having T90 of a predetermined temperature in the same range as the catalytic reforming derived gasoline substrate (I) are formulated, and (β) 10-60 vol.% of the catalytic cracking derived gasoline substrate containing an unsaturated hydrocarbon composition of a predetermined ratio and having T10 and T90 of predetermined temperatures is formulated. The gasoline composition has (γ) a predetermined Reid vapor pressure, a research method octane value, a vapor property and a composition. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a gasoline composition, and more particularly to a gasoline composition having a specified gasoline composition and a specified distillation property, which is excellent in water turbidity prevention performance and environmental performance.

Hydrocarbon components such as fuel oil for gasoline engines have a water solubility as low as several tens to several hundred ppm, and the saturation solubility varies depending on the temperature.
Gasoline may come into contact with moisture during transportation, storage, etc. In such cases, it may dissolve moisture close to saturation solubility.
If gasoline containing moisture close to saturation solubility is transported, moisture in the gasoline will begin to separate due to changes in environmental temperature during transportation, etc., resulting in turbidity in the gasoline. Conceivable.

  Recognizing the improvement of turbidity caused by water, gasoline with excellent water turbidity prevention performance, ethanol content and olefin content (see Patent Document 1), ethyl tertiary butyl ether (ETBE) content , Those specifying the total content of alcohols having 2 or more carbon atoms and ethers other than ETBE (see Patent Document 2), those specifying the content of ETBE and aromatic content (see Patent Document 3) have been proposed Yes.

JP 2007-91922 A JP 2007-45858 JP 2007-23164

  However, Patent Documents 1 to 3 all relate to gasoline containing an oxygen-containing base material such as ethanol or ETBE, and in gasoline not containing an oxygen-containing base material, the problem of improving water spill prevention performance is satisfactory. In the past, no proposal has been made that recognizes and focuses on this. However, even gasoline that does not contain an oxygen-containing base material is less susceptible to changes in the environmental temperature, and even if the environmental temperature changes when water close to saturation solubility is dissolved, Gasoline that is less prone to turbidity and excellent in water turbidity prevention performance is desired.

  In view of the situation as described above, the present invention is a gasoline composition that does not contain an oxygen-containing base material, has excellent water turbidity prevention performance, and has excellent environmental performance in consideration of the importance of environmental problems. The object is to provide a composition.

  As a result of intensive studies to achieve the above object, the present inventors have optimized the properties of catalytic reformed gasoline and catalytic cracked gasoline, which are the main base materials of the gasoline composition, and thereby the properties of the gasoline composition. By optimizing the above, it was found that a gasoline composition excellent in water turbidity prevention performance and environmental performance was obtained, and the present invention was completed. Here, the optimization of properties is a composition in which the degree of improvement in water turbidity prevention performance according to the number of carbons of aromatics and olefins is increased, and the degree of adverse effects on environmental performance is kept low. It is to make the distillation property and other properties.

That is, this invention provides the following gasoline compositions in order to achieve the said objective.
(B) The aromatic content of 7 carbon atoms is 5 to 30% by volume, the aromatic content of 8 carbon atoms is 5 to 35% by volume, and the aromatic content of 9 or more carbon atoms is 3 to 20% by volume. A catalytic reforming-derived gasoline base material having properties such that the 10 vol% distillation temperature (T10) distilled from the catalytic reformer is 40 ° C or higher and the 90 vol% distillation temperature (T90) is 160 ° C or lower ( I) 10-50% by volume, or
The aromatic content of 7 carbon atoms is 10 to 65% by volume, the aromatic content of 8 carbon atoms is 0.1 to 50% by volume, and the aromatic content of 9 or more carbon atoms is 3 to 25% by volume, A catalytic reforming-derived gasoline base material (II) having a 10% by volume distillation temperature (T10) distilled from a catalytic reformer of 100 ° C or higher and a 90% volume distillation temperature (T90) of 160 ° C or lower 10-50% by volume, and
(B) The content of unsaturated hydrocarbons having 5 carbon atoms is 1 to 20% by volume, the content of unsaturated hydrocarbons having 6 carbon atoms is 3 to 20% by volume, and the content of unsaturated hydrocarbons having 7 carbon atoms is 3 to 3%. Catalytic cracking-derived gasoline group with 25% by volume, 10% by volume distillation temperature (T10) distilled from fluid catalytic cracking unit is 45 ° C or higher, and 90% by volume distillation temperature (T90) is 190 ° C or lower A gasoline composition containing 10-60% by volume of a material,
(C) A gasoline composition characterized by satisfying the following properties.
(1) Reed vapor pressure (RVP) is 45 ~ 90kPa
(2) Research octane number (RON) is 89 or more and less than 96 (3) 50% distillation temperature (T50) is 75-110 ° C
(4) 70 ℃ distillate (E70) is 18-40% by volume
(5) Aromatic content is 15-40% by volume
(6) Olefin content is 10-30% by volume
(7) Benzene content is 1% by volume or less (8) Sulfur content is 10 mass ppm or less

  The gasoline composition of the present invention is excellent in environmental performance and exhibits excellent water turbidity prevention performance without retreating the driving performance of the vehicle by adopting the above specific configuration.

Hereinafter, the contents of the present invention will be described in more detail.
The gasoline composition of the present invention has, as a base material, 10 to 50% by volume, preferably 15 to 50% by volume of a catalytic reforming-derived gasoline base material (I) having the following properties, or a catalytic reforming-derived gasoline base material ( II) is blended in an amount of 10 to 50% by volume, preferably 15 to 50% by volume.
Catalytic reforming-derived gasoline base (I): aromatic content of 7 carbon atoms is 5-30% by volume, preferably 7-30% by volume, aromatic content of 8 carbon atoms is 5-35% by volume, preferably Is 7 to 35 vol%, and has an aromatic content of 9 or more carbon atoms of 3 to 20 vol%, preferably 3 to 18 vol%, and 10 vol% distillation temperature for distilling from the catalytic reformer (T10) is 40 ° C. or higher, preferably 45 ° C. or higher, and 90% by volume distillation temperature (T90) is 160 ° C. or lower, preferably 155 ° C. or lower.
Catalytic reforming-derived gasoline base (II): 10 to 65% by volume, preferably 10 to 62% by volume of C7 aromatics, preferably 0.1 to 50% by volume of C8 aromatics, preferably Is 0.1 to 48% by volume, and the aromatic content of 9 or more carbon atoms is 3 to 25% by volume, preferably 3 to 23% by volume. T10) is 100 ° C or higher, preferably 105 ° C or higher, and 90% by volume distillation temperature (T90) is 160 ° C or lower, preferably 158 ° C or lower.
If the aromatic content and distillation properties of the catalytic reforming-derived gasoline base (I) or (II) are within the above ranges, a gasoline composition with excellent driving performance and water turbidity prevention performance is prepared. can do.
In addition, the dissolution of water in the aromatic content tends to increase the amount of the aromatic component with a smaller carbon number, so the aromatic content of the catalytic reforming-derived gasoline base (I) or (II) If it is in said range, the water turbidity prevention property of a gasoline composition can be improved.

The gasoline composition of the present invention contains 10 to 60% by volume, preferably 15 to 60% by volume, of a base material derived from catalytic cracking having the following properties as a base material.
Catalytic cracking-derived gasoline base material: C5 unsaturated hydrocarbon content is 1-20% by volume, preferably 1-15% by volume, C6 unsaturated hydrocarbon content is 3-20% by volume, preferably Is 3 to 15% by volume, the content of unsaturated hydrocarbons having 7 carbon atoms is 3 to 25% by volume, preferably 3 to 23% by volume, and 10% by volume distillation temperature (T10 ) Is 45 ° C. or higher, preferably 47 ° C. or higher, and 90% by volume distillation temperature (T90) is 190 ° C. or lower, preferably 187 ° C. or lower.
If the unsaturated hydrocarbon content and distillation properties of the catalytic cracking-derived gasoline base material are within the above ranges, gasoline having excellent water turbidity prevention properties can be prepared.
In addition, although dissolution of water in unsaturated hydrocarbons is not as much as aromatics, unsaturated hydrocarbons with smaller carbon numbers tend to have a higher dissolved amount, so unsaturated hydrocarbons from catalytic cracking-derived gasoline base materials. When the content is within the above range, the water turbidity preventing property of the gasoline composition can be improved.

  In the gasoline composition of the present invention, the index Y represented by the following formula is preferably 4.0 or more and less than 6.0, more preferably 4.0 to 5.8.

Here, the index Y is an equation obtained by measuring the saturated water content of the gasoline composition at temperatures of 5, 15, 25, and 35 ° C., and determining the relationship between the temperature and the saturated water content.
If the index Y is within the above range, it is preferable because the occurrence of turbidity can be suppressed even when the environmental temperature changes.

The saturated water content of the gasoline composition is measured as follows.
Collect 80 ml of gasoline and 20 ml of water in a 110 ml plugged screw bottle at room temperature and place in a thermostatic chamber set to the saturation temperature in advance. After the liquid temperature reaches saturation (after about 2 hours), remove the screw bottle and shake vigorously for 2 minutes. Then, set the screw bottle again in the thermostat and leave it overnight. The next day, the upper layer and the lower layer are separated, and the water content of the upper layer is measured with a Karl Fischer, and the water content is defined as the saturated water content.
For example, the index Y of gasoline having a saturated water content of 92 mass ppm at a saturation temperature of 5 ° C., 129 mass ppm at 15 ° C., 181 mass ppm at 25 ° C., and 243 mass ppm at 35 ° C. is 5.0.

  The lead vapor pressure (RVP) of the gasoline composition of the present invention is 45 to 90 kPa, preferably 50 to 90 kPa. By setting the RVP to 90 kPa or less, the amount of evaporative 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 research octane number (RON) of the gasoline composition of the present invention is 89 or more and less than 96, preferably 89 or more and 95 or less. If RON is 89 or more, it is possible to maintain high operating performance, and if it is less than 96, the blending amount of the aromatic high-octane base material can be suppressed, and a decrease in cleanliness can be prevented. The RON is a value measured according to JIS K 2280.

  The distillation property of the gasoline composition of the present invention is that the 50% distillation temperature (T50) is 75 to 110 ° C, preferably 75 to 105 ° C, and the 70 ° C distillation amount (E70) is 18 to 40% by volume, preferably Is 20-40% by volume. If T50 and E70 are within this range, it is possible to prevent the occurrence of problems in startability, drivability, and acceleration. These distillation properties are values measured in accordance with JIS K 2254.

  The aromatic content of the gasoline composition of the present invention is 15 to 40% by volume, preferably 20 to 40% by volume. By setting the aromatic content to 15% by volume or more, water turbidity prevention is improved, and by setting it to 40% by volume or less, an increase in harmful components in the exhaust gas can be prevented. 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 gasoline composition of the present invention is 10 to 30% by volume, preferably 15 to 27% by volume. By setting the olefin content to 10% by volume or more, water turbidity prevention properties are improved, and by setting the olefin content to 30% by volume or less, a decrease in oxidation stability can be prevented. The olefin content is a value measured in accordance with the Petroleum Institute method JPI-5S-33-90 (gas chromatographic method).

  The gasoline composition 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 1% by volume or less, there is a possibility that the increase in benzene concentration in the atmosphere can be prevented and environmental pollution can be reduced. The benzene content is a value measured according to the Petroleum Institute method JPI-5S-33-90 (gas chromatographic method).

  The sulfur content of the gasoline composition of the present invention is 10 mass ppm or less, preferably 8 mass ppm or less. If this sulfur content is 10 mass ppm or less, the exhaust gas purification catalyst capacity will be prevented from decreasing, and nitrogen oxide (NOx), carbon monoxide (CO), and total hydrocarbons (THC) in the exhaust gas will be reduced. There is a possibility that concentration rise can be prevented. The sulfur content is a value measured according to JIS K 2541.

  The method for preparing the catalytic reforming-derived gasoline base (I) or (II) used in the gasoline composition of the present invention is not particularly limited, but generally, heavy straight-run naphtha and the like are conventionally known. Catalytic reforming (plating forming method, magna forming method, aromaizing method, reni forming method, hood reforming method, ultra forming method, power forming method, etc.) under high temperature and pressure in a hydrogen stream. From a catalytic reformed gasoline obtained by contact treatment with platinum carrier, rhodium and chlorine on an alumina carrier), by distillation, a light fraction (debenzene light catalytic reformed gasoline), a benzene fraction, and By distilling into a heavy fraction (debenzene heavy catalytic reformed gasoline) and mixing the light fraction and the heavy fraction, the mixing ratio can be obtained. Properties of the mixture so as to satisfy the requirements of the catalytic reforming derived gasoline base material (I) or (II), can be prepared.

  As a method for preparing a catalytic cracking-derived gasoline base material used in the gasoline composition of the present invention, generally a petroleum fraction from kerosene / light oil to atmospheric residual oil, preferably heavy gas oil or vacuum gas oil has been conventionally known. Solid acid catalyst (for example, UOP method, shell two-stage method, flexi cracking method, ultra ortho flow method, texaco method, Gulf method, ultra cat cracking method, RCC method, HOC method, etc.) The catalytically cracked gasoline obtained by cracking with silica / alumina blended with zeolite, etc.) can be suitably prepared and used so that its properties satisfy the above-mentioned regulations of the catalytic cracking-derived gasoline base material.

  The gasoline composition of the present invention contains the above-mentioned catalytic reforming-derived gasoline base material (I) or (II) and the catalytic cracking-derived gasoline base material as an essential base material, and a conventional amount as the other base material. As appropriate, various base materials used for gasoline base materials are used, and depending on the properties of the blended amount, the properties of the gasoline composition obtained are the lead vapor pressure (RVP) of the gasoline composition of the present invention, To meet the requirements of research method octane number (RON), 50% distillation temperature (T50), 70 ° C distillation amount (E70), aromatic content, olefin content, benzene content, sulfur content, etc. Can be appropriately selected and blended.

Examples of other base materials of the gasoline composition of the present invention include the following components (a) to (f).
(A) Light fraction (light catalytic cracking gasoline) of catalytic cracking gasoline divided into light and heavy fractions by distillation
(B) Desulfurized light naphtha, which is a light fraction of light fractions and heavy fractions, obtained by distilling desulfurized straight naphtha obtained by desulfurizing straight-run naphtha obtained by atmospheric distillation of crude oil. c) alkylates obtained by reacting isobutane and lower olefins (butene, propylene, etc.) in the presence of acid catalysts (sulfuric acid, hydrogen fluoride, aluminum chloride, etc.) Obtained by isomerization of C4 fraction (e) linear lower paraffinic hydrocarbons with butane and butenes as main components obtained by distillation during pressure distillation, reformed gasoline production or cracked gasoline production Isomerate or a component mainly composed of toluene, xylene or aromatics having 9 or more carbon atoms obtained from isopentane (f) catalytic reformed gasoline obtained by precision distillation of isomerate.

  In the gasoline composition of the present invention, various fuel additives can be appropriately blended as necessary. Examples of fuel additives include phenolic and amine antioxidants, metal deactivators such as thioamide compounds, surface ignition inhibitors such as organophosphorus compounds, succinimides, polyalkylamines, and polyetheramines. Cleaning agents such as polyisobutylene amine, friction modifiers such as polyhydric alcohol esters and amide compounds, anti-icing agents such as polyhydric alcohols and ethers thereof, alkali metal or alkaline earth metal salts of organic acids, higher alcohols Auxiliary agents such as sulfates, anionic surfactants, antistatic agents such as cationic surfactants and amphoteric surfactants, rust inhibitors such as alkenyl succinates, colorants such as azo dyes, etc. and known fuels An additive is mentioned. These can be added singly 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.

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

Examples 1 and 2
Prepared from C4 fraction (butane, butenes) produced from catalytic cracking unit, catalytic reforming unit or atmospheric distillation unit, debenzene light catalytic reforming gasoline and debenzene heavy catalytic reforming gasoline with properties shown in Table 1 The properties shown in Table 2 by blending the catalytic reforming-derived gasoline base (I) or (II), the catalytic cracking-derived gasoline base composed of catalytic cracked gasoline, and desulfurized light naphtha at the blending ratio shown in Table 2. A gasoline composition was obtained. Table 2 shows the properties of the catalytic reforming-derived gasoline base (I) or (II) and the properties of the catalytic cracking-derived gasoline base.

Example 3
C4 fraction described in Examples 1 and 2 (butane, butenes), debenzene light catalytic reforming gasoline, catalytic reforming-derived gasoline base (II) prepared from debenzene heavy catalytic reforming gasoline, catalytic cracking gasoline A gasoline composition having the properties shown in Table 2 was obtained by blending the catalytic cracking-derived gasoline base material, desulfurized light naphtha, and alkylate having the properties shown in Table 1 at a blending ratio shown in Table 2. The properties of the catalytic reforming-derived gasoline base material (II) and the properties of the catalytic cracking-derived gasoline base material were as shown in Table 2.

Comparative Examples 1 and 2
Catalytic reforming-derived gasoline base (I) or (II) prepared from C4 fractions (butane, butenes) described in Examples 1 to 3, debenzene light catalytic reforming gasoline, debenzene heavy catalytic reforming gasoline A gasoline composition having the properties shown in Table 2 was obtained by blending the catalytic cracking-derived gasoline base material composed of catalytically cracked gasoline, desulfurized light naphtha, and alkylate at the blending ratio shown in Table 2. The properties of the obtained gasoline composition deviated from the properties of the gasoline composition defined in the present invention. Table 2 shows the properties of the catalytic reforming-derived gasoline base (I) or (II) and the properties of the catalytic cracking-derived gasoline base.

Comparative Example 3
C4 fraction (butane, butenes) described in Examples 1 to 3, debenzene light catalytic reforming gasoline, catalytic reforming-derived gasoline base material (II) prepared from debenzene heavy catalytic reforming gasoline, and light contacting By blending cracked gasoline at the blending ratio shown in Table 2, a gasoline composition having the properties shown in Table 2 was obtained. The properties of the obtained gasoline composition deviated from the properties of the gasoline composition defined in the present invention. The properties of the catalytic reforming-derived gasoline base material (II) at this time were as shown in Table 2.

Using the gasoline compositions obtained in the above Examples and Comparative Examples, the performance evaluation test described below was performed.
(Water turbidity test)
At room temperature, take a 50 ml sample in a 100 ml plugged sample bottle and place it in a thermostatic chamber at 0 ° C. Each time the sample temperature dropped by 1 ° C., the state of the sample was visually observed, and the temperature when turbidity was detected in the sample was measured, and this was taken as the turbid temperature. The turbidity temperature is shown in Table 2.
The turbidity temperature was measured by adjusting the water content to 100 mass ppm for each sample.
(Exhaust gas test)
A domestic passenger car (total displacement 2.5L, MPI system, automatic transmission (AT), equipped with a three-way catalyst) was used to conduct an exhaust gas test in 10.15 mode, carbon monoxide (CO), all hydrocarbons ( THC) and nitrogen oxides (NOx) were measured. The measurement results are shown in Table 2.

  From the test results shown in Table 2, the gasoline compositions obtained in the examples have improved environmental performance while maintaining excellent environmental performance as compared with the gasoline compositions obtained in the comparative examples. It is clear that it is excellent.

Claims (1)

(B) The aromatic content of 7 carbon atoms is 5 to 30% by volume, the aromatic content of 8 carbon atoms is 5 to 35% by volume, and the aromatic content of 9 or more carbon atoms is 3 to 20% by volume. A catalytic reforming-derived gasoline base material having properties such that the 10 vol% distillation temperature (T10) distilled from the catalytic reformer is 40 ° C or higher and the 90 vol% distillation temperature (T90) is 160 ° C or lower ( I) 10-50% by volume, or
The aromatic content of 7 carbon atoms is 10 to 65% by volume, the aromatic content of 8 carbon atoms is 0.1 to 50% by volume, and the aromatic content of 9 or more carbon atoms is 3 to 25% by volume, A catalytic reforming-derived gasoline base material (II) having a 10% by volume distillation temperature (T10) distilled from a catalytic reformer of 100 ° C or higher and a 90% volume distillation temperature (T90) of 160 ° C or lower 10-50% by volume, and
(B) The content of unsaturated hydrocarbons having 5 carbon atoms is 1 to 20% by volume, the content of unsaturated hydrocarbons having 6 carbon atoms is 3 to 20% by volume, and the content of unsaturated hydrocarbons having 7 carbon atoms is 3 to 3%. Catalytic cracking-derived gasoline group with 25% by volume, 10% by volume distillation temperature (T10) distilled from fluid catalytic cracking unit is 45 ° C or higher, and 90% by volume distillation temperature (T90) is 190 ° C or lower A gasoline composition containing 10-60% by volume of a material,
(C) A gasoline composition characterized by satisfying the following properties.
(1) Reed vapor pressure (RVP) is 45 ~ 90kPa
(2) Research octane number (RON) is 89 or more and less than 96 (3) 50% distillation temperature (T50) is 75-110 ° C
(4) 70 ℃ distillate (E70) is 18-40% by volume
(5) Aromatic content is 15-40% by volume
(6) Olefin content is 10-30% by volume
(7) Benzene content is 1% by volume or less (8) Sulfur content is 10 mass ppm or less