JPS63317590A - Unleaded and high-octane gasoline - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a research method for lead-free high octane gasoline having an octane number of 95 or higher, and more particularly, it relates to a lead-free high octane gasoline having a specified distillation property and a specified component composition, and a specified formulation. This invention relates to a new lead-free high-octane gasoline containing a variety of materials and having excellent performance.

Problems to be solved by conventional technology and inventions The 90-91 unleaded regular gasoline that had been on the market since 1975 had the drawback of easily causing knocking depending on driving conditions.
Unleaded high-octane gasoline with a high octane number of ~98 has been released.

This unleaded high octane gasoline had better anti-knocking properties than conventional unleaded regular gasoline, but with recent improvements in automobile technology, gasoline with qualities that enable higher drivability, i.e. There has been a demand for a new unleaded, high-octane gasoline that has excellent starting performance, excellent acceleration at low speeds, medium speeds, high speeds, and when climbing, and also has excellent running stability.

Therefore, the present inventors conducted repeated research to develop a new gasoline that satisfies the above requirements, and as a result, by specifying its distillation properties and achieving the optimum distillation properties, and at the same time specifying its component composition in detail, we were able to create an extremely excellent gasoline. They discovered that a new type of lead-free high-octane gasoline with excellent performance could be obtained, and filed a patent application (Japanese Patent Application No. 123129/1982).

The unleaded octane gasoline disclosed in Japanese Patent Application No. 62-123129 has further improved acceleration performance, low-temperature starting performance, low-temperature drivability (warming-up performance), etc. compared to conventional unleaded premium gasoline. It was a gasoline with excellent performance. However, as a result of further research, the inventors of the present invention found that by blending a specific compounding material as an essential component, various acceleration characteristics were improved compared to the unleaded high octane gasoline disclosed in Japanese Patent Application No. 123129/1982. , it is possible to achieve the same performance in terms of low-temperature startability and low-temperature drivability, while reducing the content of olefinic compounds that may have an adverse effect on gasoline stability within a specific distillate range. The present inventors have discovered that it is possible to obtain a new lead-free high-octane gasoline that has a motor method octane number that is higher than that of conventional gasoline, and has completed the present invention.

Compared to conventional unleaded high octane gasoline, the present invention has the following advantages:
Acceleration from a stopped state to low speed, acceleration from low speed to medium speed, acceleration from medium speed to high speed, further acceleration at high speed, various acceleration characteristics such as climbing force, startability at low temperature, and drivability at low temperature (warm-up performance) is further improved, and the
Compared to the unleaded high octane gasoline disclosed in No. 123129, it has the same performance in various acceleration characteristics, low-temperature startability, and low-temperature drivability, while the content of olefinic compounds is lower in the specified distillation range. It is an object of the present invention to provide a new unleaded high octane gasoline having a lower and higher motor octane number.

Means for solving the problems, that is, the present invention provides distillation properties that satisfy the conditions of formulas (1) and (2) below, and (3) and (4) 1. , (5) and (6)
(A) an isomerate obtained by isomerizing pentane and/or hexane, and (B) an isomerate with a boiling point of 20 to 200°C obtained by subjecting a petroleum fraction to a molecular sieving method. Lead-free high octane gasoline with an octane number of 95 or higher, characterized by containing 5 to 40% by volume of one or more types of compounding materials selected from n-paraffin oil, based on the total amount of gasoline, 60≦T7D T30≦85 ('C) (
1) T, , -T,.

0.15≦□<0.50 (2) T7+1-T2O 0≦VO(WHOLE)≦25 (Capacity%)
(3) VA (WIIOLE)≦50 (capacity%)
(4) 0≦VO (≦Tio ) <40 (capacity%) (5) VA (≧T7a)≧85 (capacity%
) (6). In addition, T during the above ceremony! QsT7° and T, mouth indicate 30%, 7096 and 90% distillation temperature ('C) respectively, and VO (
WHOLE) and VA (WIIOLE) are the olefinic and aromatic content of the entire gasoline (% by volume)
, VQ (≦Tin) is the olefinic content (volume 96) of the total fraction distilled at temperatures below 30% distillation temperature, and VA (≧T7.) is the olefinic content (capacity 96) at temperatures above 70% distillation temperature. The aromatic content (volume %) of the total fraction to be distilled is shown.

Hereinafter, the content of the present invention will be explained in more detail.

As mentioned above, the unleaded high octane gasoline of the present invention has distillation properties that simultaneously satisfy the conditions of equations (1) and (2).■ The conditions of equations (3), (4), (5), and (6). ■ A condition in which one or more compounding materials selected from (A) isomerate and (B) deparaffinized oil are combined in amounts of 5 to 5 b based on the total amount of gasoline. It is necessary that it satisfies all of the above.

If any one of these conditions is not met,
It is not possible to obtain unleaded high octane gasoline with extremely excellent various performances as described above.

The conditions of ■ are related to the distillation properties of gasoline, and (
1) The formula is the 70% distillation temperature (T7°) and 30% of gasoline.
It shows that the difference from the distillation temperature (T3 o ) is 60 to 85°C, preferably 65 to 80°C. Also (2)
The formula is 90% distillation temperature (T,.) and 70% distillation temperature (T0
n) and T0n'r3. shown in equation (1). The ratio (T,, -T.

o /T7a -T3o) is 0.15 or more 0.5
Less than 0, preferably, shi< indicates 0.25 or more and 0.45 or less. Note that the 30% distillation temperature, 70% distillation temperature, and 90% distillation temperature in the present invention are all JI
Refers to the distillation temperature specified in SK 2254 Fuel Oil Distillation Test Method.

In the present invention, the distillation properties of gasoline are (1) and (
If the conditions of formula 2) are not satisfied at the same time, it is not preferable because various acceleration properties and low-temperature startability and drivability (warm-up performance) are poor.

The conditions in ■ are related to the composition of gasoline, and (
Equation 3) indicates that the olefin content of the entire gasoline is 0 to 25% by volume, preferably 0 to 20% by volume, and equation (4) indicates that the aromatic content of the entire gasoline is 50% by volume or less, preferably 45 capacity and 96 or less. Also, equation (5) is the 30% distillation temperature (T!

) The olefin content of the total distillate distilled at a temperature of 0
- less than 40% by volume, preferably 0 to 30% by volume, and formula (6) is 70% distillation temperature (Tall
) indicates that the aromatic content of the total fraction distilled at a temperature of 85% by volume or more, preferably 90% by volume or more. The olefin content and aromatic content in the present invention refer to values measured by the JIS K 2536 fuel oil hydrocarbon component testing method (fluorescent indicator adsorption method).

In the present invention, if the component composition of gasoline does not satisfy the conditions of equations (3) and (4), the stability of the gasoline itself may deteriorate or the materials used in the fuel system may be adversely affected. This is not desirable as it may cause harm. On the other hand, in the present invention, the component composition of gasoline is (
Satisfying the condition of formula (5) is necessary to further improve the stability of the gasoline itself, and satisfying the condition of formula (6) is necessary to further improve various acceleration properties.

The conditions (2) are related to gasoline preparation materials, and the unleaded high octane gasoline of the present invention is prepared by combining (A) isomerates obtained by isomerizing pentane and/or hexane, and (B) petroleum fractions using a molecular sieving method. 5-40% by volume, preferably 10-b%, based on the total amount of gasoline, of one or more types of compounding materials selected from n-paraffin-free oil with a boiling point of 20-200°C obtained by is necessary.

Note that (A) isomerate here refers to naphtha,
The pentane fraction, hexane fraction, or a mixture of these fractions obtained from natural gasoline, straight-run gasoline, reformed gasoline, etc., is used as a raw material for isomerization, that is, straight-chain paraffinic hydrocarbons are produced without changing the chemical composition. Boiling point range 25 obtained by converting to isomers with side chains
This refers to the fraction at ~85℃, which mainly contains branched paraffinic hydrocarbons (isopentane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2゜3-dimethylbutane, etc.). , and other unreacted linear paraffinic hydrocarbons (n-pentane, n-hexane) and naphthenic hydrocarbons (cyclopentane, methylcyclopentane, cyclohexane, etc.).

In the present invention, the catalyst, reaction conditions, process, etc. for isomerizing the pentane fraction, hexane fraction, or a mixture thereof are arbitrary, and known ones can be used.

However, in the general isomerization method, the reaction catalyst is generally an aluminum halide such as aluminum chloride or aluminum bromide, or a Friedel-Craft-type catalyst in which a halogenated hydrocarbon such as hydrogen chloride is co-existed as a co-catalyst. However, in the hydroisomerization method, which performs isomerization under hydrogen pressure, a dual-functional type is used in which metals with hydrogenation activity, such as platinum and nickel, are supported on solid acidic supports such as silica alumina, alumina, zeolite, and mordenite. A catalyst is used. Regarding the reaction conditions, the reaction temperature is usually 20 to 150°C in the general isomerization method, and 90 to 50°C in the hydroisomerization method.
The temperature is about 10°C, and the reaction pressure is 10-70k for both.
It is about g/c+#.

The main general isomerization process is the shell liquid phase isomerization process, and the hydroisomerization process is the Benex process,
The Heitzmer method, BP isomerization method, TIP method, etc. are known.

On the other hand, (B) n-paraffin removal here refers to petroleum distillates, specifically straight-run gasoline, light naphtha, heavy naphtha, reformed gasoline, cracked gasoline, isomerate, alkylate, kerosene. , light oil, etc. are subjected to a molecular sieve method to separate and remove the n-paraffin content due to its low octane number.
It means a fraction with a boiling point of 20 to 200°C, preferably 30 to 150°C, which is obtained by further fractionating it if necessary, and has branched paraffinic hydrocarbons as its main component. In the present invention, the adsorbent, treatment conditions, process, etc. used in the molecular sieve method are arbitrary, and known ones can be used. However, in general, adsorbents include molecular sieves (synthetic zeolites),
In particular, a 5A type molecular sieve is used.

The main molecular sieving processes include isosieve method,
Molex method, TSF method, etc. are known.

In the present invention, if (A) isomerate and/or non-paraffinized oil is not blended or if the blended amount is less than 5% by volume, the research method octane number and motor method octane number of gasoline cannot be increased. On the other hand, (A) isomerate and/or de-n-
If the amount of paraffin oil exceeds 40% by volume, the amount of low-boiling fractions of gasoline will be too large, resulting in increased evaporation loss and problems in high-temperature drivability, which is not preferred.

The unleaded high octane gasoline of the present invention has a research octane number of 95 or higher, preferably 98 or higher. In addition, this research method octane number is JIS
Refers to octane number as determined by the Research Methods Octane Number Test Method as specified in the K 2280 Octane Number and Sedan Number Test Methods.

The blending materials other than (A) isomerate and/or de-paraffinized oil used in producing the unleaded high octane gasoline of the present invention and their blending ratios are optional. Light naphtha obtained by fractional distillation, cracked gasoline obtained by catalytic cracking, hydrocracking, etc., reformed gasoline obtained by catalytic reforming, etc., polymerized gasoline obtained by polymerization of olefins, hydrocarbons such as isobutane Alkylates obtained by adding (alkylating) lower olefins to olefins, fractions of these in a specific boiling point range, aromatic hydrocarbons, etc. can be used as the compounding material.

The unleaded high octane gasoline of the present invention includes, for example, (A)
Isomerate and/or deparaffinized oil 5~
In addition to 40% by volume, 25% to 50% by volume of reformed gasoline, and 0 to 40% light fraction with a boiling point of about 90°C from the initial boiling point of cracked gasoline.
Volume %, 10 to 35 volume % of heavy fraction from the boiling point of reformed gasoline to the end point of about 130°C, and alkylate 5 to 25
It can be obtained by adjusting the volume %.

However, in the present invention, as mentioned above, the final blended gasoline has the distillation properties [(1)
and formula (2)] and the component composition shown in ■ [(3)
, (4), (5), and (6)], and for this purpose, the unleaded high octane gasoline of the present invention can be produced by simply mixing the ingredients as in the above example. This does not mean that it is possible, but it is necessary to strictly select the blending ratio depending on the properties of the blended material used (distillation properties, composition, etc.) and the properties of the blended material used.

Regarding the distillation properties of the unleaded high octane gasoline of the present invention, it is important to satisfy the conditions shown in (1) above.
It is desirable that the 0% distillation temperature is within the range of 150 to 175°C.

Furthermore, in the unleaded high octane gasoline of the present invention,
If necessary, phenol-based and amine-based antioxidants, surface ignition inhibitors such as metal deactivators such as Schiff-type compounds and thioamide-type compounds, and cleaning agents such as succinimide, polyalkylamines, polyetheramines, etc. dispersant,
anti-icing agents such as polyhydric alcohols and their ethers;
Combustion aids such as alkali metal and alkaline earth metal salts of organic acids and sulfuric esters of higher alcohols, antistatic agents such as anionic surfactants, cationic surfactants, and amphoteric surfactants, and colorants such as azo dyes. One type or a combination of several types of known fuel oil additives may be added. The amount of these fuel oil additives added is arbitrary, but usually
It is preferable to add so that the total amount added is 0.1 ffiQ% or less.

Furthermore, an octane improver such as an alcohol such as methanol, ethanol, isopropanol, or t-butanol, or an ether such as methyl-t-butyl ether may be added to the unleaded high octane gasoline of the present invention, if necessary. . The amount of these octane number improvers added is also arbitrary, but is usually preferably 15% by weight or less.

EXAMPLES Hereinafter, the content of the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Examples and Comparative Examples Catalytically reformed gasoline obtained from Middle Eastern crude oil 47 volumes
28 parts by volume of isomerate obtained by isomerizing pentane and hexane fractions of light straight-run naphtha, 15 parts by volume of heavy fraction of catalytically reformed gasoline obtained from Middle Eastern crude oil, and alkylation of isobutane and lower olefins. 10 parts by volume of the alkylate obtained by the reaction were blended to obtain the unleaded high octane gasoline of the present invention. Table 1 shows the properties of the base material, and Table 2 shows the properties of the resulting unleaded high octane gasoline. For comparison, the properties of commercially available unleaded premium gasoline are also listed in Table 2.

Using the gasolines of this Example and Comparative Example, various performance evaluation tests were conducted as shown below, and the results are shown in Table 3.

[Acceleration performance test 1 (stop - low speed, low speed - medium speed, medium speed - high speed)] Total exhaust m1
．． Using a 500cc, manual transmission, carburetor specification passenger car (Car A), on a flat road with the throttle valve fully open, the vehicle speed changes from 0 to 60 kx/hr by shifting in the order of low gear, second gear, and top gear.
Also, the time required for the vehicle speed to reach 440-801a/hr and 80-1201on/hr in top gear was measured.

[Acceleration Performance Test 2 (Low Speed - High Speed)] Using a passenger car (Car B) with a total exhaust of 12.000 cc, manual transmission, and fuel injection type, the vehicle speed was The time taken to reach 40→120 km/hr was measured.

[Acceleration performance test 3 (mounting force)] Using car A, on a road with a 5% uphill slope, the gears were changed in the order of low gear, second gear, top gear, and the vehicle speed was changed from 0 to 80 kll/hr, and then third gear. The time it took for the vehicle speed to reach 440-80k/hr was measured.

[Acceleration Performance Test 4 (Pitching Power)] Using a passenger car (Car C) with a total displacement I: 2,000 cc, automatic transmission, and fuel injection type, acceleration on a road with a 5% uphill slope, D range, throttle valve fully open. The time required for the vehicle speed to reach 120 km/hr from O was measured under these conditions.

[Low-temperature startability test] Using Car A and Car B, the time required for the engine to start was measured at an air temperature of θ°C.

r Low-temperature drivability test] Cars A and B were used to evaluate the drivability at a temperature of 0°C using demerit scores. The demerit score is based on CRC report NQ499 (issued in September 1978).
Test method described on pages 65 to 69 of the same and E, Driveability Rating S on pages 4 to 5 of the same
It was calculated using the calculation method described in system.
The smaller this value is, the better the drivability is.

Table 1 (2): Based on Jts K 2536.

Table 2 Table 3 Effect of the invention As is clear from the results of various performance evaluation tests in Table 3,
The unleaded high octane gasoline of the present invention is more effective at accelerating from a standstill to low speeds, from low speeds to medium speeds, from medium speeds to high speeds, and from low speeds to high speeds, compared to currently commercially available unleaded high octane gasolines. It is a gasoline with excellent performance that not only improves various acceleration performances such as acceleration and pitching power, but also significantly improves startability and drivability at low temperatures.

Claims (1)

[Scope of Claims] [1] Distillation properties that satisfy the conditions of formulas (1) and (2) below, and (3), (4), (5) and (6) below.
) has a component composition that satisfies the conditions of the formula, and (A) isomerate obtained by isomerizing pentane and/or hexane, and (B) isomerate with a boiling point of 20 to 200 ° C obtained by subjecting petroleum fraction to molecular sieving method. A lead-free high octane gasoline with a research method octane number of 95 or higher, characterized in that it contains 5 to 40% by volume of one or more compounding materials selected from n-paraffin-free n-paraffin oils, based on the total amount of gasoline. 60≦T_7_0-T_3_0≦85 (℃) (1) 0.15≦(T_9_0-T_7_0)/(T_7_0
-T_3_0)<0.50(2) 0≦VO(WHOLE)≦25(capacity%) (3) VA(WHOLE)≦50(capacity%) (4) 0≦VO(≦T_3_0)<40(capacity%) ) (5) VA (≧T_7_0)≧85 (volume%) (6) [In the above formula, T_3_0, T_7_0 and T_9_0 represent 30%, 70% and 90% distillation temperature, respectively,
In addition, VO (WHOLE) and VA (WHOLE) are the olefin content and aromatic content (volume %) of the entire gasoline.
), VO (≦T_3_0) is the olefin content (volume %) of the total fraction distilled at a temperature below 30% distillation temperature,
and VA (≧T_7_0) respectively indicate the aromatic content (volume %) of the total fraction distilled at a temperature equal to or higher than the 70% distillation temperature. ]