JPH0375595B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application Field The present invention relates to a lead-free high octane gasoline with a research method octane number of 95 or higher, and more specifically, it has a specified distillation property and a specified component composition, and contains a specified compounding material. Concerning a new unleaded high octane gasoline with 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 disadvantage of being prone to knocking depending on driving conditions.
In 1959, unleaded high-octane gasoline with a high octane number of 96 to 98 was 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 a quality that enables higher drivability,
In other words, there has been a demand for a new unleaded, high-octane gasoline that has excellent startability, excellent acceleration at low speeds, medium speeds, high speeds, and when climbing hills, as well as 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 unleaded high-octane gasoline with superior performance could be obtained, and filed a patent application (Japanese Patent Application No. 123129-1982). The unleaded high 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. did,
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. 123129/1983. , has 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 improves acceleration from a standstill to low speeds, acceleration from low speeds to medium speeds, acceleration from medium speeds to high speeds, further acceleration at high speeds, hill climbing ability, etc. In addition to further improving acceleration performance, low-temperature starting performance, and low-temperature drivability (warming-up performance), various acceleration performance and low-temperature performance are improved compared to the unleaded high-octane gasoline disclosed in Japanese Patent Application No. 123129/1983. To provide a new lead-free high-octane gasoline that has equivalent performance in startability and low-temperature drivability, has a lower content of olefinic compounds in a specific distillate range, and has a higher motor octane number. With the goal. Means for Solving the Problems That is, the present invention provides distillation properties that satisfy the conditions of the following formulas (1) and (2), and the following formulas (3), (4), (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. paraffin oil,
Lead-free high octane gasoline with an octane number of 95 or more, characterized by containing 5 to 40% by volume of one or more types of compounding materials based on the total amount of gasoline.60≦T ₇₀ −T ₃₀ ≦ 85 (℃) (1) 0.15≦T ₉₀ −T ₇₀ /T ₇₀ −T ₃₀ ＜0.50 (2) 0≦VO (WHOLE) ≦25 (capacity%) (3) VA (WHOLE) ≦50 (capacity%) (4) 0≦VO (≦T ₃₀ ) <40 (capacity%) (5) VA (≧T ₇₀ )≧85 (capacity%) (6). In the above formula, T ₃₀ ,
T ₇₀ and T ₉₀ indicate the 30%, 70% and 90% distillation temperature (°C), respectively, and VO (WHOLE) and VA (WHOLE) indicate the olefin and aromatics content (volume %) of the entire gasoline. ,VO(≦
T ₃₀ ) is the olefin content (volume %) of the total fraction distilled at a temperature below 30% distillation temperature, and
VA (≧T ₇₀ ) indicates the aromatic content (volume %) of the total fraction distilled at a temperature of 70% distillation temperature or higher. 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 condition is that one or more compounding materials selected from (A) isomerate and (B) de-n-paraffinated oil having a satisfactory component composition are blended in an amount of 5 to 40% by volume based on the total amount of gasoline. All must be satisfied. If any one of these conditions is not met, it is not possible to obtain lead-free high octane gasoline that has extremely excellent various performances as described above. The conditions are related to the distillation properties of gasoline, and equation (1) is the 70% distillation temperature (T ₇₀ ) of gasoline.
It shows that the difference from the 30% distillation temperature (T ₃₀ ) is 60 to 85°C, preferably 65 to 80°C. In addition, equation (2) is the 90% distillation temperature (T ₉₀ ) and the 70% distillation temperature (T ₇₀ ).
and the ratio of T ₇₀ − T ₃₀ (T ₉₀ −
_T70 / _T70 - _T30 ) is 0.15 or more and less than 0.50, preferably 0.25 or more and 0.45 or less. Note that the 30% distillation temperature, 70% distillation temperature, and 90% distillation temperature as used in the present invention all mean the distillation temperature specified by the fuel oil distillation test method of JIS K 2254. In the present invention, if the distillation properties of gasoline do not simultaneously satisfy the conditions of formulas (1) and (2),
It is not preferable because it is inferior. These conditions relate to the component 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 olefin content of the entire gasoline is 0 to 25% by volume, and preferably 0 to 20% by volume. indicates that the aromatic content is 50% by volume or less, preferably 45% by volume or less. In addition, equation (5) indicates that the olefin content of the total fraction distilled at a temperature below 30% distillation temperature (T ₃₀ ) is 0 to less than 40% by volume, preferably 0 to 30% by volume. , and equation (6) is 70
% distillation temperature (T ₇₀ ) or higher, the aromatic content of the total fraction distilled at a temperature equal to or higher than the distillation temperature (T 70 ) is 85% by volume or higher, preferably 90% by volume or higher, respectively. The olefin content and aromatic content in the present invention refer to values measured by the fuel oil hydrocarbon component testing method (fluorescent indicator adsorption method) of JIS K 2536. 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 satisfies the condition of equation (5) in order to further increase the stability of gasoline itself.
Also, satisfying the condition of equation (6) is necessary to further improve various acceleration characteristics. The above conditions relate to gasoline formulation materials, and the unleaded high octane gasoline of the present invention is obtained by subjecting (A) isomerate obtained by isomerization of pentane and/or hexane, and (B) petroleum fraction to molecular sieving method. The obtained n-paraffin-free oil with a boiling point of 20 to 200°C, and one or more blending materials selected from 5 to 40% of the total amount of gasoline, based on the total amount of gasoline.
It is necessary to mix it by volume %, preferably 10 to 30 volume %. Note that (A) itomerate here refers to isomerization of pentane fraction, hexane fraction, or a mixture of these fractions obtained from naphtha, natural gasoline, straight-run gasoline, reformed gasoline, etc., as a raw material, i.e. It refers to a fraction with a boiling point range of 25 to 85°C obtained by converting straight-chain paraffinic hydrocarbons into isomers with side chains without changing their chemical composition, and is a branched paraffinic hydrocarbon (isopentane). , 2-methylpentane, 2-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, aluminum halides such as aluminum chloride and aluminum bromide, or Friedel-Crafts type catalysts in which aluminum halides such as aluminum chloride and aluminum bromide are co-existed with halogenated hydrocarbons such as hydrogen chloride as co-catalysts are generally used as reaction catalysts. In addition, in the hydroisomerization method in which isomerization is performed under hydrogen pressure, a dual-functional catalyst is used in which a metal with hydrogenation activity, such as platinum or nickel, is supported on a solid acidic support such as silica alumina, alumina, zeolite, or mordenite. is used. Regarding the reaction conditions, the reaction temperature is usually about 20 to 150°C in the general isomerization method and about 90 to 510°C in the hydroisomerization method, and the reaction pressure is about 10 to 70 Kg/cm ² in both cases. The main general isomerization process is the Shell liquid phase isomerization process, and the hydroisomerization processes include the Penex process, Hysomer process, BP isomerization process, and TIP process. On the other hand, the (B) deparaffinized oil mentioned here is
Petroleum fractions, specifically straight-run gasoline, light naphtha, heavy naphtha, reformed gasoline, cracked gasoline, isomerate, alkylate, kerosene, diesel oil, etc., are subjected to molecular sieving to reduce the octane number.
- A boiling point of 20~ obtained by separating and removing the paraffin content and further fractionating it if necessary.
It means a fraction at 200°C, preferably 30 to 150°C, and contains branched paraffinic hydrocarbons as a 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, monocular sieves (synthetic zeolites), especially type 5A molecular sieves, are generally used as adsorbents. The isosieve method, Morex method, TSF method, etc. are known as the main molecular sieve methods. In the present invention, if (A) isomerate and/or deparaffinized oil is not blended or if the blended amount is less than 5% by volume, the research octane number and motor octane number of gasoline cannot be increased. On the other hand, if the blending amount of (A) isomerate and/or de-paraffinized oil exceeds 40% by volume, the amount of low-boiling fractions in gasoline will be too large, resulting in large evaporation losses and This is not preferable because it may cause problems in drivability. 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 means the octane number measured by the research method octane number test method specified in the octane number and cetane number test method of JIS K 2280. (A) Isomerate and/or desulfurized gasoline used in producing the unleaded high octane gasoline of the present invention
- Compounding materials other than paraffin oil and their blending ratios are arbitrary; light naphtha obtained by fractionating the naphtha fraction obtained by atmospheric distillation of crude oil, cracked gasoline obtained by catalytic cracking method, hydrocracking method, etc. ,
Reformed gasoline obtained by catalytic reforming, polymerized gasoline obtained by polymerizing olefins, alkylates obtained by adding (alkylating) lower olefins to hydrocarbons such as isobutane, or distillates with specific boiling point ranges. fraction, aromatic hydrocarbons, etc. can be used as a compounding material. The unleaded high octane gasoline of the present invention includes, for example, 5 to 40% by volume of (A) isomerate and/or de-n-paraffinated oil and 25 to 50% by volume of reformed gasoline.
Volume %, initial fraction of cracked gasoline to light fraction with boiling point of around 90℃ 0 to 40 volume %, reformed gasoline boiling point 130
It can be obtained by blending 10 to 35% by volume of a heavy fraction from about 0.degree. C. to the end point and 5 to 25% by volume of an alkylate. However, in the present invention, as described above, the distillation properties of the final blended gasoline [Equations (1) and (2)]
and the component compositions shown in [(3), (4), (5) and
It is important to simultaneously satisfy the conditions of Equation (6), and in order to do so, it is not enough to simply mix the lead-free high octane gasoline of the present invention with the blended materials as in the example above, but to It is necessary to strictly select the blending ratio depending on the properties of the material (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 above.
~55°C and 90% distillation temperature is preferably within the range of 150-175°C. Furthermore, in the unleaded high octane gasoline of the present invention, if necessary, antioxidants such as phenols and amines, surface ignition inhibitors such as metal deactivators such as Schiff type compounds and thioamide type compounds, and succinimide. , cleaning and dispersing agents such as polyalkylamines and polyether amines, anti-icing agents such as polyhydric alcohols and their ethers, combustion improvers such as alkali metal and alkaline earth metal salts of organic acids, sulfuric esters of higher alcohols, anionic Known fuel oil additives such as antistatic agents such as surfactants, cationic surfactants, and amphoteric surfactants, and colorants such as azo dyes may be added singly or in combination. Although the amount of these fuel oil additives added is arbitrary, it is usually preferable to add them so that the total amount added is 0.1% by weight or less. Furthermore, an octane number improver such as an alcohol such as methanol, ethanol, isopropanol, 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 optional, but is usually preferably 15% by weight or less. Examples Hereinafter, the contents of the present invention will be explained in more detail with reference to Examples and Comparative Examples. Example 1 Catalytically reformed gasoline A47 obtained from Middle Eastern crude oil
Parts by volume, 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 A of catalytically reformed gasoline obtained from Middle Eastern crude oil, and isobutane and lower olefins. 10 parts by volume of alkylate A obtained by the alkylation reaction was 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. Using the gasoline of Example 1, 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)] Passenger car with a total displacement of 1,500 c.c., manual transmission, and carburetor specification (Car A)
On a flat road with the throttle valve fully open, the vehicle speed changes from 0 to 60 Km/hr by shifting from low gear to second gear to top gear, and then from 40 to 80 Km/hr and from 80 to 120 Km/hr in top gear. The time it took to reach the target was measured. [Acceleration performance test 2 (low speed → high speed)] Using a passenger car (Car B) with a total displacement of 2000 c.c., manual transmission, and fuel injection type, the conditions were flat road, top gear, and throttle valve fully open acceleration. We measured the conditions under which the vehicle speed reached from 40 to 120 km/hr. [Acceleration performance test 3 (climbing force)] Vehicle A was used on a road with a 5% uphill slope, and the throttle valve was fully opened. The vehicle speed was changed from 0 to 80 km/hr by shifting from low gear to second gear to top gear, and then to third gear. We measured the time it took for the vehicle speed to reach from 40 to 80 km/hr. [Acceleration performance test 4 (climbing power)] A passenger car (C car) with a total displacement of 2000 c.c., automatic transmission, and fuel injection type was used, on a road with a 5% uphill slope, in D range, and with a throttle valve. The time required for the vehicle speed to reach 120 km/hr from 0 under full acceleration conditions was measured. [Low-temperature startability test] Using Car A and Car B, the time required for the engine to start was measured at a temperature of 0°C. [Low temperature drivability test] Cars A and B were used to evaluate the drivability at a temperature of 0°C using demerit scores. In addition,
The demerit rating is based on the test method described on pages 65-69 of CRC Report No. 499 (issued September 1978) and the E.Driveability Rating on pages 4-5 of the same.
It is calculated using the calculation method described in System, and the smaller this value is, the better the drivability is. Example 2 Catalytically reformed gasoline B34 obtained from Middle Eastern crude oil
35 parts by volume of isomerate obtained by isomerizing pentane and hexane fractions of light straight-run naphtha, 21 parts by volume of heavy fraction B of catalytically reformed gasoline obtained from Middle Eastern crude oil, isobutane and lower olefins 10 parts by volume of alkylate B obtained by the alkylation reaction was blended to obtain the lead-free 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. A performance evaluation test similar to that of Example 1 was conducted using the gasoline of Example 2, and the results are shown in Table 3. Example 3 Reformed gasoline B49 volume parts shown in Table 1, isomerate 25 volume parts, and reformed gasoline heavy fraction B16
parts by weight and 10 parts by volume of alkylate B,
A lead-free high octane gasoline of the present invention was obtained. Second
The properties of the lead-free high octane gasoline obtained are shown in the table. A performance evaluation test similar to that of Example 1 was conducted using the gasoline of Example 3, and the results are shown in Table 3. Comparative Example For comparison, the properties of commercially available unleaded premium gasoline are shown in Table 2. A performance evaluation test similar to that in Example 1 was conducted using the gasoline of this comparative example, and the results are shown in Table 3.

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[Table] Effects of the Invention As is clear from the results of various performance evaluation tests shown in Table 3, the unleaded high octane gasoline of the present invention has the following properties:
Compared to currently commercially available unleaded high octane gasoline, various types of acceleration such as acceleration from standstill to low speed, acceleration from low speed to medium speed, acceleration from medium speed to high speed, acceleration from low speed to high speed, hill climbing ability, etc. It is a gasoline with excellent performance, which not only improves performance but also significantly improves startability and drivability at low temperatures.

Claims (1)

[Claims] 1. Having distillation properties that satisfy the conditions of formulas (1) and (2) below, and a component composition that satisfies the conditions of formulas (3), (4), (5), and (6) below. and (A) an isomerate obtained by isomerizing pentane and/or hexane, and (B) a deparaffinized oil with a boiling point of 20 to 200°C obtained by subjecting a petroleum fraction to a molecular sieving method,
Research Method Unleaded high octane gasoline with an octane number of 95 or higher, characterized in that it contains 5 to 40% by volume of one or more blending materials selected from the following, based on the total amount of gasoline. 60≦T ₇₀ −T ₃₀ ≦85 (℃) (1) 0.15≦T ₉₀ −T ₇₀ /T ₇₀ −T ₃₀ ＜0.50 (2) 0≦VO (WHOLE) ≦25 (capacity%) (3) VA ( WHOLE)≦50 (capacity%) (4) 0≦VO (≦T ₃₀ )＜40 (capacity%) (5) VA (≧T ₇₀ )≧85 (capacity%) (6) [In the above formula, T ₃₀ , T ₇₀ and T ₉₀ indicate the 30%, 70% and 90% distillation temperature, respectively, and also the VO
(WHOLE) and VA (WHOLE) are the olefin and aromatic content of the entire gasoline (volume %)
, VO (≦T ₃₀ ) is the olefin content (volume %) of the total distillate distilled at a temperature below 30% distillation temperature,
and VA (≧T ₇₀ ) respectively indicates the aromatic content (volume %) of the total fraction distilled at a temperature equal to or higher than the 70% distillation temperature. ]