JPH0710980B2 - High performance fuel oil - Google Patents

Description

TECHNICAL FIELD The present invention relates to a high-performance fuel oil, and more particularly, to a lead-free and high octane number which is excellent in high-speed knock resistance, acceleration, flammability, startability and low-temperature drivability. Regarding fuel oil.

(Problems to be Solved by the Related Art and Invention) In recent years, since the addition of lead compounds such as tetraethyl lead to gasoline has been restricted, the development of high octane gasoline without lead has been desired, Various fuel oils have been proposed in, for example, less than 50% by volume of benzene and one or more selected from toluene, xylene and alkylbenzene.
A gasoline engine fuel consisting of 89 to 2% by volume and the balance of saturated hydrocarbon (Japanese Patent Publication No. Sho 60-10070), a mixture of benzene, toluene, and mixed xylene, 45 to 96% by volume, and a flash point-
Fuel for gasoline engines, which is obtained by adding 2 to 53% by volume of a low flash point component of 11 ° C or lower and blending the balance with a heavy oil component having a flash point of 30 ° C or higher and a boiling point of 150 ° C or higher (JP-A-59-4689). Gazette) or a heavy fraction of reformed gasoline of 10 to 55% by weight and a light fraction of cracked gasoline of 10 to 50% by weight obtained by a fluid catalytic cracking method as essential components. KAISHO 61-16985) and the like are known.

However, these fuels are not yet sufficiently satisfactory in terms of knock resistance at high speeds, acceleration, combustibility, startability, and low-temperature operability, and further improvement is desired.

[Means for solving problems]

Therefore, the inventors of the present invention should solve the above-mentioned drawbacks of conventional fuels and develop a high-performance fuel oil that is excellent in high-speed knock resistance and has good acceleration, combustibility, startability, and low-temperature drivability. We have earnestly studied. As a result, it has been found that a reformed gasoline having specific properties, an alkylate and an isopentane fraction, and optionally a light catalytic cracking gasoline are blended into a high performance gasoline satisfying all the above required characteristics. Has been completed.

That is, the present invention is (A) research method octane number 101.5
Above, Reid vapor pressure of 0.3 kg / cm ² or more and boiling point range of 30 to 2
Reformed gasoline at 00 ° C, (B) alkylate, and (C) research method octane number 90 to 95 isopentane fraction are essential components, research method octane number 99.5 or more, motor method octane number 88.6 or more, aromatic content 50% by volume. High-performance fuel oil (hereinafter referred to as "fuel oil I") characterized in that the distillate up to 70 ° C is 25% by volume or more.
In addition to (A), (B), (C) components and (D) research method octane number 93.5-96.5, Reid vapor pressure 0.6-1.05 kg / cm ² and light boiling point range 25-100 ° C. Using cracked gasoline as an essential component, research octane number of 99.5 or more, motor method octane number of 88.6 or more, aromatic content of 50% by volume or less, and distillate up to 70 ° C is 25% by volume.
The high-performance fuel oil (hereinafter referred to as "fuel oil II") characterized by the above is provided.

Fuel oil I of the present invention has three components (A), (B) and (C) as essential components, and fuel oil II has each of these components and four components (D) as essential components. It is a thing. Here, the reformed gasoline as the component (A) is generally obtained by subjecting a heavy straight-run naphtha or the like to a conventionally well-known catalytic reforming method (platform forming method, magna forming method, aromaizing method, reniforming). Method, hood reforming method, ultraforming method, power forming method, etc.), and is obtained by contact treatment with a catalyst in a hydrogen stream at high temperature and pressure. 102-104), Reed vapor pressure 0.3kg / cm ² or more (preferably 0.5kg / cm ² or more) and boiling point range 30-200 ℃ It is possible to use the provided one. However, the reformed gasoline as the component (A) of the present invention is obtained by subjecting a full range naphtha (initial boiling point 20 to 30 ° C, end point 145 to 175 ° C) obtained by atmospheric distillation of crude oil to a hydrodesulfurization device, Obtained desulfurized heavy naphtha (initial boiling point 80-100)
What was modified by the catalytic reforming method at the end temperature of 145 to 175 ° C) is most preferably used.

Next, the alkylate as the component (B) is an acid catalyst (sulfuric acid, hydrogen fluoride, aluminum chloride, etc.) using isobutane and lower olefins (butene, propylene, etc.) as raw materials.
It is obtained by reacting in the presence of. In the present invention, various alkylates can be used as the component (B), but isooctane (2,2,4-trimethylpentane)
Is preferably contained in an amount of 25 to 35% by weight, and among them, those having a research octane number of 95 or more are most suitable.

Subsequently, the isopentane fraction as the component (C) may have a research octane number of 90 to 95. Particularly, an isopentane fraction obtained by subjecting light naphtha, preferably desulfurized light naphtha to precision distillation is preferably used. To be done. For this precision distillation, conditions may be appropriately selected such that about 20% by volume of the isopentane fraction of the light (desulfurization) naphtha as a raw material is obtained in a purity range of 90 to 95%.

The fuel oil I of the present invention contains the above-mentioned components (A), (B), and (C) as essential components, and the mixing ratio varies depending on the properties of each component used and cannot be uniquely determined. . In short, it may be selected so as to satisfy the above-mentioned required properties of the fuel oil I. Usually, in the range of 100 parts by volume of reformed gasoline as the component (A), 6 to 55 parts by volume of alkylate as the component (B) and 3 to 28 parts by volume of the isopentane fraction as the component (C). It may be properly blended and mixed.

On the other hand, the fuel oil II of the present invention comprises the above (A), (B),
Along with the (C) component, a light catalytic cracking gasoline as the (D) component is an essential component. This light catalytic cracking gasoline is used for a wide range of petroleum fractions from kerosene to atmospheric residual oil, preferably heavy gas oil and vacuum gas oil, which have been widely known from the past, especially fluid catalytic cracking method (UOP). Method, shell two-stage method, flexi cracking method, ultra orthoflow method, Texaco method, Gulf method, ultracat cracking method, RCC method, HOC method, etc.) It is a light fraction of ours.
As the light catalytic cracking gasoline of the present invention, the catalytic cracking gasoline is distilled to be divided into a light component and a heavy component, of which research octane number 93.5 to 96.5, Reid vapor pressure 0.6 to 1.05.
A light component having a property of kg / cm ² and a boiling point range of 25 to 100 ° C. is used.

The fuel oil II of the present invention comprises the above (A), (B), (C),
The component (D) is an essential component, and its mixing ratio differs depending on the properties of each component used similarly to the conventional fuel oil I and cannot be uniquely determined. In short, the above-mentioned requirements for the fuel oil II are required. It may be selected so as to satisfy the property. Normally, 6 to 86 parts by volume of alkylate as the component (B) is added to 100 parts by volume of reformed gasoline as the component (A),
3 to 43 parts by volume of the isopentane fraction which is the component (C),
The light catalytic cracking gasoline which is the component (D) may be appropriately blended and mixed in the range of 3 to 58 parts by volume.

Fuel oils I and II of the present invention are all research octane numbers
99.5 or higher (usually around 100), motor octane number 88.
It has properties of 6 or more (usually around 90), aromatic content of 50% by volume or less, and distillate up to 70 ° C (ΔE70) of 25% by volume or more (usually around 27% by volume). further,
50% (volume) distillation temperature is 110 ° C or less, Reid vapor pressure is 0.7
It is preferably 5 kg / cm ² or less. If the aromatic content exceeds 50% by volume, problems such as deterioration of rubber used in the fuel system and increase of harmful substances in exhaust gas occur. Further, when ΔE70 is less than 25% by volume, startability and low-temperature drivability are poor even if the research method octane number and the motor method octane number are high.

The fuel oils I and II of the present invention have the above-mentioned essential components and properties, but a butane fraction (particularly, one containing a large amount of i-butane is preferable as long as the properties can be maintained. It is also effective to add an appropriate amount of aromatic components such as.) Or toluene or detergent additives.

〔Example〕

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Example 1 (1) (A) Preparation of reformed gasoline containing 17.2% by volume of naphthene and 11.1% by volume of aromatic content,
Desulfurization heavy naphtha (DHN) with initial boiling point (IBP) 86 ℃ and end point (EP) 156 ℃ was platformed at 516 ℃, and research octane number (RON) 102.2, motor octane number (MON) 90.7, ΔE70 is 9.0% by volume, IBP39.0 ℃, EP191.5 ℃,
Reformed gasoline with a Reid vapor pressure of 0.400 kg / cm ² was obtained.

(2) (B) Preparation of alkylate Isobutane and butene are used as raw materials and reacted under a sulfuric acid catalyst to contain about 30% by volume of isooctane, and RON96.4, MON93.
9, ΔE70 is 8.0, IBP35.0 ℃, EP203.0 ℃, Reid vapor pressure 0.42
5 kg / cm ² alkylate was obtained.

(3) Preparation of (C) isopentane fraction Desulfurized heavy naphtha (DLN) having an initial boiling point (IBP) of 27 ° C and an end point (EP) of 80 ° C is subjected to precision distillation to obtain a purity of 92% by volume, RON90.3, MON8
An isopentane fraction with a reed vapor pressure of 8.3 and a reed vapor pressure of 1.500 kg / cm ² was obtained.

(4) (D) Preparation of light catalytic cracking gasoline RON92.5, MON80.0, Reed distillation pressure 0.690kg / cm ² , IBP30 ℃, EP
Distill catalytic cracking gasoline (FCC gasoline) at 165 ℃,
Excluding heavy components, RON94.7, MON81.0, ΔE70 is 97.0
Volume%, IBP31.0 ℃, EP88.0 ℃, Reid vapor pressure 1.02kg / cm ²
A light catalytic cracking gasoline was obtained.

(5) Production of high-performance fuel oil (A) reformed gasoline obtained in (1) above, (2) above
(B) alkylate obtained in (1), (C) isopentane fraction obtained in (3) above, (D) obtained in (4) above
Mixing light catalytic cracking gasoline and butane fraction, RON1
00.0, MON89.2, Reid vapor pressure 0.667kg / cm ² , ΔE70 is 27.0
A high-performance fuel oil having properties of 4% by volume and 43.0% by volume of aromatics was produced.

(6) Evaluation of high-speed knockability and low-temperature drivability Using the high-performance fuel oil obtained in (5) above, its high-speed knockability and low-temperature drivability were evaluated. The results are shown in Table 1.

The evaluation of high-speed knock resistance was carried out on a chassis dynamometer adjusted to room temperature of 25 ° C with a displacement of 1500cc and compression ratio.
9.5, Manual mission, Passenger car with a mileage of 100,000km was installed, and the degree of knocking was examined by increasing the top gear from 30km / hr to 120km / hr with the accelerator fully opened at room temperature.

◎ ・ ・ ・ No knocking ○ ・ ・ ・ Trace knock △ ・ ・ ・ Light knock (some people feel uncomfortable) × ・ ・ ・ Heavy knock Further, the evaluation of low-temperature drivability was carried out at room temperature of 0 ° C. The measurement was performed on a sea dynamometer, and the acceleration was measured immediately after starting as follows. That is, start a carburetor type auto choke type 1300cc engine at 0 ° C, perform warm-up operation for 30 seconds, then fully open the accelerator with the top gear, measure the rotation speed for 20 seconds, and perform the same measurement after complete warm-up. Compared to the number of revolutions in time. In other words, low-temperature drivability is: low-temperature drivability = (number of revolutions after 30 seconds of warm-up operation and 20 seconds of full accelerator opening) / (number of revolutions after full warm-up and 20 seconds of full accelerator opening) x
It was defined by 100 (%). This low temperature drivability of 80% or more is good.
0 to 80% was evaluated as a little bad, and less than 60% was evaluated as bad x.

The acceleration performance was evaluated on a chassis dynamometer whose room temperature was adjusted to 25 ° C, using eight representative domestic passenger cars. The evaluation method is the time (acceleration time) until the accelerator is fully opened to 80km / hr at 40km / hr and the accelerator is fully opened to 120km / hr at 60km / hr.
It was carried out by measuring the time until acceleration (acceleration time) and comparing it with the acceleration time when using typical conventional premium gasoline.

○ ・ ・ ・ Acceleration time is shortened by 4% or more compared to conventional typical premium gasoline use △ ・ ・ ・ Acceleration time is reduced by 0 to 3% compared to conventional typical premium gasoline use The plug smolder is evaluated at room temperature. Was carried out as follows using a typical domestic passenger car (displacement 1500cc, with manual transmission, carburetor specification) on a chassis dynamometer adjusted to -10 ℃. That is, after cooling the engine, start the engine by the normal starting method, and after starting, run 350m at a top gear speed of 30km / hr, stop the engine, and restart it 5 minutes later. The insulation resistance value of the subsequent plug was measured by an insulation resistance meter.

○ ・ ・ ・ Insulation resistance value is more than 1 MΩ × ・ ・ ・ Insulation resistance value is less than 1 MΩ Evaluation of the effect on the rubber of the fuel system is based on the immersion test in the vulcanized rubber physical test method according to JIS-K-6301. A volume change and hardness test were performed and evaluated according to the following criteria.

○ ・ ・ ・ Change rate (%) is less than 25% × ・ ・ ・ Change rate (%) is 25% or more High-temperature drivability is evaluated on a chassis dynamometer with room temperature adjusted to 35 ° C. Passenger car (displacement 1600
cc, with manual transmission, carburetor specification) was used as follows. That is, start the engine in the usual way, run it in the top gear at a vehicle speed of 100 km / hr for 30 minutes, then stop the engine and start the engine in the usual way 15 minutes later.
After idling for 2 seconds, the top gear was accelerated from 40km / hr to 100km / hr with the accelerator fully opened five times, and engine startability, idling stability, and acceleration were evaluated.

Good: Engine startability, idling stability, and acceleration are all good. Poor starting, unstable idling, or poor acceleration. Example 2 (1) Preparation of reformed gasoline Naphthene content 24.5 capacity %, Aromatic content 10.0% by volume,
Desulfurization heavy naphtha (DHN) having an initial boiling point (IBP) of 84 ° C and an end point (EP) of 163 ° C is platformed at 529 ° C to produce RON1
02.6, MON90.5, ΔE70 is 14.0% by volume, IBP34.0 ℃, EP196.0
We obtained reformed gasoline with a Reed vapor pressure of 0.530 kg / cm ² at ℃.

(2) Production of high-performance fuel oil (A) reformed gasoline obtained in Example 2 (1), (B) alkylate obtained in Example 1 (2), Example 1 (3) (C) isopentane fraction obtained in
(D) Mixing the light catalytic cracking gasoline and butane fraction obtained in Example 1 (4) above, RON100.0, MON89.1, Reed vapor pressure 0.686 kg / cm ² , ΔE70 27.0% by volume, Aromatic content
A high-performance fuel oil having a property of 42.0% by volume was produced.

(3) Evaluation of high-speed knockability and low-temperature drivability High-speed knockability and low-temperature operation were performed in the same manner as in Example 1 (6) except that the high-performance fuel oil obtained in Example 2 (2) above was used. The drivability was evaluated. The results are shown in Table 1.

Example 3 (1) Production of high-performance fuel oil (A) Reformed gasoline obtained in Example 2 (1), (B) Alkylate obtained in Example 1 (2), Example above The (C) isopentane fraction and the butane fraction obtained in 1 (3) were mixed, and RON100.0, MON89.9, Reed vapor pressure 0.730 kg / cm ² , ΔE70 27.0% by volume, aromatic content 44.3 A high performance fuel oil having a volume% property was produced.

(2) Evaluation of high-speed knockability and low-temperature drivability High-speed knockability and low-temperature performance were the same as in Example 1 (6) except that the high-performance fuel oil obtained in Example 3 (1) above was used. The drivability was evaluated. The results are shown in Table 1.

Example 4 (1) Production of high-performance fuel oil (A) Reformed gasoline obtained in Example 2 (1) above, (B) Alkylate obtained in Example 1 (2) above, Example above The (C) isopentane fraction obtained in 1 (3), the (D) light catalytically cracked gasoline obtained in Example 1 (4) and the butane fraction were mixed to produce RON100.0, MON89.8, Reid vapor pressure 0.716 kg / cm ² , ΔE70 27.0% by volume, aromatic content 4
A high-performance fuel oil having a property of 4.0% by volume was produced.

(2) Evaluation of high-speed knockability and low-temperature drivability High-speed knockability and low-temperature performance were the same as in Example 1 (6) except that the high-performance fuel oil obtained in Example 4 (1) above was used. The drivability was evaluated. The results are shown in Table 1.

Comparative Example 1 (1) Production of Fuel Oil (A) Reformed gasoline obtained in Example 1 (1), (B) Alkylate obtained in Example 1 (2), Example 1 ( The (C) isopentane fraction and the butane fraction obtained in 3) were mixed, and RON100.0, MON89.0, Reed vapor pressure 0.735 kg / cm ² , ΔE70 was 22.0% by volume, aromatic content was 55% by volume.
A fuel oil having the following properties was produced.

(2) Evaluation of high-speed knockability and low-temperature drivability High-speed knockability and low-temperature drivability were obtained in the same manner as in Example 1 (6) except that the fuel oil obtained in Comparative Example 1 (1) was used. Was evaluated. The results are shown in Table 1.

Comparative Example 2 (1) Production of Fuel Oil (A) Reformed gasoline obtained in the above Examples (2) and (1), (B) Alkylate obtained in the above Example 1 (2), and the above Examples (C) Isopentane fraction obtained in 1 (3), (D) light catalytic cracking gasoline obtained in Example 1 (4) and butane fraction were mixed to obtain RON100.0, MON8.
7.9, Reid vapor pressure 0.725kg / cm ² , ΔE70 was 35% by volume, and fuel oil having the property of aromatic content 45% by volume was produced.

(2) Evaluation of high-speed knockability and low-temperature drivability High-speed knockability and low-temperature drivability were obtained in the same manner as in Example 1 (6) except that the fuel oil obtained in Comparative Example 2 (1) above was used. Was evaluated. The results are shown in Table 1.

[Advantages of the Invention] The high-performance fuel oil of the present invention not only has high RON and MON,
The balance of vapor pressure, distillation properties, and aromatics content provides excellent knock resistance, especially at high speeds, as well as low temperature drivability, startability, flammability, and acceleration. It is excellent and can be used very effectively as a fuel for gasoline vehicles, especially as a high-quality gasoline fuel for vehicles equipped with high-performance engines such as turbos and twin cams.

Claims (2)

[Claims] 1. A research method octane number of 101.5 or more,
A reformed gasoline having a Reid vapor pressure of 0.3 kg / cm ² or more and a boiling range of 30 to ²⁰⁰ ° C., (B) an alkylate, and (C) an isopentane fraction having a research octane number of 90 to 95 are essential components and a research octane number of 99.5. Above, motor method octane number above 88.6, aromatic content below 50% by volume and 70 ℃
High-performance fuel oil, characterized in that the distillate is up to 25% by volume. 2. A) Research method octane number of 101.5 or more,
Reformed gasoline having a Reid vapor pressure of 0.3 kg / cm ² or more and a boiling range of 30 to ²⁰⁰ ° C., (B) an alkylate, (C) an isopentane fraction having a research octane number of 90 to 95, and (D) a research octane number of 93.5 to 96.5, Reid vapor pressure 0.6 to 1.05
Light catalytic cracking gasoline with kg / cm ² and boiling point range of 25 to 100 ℃ is an essential component, research octane number 99.5 or more, motor method octane number 88.6 or more, aromatic content 50% by volume
High-performance fuel oil characterized in that the distillate up to 70 ° C is 25% by volume or more.