JP2001288483A - Lead-free gasoline composition and its preparation method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a unleaded gasoline composition and its manufacturing method which is excellent in antiknock property under actual driving conditions and incorporates a due consideration to the environments such as the suppression of photochemical oxidants. SOLUTION: The unleaded gasoline composition comprises a content of benzene of <=1.0 vol.%, Reid method vapor pressure of 40.0 to 65.0 kPa, motor method octane number of 80.0 to 86.0 and distribution method octane number of 88.0 to 95.0, and preferably research octane number of 89.0 to 91.0 and a sulfur content of <=50 mass ppm. Further, the preparation method of the lead- free gasoline composition comprises compounding a heavy-duty catalytic cracking gasoline base of 40 to 80 vol.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an unleaded gasoline composition having a reduced effect on the environment, and more particularly, to an unleaded gasoline which is environmentally friendly, such as reducing photochemical oxidants, and which ensures anti-knock property during actual driving. The present invention relates to a composition and a method for producing the composition.

[0002]

2. Description of the Related Art In recent years, it is well known that various improvements have been made to gasoline automobile technology in response to increasing environmental problems, and gasoline quality has been improved in response thereto. Among them, the JIS for benzene contained in gasoline was already revised in 1999, and this content was reduced to less than 1.0% by volume from January 2000.

[0003] At present, reduction of fuel evaporative gas from automobiles is being studied as a part of countermeasures against photochemical oxidants having the lowest compliance rate with environmental standards. In order to reduce this, it is conceivable to reduce the vapor pressure of gasoline as well as to improve the structure of the automobile. As a specific means, there is a method of lowering the butane mixture ratio in gasoline.

[0004] In addition, regarding the sulfur content,
Since lean NOx catalysts for reducing NOx concentration are poisoned by sulfur compounds, it is preferable to reduce the sulfur content in gasoline. As a method for reducing the sulfur content, it is conceivable to desulfurize a catalytic cracking gasoline base material, which is a gasoline base material having a relatively high sulfur content, or to limit the compounding ratio.

However, these benzene, butane and catalytic cracking gasoline base materials are all useful gasoline base materials for improving antiknock property. Therefore, a decrease in the octane number, which is an essential quality for gasoline, due to a decrease in the content of the above-described components is a concern.

As an index of anti-knock property of automobile gasoline, a research octane number (hereinafter referred to as RON) of JIS K 2280 "Petroleum products-fuel oil-Octane number and cetane number test method and cetane index calculation method" is adopted. JIS
The standard value in K 2202 "Auto gasoline" is set to 89.0 or more. Therefore, even if the composition of the gasoline base material changes as described above and the anti-knock property deteriorates, there must be a certain stop.

[0007] However, the above-mentioned RON is a specified rotation speed (600 rp).
m) is a laboratory octane number that determines the anti-knock property by comparing the knock strength of a standard fuel and a sample using a special single-cylinder engine set in m).
An anti-knock property that does not cause knocking even under running conditions where the load and the engine speed change every moment is required. RON
Is not sufficient as an index to comprehensively express such practical performance of antiknock property, and has been regarded as a problem in the past. For this reason, it is difficult to ensure practical anti-knock performance during actual driving only by satisfying the RON standard value.

[0008]

As described above, environmentally friendly gasoline, which has characteristics such as low benzene content and low vapor pressure, does not have sufficient anti-knock property during actual running. However, a method for producing environmentally friendly gasoline with sufficient practical performance has not yet been established. Therefore, the present invention is to solve these problems, and while taking into account environmental issues such as suppression of the generation of photochemical oxidants, and having excellent anti-knock properties under actual running conditions, and a production method thereof. It provides a method.

[0009]

Means for Solving the Problems The present inventor produced various environmentally friendly gasoline and evaluated the anti-knock property using an actual vehicle. It has been found that the anti-knock property at the time of actual running may be inferior even if it is almost the same as the conventional case.

Further, the present inventor has proposed that the laboratory octane number besides RON, JIS K 2280 motor method octane number (hereinafter referred to as MON), ASTM D 2886-86 “Test Method”.
for Knock Characteristics of Motor Fuels by the D
octane number (hereinafter referred to as DON) of the istribution Octane Number (DON) Method.
Therefore, the octane number of the prototype eco-friendly gasoline was also evaluated. MON
Is a laboratory octane number using a single-cylinder engine like RON, but is suitable for evaluation of anti-knock property at high speed running due to its high specified rotation speed (900 rpm). On the other hand, DON
The specified rotation speed (600 rpm) is the same as RON, but a water-cooled distribution manifold is installed between the carburetor and the intake port, and the anti-knock property of the forehead in gasoline can be evaluated. There is an advantage that the anti-knock property at the time can be evaluated.

In view of the fact that the laboratory octane numbers have characteristics as described above, the present inventor can prepare a gasoline composition having excellent anti-knock property during actual running by specifying these in combination. With the idea of being able to do so, prototypes of various environmentally friendly gasolines were made, and their anti-knock properties during actual running and the correlation between RON, MON, and DON were examined. A strong correlation with MON and DON is recognized, and it is possible to secure excellent anti-knock properties by controlling the combination of these in a certain range. (2) The anti-knock property during actual running is RON
Were found to have a weak correlation with the present invention, and came to the present invention.

That is, the unleaded gasoline composition of the present invention is an unleaded gasoline having a benzene content of 1.0% by volume or less and a Reid process vapor pressure of 40.0 kPa or more and 65.0 kPa or less.
N is 80.0 or more and 86.0 or less, and DON is 88.0 or more and 95.0 or less. In the present invention, RON is 89.0 or more 91.
Even in the case of 0 or less, if the above-mentioned MON and DON are within the specified ranges, sufficient anti-knock property during actual traveling can be secured. Further, the sulfur content is more preferably 50 mass ppm or less.

Further, the present inventor has found that the above-mentioned unleaded gasoline composition of the present invention can be easily produced by blending a heavy catalytic cracking gasoline base material in a specific amount. That is,
The present invention relates to a method for converting a heavy catalytic cracking gasoline
The above-mentioned lead-free gasoline composition is manufactured by blending the content of the gas in an amount of not more than% by volume. Further, such a heavy catalytic cracking gasoline base material has a benzene content of 1.0% by volume or less and a vapor pressure of 6% by the Reed method.
0.0 kPa or less, sulfur content 50 mass ppm or less, and unwashed real gum 2
More preferably, it has a property of mg / 100 ml or less.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The unleaded gasoline composition according to the present invention has a benzene content of 1.0% by volume or less, a vapor pressure of Reed method of 40.0 kPa or more and 65.0 kPa or less, and a MON of 80.0 or more.
0 or less and DON is 88.0 or more and 95.0 or less. Here, the benzene content is based on JIS K 2536 “Petroleum products-Component testing method”.
Can be measured. Benzene content is below 1.0% by volume,
It is preferably 0.9% by volume or less, and the lower the better, the better.

[0015] The vapor pressure of the Reed method can be measured by JIS K 2258 "Test method for crude oil and fuel oil vapor pressure (Reed method)". Reed method vapor pressure is 40.0 kPa or more and 65.0 kPa or less, preferably 40.0 kPa or more and 60.0 kPa or less, more preferably 50.0 kP or less.
It is not less than a and not more than 60.0 kPa. When the vapor pressure of the Reed method is lower than this range, it is not preferable because starting failure and deterioration of drivability are caused particularly in winter.

MON can be measured by the motor method octane number test method of JIS K 2280. MON is 80.0 or more and 86.0 or less,
It is preferably from 80.5 to 85.0, more preferably from 81.0 to 83.0. When MON is higher than this range, there is no particular problem, but it is not preferable because gasoline production cost is too high and practical performance commensurate with cost cannot be obtained.

DON can be measured by the distribution method octane number test method of ASTM D 2886-86. Among them, as a water-cooled distribution manifold,
Waukesha of the United States (Waukesha Engine Div., Fuel Resea
rch Dept., Waukesha, Wis. 53186) and ASTM D 288
Other brands can be used if they meet the specifications of 6-86. DON is 88.0 or more and 95.0 or less, preferably 88.0 or more and 94.0 or less
And more preferably 89.0 or more and 94.0 or less. DON
Is higher than this value, the aromaticity of the trailing portion is relatively reduced, and sticking of the fuel injection nozzle and the tendency of deposit formation appear, which is not preferable.

RON can be measured by the octane number test method of the research method of JIS K 2280. RON has a weak correlation with anti-knock property during actual driving, but it is 89.0 or more and 96.0 or less, especially 8
It is preferably from 9.0 to 94.0, more preferably from 89.0 to 92.0. If RON is higher than this range, performance improvement corresponding to the increase in cost related to gasoline production cannot be obtained and high RON
Unfavorable use of the base material is not preferable because the gasoline's distillation properties are distorted. On the other hand, if the gasoline is too low, it is not preferable because knocking tends to occur particularly during acceleration on a hill. RO
N is 89.0 or more if MON and DON are within the above specified range.
Even with 1.0 or less, sufficient anti-knock property during actual driving can be achieved.

The sulfur content is more preferably 50 ppm by mass or less. The unleaded gasoline composition of the present invention is not particularly limited with respect to properties other than those described above.As a fuel for an internal combustion engine, the density (15 ° C.) is 0.71 to 0.75 g / cm ³ , and the distillation property is 20 to 220 ° C. It is desirable that the oxidation stability is 400 min or more and the corrosion of the copper plate is 1 or less.

The heavy catalytic cracking gasoline base material used in the method for producing a lead-free gasoline composition of the present invention is one of the heavy catalytic cracking gasoline base materials obtained by catalytically cracking the feed oil in a catalytic cracking device. It is a gasoline fraction. As the properties of the heavy catalytic cracking gasoline base material, preferred distillation properties are:
90% distilling temperature is 175 ° C or higher, preferably 175 to 190 ° C, 50% distilling temperature is 95 ° C or higher, preferably 95 to 120 ° C, and 10% distilling temperature is 55 ° C or higher, preferably 55-70 ° C. Other properties are density (15 ° C) 0.73-0.76 g / cm ³ ,
Reed method vapor pressure is 40 ~ 60kPa, RON is 91 ~ 94, distillation temperature range is about 30 ~ 210 ° C, sulfur content is 50 mass ppm or less,
Benzene content of 1.0% by volume or less, JIS K2261 "Petroleum products-Automotive gasoline and aviation fuel oil-Real gum test method-
It is preferable that the unwashed real gum by the “jet evaporation method” is 2 mg / 100 ml or less.

The process for producing the heavy catalytic cracking gasoline base material used in the present invention is not particularly limited to a catalytic cracking device, a feedstock, and operating conditions, and any known production process can be adopted. The catalytic cracking device is amorphous silica alumina,
Using a catalyst such as zeolite, in addition to petroleum fractions from gas oil to reduced pressure gas oil, contact with degassed oil obtained from heavy oil indirect desulfurization unit, directly desulfurized oil obtained from heavy oil direct desulfurization unit, normal pressure residue oil, etc. This is a device to obtain a high octane gasoline base material by cracking. For example, the fluid catalytic cracking methods such as the UOP catalytic cracking method, flexicracking method, ultra-ortho-flow method, and Texaco fluid catalytic cracking method described in the Petroleum Institute's “New Petroleum Refining Process”, RCC method, HOC method, etc. There is an oil fluidized catalytic cracking method and the like.

The general properties of the catalytic cracking gasoline base material obtained from the catalytic cracking device are as follows: the density (15 ° C.) is 0.72 to 0.76 g /
cm ³ , Reed method vapor pressure is 40-70 kPa, RON is 92-95, and distillation property is about 20-210 ° C. The heavy catalytic cracking gasoline base material specified in the present invention is typically used as a heavy fraction obtained by distilling the catalytic cracking gasoline base material and removing the light catalytic cracking gasoline base material. The fraction can also be obtained by mixing the fraction with a catalytic cracking gasoline base material to increase the ratio of the heavy fraction. The properties of the light catalytic cracked gasoline base material separated from the catalytic cracked gasoline base material were as follows: density (15 ° C): 0.60 to 0.70 g / cm ³ ;
It has 0 kPa, RON of 93 to 96, and a distillation temperature range of about 20 to 110 ° C., and can be used for producing premium gasoline and the like.

The compounding amount of the heavy catalytic cracking gasoline base material is preferably 40% by volume or more and 80% by volume or less, particularly 40 to 75% by volume, more preferably 45 to 70% by volume based on the total amount of gasoline.
It is. If the amount of the heavy catalytic cracking gasoline base material is below this range, the effect of improving antiknock properties during actual running is weak, and if it exceeds this range, the oxidation stability may deteriorate, which is not preferable.

Other gasoline base materials include straight run naphtha obtained by distilling crude oil at normal pressure, desulfurized naphtha obtained by desulfurizing straight run naphtha, reformed gasoline obtained by subjecting desulfurized heavy naphtha to catalytic reforming, and light oil. Catalytic cracking gasoline base material, low-grade olefin obtained by catalytic cracking of petroleum fractions up to vacuum gas oil or oil obtained from indirect desulfurization equipment for heavy oil, direct desulfurization oil obtained from direct desulfurization equipment for heavy oil, and residual oil under atmospheric pressure Alkylate and light naphtha obtained by reacting benzene and isobutane in the presence of an acid catalyst, and isomerate with high octane value by isomerization, LPG fraction and light naphtha recovered from crude oil and various secondary refiners There are butane, isopentane, and the like obtained by precision distillation of these, and these can be appropriately selected and mixed at an appropriate ratio to produce the unleaded gasoline composition of the present invention. The blending amount of these base materials is arbitrary as long as it does not deviate from the gist of the present invention, but is preferably from 20% by volume to 60% by volume, more preferably from 25 to 60% by volume, based on the total amount of gasoline, 30-55% by volume
Is more preferred. Further, a gasoline base material composed of an oxygen-containing compound such as methyl tertiary butyl ether, ethyl tertiary butyl ether, and tertiary amyl methyl ether can also be used. When the oxygen-containing compound is blended, the blending amount is preferably about 1 to 10% by volume.

Known fuel additives can be added to the unleaded gasoline composition of the present invention, if necessary. The amount of these additives can be selected as appropriate, but it is usually preferable to set the total amount of additives to 0.1% by weight or less. Examples of additives that can be used in the lead-free gasoline composition of the present invention include amine-based, phenol-based, aminophenol-based antioxidants, Schiff-type compounds, metal deactivators such as thioamide-type compounds, and organic phosphorus. Surface ignition inhibitors such as
Detergents and dispersants such as succinimide, polyalkylamines and polyetheramines; deicing agents such as polyhydric alcohols and their ethers; alkali metal and alkaline earth metal salts of organic acids; and sulfuric esters of higher alcohols. Examples include flame retardants, anionic surfactants, cationic surfactants, antistatic agents such as amphoteric surfactants, rust inhibitors such as alkenyl succinates, discriminants such as quinizarin, coumarin, and coloring agents such as azo dyes. be able to.

[0026]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

Properties of gasoline base materials of catalytic cracked gasoline, heavy catalytic cracked gasoline, reformed gasoline, straight run light naphtha, desulfurized light naphtha and cracked butane used in the production of the lead-free gasoline compositions of Examples and Comparative Examples Are shown in Table 1.
The heavy catalytic cracking gasoline base material rectifies a light catalytic cracking gasoline base material that is a base material for premium gasoline production from a catalytic cracking gasoline base material obtained by catalytically cracking desulfurized heavy gas oil having a sulfur content of 0.29% by mass. It is produced by mixing the removed product with a catalytic cracking gasoline base material. The 90% distillation temperature of this heavy catalytic cracking gasoline base material is 181.0 ° C, the 50% distillation temperature is 111.5 ° C, and the 10% distillation temperature is 61.0 ° C.

[0028]

[Table 1]

Using the gasoline base material of Table 1, lead-free gasoline compositions of Examples 1 to 3 and Comparative Examples 1 to 4 shown in Tables 2 and 3 were prepared. The unleaded gasoline composition of Example 1 was composed of 3 parts of catalytic cracking gasoline, 57 parts of heavy catalytic cracking gasoline, 22 parts of reformed gasoline, and 5 parts of straight run light naphtha 5 by volume.
In Example 2, 60 parts of heavy catalytic cracking gasoline and 27 parts of reformed gasoline were used.
In Example 3, 60 parts of heavy catalytic cracking gasoline, 20 parts of reformed gasoline, 5 parts of straight-run light naphtha, and 15 parts of desulfurized light naphtha were blended.

The unleaded gasoline composition of Comparative Example 1 shown in Table 3 was composed of 35 parts of catalytic cracked gasoline and 29 parts of heavy catalytic cracked gasoline.
Parts, 20 parts of reformed gasoline, and 16 parts of desulfurized light naphtha,
Comparative Example 2 included 35 parts of catalytic cracking gasoline, 38 parts of heavy catalytic cracking gasoline, 8 parts of reformed gasoline, 18 parts of straight-run light naphtha, and 1 part of desulfurized light naphtha. Comparative Example 3 included a catalytic cracking gasoline base material. 44 parts, heavy catalytic cracking gasoline base material 26 parts, reformed gasoline 15 parts, straight-run light naphtha 9 parts, desulfurized light naphtha 6 parts, and Comparative Example 4 shows 34 parts of catalytic cracking gasoline, heavy catalytic cracking 35 parts of gasoline, 12 parts of reformed gasoline, and 19 parts of desulfurized light naphtha were blended. The lead-free gasoline compositions of Examples and Comparative Examples include a coloring agent (CL, manufactured by Shirad Chemical Co., Ltd.).
-53) 2mg / l, antioxidant (Sumitomo Chemical Industries Sumilizer
4ML) 20 mg / l, and in Example 1, 100 mg / l of a detergent / dispersant (Keropur AP-95 manufactured by BSF) was added.

The density (15%) of the unleaded gasoline compositions of Examples 1 to 3 and Comparative Examples 1 to 4 prepared as described above
° C), distillation properties, benzene content, Reed method vapor pressure, sulfur content, unwashed real gum, RON, MON, DON and running octane number (hereinafter referred to as RdON) were measured and evaluated by the following methods. RdON is an index for evaluating anti-knock property during actual running.

The density (15 ° C.) is determined by the vibration type density test method of JIS K 2249 “Crude oil and petroleum products-Density test method and density / mass / volume conversion table”. The benzene content is determined by the JIS K 2536 tandem gas chromatography component test method, and the Reed method vapor pressure is determined by the normal pressure distillation test method (addition loss) in
According to JIS K 2258, sulfur content is determined by microcoulometric titration oxidation method of JIS K 2541 `` Crude oil and petroleum products-Sulfur content test method '', unwashed real gum is JIS K 2261, RON is JIS K 2280
According to the research octane number test method of MON, JIS K 2
280 motor method octane test method, DON is AS
Determined by TM D 2886-86.

RdON was determined by the modified uniontown method of CRC F28-70. The modified Uniontown method is a method of actually using a vehicle and changing the ignition timing at the time of idling, thereby advancing the ignition timing during acceleration to cause knocking during traveling, and obtaining an octane number during actual traveling. In this embodiment, the engine is equipped with a single point injection specification, and the transmission type is a manual displacement of 1,60.
Using a 0cc domestic small passenger car as a test vehicle, the traveling load was set on a chassis dynamometer equivalent to the traveling load on an asphalt flat road, and the measurement was performed by controlling the intake air temperature and humidity to be constant. The acceleration was evaluated at full throttle and the engine speed range was from 1000 to 3000 rpm. The criterion for determining RdON in this example was 88.0, and a value higher than this was regarded as good.

Tables 2 and 3 show the measurement and evaluation results of Examples 1 to 3 and Comparative Examples 1 to 4, respectively.

[0035]

[Table 2]

[0036]

[Table 3]

From Examples 1 to 3 in Table 2, the benzene content is 1.0% by volume or less, and the vapor pressure of Reed method is 40.0 kPa to 65.0 kP.
a or less, MON is 80.0 or more and 86.0 or less, and DON is 88.0
It is clear that the unleaded gasoline composition having a value of 95.0 or less has an excellent RdON. In addition, it can be seen that even when the RON is 89.0 or more and 91.0 or less, the above-mentioned unleaded gasoline composition has good anti-knock property. The unleaded gasoline composition of the comparative example has a low RdON because the value of MON or DON is out of the range of the present invention due to a difference in the base material composition, so that a problem may occur during actual running.

[0038]

The unleaded gasoline composition according to the present invention has a benzene content of 1.0% by volume or less and a vapor pressure of the Reed method of 40.0%.
~ 65.0kPa, motor method octane number is 80.0 ~ 86.0 and distribution method octane number is 88.0 ~ 95.0,
It is a fuel that takes environmental issues into consideration, such as photochemical oxidants, and at the same time, exhibits good anti-knock characteristics when used in actual gasoline vehicles whose load and engine speed change every moment. It is useful as a fuel for use. Further, the method for producing a lead-free gasoline composition according to the present invention comprises mixing 40 to 80% by volume of a heavy catalytic cracking gasoline base material. A lead-free gasoline composition exhibiting antiknock properties at the time can be easily produced.

Claims (5)

[Claims] 1. A benzene content of 1.0% by volume or less, a vapor pressure of a Reed method of 40.0 kPa or more and 65.0 kPa or less, an octane number of a motor method of 80.0 or more and 86.0 or less, and an octane value of a distribution method of 88.0 or more and 95.0 or less. Unleaded gasoline composition. 2. The unleaded gasoline composition according to claim 1, which has a research octane number of 89.0 or more and 91.0 or less. 3. The method according to claim 1, wherein the sulfur content is 50 ppm by mass or less.
Or the unleaded gasoline composition according to 2. 4. The unleaded gasoline composition according to claim 1, wherein the heavy catalytic cracking gasoline base material is blended in an amount of 40% by volume or more and 80% by volume or less. Production method. 5. The heavy catalytic cracking gasoline base material has a benzene content of 1.0% by volume or less, a vapor pressure of Reid method of 60.0 kPa or less, a sulfur content of 50 mass ppm or less, and an unwashed real gum of 2 mg / 100 ml or less. The method for producing a lead-free gasoline composition according to claim 4.