JP3075781B2 - Automotive fuel with improved properties - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to gasoline fuel compositions having excellent environmental and service properties.

As is well known, the lighter portions of gasoline tend to evaporate to the atmosphere, especially on warm or hot days, but these lighter portions are removed to reduce atmospheric pollution. Attempting to reduce it will lower the octane number. Increasing the proportion of aromatic hydrocarbon gasoline components with high octane number, such as benzene, toluene and xylene, can compensate for the decrease in octane number.
However, since aromatics are particularly undesirable in terms of toxicity, it would be desirable to provide a method for reducing the volatility of gasoline in the final stage without increasing the aromatics content.

[0003] The gasoline fuel composition of the present invention comprises a raid (R)
eid) has a vapor pressure (ASTM test method D-323) of 8.
5 psi (58.6 kPa) or less, preferably 8.0p
si (55.2 kPa) or less, and as a cyclopentadienyl manganese tricarbonyl compound soluble in at least one fuel, up to 1/32 g per gallon (0.
008 g / l) of manganese. Using cyclopentadienyl manganese tricarbonyl,
Without increasing volatility and without increasing aromatics content, the octane number of gasoline with low raid vapor pressure is increased. It has also been found that these manganese compounds tend to have a greater effect on improving the octane number on paraffins and naphthenic hydrocarbons than on aromatic hydrocarbons in gasoline. Further, the use of the fuel of the present invention reduces emissions of carbon dioxide and nitric oxide (NOx) during operation of the engine and has little effect on the amount of hydrocarbons emitted into the exhaust pipe. The fuel of the present invention also has substantially no adverse effect on exhaust gas catalysts and oxygen sensors of the type commonly used in modern vehicles. Thus, the fuel of the present invention is an "environmentally friendly" fuel.

In another embodiment of the present invention, (1)
Gasoline boiling range [typically 70-440 ° F (2
1.1 to 226.7 [deg.] C.)] to form gasoline by blending suitable hydrocarbons with each other in appropriate proportions.
And / or (2) the method of refueling and / or consuming vehicles with gasoline is improved.

[0005] In the improved gasoline production process of the present invention, the fuel containing cyclopentadienyl manganese tricarbonyl and having a low vapor pressure of raid can be obtained by any suitable method, for example, (a) during the gasoline blending step. Or thereafter adding a fuel-soluble additive to the gasoline, or (b) prior to compounding the feed stream, adding the additive to one or more gasoline hydrocarbon feed streams or other compounding components such as oxygen It is blended by blending with the contained fuel blending component. Storing the high octane gasoline thus obtained in at least one storage tank of a storage base as required before distributing the fuel to the vehicle for use;
This can then be distributed to each car.

According to such an improved method, the amount of volatile hydrocarbons released into the atmosphere during storage and / or during refueling of the vehicle is reduced, and cyclopentadienyl manganese tricarbonyl is reduced. The amount of carbon monoxide and nitric oxide discharged into the atmosphere when the vehicle is running is reduced as compared with the case where the corresponding fuel containing no is used.

As described above, the unleaded gasoline used in the method of the present invention has a raid vapor pressure of 8.5 psi (5 psi).
8.6 kPa) or less, preferably 8.0 psi (55.
2 kPa) or less. As is known, raid vapor pressure is determined at 100 ° F (37.8 ° C). Such gasoline contains trace amounts of lead as impurities, but is lead-free in the sense that no organic lead anti-knock agent is included in the fuel. Hydrocarbon gasoline base stocks used to make gasoline blends include direct distillate feedstocks, light naphtha fractions, cracked gasoline feedstocks obtained by pyrolysis or catalytic cracking, hydrocracking or similar methods, A reformed product obtained by a catalytic reforming method or a similar method, a polymerized gasoline obtained by polymerization of an olefin, an alkylate obtained by adding an olefin to isobutane, or another hydrocarbon obtained by an alkylation method; Contains lower linear paraffins, e.g., isomerized products obtained by isomerization of n-hexane, n-heptane, etc., and other hydrocarbons having a gasoline boiling range obtained by suitable petroleum refining processes. . If desired, appropriate amounts of suitable hydrocarbons obtained by other methods, such as during coal or shale mining, can be included. For example, Fischer-Tropsc
h) A reformed product based on a liquid fuel obtained by the process can be included in the formulation. The gasoline obtained in all cases meets the requirements for the raid vapor pressure of the present invention, and also has the usual unleaded regular, medium,
Must have the distillation characteristics typical of premium or super premium gasoline. Thus, these automotive gasolines fall within the parameters of ASTM D48414 and typically have an initial boiling point of 70-115 ° F (21.4-46.1 ° C) as measured by the standard ASTM distillation test method (ASTMD 86). )
The final boiling point is 370-440 ° F (187.8-226.
7 ° C.). The composition of gasoline hydrocarbons by volume percentage of saturated compounds, olefins and aromatics is typically determined by ASTM test method D1319.

Generally, substrate gasoline is a blend of feedstocks obtained in various refining steps. The final formulation also hydrocarbons obtained in other ways, for example alkylate obtained by reacting using an acid catalyst such as sulfuric acid or hydrofluoric acid and C ₄ olefins and butanes, and modified processes And aromatic compounds obtained from

[0009] The saturated gasoline component consists of paraffin and naphthene. These saturated compounds are generally (1) fresh gasoline obtained by distillation (direct gasoline), (2) alkylation step (alkylate), and (3) isomerization step (high octane branched from normal paraffins). (Isomerization to paraffin). The saturated gasoline component is also obtained as so-called natural gasoline. In addition to these, pyrolysis gasoline, catalytic cracking gasoline and catalytic reforming products contain some amount of saturated components.

[0010] The olefin gasoline component is usually made using a pyrolysis method and a catalytic cracking method. The process of dehydrogenating paraffins to olefins supplements the gaseous olefins produced in the refinery and can be used as feedstock for the polymerization or alkylation step.

[0011] Gasoline base stock formulations containing the cyclopentadienyl manganese tricarbonyl additive according to the present invention generally contain 40 to 80% by volume of saturated components, 1 to 30% by volume of olefins and up to 45% by volume of aromatic compounds. Contains%. Preferred gasoline base stock formulations used in the present invention contain no more than 40% by volume of aromatics, preferably no more than 30% by volume, more preferably no more than 28% by volume, and most preferably no more than 25% by volume. . Preferably, the fuel composition as a whole contains no more than 1% by volume of benzene, most preferably no more than 0.8% by volume.

Particularly preferred unleaded gasolines made and / or used according to the invention not only meet the above-mentioned laid vapor pressure criteria, but also have (1) a maximum sulfur content of 3
(2) the maximum number of bromine is 20;
(3) the maximum content of the aromatic compound is 20% by volume,
(4) the maximum content of benzene is 1% by volume, and (5) the minimum content of oxygenates in the form of at least one monoether or polyether is 1% by weight. Gasoline is one gallon (3.8) as methylcyclopentadienyl manganese tricarbonyl.
Contains up to 1/32 g of manganese dissolved per liter). This type of gasoline without manganese additives is often referred to as reformed gasoline. For example, oil
And Gas Journal (Oil & Gas Jo)
urnal), April 9, 1990, pp. 43-48.

From an octane number standpoint, a preferred gasoline base stock formulation is one having an octane number of 78-95, represented by (R + M) / 2.

Various cyclopentadienyl manganese tricarbonyl compounds, for example, US Pat. No. 2,818,41
Any of the compounds described in No. 7 can be used in the present invention. Examples of these manganese compounds include cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, ethylcyclopentadienyl ,
Diethylcyclopentadienyl, propylcyclopentadienyl, isopropylcyclopentadienyl, t-butylcyclopentadienyl, octylcyclopentadienyl, dodecylcyclopentadienyl, ethylmethylcyclopentadienylmanganese tricarbonyl, and Includes nilmanganese tricarbonyl, and mixtures of two or more of these compounds. Generally speaking, suitable compounds or mixtures of compounds are those which are liquid at normal ambient temperatures, such as methylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, cyclopentadienyl manganese tricarbonyl And methylcyclopentadienyl manganese tricarbonyl, and a mixture of methylcyclopentadienyl manganese tricarbonyl and ethylcyclopentadienyl manganese tricarbonyl. The most preferred compound, which is commercially available and has an excellent combination of properties and effects, is methylcyclopentadienyl manganese tricarbonyl.

The following examples illustrate the invention and its various embodiments. In these examples, unless otherwise specified, the proportion of gasoline hydrocarbons is by volume. These examples do not limit the invention.

[0016]

EXAMPLE 1 58.9 Saturated hydrocarbons all having gasoline boiling range
% Of olefinic hydrocarbons and 23.6% of aromatic hydrocarbons. The raid vapor pressure of this formulation was 8.5 psi (5
8.6 kPa). 1/32 g (0.008 g / liter) per gallon of methylcyclopentadienyl manganese tricarbonyl as manganese in this substrate fuel
And 4-methyl-2.6-di-t-
Butylphenol was formulated at a concentration of 7.5 pounds per 1000 barrels (21.4 g / m ³ ). After storing the vehicle gasoline in water in the storage tanks outside the storage base, the product was transported to a gas station by a gasoline transporter where the vehicle was refueled on demand. While driving, the car consumes this gasoline.

Example 2 56.9 saturated hydrocarbons all having gasoline boiling range
% Of an olefinic hydrocarbon and 23.1% of an aromatic hydrocarbon. The ingredients have a formulation vapor pressure of 8.4.
psi (57.9 kPa). 2,6-
A t-butyl phenol antioxidant mixture containing 85% by weight of di-t-butyl phenol was used at a concentration of 6.5 lb /
Formulated in fuel at 1000 barrels (18.5 g / m ³ ). 1/32 g of methylcyclopentadienylmanganese tricarbonyl per gallon in the obtained fuel
(0.008 g / liter). The fuel was stored, transported, refueled and used for driving a car. Most of these vehicles had catalytic converters.

Example 3 Unleaded automotive gasoline having a raid vapor pressure of 8.0 (saturated component 67.7%, olefin 7.5%, aromatic component 24.
8%), the fuel obtained is 1 / 32g per gallon
(0.008 g / l) manganese and 2.7% by weight
And methylcyclopentadienyl manganese tricarbonyl and t-butyl ether in such an amount as to contain oxygen as t-butyl ether. The finished fuel can contain, and preferably contains, conventional amounts of antioxidants, metal deactivators, and carburetor detergents, which are refueled for passenger cars, buses, trucks, box trucks. And can be used for driving motorcycles.

Example 4 Examples 1 to 3 were repeated, but in some cases each vehicle fuel was 1/40 g per gallon (0.007 g).
g / l) of manganese, 1/50 g per gallon (0.005 g / l) in other cases, and 1/64 g / gallon in the third case.
(0.004 g / liter) of manganese, and in yet another case, 1/100 g (0.003 g / gal).
g / l) of manganese.

Example 5 Examples 1 to 4 were repeated, but in each case the same concentration of manganese was added as cyclopentadienyl manganese tricarbonyl instead of methylcyclopentadienyl manganese tricarbonyl.

Example 6 Examples 1-4 were repeated, but in one series of experiments each fuel was replaced with 90% by weight of methylcyclopentadienyl manganese tricarbonyl instead of methylcyclopentadienyl manganese tricarbonyl. % By weight of a mixture with cyclopentadienyl manganese tricarbonyl,
Each fuel was added in an amount such that it contained the same concentration of manganese as the fuels of Examples 1-4. In other series, Examples 1 to
Each fuel of No. 4 contained dimethylcyclopentadienyl manganese tricarbonyl instead of methylcyclopentadienyl manganese tricarbonyl at the same manganese concentration. In yet another series, specific manganese concentrations of the fuels of Examples 1-4 were provided by t-butylcyclopentadienyl manganese tricarbonyl. In yet another series, indenyl manganese tricarbonyl was used in place of methylcyclopentadienyl manganese tricarbonyl as the manganese additive used to make the automotive fuel composition.

Example 7 Contains 40.1% of a saturated component, 15.3% of an olefin, 44.6% of an aromatic component, and has a raid vapor pressure of 8.3 psi.
(57.2 kPa) was blended with the following components in unleaded gasoline.

5 pounds of a phenol mixture consisting of 75% 2,6-di-tert-butylphenol, 10-15% 2-tert-butylphenol, and 10-15% 2,4,6-tri-tert-butylphenol / 1000 barrels (14.3 g / m ³ ) N, N'-disalicylidene-
1,2-propanediamine 1 pound / 1000 barrels (2.9 g / m ³ ) followed by 1 manganese per gallon
/ 32 g (0.008 / liter) of methylcyclopentadienyl manganese tricarbonyl.

Example 8 72.5% saturates, 4.0% olefins and 2
From 3.5% aromatics (wherein benzene is less than 3% by volume, and therefore the fuel contains less than 1% by volume benzene) from a raid vapor pressure of 7.8 psi (53.8 psi)
(kPa) unleaded automotive gasoline. A sufficient amount of methyl t-butyl ether is incorporated so that the oxygen content in the fuel becomes 2.0% by weight. Thereafter, 1/35 g of manganese per gallon (0.035 g) was added to the obtained automobile fuel.
08 / liter) of methylcyclopentadienyl manganese tricarbonyl.

Example 9 Example 8 was repeated, except that (a) the first gasoline blend had a laid vapor pressure of 7.9 psi (54.5 kPa), 75.7% saturated, 4.8% olefin. And 19.5% of the aromatic component (3.5% by volume of the aromatic component is benzene), and (b) a mixture of methyl tert-butyl ether and ethyl tert-butyl ether has an oxygen content in the fuel of It was incorporated into gasoline at a concentration corresponding to 2.5% by weight.

Example 10 Example 8 was repeated except that (a) the first gasoline blend had a laid vapor pressure of 7.7 psi (53.1 kPa), 78.6% saturate, 4.4% olefin. And 17.0% of aromatic components (again, the benzene content of the entire fuel formulation is less than 1% by volume);
(B) Instead of methyl t-butyl ether, t-amyl ether was blended into gasoline at a concentration corresponding to an oxygen content in the fuel of 2.7% by weight.

Example 11 Each of the fuels of Examples 7 to 10 was treated with a conventional concentration of 100 pounds / 1000 barrels (285.3 g / m ³ ) of oronite.
Chemical Company (Oronite Chemical C
o. ) OGA-480, a commercially available polyetheramine precipitation inhibitor.

EXAMPLE 12 Ethyl Petroleum Additives (Ethyl Petro) at the usual concentration of 100 pounds / 1000 barrels (285.3 g / m ³ ) for each fuel of Examples 7-10.
leum Additives, Ltd. A commercially available polyalkenyl succinoimide precipitation inhibitor was added as a HITEC 4450 additive.

EXAMPLE 13 Each fuel of Examples 7 to 10 was treated with a standard concentration of 100 pounds / 1000 barrels (285.3 g / m3) of oronite.
A polyisobutenylamine precipitation inhibitor commercially available as OGA-472 manufactured by Chemical Co., Ltd. was compounded.

As can be seen from the above examples, the fuel of the present invention may and preferably includes additives in addition to cyclopentadienyl manganese tricarbonyl.
Such other additives include antioxidants, sedimentation inhibitors (also referred to as derivative cleaning additives or fuel detergents), and oxygen containing materials such as dialkyl ethers. All of these materials must not increase the vapor pressure of the fuel beyond the raid vapor pressure limit required by the present invention due to their volatility. It included Other additives used, supplemental antiknock agents, such as aromatic amines, antiknock agents, such as N- methyl aniline, the nickel-based antiknock agents such as cyclo-pentadienyl nickel nitrosyl It is. Corrosion inhibitors, metal deactivators, emulsifiers and dyes are other types of additives that can also be used.

Suitable oxygen-containing materials which can and preferably are incorporated in the fuels of the present invention are suitably low volatility ethers such as methyl t-butyl ether, ethyl t-butyl ether, t-amylmethyl Ether, and 2,2-diethyl-1,3-propanediol. The fuel-soluble ester le with a suitable low volatility, such as acetic acid t- butyl Le also useful. Usually such oxygen-containing compounds are used in amounts sufficient to provide up to 3-4% by weight oxygen in the fuel without violating existing or proposed regulations. Other suitable oxygen containing compounds include p-cresol, 2,4-xylene, 3-methoxyphenol, 2-methylfuran, cyclopentanone, isovaleraldehyde, 2,4-pentanedione, and similar oxygen-containing compounds. Includes compounds.

Suitable antioxidants for the fuels of the present invention are sterically hindered phenolic antioxidants, such as 2,2
6-di-t-butylphenol, 2,4-dimethyl-6
-T-butylphenol, 4-methyl-2,6-di-t
A mixture of -butylphenol, 4-ethyl-2,6-di-t-butylphenol, 4-butyl-2,6-di-t-butylphenol, and t-butylphenol consisting mainly of 2,6-di-t-butylphenol. is there. In some cases it has proven advantageous to use aromatic amine antioxidants alone or in combination with phenolic antioxidants. Antioxidant is usually 1000
It is used in amounts up to 25 pounds per barrel (71.3 g / m ³ ), depending on the stability (eg olefin content) of the gasoline in any given case.

Other types of additives preferably used in the fuel of the present invention include ashless detergents such as polyetheramines, polyalkenylamines, alkenylsuccinoimides, polyetheramidoamines, and the like. Such additives can range from 50 to 500 pounds per 1000 barrels (14
2.6-1426.4 g / m ³ ), especially 100-200
Pounds / 1000 barrels (285.3-570.6 g /
m ³ ).

The cyclopentadienyl manganese tricarbonyl compound as well as other auxiliary additives or compounding agents can be mixed with the base fuel in a known manner using conventional mixing equipment. The present invention is meant to include all fuels that meet the primary requirements of the invention.

Driving tests were conducted on 48 vehicle units for a total distance of more than 3,000,000 test miles (4.8 × 10 ⁶ km). Half of the cars in each model group are "clean" (ie, without manganese additives)
Ran on test fuel. The other half was run on the same fuel containing 1/32 g (0.008 g / l) of manganese per gallon as methylcyclopentadienyl manganese tricarbonyl. The test data for the substrate fuel is shown in the table below.

[0036]

TABLE 1 HOWELL EEE test fuel ASTM Certified Fuel Standard Typical Test Method Minimum Highest Specific Gravity, API D1298 59.2 Raid Vapor Pressure, psi D 323 8.7 9.2 9.2 Sulfur, wt% D3120 0.20 0.001 Lead, g / gallon D3237 0.0 0.05 0.001 Phosphorus, g / gallon D3120 0.20 Nil Distillation characteristics, ° F D 86 IBP 75 95 92 10% 120 135 128 50% 200 230 218 95% 300 325 313 Endpoint 415 373 Composition of hydrocarbons D1319 Saturated component, volume% 66.5 olefin, volume 101.8 aromatic, Volume% 35 31.7 Dissolved rubber, mg / 100ml D 381 0.8 Copper extraction corrosion D 130 1 Test octane number D2699 93.0 96.8 Motor octane number D2700 88.5 The mileage of the vehicle unit is 75,000 miles (12
0,701 km), the conversion efficiency of the catalyst, that is, the catalyst for automobiles is composed of hydrocarbon (HC), carbon monoxide (C
The ability to convert O) and nitric oxide (NO _x ) release controlled substances into uncontrolled substances was tested. Compared to the conversion efficiency of the catalyst performed on the "clean" test fuel, the conversion efficiency for the manganese-containing fuel is substantially the same for HC, about 1.1 percentage points better for CO, NO
It was found to be 3.3 percentage points better for _x .

50,000 miles (80,467 km)
After running, the behavior of the oxygen sensor was tested. The oxygen sensor was removed from the car for each model and tested individually. There was virtually no difference in the behavior of the oxygen sensor between the car running on clean fuel and the car running on fuel containing the manganese additive.

75,000 miles (120,701k)
m) At the end of the run, a test was made as to whether a plugging of the catalyst had occurred. This was done by measuring the pressure before the exhaust gas entered the catalyst system. There was no evidence of catalyst clogging on any of the cars.

Although the substrate fuel used in the above test does not describe the requirements for the raid vapor pressure of the present invention, according to the results of the above test, cyclopentadienyl manganese tricarbonyl was specified in the present invention. It is shown that the use at concentrations does not clog the catalyst and does not degrade the behavior of the vehicle's exhaust system. Thus, by reducing the raid vapor pressure to the value specified in the present invention, all of the above advantages are achieved, while at the same time reducing the extent to which light gasoline evaporates into the atmosphere during storage, transport and fuel consumption. .

The main features and aspects of the present invention are as follows. 1. Raid vapor pressure (ASTM test method D-323) of 8.5 psi (58.6 kPa) or less and at least 1/32 per gallon of at least one fuel-soluble cyclopentadienyl manganese tricarbonyl compound.
An unleaded gasoline fuel composition comprising g (0.008 g / l) manganese.

2. Gasoline raid vapor pressure is 8.0ps
The composition according to the above 1, wherein the composition is not more than i (55.2 kPa).

3. 3. The composition of claim 1 or 2, wherein the at least one fuel-soluble cyclopentadienyl manganese tricarbonyl compound is substantially methylcyclopentadienyl manganese tricarbonyl.

4. Substrate gasoline contains 25 aromatic hydrocarbons
4. The composition of claim 1, 2 or 3 wherein the composition comprises less than 1% by volume and the benzene content is less than 1% by volume.

5. Substrate gasoline is at least 50% by volume
5. The composition according to any one of the above items 1 to 4, comprising a saturated hydrocarbon component of the formula (1).

6 A composition according to any of the preceding claims, further comprising up to about 4% by weight of oxygen as at least one oxygen-containing fuel blending component.

7. (1) Raid vapor pressure (ASTM test method D-323) is 8.5 psi (58.6 kPa) or less, (2) maximum sulfur content is 300 ppm, (3) maximum bromine number is 20, and (4) maximum aroma. Group content is 20% by volume, (5) the highest benzene content is 1% by volume, (6) the minimum content of oxygen in the form of at least one monoether or polyether is 1% by weight, methylcyclopentane A lead-free gasoline fuel composition containing up to 1/32 g (0.008 g / l) of manganese dissolved per gallon as dienyl manganese tricarbonyl.

8. In the gasoline production process, the raid vapor pressure (ASTM test method D-323) is 8.5 psi (5 psi).
Substrate unleaded gasoline up to 8.6 kPa) is prepared and up to 1/32 g (0.008 g / l) of manganese per gallon is added to the fuel as at least one cyclopentadienyl manganese tricarbonyl compound soluble in fuel. Improvement method.

9. In the method of producing and distributing gasoline, the raid vapor pressure (ASTM test method D-323) is 8.
5 psi (58.6 kPa) or less of unleaded gasoline, to which at least 1/32 g (0.008 g / l) of manganese per gallon as a fuel-soluble cyclopentadienyl manganese tricarbonyl compound. In addition, make gasoline with higher octane number,
An improved method of storing the high octane gasoline in at least one storage tank of a storage base and then distributing the high octane gasoline for refueling a vehicle.

10. A method for using gasoline in an automobile, wherein the raid vapor pressure (ASTM test method D-323) is 8.5 psi (58.6 kPa) or less, and at least one fuel-soluble cyclopentadienyl manganese tricarbonyl compound is used. Up to 1/32 per gallon
An improved method of using unleaded gasoline containing g (0.008 g / l) manganese in automobiles.

────────────────────────────────────────────────── ─── Continued on front page (72) Inventor William Maynard Hageya 63011 Ellis, Missouri, United States 1517 Virginia Avenue 1517 (72) Inventor Lawrence Joesef Cunningham 63122, Missouri, United States 63122 Kirk Woods Windy Hill 1928 (56) References U.S. Pat. No. 4,139,349 (US, A) WO 87/1384 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C10L 1/30

Claims (6)

(57) [Claims] 1. Raid vapor pressure (ASTM test method D-32)
3) is 8.5 psi (58.6 kPa) or less and is at least one cyclopentadienyl manganese tricarbonyl compound soluble in fuel at a maximum of 1 per gallon.
/ 32 g ( 0.008 g / l) of manganese (excluding iron-based antiknock agents and aliphatic alcohols)
) , The content of aromatic components is up to 30% by volume,
An unleaded gasoline fuel composition having a benzene content of at most 1% by volume. 2. Raid vapor pressure (ASTM test method D)
-323) is 8.5 psi (58.6 kPa) or less, (2) the maximum sulfur content is 300 ppm, (3) the maximum bromine number is 20, and (4) the maximum aromatic component content is 20% by volume.
(5) a maximum benzene content of 1% by volume, (6) a minimum content of oxygen in the form of at least one monoether or polyether of 1% by weight, and 1 gallon of methylcyclopentadienyl manganese tricarbonyl It contains up to 1/32 g (0.008 g / l) of manganese dissolved per iron (provided that iron-based antiknock agent and
And free of aliphatic alcohols) . 3. The method for producing gasoline, wherein the raid vapor pressure (ASTM test method D-323) is 8.5 psi (5 psi).
Substrate unleaded gasoline ( 8.6 kPa) or less (however,
Phosphorus contains iron-based antiknock agents and fatty alcohols.
And at least 1/32 g (0.008 g / gal) per gallon thereof as at least one fuel-soluble cyclopentadienyl manganese tricarbonyl compound.
Liter) of manganese. 4. A method for producing and distributing gasoline, wherein the raid vapor pressure (ASTM test method D-323) is 8.
5 psi (58.6 kPa) or less of unleaded gasoline, to which at least 1/32 g (0.008 g / l) of manganese per gallon as a fuel-soluble cyclopentadienyl manganese tricarbonyl compound. In addition, gasoline with an increased octane number (however,
Gasoline is an iron anti-knock agent and aliphatic alcohol
) , And storing the high octane gasoline in at least one storage tank of a storage base, and then distributing the high octane gasoline for refueling the vehicle. 5. A method for using gasoline in an automobile, wherein the raid vapor pressure (ASTM test method D-323) is 8.8.
5 psi (58.6 kPa) or less and up to 1/32 g per gallon as at least one fuel-soluble cyclopentadienyl manganese tricarbonyl compound
Contains manganese (0.008 g / l)
(However, iron-based antiknock agents and fatty alcohols
(Not included) An improved method characterized by using unleaded gasoline in an automobile. 6. A lead-free gasoline fuel composition comprising a variety of hydrocarbons in the gasoline boiling range, comprising up to 30% by volume of aromatic components and up to 1% by volume of benzene.
Up to 1/32 g per gallon as at least one cyclopentadienyl manganese tricarbonyl compound
Contains manganese (0.008 g / l)
(However, iron-based antiknock agents and fatty alcohols
NOx from the combustion of the gasoline fuel in internal combustion engines that the contained no) fuel comprising be burned in the engine
Ways to reduce emissions.