JP2003193070A - Fuel oil composition and fuel additive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a cleaner for an additive for a fuel oil, reducing the occurrence of intake valve sticking when starting an automobile at a low temperature when added to the fuel oil for the automobile. <P>SOLUTION: The additive for the fuel oil comprises an aliphatic amine having an alkylene oxide added thereto in an amount of 3-20 mol per mol of the aliphatic amine [ether group-containing hydroxyalkyl- (or alkenyl-)amine]. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an additive to be added to fuel oil for automobiles. In particular, the present invention is a fuel oil additive effective in reducing intake valve sticking that tends to occur when a vehicle running by burning hydrocarbon fuel oil such as gasoline or diesel fuel oil in an internal combustion engine is started at low temperature. Regarding

[0002]

2. Description of the Related Art Japanese Patent Publication No. 3-20437 (corresponding to US Pat. No. 4,409,000) discloses an engine cleaner or carburetor comprising a hydroxyalkyl (or alkenyl) amine and a carboxylic acid dispersant. Compositions that are effective as detergents are described.

EP0869163A1 describes that it is effective to add N, N-bis (hydroxyalkyl) alkylamine to gasoline in order to reduce friction during operation of an internal combustion engine.

[0004]

According to the research conducted by the present inventor, when a hydroxylamine such as N, N-bis (hydroxyalkyl) alkylamine is added to a hydrocarbon fuel oil such as gasoline, the fuel is obtained. It has been found that intake valve sticking tends to occur when a vehicle using oil is started at a low temperature. That is, in order to prevent soot and the like generated in the engine chamber of an internal combustion engine from accumulating on the intake valve, intake port, injector, throttle, etc., a cleaning agent has been conventionally added to fuel. Detergents such as hydroxylamines such as (hydroxyalkyl) alkylamine cause viscosity increase on the sliding surface of the stem portion of the intake valve when the internal combustion engine is started at low temperature.
Inventor's research revealed that intake valve sticking occurs.

Therefore, it is a main object of the present invention to provide a fuel oil additive which reduces the occurrence of intake valve sticking when the vehicle is started at a low temperature even when added to the fuel oil of the vehicle. .

The present invention also provides a fuel oil composition which causes less intake valve sticking when a vehicle running by burning a fuel oil such as a hydrocarbon oil in an internal combustion engine is started at a low temperature. , And its purpose.

[0007]

SUMMARY OF THE INVENTION The present invention is directed to an automotive amine containing an aliphatic amine having an alkylene oxide added in an amount ranging from 3 to 20 moles per mole of the fuel.
The fuel oil composition is added in an amount within the range of 0 to 10000 ppm weight / weight ratio. The present invention also resides in a fuel oil additive consisting of an aliphatic amine with an amount of alkylene oxide added in the range of 3 to 20 moles per mole of aliphatic amine.

The present invention also provides an automobile equipped with a gasoline engine with an aliphatic amine obtained by adding alkylene oxide to gasoline in an amount in the range of 3 to 20 mol per mol [in the following description, an ether group-containing hydroxyalkyl group]. (Or alkenyl) amine, also referred to as]
There is also a running method of a gasoline engine vehicle, which comprises running the gasoline composition added in an amount within a range of 10000 ppm weight / weight ratio. The present invention is further characterized by adding to the gasoline an alkylene oxide-added aliphatic amine in an amount in the range of 3 to 20 mol per mol in an amount of 10 to 10,000 ppm weight / weight ratio. There is also a method of reducing the occurrence of intake valve sticking during cold start of a gasoline vehicle.

[0009]

Preferred embodiments of the present invention are as follows. (1) The alkylene oxide added to the aliphatic amine is ethylene oxide, propylene oxide, butylene oxide, or a mixture of two or three of these. (2) The alkylene oxide added to the aliphatic amine is a mixture of two or three kinds of ethylene oxide, propylene oxide and butylene oxide. (3) The molar amount of alkylene oxide added to the aliphatic amine is in the range of 3 to 14 mols based on the aliphatic amine.

(4) The aliphatic amine is an alkylamine or alkyleneamine containing 4 to 50 carbon atoms. (5) The aliphatic amine is an alkylamine or alkyleneamine containing 10 to 30 carbon atoms. (6) The amount of the aliphatic amine added to the automobile fuel is in the range of 10 to 5000 ppm weight / weight ratio. (7) Automotive fuel is gasoline.

The ether alkyl group-containing hydroxyalkyl (or alkenyl) amine-based detergent for the addition of fuel oil used in the present invention comprises an aliphatic amine added with an alkylene oxide in an amount of 3 to 20 mol per mol as an active ingredient. It is what Typical examples of the alkylene oxide-added aliphatic amine of the present invention include compounds represented by the following chemical formulas.

[0012]

[Chemical 1]

[In the above chemical formula, R ¹ represents an alkyl group or an alkenyl group having 4 to 50 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ are each independently,
It represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a, b, c and d each independently represent an integer of 0 to 20. However, a + b + c + d is an integer of 3 to 20 (preferably 3 to 14). ]

The ether-containing hydroxyalkyl (or alkenyl) amine detergent of the present invention is usually
Since it may be used as a mixture of the compounds represented by the above chemical formulas, the average value of each of a, b, c and d in the ether group-containing hydroxyalkyl (or alkenyl) amine detergent of the present invention is an integer. In some cases it may not.

In the above chemical formula, [(CH ₂ --CHR ² )
_{O], [(CH 2 -CHR} 3) O], [(CH 2 -CH
The alkylene oxide represented by R ⁴ ) O] and [(CH ₂ —CHR ⁵ ) O] is preferably ethylene oxide, propylene oxide, or butylene oxide, and a hydroxyalkyl (or alkenyl) amine has two diamines in one molecule. The above alkylene oxides may be mixed. An ether group-containing hydroxyalkyl (or alkenyl) amine in which two or more alkylene oxides are mixed and added is also preferable.

For example, it is preferable that ethylene oxide and propylene oxide are mixed in one molecule of an ether group-containing hydroxyalkyl (or alkenyl) amine, or that propylene oxide and butylene oxide are mixed.

When ethylene oxide and propylene oxide are mixed in one molecule of an ether group-containing hydroxyalkyl (or alkenyl) amine, the molar ratio of propylene oxide (the molar ratio to the total amount of ethylene oxide and propylene oxide) is It is preferably 20 mol% or more, and more preferably 50 mol% or more.

When propylene oxide and butylene oxide are mixed in one molecule of an ether group-containing hydroxyalkyl (or alkenyl) amine, the molar ratio of propylene oxide (the molar ratio to the total amount of propylene oxide and butylene oxide). Is preferably 20 mol% or more, more preferably 50 mol% or more, and particularly preferably in the range of 55 to 80 mol%.

The ether group-containing hydroxyalkyl (or alkenyl) amine (detergent) of the present invention has an aliphatic amine addition amount of 10 to 10000 p to fuel oil.
It is used in the range of pm weight / weight ratio, but in particular, 10
It is preferably used in the range of ˜5000 ppm weight / weight ratio. The effect of the detergent of the present invention is remarkable especially when it is added to gasoline, but other fuel oils, for example, other hydrocarbon fuel oils such as diesel fuel oils, or alcohol-based or ether-based fuels. It can also be added to oil.

When the ether alkyl group-containing hydroxyalkyl (or alkenyl) amine of the present invention is added to fuel oil, it is dissolved in a carrier oil (or diluent oil) capable of dissolving or dispersing the amine to obtain a solution state. After that, it is preferable to add it to the fuel oil. As carrier oil, polypropylene glycol monobutyl ether, poly-α-olefin, polybutene,
Mineral oil, polyoxypropylene alcohol, polyoxybutylene alcohol, etc. can be mentioned.

The ether-containing hydroxyalkyl (or alkenyl) amine of the present invention may be added to the fuel oil alone, but is preferably used in combination with a known detergent for adding fuel oil. Examples of such known detergents for adding fuel oil include polybutene amine, polyether amine, succinimide, and alkylphenol amine.

When using the ether group-containing hydroxyalkyl (or alkenyl) amine of the present invention, a rust inhibitor, an antioxidant, a metal deactivator, a corrosion inhibitor, an antiemulsifier, an antistatic agent, and a haze. You may use an inhibitor etc. together.

[0023]

Examples [Example 1] -Evaluation test for occurrence of intake valve sticking (1) Evaluation method The additive composition to be evaluated placed in a beaker was heated to 160 ° C.
Then, air was continuously blown for 2 hours to evaporate the volatile components of the additive composition, leaving only the solid components as a residue. This solid residue was uniformly applied to the sliding surface of the intake valve, and then mounted on the stem guide. After cooling this at -20 degreeC for 12 hours, the valve sliding load in this sliding surface was measured using the digital force gauge DPRSX-20T (made by Imada Co., Ltd.).

(2) Additive composition Additive No. 1: polybutenamine (13.27 parts: parts by weight, the same applies hereinafter) + polypropylene glycol monobutyl ether (15.93 parts) Additive No. 2: polybutenamine (13. 27 parts) + polypropylene glycol monobutyl ether (15.9)
3 parts) + soybean amine 2EO (addition product obtained by adding 2 mol of ethylene oxide to 1 mol of an amine having an aliphatic alkyl group having 12 carbon atoms (hereinafter the same), 70.8 parts) Additive No. 3: polybutene amine (13.27 parts) + polypropylene glycol monobutyl ether (15.9)
3 parts) + soybean amine 2PO (propylene oxide 2 mol adduct, 70.8 parts) Additive No. 4: polybutene amine (13.27 parts) + polypropylene glycol monobutyl ether (15.9)
3 parts) + soybean amine 4EO (ethylene oxide 4 mol adduct, 70.8 parts) Additive No. 5: polybutene amine (13.27 parts) + polypropylene glycol monobutyl ether (15.9)
3 parts) + soybean amine 4PO (propylene oxide 4 mol adduct, 70.8 parts) Additive No. 6: polybutene amine (13.27 parts) + polypropylene glycol monobutyl ether (15.9)
3 parts) + soybean amine 6EO (ethylene oxide 6 mol adduct, 70.8 parts) Additive No. 7: polybutene amine (13.27 parts) + polypropylene glycol monobutyl ether (15.9)
3 parts) + soybean amine 6PO (propylene oxide 6 mol adduct, 70.8 parts) Additive No. 8: polybutene amine (13.27 parts) + polypropylene glycol monobutyl ether (15.9)
3 parts) + soybean amine 12EO (ethylene oxide 12 mol adduct, 70.8 parts) Additive No. 9: polybutene amine (13.27 parts) + polypropylene glycol monobutyl ether (15.9)
3 parts) + soybean amine 12PO (propylene oxide 12
Molar adduct, 70.8 parts) Additive No. 10: polybutenamine (13.27 parts) +
Polypropylene glycol monobutyl ether (15.
93 parts) + soy amine 2EO.10PO (addition product of ethylene oxide 2 mol and propylene oxide 10 mol,
70.8 parts) Additive No. 11: polybutenamine (13.27 parts) +
Polypropylene glycol monobutyl ether (15.
93 parts) + soybean amine 4EO.8PO (addition product of ethylene oxide 4 mol and propylene oxide 8 mol, 7
0.8 part) Additive No. 12: soybean amine 2EO (ethylene oxide 2 mol adduct) only Additive No. 13: soybean amine 2PO (propylene oxide 2 mol adduct) Additive No. 14: soyamine 6EO (ethylene oxide 6 mol) Additive only) Additive No. 15: Soy amine 6PO (6 mol propylene oxide adduct) Only additive No. 16: Soy amine 12EO (ethylene oxide 12 mol adduct) Only additive No. 17: Soy amine 12PO (propylene oxide 12 mol) Additive only) Additive No. 18: Soy amine 2EO.10PO (addition product of 2 mol ethylene oxide and 10 mol propylene oxide) Only additive No. 19: Soy amine 4EO.8PO (4 mol ethylene oxide and 8 mol propylene oxide) Only)

(3) Measurement Results (Measured Valve Sliding Load Value) The measurement results were measured using an additive composition system (additive Nos. 1 to 10) using polybutene amine and polypropylene glycol monobutyl ether, and soybean amine. The alkylene oxide adduct alone (additive numbers 11 to 17) are separately described in Table 1 and Table 2, respectively.

[0026]

[Table 1]                                 Table 1 ──────────────────────────────────── Additive No. Alkylene oxide adduct Valve sliding load (Kgf) ────────────────────────────────────     1 None 4.0     2 2EO 15.0     3 2PO 12.6     4 4 EO 0.5     5 4PO 0.5     6 6 EO 0.5     7 6PO 0.5     8 12 EO 0.5     9 12PO 0.5   10 2 EO ・ 10 PO 0.7   11 4EO / 8PO 0.2 ────────────────────────────────────

[0027]

[Table 2]                                 Table 2 ──────────────────────────────────── Additive No. Alkylene oxide adduct Valve sliding load (Kgf) ────────────────────────────────────   12 2EO 2.6   13 2PO 1.2   14 6EO 0.4   15 6PO 0.4   16 12 EO 0.8   17 12PO 0.3   18 2EO / 10PO 0.3   19 4EO / 8PO 0.2 ────────────────────────────────────

From the results shown in Tables 1 and 2, the aliphatic amine added with alkylene oxide in an amount in the range of 3 to 20 mol per mol according to the present invention reduces the sliding load of the intake valve sticking. It turns out to be effective.

[0029] [Example 2] -Evaluation test for occurrence of intake valve deposit (1) Test engine   Toyota 3S-FE engine:                        Displacement: 2000cc                        Number of cylinders: 4 cylinders                        Valve: 16                        Fuel supply system: PFI (2) Test conditions

[0030]

[Table 3]                                 Table 3 ────────────────────────────────────                                        Stage 1 stage 2 ────────────────────────────────────        Engine speed (rpm) 2000 3000        Inhalation negative pressure (-mmHg) 425 340        Oil temperature (℃) 105 105        Water temperature (℃) 90 95 ────────────────────────────────────        Test time 100 hours in total ────────────────────────────────────

(3) Test cycle The engine is accelerated from 2000 rpm to 3000 rpm in 40 seconds and maintained at 3000 rpm for 20 seconds. afterwards,
The speed is reduced to 2000 rpm in 2 minutes and maintained for 1 minute under these conditions. This cycle is carried out for a total of 100 hours.

(4) Evaluation sample (gasoline composition) A: Commercial regular gasoline B: Additive No. 17 (soy amine EO 2 mol adduct) Soy amine PO 12 mol adduct 100 ppm (weight / weight) in commercial regular gasoline Addition. C: Additive No. 19 (4 moles of soybean amine EO / 8 moles of PO) Soybean amine EO 4 moles / P in commercially available regular gasoline
Add 100 ppm of O8 mole adduct (weight / weight).

(5) Evaluation Results When the intake valve deposit (IVD) after the test using each of the gasoline composition A and the gasoline composition B was measured, the following results were obtained.

[0034]

[Table 4]                                 Table 4 ────────────────────────────────────                Test gasoline IVD ────────────────────────────────────        Regular gasoline (A) 244.1mg        Gasoline composition (B) 151.5 mg        Gasoline composition (C) 130.7 mg ────────────────────────────────────

[0035]

When a conventional hydroxyalkyl (or alkenyl) amine type engine detergent such as N, N-bis (hydroxyalkyl) alkylamine or an engine friction reducing agent is added to the fuel oil, the fuel can be used. An automobile equipped with an internal combustion engine using oil is apt to cause intake valve sticking at the time of starting at a low temperature, but when the ether group-containing hydroxyalkyl (or alkenyl) amine-based engine detergent of the present invention is used, The occurrence of intake valve sticking during startup at such low temperatures is greatly reduced. Further, the ether group-containing hydroxyalkyl (or alkenyl) amine of the present invention reduces intake valve sticking in a gasoline engine using gasoline as fuel oil.

Claims (18)

[Claims] 1. An aliphatic amine prepared by adding alkylene oxide to an automobile fuel in an amount in the range of 3 to 20 mol per mol in an amount in the range of 10 to 10000 ppm weight / weight ratio with respect to the fuel. A fuel oil composition added. 2. The fuel oil composition according to claim 1, wherein the alkylene oxide is ethylene oxide, propylene oxide, butylene oxide, or a mixture of two or three of these. 3. The fuel oil composition according to claim 2, wherein the alkylene oxide is a mixture of two or three kinds of ethylene oxide, propylene oxide and butylene oxide. 4. The fuel oil composition according to claim 1, wherein the addition mole amount of the alkylene oxide to the aliphatic amine is in the range of 3 to 14 moles relative to the aliphatic amine. . 5. The fuel oil composition according to any one of claims 1 to 4, wherein the aliphatic amine is an alkylamine containing 4 to 50 carbon atoms or an alkyleneamine. 6. The fuel oil composition according to claim 5, wherein the aliphatic amine is an alkylamine or alkyleneamine containing 10 to 30 carbon atoms. 7. The fuel oil composition according to claim 1, wherein the amount of the aliphatic amine added to the vehicle fuel is in the range of 10 to 5000 ppm weight / weight ratio. 8. The fuel oil composition according to claim 1, wherein the vehicle fuel is gasoline. 9. A fuel oil additive comprising an aliphatic amine with an amount of alkylene oxide added in the range of 3 to 20 moles per mole of aliphatic amine. 10. The fuel oil additive according to claim 9, wherein the alkylene oxide is ethylene oxide, propylene oxide, butylene oxide, or a mixture of two or three of these alkylene oxides. 11. The fuel oil additive according to claim 10, wherein the alkylene oxide is a mixture of two or three kinds of ethylene oxide, propylene oxide, and butylene oxide. 12. The molar amount of alkylene oxide added to the aliphatic amine is 3 to 14 with respect to the aliphatic amine.
The fuel oil additive according to any one of claims 9 to 11 in the molar range. 13. The fuel oil additive according to any one of claims 9 to 12, wherein the aliphatic amine is an alkylamine containing 4 to 50 carbon atoms or an alkyleneamine. 14. The fuel oil additive according to claim 13, wherein the aliphatic amine is an alkylamine or alkyleneamine containing 10 to 30 carbon atoms. 15. An automobile equipped with a gasoline engine is provided with 10 to 10 aliphatic amines obtained by adding alkylene oxide in an amount of 3 to 20 mol per mol to gasoline.
A method for running a gasoline engine vehicle, which comprises running a gasoline composition added in an amount within a range of 10000 ppm weight / weight ratio. 16. The gasoline engine vehicle according to claim 15, wherein the alkylene oxide added to the aliphatic amine is ethylene oxide, propylene oxide, butylene oxide, or a mixture of two or three of these alkylene oxides. Driving method. 17. A gasoline is added with an aliphatic amine to which alkylene oxide is added in an amount of 3 to 20 mol per mol in an amount of 10 to 10,000 ppm weight / weight ratio. A method for reducing the occurrence of intake valve sticking during cold start of a gasoline vehicle. 18. Intake valve sticking generation according to claim 17, wherein the alkylene oxide added to the aliphatic amine is ethylene oxide, propylene oxide, butylene oxide, or a mixture of two or three of these alkylene oxides. Reduction method.