JPH0770570A - Fuel additive and fuel oil composition - Google Patents

Abstract

PURPOSE:To reduce the amt. of air pollutant emitted from an internal combustion engine and improve the cetane number of a fuel oil by adding, to the oil, a compd. which is an org. peroxide and simultaneously a perbasic compd. of a metal salt of an org. acid. CONSTITUTION:A compd. which is an org. peroxide and simultaneously a perbasic compd. of a metal salt of an org. acid is prepd. A perbasic compd. is such a salt compd. that the amt. of the salt-constituting metal contained is higher than equivalent to that of the salt-constituting acid contained. Such a compd. is obtd. e.g. by putting an org. acid (an unsatd. carboxylic acid is esp. pref.), a diluent (e.g. n-hexane), a metal hydroxide (a Ca salt is esp. pref.), and if necessary a perbasic accelerator (e.g. an alcohol) into a reactor, raising the temp. of the reaction system, converting it into a carbonate to thereby convert the resulting perbasic compd. into a colloidal dispersion, and blowing oxygen into the dispersion. The molar ratio of the metal to the acid is 2-40. Thus obtd. peroxide is added to a fuel oil (e.g. light oil) in a metal concn. of 20-5,000ppm, reducing the emission of soot, etc., and improving the cetane number.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an additive for improving combustion by adding it to fuel oil, and more specifically, a fuel additive for suppressing emission of air pollutants and improving cetane number, and a fuel additive for the same. The present invention relates to a fuel oil composition added to oil.

[0002]

2. Description of the Related Art In recent years, air pollution has become more serious with the rapid development of industry, and urgent measures are required.
The main air pollutants are particulate matter mainly containing soot called PM and nitrogen oxides, but these are in a trade-off relationship, and it is extremely difficult to reduce both at the same time.

In order to solve this problem, automobile manufacturers and the like are advancing the improvement of the engine and the development of the trap that collects PM, but the effect has not yet been sufficiently achieved, and the problem of deterioration of fuel and the like has been encountered. Is also occurring.

On the other hand, attempts have been made to reduce the emission of air pollutants by using fuel additives.
For example, JP-B-61-37314, JP-A-2-142894, JP-A-4-213391 and the like are methods using a metal salt of an overbased organic acid, and JP-A-61-188493. JP-A-63-77995 and JP-A-63-77995 disclose methods using hydroperoxide.

[0005]

However, all of these additives are not sufficiently effective, and it is difficult to meet the emission control value which will be further strengthened in the future. Development is desired.

Therefore, the present invention is intended to solve the above-mentioned problems of the prior art, and an object thereof is to provide a fuel additive which works effectively even in a small amount and a fuel oil composition to which the additive is added.

[0007]

Under such circumstances, the inventors of the present invention have conducted extensive studies and as a result, have developed a fuel additive capable of suppressing the emission of air pollutants with a small amount and improving the cetane number. I arrived.

That is, the present invention is an organic peroxide,
The present invention also relates to a fuel additive containing a compound which is an overbased compound of a metal salt of an organic acid.

In the present invention, the organic peroxide means H--O.
A compound in which one or both of hydrogen of -OH is substituted by an alkyl group, an alkenyl group, an alkoxyl group, an aryl group, a carboalkoxyl group, etc., and a peroxide value of 10 m.
It is preferably eq / kg or more. Here, the peroxide value refers to that represented by the number of milliequivalents of iodine liberated when potassium iodide is added to 1 kg of a sample.

Examples of the organic acid used in the present invention include carboxylic acids (aliphatic carboxylic acids such as palmitic acid and linoleic acid, aromatic carboxylic acids such as benzoic acid and salicylic acid), sulfonic acids (alkylbenzenesulfonic acid, Alkylnaphthalenesulfonic acid, petroleum sulfonic acid, etc.), phenolic acid and the like can be mentioned, but among them, those having an unsaturated bond, particularly unsaturated carboxylic acid are preferable.

In the present invention, the overbased compound of a metal salt is
The metal that constitutes the metal salt is one that is contained in an equivalent amount or more with respect to the organic acid that constitutes the metal salt, and the portion where the metal and the organic acid react in an equivalent amount is the neutralizing portion, the remaining The part is called an overbased part.

The metals used in the present invention include Ca and B.
Although a, Fe, Mn, Mg, K, Li, Na and the like are mentioned as preferable ones, Ca is particularly preferable in view of toxicity and the like.
The equivalent ratio of metal to organic acid in the fuel additive of the present invention is preferably 2-40. If it is less than 2, the effect of overbasing is not sufficient, and if it exceeds 40, it is not economical. Further, it is preferable that the fuel additive of the present invention contains metal in an amount of 3% by weight or more. If it is less than 3% by weight, many fuel additives must be added in order to exert the effect of the metal, which is not economical.

The fuel additive of the present invention must be present in the fuel oil as a stable, colloidal, oil-soluble dispersion for which the overbased portion uses carbon dioxide to form a metal carbonate. It is preferably shaped.

In the present invention, alcohols, diol compounds, or monoalkyl ethers of diols can be used as an overbasing accelerator, if necessary. Examples of alcohols include methanol and ethanol, and examples of diol compounds include ethylene glycol, propylene glycol, 1,3-butanediol, 1,
4-Butanediol and the like, and examples of its monoalkyl ether derivative include ethoxyethanol, propoxyethanol, butoxyethanol and the like. Further, diethylene glycol and its monoalkyl ether derivative can also be used. Examples of the monoalkyl ether derivative of diethylene glycol include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropoxy ether and the like. The amount of these overbasing accelerators used is not particularly limited, but is preferably 0.5 to 2 times by weight the fuel additive.

Further, in the present invention, a solvent can be used as a diluent if necessary. As the solvent, n-
Examples thereof include saturated aliphatic hydrocarbons such as hexane and n-dodecane, aromatic hydrocarbons such as xylene and toluene, and fuel oil such as light oil. The amount of these diluents used is not particularly limited as long as it does not hinder the fuel, but is preferably 0.1 to 10 times by weight the fuel additive.

The fuel additive of the present invention can be manufactured, for example, as follows. A four-diameter flask equipped with a thermometer, a stirrer and a dehydration tube is used to prepare a predetermined amount of organic acid, diluent,
A metal hydroxide and an overbasing accelerator are charged, and after heating, carbon dioxide is blown to carry out carbonation to obtain an overbased compound as a stable colloidal dispersion. Then, the fuel additive of the present invention is an organic peroxide and an overbased compound of a metal salt of an organic acid by performing distillation and filtration as needed and blowing oxygen into the resulting solution to oxidize the solution. Is obtained. Of course, the fuel additive of the present invention can also be produced by forming the organic peroxide by various methods or by using the organic peroxide as a raw material and overbasing the organic peroxide.

The fuel additive of the present invention can be used for various fuel oils, for example, petroleum fractions, alcohols, LNG, vegetable oils, etc., which can be used as fuels for internal combustion engines. By adding a small amount, the fuel oil composition of the present invention can be obtained. The addition of the fuel additive of the present invention suppresses the emission of air pollutants. For example, when added to light oil, it suppresses the emission of air pollutants such as soot and improves the cetane number.

The amount of the fuel additive used in the present invention is preferably 20 ppm or more and 5000 ppm or less in terms of metal concentration (weight) with respect to the fuel oil. If it is less than 20 ppm, the effect of addition is not sufficient,
If it exceeds 5000 ppm, the effect is not improved for the added amount, which is not economical.

In the fuel oil composition of the present invention, in addition to the fuel additive of the present invention, if necessary, other fuel additives,
For example, a detergent, an antioxidant and the like can be added.

[0020]

The action mechanism of the fuel additive of the present invention is not clear, but the soot reburning promotion effect and the soot suppression effect by the metal,
It is believed that the synergistic effect of the reaction acceleration effect of peroxide and the catalytic effect of carbon dioxide gas exerts a great effect on the suppression of the emission of air pollutants and the improvement of the cetane number.

[0021]

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

Example 1 A 5-liter diameter flask equipped with a thermometer, a stirrer and a dehydration tube was charged with 518 g of calcium hydroxide and 840 g of linoleic acid.
150 g of neutral oil and 500 g of Oxocol 900 (manufactured by Kyowa Fermentation Co., Ltd.) were charged, the temperature was raised to 140 ° C., and 409 g of ethylene glycol was added dropwise over 1 hour. Then
After reacting at 150 ° C. for 1 hour, 90 liters of carbon dioxide were blown in to obtain an overbased compound of a calcium salt of an organic acid. Thereafter, the temperature was gradually raised while raising the temperature to 190 ° C., and oxochol and ethylene glycol were distilled off. Peroxidation was carried out by bubbling air through the dark brown liquid remaining in the flask, and finally the solid matter was removed by filtration to obtain the fuel additive of the present invention. By adding 5 ml of this fuel additive to 5 liters of No. 2 light oil, a fuel oil composition of the present invention (Invention product 1) having a Ca content of 137 ppm (weight) was obtained.

Example 2 A fuel additive of the present invention was obtained in the same manner as in Example 1 except that 1197 g of barium hydroxide was used instead of calcium hydroxide and 1000 g of 150 neutral oil was used. By adding 5 ml of this fuel additive to 5 liters of No. 2 light oil, a fuel oil composition of the present invention (Invention product 2) having a Ba content of 299 ppm (weight) was obtained.

Example 3 Oleic acid 504 was used instead of linoleic acid in Example 1.
g and methyl alkylsalicylate 246 g (1 mol) were used in the same manner as above to obtain a fuel additive of the present invention. By adding 5 ml of this fuel additive to 5 liters of No. 2 gas oil, a fuel oil composition of the present invention (Invention product 3) having a Ca content of 144 ppm (weight) was obtained.

Example 4 A fuel additive of the present invention was obtained in exactly the same manner as in Example 1, except that 744 g of palm methyl ester was used instead of linoleic acid. 2 ml of this fuel additive
By adding 5 liters of No. diesel oil, the Ca content is 145
A ppm (weight) of the fuel oil composition of the present invention (Invention product 4) was obtained.

Test Example 1 The products 1 to 4 of the present invention obtained in Examples 1 to 4 and a sample before comparison in Example 1 for comparison were partially sampled and added to No. 2 gas oil. The soot concentration and cetane number of the fuel oil composition (Comparative Product 1) adjusted to the above concentration were measured using an Isuzu 4BE1 engine. The results are shown in Table 1. The soot concentration was measured using a smoke meter (manufactured by Banzai Co., Ltd.), and the cetane number was measured using ASTM.
The method of D613 was performed.

[0027]

[Table 1]

[0028]

By using the fuel additive of the present invention, the soot emission of fuel oil can be remarkably reduced and the cetane number can be improved with a small amount.

Claims (4)

[Claims] 1. A fuel additive containing a compound which is an organic peroxide and is an overbased compound of a metal salt of an organic acid. 2. The fuel additive according to claim 1, wherein the overbased portion of the overbased compound is a carbonate. 3. The fuel additive according to claim 1, wherein the equivalent ratio of metal to organic acid is 2 to 40. 4. A fuel oil composition obtained by adding the fuel additive according to any one of claims 1 to 3 to fuel oil.