JP2851908B2 - Fuel oil composition - Google Patents

Abstract

Sediment and colour formation are reduced in a diesel or heating fuel by incorporating in the fuel a quaternary ammonium salt, the cation of which is the reaction product of a tertiary amine, an olefin oxide and water.

Description

The present invention relates to fuel oil compositions, and more particularly to fuel oil compositions containing cracking components that are stabilized against sediment formation and color formation during storage. Cracking components are often included to provide high yields of diesel fuel and heating oil.

However, when diesel and heating oils containing cracking components are stored in air at room temperature or elevated temperatures, they discolor and precipitate sludge or sediment.

It is clear that the problem of discoloration and sediment formation is exacerbated by the presence of cracking components in the fuel. This is shown by the results in Table 1 which show the amount of reserve formed and the color change when various fuel formulations were tested in the AMS 77.061 accelerated stability test. Published studies [eg Offenhauer et al., Industrial and Engineering Chemistry
Engineering Chemistry, 1957, 47, 1265, and Proceedings of the 2nd International Conference on long-term stability of liquid fuels
on the Long Ferm Stablity of Liquid Fuels, San Antonio, Texas, October 1986, see), suggest that discoloration and sedimentation result from oxidation of sulfur and nitrogen compounds present in the fuel. Analysis of the degradation components is consistent with this. The results in Table 2 show that the cracked components contain much more nitrogen and sulfur than the straight distillate. Also, the addition of nitrogen and sulfur compounds to a stable straight distillate resulted in an increase in both sediment and color in the AMS 77.061 test (Table 3), when both nitrogen and sulfur compounds were present in the fuel. The worst results are obtained.

It has been found that sediment and color formation can be substantially reduced in diesel or heated fuels, especially those containing cracking components, by the addition of certain quaternary ammonium compounds. According to the present invention, a fuel composition is prepared in the presence of a base fuel, which can include a cracking component, and an excess of water, the cation of which forms a solution of a quaternary ammonium hydroxide with a tertiary amine and an olefin oxide. The anion comprises a quaternary ammonium salt derived from an organic acid provided that the alkane is a linear alkane when the acid is an alkane monocarboxylic acid.

A quaternary ammonium salt can be prepared in two steps: in a first step a tertiary amine is reacted with an olefin oxide in the presence of excess water to form a solution of a quaternary ammonium hydroxide, for example , Wherein each R ′ can be the same or different and is an organic group, and each R ″ can be the same or different and is hydrogen or an organic group.

In a second step, the quaternary ammonium hydroxide is neutralized with an organic acid to form a quaternary ammonium salt, Examples of suitable tertiary amines include the following: (i) Formula: R ¹ R ² R ³ N, wherein R ¹ , R ² and R ³ can be the same or different. , Each substituted or unsubstituted alkyl,
Amines which are cycloalkyl, alkenyl, cycloalkenyl or aryl). Each group R ^1, R ² and R ³ preferably has 1 to 20 carbon atoms. Examples of amines of this type are trimethylamine; ethyldimethylamine; n-propyldimethylamine; triethanolamine; N, N-dimethylbenzylamine; N, N-dimethylcyclohexylamine; N, N-dimethylaniline; Dimethyl- (4-methylcyclohexylamine) and N, N-dimethyl-p-
Toluidine.

(Ii) Formula: R ⁴ R ⁵ N (CH ₂ ) _n NR ⁶ R ⁷ (where n is an integer of 1 or more, and R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different it can, diamines in which) as shown previously for R ^1. Therefore, N, N, N ', N'-tetramethylethylenediamine can be used.

(Iii) Formula: (Wherein m is an integer of 1 or more, and R ⁸ , R ⁹ ,
R ¹⁰ , R ¹¹ and R ¹² can be the same or different;
^{As described for 1} ) fully alkylated alkylene polyamines.

(Iv) Pyridine and substituted pyridines such as α, β and γ-picoline, quinoline and substituted quinolines and similar heterocyclic tertiary amines.

Equation (v): (Wherein R ¹³ is as indicated for R ¹ ).

(Vi) Formula: Wherein R ¹⁴ is as indicated for R ¹ .

(Vii) Formula: (Wherein R ¹⁵ is as indicated for R ¹ ).

(Viii) Formula: Wherein n is an integer of 2 or more, such as triethylenediamine.

(Ix) hexamethylenetetramine (CH _{2) 6} N ₄ (hexamine).

The olefin oxide preferably has the formula: Wherein R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ can be the same or different and are each hydrogen or substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl. Particular examples are ethylene oxide, propylene oxide, but-1-eneoxide, but-2-eneoxide, octo-1-eneoxide and styrene oxide.

The organic acid that can be used in the second stage of the reaction and thus forms the anion in the quaternary ammonium salt can be, for example, a carboxylic acid, carboxylic anhydride, phenol, sulfurized phenol, or sulfonic acid; In the context of the present invention, which is a composition, unless limited in terms of type, provided that the alkane is a straight-chain alkane when the acid is an alkane monocarboxylic acid, preferably the acid is an alkane 1-carboxylic acid .

The carboxylic acid can be, for example: i) of the formula: R-COOH, wherein R is hydrogen or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl group. acid. Examples of such acids include formic, acetic, propionic, butyric, valeric, palmitic, stearic, cyclohexanecarboxylic, 2-methylcyclohexanecarboxylic, 4-methylcyclohexanecarboxylic, oleic, linoleic, Linolenic acid, cyclohex-2-enoic acid, benzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 2-hydroxy-4-methylbenzoic acid, 2-hydroxy-4-ethylsalicylic acid ,
p-hydroxybenzoic acid, 3,5-di-t-butyl-4-
Hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, o-methoxybenzoic acid and p-methoxybenzoic acid are included.

ii) formula: HOOC- (CH ₂₎ in _n -COOH (wherein dicarboxylic acid and n is 0 or an integer), such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid and suberic acid Is included. Also the formula: Wherein x is 0 or an integer, y is 0 or an integer, and x and y can be equal or different,
R is as shown in (i)). Examples of such acids are alkyl or alkenyl succinic acids, 2-methylbutanedioic acid, 2-ethylpentanedioic acid, 2-n-dodecylbutanedioic acid, 2-n
-Dodecenylbutanedioic acid, 2-phenylbutanedioic acid and 2- (p-methylphenyl) butanedioic acid.
Also included are polysubstituted alkyl dicarboxylic acids wherein other R groups as described above can be substituted on the alkyl chain.
These other groups can be substituted on the same carbon atom or on different atoms. Such examples include 2,2-dimethylbutanedioic acid: 2,3-dimethylbutanedioic acid; 2,3,4-trimethylpentanoic acid; 2,2,3-trimethylpentanedioic acid and 2-ethyl-3 -Methylbutanedioic acid.

The dicarboxylic acids also the _{formula: HOOC- (C r H 2r-} 2) COOH ( wherein, r is a is 2 or more integer), and the acid. Examples include maleic acid, fumaric acid, pent-2-enedioic acid, hex-2-enedioic acid;
Enedioic acid; 5-methylhex-2-enedioic acid: 2,3-dimethylpent-2-enedioic acid; 2-methylbut-2-enedioic acid; 2-dodecylbut-2-enedioic acid and 2-poly Isobutylbut-2-enedioic acid.

Dicarboxylic acids also include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and the formula: Wherein R is as shown in (i), n = 1,
2, 3 or 4 and when n> 1, the R groups can be the same or different). Examples of such acids include 3-
Methylbenzene-1,2-dicarboxylic acid; 4-phenylbenzene-1,3-dicarboxylic acid; 2- (1-propenyl) benzene-1,4-dicarboxylic acid and 3,4-dimethylbenzene-1,2-dicarboxylic acid Contains acids.

Carboxylic anhydrides include acid anhydrides that can be derived from the carboxylic acids. Also included are acid anhydrides that can be derived from any mixture of the carboxylic acids. Specific examples include acetic anhydride, propionic anhydride, benzoic anhydride, maleic anhydride, succinic anhydride, dodecyl succinic anhydride, dodecenyl succinic anhydride, optionally substituted polyisobutylene succinic anhydride,
Preference is given to those having a molecular weight of from 500 to 3000 Daltons, phthalic anhydride and 4-methylphthalic anhydride.

Phenols capable of deriving anions of quaternary ammonium compounds have many different types. Examples of suitable phenols include: (i) Formulas Wherein n = 1, 2, 3, 4 or 5; R ²⁰ is as follows; and when n> 1, the substituents can be the same or different. R ²⁰ can be hydrogen or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, or aryl group. The hydrocarbon group (s) can be attached to the benzene ring by a keto or thio-keto group. Or hydrocarbon group (s)
Can be linked through an oxygen, sulfur or carbon atom. Examples of such phenols are o-cresol; m-cresol; p-cresol; 2,3-dimethylphenol; 2,4-dimethylphenol; 2,3,4-trimethylphenol; 3-ethyl-2, 4-dimethylphenol; 2,3,4,5
-Tetramethylphenol; 4-ethyl-2,3,5,6-tetramethylphenol; 2-ethylphenol; 3-ethylphenol; 4-ethylphenol; 2-n-propylphenol; 2-isopropylphenol; 4- 4-isopropylphenol; 4-n-butylphenol; 4-isobutylphenol; 4-s-butylphenol; 4-tert-butylphenol; 4-nonylphenol; 2-dodecylphenol; 4-dodecylphenol; 4-octadecylphenol; 2-cyclohexylphenol; 4-cyclohexylphenol; 2
-Allylphenol; 4-allylphenol; 2-hydroxydiphenyl; 4-hydroxydiphenol; 4-methyl-
4'-hydroxydiphenyl;o-methoxyphenol; o
-Methoxydiphenol; p-methoxyphenol; p-phenoxyphenol; 2-hydroxydiphenyl sulfide; 4-hydroxydiphenyl sulfide; 4-hydroxyphenylmethyl sulfide; and 4-hydroxyphenyldimethylamine. Also included are alkylphenols whose alkyl groups are obtained by polymerization of low molecular weight olefins, such as polypropylphenol or polyisobutylphenol.

formula: Wherein R ²⁰ and R ²¹ can be the same or different and are as indicated above for R ²⁰ , m and n
Is an integer and each R for each m or n greater than 1
²⁰ or R ²¹ can be the same or different). Examples of such phenols are 2,2'-dihydroxy-5,5'-dimethyldiphenylmethane;5,5'-dihydroxy-2,2'-dimethyldiphenylmethane;4,4'-dihydroxy-2,2'-Dimethyldiphenylmethane;2,2'-dihydroxy-5,5'-
Dinonyldiphenylmethane; 2,2'-dihydroxy-5,
5'-didodecylphenylmethane; 2,2 ', 4,4'-tetra-tert-butyl-3,3'-dihydroxy-5,5'-didodecylphenylmethane and 2,2', 4,4 '-Tetra-t-butyl-3,3'-dihydroxydiphenylmethane.

formula: Wherein R ²⁰ and R ²¹ can be the same or different and are as indicated above, m and n are integers, and each R ²⁰ or R ²¹ for each m and n greater than 1
Can be the same or different, and x is 1, 2, 3 or 4). Examples of such phenols are: 2,2'-dihydroxy-5,5'-dimethyldiphenyl sulfide; 5,5'-dihydroxy-2,2'-di-tert-butyldiphenyl disulfide; 4,4 '2,2'-dihydroxy-5,5'-dinonyldiphenyldisulfide;2,2'-dihydroxy-5,5'-didodecyldiphenyldisulfide;-dihydroxy-3,3'-di-t-butyldiphenylsulfide;2,2'-dihydroxy-5,5'-didodecyldiphenyltrisulfide; and 2,2'-dihydroxy-5,5'-didodecyldiphenyltetrasulfide.

Sulfonic acids capable of deriving the anion of a quaternary ammonium salt include alkyl and aryl sulfonic acids having a total of 1 to 200 carbon atoms per molecule, although the preferred range is 10 to 80 atoms per molecule.

This statement has the formula: Where p = 1, 2, 3, 4, 5 and when p> 1, the substituents can be the same or different and R ²² can represent R ²⁰ as described above. Arylsulfonic acid.

The hydrocarbon group (s) can be attached to the benzene ring through a carbonyl group or a thio-keto group. Alternatively, the hydrocarbon group (s) can be attached to the benzene ring through a sulfur, oxygen or nitrogen atom. Thus, examples of sulfonic acids that can be used include benzenesulfonic acid; o-toluenesulfonic acid; m-toluenesulfonic acid; p-toluenesulfonic acid; 2,3-dimethylbenzenesulfonic acid; 2,4-dimethylbenzenesulfonic acid; 2,3,4-trimethylbenzenesulfonic acid; 4-ethyl-2,3-dimethylbenzenesulfonic acid; 4
-Ethylbenzenesulfonic acid; 4-n-propylbenzenesulfonic acid; 4-n-butylbenzenesulfonic acid; 4-isobutylbenzenesulfonic acid; 4-s-butylbenzenesulfonic acid; 4-t-butylbenzenesulfonic acid; 4- Nonylbenzenesulfonic acid; 2-dodecylbenzenesulfonic acid; 4-
Dodecylbenzenesulfonic acid; 4-cyclohexylbenzenesulfonic acid; 2-cyclohexylbenzenesulfonic acid; 2
-Allylbenzenesulfonic acid; 2-phenylbenzenesulfonic acid; 4- (4'-methylphenyl) benzenesulfonic acid; 4-methylmercaptobenzenesulfonic acid; 2-methoxybenzenesulfonic acid; 4-phenoxybenzenesulfonic acid; 4- Methylaminobenzenesulfonic acid; 2-dimethylaminobenzenesulfonic acid; and 2-phenylaminobenzenesulfonic acid. R ²² is the type sulfonic acid derived from the polymerization of low molecular weight olefins, such as poly propyl benzenesulfonic acid and polyisobutylene benzenesulfonic acid are also included.

Wherein: R ²³ -SO ₃ H (wherein, R ²³ is a substituted or non-substituted alkyl, cycloalkyl, alkenyl or cycloalkenyl) are also included acid. Examples of such sulfonic acids that can be used include methyl sulfonic acid; ethyl sulfonic acid; n-propyl sulfonic acid; n-butyl sulfonic acid; isobutyl sulfonic acid; s-butyl sulfonic acid; t-butyl sulfonic acid; Dodecylsulfonic acid; polypropylsulfonic acid; polyisobutylsulfonic acid; cyclohexylsulfonic acid; and 4-methylcyclohexylsulfonic acid.

In the present invention, the organic acid capable of deriving the anion of the quaternary ammonium salt does not include salicylic acid and ethyl hydrogen sulfate.

Quaternary ammonium salts can be prepared in two steps, the first of which involves the reaction of a tertiary amine with an olefin oxide.

In general, one mole of tertiary amine is reacted with A moles of olefin oxide (where A is the number of tertiary nitrogens in the amine molecule) in the presence of an excess of water required by the stoichiometry of the reaction. ).

Thus, pyridine (1 mol) is treated with olefin oxide (1 mol) in water (> 1 mol). Triethylenediamine (1 mol) is treated with olefin oxide (2 mol) in water (> 2 mol). Hexamine (1 mol) is treated with olefin oxide (4 mol) in water (> 4 mol).

However, the olefin oxide can be used in excess if needed or desired, and the excess olefin oxide is then reacted with the quaternary ammonium hydroxide.
One possible mechanism for further reaction with this olefin oxide is the formula: Is indicated by

As mentioned above, any amount of water can be used as long as it corresponds to an excess over that required by the stoichiometry of the reaction.

The reaction can be carried out in the following manner: (i) The amine is stirred with the olefin oxide in the reactor and water is added to the reaction mixture. The rate of water addition does not affect the quality of the final product, but a slow addition of water can be used to control the exothermic reaction.

(Ii) The amine is mixed with water in the reactor and the olefin oxide is added to the stirred reaction mixture. The olefin oxide may be (a) a gas, pure or diluted with an inert carrier (eg, nitrogen), (b) a liquid, (c) a solution in water, (d) a water-miscible organic solvent (eg, methyl alcohol or ethyl alcohol). ) Can be added as

The rate of addition of the olefin oxide is not critical to the quality of the final product, but a slow rate of addition can be used to control the exothermic reaction.

(Iii) mixing the olefin oxide with water in the reactor;
The amine is added to the reaction mixture. The amine can be added as (a) a pure gas, liquid or solid, (b) a solution in water, (c) a solution in a water-soluble organic solvent.

Exothermic reactions can be controlled using slow addition of amines as well as olefin oxide and water.

To promote the reaction, the mixed reactants can be heated together at a constant temperature while the third reactant can be added at a rate sufficient to maintain a stable reaction. Alternatively, the reactants can be heated in a pressure vessel, but temperatures above 100 ° C. when heating with the reactants to promote the reaction should be avoided to prevent decomposition of the quaternary ammonium hydroxide .

The second stage of the reaction involves the neutralization of the quaternary ammonium hydroxide formed in the first stage with an organic acid.

Generally, sufficient acid to neutralize the quaternary ammonium hydroxide is mixed with the solution obtained from the first step. However, if desired, an excess of acid can be used, for example, when neutralizing only one carboxylic acid group of a polybasic acid. The neutralization reaction is carried out by (i) in the absence of a solvent, (ii) in the presence of an alcohol such as methanol, ethanol, isopropanol, ethyl cellosolve ™ or ethylene glycol, and (iii) another polar organic solvent such as acetone. (Iv) a hydrocarbon solvent such as hexane, heptane, white spirit, benzene, toluene or xylene, in the presence of methyl ethyl ketone, chloroform, carbon tetrachloride or sym-tetrachloroethane.
(V) in the presence of any mixture of the above-mentioned solvents.

The neutralization reaction can be performed at room temperature, but generally higher temperatures are used. When the reaction is over, the water and the solvent used can be removed by heating under reduced pressure. The product is generally diluted with mineral oil, diesel fuel, kerosene or an inert hydrocarbon solution to prevent the product from becoming too viscous.

The fuel composition advantageously comprises a small proportion by weight of quaternary ammonium compounds, preferably less than 1% by weight, more preferably
0.000001 to 0.1%, especially 2 to 200 ppm.

Cracking components in fuel oils that produce undesirable color formation and sedimentation are generally obtained by cracking heavy oils, and can be fuel oils whose major component is a distillate obtained from the resid.

Typical methods available for pyrolysis are visbreaking and delayed coking. Alternatively, the fuel can be obtained by catalytic cracking, the main methods being moving bed cracking and fluidized bed cracking. After the cracking, the distillate is separated by distillation under normal pressure or reduced pressure, and the obtained distillate has a boiling point of usually 60 to 500 ° C., which is referred to as light cycle oil, preferably 150 to 400 ° C. It is a fraction corresponding to the boiling range. Compositions consisting entirely of this fuel or fuel which is a mixture of cracked fraction and atmospheric distillate can be used in the present invention.

The weight ratio between the straight cut and the cracked cut in the fuel oil composition that is a mixture can vary significantly, but usually from 1: 0.03 to 1:
2, preferably 1: 0.05 to 1: 1. Typically, the content of cracked fraction is usually 5-97%, preferably 10-50%, based on the weight of the composition.

Accordingly, the invention also relates to a fuel comprising a distillate fraction and a cracking fraction and a quaternary ammonium compound wherein the cation is the reaction product of a tertiary amine, an olefin oxide and water and the anion is derived from an organic acid. An oil composition is provided. The present invention also provides the use of such compounds in controlling the formation of sediments and colors in fuel oil compositions, especially compositions comprising components obtained by cracking heavy oil.

The fuel oil composition of the present invention may contain other additives, such as antioxidants, anticorrosives, flow improvers, UV absorbers, detergents, dispersants and cetane improvers in small amounts (e.g., (Typically less than 2% by weight).

Details and examples of the synthesis of quaternary ammonium compounds are given in GB 1,445,993, the disclosure of which is incorporated by reference. The product was converted to a stable distillate (Fuel A) containing 50 ppm nitrogen and 0.24% sulfur with 695 ppm nitrogen and
It was tested in a fuel that was blended with a non-hydrorefined catalytic cracking gas oil with 1.11% sulfur (Fuel B). The invention is illustrated by the following example.

Table 1 shows the effect of blending various amounts of straight distillate oil fuel with non-hydrorefined catalytic cracking gas oil on sediment and color in the AMS 77.061 test.

 Table 2 shows the nitrogen and sulfur contents of various fuels.

Table 3 shows the effect of stable fuel (A) doping with nitrogen and sulfur containing compounds on color and sediment.

Table 4 shows the degradation components of 100 ppm of the quaternary ammonium compound.
2 shows the effect of addition to fuel containing% on sediment and color in the AMS 77.061 test. Comparison of the results for fuels treated with quaternary ammonium compounds with those for untreated fuels indicates that the compounds of the present invention control sediment and color.

Table 5 shows the long-term storage characteristics of the fuel to which 100 ppm of the quaternary ammonium compound was added. It can be seen that the sediment and color of the treated fuel is better over the long term than that of the untreated fuel.

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Claims (11)

(57) [Claims] 1. A fuel oil composition comprising a diesel fuel oil or a heated fuel oil and a quaternary ammonium salt, wherein the cation of the quaternary ammonium salt is formed by reacting a tertiary amine, an olefin oxide and water. Wherein the anion is phenol, sulfurized phenol and a compound of the formula: Wherein R ²² is hydrogen or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl group, p is an integer of 1 to 5,
R ²² can be the same or different when is greater than one. The above fuel oil composition, which is derived from an organic acid selected from the group consisting of sulfonic acids represented by the formula: 2. The composition according to claim 1, comprising a decomposition component derived from heavy oil. 3. The composition according to claim 2, wherein the decomposition component derived from heavy oil is contained in an amount of 5 to 97% by weight based on the weight of the composition. 4. A tertiary amine having the formula: R ¹ R ² R ³ N (wherein R ¹ , R ²
And R ³ can be the same or different and each is independently a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl group). A composition according to claim 1. 5. The composition according to claim 4, wherein each group R ¹ , R ² and R ³ has up to 20 carbon atoms. 6. The tertiary amine has the formula: R ⁴ R ⁵ N (CH ₂ ) _n NR ⁶ R
⁷ (where n is an integer of 1 or more, and R ⁴ , R ⁵ , R
₆ and R ⁷ can be the same or different and are each independently an unsubstituted or substituted alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl group) diamine. A composition according to any one of the preceding claims. 7. An olefin oxide having the formula: Wherein R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ can be the same or different and are each hydrogen or an unsubstituted or substituted alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl group. The composition according to any one of claims (1) to (6). 8. The method according to claim 1, wherein the anion of the quaternary ammonium salt is derived from a monoalkylphenol.
The composition according to any one of (7). 9. An anion of a salt having the formula: Of methylene bis-phenol, or of the formula: Wherein R ²⁰ and R ²¹ can be the same or different and are hydrogen or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl group, and m and n are the same Or each may be 0 or an integer from 1 to 4, each R ²⁰ or R ²¹ for each m or n greater than 1.
Can be the same or different, and x is 1, 2, 3 or 4), wherein the composition is derived from (1) to (7). 10. The composition according to claim 1, comprising a main weight proportion of diesel or heated fuel oil and a small weight proportion of quaternary ammonium salts. 11. A fuel oil additive containing a quaternary ammonium salt, wherein the cation of the quaternary ammonium salt is
A reaction product of a tertiary amine, an olefin oxide and water, wherein the anion is phenol, sulfurized phenol and a compound of the formula: Wherein R ²² is hydrogen or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl group, p is an integer of 1 to 5,
R ²² can be the same or different when is greater than one. The above-mentioned additive for fuel oil, which is derived from an organic acid selected from the group consisting of sulfonic acids represented by the formula: