JP2770004B2 - Fuel oil composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel oil having excellent lubricity. In particular, the present invention relates to a fuel oil composition having excellent lubricity even with a low-sulfurized diesel fuel oil.

[0002]

2. Description of the Related Art In the late 1960's when hydrogen treatment was introduced as a refining process for kerosene-type jet fuel oil, a problem occurred due to corrosion wear of a fuel injection pump of a jet engine due to lubricity of jet fuel. As a countermeasure, the addition of a corrosion inhibitor such as a fatty acid or a fatty acid ester was effective and employed. However, at present, measures are taken to change the pump material, and the addition of a corrosion inhibitor has been stopped.

[0003] On the other hand, regarding the diesel fuel, in recent years, the emission gas regulations for the protection of the global environment and the reduction of the sulfur content in the diesel fuel oil have been promoted. The reduction in the sulfur content of diesel fuel oil has been realized by reducing sulfur-containing aromatic components such as benzothiophene by hydrogen treatment, as in the case of kerosene-type jet fuel. Sulfur-containing aromatic components contribute to the lubricity of diesel fuel oil, and therefore, diesel fuel oil containing less sulfur-containing aromatic components has reduced lubricity. For this reason,
As the sulfur content decreases, lubricity decreases, and engine troubles caused by wear of the fuel injection pump occur. As a countermeasure, a diesel fuel oil to which the same fatty acid and fatty acid ester as those used for the kerosene-type jet fuel are added has been studied.

[0004]

However, fuel oils containing fatty acids and fatty acid esters have insufficient lubricating properties, and no satisfactory diesel fuel oil having a low sulfur content has been obtained.

[0005]

Means for Solving the Problems As a result of intensive studies on this problem, the present inventors have found that by adding a bis- (alkenyl succinic acid) ester having a specific chemical structure, the sulfur content can be reduced to 0.3% by weight. % Lubricating oil has been found to be excellent even in low-sulfurized diesel fuel oil of less than 10%.

That is, the present invention is a fuel oil composition comprising a bis- (alkenyl succinic acid) ester represented by the general formula (1) and a diesel fuel oil having a sulfur content of 0.3% by weight or less. (In the formula, R1 and R2 may be the same or different and each represents an alkenyl group having 6 to 18 carbon atoms. A is an ethylene group or a substituted ethylene group, and the substituent has 1 carbon atom.
Represents a straight-chain or branched alkyl group or phenyl group, and when n is 2 or more, it may be the same or different.
n shows the integer of 1-4. )

As a specific example of the bis- (alkenyl succinic acid) ester (A) represented by the general formula (1), an alkenyl succinic anhydride is reacted with an ethylene glycol derivative in a 2: 1 (molar ratio). It is obtained by doing. . The fuel composition of the present invention contains one or more bis- (alkenyl succinic acid) esters (A). Specific examples of the alkenyl succinic anhydride include hexenyl succinic anhydride, nonenyl succinic anhydride, dodecenyl succinic anhydride, pentadecenyl succinic anhydride, and carbon number of the alkenyl group such as octadecenyl succinic anhydride. Of 6 to 18. These alkenyl succinic anhydrides can be used alone or as a mixture thereof. Preferably, it is an alkenyl succinic anhydride having 9 to 15 carbon atoms in the alkenyl group. When the carbon number of the alkenyl group is 5 or less, the obtained bis- (alkenyl succinic acid) ester has insufficient solubility in diesel fuel oil, and when it is 19 or more, the resulting fuel oil composition has insufficient lubricity.

Specific examples of the ethylene glycol derivatives include, in addition to ethylene glycol, for example, an alkyl group-substituted ethylene glycol having 1 to 4 carbon atoms such as propylene glycol and butylene glycol, and 1,2-dihydroxy-1-phenylethane. And one or more of these can be used as a mixture. Preferably,
It is a hydrolyzate of propylene glycol and phenylene oxide. With an alkyl group-substituted ethylene glycol having 5 or more carbon atoms in the substituted alkyl group, the lubricating properties of the obtained diesel fuel oil are insufficient.

Further, as specific examples of the ethylene glycol derivative, those having a higher molecular weight than the former include ethylene oxide dimer to tetramer, and for example, propylene oxide, 1,2-butylene oxide and the like having 1 to 4 carbon atoms.
And a styrene oxide dimer and tetramer, and one or more of these can be used as a mixture. In addition, two or more of ethylene oxide, propylene oxide, styrene oxide and the like can be obtained by copolymerization.
To tetramers. Preferred are propylene oxide dimer (dipropylene glycol) and styrene oxide dimer. Also, ethylene glycol, propylene glycol, etc., and ethylene oxide 2 to 4
It can be used even if it is mixed with a monomer, a propylene oxide dimer or tetramer, or the like. Those using a bis- (alkenyl succinic acid) ester (A) derived from other than a dimer or tetramer of an alkyl group-substituted or phenyl group-substituted ethylene oxide having 1 to 4 carbon atoms have insufficient lubricity. Or
Solubility in diesel fuel oil may be insufficient.

Specific examples of the diesel fuel oil having a sulfur content of 0.3% by weight or less in the present invention include JIS No. 1 light oil obtained by ordinary distillation of low sulfur crude oil (for example, southern crude oil such as Minas crude oil). JIS No.2 light oil, JIS3
No. diesel, JIS Japanese No. 3 gas oil; desulfurized gas oil is produced through a hydrodesulfurization process from conventional crude oil; gas oil fraction obtained by blending the desulfurized gas oil and straight run gas oil (hydrodesulfurization step prior to the gas oil) JIS No. 1 light oil manufactured from Min_, JIS
No. 2 gas oil, JIS No. 3 gas oil, and JIS special No. 3 gas oil. Particularly preferably, J is produced using 50% by weight or more of desulfurized gas oil produced through a hydrodesulfurization treatment step.
IS1 light oil, JIS2 light oil, JIS3 light oil, JI
It is S special No. 3 light oil. If the sulfur content exceeds 0.3% by weight, there is no particular problem in lubricity even if the bis- (alkenylsuccinic acid) ester represented by the general formula (1) is not contained.

The content of the bis- (alkenyl succinic acid) ester in the fuel oil composition of the present invention is usually 30 to 1,0.
00 ppm, preferably 50 to 200 ppm. 3
If it is less than 0 ppm, lubricity is insufficient, and
If the amount exceeds m, the efficiency of addition in lubricity will be poor and the economic efficiency will be impaired.

The fuel oil of the present invention may contain other known additives. These known additives include, for example, flow improvers (eg, EVA flow improvers, alkenyl succinamide flow improvers, polymethacrylate flow improvers), detergents (eg, dibutylamine Ethylene oxide adducts, ethylene oxide adducts of butanol) and antioxidants.

[0013] The lubricity of diesel fuel oil can be measured by a conventional frictional wear evaluation table test method, for example, a test using a Falex block-on-ring friction / wear tester, BOCL.
Test using E tester (ASTM D5001), SR
HFRR developed to test lubrication of diesel fuel oil using a V tester (manufactured by Optimol, Germany)
It can be evaluated by tests and the like. In particular, the HFRR test (UK
Evaluation by PCS Instruments Co., Ltd. has a high correlation with actual fuel pump wear and is widely used.

[0014]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the examples, parts and% represent parts by weight and% by weight, respectively.

[0015]

【Example】

Production Examples 1 to 4 [Preparation of bis- (dodecenyl succinic acid) ester] Dodecenyl succinic anhydride was prepared by mixing ethylene glycol, propylene glycol, dipropylene glycol, ethylene oxide / propylene oxide copolymer (molar ratio 1: 1 all trimers) ), Into a flask at a molar ratio of 2: 1 based on the total acid value and the total hydroxyl value, and reacted under stirring at 100 to 110 ° C for 9 hours to obtain four kinds of bis-
Alkenyl succinates (S-1, S-2, S-
3, S-4) was prepared. The total acid value of each is 193,
194, 180 and 173.

Production Examples 5 to 8 [Preparation of bis- (octadecenylsuccinic acid) ester]
Octadecenyl succinic anhydride, ethylene glycol, propylene glycol, diethylene glycol, with each of the hydrolyzate of styrene oxide,
The mixture was charged into a flask at a molar ratio of 2: 1 based on the total acid value and total hydroxyl value, and reacted at 90 to 110 ° C. for 12 hours with stirring to obtain four types of bis-alkenyl succinates (S-
5, S-6, S-7, S-8). The total acid numbers for each were 155, 148, 142, 136.

Production Examples 9 to 12 [Preparation of bis- (nonenyl succinic acid) ester] Nonenyl succinic anhydride was obtained by hydrolyzing ethylene glycol, propylene glycol and styrene oxide,
Each of the propylene oxide / styrene oxide copolymer (molar ratio 1: 1, all trimers) and the molar ratio 2: 1 based on the total acid value and the total hydroxyl value are charged into a flask,
The mixture was reacted at 90 to 110 ° C. for 10 hours with stirring to obtain four kinds of bis-alkenyl succinates (S-9, S-10,
S-11 and S-12) were prepared. The total acid numbers for each were 148, 144, 131, 120.

Comparative Production Examples 1 to 4 [Preparation of bis- (alkenyl succinic acid) ester] Dodecenyl succinic anhydride was prepared by mixing polyethylene glycol (hexamer) and polypropylene glycol (hexamer) with a total acid value and The mixture was charged into a flask at a molar ratio of 2: 1 based on the total hydroxyl value, and reacted at 90 to 110 ° C. for 10 hours with stirring to prepare two types of bis-alkenyl succinates (R-1 and R-2). . The total acid value of each was 141,129. Eicosenyl succinic anhydride was charged into a flask at a molar ratio of 2: 1 based on ethylene glycol and propylene glycol, respectively, based on the total acid value and the total hydroxyl value.
The mixture was reacted at 10 ° C. for 12 hours to prepare two kinds of bis-alkenyl succinates (R-3 and R-4). The total acid value of each was 144,141.

Comparative Production Examples 5 and 6 [Preparation of fatty acid ester] Oleic acid and dodecyl alcohol were charged into a flask at a molar ratio of 1: 1 based on the total acid value and the total hydroxyl value, and the same amount as the total amount was added. Of xylene and 1% by weight of para-toluenesulfonic acid of the total amount were added, and the xylene was refluxed with heating and stirring to carry out an esterification reaction while removing generated water. After completion of the reaction, xylene was distilled off to obtain dodecyl oleate (R-5). Also, oleic acid and propylene glycol were charged into the flask at a molar ratio of 2: 1 based on the total acid value and the total hydroxyl value, and propylene glycol dioleate (R-6) was obtained in the same manner as described above.

Examples 1 to 12 and Comparative Examples 1 to 4 Diesel fuel oil corresponding to JIS No. 2 having a sulfur content of 0.04% by weight and a bis- (alkenylsuccinic acid) ester of S-1 to S-12 at a concentration of 200 ppm. Dissolved in Example 1
Twelve fuel oils were made. All of the obtained fuel oils were transparent, and no blemishes were observed. 12 kinds of fuel oil, temperature 60 ℃, stroke length 1mm, frequency 50H
An HFRR wear test was performed under the conditions of z and a time of 75 minutes to measure the friction coefficient and the size of the wear mark. At the same time, a blank test using only fuel oil to which nothing was added was also performed. Table 1 shows the evaluation results. Similarly, Comparative Reference Examples R-1 to R-6
Were dissolved at a concentration of 200 ppm to prepare fuel oils of Comparative Examples 1 to 6. It was confirmed that Comparative Example 1 was completely hazy after being left at about 5 ° C. for 3 hours. In addition, R-1 to
For R-6, an HFRR wear test was performed under the same conditions as above, and the coefficient of friction and the size of wear marks were measured. Table 1 also shows the evaluation results. As is apparent from Table 1, the diesel fuel oil composition of the present invention has a small coefficient of friction and a small wear mark, and is excellent in lubricity.

[0021]

Table 1 Friction coefficient Wear mark (μm) ---------------------------------------------------------------------------------------------------------- Example 1 0.16 380 Example 2 0.15 350 Example 3 0.16 370 Example 4 0.16 370 Example 5 0.22 420 Example 6 0.22 440 Example 7 0.20 410 Example 8 0.23 470 Example 9 0.25 470 Example 10 0.24 450 Example 11 0.24 440 Example 12 0.24 440 −−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−− Comparative example 1 0.30 650 Comparative example 2 0.30 600 Comparative example 3 0.29 580 Comparative example 4 0.28 530 Comparative example 5 0.28 520 Comparative example 6 0 .28 520 ----------------------------------------- − Blank 0.51 750 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−

[0022]

As described above, the fuel oil composition of the present invention has excellent lubricity. Therefore, even if regulations such as low sulfur are strengthened in the future due to environmental problems such as acid rain, abrasion of the fuel injection pump of the diesel engine will occur. Engine trouble can be prevented.

Continued on front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C10L 1/18 CA (STN)

Claims (3)

(57) [Claims] 1. A fuel oil composition comprising a bis- (alkenylsuccinic acid) ester (A) represented by the general formula (1) and a diesel fuel oil (B) having a sulfur content of 0.3% by weight or less. (In the formula, R1 and R2 may be the same or different and each represents an alkenyl group having 6 to 18 carbon atoms. A is an ethylene group or a substituted ethylene group, and the substituent has 1 carbon atom.
Represents a straight-chain or branched alkyl group or phenyl group, and when n is 2 or more, it may be the same or different.
n shows the integer of 1-4. ) 2. The fuel oil composition according to claim 1, wherein the content of the bis- (alkenyl succinic acid) ester (A) is 30 to 1,000 ppm. 3. The fuel oil composition according to claim 1, wherein at least 50% by weight of the sulfur-containing diesel fuel oil (B) is a hydrodesulfurized light oil.