TWI391480B - Low sulphur fuel oil for reducing wear agent - Google Patents

Description

Low sulphur fuel oil for reducing wear agent

The invention relates to a low-sulphur fuel oil reducing wear agent and a fuel oil composition, in particular to a fuel additive and a fuel oil composition, wherein the fuel additive can improve lubricating properties of low sulfur diesel and effectively reduce fuel injection pump The wear is further provided with rust prevention which prevents rust in the engine caused by condensed water.

In recent years, due to the increasing emphasis on global environmental issues, so-called desulfurized diesel fuel has been circulated in countries around the world to promote the emission control of diesel vehicles and the reduction of sulfur content in diesel. It can be seen that in order to reduce the sulfur content of diesel oil, it is necessary to carry out deep desulfurization of the diesel base material, and at the same time, the lubricating substance in the diesel oil is simultaneously removed, resulting in a decrease in lubricating performance. Since the European and American countries have reported the following example: the fuel injection pump of the diesel engine is lubricated by diesel fuel. Therefore, if such a lubricated diesel oil is used, the fuel injection pump is abnormally worn and the engine is poorly rotated. . In view of the above-mentioned problem of reducing the lubricity of diesel oil, it has also been dealt with from the parts of diesel engines. However, it is also required to deal with the fuel, so that it has been studied so far.

As a result, various types of wear reducing agents are now added to diesel fuel. For example, a specific ester compound-based additive [International Publication No. 94/1760 (1994) or the like) or a specific carboxylic acid compound-based additive (Japanese Patent Laid-Open No. Hei 10-110175, etc.) is disclosed.

However, the previously added reducing wear agent does not produce sufficient wear resistance, and if the amount of use is increased, it often causes problems such as oxidative stability of the fuel oil. Therefore, it is desirable to have a low-sulfur fuel oil reducing wear agent which can exhibit excellent wear resistance even if the wear agent does not cause a problem in that the oxidation stability of the fuel oil is low.

SUMMARY OF THE INVENTION An object of the present invention is to provide a low-sulfur fuel oil composition for reducing low-sulfur fuel oil which has excellent wear resistance even when added in a low amount, and further provides a low sulfur fuel oil composition containing the reduced wear agent.

The inventors have conducted intensive studies and found that a carboxylic acid having a specific dynamic viscosity can provide an excellent low sulfur reducing wear agent, thereby completing the present invention.

Embodiments of the present invention will be described below.

In the present invention, the mixture (A) of the saturated carboxylic acid having 14 to 22 carbon atoms and the unsaturated carboxylic acid contains at least one saturated carboxylic acid having 14 to 22 carbon atoms and at least one unsaturated carboxylic acid. Further, (A) has a kinematic viscosity at 40 ° C of 15 to 21 mm ² /s, preferably 16 to 20 mm ² /s. If the dynamic viscosity of (A) at 40 ° C is less than 15 mm ² /s, the effect of reducing the wear of low sulfur fuel oil is not sufficient; if it exceeds 21 mm ² /s, the viscosity at low temperature is increased, so it is difficult to operate. . (A) The dynamic viscosity at 40 ° C can be measured by JIS K 2283 "Test Method for Dynamic Viscosity of Crude Oil and Petroleum Products".

Examples of the carboxylic acid contained in (A) include a saturated monocarboxylic acid (a1) having a carbon number of 14 to 22, a monounsaturated monocarboxylic acid having a carbon number of 14 to 22 (a2), and a carbon number of 14 to 22. a di-unsaturated monocarboxylic acid (a3), a tri-condensed monocarboxylic acid having a carbon number of 14 to 22 (a4).

Examples of the saturated monocarboxylic acid (a1) having 14 to 22 carbon atoms include myristic acid, pentadecyllic acid, palmitic acid, margaric acid, and stearic acid. (stearic acid), arachidic acid, and behenic acid. Among the (a1), a saturated monocarboxylic acid having a carbon number of 16 to 18 is preferred, and palmitic acid, stearic acid, and the like are preferably used in combination. When palmitic acid and stearic acid are used together, the weight is preferably (palmitic acid/stearic acid) of 1/1 to 1/2.5, more preferably 1/1 to 1/2.

The monounsaturated monocarboxylic acid (a2) having 14 to 22 carbon atoms may, for example, be myristoleic acid, palmitoleic acid, petroselinic acid, oleic acid, or the like. Elaidic acid, asclepinic acid, vaccenic acid, gadoleic acid, Gondoc acid, ceteleic acid, erucic acid, brassic acid, and the like. In (a2), the number is preferably a monounsaturated monocarboxylic acid having a carbon number of 14 to 20, and particularly preferably oleic acid. When the carbon number is less than 14 or exceeds 22, there is a case where the solubility in diesel fuel oil is insufficient or the lubricity is insufficient.

The carbon number 14 to 22 bis unsaturated monocarboxylic acid (a3) can be exemplified by: linoleic acid, trans-2-decadienoic acid, cis-4-decadienoic acid, anti--10-18 Carhaned acid and trans-12-octadecadienoic acid. In (a3), a dicarboxylic acid having a carbon number of 14 to 20 bis is preferred, and linoleic acid is particularly preferred.

Examples of the unsaturated monocarboxylic acid (a4) having 14 to 22 carbon atoms include α-eleostearic acid, β-tungstic acid, punicic acid, and linolenic acid. Γ-linolenic acid, docosatrienoic acid, and eicosatrienoic acid. Among the (a4), a tetracarboxylic acid having a carbon number of 14 to 20 is preferred, and particularly preferred is linoleic acid.

These carboxylic acids can be obtained from natural oils such as refined coconut oil, palm oil, groundnut oil, soybean oil, olive oil, castor oil, sunflower oil, rice bran oil, rapeseed oil, butter and whale oil, either alone or in combination. These carboxylic acids can be arbitrarily changed in ratios (a1) to (a4).

The preferred content of each of (a1) to (a4) in (A) is: calculated as the weight of (A), (a1) is 1.5 to 8.0 weight percent (wt%), (a2), and (a3) The total is 84.0~96.5 wt%, and (a4) is 2.0~8.0 wt%.

More preferably, (a1) is 1.5 to 4.5 wt%, (a2) and (a3) are 88.5 to 96.5 wt%, and (a4) is 2.0 to 7.0 wt%. When the content is in the above range, the oxidative stability as a reducing wear agent is further improved, and the emulsification resistance is good.

The anti-wear agent of the present invention may contain, in addition to the above (A), an antioxidant selected from the group consisting of an antioxidant (B), a cloud point reducing agent (C), and a diluent (D) in order to improve oxidative stability or workability at low temperature. One type or more types.

Examples of the antioxidant (B) include an amine compound (naphthylamine compound, a diphenylamine compound, a p-phenylenediamine compound, and the like), and a phenol compound. .

Examples of the diphenylamine-based compound in the amine compound include p-(p-toluenesulfonamide)-diphenylamine and 4,4'-(α,α'-dimethylbenzyl)diphenyl. High temperature reactant of amine, 4,4'-dioctyldiphenylamine, 4-monooctyldiphenylamine, diphenylamine and acetone, low temperature reactant of diphenylamine and acetone, A low temperature reactant of diphenylamine with aniline and acetone, a reaction product of diphenylamine with diisobutylene, and a mixture of octylated diphenylamine.

Examples of the phenolic compound include an alkylphenol such as p-nonphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-t-butylphenol, and 2,6-di-3. Butyl-p-cresol, tert-butylhydroxymethoxybenzene, 4,4-methylenebis-(2,3-di-t-butylphenol), and N-butyl-p-aminophenol.

Preferred among these antioxidants are p-(p-toluenesulfonamide)-diphenylamine, 4,4'-(α,α'-dimethylbenzyl)diphenylamine, 4,4'- Dioctyldiphenylamine, 4-monooctyldiphenylamine, alkanol, and 2,4-dimethyl-6-tert-butylphenol.

The amount of the antioxidant (B) to be added is usually 0.5 parts by weight or less, preferably 0.1 to 0.3 parts by weight, per 100 parts by weight of (A).

Examples of the cloud point reducing agent (C) include a poly(meth)acrylate-based pour point depressant (C1), an ethylene-vinylacetate (EVA)-based pour point depressant (C2), and Alkenyl succinic acid (ASA) is a pour point depressant (C3) or the like from the following compounds used previously.

The poly(meth)acrylate-based pour point depressant (C1) may, for example, be a polymer containing an alkyl (meth)acrylate as an essential constituent monomer, and the alkyl (meth)acrylate has a carbon number of 1 a linear or branched alkyl group of ~40. Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, decyl methacrylate, dodecyl (meth)acrylate, and tridecyl (meth)acrylate. , tetradecyl (meth)acrylate, penta(meth)acrylate, hexadecyl (meth)acrylate, and octadecyl (meth)acrylate. For example, the polymer described in Japanese Laid-Open Patent Publication No. 2001-354980 can be mentioned.

The EVA-based pour point depressant (C2) may, for example, be an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate-ethylhexanoic acid vinyl ester terpolymer, and Japanese Patent Laid-Open Publication No. Hei 11-240905 The polymer described.

The ASA-based pour point depressant (C3) may, for example, be an alkenyl succinamide having an alkenyl group having a carbon number of 8 to 50.

From the viewpoint of easy adjustment to an arbitrary crystallization starting temperature, (C) is preferably a poly(meth)acrylate-based pour point depressant (C1). The amount of the cloud point reducing agent (C) to be added is usually 1.0 part by weight or less, preferably 0.1 to 0.5 part by weight, per 100 parts by weight of (A).

The diluent (D) is exemplified by a hydrocarbon solvent.

Specific examples of the hydrocarbon solvent include, for example, "Pegasol 3040", "Pegasol AN-45", "Pegasol AS-100", and "Exxsol D40" manufactured by Exxon Mobil Chemical Co., Ltd. "Solvesso100" manufactured by Exxon Mobil Chemical Co., Ltd. and "CACTUS SOLVENT P-150" manufactured by JAPAN ENERGY Co., Ltd. with parameters (SP value) of 6 to 8; A high boiling point aromatic industrial solvent having an SP value of 8.5 to 10; and a cycloalkane solvent having an SP value of about 8 and containing an aromatic hydrocarbon and a cycloalkane. These hydrocarbon-based solvents may be used singly or in combination of two or more.

The amount of the diluent (D) to be added is usually 1.0 part by weight or less, preferably 0.5 part by weight or less based on 100 parts by weight of (A). If it exceeds this range, the ignition point is lower.

In the wear reducing agent of the present invention, the respective contents of the components (A) to (D) are based on the weight of the reducing agent, and are usually (A) 97.5 to 100.0% by weight, preferably 98.0 to 99.7% by weight, (B) It is 0.5 wt% or less, preferably 0.1 to 0.3 wt%, (C) is 1.0 wt% or less, preferably 0.1 to 0.5 wt%, and (D) is 1.0 wt% or less, preferably It is 0.1~0.5 wt%.

Preferably, the cloud point of the wear reducing agent of the present invention is 10 ° C ~ -10 ° C, preferably 8 ~ -8 ° C, more preferably 7 ~ -7 ° C, and the flow point is 5 ° C ~ -12.5 ° C Preferably, it is 5.0 to -10.0 ° C, more preferably 2.5 to -10.0 ° C, and the ignition point is 200 ° C or more, preferably 210 ° C or more. When the cloud point, the flow point, and the ignition point are outside the range, when the storage is performed at a temperature of 10 ° C or more, crystallization of the carboxylic acid may occur or the workability of the wear agent may be lowered.

The wear reducing agent of the present invention can be obtained by uniformly mixing (A) and, if necessary, (B) to (D). Further, two or more kinds of carboxylic acids constituting (A) may be added separately.

The low sulfur fuel oil composition of the present invention comprises a low sulfur fuel oil and 20 to 300 ppm of the above-mentioned reduced wear agent. The low sulfur fuel oil has an initial boiling point (IBP) of 140 to 200 ° C, a 10% distillation temperature of 170 to 260 ° C, a 50% distillation temperature of 240 to 310 ° C, and a 90% distillation temperature of 310 to 350 ° C. The distillation end point (EP) is a distillation property of 340 to 380 ° C, the density (15 ° C) is 0.8200 to 0.8400 g / cm ³ , the wax precipitation at -10 ° C is 1.0 to 4.0%, and the sulfur content is 1 to 500 ppm.

The low-sulfur fuel oil to be used in the present invention may be JIS No. 1 diesel, JIS No. 2 diesel, JIS No. 3 diesel, and JIS No. 3 diesel obtained by blending two or more of the following diesel oils as needed. The diesel oil is obtained from a normal-pressure distillation apparatus obtained from an atmospheric distillation apparatus of a low-sulfur crude oil (for example, a southern crude oil such as Minas crude) and a normal-pressure distillation apparatus. Hydrogenated diesel oil obtained by straight-run heavy oil or residual oil, hydrogenated refined diesel oil obtained by hydrogenating a straight-run diesel oil or a vacuum-reduced diesel oil by a hydrorefining apparatus, and hydrodesulfurization obtained by hydrodesulfurization under more severe conditions than hydrorefining Hydrogen-decomposed diesel oil obtained by further hydrolyzing and decomposing the diesel base material.

Among the above, JIS No. 1 diesel, JIS No. 2 diesel, JIS No. 3 diesel, and JIS No. 3 diesel produced by using hydrorefined diesel oil of 50 wt% or more and hydrogenated desulfurized diesel oil are preferably used.

The distillation property of the low sulfur diesel oil of the present invention is preferably as follows.

Distillation initial boiling point (IBP)=140~200°C 10% distillation temperature=170~260°C 50% distillation temperature=240~310°C 90% distillation temperature=310~350°C distillation end point (EP)=340~380 °C

Here, the distillation property is a value measured by JIS K2254 "Petroleum Products - Distillation Test Method".

The low sulfur diesel of the present invention has a density (15 ° C) of 0.8200 to 0.8400 g/cm ³ . It is preferably 0.8250 to 0.8350 g/cm ³ . If the density of the low sulfur diesel is within this range, the diesel engine's fuel consumption, engine power, and high temperature startability are good. Here, the density (15 ° C) is a value measured by JIS K2249 "crude oil and petroleum products - density, mass, capacity conversion table".

The low sulfur diesel of the present invention has a wax precipitation of -10 ° C of 1.0 to 4.0%. It is preferably 1.0 to 3.0%. If the amount of wax precipitated at -10 ° C is within this range, the low sulfur fluidity of the low sulfur diesel is good. Here, the amount of wax precipitated at -10 ° C was measured by the following method.

20 ml of diesel was cooled to a temperature of about 3 ° C above the turbidity point and further cooled to -10 ° C in a filter in a cryostat. Further, the precipitated wax was collected by a suction filtration on a filter (pore diameter: 5 μm, diameter: 47 mm). Next, the filter was washed with 2-butanone, dried, and the weight of the filter was measured to quantify the amount of wax.

The amount of the reducing agent is usually 20 to 300 ppm, preferably 30 to 200 ppm, more preferably 50 to 170 ppm. If it is less than 20 ppm, the abrasion resistance is insufficient, and if it exceeds 300 ppm, the addition efficiency is poor and the economy is impaired.

The evaluation of the abrasion resistance of the low sulfur fuel oil composition of the present invention can be carried out by a bench test method for the usual friction and wear evaluation of the lubricity evaluation of diesel fuel oil or the like. For example, it can be evaluated by the following test: a test using a Falex Brock on ring friction wear tester, a test using a BOCLE test machine (ASTM D5001), a test using an SRV test machine (manufactured by ORTIMOL), and High frequency reciprocating test (HFRR test), etc. Among these, the evaluation by the high-frequency reciprocating test (manufactured by British PCS INSTRUMENTS Co., Ltd.) has a high correlation with the wear of the fuel pump of the actual diesel fuel oil, and therefore it is preferable to use the test machine for evaluation.

The low sulfur fuel oil composition of the present invention is suitable for use in a low sulfur fuel oil (diesel) having a sulfur content of 1 to 500 ppm for a diesel engine or a boiler, or a fuel oil for a jet engine such as an airplane.

[Examples]

The invention is described in detail below by means of examples, but the invention is not limited to the examples.

[Reducing the modulation of the abrasive agent]

Examples 1 to 12 and Comparative Examples 1 to 5 were formulated with the compounding compositions shown in Table 1 below, as (A-1) to (A-5) of the carboxylic acid mixture (A) and as an antioxidant (B). "CACTUS SOLVENT P-150" manufactured by Japan Energy Co., Ltd. as a cloud point reducing agent (C-1) to (C-2) as a cloud point reducing agent, Thereby modulating the wear agent.

The composition of (A-1) to (A-5) is shown in Table 2, and the dynamic viscosity at 40 ° C measured by JIS K 2283 "Crude Oil and Petroleum Products - Dynamic Viscosity Test Method" is shown in Table 2.

The composition and manufacture of (C-1) and (C-2) are as described in Production Examples 1 and 2 below.

In addition, the cloud point and the flow point of these reducing wear agents were measured by JIS K 2269 "Pour point of crude oil and petroleum products and cloud point test method of petroleum products", and the results are shown in Table 1.

Manufacturing example of cloud point reducing agent

Production Example 1 [Production of (C-1)] 28 g of toluene was placed in a reactor equipped with a stirring device, a heating device, a thermometer, and a nitrogen gas injection tube, and the inside was set to a nitrogen atmosphere, and the temperature was raised to 85 °C. Then, while stirring the toluene in the reactor, 250 g of an alkyl (meth) acrylate mixture (dodecyl methacrylate: tetradecyl methacrylate: hexadecyl methacrylate: methacrylic acid ten) Octa-ester = 10:10:40:40 by weight of the formulation), and a solution of 1.5 g of 2,2'-azobis-2,4-dimethylvaleronitrile dissolved in 20 g of toluene. They were all dropped from the different dropping funnels into the reactor at 2 hours and at the same speed. After the completion of the dropwise addition, polymerization was carried out at 85 ° C for 2 hours. After completion of the reaction, toluene was distilled off at 130 ° C to obtain a polymer, which was used as a cloud point reducing agent (C-1).

Production Example 2 [Production of (C-2)] except that the alkyl (meth)acrylate mixture was set to dodecyl methacrylate: tetradecyl methacrylate: hexadecyl methacrylate: methacrylic acid Polymer was polymerized in the same manner as in Production Example 1 except that the octaester = 25:25:25:25 by weight ratio, and this was used as a cloud point reducing agent (C-2).

[Modulation and evaluation of fuel oil composition]

In Examples 13 to 24 and Comparative Examples 6 to 10, 100 ppm of the reducing abrasives S1 to S12 or R1 to R5 were dissolved in the diesel fuel oil to prepare a fuel oil composition having the initial boiling point of distillation ( IBP) is a distillation property of 170 ° C, a 10% distillation temperature of 205 ° C, a 50% distillation temperature of 305 ° C, a 90% distillation temperature of 338 ° C, and a distillation end point (EP) of 360 ° C, and a density (15 ° C). ) is 0.8320 g/cm ³ , the wax precipitation amount at -10 ° C is 2.3%, and the sulfur content is 10 ppm, which is equivalent to JIS No. 2 diesel fuel oil.

The abrasion resistance, water separation property, oxidation stability, and rust resistance of these fuel oil compositions were evaluated.

The test method is as follows. The test results are shown in Table 3.

<Abrasion resistance> The high frequency reciprocating test (HFRR) was carried out by the Petroleum Society Standard JPI-5S-50-98 "Diesel-Lubricity Test Method", and the size of the wear marks of the test balls was evaluated. The device is manufactured by PCS INSTRUMENTS, UK.

<Water Separability> The water solubility test method of the "Aviation Fuel Oil Test Method" described in JIS K 2776 is carried out.

80 ml of the sample and 20 ml of the buffer were weighed in a 100 ml plugged cylinder, and the mixture was vibrated and mixed under the established conditions. The volume change of the buffer portion after standing, the visual interface state and the separation state were determined according to the following criteria. Conduct an evaluation.

Evaluation of interface state: 1: Transparent, clean state 1b: The area of the small and transparent bubble is less than or equal to 50% of the interface, and there is no state of small pieces, lace-like or film-like substances.

Evaluation point of separation state: (1): no emulsion or precipitate in the upper part of the two layers or the sample layer (2): the same as (1) except that there are small bubbles or water droplets in the sample layer. status

<Oxidation Stability> The test was carried out by an ISOT test (Indiana Stirring Oxidation Test) capable of testing whether or not engine deposits were generated in a real vehicle at a temperature of 110 ° C, a number of revolutions of 700 rpm, and a test time of 8 hours. The evaluation criteria are as follows.

Evaluation points of oxidative stability: 1: There is almost no deposit on the wall 2: only a little attachment is produced on the wall 3: Some deposits are formed on the wall 4: The wall is covered with attachments

ㄑAnti-rust property> The rust prevention property was measured by the rust-proof test of JIS K 2510.

[Effects of the Invention]

According to Table 3, the low-sulfur fuel oil reducing wear agent of the present invention and the fuel oil composition containing the low-sulfur fuel oil reducing wear agent can exhibit not only the same or equivalent wear resistance as the prior additive. It also exhibits excellent performance in terms of workability, oxidation stability, and water separation.

Claims (7)

A low-sulfur fuel oil reducing wear agent, characterized in that the reducing wear agent is a mixture (A) containing a saturated carboxylic acid having a carbon number of 14 to 22 and an unsaturated carboxylic acid, and the (A) is moved at 40 ° C The viscosity is 15~21 mm ² /s. The low-sulfur fuel oil reducing wear agent according to claim 1, wherein the above (A) comprises: a saturated monocarboxylic acid having a carbon number of 14 to 22 (a1), and a monounsaturated carbon number of 14 to 22. a monocarboxylic acid (a2), a carbon number 14-22 diunsaturated monocarboxylic acid (a3), and a carbon number 14-22 triunsaturated monocarboxylic acid (a4), calculated as the total weight of (A), A1) is 1.5 to 8.0 weight percent, (a2) and (a3) are 84.0 to 96.5 weight percent, and (a4) is 2.0 to 8.0 weight percent. The anti-wear agent for a low-sulfur fuel oil according to claim 2, wherein the saturated monocarboxylic acid (a1) comprises palmitic acid and stearic acid, and the weight ratio (palmitic acid/stearic acid) is 1/ 1~1/2.5. The anti-wear agent for a low-sulfur fuel oil according to claim 2, wherein the monounsaturated monocarboxylic acid (a2) is oleic acid, and the di-unsaturated monocarboxylic acid (a3) is linoleic acid. And the above tri-unsaturated monocarboxylic acid (a4) is linolenic acid. The anti-wear agent for a low-sulfur fuel oil according to claim 1, wherein the anti-wear agent further comprises one selected from the group consisting of an antioxidant (B), a cloud point reducing agent (C), and a diluent (D). One or more kinds. The low-sulfur fuel oil reducing wear agent according to claim 1, wherein the clouding point of the reducing wear agent is 10 ° C ~ -10 ° C, the flow point is 5 ° C ~ -12.5 ° C, and the ignition point is greater than Equal to 210 ° C. A low-sulfur fuel oil composition, comprising: a low-sulfur fuel oil, and a low-sulfur fuel oil reducing wear agent according to any one of claims 1 to 6 of 20 to 300 ppm. The low sulfur fuel oil has an initial boiling point (IBP) of 140 to 200 ° C, a 10% distillation temperature of 170 to 260 ° C, a 50% distillation temperature of 240 to 310 ° C, and a 90% distillation temperature of 310 to 350. °C, distillation end point (EP) is 340 ~ 380 ° C distillation, density (15 ° C) is 0.8200 ~ 0.8400 g / cm ³ , -10 ° C wax precipitation is 1.0 ~ 4.0%, sulfur content is 1 ~ 500 ppm .