JP2001271077A - Diesel gas oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a diesel gas oil composition having an extremely decreased sulfur content, maintaining excellent lubricating performances even in the case of adding a cetane number improver, not causing a bad condition in a fuel injection pump of an engine of a diesel automobile and not deteriorating an exhaust gas by using a deep-desulfurized gas oil base. SOLUTION: This diesel gas oil composition contains <=0.05 mass % sulfur content and comprises a cetane number improver and an imparter for lubricating properties.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a diesel light oil composition, and more particularly to a light oil composition for a diesel engine used in automobiles, ships, generators and the like.

[0002]

2. Description of the Related Art In recent years, it has been required to reduce the sulfur content of diesel engine diesel oil in order to comply with exhaust gas regulations. However, it has been known that when deep desulfurization is performed on a gas oil base for such low sulfur, the lubricating performance of the obtained gas oil product is reduced. Further, it has been clarified that when a cetane number improver is added to the deep-desulfurized light oil base material in order to improve the combustibility of diesel fuel, the lubricating performance further decreases. That is, due to such a decrease in lubrication performance, wear of each part of a fuel injection pump of a diesel engine lubricated with light oil as a fuel increases, and as a result, inconveniences such as poor rotation of the engine and deteriorated operability occur. Have been reported. In particular, due to the decrease in slidability of the governor sleeve,
It has been reported that a forklift or the like has a problem that the engine stops when idling. Further, some markets have reported cases in which fuel injection becomes impossible due to wear of the face cam and catastrophic failure of the pump occurs.

[0003] To cope with such a decrease in the lubricating performance of light oil, measures have been taken from the hardware side, but on the other hand, measures have been required from the fuel side, and studies have been made on this. No corresponding response was found.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above, and is excellent even when a deep desulfurized gas oil base material is used, the sulfur content is significantly reduced, and a cetane number improver is added. An object of the present invention is to provide a diesel light oil composition which maintains lubricating performance, does not cause a problem in a fuel injection pump of a diesel engine, and does not cause deterioration of exhaust gas.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by adding a lubricity-imparting agent to deep desulfurized gas oil having a specific composition to which a cetane number improver has been added, a lubricating agent has been added. It has been found that the object of the invention can be effectively achieved, and the present invention has been completed. That is, the present invention
It is intended to provide a diesel light oil composition containing a sulfur content of 0.05% by mass or less and having a cetane number improver and a lubricity imparting agent added thereto.

[0006]

Embodiments of the present invention will be described below. The characteristics of the gas oil used in the diesel gas oil composition of the present invention are based on Japanese Industrial Standards (JIS K220).
It satisfies 4), and particularly contains 0.05% by mass or less of sulfur. Also preferably, 3
It has a kinematic viscosity at 0 ° C. of 1.7 mm ² / s or more. For example, hydrodesulfurized light oil (DGO), hydrocracked light oil (HCGO), or the like, or a mixture thereof is prepared to have a sulfur content within the above range. Things can be used.

The diesel light oil composition of the present invention has a composition of 0.05
However, if light oil having a sulfur content exceeding 0.05% by mass is used in diesel vehicles, exhaust gas recirculation (EG
In a vehicle employing R), engine wear increases. Further, the exhaust gas purifying catalyst is poisoned, and the exhaust gas deteriorates. Furthermore, the amount of sulfate in particulate matter (PM) and the amount of sulfur oxide in exhaust gas increase.

[0008] The hydrodesulfurized light oil (DGO) generally has a boiling point in the range of 140 to 390 ° C and a density of 0.1.
Those having a range of 80 to 0.90 can be appropriately used. Also,
The hydrodesulfurized light oil (DGO) has a sulfur content of 0.0
Those having a concentration of 0.5 to 0.5% by mass can be generally used,
Those having a content of not more than 05% by mass can be suitably used. The hydrodesulfurized gas oil (DGO) is specifically prepared by converting a straight-run gas oil (LGO) as a feedstock oil into a Co-
In the presence of a catalyst such as a Mo / alumina catalyst or a Ni-Mo / alumina catalyst, 2.94 to 9.81 MPa · G (30 to
100 kg / cm ² G), preferably 4.90 to 6.8
Under a pressure of 6 MPa · G (50 to 70 kg / cm ² G),
300 to 400 ° C., preferably at temperatures of three hundred and thirty to three hundred sixty ° C., liquid hourly space velocity (LHSV) 0.5~5hr ^-1, preferably followed by desulfurization reaction conditions 1~2hr ^-1, and hydrogen sulfide in a subsequent stripper It is obtained by removing naphtha.

The above-mentioned hydrocracked gas oil (HCGO) is defined as hydrocracked heavy gas oil (HGO), vacuum gas oil (VGO) or a mixture thereof in the presence of a catalyst, and the cracked oil is distilled and separated. It has a boiling point in the range of 140 to 390 ° C and a distillation property of 50%
Those having a distillation point in the range of 220 to 340 ° C are generally used. As the hydrocracked gas oil (HCGO), those having a sulfur content of 0.0001 to 0.2% by mass can be generally used.

[0010] In addition to the above gas oil base material, if necessary, a gas oil fraction generally used, for example, a straight gas oil (LG)
O), by-product light oil (DSGO) from heavy oil direct desulfurization unit,
By-product light oil (LCO) from catalytic cracking unit, desulfurized L
CO (DSLCO), by-product light oil (V
HLGO), dewaxed gas oil (DWLGO), dewaxed desulfurized gas oil (DWDGO), desulfurized kerosene fraction (DK), and the like can be used in combination.

The diesel light oil composition of the present invention comprises a cetane number improver added to the above light oil in order to improve the combustibility of diesel fuel. Specific examples of the cetane number improver usable herein include aliphatic hydrocarbon compounds such as acetylene, allylene, divinylacetylene, and butadiene; diethyl ether, acetone, butyl carbinol, diethyl carbinol, methyl acetate, and formaldehyde. Oxygenated compounds such as butyl peroxide, caproyl peroxide, heptylyl peroxide, oleyl peroxide, triacetone peroxide, acetylbenzoyl peroxide, etc .; isopropyl nitrate, butyl nitrate, amyl nitrate, hexyl nitrate , Octyl nitrate, alkyl nitrate compounds such as cyclohexyl nitrate; nitro compounds such as nitromethane, nitroethane, nitropropane, nitrobenzene, and nitronaphthalene; nitrosation such as nitrosomethylurethane Things; four polysulfide sulfide diethyl like; barium nitrate, copper oleate, MnO _2, V ₂ O ₅ metal compounds such like.

Of the above-mentioned cetane number improvers, an alkyl nitrate compound is preferably used in the present invention in view of the effect and ease of handling. In the present invention, the cetane number improver is preferably contained in the diesel gas oil composition in an amount of 100%.
5,000 mass ppm, more preferably 200-3,
000 mass ppm is added. The above addition amount is 5,000
When the content exceeds ppm by mass, it may not be completely dissolved in the diesel gas oil composition,
If it is less than m, the effect as a cetane number improver may not be sufficiently exhibited.

The diesel light oil composition of the present invention further comprises
A lubricity imparting agent is added. Lubrication available here
Specific examples of the property imparting agent include lauric acid, olein
Acid, stearic acid, dodecyl succinic acid, dodecenyl succinic acid
Higher fatty acids such as citric acid, linoleic acid and dilinoleic acid;
Decyl alcohol, oleyl alcohol, linolenylua
Higher alcohols such as rucol; stearic acid amide,
Oleic acid amide, bis-stearate (polyethylene glycol)
Recall) amide, dodecenyl succinamide, dodece
Nylsuccinic acid (hydroxyethyl) amide, alkenyl
Amides such as succinamide; dodecylamine, stear
Amine phosphate, dimethylamine stearate, cyclohexane
Xylamine, dodecylbis (diethylene glycol)
Amine compounds such as amines; phenyl-α-naphthylua
Min, bisoctylphenylamine, bisnonylpheny
Ruamine, diphenyl-p-phenylenediamine, dipi
Lysylamine, phenothiazine, N-methylphenothi
Other amides such as azine and N-ethylphenothiazine
Compounds: methyl laurate, stearic acid
Methyl ester, sorbitan monooleate, pentae
Risuritol monostearate, linolenin, etc.
Esters: dibutyl disulfide, dioctyldis
Disulfides such as sulfide and didodecyl disulfide
Chlorinated paraffin wax, chlorinated naphthalene, salt
Chlorinated hydrocarbons such as alkylated benzene; n-butyl
Phosphinates such as rudi-n-octyl phosphinate
And di-n-butylhexylphosphonate, di-n-butyl
Phosphonates such as tylphenylphosphonate; Trib
Cyl phosphate, tricresyl phosphate, trio
Rail phosphate, di-2-ethylhexyl phosphate
Phosphates such as phosphates; (C_FourH₉O)_TwoPONR₁
R_Two[Where R₁And R_TwoIs hydrogen or -C _FourH
₉Represents a group], (C_FourH₉O)_TwoPOR₁R_TwoR_ThreeR_Four
[Where R₁~ R_FourIs hydrogen, -C_FourH₉Group or-
C₈H₁₇An amine-based phosphate;
6-di-t-butyl-P-cresol, 2,2'-methyl
Lenbis (4-methyl-6-t-butylphenol),
2,2'-methylenebis (4-ethyl-6-t-butyl
Phenol), 2,5-di-t-amylhydroquinone,
2,5-di-t-butylhydroquinone, 4,4'-thio
Bis (6-t-butyl-m-cresol), octadecy
Ru-3- (3,5-di-tert-butyl-4-hydroxyphenyl)
Enyl) propionate, 3,5-di-t-butyl-4
-Hydroxy-benzylphosphonate-diethyl ester
Triethylene glycol bis [3- (3-t-butyl)
5-methyl-5-hydroxyphenyl) propione
Phenols; ethylene-vinyl acetate copolymer
, Ethylene-alkyl alkylate copolymer, polya
Alkyl (meth) acrylate, α-olefin- (none
Water) and a copolymer such as a maleic acid copolymer.

Among the above-mentioned lubricity-imparting agents, in the present invention, preferred are higher fatty acids, amine compounds, ester compounds, phenols, alkyl phosphates, amine phosphates, ethylene-vinyl acetate copolymers, ethylene-alkyl alcohols. Chelate copolymers, polyalkyl acrylates, alkenyl succinamides, dilinoleic acid compounds and the like are used. More preferably, various compounds used as antioxidants among amine compounds or phenols, various compounds used as corrosion inhibitors among compounds selected from alkyl phosphates and amine phosphates, ethylene-vinyl acetate copolymer, Ethylene-alkyl acrylate copolymer, various compounds used as low-temperature fluidity improver among compounds selected from polyalkyl acrylate and alkenyl succinamide, and various compounds used as lubricity improver among dilinoleic acid-based compounds At least one selected is used. Among the above compounds, in the present invention, higher fatty acids, amine compounds and ester compounds are particularly preferably used.

In the present invention, the lubricity imparting agent is
It is preferably added to the diesel light oil composition in an amount satisfying the following formula (I). A × 0.05 + 50 <B <1,000 (I) [wherein A represents the amount (mass ppm) of the cetane number improver added, and B represents the amount added (mass ppm) of the lubricity imparting agent. ppm). In the formula (I), (A × 0.05 + 5)
When 0 <B) is not satisfied, the effect of the present invention for maintaining lubricity may not be sufficiently exhibited, and (B <1,
000) may not be completely dissolved in the diesel composition. Also, preferably,
What is necessary is to satisfy (B <500) in terms of the addition efficiency.

The diesel light oil composition of the present invention may contain a fluidity improver, a detergent, an antioxidant, a metal deactivator, a microbial disinfectant, an anti-icing agent, if necessary, as long as the effects of the present invention are not impaired. Additives such as an antistatic agent, a corrosion inhibitor, an antifoaming agent, a rust preventive, a flame retardant, a colorant, and a marker can be appropriately added.

[0017]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto. Examples 1 to 4 and Comparative Examples 1 and 2 0.027 mass% of sulfur content, kinematic viscosity at 30 ° C 5.2
Octyl nitrate as a cetane number improver and a lubricity-imparting agent were added to a 9 mm ² / s deep desulfurized gas oil at the ratios shown in Table 1, and the lubricating performance of each of the obtained gas oil compositions was determined by the following method. evaluated.

Evaluation of Lubrication Performance HFRR [High Frequency Reciprocation Wear Rig,
PSC Instruments Co., Ltd.], a bearing ball of 6 mm in diameter and material EN31 / 52100 was slid on a disk of 10 mm in diameter and material EN31 / 52100 in a test fuel bath under the following conditions. Test oil temperature: 60 ° C. Room temperature: 25 ° C. Relative humidity: 50% Load: 200 g Vibration stroke: 1 mm Vibration frequency: 50 Hz Test time: 75 minutes After the test, the diameter of the wear mark of the ball was measured in the X and Y directions.
The average value is shown in Table 1 as a wear width (μm). The measurement of the wear mark was performed with a measuring microscope at a measuring accuracy of about 2 μm.

[0019]

[Table 1]

As is evident from Table 1, the addition of a lubricity-imparting agent significantly reduces the sulfur content, and even when a cetane number improver is added, a gas oil composition having excellent lubricating performance can be obtained. Was. The properties and performance of light oil were determined by the following methods. In addition, the lubricity imparting agents a and b used
Is as follows. (1) Sulfur content: Measured according to JIS K2541. (2) Kinematic viscosity: measured in accordance with JIS K 2283. (3) Abrasion width: measured according to the method using the HFRR. (4) Additive a: a commercially available additive containing oleic acid as a main component. (5) Additive b: 60% of industrial oleic acid and glycerin monoester containing 70% or more of oleic acid and about 10% of saturated acid, A mixture of 20% diester and 20% triester

[0021]

According to the present invention, a deep desulfurized gas oil base material is used, the sulfur content is remarkably reduced, and excellent lubricating performance is maintained even when a cetane number improver is added. It is possible to provide a diesel light oil composition which does not cause a problem in the fuel injection pump of the above and does not deteriorate the exhaust gas.

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Claims (4)

[Claims] Claims 1. A sulfur content of 0.05% by mass or less,
A diesel light oil composition to which a cetane number improver and a lubricity imparting agent are added. 2. The amount of the cetane number improver added is 100 to 5,
The diesel gas oil composition according to claim 1, wherein the amount is 000 ppm by mass. 3. The diesel light oil composition according to claim 1, wherein the amount of the lubricity imparting agent added is within a range represented by the following formula (I). A × 0.05 + 50 <B <1,000 (I) [wherein A represents the amount (mass ppm) of the cetane number improver added, and B represents the amount added (mass ppm) of the lubricity imparting agent. ppm). ] 4. The lubricating agent may be a higher fatty acid, an amine compound, an ester compound, a phenol, an alkyl phosphate, an amine phosphate, an ethylene-vinyl acetate copolymer, an ethylene-alkyl acrylate copolymer, or a polyalkyl. The diesel gas oil composition according to any one of claims 1 to 3, which is at least one selected from acrylates, alkenylsuccinamides, and dilinoleic acid-based compounds.