JP2754462B2 - Low sulfur gas 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 low sulfur gas oil composition having excellent wear resistance and excellent sliding properties.

[0002]

2. Description of the Related Art In order to cope with environmental problems, low-sulfur treatment of gas oil base materials (specifically, deep desulfurization, indirect desulfurization, direct desulfurization, hydrocracking, etc. Low-sulfur gas oils having a sulfur content of 0.05% by weight or less obtained by mixing a light fraction such as kerosene or any other process that leads to sulfuration. However, it has been pointed out that these low-sulfur light oils have lower lubricity than conventional light oils. this is,
In some parts of the United States and Europe, where the regulation on sulfur content of diesel fuel under 0.05% by weight has already begun, breakdown accidents due to malfunctions and reduced durability of distribution type fuel injection pumps that supply fuel to diesel engines have been reported. It originated in the frequent occurrence. This distribution type fuel injection pump is mainly mounted on small and medium-sized diesel vehicles, and is characterized by lubricating the movable parts inside the pump by the lubrication performance of light oil itself,
The relationship between a decrease in the lubricity of light oil and malfunction or deterioration in durability has been reported. Therefore, the response is urgently needed. As a method for improving these properties, a commercially available corrosion inhibitor for fuel oil (CI) having a lubricating property improving function or a lubricating property improving agent (LI) is added to improve the lubricating property in the wear test evaluation of low sulfur gas oil. There are many examples of research aimed at improving the sexuality.

[0003]

However, although the improvement method using these additives is effective to some extent against the wear inside the pump, it has been found that there are the following drawbacks. 1. The use of additives causes the gas oil composition to deteriorate in properties other than lubricity, such as sludge formation, oxidative stability, thermal stability, and adverse effects on diesel engines and exhaust gas. 2. The internal mechanism of a distributed fuel injection pump is complex, and simply improving wear cannot maintain the performance of the pump. In particular, high-performance distributive fuel injection pumps for diesel engine exhaust gas countermeasures have many moving parts that require high slidability. Performance cannot be fully demonstrated. The sliding property is a characteristic of a resistance force (sliding friction) acting in a direction opposite to an external force applied when another object slides on the surface of an object without rolling, and the resistance force acting on the sliding surface is small. It is preferable that the object slides smoothly on the sliding surface. A large number of such sliding surfaces exist inside the pump. If the sliding property of light oil is poor, the mechanical control portion of the pump is adversely affected. The present invention has been made in view of the state of the prior art described above, and has as its object to provide a low-sulfur gas oil composition having excellent wear resistance and excellent sliding properties.

[0004]

Means for Solving the Problems Accordingly, the present inventors have
As a result of intensive studies on the lubricity of low sulfur gas oil,
Excellent abrasion resistance without using additives by containing a predetermined amount of gas oil base with low sulfur content obtained by atmospheric distillation without performing desulfurization process from low sulfur content crude oil, without using additives The present inventors have found that a low-sulfur light oil composition having both good slidability and excellent slidability can be obtained, and have completed the present invention. That is, the present invention contains a low-sulfur gas oil fraction having a sulfur content of 0.1% by weight or less obtained by atmospheric distillation of a low-sulfur content crude oil as a gas oil base material in an amount of 3% by volume or more. It is intended to provide a low sulfur gas oil composition having a sulfur content of 0.05% by weight or less.
Hereinafter, the present invention will be described in detail.

The low-sulfur gas oil fraction having a sulfur content of 0.1% by weight or less used in the present invention is obtained by distilling a low-sulfur crude oil at normal pressure. Here, the atmospheric distillation means a general atmospheric distillation process in a petroleum refining process. The low-sulfur crude oil used as the raw material is a crude oil in which the sulfur content of the gas oil fraction obtained by atmospheric distillation is 0.1% by weight or less, preferably 0.07% by weight or less, more preferably 0.05% by weight or less. Yes, generally, there are many Chinese and southern, and specifically, crude oils such as Sumatralite, Sinta, Backfor, Handel, Jackson, and Daqing. Here, the gas oil fraction refers to a distillation property temperature range of 160 to 3 according to the atmospheric pressure distillation test method specified in JIS K2254.
It is a fraction in the range of 90 ° C. This low sulfur crude oil
It does not matter whether the seeds are used alone or in combination of two or more kinds, and those satisfying the above conditions by blending of crude oil are not particularly limited.

The low-sulfur gas oil fraction having a sulfur content of 0.1% by weight or less obtained by atmospheric distillation used in the present invention is a gas oil fraction obtained by atmospheric distillation of low-sulfur crude oil. And the sulfur content is 0.1% by weight or less, preferably 0.07% by weight or less, and more preferably 0.05% by weight or less. The composition of the low-sulfur gas oil fraction is not limited as long as it is within a normal gas oil fraction, but the distillation characteristics of the low-sulfur gas oil fraction are usually about 230 to 310 ° C. at a 10% distillation point. 290-310 ° C., 50% distillation point, usually about 250-
340 ° C., preferably 300-340 ° C., usually about 270-360 ° C., preferably 320-360 at 90% distillation point.
The temperature is usually about 280 to 380 ° C, preferably 320 to 380 ° C at 95 ° C and a 95% distillation point. In addition, this distillation property is J
It is a distillation property by a normal pressure distillation test method specified in IS K2254. These low sulfur gas oil fractions may be used alone or in combination of two or more.

[0007] The low sulfur gas oil composition of the present invention contains the above low sulfur gas oil fraction as a gas oil base material in an amount of 3% by volume or more and the total sulfur content is 0.05% by weight or less. The content ratio of the low-sulfur gas oil fraction can be easily adjusted by mixing the low-sulfur gas oil fraction with another gas oil base material. Other gas oil base materials to be mixed with the low sulfur gas oil fraction have a sulfur content of 3% by volume or more, preferably 5% by volume or more, more preferably 10% by volume or more, even if the low sulfur gas oil fraction is mixed. With a sulfur level that can be adjusted to 0.05% by weight or less,
Any base material may be used as long as there is no problem in the properties of the product gas oil. Specific examples of other gas oil base materials in which the low sulfur gas oil fraction is mixed as a gas oil base material in an amount of 3% by volume or more include:
For example, a low-sulfur gas oil base material obtained through a low-sulfurization treatment, a light low-sulfur gas oil base material such as a kerosene fraction, and the like can be mentioned. These other light oil base materials may be used alone or in combination of two or more. The sulfur content of other gas oil bases mixed with the low sulfur gas oil fraction is usually 0.1%.
The amount is preferably 1% by weight or less, more preferably 0.07% by weight or less, and further preferably 0.05% by weight or less.

The content of the low-sulfur gas oil fraction may be determined so that the sulfur content after mixing is 0.05% by weight or less in consideration of the sulfur content of another gas oil base material to be mixed. For example, the sulfur content of the low sulfur gas oil fraction is 0.05% by weight or more,
When the content is 0.1% by weight or less, the lubricating property improving effect is taken into consideration,
3% by volume or more, preferably 5% by volume of low sulfur gas oil fraction
As described above, the sulfur content of the gas oil base material to be mixed is restricted so as to be more preferably mixed at 10% by volume or more.
That is, the sulfur content of the low sulfur gas oil fraction is 0.09% by weight.
In the case where the sulfur content of the other gas oil base material to be mixed is 0.04% by weight, the content ratio of the low sulfur gas oil fraction is 20%
% By volume or less (when the substrate density is the same).
On the contrary, the sulfur content of the low sulfur gas oil fraction is 0.05% by weight or less, and the sulfur content of the other gas oil base material to be mixed is 0.05% by weight.
In the case where the amount of the low sulfur gas oil fraction is not less than 0.05% by weight, the low sulfur gas oil fraction needs to be mixed with the low sulfur gas oil fraction to be 0.05% by weight or less. Will increase. That is, when the sulfur content of the low sulfur gas oil fraction is 0.02% by weight and the sulfur content of the other gas oil base material to be mixed is 0.06% by weight, the low sulfur gas oil fraction is reduced by 2%.
It is necessary to mix 5% by volume or more (when the substrate density is the same). In addition, when the sulfur content of both the low sulfur gas oil fraction and the other gas oil base is 0.05% by weight or less, the upper limit of the content ratio of the low sulfur gas oil fraction is not particularly limited.

In any of the above cases, when the content of the low sulfur gas oil fraction is high, the selection may be made in consideration of the effect on the properties of the product gas oil, for example, the effect of low temperature fluidity, etc. If necessary, various additives such as a fluidity improver and a cetane number improver can be used.
The content ratio of the low sulfur gas oil fraction depends on the distillation properties, sulfur content, and other properties, but is usually preferably from 3 to 40% by volume, more preferably from 5 to 35% by volume, and still more preferably. It is 10 to 30% by volume. The low-sulfur light oil composition of the present invention contains other various additives such as a preservative, a rust inhibitor, a defoamer, a detergent, an antioxidant, a hue improver, and a lubricity improver. May be.

[0010]

Next, the present invention will be described more specifically with reference to examples and comparative examples. The present invention is not limited by these examples. Table 1 shows the general properties of the gas oil used in the examples and comparative examples. The deeply degassed gas oil bases (1) and (2) in Table 1 are obtained by subjecting a light oil fraction obtained from a crude oil mainly composed of Middle Eastern crude oil to atmospheric distillation to a sulfur content of 0.05% by weight or less through a deep desulfurization process. It is a light oil base material formed in the above. No. 2 light oil (1), (2)
Is a product light oil that complies with the provisions of light oil type 2 in Japanese Industrial Standard JIS K 2204. The low-sulfur gas oil fractions A, B, C, and D are gas oil fractions obtained by distilling low-sulfur crude oil at atmospheric pressure, and are sulfur components obtained by atmospheric distillation, which is an essential component of the present invention. Corresponds to a low sulfur gas oil fraction of 0.1% by weight or less. Table 2 shows various properties of the additives used in Comparative Examples.

[0011]

[Table 1] Note The abbreviations in Table 1 have the following meanings. TD%: Total distillate RO: Residual oil LOSS: Loss

[0012]

[Table 2] Note: In Table 2, the words shown in the first line of the product name mean the following company names. Ethyl: Ethyl Petroleum Add
itives. Inc. DuPont: DuPont Company Lubrizol: Lubrizol Corpora
tion

The evaluation tests of the examples and the comparative examples were performed by the following methods. (1) Wear test The wear test was performed using a vibration friction wear tester manufactured by Optimol Corporation. The test conditions are as follows. Load: 3N Amplitude: 0.60 mm Frequency: 60 Hz Sample temperature: 60 ° C. Metallurgy-ball: SUJ 2 Metallurgy-flat: SUJ 2 Ball diameter: 10 mm Test time: 60 minutes Abrasion was evaluated by examining the wear mark on the test ball. Performed by diameter. The diameter of the wear mark is the average value of the diameter in the vibration direction and the diameter in the vertical direction. When using the deeply lightened gas oil base material (1) as the other light oil base material, the deeply lightened gas oil base material (1) is used. )
Is expressed by the relative wear scar diameter when the wear scar diameter is 100, and when the deeply lightened gas oil base material (2) is used as another light oil base material, the wear scar diameter of the deeply lightened gas oil base material (2) is 100
In the case of using a mixture of the deeply lightened gas oil base material (1) and the deeply lightened gas oil base material (2) as the other light oil base material, the deeply lightened gas oil base material (1) And the wear scar diameter of the mixture of the mixture of the gas oil base material and the deeply degassed oil base (2) was defined as 100.

(2) Measurement of Coefficient of Friction Each sample was placed on a Millipore filter paper (material: HA, size: 0. 1).
A pretreatment for removing impurities such as dust was performed by suction filtration at 45 μm. For the measurement of the friction coefficient, the boundary friction coefficient was measured using a Soda T-shaped pendulum friction tester type II. The measurement conditions are as follows. Initial amplitude: 0.5 radian Horizontal weight: 30 g Horizontal weight distance: 340 mm Vertical weight: 15 g Vertical weight distance: 100 mm Steel ball: Advanced 3/16 class, SUJ2 Roller pin: SUJ2 Sample temperature: 25 ° C. , Repeatedly (50-80 times) swing the pendulum,
Calculate the average value after reaching the steady state (20 to 40 times), repeat this 1 to 3 times, and use the average as the friction coefficient,
When using the deeply degassed light oil base material (1) as another light oil base material, the depth is expressed by a relative friction coefficient when the friction coefficient of the deeply delighted light oil base material (1) is set to 100. When using the lightly degassed oil base material (2), it is represented by a relative friction coefficient when the friction coefficient of the deeply degassed light oil base material (2) is set to 100, and the deeply lightened gas oil base material (1) When the mixture of the deeply lightened oil base material (2) and the deeply lightened oil base material (2) is used, the
It was represented by the relative friction coefficient when it was set to 0.

Examples 1 to 5 Low sulfur sulfur gas oil fraction A shown in Table 3 and each base material of deeply degassed diesel oil base (1) were blended and mixed in proportions shown in Table 3 to obtain low sulfur gas oil. A light oil composition was prepared. Table 3 shows the total sulfur content of these low sulfur gas oil compositions. For these low sulfur gas oil compositions, a wear test and measurement of a coefficient of friction were performed. Table 3 shows the results.

Example 6 A low sulfur gas oil composition comprising only low sulfur gas oil fraction A was prepared. This low sulfur gas oil composition was subjected to a wear test and measurement of a coefficient of friction. Table 3 shows the results.

Example 7 The low sulfur gas oil fraction A shown in Table 3 and the base material of the deeply degassed gas oil base material (2) were blended in the ratio shown in Table 3 and mixed.
A low sulfur gas oil composition was prepared. Table 3 shows the total sulfur content of this low sulfur gas oil composition. This low sulfur gas oil composition was subjected to a wear test and measurement of a coefficient of friction. Table 3 shows the results.

Examples 8 to 12 The base materials of the low sulfur gas oil fraction B and the deeply desorbed gas oil base material (1) shown in Tables 3 and 4 were blended in the proportions shown in Tables 3 and 4. By mixing, a low sulfur gas oil composition was prepared. Tables 3 and 4 show the total sulfur content of these low sulfur gas oil compositions. For these low sulfur gas oil compositions, a wear test and measurement of a coefficient of friction were performed. The results are shown in Tables 3 and 4.

Example 13 A low sulfur gas oil composition comprising only low sulfur gas oil fraction B was prepared. This low sulfur gas oil composition was subjected to a wear test and measurement of a coefficient of friction. Table 4 shows the results.

Example 14 The low sulfur gas oil fraction B shown in Table 4 and the base material of the deeply degassed gas oil base material (2) were blended in the ratio shown in Table 4 and mixed.
A low sulfur gas oil composition was prepared. Table 4 shows the total sulfur content of this low sulfur gas oil composition. This low sulfur gas oil composition was subjected to a wear test and measurement of a coefficient of friction. Table 4 shows the results.

Examples 15 to 18 Each of the low-sulfur gas oil fraction C and the deeply-desorbed gas oil base (1) shown in Table 4 was blended in the proportions shown in Table 4 and mixed. A light oil composition was prepared. Table 4 shows the total sulfur content of these low sulfur gas oil compositions. For these low sulfur gas oil compositions, a wear test and measurement of a coefficient of friction were performed. Table 4 shows the results.

Example 19 A low sulfur gas oil composition comprising only low sulfur gas oil fraction C was prepared. This low sulfur gas oil composition was subjected to a wear test and measurement of a coefficient of friction. Table 4 shows the results.

Examples 20 to 23 Each of the low sulfur gas oil fraction D and the deeply desorbed gas oil base material (1) shown in Table 5 was blended and mixed at the ratio shown in Table 5 to obtain a low sulfur gas oil base material. A light oil composition was prepared. Table 5 shows the total sulfur content of these low sulfur gas oil compositions. For these low sulfur gas oil compositions, a wear test and measurement of a coefficient of friction were performed. Table 5 shows the results.

Example 24 A low sulfur gas oil composition comprising only the low sulfur gas oil fraction D was prepared. This low sulfur gas oil composition was subjected to a wear test and measurement of a coefficient of friction. Table 5 shows the results.

Example 25 Low-sulfur gas oil fraction B shown in Table 5, deeply degassed gas oil base material (1)
The low-sulfur gas oil composition was prepared by blending and mixing each base material of the deeply-desorbed gas oil base material (2) in the following ratio. The total sulfur content of this low sulfur gas oil composition was 0.038% by weight. Low sulfur gas oil fraction B 20% by volume Deeply light gas oil base material (1) 40% by volume Deeply light gas oil base material (2) 40% by volume For this low sulfur gas oil composition, an abrasion test and measurement of a coefficient of friction were performed. As a result, as compared with the case of using the deeply-desorbed light oil base material (1) alone, the wear effect was reduced by 40% and the friction coefficient was reduced by 20%.

Example 26 Each of the low sulfur gas oil fraction A, the low sulfur gas oil fraction B, the deep gas oil base material (1) and the deep gas oil base material (2) shown in Table 5 was used. A low sulfur gas oil composition was prepared by mixing and mixing at the following ratios. The total sulfur content of this low sulfur gas oil composition is:
0.035% by weight. Low-sulfur gas oil fraction A 15% by volume Low-sulfur gas oil fraction B 5% by volume Deep-desorbed gas oil base (1) 40% by volume Deep-desorbed gas oil base (2) 40% by volume About this low-sulfur gas oil composition When the wear test and the measurement of the coefficient of friction were performed, there was a 35% reduction in abrasion and a 20% reduction in the coefficient of friction as compared with the case of using the deeply-desorbed light oil base material (1) alone.

[0027]

[Table 3]

[0028]

[Table 4]

[0029]

[Table 5]

Comparative Examples 1-4 Deep-light oil base material (1), deep-light oil base material (2),
A light oil composition comprising only No. 2 light oil (1) and No. 2 light oil (1) was prepared. For this light oil composition, a wear test and measurement of a coefficient of friction were performed. Table 4 shows the results.

Comparative Examples 5 to 8 Each of the additives shown in Table 2 was mixed at a ratio of 30 mg / l with the deeply-desorbed gas oil base material (1) to prepare gas oil compositions. For this light oil composition, a wear test and measurement of a coefficient of friction were performed. Table 4 shows the results.

[0032]

[Table 6]

As is clear from the above table, in Comparative Examples 1 and 2, which consist only of the deeply desorbed light oil base material, the wear resistance is large and the coefficient of friction is high, so that both the wear resistance and the sliding property are poor. . Comparative Examples 3 and 4 consisting only of No. 2 light oil were:
Sulfur content far exceeds 0.05% by weight, causing significant environmental pollution. In Comparative Examples 5 to 8, in which 30 mg / l of various additives were added to the deeply lightened gas oil base material (1), the wear was reduced to a level close to that of No. 2 light oil, but it was completely effective in reducing the friction coefficient. There was no. In contrast, the low-sulfur gas oil composition of the present invention has the effect of reducing abrasion as the content of the low-sulfur gas oil fraction increases, and in any case, mixing of about 25% by volume or more and 20% or more A wear reduction effect is observed. In particular, for the low sulfur gas oil fraction B, 10% by volume
A significant improvement in abrasion of at least 40% can be confirmed with a certain degree of mixing. As described above, by mixing the low sulfur gas oil fraction used in the present invention with a base material having poor abrasion, such as a deeply degassed gas oil base material, the wear can be significantly reduced. Further, the low-sulfur gas oil composition of the present invention has the effect of reducing the coefficient of friction as the content of the low-sulfur gas oil fraction increases, and in any case, the mixing of about 25% by volume or more results in a friction of 10% or more. A coefficient reduction effect is recognized, and it can be reduced to a level equivalent to or higher than that of No. 2 light oil. In particular, low sulfur gas oil fraction B
Regarding the above, a significant improvement in the coefficient of friction can be confirmed by mixing about 10% by volume. Therefore, the low-sulfur gas oil composition of the present invention not only has excellent or equal wear resistance than lubricity improvement by conventional additives, but also has more excellent sliding properties. It is clear that

[0034]

According to the present invention, an additive is prepared by a simple means of using a fixed amount of a low sulfur gas oil fraction having a sulfur content of 0.1% by weight or less obtained by atmospheric distillation as a gas oil base material. Without using it, it is possible to provide a low sulfur gas oil composition having both excellent wear resistance and excellent slidability. Therefore, the low sulfur gas oil composition of the present invention is extremely useful in practice.

Continuation of the front page (72) Inventor Yasuo Iwamiya 1134-2 Gongendo, Satte City, Saitama Prefecture Cosmo Research Institute, Inc. Research and Development Center (56) References JP-A-5-311179 (JP, A) (58) Survey Field (Int.Cl. ⁶ , DB name) C10L 1/04

Claims (1)

(57) [Claims] 1. A low-sulfur gas oil fraction having a sulfur content of 0.1% by weight or less obtained by atmospheric distillation of a low-sulfur crude oil ,
A low-sulfur gas oil composition containing 3% by volume or more as a gas oil base material and having a total sulfur content of 0.05% by weight or less.