JPH09235574A - Fuel oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fuel oil composition low in a modified filter plugging point in a simplified simulation test, substantially not causing a trouble such as the plugging of a filter under practical operating conditions, and improved in low temperature flowability by adding a specific fuel oil additive to a middle to heavy distillate fuel oil having a residual carbon content. SOLUTION: This fuel oil composition comprises 100 pts.wt. of a fuel oil having a 10% residual carbon content in an amount of 0.1-1.5wt.% and 0.0005-1.0 pt.wt. of an ethylene-α-olefin copolymer having a penetration rate of 20-600, an ethylene content of 70-85mol.% and an intrinsic viscosity of 0.1-1.0dl/g.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fuel oil composition, and more particularly to a fuel oil composition having improved low temperature fluidity of a medium to heavy distillate fuel oil containing residual carbon content.

[0002]

2. Description of the Related Art Hydrocarbon-based medium to heavy distillate fuel oil (light oil to heavy oil) causes wax to deposit in fuel systems such as automobiles and trucks at low temperatures, causing troubles such as clogging of filters. There are cases. In addition, when the product is transported by a tanker or stored in a tank, the deposited wax deposits on the bottom of the tank to form a compact wax layer.

In order to solve such problems, many fuel oil additives have been disclosed so far. For example,
Ethylene-α-olefin copolymer (Japanese Patent Publication No. 60-35
395, 60-35396), ethylene-vinyl acetate copolymer (US Pat. No. 2,048,479, JP-A-55-137193), etc., ethylenic polymer type additives, aromatic dicarboxylic acids. Acid amide
Amine salt and ethylene-vinyl acetate copolymer and ethylene-
Combination with α-olefin copolymer (JP-A-56-
92996 and 58-1792).

Further, alkenyl succinamide (JP-A-56-43391), polyoxyalkylene ester (JP-A-57-177092, US Pat. No. 4).
There is also a surfactant type fuel oil additive such as JP-A-464182) and a combination type such as a combination of an ethylene-vinyl acetate copolymer and an alkenyl succinic acid alkyl ester in combination with an existing fluidity improver. And other additives (British Patent No. 2129012) are known.

However, in recent years, due to an increase in demand for kerosene, the properties of medium to heavy distillate fuel oils have a narrow distillation temperature range, and the distillation temperature range is widened to the higher side, so that it tends to be heavy. It is in. In addition, the fuel base oil is diversified by the use of cracked distillate obtained by vacuum distillation residue oil or heavy oil by heat or catalytic cracking, and the low-temperature properties of fuel oil have changed significantly. Additives are no longer effective.

Particularly, regarding the effect of improving low temperature fluidity for heavy distillate fuel oil such as heavy oil A containing residual carbon content, many troubles occur under actual use conditions, and improvement is desired. is the current situation. For details, to date, in order to determine the clogging property of the fuel oil pipe filter at low temperature, the clogging point (Cloud Filter P
lugging Point; hereinafter referred to as CFPP)
Tests have been used. This test quenches the sample oil,
It is a method in which the filter is passed every time the temperature decreases by 1 ° C. and the clogging property of the filter is evaluated.

This CFPP test is a test method mainly developed for light oils, and when applied to heavy distillate fuel oils such as heavy fuel oil A, there are cases where CFPP does not show the low temperature limit temperature. I've come to understand. This is CFP
The cooling rate of the sample oil in the P test is rapid cooling (about 40 ° C / hour), and it greatly depends on the cooling rate of the temperature in the fuel oil tank (about 1-2 ° C / hour) under actual use conditions. It is thought that there is a cause for being far away. In general, if the cooling rate is rapid, the precipitated wax crystals become small and easily pass through the filter. On the contrary, if the wax crystals are loose, the wax crystals that are deposited become large and the filter is likely to be clogged.

That is, a heavy distillate fuel oil such as A heavy oil, which is quality-controlled by the CFPP test, has a sufficient possibility of causing filter clogging at a temperature higher than the low temperature operation limit temperature. When the above-mentioned fuel oil additive is added to heavy distillate fuel oil such as heavy fuel oil A containing residual carbon content, it interacts with the asphaltene content in the residual carbon content, and this asphaltene content becomes the core and becomes the fuel oil. Part of the additive is combined to form a huge wax, which tends to cause the clogging of the filter.

As described above, when applied to heavy distillate fuel oil such as A heavy oil containing residual carbon content, in the CFPP test developed for light oil, the cooling rate is rapidly cooled and the crystals become small, and Asphaltene content in carbon may adversely affect wax and may not exhibit a low temperature operating limit. That is, there is a problem in managing the heavy distillate fuel oil such as heavy oil A containing residual carbon content in the CFPP test.

Therefore, in order to estimate the actual low temperature operating limit temperature, a Simulated test (cooling condition: 1 ° C./hour) was conducted by the A Heavy Oil Special Committee of the Fuel Oil Subcommittee of the Japan Petroleum Institute.
Was examined. Modified clogging point that correlates with this shimirate test [Petroleum product discussion meeting (November 1994 1
0th, 11th) "Examination of low-temperature fluidity evaluation method of heavy oil A"
Among the correction methods described in Table 3 <Correlation between various corrected clogging points and oil passage limit temperature> on page 44, "corrected 4 clogging point" with the best oil passage limit temperature and correlation coefficient; In the so-called simulated test] (cooling condition: 1 ° C / hour), the existing fuel oil additive has a small effect of improving low temperature fluidity,
In particular, it has been found that there is no effective one for heavy distillate fuel oil such as A heavy oil containing residual carbon content.

[0011]

SUMMARY OF THE INVENTION In light of the above-mentioned conventional circumstances, the present invention provides a simple method by adding a specific fuel oil additive to a medium to heavy distillate fuel oil containing residual carbon content. A fuel with improved low-temperature fluidity, which has a low modified clogging point in the Similates test, and therefore has a low oil passage limit temperature, and is unlikely to cause problems such as filter blockage under actual use conditions. The purpose is to obtain an oil composition.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, have found that a specific ethylene-α can be obtained for medium to heavy distillate fuel oil containing residual carbon content. −
By adding the olefin copolymer, the oil passage limit temperature is low, it is hard to cause troubles in use such as a greenhouse air heater and a ship, and a fuel oil composition with improved low temperature fluidity can be obtained. And was able to complete the present invention.

That is, according to the present invention, 100 parts by weight of fuel oil having 10% residual carbon content of 0.1 to 1.5% by weight (that is, medium to heavy distillate fuel oil containing residual carbon content) is used. , Penetration of 20-600, ethylene content of 70-85 mol%,
Ethylene-α having an intrinsic viscosity of 0.1 to 1.0 dl / g
-The fuel oil composition (Claim 1), wherein 0.0005 to 1.0 part by weight of the olefin copolymer is added.

The present invention also provides the above fuel oil composition containing an ethylene-α-olefin copolymer having an ethylene content of 70 to 85 mol% and an intrinsic viscosity of 0.1 to 1.0 dl / g. A fuel oil composition having an amount of 0.005 to 0.2 parts by weight (claim 2) can be provided as a particularly preferable fuel oil composition.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Fuel oil having a residual carbon content of 0.1 to 1.5% by weight in the present invention means 10% by volume.
Residual carbon content of residual oil is in the above range, so-called medium quality ~
Heavy distillate fuel oil refers to such a fuel oil, as described above, it is difficult to obtain the effect of improving the low temperature fluidity, but this problem is a specific ethylene-α as a fuel oil additive in the present invention.
-Solved by using olefin copolymers.

As such fuel oil, (a) medium to heavy distillate fuel oil obtained by directly distilling petroleum under atmospheric pressure or reduced pressure, and (b) hydrodesulfurization or catalytic reforming treatment were carried out. Medium to heavy distillate fuel oils, (c) medium to heavy distillate fuel oils that have undergone cracking treatment such as thermal cracking, catalytic cracking, hydrocracking, (d) oil shells, oil sands, coal, etc. There are one kind or a mixture of two or more kinds of cracked oil such as medium to heavy distillate fuel oil, and (e) carbonization containing oxygen such as fats and oils, fatty acids, alcohols, ethers and ketones. It is also possible to use a mixture of a hydrogen-based compound with a medium to heavy distillate fuel oil, (f) residual oil producing residual carbon content, and the like.

Examples of the (f) residual oil producing residual carbon content include, for example, a distillation residual oil obtained by distilling (f ₁ ) petroleum under atmospheric pressure or reduced pressure, (f ₂ ) hydrodesulfurization or catalytic contact. Distillation residual oil of the treated oil that has been subjected to the reforming treatment, (f ₃ ) Distillation residual oil of the cracked oil by thermal decomposition, catalytic decomposition, hydrocracking, etc.
(F ₄₎ heavy extract generated from the lubricating oil manufacturing process, (f ₅₎ various petroleum refining process asphalt membrane-resinous byproduct generated from, (f ₆₎ unsaturated higher olefins and polyolefins, ( f ₇ ) oil shell, oil sand, (f ₈ ) distillation residue of these cracked oils,
(F ₉ ) One or two of heavy distillate fuel oil such as other high molecular weight and / or polymerizable hydrocarbon-based substances
Mixtures of more than one species.

The ethylene-α-olefin copolymer as a fuel oil additive in the present invention is ethylene and propylene, 1-butene, 1-pentene, 1-hexene, 1-
One or more α selected from octene, etc.
-Copolymer with olefin, and such a copolymer can be produced by a method such as anionic polymerization or bulk polymerization known as a general polymerization method.

The ethylene-α-olefin copolymer produced in this manner has an ethylene content (ratio in the total amount with α-olefin) of 70 to 85 mol%, preferably 75 to 83 mol%. It is necessary to be. If the amount is less than 70 mol% or more than 85 mol%, the corrected clogging point in the simple Simulate test does not decrease and it is difficult to obtain the effect of improving low temperature fluidity.

The ethylene-α-olefin copolymer has a penetration of 20 to 600, preferably 30 to 55.
0, more preferably 40 to 500, particularly preferably 5
It has a range of 0 to 450 and an intrinsic viscosity of 0.1 to
It is necessary that the content of the copolymer is 1.0 dl / g, preferably 0.2 to 0.5 dl / g, and a copolymer showing such a penetration and an intrinsic viscosity can be corrected by a simple simulating test. It has good results in lowering the plugging point and, in turn, improving low temperature fluidity.

In this specification, "penetration"
In accordance with JIS K2207, put the sample in a test container with an inner diameter of 7 cm and a height of 8 cm so that no bubbles enter,
After leaving it in a constant temperature and humidity room at ℃ for 24 hours, Nippon Oil Testing Machine Industry Co., Ltd. “TESTERTYPE 201, MF
G. FIG. No. 4519 1990 ", the needle is inserted into the sample for 2 seconds with the weight of the needle alone (50 g) without a weight, and the measurement is performed, and the average value of the three times is used as the needle penetration. is there. The "intrinsic viscosity" is obtained by calculation by measuring the flow-down time of a sample decalin solution at 135 ° C using a glass capillary viscometer.

In the present invention, the reason why the low-temperature fluidity is favorably improved is not always clear when the penetration and intrinsic viscosity of the ethylene-α-olefin copolymer are within the above ranges. According to a wide range of experimental studies, if the penetration is less than 20 or more than 600, the modified clogging point in the simple Simulate test becomes high, and if it is less than 20, there is a problem in handleability and the intrinsic viscosity is 0.1.
If it is less than dl / g, the corrected clogging point in the simple simulating test becomes high, and if it exceeds 1.0 dl / g, there is a problem in handleability. The optimum values of penetration and intrinsic viscosity differ depending on the type of fuel oil, properties, etc., and depending on the individual fuel oil used, the type of α-olefin of the copolymer and the ethylene content are appropriately selected, and The penetration and the intrinsic viscosity may be appropriately selected within the above range.

In the present invention, the amount of ethylene-α-olefin copolymer added is 100 parts by weight of fuel oil.
0.0005 to 1.0 part by weight, preferably 0.001 to
Suitably 0.5 part by weight, particularly preferably 0.005 to 0.2 part by weight, most preferably 0.01 to 0.1 part by weight. If it is too small, there is no addition effect, and if it is too large, the addition effect saturates, and it is difficult to improve the effect corresponding to the addition amount.

The fuel oil composition of the present invention contains various additives such as antioxidants, corrosion inhibitors, combustion aids, anti-sludging agents, demulsifiers and lubrication agents which are added to general fuel oils. You may use together.

[0025]

EXAMPLES Next, the present invention will be specifically described with reference to Examples. In addition, the properties of the fuel oil used in the examples,
It is shown in Table 1. The 10% residual carbon content (that is, the residual carbon content of the 10% by volume residual oil) is a value measured based on JIS K 2270. Further, the distillation property is a value measured based on JIS K 2254.

[0026]

Also, the ethylene-α-olefin copolymers A to H used in the examples and the ethylene-α-olefin used in the comparative examples.
Table 2 shows the types of α-olefin, the ethylene content, the intrinsic viscosity, and the penetration of the olefin copolymers I to O.

[0028]

Example 1 To 100 parts by weight of fuel oil, 0.003 parts by weight of ethylene-α-olefin copolymers A to H or ethylene-α-olefin copolymers I to O were added, and well mixed by stirring. By doing so, 15 types of fuel oil compositions were prepared. Further, instead of the above-mentioned copolymer, an ethylene-vinyl acetate copolymer (ethylene content 76.0 wt%, intrinsic viscosity 0.350 dl / g, needle penetration 87) was used as "conventional product P".
Two kinds of fuel oil compositions were prepared by using dibehenyl ester of polyethylene glycol (average molecular weight 600) as "conventional product Q" in the same amounts as above.

The low temperature fluidity of these fuel oil compositions was evaluated by examining the clogging point [CFPP], the modified clogging point and the pour point [PP] by the simple simulating test. The results are shown in Table 3 below. As a control example, the same table also shows the results when no additive was added.

The clogging point [CFPP] is JIS
It measured based on K-2288. Also, the corrected clogging point by the simple simulator test is JIS K-2288.
Wire mesh (149 μm), cooling rate (1 ° C./hour),
The suction time (30 seconds) was changed, and measurement was performed in an air bath. Furthermore, the pour point [PP] is JIS K-2269.
It measured based on.

Example 2 To 100 parts by weight of fuel oil, 0.003 parts by weight of ethylene-α-olefin copolymers A to H or ethylene-α-olefin copolymers I to O were added, and well mixed by stirring. By doing so, 15 types of fuel oil compositions were prepared. Further, instead of the above copolymer, "conventional product P" and "conventional product Q" described in Example 1 were respectively used in the same amounts as above to prepare two types of fuel oil compositions. .

For these fuel oil compositions, the clogging point [CFPP], the modified clogging point and pour point [PP] by the simple simulating test were examined in the same manner as above,
The low temperature fluidity was evaluated. The results are shown in Table 4 below. As a control example, the same table also shows the results when no additive was added.

Example 3 To 100 parts by weight of fuel oil, 0.003 parts by weight of ethylene-α-olefin copolymers A to H or ethylene-α-olefin copolymers I to O were added, and mixed well with stirring. By doing so, 15 types of fuel oil compositions were prepared. Further, instead of the above copolymer, "conventional product P" and "conventional product Q" described in Example 1 were respectively used in the same amounts as above to prepare two types of fuel oil compositions. .

For these fuel oil compositions, the clogging point [CFPP], the modified clogging point and pour point [PP] by the simple simulating test were examined in the same manner as above,
The low temperature fluidity was evaluated. The results are shown in Table 5 below. As a control example, the same table also shows the results when no additive was added.

Example 4 To 100 parts by weight of fuel oil, 0.003 parts by weight of ethylene-α-olefin copolymers A to H or ethylene-α-olefin copolymers I to O were added, and mixed well with stirring. By doing so, 15 types of fuel oil compositions were prepared. Further, instead of the above copolymer, "conventional product P" and "conventional product Q" described in Example 1 were respectively used in the same amounts as above to prepare two types of fuel oil compositions. .

For these fuel oil compositions, the clogging point [CFPP], the modified clogging point and pour point [PP] by the simple simulating test were examined in the same manner as above, and
The low temperature fluidity was evaluated. The results are shown in Table 6 below. As a control example, the same table also shows the results when no additive was added.

Example 5 To 100 parts by weight of fuel oil, 0.03 parts by weight of ethylene-α-olefin copolymers A to H or ethylene-α-olefin copolymers I to O was added and mixed well with stirring. By doing so, 15 types of fuel oil compositions were prepared. Also,
Instead of the above copolymer, "conventional product P" and "conventional product Q" described in Example 1 were used in the same amounts as above to prepare two types of fuel oil compositions.

For these fuel oil compositions, the clogging point [CFPP], the modified clogging point by the simple simulator test and the pour point [PP] were examined in the same manner as above,
The low temperature fluidity was evaluated. The results are as shown in Table 7 below. As a control example, the same table also shows the results when no additive was added.

Example 6 To 100 parts by weight of fuel oil, 0.01 parts by weight of ethylene-α-olefin copolymers A to H or ethylene-α-olefin copolymers I to O were added, and mixed well with stirring. By doing so, 15 types of fuel oil compositions were prepared. Also,
Instead of the above copolymer, "conventional product P" and "conventional product Q" described in Example 1 were used in the same amounts as above to prepare two types of fuel oil compositions.

For these fuel oil compositions, the clogging point [CFPP], the modified clogging point by the simple simulator test and the pour point [PP] were examined in the same manner as above,
The low temperature fluidity was evaluated. The results were as shown in Table 8 below. As a control example, the same table also shows the results when no additive was added.

Example 7 To 100 parts by weight of fuel oil, 0.006 parts by weight of ethylene-α-olefin copolymers A to H or ethylene-α-olefin copolymers I to O were added, and well mixed by stirring. By doing so, 15 types of fuel oil compositions were prepared. Further, instead of the above copolymer, "conventional product P" and "conventional product Q" described in Example 1 were respectively used in the same amounts as above to prepare two types of fuel oil compositions. .

For these fuel oil compositions, the clogging point [CFPP], the modified clogging point and pour point [PP] by the simple simulating test were examined in the same manner as above,
The low temperature fluidity was evaluated. The results are as shown in Table 9 below. As a control example, the same table also shows the results when no additive was added.

Example 8 To 100 parts by weight of fuel oil, 0.003 parts by weight of ethylene-α-olefin copolymers A to H or ethylene-α-olefin copolymers I to O were added, and well mixed by stirring. By doing so, 15 types of fuel oil compositions were prepared. Further, instead of the above copolymer, "conventional product P" and "conventional product Q" described in Example 1 were respectively used in the same amounts as above to prepare two types of fuel oil compositions. .

For these fuel oil compositions, the clogging point [CFPP], the modified clogging point and pour point [PP] by the simple simulating test were examined in the same manner as described above,
The low temperature fluidity was evaluated. These results are shown in Table 10 below.
It was as shown in. In the table, as a control example,
The results when no additives were added are also shown.

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

From the results of Tables 3 to 10 above, the fuel oil composition of the present invention using ethylene-α-olefin copolymers A to H as the fuel oil additive is the fuel oil composition of Examples It can be seen that in any of cases 1 to 8, very good results were obtained in the simple simulator test having a correlation with the actual low temperature operation limit temperature.

On the other hand, ethylene-α-other than the present invention
The fuel oil compositions of Comparative Examples using the olefin copolymers I to O as fuel oil additives are equivalent to the fuel oils of the Comparative Examples without additives, and show almost no effect. Further, the conventional product P using an ethylene-vinyl acetate copolymer as a fuel oil additive has not been effective. In addition, the conventional product Q, in which polyethylene glycol dibehenyl ester was used as a fuel oil additive, had the effect of CFPP, but a simple simulating test that correlates with the actual low temperature operating limit temperature. Then, the effect is not obtained at all.

[0056]

INDUSTRIAL APPLICABILITY As described above, the fuel oil composition of the present invention can lower the modified clogging point and pour point in the simple simulating test according to the practical use of fuel oil.
When using heavy distillate fuel oil with a relatively high boiling point in warm air blowers for greenhouses, trucks, etc., or during storage or transportation, low temperature fluidity such as filter clogging or sedimentation layer consolidation. It is possible to solve various problems related to. Further, since it is possible to utilize even the high boiling point fraction as described above as the fuel oil, a great advantage can be obtained for the production of the heavy distillate fuel oil.

Claims (2)

[Claims] 1. A penetration amount of 20 to 60 per 100 parts by weight of fuel oil having a residual carbon content of 0.1 to 1.5% by weight.
0, ethylene content 70-85 mol%, intrinsic viscosity 0.
A fuel oil composition comprising 0.0005 to 1.0 part by weight of an ethylene-α-olefin copolymer having a concentration of 1 to 1.0 dl / g. 2. A needle penetration of 20 to 600, an ethylene content of 70 to 85 mol%, and an intrinsic viscosity of 0.1 to 1.0 dl / g.
The fuel oil composition according to claim 1, wherein the added amount of the ethylene-α-olefin copolymer is 0.005 to 0.2 part by weight.